Vrije Universiteit Brussel e-Book of abstracts of ICTAC 2020 ...

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e-Book of abstracts of ICTAC 2020Mangialetto, Jessica; Ehrhardt, Dorothee; Cuvellier, Audrey; Verhelle, Robrecht René;Brancart, Joost; Van Assche, Guy; Rahier, Hubert; Van den Brande, Niko; Van Mele, BrunoPublished in:International Congress on Thermal Analysis and Calorimetry 2020

Publication date:2021

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Citation for published version (APA):Mangialetto, J., Ehrhardt, D., Cuvellier, A., Verhelle, R. R., Brancart, J., Van Assche, G., ... Van Mele, B. (2021).e-Book of abstracts of ICTAC 2020. In International Congress on Thermal Analysis and Calorimetry 2020 (pp.93-185). [S4_O-10] Wydawnictwo Naukowe WNPiD UAM.

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Download date: 06. Feb. 2022

https://researchportal.vub.be/en/publications/2416dee5-1e61-49eb-8a52-50933241a905

Edited by: Agnieszka Łącz and Marcin Środa

AGH University of Science and Technology, Kraków

The Authors are fully responsible for the content and form of the submitted abstracts.

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© Copyright by Wydawnictwo Naukowe AKAPIT, Kraków 2021

Wydawnictwo Naukowe „Akapit”

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www.akapit.krakow.pl

17th INTERNATIONAL CONGRESS

ON THERMAL ANALYSIS AND CALORIMETRY

8th

JOINT CZECH-HUNGARIAN-POLISH-SLOVAKIAN

THERMOANALYTICAL CONFERENCE

14th

CONFERENCE ON CALORIMETRY AND THERMAL ANALYSIS

OF THE POLISH SOCIETY OF CALORIMETRY AND THERMAL

ANALYSIS

ORGANIZERS:

THE POLISH SOCIETY OF CALORIMETRY AND THERMAL ANALYSIS

MEMORIAL OF WOJCIECH ŚWIĘTOSŁAWSKI

AGH UNIVERSITY OF SCIENCE AND TECHNOLOGY,

FACULTY OF MATERIALS SCIENCE AND CERAMICS

CRACOW UNIVERSITY OF TECHNOLOGY,

FACULTY OF CHEMICAL ENGINEERING AND TECHNOLOGY

SPONSORS:

GOLD SPONSOR

SILVER SPONSOR

BRONZE SPONSORS

REGULAR SPONSORS

PREFACE

On behalf of the Organizing Committee of the 17th

International Congress

on Thermal Analysis and Calorimetry (ICTAC2020) including 8th

Joint

Czech-Hungarian-Polish-Slovakian Thermoanalytical Conference and 14th

Conference on Calorimetry and Thermal Analysis of the Polish Society of

Calorimetry and Thermal Analysis – I would like to welcome you cordially at

this on-line event.

The Congress contains seven sessions - Thermodynamics, Thermochemistry

and Kinetics; Instrumentation; Inorganic Materials; Polymers and Organic

Compounds; Materials Science and Energy; Life Science; V4 and CCTA

conference. During the Congress Robert Mackenzie memorial lecture, and

several plenary and invited lectures will be given by outstanding scientists.

For young scientists, Rigaku-ICTAC Young Scientist Award has been

given. An essential part of the conference is educational Workshop titled

„Good laboratory practice in thermal analysis and calorimetry”.

I would like to thank the ICTAC Executive Board with the President Wim

de Klerk, the Dean of the Faculty of Materials Science and Ceramics of the

AGH University of Science and Technology in Krakow, prof. Jerzy

Jedliński, the Dean of Faculty of Chemical Engineering and Technology at

the Cracow University of Technology, Prof. Piotr Michorczyk, Presidents of

thermal analysis and calorimetry societies in V4 countries, members of the

Advisory Committee, as well as members of the International Scientific

Committee for continuous support and advise. Deep thanks go to the

members of the Organizing Committee who devoted plenty of time to make

this conference a successful event. We are grateful to the City of Krakow

and our sponsors for supporting the conference, and to the Editors of the

“Journal of Thermal Analysis and Calorimetry” for establishing a Special

Issue dedicated to the Congress.

I wish you a pleasant and productive – although remote – conference and

hope that our Congress will help to develop new scientific inspirations in

the broad area of thermal analysis and calorimetry.

Thank you!

Yours sincerely,

Krzysztof Pielichowski

ICTAC2020 Chair

SCIENTIFIC AND ORGANISING COMMITTEE

CONFERENCE CHAIR KRZYSZTOF PIELICHOWSKI (POLAND)

CONFERENCE VICE-CHAIR AGNIESZKA ŁĄCZ (POLAND)

PROGRAM CO-CHAIRS RIKO OZAO (JAPAN)

CRISAN POPESCU (GERMANY/ROMANIA)

ERIC SCHOCH (AMERICAS)

V4 CONFERENCE CO-CHAIRS JÁNOS KRISTÓF (HUNGARY)

PETER ŠIMON (SLOVAKIA)

PETRA ŠULCOVÁ (CZECH REPUBLIC)

LOCAL COMMITTEE EWA DROŻDŻ

EDYTA HEBDA

MAŁGORZATA JÓŹWIAK

BARBARA PACEWSKA

KINGA PIELICHOWSKA

PRZEMYSŁAW RYBIŃSKI

MAGDALENA SZUMERA

MARCIN ŚRODA

ICTAC EXECUTIVE COMMITTEE

PRESIDENT WIM DE KLERK (THE NETHERLANDS)

VICE PRESIDENT NOBUYOSHI KOGA (JAPAN)

SECRETARY QUEENIE KWOK (CANADA)

TREASURER VESA-PEKKA LEHTO (FINLAND)

MEMBERSHIP SECRETARY JUNKO MORIKAWA (JAPAN)

IMMEDIATE PAST PRESIDENT DONALD BURLETT (USA)

CHAIRMAN OF THE SCIENTIFIC COMMISSION CRISAN POPESCU

(GERMANY/ROMANIA)

VICE-CHAIRMAN OF THE SCIENTIFIC COMMISSION RANJIT K. VERMA

(INDIA)

GUEST OF THE EXECUTIVE – WEBMASTER WOLF - ACHIM KAHL

(GERMANY)

ADVISORY COMMITTEE: ÉDER CAVALHEIRO (BRAZIL)

PIERRE LE PARLOUËR (FRANCE)

ROSA NOMEN (SPAIN)

RIKO OZAO (JAPAN)

JEAN ROUQUEROL (FRANCE)

INTERNATIONAL SCIENTIFIC COMMITTEE

GIUSEPPE ARENA (ITALY)

GUY VAN ASSCHE (BELGIUM)

GUANGYUE BAI (CHINA)

IGNAZIO BLANCO (ITALY)

JERZY BŁAŻEJOWSKI (POLAND)

PIERRE BRODARD (SWITZERLAND)

EDWARD CHARSLEY (UK)

JANUSZ DATTA (POLAND)

WIM DE KLERK (THE NETHERLANDS)

ELŻBIETA FILIPEK (POLAND)

KONSTANTIN GAVRICHEV (RUSSIA)

CHEILA GONÇALVES MOTHÉ (BRAZIL)

BOB HOWELL (USA)

MAŁGORZATA JÓŹWIAK (POLAND)

JAN KAZIOR (POLAND)

JÁNOS KRISTÓF (HUNGARY)

GIUSEPPE LAZZARA (ITALY)

VESA-PEKKA LEHTO (FINLAND)

CHRISTOPHER LI (USA)

GYÖRGY LIPTAY (HUNGARY)

VLADIMIR LOGVINENKO (RUSSIA)

DÉNES LŐRINCZY (HUNGARY)

RENATA ŁYSZCZEK (POLAND)

JIRI MÁLEK (CZECH REPUBLIC)

VINCENT MATHOT (BELGIUM)

LIEZEL VAN DER MERWE (SOUTH AFRICA)

BARBARA PACEWSKA (POLAND)

HENRYK PIEKARSKI (POLAND)

KINGA PIELICHOWSKA (POLAND)

KRZYSZTOF PIELICHOWSKI (POLAND)

MAREK PYDA (POLAND)

ANDREI ROTARU (ROMANIA)

KAZUYA SAITO (JAPAN)

CHRISTOPH SCHICK (GERMANY)

PEER SCHMIDT (GERMANY)

JAROSLAV ŠESTÁK (CZECH REPUBLIC)

PETER ŠIMON (SLOVAKIA)

PETRA ŠULCOVÁ (CZECH REPUBLIC)

JUAN JOSE SUÑOL MARTINEZ (SPAIN)

IRENA SZCZYGIEŁ (POLAND)

IMRE MIKLÓS SZILÁGYI (HUNGARY)

MAREK ŚCIĄŻKO (POLAND)

RANJIT K. VERMA (INDIA)

SERGEI VYAZOVKIN (USA)

MAREK WESOŁOWSKI (POLAND)

CONTENTS

PLENARY AND INVITED LECTURES ................................................................ 13

ORALS AND POSTERS .................................................................................... 20

SESSION 1: THERMODYNAMICS, THERMOCHEMISTRY AND KINETICS .... 21

SESSION 2: INSTRUMENTATION .............................................................. 50

SESSION 3: INORGANIC MATERIALS ....................................................... 64

SESSION 4: POLYMERS AND ORGANIC COMPOUNDS ............................... 81

SESSION 5: MATERIALS SCIENCE AND ENERGY.................................... 112

SESSION 6: LIFE SCIENCE ..................................................................... 145

SESSION 7: V4 8 & CCTA14 .............................................................. 158

SPONSOR LECTURES .................................................................................... 167

THERMAL ANALYSIS WORKSHOP ............................................................... 173

LIST OF AUTHORS ....................................................................................... 179

PLENARY

AND INVITED LECTURES

Robert C. Mackenzie’s heritage and one century of thermal analysis and calorimetry

JEAN ROUQUEROL

Aix-Marseille University – CNRS

MADIREL Laboratory

e-mail: [email protected] Keywords: Robert C. Mackenzie, Thermal Analysis Nomenclature, Calorimetry Nomenclature, Recent History of Thermal Analysis and Calorimetry

This lecture will first pay tribute to the major part played by R.C. Mackenzie

in the foundation, developement and spirit of ICTAC. After a few memories, his decisive role in establishing a thermal analysis nomenclature in this new growing field will be stressed, together with the recognition that his initial impulse was not a one-shot effort but is still effective today. Extending this work to the second field of interest of ICTAC, calorimetry, will be shown to be more difficult although in good progress. His more general action to extend our community to any country, and to develop a friendly spirit of collaboration will also be reminded.

This will bring us to a broader view of the development, over a century, of our field and community of thermal analysis and calorimetry.

1880-1950: a period of slow start, thanks to scientists with bright ideas and good manual skill, like Le Chatelier (automatic registration of a heating curve), Roberts-Austen (the differential method), Kurnakov (the photographic recording drum) Honda (the thermobalance), Tian (the heat-flowmeter microcalorimeter), Swietoslawsky (the adiabatic microcalorimeter)…

1950-1975: explosion of novelties mainly developed in academic laboratories and then made commercially available: automated thermobalance (Chévenard), vacuum and null thermobalance (Eyraud), simultaneous TG-DTA (Paulik, Wiedeman), heat-flow microcalorimeter (Calvet), power-compensation DSC (Wat-son and O’Neil)...Important books are published by Calvet, Mackenzie, Duval, Garn, Wendlandt, and methods of data processing are developed by Kissinger, Friedman, Ozawa, Flynn, Brown and others.

1975-2000: academic laboratories become less involved in the development of new set-ups, equipment is mainly developed by instrument manufacturers and is computerized. Also, it is felt reasonable to bring together thermal analysts and cal-orimetrists. This occurs at a national level and, to correctly embrace all societies, ICTA logically becomes ICTAC in 1992.

2000-2021: we are enjoying a nice time for thermal analysis and calorimetry, with magnificent instruments, but we are losing part of the strong previous need of being inventive, of fighting against some laws of physics and drawing benefit from others. This is why we shall end by advocating the use of cheap experimental tools for developing among students experimental skills and a real pleasure in carrying out and understanding experiments of thermal analysis and calorimetry.

ICTAC 2020 17th International Congress on Thermal Analysis and Calorimetry, 29 Aug. – 2 Sept. 2021

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Thermal and kinetic analysis on pyrolysis reaction of hydroxylammo-nium nitrate solution

KENTO SHIOTA¹*

1Institute of Advanced Sciences, Yokohama National University, Yokohama, Japan

*Corresponding author: e-mail: [email protected]

Keywords: thermal analysis, kinetic analysis, hydroxylammonium nitrate, pyrolysis

Hydroxylammonium nitrate (HAN, [NH3OH]+[NO3]-) has attracted attention as

a new generation liquid propellants because it has a good oxygen balance and high performance, and contains no halogen atoms. It is helpful to have information re-garding the decomposition and combustion behaviour of propellant ingredients such as HAN when developing comprehensive ignition and combustion models for rocket motor and gas generators employing these materials. The present study focuses on condensed phase reaction of HAN to understand pyrolysis reaction pathways before combustion. On the other hand, the pyrolysis reaction of HAN solution in condensed phase is complex.

The aim of this study was to conduct thermal and kinetic analysis on pyrolysis reaction of HAN solution with thermal measurements. The thermal behaviour of HAN was measured with micro calorimeter C80 (SETARAM instrumentation) using pseudo sealing glass-tube at several constant heating rates. Then, these C80 curves were separated into some peaks using deconvolution functions. The deconvoluted peaks were elaborated. The activation energy of condensed phase reaction of HAN was calculated with kinetic analysis using the deconvoluted peaks. The mechanism of pyrolysis reaction of HAN was discussed by comparing the result of kinetic from thermal analysis to the results of thermal decomposition of HAN modelled based on our previous study [1,2].

References [1] Y. Izato and A. Miyake, Identification of radical reactions and products for aqueous hydroxylamine

nitrate (HAN) solution based on ab initio calculations, Sci. Technol. Energ. Mater. 79:108-114, 2018

[2] Y. Izato, M. Koshi, A. Miyake, Initial Decomposition Pathways of Aqueous Hydroxylamine Solu-tions, J. Phys. Chem. B. 121:4502-11, 2017


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THERMAL ANALYSIS FOR COMBUSTION RESEARCH: DATA

INTERPRETATION AND CHALLENGES

Jun Liu1, Tao Wang1, and Wei-Ping Pan,1,2*

1 North China Electric Power University, Beijing, China 2 Western Kentucky University, Bowling Green, KY, USA, 42101

* E-mail: [email protected]

Keywords: VOCs emission; TG-FTIR-GC/MS, bimetallic oxide modified fly ash

The emission of volatile organic compounds (VOCs) during coal combustion at dif-ferent heating rates in a power plant boiler, a drop tube furnace, and a TGA reactor was studied. The results indicate that TG-FTIR-GC/MS with a slow heating rate is a better method to obtain the release of VOCs during coal pyrolysis. This technique provides information about VOC formation as a function of time and the mechanism of VOC formation during coal pyrolysis. The majority of the VOCs identified in the TG study may not be observed in a large-scale coal boiler. Thus, an intermediate heating rate device, such as a drop tube furnace, can be used to determine the effect of a fast heating rate on the formation of VOCs. This study demonstrated that the drop tube furnace results were similar to that from a large-scale coal boiler. For the control of VOCs in coal-fired flue gas, the modified fly ash injection technology is regarded as a potential strategy to remove VOCs. The TG could evaluate the reaction rate of the sorbents, contributing to understanding the reaction mechanism and predicting the removal performance in the coal-fired power plants. The best performance of sorbent at different reaction conditions was quickly obtained in the fixed bed system combined with multiple characterizations using BET, H2-TPR, and O2-TPD. In addition, the real flue gas with different injection processes was accurately studied in the drop-tube furnace system to evaluate the reliability of the application. The results showed that Ce-Mn bimetallic oxide modified fly ash with the surface regulation of organic acid ligands exhibited the highest activity for the control of the VOCs. However, the advantage of the effect of air pollution control devices on the VOCs emission can only be obtained from power plant tests. Utilized together, results from the fixed bed reactor, drop tube furnace and boiler, provide a complete VOC profile than one technique alone.

References

[1] Jun Liu, Tao Wang, Ji Cheng, Yongshen Zhang, Wei-Ping Pan, “The Distribution

of Organic Compounds in Coal-fired Power Plant Emissions” Energy and Fuels,

2019; 33:5430-7.

[2] Jun Liu, Jiawei Wang, Ji Cheng, Yongsheng Zhang, Tao Wang, Wei-Ping Pan,

“Distribution and emission of speciated volatile organic compounds from a coal-

fired power plant with ultra-low emission technologies” Journal of Cleaner Pro-

duction, 2020; 264:121686.


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Kinetic Description for the Thermal Decomposition of Solids with

Three Variables: Temperature, Conversion, and Partial Pressure

NOBUYOSHI KOGA¹*, TAIGA TONE1, MITO HOTTA1, LOIC FAVERGEON2

1Hiroshima Univ., Grad. Sch. Humanities and Social Sciences, Dept. Science Education

2Mines Saint-Etienne, University of Lyon, CNRS


Keywords: thermal decomposition, inorganic solids, universal kinetic description

Beyond the conventional kinetic description of the chemical processes in solid–

gas system using temperature (T) and conversion (α), universal kinetic descriptions

considering the partial pressure of product or reactant gases (p(gas)/kPa), have long

been desired. Based on mechanistic considerations of both nucleation and growth

process, we recently proposed the introduction of an analytical form of the accom-

modation function (AF; h(p(gas), Peq(T))) in the conventional kinetic equation for

describing the different types of dependencies of reaction rate on p(gas) [1].

ℎ (𝑝(gas), 𝑃eq(𝑇)) = (𝑃°

𝑝(gas))𝑎

[1 − (𝑝(gas)

𝑃eq(𝑇))

𝑏

] (1)

where (Pº/kPa) and (Peq(T)/kPa) are the standard pressure and equilibrium pressure

for the reversible process, respectively. The exponents (a, b) in AF are variables to

accommodate the different types of p(gas) dependence. The practical applicability

of the kinetic equation with AF was tested for the thermal decomposition of metal

hydroxides [1-3], thermal dehydration of a crystalline hydrate [4], and thermal de-

composition of a metal carbonate [5] through different kinetic calculation ap-

proaches. In this presentation, the universal kinetic approach considering p(gas) is

demonstrated for the thermal decomposition of CaCO3 at different p(CO2) values.

The novel findings of the kinetics in solid-gas system revealed by the universal ki-

netic approach are discussed through reviewing different types of p(gas) dependence.

References

[1] N. Koga, L. Favergeon, S. Kodani. Impact of atmospheric water vapor on the thermal decomposi-

tion of calcium hydroxide: a universal kinetic approach to a physico-geometrical consecutive

reaction in solid-gas systems under different partial pressures of product gas. Phys. Chem.

Chem. Phys. 21:11615–11632, 2019.

[2] M. Fukuda, L. Favergeon, N. Koga. Universal kinetic description for thermal decomposition of

copper(II) hydroxide over different water vapor pressures. J. Phys. Chem. C. 123:20903–20915,

2019.

[3] S. Kodani, S. Iwasaki, L. Favergeon, N. Koga. Revealing the effect of water vapor pressure on the

kinetics of thermal decomposition of magnesium hydroxide. Phys. Chem. Chem. Phys. 22:13637–

13649, 2020.

[4] Y. Yamamoto, L. Favergeon, N. Koga. Thermal dehydration of lithium sulfate monohydrate revis-

ited with universal kinetic description over different temperatures and atmospheric water vapor

pressures. J. Phys. Chem. C. 124:11960–11976, 2020.

[5] N. Koga, Y. Sakai, M. Fukuda, D. Hara, Y. Tanaka, L. Favergeon. Universal kinetics of the thermal

decomposition of synthetic smithsonite over different atmospheric conditions. J. Phys. Chem. C.

125:1384–1402, 2021.


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Thermal analysis in development of solid drug formulations

MAREK WESOLOWSKI¹*

1Medical University of Gdansk, Faculty of Pharmacy, Department of Analytical Chemistry Gen. Hallera 107, 80-416 Gdansk, Poland

*Corresponding author: e-mail: [email protected] Keywords: methods of thermal analysis, solid drug formulations, DSC, TGA

The most important issue in the pharmaceutical technology is development of a

stable, safe and efficient drug dosage form (drug formulation, pharmaceutical prod-uct) that contains prescribed dose of active pharmaceutical ingredient (API, drug substance) and is intended for human or veterinary use. Besides API, drug formula-tion also contains excipients (auxiliary substances). The excipients allow to desig-nate pharmaceutical product with the optimum API dosage that achieve a high con-centration of drug substance at target site, produce a long-acting or delayed drug substance effect, alleviate or reduce the undesirable smells and taste associated with drug substance oral administration, and to resist action by gastric fluids or prevent nausea and vomiting. The application of thermal analysis methods in de-velopment of the solid drug formulations includes (a) characterization of physical and chemical profiles of APIs and excipients, (b) optimization of the formulation process of dosage forms, and (c) quality control and drug substances quantitation in the final pharmaceutical products.

The use of methods of thermal analysis in the pharmaceutical technology is a promising way to investigate the solid-state properties of APIs, excipients and drug formulations as a function of temperature when heated or cooled in a controlled temperature program. Among the various methods of thermal analysis, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) are techniques which are of prime importance in the study of physical properties of pharmaceutical materials, such as melting, crystallization, glass transitions, evaporation, sublimation, crystalline transitions, phase diagrams, and chemical properties reflected by degrada-tion of pharmaceutical materials under different conditions. The key advantage of these methods lay in a small amount of sample required for analysis, a simple pre-treatment of a sample and a fast run of measurements. Recently, thermomechanical analysis (TMA) and dynamic mechanical analysis (DMA) have also gained a great application to characterize thermal properties of solid-state pharmaceutical materials. Thus, the purpose of this presentation is to review current applications of thermal methods in the development of solid drug formulations. A special attention has been paid on the evaluation of API polymorphism, detection of incompatibilities between drug substances and excipients, characterization of effect the various technological processes on the physical and chemical properties of APIs, thermal and thermooxi-dative degradation of pharmaceutical materials, and the quality control and quantita-tion of APIs contained in dosage forms.


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POSS molecules’ use in polymer thermal stabilization: state of the art and future developments

I. BLANCO¹*

1Department of Civil Engineering and Architecture and INSTM UdR , University of Catania, V.le a.

Doria 6, 95125 Catania, Italy *Corresponding author: e-mail: [email protected] Keywords: thermal anlysis, POSS, hybrid materials, composites

Polymer was the defining material of the twentieth century whilst, both for the

considerable increase in articles published in literature and for the growth of appli-cations over the last fifteen years the defining material platform of the twenty-first century could very well be the hybrid material. The design of an hybrid material is related with the combination of two or more components in a single material to give new and previously unattainable combinations of useful properties [1]. For the prep-aration of these materials are required building blocks like carbon nanotubes, gra-phene and polyhedral oligomeric silsesquioxanes (POSSs). The set of knowledge regarding these latter expanded rapidly over a very short period of time as highly efficient synthesis methodologies were developed. Efforts to develop practical ap-plications for discrete POSS frameworks gained a major champion in the early 1990’s when Joseph D. Lichtenhan initiated a research program at Edwards Air Force Base (California, USA) to use POSS-containing polymers as precursors to hy-brid inorganic/organic materials [2]. The interest observed for these nanomaterials since the nineties, was probably due to an increased focus on mechanistic studies involving POSS frameworks, and the deliberate use of POSS as precursors to more complex Si/O and Si/O/M frameworks. Since the existence of reports consistent with silsesquioxane formation back as far as the 1870s [3], we can consider this new de-velopment as a real rebirth of POSS. Today POSSs, due to their thermal and chemi-cal stability, cover with their use various fields, ranging from high-performance ma-terials to flame-resistant materials, novel homogeneous POSS-supported catalyst and applications in proton exchange membranes [4]. POSS molecule has been con-sidered a next generation material in several biological fields, due to its excellent mechanical properties and biodegradability provided by Si–O–Si bonds. Accord-ingly, POSSs have been used as tissue engineering and biomedical materials and to improve the efficiency and pathway of delivery in drug delivery systems [4].

References [1] I. Blanco. The Rediscovery of POSS: A Molecule Rather than a Filler. Polymers 10:904, 2018. [2] J.D. Lichtenhan, K. Pielichowski, I. Blanco. POSS-Based Polymers. Polymers 11:1727, 2019. [3] A. Ladenburg. Ueber aromatische Verbindungen, welche Silicium enthalten. Ber. Dtsch. Chem. Ges. 6:379–381,1873. [4] I. Blanco, L. Abate, F.A. Bottino. Mono substituted octaphenyl POSSs: The effects of substituents on thermal properties and solubility. Thermochim. Acta 655:117-123, 2017.


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ORALS AND POSTERS

SESSION 1:

THERMODYNAMICS,

THERMOCHEMISTRY

AND KINETICS

Determining preexponential factor in model-free kinetic methods: how and why?

SERGEY VYAZOVKIN¹*

1Department of Chemistry, University of Alabama at Birmingham, 901 S. 14th Street, Birmingham,

AL 35294, USA *Corresponding author: e-mail: [email protected]

Keywords: Arrhenius equation, condensed-phase reactions, kinetics

Determining the preexponential factor is an integral part of model-free kinetic

analysis. The use of the compensation effect provides an efficient way of evaluating the preexponential factor for both single- and multi-step kinetics. It is stressed that many effects observed experimentally as the reaction temperature shifts usually involve changes in both activation energy and preexponential factor and, thus, are better understood by combining both parameters into the rate constant. A technique for establishing the temperature dependence of the rate constant by utilizing the isoconversional values of the activation energy and preexponential factor is explained. Attention is drawn to the fact that the experimental effects that involve changes in the preexponential factor can be traced to the activation entropy changes that may help in obtaining deeper insights into the process kinetics.


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Determination of polymer crystallization kinetics with the NPK method

MONZÓN, F.¹*, ROVIRA, M.D.¹, SEMPERE, J.2, NOMEN, R.2

1Universidad Centroamericana José Simeón Cañas

2Universidad Ramon Llull, IQS School of Engineering

*Corresponding author: [email protected]

Keywords: thermal analysis, NPK method, polymer crystallization

Since 1998, the NPK method developed by R. Serra, J. Sempere and R. Nomen1

is being used by many research groups to simulate and even sometimes better under-

stand the thermal behaviour of many chemical reactions. The NPK method has never

been used for crystallization processes, nor pure products or polymers. It is well

known that the degree of crystallization of a polymer is a function of its processing

and has crucial consequences on its final

properties, so a considerable number of

papers have been published to describe

this phenomenon. Between them, we can

find the description of phenomenological

models like the ones of Lauritzen-Hoff-

man, Avrami, Bergreen-Sestak, or Sbir-

razzuoli or functional methods like the

model-free method of Vyazovkin.

Our work aims to study the applicabil-

ity of the NPK method to a polymer crys-

tallisation phenomenon to use thermal an-

alytical data to predict the behaviour of the

processing at different conditions or design

new industrial processes. This contribution

shows the first results working with low-

density polyethylene (LDPE), polypropyl-

ene (PP), and other polymers. As an exam-

ple, Figure (a) shows the crystallization

curves of LDPE. Vectors v (b) and u (c)

obtained from NPK method and some fit-

tings for vector u according to the Sĕstak-

Berggren and Kolmogorov-Johnson-Mehl-

Avrami models are shown. References

[1] R. Serra, J. Sempere, R. Nomen. A new method

for the kinetic study of thermoanalytical data: The

non-parametric kinetics method. Thermochimica

Acta. 316: 37-45.

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Continuing the study of energetic ionic liquids: dimethylammonium ni-trate and ethylammonium nitrate

CHRISTOPHER BADEEN¹, JONATHAN LAVOIE¹, SHANTI SINGH¹*, BARBARA

ACHESON¹, RICHARD TURCOTTE¹

1 Canadian Explosives Research Laboratory, Natural Resources Canada

*Corresponding author: e-mail: [email protected] Keywords: thermal analysis, DSC, ARC, energetic ionic liquid

CanmetCERL has continued the thermal hazards examination of energetic ion-

ic liquids (EILs). Decomposition of dimethyl ammonium nitrate (DMAN) and ethyl ammonium nitrate (EAN), in sealed glass ampoules, was assessed by apply-ing Friedman model-free isoconversional kinetic analyses to obtain the apparent activation energy, Ea, as a function of degree of conversion. Over the full conver-sion range Ea varied between 81-146 kJ mol-1 for DMAN, and 83 – 162 kJ mol-1 for EAN. The shape of these curves indicated that the reaction rate tends to become diffusion limited at elevated conversion. Comparison is made with the Kissinger method of analyses, and predictions of isothermal (aging) decomposition behav-iour. Similar to the well-studied decomposition of pure AN, when increasing the sample size for assessing thermal stability by accelerating rate calorimetry (ARC), DMAN and EAN each exhibited an onset to decomposition at least 20°C lower than observed in DSC kinetic analyses.

© Her Majesty the Queen in Right of Canada, as represented by the Minister of Natural Resources


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The phase transition behaviour and heat capacity of

1-butyl-2-methylpyridinium and 1-butyl-4-methylpyridinium

bis(trifluoromethylsulfonyl)imide

PAWEŁ GANCARZ, EDWARD ZORĘBSKI*

University of Silesia in Katowice, Institute of Chemistry


Keywords: heat capacity, phase transition, pyridinium ionic liquids

The twin ionic liquids based on pyridinium were investigated by differential scan-

ning calorimetry, i.e., 1-butyl-2-methylpyridinium and 1-butyl-4-methylpyridinium

bis(trifluoromethylsulfonyl)imide ([B2MPy][NTf2] and [B4MPy][NTf2], respec-

tively). These two ionic liquids with the equal molecular formula (C12H16F6N2O4S2)

and molar masses (430.38 gmol-1) but differently located methyl groups are inter-

esting for the study of the influence of the steric effect/methyl group location on the

physicochemical properties [1].

Samples (IoLiTec, Germany) were specially dried and degassed under vacuum

down to 5 ppm H2O and handled over an argon atmosphere. Phase transition behav-

iour was observed at different cooling and heating rates (5 K·min-1 to 50 K·min-1 in

the range of -88°C to 50°C). The phase transition behaviour differs significantly. For

[B4MPy][NTf2] apparent solidification, as well as melting temperature, can be ob-

served. Oppositely, [B2MPy][NTf2] exhibits only glass transition and the evident

melting temperature does not occur as in the previous case. On the other hand, the

experimental isobaric heat capacities of both substances are quite similar. The ex-

perimental isobaric heat capacities were also compared with values determined by

group-contribution predictive methods developed by Ge et al.[2] and further by Oster

et al.[3]. Both group-contribution methods are not selective for the arene substitution

patterns, thus giving the same values for both ionic liquids (629 J·mol-1·K-1 and 594

J·mol-1·K-1 in the case of Ge et al.[2] model and Oster et al.[3] model, respectively).

All results are discussed together with available very scarce literature data for all

three isomers, i.e., 1-butyl-2-methyl-, 1-butyl-3-methyl-, and 1-butyl-4-methyl-.

References

[1] B. Bittner, R. J. Wróbel, E. Milchert. Physical properties of pyridinium ionic liquids. J. Chem.

Thermodyn. 55:159–165, 2012.

[2] R. Ge, C. Hardacre, J. Jacquemin, P. Nancarrow, D. W. Rooney. Heat capacities of ionic liquids

as a function of temperature at 0.1 MPa. Measurement and prediction, J. Chem. Eng. Data.

53:2148–2153, 2008.

[3] K. Oster, J. Jacquemin, C. Hardacre, A. P. C. Ribeiro, A. Elsinawi. Further development of the

predictive models for physical properties of pure ionic liquids: Thermal conductivity and heat

capacity. J. Chem. Thermodyn. 118:1–15, 2018.


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Model-free kinetic approaches in accelerating rate calorimetry

JIONG. DING¹,2*, JIN YU. CHEN1, JIN XIN. XU¹,2, SHU LIANG. YE¹,2*

1 Institute of Industry and Trade Measurement Technology, College of Metrology and Measurement

Engineering, China Jiliang University, Hangzhou, China

2 Zhejiang Engineering Laboratory of Chemicals Safety Testing Technology and Instruments, Hang-zhou, China.

*Corresponding author: e-mail: [email protected]; [email protected] Keywords: model-free kinetics, accelerating rate calorimetry, thermal decomposa-tion

Accelerating rate calorimetry (ARC) is an important tool in thermal hazard as-sessment of chemicals. However, the model-fitting methods based on a single ex-periment are dominant in ARC kinetic computation. To change this phenomenon, the feasibilities of some model-free kinetic approaches in ARC data processing are investigated in our recent work.

Firstly, the differential and integral isoconversional methods are applied in ARC based kinetic computation [1-2]. The accuracy of the kinetic results are com-pared between the Friedman and advanced nonlinear algorithms. The feasibility of these isoconversional methods to process ARC data is veirified through numerical simulations and experiemtns.

Secondly, a model-free kinetic determination of pre-exponential factor and re-action mechanism based on compensation effect is applied in ARC data processing [3]. The uncertainty of using this approach to calculate the kinetic parementers is analysed by numerical simulations. The applicability of this kinetic approach is investigated by studying the effect of NaOH on the thermal decomposition of cu-mene hydroperoxide/cumene solutions.

Thridly, an approach mearging model-free and model-fitting methods is ap-plied in ARC data processing for analysis multi-step kinetics [4]. Seleting 2,4-dichlorobenzoyl peroxide as example, the feasibility of this approach is analysed in autocatalytic thermal decomposition mechanism study.

The demonstration of the feasibilities of serial model-free kenitic appraoches in ARC data process may enrich the selection in self-reactive chemicals reaction mechanism and thermal hazard assessment based on ARC.

References [1] S. Vyazovkin, A.K. Burnham, J.M. Criado, L.A. Pérez-Maqueda, C.Popescu, N. Sbirrazzuoli.

ICTAC kinetics committee recommendations for performing kinetic computations on thermal analysis data, Thermochim. Acta, 520: 1-19, 2011.

[2] J. Ding, L.X. Chen, Q.Y. Xu, S.J. Yang, J.C. Jiang, S.L. Ye. Differential isoconversial kinetic approach for accelerating rate calorimetry, Thermochim. Acta, 689: 178607, 2020.

[3] N. Sbirrazzuoli. Model-free isothermal and nonisothermal predictions using advanced isoconver-sional methods, Thermochim. Acta, 697: 178855, 2021.

[4] S. Vyazovkin, A.K. Burnham, L. Favergeon, N. Koga, E.Moukhina, L.A. Pérez-Maqueda, N. Sbirrazzuoli. ICTAC kinetics committee recommendations for analysis of multi-step kinetics, Thermochim. Acta, 689: 178597, 2020.


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Kinetics Study of the Main Forest Residues Used in a Portuguese

Power Plant

JOÃO SILVA1,2*, SENHORINHA TEIXEIRA 2, BERNHARD PETERS 3,

AND JOSÉ TEIXEIRA 1

1MEtRICs Research Centre, University of Minho, Guimarães, Portugal

2ALGORITMI Research Centre, University of Minho, Guimarães, Portugal

3University of Luxembourg, Faculty of Science and Technology, and communication


Keywords: biomass, combustion, kinetics

The application of computer simulation approaches to the design of a wide range

of products has grown during the past two decades. Computational Fluid Dynamics

(CFD) modeling of the entire process inside a biomass boiler is a promising alterna-

tive to meet economic and environmental demands on the operation of grate furnaces

allowing a better understanding of the combustion process. However, most of the

CFD commercial packages are limited in handling the conversion of biomass as they

are mainly designed to simulate the combustion of gaseous fuels. Thus, in most

cases, the commercial software must be complemented by self-written code for the

fuel bed conversion. Therefore, considering the needs of a fuel bed conversion model

to the CFD software, a deep knowledge of the composition and thermal behavior, as

well as the kinetics of the biomass combustion process, is essential.

In this way, this work presents a study of the kinetics of the forest residues ther-

mal degradation. The thermal conversion is analyzed using a thermogravimetric an-

alyzer to obtain the combustion behavior and, subsequently, the combustion kinetics

parameters are determined. The conversion kinetics of the different fuels is analyzed

through different mathematical approaches developed to obtain the parameters that

characterize the reaction kinetics. In this way, model-free methods (isoconversional)

and model-based methods are used to understand which model provides better re-

sults when used in a mathematical model to predict the fuel mass loss and compared

with thermogravimetric results.

This knowledge, beyond its importance in CFD modeling, is required for the

design and operation of biomass combustion equipment. In the future, this study will

be very useful to study and optimize the combustion in industrial grate-fired boilers

regarding its efficiency.


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Apparent Autocatalysis Due to Liquefaction: Thermal Decomposition

of Ammonium 3,4,5-Trinitropyrazolate

NIKITA V. MURAVYEV1*, KONSTANTIN A. MONOGAROV1, IGOR L. DALINGER2,

NOBUYOSHI KOGA3, ALLA N. PIVKINA1

1Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

2Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences 3Hiroshima Univ., Grad. Sch. Humanities and Social Sciences, Dept. Science Education


Keywords: thermal decomposition, autocatalysis, kinetics, liquefaction

Thermal decomposition of solids is often accompanied by autocatalysis, one of

the possible causes of which is the formation of a liquid phase. The kinetic model

considering the liquefaction of solid reactant under isothermal conditions was pro-

posed by Bawn in the 1950s. Present study reports the application of the Bawn model

to the thermolysis of 3,4,5-trinitropyrazole ammonium salt (ATNP) under noniso-

thermal conditions. The thermal decomposition of ATNP comprises of low-temper-

ature and high-temperature stages. The low-temperature stage exhibits two distinct

exothermic peaks in differential scanning calorimetry (DSC), fitted by two consec-

utive two autocatalytic reactions with a model-fitting kinetic analysis. The liquefac-

tion of the solid reactant during the first reaction is directly observed, giving a mech-

anistic evidence for the Bawn model. We have expressed the Bawn model by a com-

bination of two extended Prout–Tompkins (ePT) equations with the activation en-

ergy for the leading liquid-state reaction of Ea = 140.6 ± 0.3 kJ mol−1. The release of

ammonia is detected from the beginning, suggesting the thermal dissociation of

ATNP to 3,4,5-trinitropyrazole to be an initiation reaction of the thermal decompo-

sition. We proposed the ATNP liquefication, leading to the apparent autocatalytic

behavior of the first global decomposition reaction, is caused by the eutectic for-

mation between ATNP and 3,4,5-trinitropyrazole, as it was confirmed by DSC anal-

ysis of the artificial mixture. The presented approach of the combination of ePT for-

malism with a Bawn model is generally applicable to a broader range of thermal

processes accompanied by liquid phase formation and apparent acceleration.

References

[1] N.V. Muravyev, KA. Monogarov, I.L. Dalinger, N. Koga, A.N. Pivkina. Apparent autocatalysis

due to liquefaction: Thermal decomposition of ammonium 3,4,5-trinitropyrazolate. Phys. Chem.

Chem. Phys. DOI: 10.1039/D1CP01530C.


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Interpretation and physical meaning of kinetic parameters obtained from isoconversional kinetic analysis of polymers

N. SBIRRAZZUOLI*

Université Côte d’Azur, Institute of Chemistry of Nice, CNRS UMR 7272, Nice, France

* [email protected]

Keywords: Kinetics; isoconversional methods; polymers; nanocomposites.

Obtaining kinetic parameters with a real physical meaning in the case of complex reactions is not straightforward. Isoconversional methods are amongst the more re-liable kinetic methods for the treatment of thermoanalytical data [1,2]. These meth-ods are very effective when the reaction mechanism is not known and / or in the case of complex reactions involving several parallel, consecutive steps or a combination of these, as well as large variations in viscosity during polymerizations. The main advantages of isoconversional methods are that they afford an evaluation of the ef-fective activation energy, Eα, without assuming any particular form of the reaction model and can detect changes in the rate limiting steps of the overall reaction rate as measured with thermoanalytical techniques. Changes in the reaction mechanism are obtained by analyzing the changes in the Eα variation, called the Eα-dependency. For this reason, isoconversional methods have largely been used for studying the curing kinetics of numerous thermoset resins, but were also found to be very efficient in elucidation of physical transition kinetics, such as crystallization, glass transition of polymers, gelation of biopolymers and melting [1,3]. This work aims at presenting several successful examples were physically sounded kinetic information was ob-tained from thermoanalytical data in different application fields of polymer science and to explain how the kinetic parameters obtained can be interpreted in term of reaction mechanisms or changes in the rate-limiting step of the overall process. These examples show that advanced isoconversional methods affords for obtaining kinetic parameters with a real physical meaning and, in some cases, can be used to extract model-fitting parameters [4-6]. References [1] S. Vyazovkin, N. Sbirrazzuoli, Isoconversional kinetic analysis of thermally stimulated processes in polymers. Macromol. Rapid Commun. 27:1515-1532, 2006. [2] S. Vyazovkin, A. K. Burnham, J. M. Criado, L. A. Pérez-Maqueda, C. Popescu, N. Sbirrazzuoli. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim. Acta. 520:1-19, 2011. [3] S. Vyazovkin, Isoconversional Kinetics of Thermally Stimulated Processes. Springer: Berlin, Ger-many, 2015. [4] N. Sbirrazzuoli. Determination of pre-exponential factors and of the mathematical functions f(α) or G(α) that describe the reaction mechanism in a model-free way. Thermochim. Acta 564, 59–69, 2013. [5] N. Sbirrazzuoli. Advanced Isoconversional Kinetic Analysis for the Elucidation of Complex Reac-tion Mechanisms: A New Method for the Identification of Rate-Limiting Steps. Molecules 24:1683-1699, 2019. [6] S. Vyazovkin, A. Burnham, N. Koga, E. Moukhina, N. Sbirrazzuoli. ICTAC Kinetics Committee recommendations for analysis of multi-step kinetics. Thermochim. Acta 689:178597, 2020.


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Evaluation on migration of radioactive metal in irradiated graphite

waste during an innovative thermal treatment based upon the Gibbs

free energy minimization

KUN FU1,2, MEIQIAN CHEN1,2*

1Institute of Thermal Engineering, School of Mechanical, Electronic and Control Engineering, Beijing

Jiaotong University, Beijing 100044, China 2Beijing Key Laboratory of Flow and Heat Transfer of Phase Changing in Micro and Small Scale,

Beijing 100044, China


A novel treating technique for irradiated graphite waste in nuclear power plant

was proposed in order to extract the radioactive metal by adding chlorinating agent

during thermal treatment. The migration behavior of radioactive metal was estimated

based upon the Gibbs free energy minimization. The effects of chlorinating agent,

temperature, and oxygen partial pressure on decontamination of radioactive metal

were addressed. Except for cesium-134,137 (134,137Cs), Tin-121m (121mSn), and lead-

107 (107Pb), most radioactive metals existed with stable chemical solid species during

traditional thermal treatment. However, most radioactive metals could evaporate to

gaseous species with increasing the temperature by adding 1 wt. % AlCl3 or NH4Cl.

At 400 °C, cobalt-60 (60Co), iron-55 (55Fe), nickel-63 (63Ni), and other key nuclides

could release as gaseous metal chlorides. Plutonium-238 (238Pu) and calcium-41

(41Ca) only released at about 800 °C. With rising the oxygen partial pressure, decon-

tamination ratios of radioactive metals increased. An off-gas treatment system that

condenses the gaseous species was necessary to avoid gaseous metal chloride emit-

ting. This work could provide a new technical route and basic data for decontamina-

tion of the radioactive metal in irradiated graphite.

Keywords: radionuclide migration, irradiated graphite waste, chemical equilibrium,

thermal treatment, decontamination


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Physical aging of selenium glass: assessing the double mechanism of

equilibration and the crystallization process.

A. MORVAN¹*, N. DELPOUVE1, A. VELLA1,2, A. SAITER1

1 Normandie Univ, UNIVROUEN, INSA Rouen, CNRS, Groupe de Physique des Matériaux, 76000

Rouen, France. 2 Institut Universitaire de France

*Corresponding author : e-mail : [email protected]

Keywords: Enthalpy of recovery, FSC, DSC, chalcogenide glass.

Physical aging is a phenomenon occuring on the amorphous phase when the glass is

maintained for a certain time below its glass transition temperature. It is important

to know this aging process in order to predict the evolution of the properties over the

time.

Amorphous selenium is considered as model material for a large number of glass

physicists, this work focuses on the study of the physical aging by differential scan-

ning calorimetry (DSC) and fast scanning calorimetry (FSC). Aged samples 30 and

40 years at room temperature were analyzed by DSC, and their enthalpies of recov-

ery were calculated, showing that the glass has reached the thermodynamic equilib-

rium and is stable over time.

Accelerated physical aging using FSC[1] enables the physical aging kinetics of glass

to be reproduced up to its thermodynamic equilibrium within a reasonable time at

the laboratory scale. This study has shown an approach to the equilibrium in one or

two steps depending on the difference between the aging temperature and the glass

transition temperature[2], resulting from the difference in mechanisms governing

the relaxation process[3].

The second phenomenon observed during this study is the crystallization of the glass

once the equilibrium has been reached for aging temperatures close to the glass tran-

sition temperature. This phenomenon is demonstrated by the presence of a melting

peak following the enthalpy recovery peak as already observed in the literature[4].

References

[1] X. Monnier, A. Saiter, and E. Dargent, ‘Physical aging in PLA through standard DSC and fast

scanning calorimetry investigations’, Thermochimica Acta, vol. 648, pp. 13–22, Feb. 2017, doi:

10.1016/j.tca.2016.12.006.

[2] D. Cangialosi, ‘Chapter 8 - Glass Transition and Physical Aging of Confined Polymers Investi-

gated by Calorimetric Techniques’, in Handbook of Thermal Analysis and Calorimetry, vol. 6, S.

Vyazovkin, N. Koga, and C. Schick, Eds. Elsevier Science B.V., 2018, pp. 301–337.

[3] M. C. Righetti and E. Mele, ‘Structural relaxation in PLLA: Contribution of different scale mo-

tions’, Thermochimica Acta, vol. 672, pp. 157–161, Feb. 2019, doi: 10.1016/j.tca.2018.12.027.

[4] R. Androsch, E. Zhuravlev, J. W. P. Schmelzer, and C. Schick, ‘Relaxation and crystal nucleation

in polymer glasses’, European Polymer Journal, vol. 102, pp. 195–208, May 2018, doi:

10.1016/j.eurpolymj.2018.03.026.


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Thermal degradation kinetics of polyurethanes and its analysis by

model free kinetics and kinetic modelling

PRAKHAR POURANICK¹, JOOST BRANCART1, ROBRECHT VERHELLE1, GUY VAN

ASSCHE1*

1 Physical Chemistry and Polymer Science, Department of Materials and Chemistry (MACH),

Vrije Universiteit Brussel, Belgium


Keywords: thermal gravimetric analysis, polyurethanes, kinetic model

Polyurethane (PUR) foams find application as an insulating material in

buildings, furniture, and transportation. Due to its high flammability and fast spread

of flame during a fire, there is an emphasis on studying the thermal degradation of

PUR, including the study of the production of volatile gases that fuel combustion

[1].

One of the objectives of this work is to get a detailed understanding of the

thermal degradation of PUR and PUR-derived products, like foams, and their

degradation kinetics, aiming at making the relationship between the thermal

degradation kinetics of PUR and its monomer polyols. Studying degradation

mechanisms and developing composition-based thermal degradation kinetic models

will facilitate predicting the degradation behaviour of PUR of different compositions

under a range of conditions.

The degradation kinetics of PUR and its polyols and the degradation products

formed, including residues or char and evolved gases, are studied in detail using

TGA and spectroscopic techniques. TGA studies performed on polyether-based PUR

foams and its constituting monomer polyether polyols revealed relations between

their degradation paths. These findings are further supported by Hi-Res™ TGA

experiments, which separated the degradation steps more clearly. TGA-MS is used

for simultaneous evolved gas analysis and FTIR spectroscopy is used for the analysis

of residues at different instances in the degradation process. Such relations between

the chemical composition and structure of the PUR and the resulting thermal

degradation behaviour can be employed to judiciously tune the material properties.

Thermal data, obtained in TGA under different atmospheres and for different

temperature programs, were kinetically analysed by applying model-free kinetics

(MFK), providing information for the development of a more comprehensive

degradation kinetics model [2].

References

[1] S. Duquesne, M. Le Bras, S. Bourbigot, R. Delobel, G. Camino, B. Eling, C. Lindsay, and T. Roles.

Thermal degradation of polyurethane and polyurethane/expandable graphite coatings. J. Polym.

Degrad. Stab. 74(3):493–499, 2001.

[2] S. Vyazovkin, A. K. Burnham, J. M. Criado, L. A. Pérez-Maqueda, C. Popescu, and N. Sbirrazzuoli.

ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal

analysis data. J. Thermochim. Acta. 520(1-2):1–19, 2011.


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Thermal analysis of polish copper concentrates

R. URBANIAK¹*, B. HADAŁA1, A. MAGIERA1

1AGH University of Science and Technology, Faculty of Materials Engineering and Computer Sci-

ence


Keywords: thermal anlysis, copper concentrate, copper productions

To investigate the properties of Polish copper-bearing concentrates, their thermal

analysis was performed. The research covered concentrates from the Rudna, Pol-

kowice and Lubin mines and their selected grain fractions. The tests were carried out

in the temperature range from 40 to 1000° C with a heating rate of 10 K/min, using

a gas mixture: 50 ml/min of synthetic air (21% O2, 79% N2) and 25 ml/min of argon

with TG 209 Libra F1 thermobalances by Netzsch. Thermal properties with 40%

oxygen enrichment, 50 ml/min of synthetic air and oxygen in the temperature range

up to 1400° C were also tested.

It has been found that the thermogravimetric curves were quite similar. For all

tested samples, the thermal properties depended on the content of organic matter and

sulphide sulfur. The results of selected grain fractions also depended mainly on the

content of these compounds.

The greatest weight loss for all samples was related to the combustion of carbo-

naceous substance, decomposition of carbonates, dissociation of complex metal sul-

phides. The maximum transformation rates were observed at 378° C for Polkowice,

400°C for Rudna Uboga, 405°C for Rudna Bogata and 458°C for the Lubin concen-

trate. The increase in mass of the samples was caused by the formation of sulphates

and occur at the following temperatures: Polkowice 537 ° C, Rudna Bogata 544.3˚C,

Rudna Uboga 570.8˚C and for Lubin at 571.2 ° C.

Comparing air and air enriched in oxygen, differences in the measured tempera-

ture values were found. They resulted from the specificity of the oxidation reactions

taking place, which were directly related to the oxidation kinetics of the carbon ele-

ment. At higher oxygen concentrations, an earlier start of the reaction was observed.

On the other hand, for the oxidation of sulfur compounds (ore roasting), the increased

oxygen concentration probably slowed down the release of SO2 from the surface,

which transfered into a shift of the maximum towards higher temperatures [1].

Work carried out under the Implementation Doctorate Programme

References

[1] T. Sak, P. Madej, G. Krawiec, Ł. Kortyka. Wpływ właściwości koncentratów miedzi naprzebieg

procesu przetopu w piecach zawiesinowych HMG –Etap 1, KGHM PM S.A., Sieć Badawcza Łukasie-

wicz- Instytut Metali Nieżelaznych, Gliwice, 28.11.2019 r.


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Sublimation study of six 5-substituted-1,10-phenanthrolines by Knudsen Effusion Mass Loss and Solution Calorimetry

B. BRUNETTI¹, A. CICCIOLI2, A. LAPI2, A.V.BUZYUROV3,

M.A. VARFOLOMEEV3, S. VECCHIO CIPRIOTI4*

1National Research Council, Sapienza University of Rome 2Sapienza University of Rome, Department of Chemistry

3Kazan Federal University, Butlerov Institute of Chemistry 4Sapienza University of Rome, Department of Basic and Applied Sciences for Engineering

*Corresponding author: e-mail: [email protected] Keywords: 5-substituted-1,10-phenanthrolines, Knudsen Effusion, Solution Calo-rimetry, Standard molar sublimation enthalpy, Standard molar sublimation entropy, Standard molar sublimation Gibbs energy

Some years ago thermogravimetry (TG), differential scanning calorimetry (DSC)

and Knudsen Effusion Mass Loss (KEML) were used to determine melting, vaporiza-tion and sublimation characteristics of six N-hetero tricyclic compounds and compared with available literature data [1]. In this study, the vapor pressures of six solid 5-x-1,10-phenanthrolines (where x=Cl, CH3, CN, OCH3, NH2, NO2) were determined in suitable temperature ranges by Knudsen Effusion Mass Loss (KEML). From the temperature dependencies of vapor pressure the molar sublimation enthalpies at the corresponding averages áTñ of the explored temperature ranges, ∆cr

gH0m(<T>), were calculated. Since,

to the best of our knowledge, no heat capacity data seems to be available in literature regarding these compounds, the ∆cr

gH0m(<T>) values obtained by KEML experiments

were adjusted to 298.15 K using a well-known empirical procedure reported in litera-ture [2]. The so obtained standard (p0= 0.1 MPa) molar sublimation enthalpies ∆cr

gH0m(298.15 K) were compared with those determined using solution calorimetry,

according to a procedure recently proposed and validated using a sufficient number of thermochemical data of molecular compounds [3]. A good agreement was found be-tween the values derived by the two different approaches, and final mean ∆cr

gH0m(298.15 K) values were recommended. Finally, the standard molar entropies

and Gibbs energies of sublimation were derived at T=298.15 K.

References [1] B. Brunetti, A. Lapi, S. Vecchio Ciprioti.Thermodynamic study on six tricyclic nitrogen heterocyclic com-

pounds by thermal analysis and effusion techniques. Thermochim. Acta, 636:71-84, 2016. [2] W. Acree Jr., J.S. Chickos. Phase transition enthalpy measurements of organic and organometallic com-

pounds. Sublimation, vaporization and fusion enthalpies from 1880 to 2010. J. Phys. Chem. Ref. Data. 39:043101, 2016.

[3] B.N. Solomonov, M.A. Varfolomeev, R.N. Nagrimanov, D.H. Zaitsau, S.P. Verevkin, Solution calorimetry as a complementary tool for the determination of enthalpies of vaporization and sublimation of low volatile compounds at 298.15 K. Thermochim. Acta, 589:164–173, 2014.


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Study of hydrophobic hydration of selected glymes

in the mixture of N,N-dimethylformamide with water

MAŁGORZATA JÓŹWIAK¹*, MARLENA KOMUDZIŃSKA¹,

MAGDALENA TYCZYŃSKA1

1University of Lodz, Faculty of Chemistry


Keywords: glymes+DMF+W systems, volumetric, acoustic and thermal properties

The following work concerns the analysis of the densimetric, acoustic and

calorimetric investigations results of monoglyme, diglyme, triglyme, tetraglyme,

pentaglyme and hexaglyme in the whole range of composition of mixed solvent

N,N-dimethylformamide (DMF) and water at four temperatures (293,15 K - 308,15) K.

The obtained experimental values of density, speed of sound and specific heat

capacity of mixtures allow calculation of some excess, apparent and partial molar

quantities that describe intermolecular interactions between solution constituents.

On the basis of densimetric results, the values of excess apparent

and standard partial molar volume of selected glymes in

DMF+water mixtures were analyzed. It was also possible to discuss the values of

isobaric molar thermal expansibilities of the studied systems.

Based on the sound velocity results of examined mixtures the values of isentropic

and molar isentropic compressibilties as well as apparent

and standard partial molar isentropic compressibilities of six glymes in

DMF+W mixtures at four temperatures were calculated.

The values of apparent molar isobaric heat capacity of mono-,di-,

tri-, tetra-, penta- and hexaglyme in the mixture of (DMF+W) were calculated and

analyzed in therms of intermolecular interactions between solution constituents.

The nature of the changes in the analyzed relationships obtained for all exam-

ined glymes is similar. In water rich area one could observe characteristic changes

connected with hydrophobic hydration of glymes. The changes are the more in-

tense, the more hydrophobic the properties of the linear polyether are. Based on the

results obtained for the mixed solvent only, one could assume that DMF shows

weak hydrophobic properties. The presence of a linear polyether in DMF+W mix-

ture causes disruption of the structure of the mixed solvent and changes the inter-

molecular interactions between the components of the system.

On the basis of adiabatic compressibilities, the hydration numbers of glymes

) and its values at infinitely diluted solution were calculated.

Additionally, the group contribution of –CH2– and –O– to the values of stand-

ard partial molar volume , isobaric limited molar thermal expansibility

and standard partial molar compression of glyme in the mixture of DMF

with water ( were estimated.


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Isobaric and isochoric heat capacity of

1-(2-hydroxyethyl)-3-methylimidazolium

bis(trifluoromethylsulfonyl)imide

PAWEŁ GANCARZ, EDWARD ZORĘBSKI*

University of Silesia in Katowice, Institute of Chemistry


Keywords: heat capacity, acoustic method, compressibility, ionic liquids

Although isobaric and isochoric heat capacities are among the most important

properties of matter, such simultaneous reports of both capacities are unfortunately

very rare. In this work, we report consistent data on both heat capacities of a func-

tionalized imidazolium-based ionic liquid, namely 1-(2-hydroxyethyl)-3-methylim-

idazolium bis(trifluoromethylsulfonyl)imide (407.31 gmol-1). While the reported

isobaric heat capacity was determined directly by differential scanning calorimetry,

the isochoric heat capacity was obtained indirectly by using an acoustic method that

is a well-established method based on the speed of sound and density measurements.

The measured (isobaric heat capacity, speed of sound, and density) and deter-

mined (isochoric heat capacity, isentropic and isothermal compressibility) quantities

are discussed with relation to the available very scarce literature data [1] and earlier

results for 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (391.31

gmol-1) [2,3]. In the case of the tested functionalized ionic liquid, the specific iso-

baric heat capacity, speed of sound and density values are higher (at the temperature

of 298.15 K, 5.1%, 5.7% and 3.8%, respectively). In turn, the isothermal compress-

ibility for functionalized ionic liquid is about 15% lower.

The experimental molar isobaric heat capacities were also compared with values

determined by group-contribution predictive methods developed by Ge et al.[4] and

by Oster et al.[5]; at 298.15 K, the values are 546.9 J·mol-1·K-1, 601,2 J·mol-1·K-1

and 603.2 J·mol-1·K-1, respectively.

References [1] Q. Liu, L. Zhao, L. Ma, J. Chu, J. Wang, Y. Zang, Hydroxyethyl group effect on properties of

bis[(trifluoromethyl)sulfonyl]imide-type ionic liquids, J. Chem. Eng. Data. 65:4780–4789, 2020.

[2] E. Zorębski, M. Zorębski, M. Dzida, P. Goodrich, J. Jacquemin. Isobaric and isochoric heat ca-

pacities of imidazolium-based and pyrrolidinium-based ionic liquids as a function of temperature.

Modeling of isobaric heat capacity. Ind. Eng. Chem. Res. 56:2592–2606, 2017.

[3] E. Zorębski, M. Geppert-Rybczynska, M. Zorębski, Acoustics as a tool for better characterization

of ionic liquids: A comparative study of 1‑ alkyl-3-methylimidazolium bis[(trifluoromethyl)sul-

fonyl]imide room-temperature ionic liquids, J. Phys. Chem. B. 117: 3867−3876, 2013. [4] R. Ge, C. Hardacre, J. Jacquemin, P. Nancarrow, D. W. Rooney. Heat capacities of ionic liquids

as a function of temperature at 0.1 MPa. Measurement and prediction, J. Chem. Eng. Data.

53:2148–2153, 2008.

[5] K. Oster, J. Jacquemin, C. Hardacre, A. P. C. Ribeiro, A. Elsinawi. Further development of the

predictive models for physical properties of pure ionic liquids: Thermal conductivity and heat

capacity. J. Chem. Thermodyn. 118:1–15, 2018.


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The kinetic study of juice industry residues drying process based on TG-DTG experimental data

MIHAILO M. MILANOVIĆ¹, MIRKO S. KOMATINA², BOJAN Ž. JANKOVIĆ³,

DRAGOSLAVA D. STOJILJKOVIĆ², NEBOJŠA G. MANIĆ²*

¹University of Belgrade, Innovation Center of the Faculty of Mechanical Engineering, Serbia ²University of Belgrade Faculty of Mechanical Engineering, Serbia

³University of Belgrade, Department of Physical Chemistry, Vinča Institute of Nuclear Sciences - Na-tional Institute of thе Republic of Serbia

*Corresponding author: [email protected] Keywords: juice industry residues, TG analysis, drying process, kinetic study, de-composition mechanisms

To achieve sustainable development and mitigate the climate change challenges,

the use of food industry residues is an important part of the modern circular econ-omy. The residues from the fruit juice production industry are nowadays commonly used raw materials for producing different value-added products. In order to improve the energy efficiency aspects of the industry residue treatment, generally, the drying process as the first step of the whole processing chain should be further analyzed. Regarding these facts, a comprehensive kinetic study was performed to provide the detailed mechanisms of moisture removal from the base raw material. The industrial residues from apple juice production were used for experimental isothermal TG anal-ysis in the air atmosphere at five different temperatures. Based on experimental data, different kinetic models were applied to determine the kinetic parameters and dom-inant conversion functions. The obtained results of activation energy were compared with literature data and further discussion about the decomposition mechanisms was provided. The results of this research will be further used for developing the univer-sal mathematical model of the drying process which could be applied for other sim-ilar food materials and could provide new data for the energy efficiency improve-ment of the food residues processing industry.


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Physicochemical and thermodynamic characteristics of the newly pro-posed working pairs in absorption refrigeration technology

MICHAŁ SKONIECZNY¹*, MARTA KRÓLIKOWSKA2,3

1Doctoral School No. 1, Faculty of Chemistry, Warsaw University of Technology

2Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology 3Thermodynamics Research Unit, School of Engineering, University of KwaZulu-Natal

*Corresponding author: e-mail: [email protected] Keywords: thermal analysis, excess enthalpy of mixing, vapor-liquid equilibrium, absorption refrigeration technology

The demand for electricity is growing every year and refrigeration is a technol-

ogy that uses enormous amounts of that kind of energy. The main technological way to achieve coldness is compressor refrigeration technology, which requires electric-ity to function. However, an alternative, more ecological and requiring minimal elec-tricity consumption method is more and more often used, which is absorption refrig-eration technology. In this type of refrigeration, the chillers use working pairs, which allow to obtain relatively low values of the Coefficient of Performance (COP), which is a measure of cooling efficiency, and have other disadvantages. Therefore, there is a need to find less problematic working pairs with higher COP values, bearing in mind the ecological aspect at the same time.

As part of the work, the characteristics of new working pairs (ionic liquid + ethyl alcohol) was performed. Ionic liquids due to their properties can be a very effective absorbent. Absorbate, ethyl alcohol, allows deep cooling and has a low vapor pres-sure. Previous research in systems with water has shown that working pairs with ionic liquids can be an attractive alternative. [1] A wide characterization of such systems was made in order to determine their application possibilities in absorption refrigeration technology. Calorimetric measurements including thermal analysis of pure absorbents by Differential Scanning Calorimetry (DSC) and measurement of excess enthalpy of mixing were determined. Measurements of Vapor-Liquid Equi-librium (VLE) and transport physicochemical properties: viscosity and density were also investigated. Calculations of thermodynamic functions i.e. the excess volume of mixing or Gibbs free energy were presented. The experimental data were success-fully correlated with appropriate equations.

Examined ionic liquids consisting of dimethyl- and diethylphosphate anions have been shown to be suitable as possible absorbents in terms of thermal stability. The systems show negative deviations from the Raoult’s law and negative deviations of excess enthalpy of mixing, which is favourable from absorption refrigeration point of view. It is concluded that the proposed working pairs would provide an interesting alternative to the existing, commonly used working pairs.

References [1] M. Królikowska et al. (Vapor + liquid) Phase Equilibria of an Aqueous Solution of Bromide-based

Ionic Liquids - Measurements, Correlations and Application to Absorption Cycles. Fluid Phase Equilib. 494:201-211, 2019.


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Physicochemical characteristics of benzoxazole derivatives as potential

therapeutic substances

AGNIESZKA ŚLIWIŃSKA¹*, ANETA POBUDKOWSKA², ANNA KOWALKOWSKA3

1 Doctoral School No. 1, Faculty of Chemistry, Warsaw University of Technology

2 Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology 3 Department of Biotechnology of Pharmaceuticals and Cosmetics, Faculty of Chemistry, Warsaw

University of Technology


Keywords: thermal analysis, solid-liquid equilibrium, solubility, ionization con-

stant, benzoxazole

Modern medical awareness and progress in the diagnosis and treatment of dis-

eases lead to an increasing need for new therapies. Therefore, the process of de-

signing and improving new active substances is particularly important and neces-

sary to increase the comfort of life. Apart from the biological activity itself, poten-

tial therapeutic substances must also be characterized by appropriate physicochem-

ical properties such as solubility or degree of ionization.

The selected group of compounds studied were benzoxazoles. Chemical com-

pounds based on benzoxazole core are currently the subject of research of many

scientists because of their biological activity. They show antifungal and antibacte-

rial properties among others. In terms of structure, they show similarity to nucleic

bases, which affects the possibility of their interaction with biopolymers. [1]

The aim of this work is to determine the basic physicochemical properties of

selected 2-(2-phenylethylsulfanyl)-1,3-benzoxazole derivatives. Substances were

synthesized and purified. Confirmation of the desired compounds was obtained by

spectroscopic techniques. In the case of pure components, calorimetric analyses

using Differential Scanning Calorimetry (DSC) and Modulated Differential Scan-

ning Calorimetry (MDSC) were performed to obtain information on thermal transi-

tions that benzoxazole derivatives may undergo and possible occurrence of decom-

position. Solid-liquid phase diagrams in binary systems were determined and the

data obtained were correlated with equations based on the local concentration theo-

ry. The solvents were water, ethanol and 1-octanol. The last parameter examined

was the ionization constants at temperatures 298.15 K and 310.15 K.

References

[1] N. Aggarwal, A. Kaur, K. Anand, H. Kumar, S. R. Wakode. Biologically active Benzoxazole: A

comprehensive review. IJPSR. 2:01-05, 2017.


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Decomposition kinetics of EDTA chelates of iron, zinc, copper and

manganese

MARCIN BIEGUN1*, MACIEJ KANIEWSKI1, EWELINA KLEM-MARCINIAK1,

JÓZEF HOFFMANN1

1Wroclaw University of Science and Technology, Faculty of Chemistry


Keywords: thermal analysis, kinetic model, EDTA chelates, activation energy, ther-

mal decomposition

The most commonly applied chelators in industrial chemistry are ethylenedia-

minetetraacetic acid (EDTA) compounds. EDTA chelates belong to the group of

aminopolycarboxylic acid (APCA) compounds. Application of APCA chelates as

stabilizers in the food industry used as substitutes for sodium triphosphate (STPP)

and as heavy metal chelating agents in wastewater is well defined in literature [1, 2,

3]. EDTA chelates also represent the most used source of microelements in agricul-

ture. The carried out research focused on the application of EDTA chelates as addi-

tives in fertilizers products. For this reason, thermal stabilities of Cu, Fe, Zn and Mn-

EDTA chelates were examined.

Obtained results allowed to distinguish two main stages of observed processes

- dehydration and thermal decomposition of examined EDTA chelates. In this work,

International Confederation for Thermal Analysis and Calorimetry (ICTAC) recom-

mendations for using thermogravimetry data in the kinetic calculation were applied

[4, 5, 6]. Model-free and model fitting methods were used to define kinetic triplets

for observed processes during thermal analysis of every studied chelate. Appropriate

models were suggested for dehydration and thermal decomposition of examined

EDTA chelates.

To obtain necessary data, NETZSCH STA 499 F3 Jupiter with thermobalance

was used. Differential thermal analysis coupled with thermogravimetry and mass

spectrometry were chosen as appropriate methods in order to further understand

studied processes. Analyses of samples at heating rates of 3°C·min-1, 5°C·min-1 and

15°C·min-1 were performed.

References

[1] R.S. Juang, S.H. Lin, T. Y. Wang. Removal ofmetal ions from the complexed solutions in fixed bed

using a strong-acid ion exchange resin. Chemosphere. 53:1221–1228, 2003.

[2] S.I. Amer. Simplified removal of chelated metals. Metal Finishing. 102:36–40, 2004.

[3] T. P. Knepper. Synthetic chelating agents and compounds exhibiting complexing properties in the

aquatic environment. T. Anal. Chem. 22:10:708–724, 2003.

[4] S. Vyazovkin, A. K. Burnham, J. M. Criado, L. A. Perez-Maqueda, C. Papescu, N. Sbirrazzuoli.


analysis data. Thermochim Acta. 520:1–19, 2011.

[5] S. Vyazovkin, K. Chrissafis, M. L. Di Lorenzo, N. Koga, M. Pijolat, B. Roduit, N. Sbirrazzuoli, J.

J Sunol. ICTAC Kinetics Committee recommendations for collecting experimental thermal anal-

ysis data for kinetic comutations. Thermochim Acta. 590:1–23, 2014.

[6] S. Vyazovkin, A. K. Burnham, L. Favergeon, N. Koga, E. Moukhina. L. A. Perez-Maqueda, N.

Sbirrazzuoli. ICTAC Kinetics Committee recommendations for analysis of multi-step kinetics.

Thermochim Acta. 689:178597, 2020.


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Differential Scanning Calorimetry − indispensable tool in the study of

low-temperature eutectic Phase Change Materials

MIKOŁAJ T. WIĘCKOWSKI¹*, MAREK KRÓLIKOWSKI2

1Warsaw University of Technology, Doctoral School No. 1 2Warsaw University of Technology, Faculty of Chemistry


Keywords: differential scanning calorimetry, phase diagrams, solid − liquid equi-

librium, phase change materials

Unrestrained progress and the demand for thermal and electrical energy moti-

vate to improve the current ones and search for new technological solutions allow-

ing for effective energy storage. Among all methods of heat storage and, at the

same time, stabilization of temperature conditions, the most promising are those

using phase transition, i.e. Phase Change Materials (PCMs). Among them, on the

other hand, alkanes, as well as fatty acids and alcohols, have the greatest latent heat

storage capacities, and their eutectic mixtures can serve as effective stabilizers of

low-temperature conditions.[1]

This work focuses on the use of calorimetric techniques to determine and then

characterize eutectic PCMs composed of alkanes (from n-tetradecane to n-

heptadecane) as well as 1-decanol or decanoic acid. Phase diagrams in the full

range of compositions were determined for all eight systems, while for the {penta-

decane (1) + 1- decanol (2)} system, two techniques for determining phase dia-

grams were compared: the dynamic (synthetic) method with the calorimetric meth-

od (DSC). To analyse the possibility of eliminating the experiment, the ideal solu-

bility and predictions based on the group assignment method were used - the modi-

fied (Dortmund) UNIFAC model.[2] The obtained eutectic mixtures were exam-

ined using the DSC technique and the experimental results of melting enthalpy

were compared with the theoretical predictions.[3]

Low-temperature PCMs with transformation temperatures from 0 to 17°C

were obtained, of which mixtures containing decanoic acid are characterized by

higher values of latent heat (even > 215 J/g). Moreover, the possibility of predict-

ing (using UNIFAC method) eutectic composition and melting point of mixtures

containing acids or fatty alcohols with alkanes was confirmed.

References

[1] P. Singh, R. K. Sharma, A. K. Ansu, R. Goyal, A. Sarı, V. V. Tyagi. A comprehensive review on

development of eutectic organic phase change materials and their composites for low and me-

dium range thermal energy storage applications. Sol. Energy Mater. Sol. Cells. 223:110955,

2021.

[2] U. Weidlich, J. Gmehling. A Modified UNIFAC Model. 1. Prediction of VLE, hE, and γ∞. Ind. Eng.

Chem. Res. 26:1372–1381, 1987.

[3] S. Kahwaji, M. A. White. Prediction of the properties of eutectic fatty acid phase change materi-

als. Thermochim. Acta. 660:94–100, 2018.


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Thermal Dehydration of Monosodium L-Glutamate Monohydrate:

Influence of Liquefaction on the Kinetic Process in Solids

TAKAHIRO OKAZAKI1, MASAMI HARA1, NIKITA V. MURAVYEV 2,

NOBUYOSHI KOGA¹*

1Hiroshima Univ., Grad. Sch. Humanities and Social Sciences, Dept. Science Education

2Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences


Keywords: thermal dehydration, crystalline hydrates, kinetics, liquefaction

Contributions of liquid phase on the thermal dehydration/decomposition of sol-

ids result in further complication of the heterogeneous reaction [1-4]. Formation of

liquid phases during the thermal decomposition of solids occurs by different physical

processes in reactant or product solids including melting, glass transition of amor-

phous phase, dissolution into condensed water, and gelation, which dramatically al-

ter the apparent kinetic behavior of the thermal decomposition. Therefore, various

types of liquefaction phenomena of the reacting system midway through the reaction

and its influence on the overall kinetics caused by the significant variations in phys-

ico-geometrical constraints should be clarified to gain further insight into the specific

type of thermal dehydration/decomposition of solids.

Thermal dehydration of monosodium L-glutamate monohydrate occurs via well-

separated two-step mass-loss processes attributed to the thermal dehydration of crys-

talline water and the intermolecular dehydration. Contributions of liquefaction phe-

nomena were observed in both thermal dehydration processes. During the thermal

dehydration of crystalline water, liquefaction of the solid product layer is observed

midway through the reaction and the subsequent reaction proceeds in a geometrical

constraint of the reactant solid covered by the liquid surface layer and form the solid

anhydride. The intermolecular dehydration of solid anhydride forms the liquid prod-

uct on the surface of the reacting particles and the internal solid reactant dissolves

into the liquid product. Subsequently, the intermolecular dehydration proceeds in the

liquid phase. Kinetic modeling of these complex processes was examined based on

systematic thermoanalytical measurements and in situ microscopic observations.

References

[1] N. Koga, Y. Suzuki, T. Tatsuoka. Thermal dehydration of magnesium acetate tetrahydrate: For-

mation and in situ crystallization of anhydrous glass. J. Phys. Chem. B. 116:14477–14486, 2012.

[2] N. Kameno, N. Koga. Heterogeneous kinetic features of the overlapping thermal dehydration and

melting of thermal energy storage material: Sodium thiosulfate pentahydrate. J. Phys. Chem. C.

122:8480–8490, 2018.

[3] T. Okazaki, N. Koga. Physico-geometrical interpretation of the kinetic behavior of the thermal

dehydration of β-maltose monohydrate. Ind. Eng. Chem. Res. 59:17828–17836, 2020.

[4] N.V. Muravyev, KA. Monogarov, I.L. Dalinger, N. Koga, A.N. Pivkina. Apparent autocatalysis

due to liquefaction: Thermal decomposition of ammonium 3,4,5-trinitropyrazolate. Phys. Chem.

Chem. Phys. DOI: 10.1039/D1CP01530C.


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A map of ionic liquids in terms of glass transition and fragility

YUKIO TERASHIMA*, TAISUKE HIRAI

Naruto University of Education


Keywords: glass transition, fragility, ionic liquids

For ionic liquids (ILs), a wide variety of applied research such as battery and

organic synthesis have been developed. However, systematic investigations focusing on its glass-transition kinetics and thermodynamics have been still relatively few.

This study aims to map and classify typical ILs clearly in terms of the glass-transition temperature (Tg), the heat-capacity change (ΔCp) at Tg and the fragility index (m) as a function of its formula weight (FW). For 16 kinds of ILs including imidazolium, pyrrolidinium, pyridinium, phosphonium and ammonium cation groups, the experimental thermodynamic parameters of Tg and ΔCp were determined from differential scanning calorimetry (DSC) measurements. The kinetic parameter m and one of the VFT paraeters, T0, as an ideal glass transition temperature, were

calculated from the scanning-rate dependence of Tg in the same manner as previous thermal studies [1,2].

We examined the FW dependences of Tg, T0, ΔCp and m among the 16 samples in addition to cations’ and anions’ effects on the parameters. Overall, we found fol-lowing trends: With increasing FW, Tg decreases slightly, whereas T0 increases grad-ually, and the gap between them narrows. The relationship of Tg with the temperature of melting (Tm) can be different from an empirical rule of Tg = 2Tm/3 [3]. the heat-

capacity change (ΔCp) depends on FW, especially its cations’ part. The fragility m correlates with FW, splitting into two categories. Contrary to ΔCp, m seems to be more dependent on anions than cations.

Mapping and classification of ILs like this study are expected to be useful for easily prediction of the glass-transtion and the fragility of ILs and related compounds.

References

[1] K. J. Crowley, G. Zografi. The use of thermal methods for predicting glass-former fragility. Ther-

mochim. Acta. 380:79-93, 2001.

[2] Y. Terashima, N. Sugimoto, M. Mori, N. Kinoshita, K. Takeda. Effects of solvents and solutes on

glass transition thermodynamics and kinetic fragility for amine and alcohol solutions of inorganic

salts. J. Therm. Anal. Calorim. 135(5): 2797–2805, 2019.

[3] L. M. Wang, C. A. Angell, R. Richert. Fragility and thermodynamics in nonpolymeric glass-forming

liquids. J. Chem. Phys. 125(7): 074505, 2006.


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Harmful Reagent-free Separation/Concentration system -Use of eutectic mixture of salt and water-

ARAI M.¹, OGINO Y.1, NISHIMOTO Y.1*

1Kanagawa University, Faculty of Science *Corresponding author: e-mail: [email protected]

Keywords: eutectic mixture of salt and water, DSC, alkali chloride

Keeping the salt solution at sub-zero temperatures forms a eutectic of salt and

water. The eutectic of salt and water dissolves amino acid and sugars in the pres-ence of dissolved oxygen. Above the eutectic point and below the melting point of ice, only the eutectic mixture exists as a liquid phase, so a new separa-tion/concentration method at low temperatures can be constructed. Since the eutec-tic point varies depending on the alkali metal ion, the applied temperature range varies depending on the alkali chloride used.

In this study, aqueous solutions of inorganic salts were used as eluent. KCl and NaCl were compared as the salts forming the stationary phase. We are developing a system that can separate and concentrate inorganic cations by keeping the aqueous solution of alkali chloride at -5~0°C, which is higher than the eutectic point of al-kali chloride and water and lower than the melting point of water.

It also reports the optimal conditions and accuracy using the newly constructed system.

References [1] M. Arai, Y. Nishimoto, Analysis of Functional Water, Bunseki Kagaku, 69,:673-678, 2020. [2] S. Fujiwara, Y. Nishimoto, Anal. Sci. 21,359-360,2005. Aknowledgement This work was supported by JSPS KAKENHI Grand Number 20K12242.


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Kinetics of Thermal Decomposition of Potassium Hydrogen Carbonate:

Particle Size Effect on Physico-Geometrical Consecutive Reaction

MITO HOTTA1, TAIGA TONE1, NOBUYOSHI KOGA¹*

1Hiroshima University, Graduate School of Humanities and Social Sciences, Division of Educational

Sciences, Department of Science Education


Keywords: thermal decomposition, kinetics, physico-geometrical consecutive pro-

cess, particle size effect

Thermal decomposition of solids proceeds in many cases by contracting geom-

etry of the reaction interface, induced by surface reaction (SR). A distinguishable

induction period (IP) for the SR is also a specific character in some reactions. There-

fore, the overall kinetics is described by the physico-geometrical consecutive process

comprised of IP, SR, and phase boundary-controlled reaction (PBR) [1,2]. The con-

secutive reaction kinetics are influenced by different factors including heating and

atmospheric conditions. The particle size is one of the factors to determine the con-

tribution of each component reaction step to the overall kinetics [3].

In this study, the thermal decomposition of potassium hydrogen carbonate was

selected as the model reaction for describing the effect of particle size on the phys-

ico-geometrical consecutive IP–SR–PBR process, because less sensitivity of the

overall kinetics to the heating and atmospheric conditions has been demonstrated for

the analogous compound of sodium hydrogen carbonate [4,5]. The kinetic data for

the thermal decomposition of potassium hydrogen carbonate particles characterized

by different particle size were recorded using TG with different temperature program

modes of isothermal, linear nonisothermal, and constant transformation. The system-

atic series of kinetic data were universally analyzed through the conventional iso-

conversional kinetic calculation for finding the overall kinetic behavior. Furthermore,

the kinetics of IP, SR, and PBR process were separately analyzed based on the dif-

ferential kinetic equation for the consecutive IP–SR–PBR model [1] for identifying

the effect of particle size on each component reaction step.

References

[1] H. Ogasawara, N. Koga. Kinetic modeling for thermal dehydration of ferrous oxalate dihydrate

polymorphs: A combined model for induction period-surface reaction-phase boundary reaction.

J. Phys. Chem. A. 118:2401–2412, 2014.

[2] L. Favergeon, M. Pijolate, M. Soustelle. Surface nucleation and anisotropic growth models for

solid-state reactions. Thermochim. Acta. 654:18–27, 2017.

[3] S. Kodani, N. Koga. Kinetics of contracting geometry-type reactions in the solid state: implications

from the thermally induced transformation processes of α-oxalic acid dihydrate. Phys. Chem.

Chem. Phys. 22:19560–19572, 2020.

[4] S. Yamada, N. Koga. Kinetics of the thermal decomposition of sodium hydrogen carbonate evalu-

ated by controlled rate evolved gas analysis coupled with thermogravimetry. Thermochim. Acta.

431:38–43, 2005.

[5] N. Koga, S. Maruta, T. Kimura, S. Yamada. Phenomenological kinetics of the thermal decomposi-

tion of sodium hydrogencarbonate. J. Phys. Chem. A. 115:14417–14429, 2011.


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Influence of particle size on the thermal degradation of chitin

SHUTO YAMADA¹*, RYUSEI NAKATSU¹, MASAHIRO TSUCHIYA1, NOBUYOSHI KOGA2

1National Defense Academy of Japan, Department of Applied Chemistry

2Hiroshima University, Graduate school of Humanities and Social Sciences *Corresponding author: e-mail: [email protected]

Keywords: thermal degradation, kinetic analysis, deconvolution, chitin

The thermal degradation of chitin is a typical solid-state reaction, and it has been reported to exhibit partially overlapped two-step reaction feature that changes depending on deacetylation degree [1]. A large and abnormal particle size distribu-tion in the sample may also cause partially overlapped reaction process during the cource of degradation process, because of the phygico-geometric constraints of the solid-state reaction described by the contraction of the reaction interface [2, 3].

In the present study, the effect of particle size on the kinetic behaviors of the thermal degradation of chitin was investigated on the basis of mass-loss curves recorded under linear nonisothermal conditions at various heating rates. The chitin was sieved to different particle size fractions. TG curves of the thermal degradation of chitin in flowing N2 indicated the initiation of mass loss process at approximate-ly 500 K and partially overlapping two-step reaction feature eapscially for the sam-ple with smaller particle size, i.e., 25–75 μm. The mass-loss value of the second reaction step increased with increasing the particle size. Gaseous products of the thermal degradation of chitin, measured using pyrolysis-gas chromatography/mass spectrometry, were invariant irrespective of the particle size of the sample. Howev-er, a larger amount of product component derived from the constituent unit was observed at low temperature range for the sample with smaller particle size.

The results of the kinetic deconvolution analysis [4] applied to the multi-step thermal degradation of chitin indicated that the changes in the apparent kinetic be-havior of the reaction with particle size was owing to variations in the contributions of the surface and internal process of the reactant. Possible changes in the diffusivi-ty of the evolved gas thorugh the surface product layer and formation of intermedi-ate during the thermal degradation process are discussed for describing the influ-ence of the particle size on the thermal degradation of chitin.

References [1] M.A. Gámiz-González, et.al.. Kinetic study of thermal degradation of chitosan as a function of

deacetylation degree. Carbohydr. Polym. 167:52–58, 2017. [2] N. Koga, J. M. Criado. Influence of the particle size distribution on the CRTA curves for the solid-

state reactions of interface shrinkage. J. Therm. Anal. 49:1477–1484, 1997. [3] N. Koga, J. M. Criado. Kinetic analyses of solid-state reactions with a particle-size distribution. J.

Am. Ceram. Soc. 81:2901–2909, 1998. [4] N. Koga, Y. Goshi, S. Yamada, L. A. Perez-Maqueda. Kinetic approach to partially overlapped

thermal decomposition process. J. Therm. Anal. Calorim. 111:1463–1474, 2013.


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Partial molar heat capacities of aqueous solutions of diethylene glycol

monobutyl ether. Two-point scaling analysis.

MAŁGORZATA JÓŹWIAK¹*, MICHAŁ WASIAK¹, MARIOLA TKACZYK¹,

MAGDALENA TYCZYŃSKA¹

1University of Łódź, Department of Physical Chemistry


Keywords: heat capacity, scaping theory, diethylene glycol monobutyl ether

Two-point scaling theory is an extetion of conventional scaling theory. It de-

scribes the system which can appear in two “phases” and is based on the same as-

sumptions as in the convetional theory that thermodynamic potentials are homoge-

neous functions. The difference is that observed singularities are related to stability

limits of each “phase” rather than to the transition temperature. In the case of solu-

tions the behaviour of partial molar propertis is analysed instead of molar proper-

ties of pure substances and the aggregation process is induced by the change in

concentration rather than temperature [1].

Specific isobaric heat capacities of aqueous solutions of diethylene glycol

monobutyl ether (C4E2) were measured over wide range of concentration in the

(278,15 – 343,15) K temperature range, by means of differential scaning calorime-

ter (Staram, microDSCIII). Apparent and partial molar heat capacities of the solute

(C4E2) in the solutions were calculated in order to analyse the aggregation behav-

iour of the amphiphile in solution using so-called two-point scaling theory [1].

The obtained values of critical indices α, in the range before and after aggrega-

tion were compared with values obtained earlier for the solution of similar amphi-

philes [2-5], and discussed in relation to the structure of aggregates. Obtained re-

sults indicates that two-point scaling theory describes well aggregation in the solu-

tion. Analysis of the heat capacities changes related to the concentration of the so-

lution can give an insight into the aggregates in the solutions and influence of tem-

perature on the process under investigation.

References

[1] H. Piekarski, M. Wasiak, L. Wojtczak. Modification of the two-point scaling theory for the de-

scription of the phase transition in solution. Analysis of sodium octanoate aqueous solutions. J. Solu-

tion Chem. 41:318–334, 2012.

[2] L. Wojtczak, H. Piekarski, M. Tkaczyk, I. Zasada, T. Rychtelska, Application of two-point scaling

to the pseudophases coexistence. J. Mol. Liq. 95:229−241, 2002.

[3] H. Piekarski, M. Tkaczyk, M. Wasiak. Heat capacity of aqueous 2-(2-hexyloxyethoxy)-ethanol

solutions by DSC. Application of two-point scaling to pseudophases coexistence. J. Therm. Anal. and

Cal., 82:711–718, 2005.

[4] M. Wasiak, M. Tkaczyk, H. Piekarski, P. Góralski. Heat capacity and phase behaviour of {1-

propoxypropan-2-ol--water} system: Two-point scaling analysis. J. Mol. Liq. 224(Part A):842–848,

2016.

[5] M. Wasiak, M. Tkaczyk, H. Piekarski. Heat capacity and phase behaviour of aqueous solutions of

triethylene glycol monopentyl ether. Two point scaling analysis. Fluid Phase Equilibr. 431:16–23,

2017.


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Kinetic modeling and parameter optimization of brewer’s spent grain

pyrolysis

F. DESSÌ¹*, M. MUREDDU¹, F. FERRARA¹, A. PETTINAU¹, A. ORSINI¹

1Sotacarbo S.p.A.


Keywords: kinetic analysis, brewer’s spent grain (BSG), pyrolysis

Brewer's spent grain (BSG) is the major byproduct of the brewing industry that

represent approximately 85%. The most interesting method to use the BSG is via

pyrolysis to produce energy and value-added products [1].

In this study, the thermal degradation behavior from pyrolysis of brewer’s spent

grain (BSG) of different types of malt (Pils and Weizen) has been investigated with

a focus on the degradation of the pseudo-components, i.e. extractives, hemicellulose,

cellulose and lignin, obtained by deconvoluting the peaks of the DTG curves. Bio-

mass characterization has been carried out through thermogravimetric analysis

(TGA) under nitrogen atmosphere (99.999 vol.%) at different heating rates (10, 15,

20 and 40 °C/min).

The kinetic results have been obtained by using the four independent parallel

reactions (IPR) model. A correct estimation of the kinetic parameters requires find-

ing the absolute minimum of an objective function: this procedure has been per-

formed by using a multi-dimensional nonlinear regression function. The correspond-

ing kinetic parameters are optimized iteratively to minimize the difference between

the deconvoluted and simulated curves. In this case, the initial and boundary

conditions of activation energy (Ea), pre-exponential factor (A) and reaction order

(ni) parameters have been obtained from integral isoconversional methods (by using

Kissinger-Akahira-Sunose (KAS) and Starink methods), and from Master Plot

method [2].

The kinetic triplet of each pseudo-component has been calculated for all the

heating rates. The overall reaction mechanism of each biomass can be interpreted as

the combined effect of reaction-order (F) and nucleation (A) models. The developed

model help us understand the system better for process optimization and designing

a BSG pyrolytic processing system. In particular, these kinetic results will be used

to set up and validate a Computational Fluid Dynamics (CFD) model of a pilot-scale

down-draft gasifier (under construction).

References

[1] S. I Mussatto. Brewer’s spent grain: a valuable feedstockfor industrial applications. J. Sci. Food

Agric. 94:1264-1275, 2014.

[2] S. Vyazovkin, A. K. Burnham, L. Favergeon, N. Koga, E. Moukhina, L. A.Pérez-Maqueda, N.

Sbirrazzuoli. ICTAC Kinetics Committee recommendations for analysis of multi-step kinetics. Ther-

mochim. Acta 689:178597, 2020.


48

https://www.sciencedirect.com/science/article/pii/S004060312030246X#!








https://www.sciencedirect.com/science/journal/00406031

https://www.sciencedirect.com/science/journal/00406031

https://www.sciencedirect.com/science/journal/00406031/689/supp/C

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Influence of melting effect on the thermal decomposition characteristics of anthraquinone dyes hazardous waste

WENQIAN WU¹*, ZEYUAN XIA¹, WANGHUA CHEN¹, LIPIN CHEN¹, ZICHAO GUO1

1 Department of Safety Engineering School of Chemical Engineering, Nanjing University of Science

and Technology

*Corresponding author: e-mail: [email protected] (W.H. Chen) Keywords: melting effect, thermal decomposition, anthraquinone dyes, hazardous waste, bond order

The thermal decomposition of the mixture composed with the typical hazard-

ous waste like anthraquinone, 1-nitroanthraquinone, 1,5-dinitroanthraquinone and 1,8-dinitroanthraquinone was tested through the differential scanning calorimetry, and the components interaction was analyzed through the experimental combined with the model-free method. The test results show that melting makes the solid-phase decomposition of 1,5-dinitroanthraquinone weakened as that the activation energy is reduced by about 142.08kJ/mol. In addition, anthraquinone also affects the decomposition intermediates of polynitroanthraquinones. The spatial configura-tion of each substance was optimized based on quantum mechanics tools, and its microscopic decomposition mechanism was speculated. The calculation results of the Laplace bond show that in the decomposition of anthraquinone nitro com-pounds, the C-NO2 bond is broken first, followed by the break of the single bond of the middle ring adjacent to the substituent. A molecule containing two nitro groups cannot form a stable molecular structure after the nitro group is removed, and the -CO group needs to be removed to form a stable benyne group which can react with anthraquinone. The reactivity rating number classification simulated by the kinetic equation obtained by the model fitting method in the extreme fire conditions results show that mixture without anthraquinone has the characteristics of violent chemical reaction under high temperature and high pressure. The melting effect of anthra-quinone will make the mixture more stable except under elevated temperature and pressure.

References [1] S Sivaraman, S Varadharajan. Investigative consequence analysis: A case study research of beirut

explosion accident[J]. Journal of Loss Prevention in the Process Industries, 2021, 69: 104387. [2] H L Friedman. Kinetics of thermal degradation of char‐forming plastics from thermogravime-

try[J]. Application to a Phenolic Plastic, 1964, 6: 183-195. [3] V Sergey. Kinetic concepts of thermally stimulated reactions in solids: A view from a historical

perspective[J]. International Reviews in Physical Chemistry, 2000, 19(1): 45-60. [4] T Lu and F Chen. Bond Order Analysis Based on the Laplacian of Electron Density in Fuzzy

Overlap Space. The journal of physical chemistry A, 2013, 117(14): 3100−3108.


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SESSION 2:

INSTRUMENTATION

Fast scanning calorimetry for determining specific heat capacity

CHRISTOPH SCHICK 1,2*

1Butlerov Institute of Chemistry, Kazan Federal University

2Institute of Physics and Competence Centre °CALOR, University of Rostock


Keywords: fast scanning calorimetry, specific heat capacity, sample mass

Fast Scanning Calorimetry (FSC) allows preventing phase transitions during

rapid cooling and rapid heating. In this way, supercooled or superheated states of

matter can be investigated. Calorimetry, in general, allows the determination of the

specific heat capacity - a fundamental thermodynamic property. Specific heat capac-

ity defines the temperature dependence of essential thermodynamic functions such

as enthalpy, entropy, and Gibbs energy. Therefore, the measurement of specific heat

capacity by FSC is an exciting task, as it allows the investigation of samples in non-

equilibrium states that are otherwise not easily accessible. However, such measure-

ments require at least the solution of three problems:

1. calibration of the measured heat flow rate

2. correction for heat losses to the environment

3. determination of the sample mass

I will present my personal view of the different approaches available in the lit-

erature on how to solve the listed problems [1-8].

References

[1] Adamovsky, S.A., A.A. Minakov, and C. Schick, Scanning microcalorimetry at high cooling rate.

Thermochimica Acta, 2003. 403(1): p. 55-63.

[2] Efremov, M.Y., et al., Thin-film differential scanning nanocalorimetry: heat capacity analysis.

Thermochimica Acta, 2004. 412(7): p. 13-23.

[3] Lopeandia, A.F., J. Valenzuela, and J. Rodríguez-Viejo, Power compensated thin film calorimetry

at fast heating rates. Sensors and Actuators A: Physical, 2008. 143(2): p. 256-264.

[4] Zhuravlev, E. and C. Schick, Fast scanning power compensated differential scanning nano-calo-

rimeter: 2. Heat capacity analysis. Thermochimica Acta, 2010. 505(1-2): p. 14-21.

[5] Cebe, P., et al., Using flash DSC for determining the liquid state heat capacity of silk fibroin. Ther-

mochimica Acta, 2015. 615: p. 8-14.

[6] Franke, E., D.A. LaVan, and C.A. Volkert, Quantifying DC Differential Scanning Nanocalorimetry

for Determining Heat Capacities. Thermochimica Acta, 2018. 668: p. 116-125.

[7] Quick, C.R., et al., Measurement of specific heat capacity via fast scanning calorimetry—Accuracy

and loss corrections. Thermochimica Acta, 2019. 677: p. 12-20.

[8] Bolmatenkov, D.N., et al., A new method for heat capacity determination in supercooled liquid

state using fast scanning calorimetry: thermochemical study of 9,9'-bifluorenyl. Thermochimica

Acta. 2020. 694: p. 178805.


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In-situ visual observation thermal analysis with live captured camera images

TADASHI ARII*, LANI LLEGO CELIZ

Thermal Analysis Divison, Rigaku Corporation

*Corresponding author: e-mail: [email protected] Keywords: sample observation, thermal degradation, in-situ analysis

Simultaneous Thermal Analysis (STA) or Differential Scanning Calorimetry (DSC) equipped with sample observation capability has increasingly becoming popular in the field of material characterization evaluation using thermal analysis. With this attachment, conventional results of STA or DSC as well as capturing the sample’s actual changes in color, shape and volume can be observed visually thru live captured images providing a more detailed information.

Figure 1 shows the TG-DTA result of an epoxy resin pellet in air atmosphere by Rigaku Thermo plus EVO2 STA8122 equipped with a sample observation attach-ment. With incresing tempera-ture, a slight mass loss due to the initial thermal degradation can be observed around 180℃ accompanied with a gradual color change of the sample surface from white to light brown. As the mass loss due to thermal degradation pro-ceeds, an exothermic peak due to oxidation appeared prominently on the DTA, followed by the cracks which were visually evident due to an increase in the internal pressure within the sample caused by a sudden evolution of gases around 370°C, while the remarkable sample cracking phenomenon did not reveal any effect on both TG and DTA curves. After that, a second exothermic peak appeared slightly around 450°C, and the thermal degradation was completed at 600°C.

To demonstrate the effectiveness of the unique in-situ visual sample observa-tion function equipped with STA and DSC, the results of the application to several materials will be presented and discussed References [1] M. Hebda, M. Laska, M. Szechyn´ska-Hebda, J Therm Anal Calorim, 114, 1099, 2013. [2] T. Arii, Book of Abstract, ESTAC12, OP1.09, 65, 2018.

TG

DTA

DTG

-20.71 %

371.7 ℃

185.4 ℃

573.7 ℃

352.7 ℃

447.0 ℃

T e m p e r a t u r e / ℃

+00

30.0 100.0 200.0 300.0 400.0 500.0 600.0 700.0

Weight/%

+00

-35.00

-30.00

-25.00

-20.00

-15.00

-10.00

-5.00

0.00

5.00

Heat Flow/μ

V

+00

-50.0

-40.0

-20.0

0.0

20.0

40.0

60.0

80.0

100.0

120.0

140.0

160.0

180.0

200.0

DTG/%/min

+00

-7.00

-6.00

-5.00

-4.00

-3.00

-2.00

-1.00

0.00

1.00

2.00

Fig.1 Sample observation STA result of epoxy resin


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Precise calorimetric mass estimation for Indian rubidium atomic

frequency standard

RICHA SHARMA KESARKAR¹, DEEPAK ATTRI1, TVS RAM1, KS PARIKH1,

THEJESH N. BANDI1

1Affiliation: Space Applications Centre (SAC), Indian Space Research Organization (ISRO),

Ahmedabad, Gujarat-380058, India.


Keywords: rubidium, glass-bulb, calorimetry, cold-point, frequency-standard.

Rubidium (Rb) atomic clocks/frequency-standards are the workhorses of satellite navi-

gation [1]. The metallic Rb present inside a Rb-filled-glass-bulb is a critical parameter

for onboard clocks and should be precisely validated [2]. Since, non-destructive calori-

metric mass estimation gives an accurate method to validate the inner metallic Rb con-

tent of a bulb, collection of entire Rb at a single spot before estimation becomes im-

portant [3].

We present successful usage of a cold-point formation apparatus (CPA), to efficiently

collect all metallic Rb onto a single spot and hence demonstrate precise calorimetric

mass estimation (≥ 40 µg) with a CPA treated bulb. The involved process is repeatable

and hence renders more confidence to the overall measurement. This helps us to even-

tually estimate for the actual required Rb content inside the glass-bulb, in order to ensure

the overall life of our Rb clock upto 15 years or more.

References

[1] J.C. Camparo, The rubidium atomic clock and basic research. No. TR-2007 (8555)-5. Aerospace Corp

el Segundo ca Physical Sciences labs, 2007.

[2] C.H. Volk, R.P. Frueholz, T.C. English, T.J. Lynch, R.J. Riley. Lifetime and Reliability of Rubidium

Discharge Lamps for Use in Atomic Frequency Standards. No. TR-0084A (5404-30)-1. Aerospace Corp el

segundo ca Chemistry and Physics lab, 1984.

[3] C.M. Klimcak, M. Huang, J. C. Camparo. Alkali metal consumption by discharge lamps fabricated from

GE-180 alum inosilicate glass. 2015 Joint Conference of the IEEE International Frequency Control Sym-

posium & the European Frequency and Time Forum. IEEE, 2015.


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Identification of transport-derived errors in thermal analysis testing

REBECCA L. GIBSON1,2*, MARK J SIMMONS2, E. HUGH STITT1, LI LIU1,

ROBERT W. GALLEN1 1. Johnson Matthey

2. School of Chemical Engineering, University of Birmingham


Keywords: thermal analysis, mass transport, heat transport, kinetics

During the production of catalysts and other inorganic materials, there are many

energy-intensive thermal processing steps, and these can be critical to both the per-

formance of the final product and the economics of manufacture. To design efficient,

optimised calcination and drying processes for new formulations, kinetic infor-

mation must be extracted from thermal analysis data.

A modified Sestak-Berggren methodology [1], has been successfully used to ex-

tract kinetic information from experimental thermal analysis data. However, in cer-

tain cases, such as thermogravimetric analysis (TGA) data from a pan-style reactor,

the results appeared statistically inadequate and inconsistent between ramp rate ex-

periments. This prompted investigation into transport phenomena.

Although thermal analysis is a well-developed field, reaction engineering princi-

ples, such as considerations of heat and mass are not widely applied. This study uses

computational fluid dynamics (CFD) to investigate possible transport limitations.

Transient tracer experiments have been modelled by introduction of a passive sca-

lar into the simulations to characterise the heat and mass transport rates. Different

equipment configurations were compared through analysis of residence time distri-

butions and dimensionless analysis. This indicated clearly that equipment configu-

ration has a large impact on the transport phenomena occurring and that the observed

rates are indeed transport limited [2].

This quantification of transport rates explains the poor quality of fit achieved us-

ing the Sestak-Berggren model, which only captures the behaviour inside the solid.

This study highlights that thermal analysis data are susceptible to transport limita-

tions, even though these have rarely been considered in the literature. This presenta-

tion will present data and modelling to highlight this failing and suggest strategies to

improve data analysis and modelling approaches.

References

[1] J. Sestak and G. Berggren, ‘Study of the kinetics of the mechanism of solid-state reactions at

increasing temperatures’, Thermochim. Acta, vol. 3, pp. 1–12, 1971.

[2] R. L. Gibson, M. J. H. Simmons, E. H. Stitt, L. Liu, and R. W. Gallen, ‘Non-kinetic phenomena

in thermal analysis data; Computational fluid dynamics reactor studies’, Chem. Eng. J., vol. 426,

p. 130774, Dec. 2021, doi: 10.1016/j.cej.2021.130774.


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Self-heating evaluation on thermal analysis of energetic materials

ALAIN ALONSO1, DAVID LÁZARO1, MARIANO LÁZARO1, DANIEL ALVEAR2

1 GIDAI Group, University of Cantabria

2 General Directorate of Industry, Energy and Mines, Government of Cantabria


Keywords: thermal anlysis, energetic materials, polymers, DSC, TGA

Thermal analysis has been proven to be an efficiently technique to analyse ther-

mal decomposition reactions of different material typologies. This technique is

widely used in different fields. One of them is fire science where energetic materials

are very common, being the combustion reactions a recurrent issue on these analyses.

In this field large heating rates are commonly used to try to approximate fire expo-

sure conditions. Thermal analysis of energetic materials has some singularities, e.g.

self-heating, that could alter the thermal analysis results.

Thermal analysis equipments require the definition of certain boundary condi-

tions [1]. Although detailed studies of the International Confederation for Thermal

Analysis and Calorimetry (ICTAC) [2] recommends how to set the boundary condi-

tions in the thermogravimetry (TGA) and differential scanning calorimetry (DSC),

different standards [3,4] recommend different boundaries conditions, spetially re-

ferred to the mass of the sample, that does not fit with the ICTAC recommendations.

This work presents a study to show the influence of sample mass, atmospheres,

and heating rate in the TGA/DSC results of energetic materials. It also includes how

to check if TGA/DSC results are valid or should be descarted. The selected energetic

materials are the PMMA and LLDPE. A series of 16 experimental tests have been

performed in the present study. These experimental tests allow evaluating the influ-

ence of the boundary conditions on the mass loss, the heat flux, and the influence of

the materials decomposition reactions on the temperature of the sample.

Results show the impact of each different boundary conditions in the thermal

decomposition and represent an aid to define the suitable conditions to perform

TGA/DSC test on PMMA and LLDPE. This is done by the evaluation of the influ-

ence of the boundary conditions of the tests in parameters as the thermal lag, on the

reactions heat fluxes, and in the difference between the sample and the program tem-

perature. It is remarkable the PMMA autoignition temperature effect on the

TGA/DSC results. Finally, some useful recommendations have been defined.

References

[1] D. Lázaro, M. Lázaro, A. Alonso, P. Lázaro, D. Alvear. Influence of the STA boundary conditions

on thermal decomposition of thermoplastic polymers. Journal of Thermal Analysis and Calorim-

etry, 138 (2019) 2457-2468

[2] S. Vyazovkin, K. Chrissafis, M. L. Di Lorenzo, N. Koga, M. Pijolat, B. Roduti, N. Sbirrazzuoli, J.

J. Suñol. ICTAC Kinetic Committee recommendations for collecting experimental thermal anal-

ysis data for kinetic computations. Thermochimica Acta, 590 (2014) 1-23

[3] EN ISO11358-1:2015 Plastics-Thermogravimetry of Polymers-Part1: General principles

[4] EN ISO11357-1:2017 Plastics -Differential Scanning Calorimetry-Part1: General principles


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Application of the Non-Stationary Millimeter Wave Spectrometry for

Analyzing the Gaseous Products of the Thermal Decomposition of

Energetic Materials

ILYA A. LUKYANENKO ¹*, YURIY V. SHEYKOV1, VLADIMIR L. VAKS

2,

ELENA G. DOMRACHEVA², MARIA B. CHERNYAEVA2, SERGEY I. PRIPOLZIN²,

VLADIMIR YU. BALAKIREV2, VLADIMIR A. ANFERTYEV²,

ANTON A. YABLOKOV2, SERGEY A. VAKHMISTROV

1,

SERGEY V. ERUNOV1, ANATOLY L. MIKHAYLOV

1

1 Russian Federal Nuclear Center, All-Russian Research Institute of Experimental Physics

2 Institute for Physics of Microstructures of the Russian Academy of Sciences


Keywords: thermal analysis, gaseous decomposition products, energetic materials,

millimeter wave spectrometry

Studying the mechanisms of energetic materials thermal decomposition im-

poses strong demands on analytical methods being applied. The products of ener-

getic materials decomposition are mostly gases [1], and they usually appear in the

form of very complex gas mixtures which should generally go through a time-

consuming separation procedure to be analyzed in details. At the same time, in or-

der to provide valuable supplementary information, the composition of gaseous

products should be studied in real time, and both major and minor products are to

be analyzed. The spectral methods (such as mass-spectrometry, FTIR spectrometry,

etc.) which are commonly used in combination with thermal analysis, do not ensure

sufficient selectivity for analyzing non-separated gas mixtures containing dozens of

components [2].

In this study, the non-stationary millimeter wave rotational spectrometry was

introduced as a method which is capable of performing fast, sensitive and selective

determination of gas mixtures emitted during the decomposition of energetic mate-

rials. The crucial advantage of the rotational spectrometry is that the small width of

rotational lines provides the opportunity for distinguishing between different com-

pounds without need for separating them.

To prove the capabilities of the method, an experimental facility was built and

the thermal decompositions of several energetic materials were studied. The exper-

iments show that with the use of the non-stationary millimeter wave spectrometry,

the rotational lines of all the expected decomposition products can well be ob-

served independently in real time throughout the decomposition process. The esti-

mated limits of detection of typical decomposition products are in the range from

10 pg (H2CO) to 10 ng (HCN).

References

[1] A. Benhammada et al. Thermal decomposition of energetic materials using TG-FTIR and TG-MS:

a state-of-the-art review. Appl. Spectrosc. Rev., 2019. DOI: 10.1080/05704928.2019.1679825.

[2] W. Xie et al. Thermal characterization of materials using evolved gas analysis. J. Therm. Anal.

Calorim. 65:669–685, 2001.


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Hot-Stage Microscopy Direct Analysis in Real-Time Mass Spectrome-try, The Integration of Thermal Analysis and Ambient Ionisation.

GAGE P. ASHTON¹*, LINDSAY P. HARDING1, GARETH M.B. PARKES,1

1Thermal Methods Research Unit, School of Applied Sciences, The University of Huddersfield, UK.

*Corresponding author: e-mail: [email protected] Keywords: Thermomicroscopy, Mass Spectrometry, Instrumental Development

Thermomicroscopy (aka hot-stage microscopy) is a technique that is routinely used to study the visual behaviour of a sample as a function of temperature. Key physical events may be observed including meltings, crystallisations and decompo-sitions of a sample as it is heated. These events are then reviewed as light/colour changes or as a series of micrographs.

As with many thermal analysis methods, thermomicroscopy suffers from the fact that no chemical information is gained about the investigated material during analysis. Thermal analysis in general compensates for this lack of information through the hyphenation of additional techniques such as spectroscopy, chromatog-raphy and mass spectrometry. Although techniques such as thermogravimetric anal-ysis (TGA) and differential scanning calorimetry (DSC) have been hyphenated for use with EGA systems the application of thermomicroscopy as an EGA technique remains largely unexplored.

Recently mass spectrometry has received a large amount of development in the field of ambient ionisation mass spectrometry thanks to mechanical developments in atmospheric pressure interfaces. Direct analysis in real-time mass spectrometry (DART-MS) is one of the most widely used ambient ionisation methods introduced in recent years. DART uses a heated stream of energetic species to thermally desorb and ionise samples prior to introduction to the mass spectrometer.

The system described here termed HDM combines thermomicroscopy and DART-MS allowing for the simultaneous collection of physical and chemical infor-mation. A bespoke instrument developed in-house from custom software and hard-ware creates an instrument that links optical physical events with the obtained mass spectra.[1]

The presentation will focus on a range of recent applications studied using HDM, topics will include; optical means of temperature calibration, the characteri-sation of organometallic complexes, the identification of environmental microplas-tics and the analysis of trace quantities of energetic materials.

To summarise, HDM provides complementary data that links a material’s ex-ternal visual appearance to mass spectra obtained through thermal desorption and ionisation of thermally labile analytes.

References [1] G.P. Ashton, L.P. Harding, G.M.B. Parkes, An Integrated Hot-Stage Microscope-Direct Analysis

in Real Time-Mass Spectrometry System for Studying the Thermal Behavior of Materials, Anal. Chem. 89(24):13466-13471, 2017.


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Multiple simultaneous measurements of STA coupled with evolved gas analysis, MS/FTIR, and sample observation

LANI LLEGO CELIZ* , TADASHI ARII

Thermal Analysis Divison, Rigaku Corporation

*Corresponding author: e-mail: [email protected] Keywords: evolved gas analysis, sample observation, thermal oxidation

Hyphenated thermal analysis techniques that combine simultaneous thermal analysis (STA) with evolved gas analysis using mass spectrometry (MS) or Fourier transform spectroscopy (FTIR), as well as sample observation capability have in-creasingly becoming popular in the field of material characterization.

Multiple simultaneous measurements using these attachments not only provide the conventional results of TG-DTA/DSC, but also allow the identification of de-tailed chemical species of gases evolved from the sample, as well as capturing the sample’s actual changes in color, shape and volume thru live captured images.

Figure 1 shows the sam-ple observation STA result of red palm oil. As the tem-perature increases, an endo-thermic peak due to melting can be observed at 41℃ fol-lowed by several stages of mass losses that can be ob-served accompanied with various exothermic reactions from 150℃ . It revealed thermal events namely auto-oxidation phenomena caus-ing discoloration at 218℃, followed immediately by the oxidative decomposition

at 316℃ indicating a change in color from transparent to yellowish brown. Then at

388℃, the sample’s color changed to black due to carbonation followed by com-

bustion from 420℃.

To demonstrate the effectiveness of the STA combined with the multiple sim-ultaneous measurement attachments, the unique results of the application to several materials will be presented and discussed.

References [1] L. L. Celiz, T. Arii. J Therm Anal Calorim, 116, 1435, 2014. [2] T. Arii, Book of Abstract, ESTAC12, OP1.09, 65, 2018.

Fig.1 Sample observation STA result of red palm oil


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Advantages of in vivo measurement of human skin thermal conduct-ance using a calorimetric sensor

PEDRO JESÚS RODRÍGUEZ DE RIVERA1, 2, MIRIAM RODRÍGUEZ DE RIVERA1,

FABIOLA SOCORRO1, GUSTAVO MARRERO CALLICÓ2, AND MANUEL RO-DRÍGUEZ DE RIVERA1

1University of Las Palmas de Gran Canaria, Department of Physics

2University of Las Palmas de Gran Canaria, Institute for Applied Microelectronics (IUMA) *Corresponding author: [email protected]

Keywords: direct calorimetry; medical calorimetry; skin heat loss; skin thermal properties; thermal conductance; thermal physiology

Thermal conductivity of the skin has been measured by in vivo procedures since the 1960s [1]. These devices usually consist of temperature sensors and heat-ing elements, although techniques based on digital thermography are also used [2]. In vivo measurement of skin thermal conductivity involves several difficulties. It is necessary to adequately characterize the disturbance produced by the measurement. In addition, the thermal penetration depth of each instrument is different. These factors have led to the development of a multitude of techniques to measure this quantity. The interest of these in vivo thermal measurements is growing. A recent application is the use of these measures for skin cancer detection [3]. In our case, we have built a calorimetric sensor designed to measure this magnitude directly and non-invasively. The device implements the basic principles of calorimetry, and is capable of characterizing the thermal magnitudes of a 2 x 2 (4) cm2 skin region, with a thermal penetration depth of 4 mm. The sensor consists of a measuring thermopile with a thermostat cooled by Peltier effect. Several measurements have been performed on the human body under different conditions, resulting in a ther-mal conductance ranging from 0.017 to 0.050 WK-1. This magnitude, measured in vivo, is different in each studied area and depends on physiological and pathologi-cal factors. For example, thermal conductance increases when erythema is present, and can vary from 0.020 to 0.038 WK-1 at the same location depending on the con-dition of the subject. References [1] W.J.B.M. van de Staak, et al. Measurements of the Thermal Conductivity of the Skin as an Indica-

tion of Skin Blood Flow. Journal of Investigative Dermatology, 51 (3), 149-154, 1968. [2] Otsuka, K, et al. Imaging of skin thermal properties with estimation of ambient radiation tempera-

ture. IEEE Engineering in Medicine and Biology Magazine, 21 (6), 49-55, 2002. [3] Okabe, Takahiro, et al. First-in-human clinical study of novel technique to diagnose malignant

melanoma via thermal conductivity measurements. Scientific Reports, 9, 3853, 2019.


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Heat generation measurement of lithium-ion battery during charging

and discharging with two different methods

JINXIN XU ¹*, JIONG DING¹, SHULIANG YE¹

1Institute of Industry and Trade Measurement Technology, College of Metrology and Measurement

Engineering, China Jiliang University, Hangzhou, PR China


Keywords: Lithium-ion batteries, Heat generation measurement, Isothermal calo-

rimetry

Lithium-ion batteries have been widely used in portable electronics, electric

vehicles, and energy storage applications owing to their high power density and

energy density [1]. As a complicated electrochemical power source, lithium-ion

battery’s performance and safety are greatly affected by its operating temperature

[2]. Therefore, the heat generation of lithium-ion battery during charg-

ing/discharging process should be measured accurately to establish an appropriate

strategy for the battery thermal management. A widely used theoretical model of

the heat generation rate [3] is presented as follows:

( ) OCVOCV sr mix

Uq I U V IT q q

T

= − − + +

, (1)

where q is the heat generation rate (positive for heat generation and negative for

heat absorption), I, V and T are current, voltage and temperature, respectively,

Uocv is the open circuit voltage. The first term on the right side of equation (1)

accounts for resistive joule heat which is irreversible heat. The second term is the

reversible entropic heat or reaction heat. The third term qsr is the heat of the side

reaction indicating the aging process and the fourth term qmix is the heat in mixing

process. The first measurement method of the heat generation is to measure all the

parameters on the right side of equation (1). Under constant charge/discharge cur-

rent, qsr and qmix are usually ignorable comparing with joule and reaction heat.

Therefore, the first method only calculate the first term and second term of equa-

tion (1). The second measurement method of the heat generation is based on the

calorimetry. A home-made isothermal calorimetry with power compensation meth-

od will be used to measure the heat generation of lithium-ion batteries at different

temperatures. Compared with the first method, the second method measures all the

heating terms in equation (1), but it can not obtain irreversible heat and reversible

heat respectively. Different types of lithium-ion batteries will be measured with the

two methods and the results will be analyzed and compared in the manuscript.

References

[1] Zhang J, Lee J. A review on prognostics and health monitoring of Li-ion battery. J Power Sources.

196:6007–14, 2011.

[2] K. Murata, M. Ota. Proposal for evaluation method of bettery safety through thermal analysis. J

Energy Storage. 20: 576-580, 2018.

[3] Liu G, Ouyang M, Lu L, et al. Analysis of the heat generation of lithium-ion battery during charg-

ing and discharging considering different influencing factors. J Thermal Analysis & Calorimetry.

116:1001-1010, 2014 .


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In vivo measurement of skin heat capacity: advantages of the scanning calorimetric sensor

PEDRO JESÚS RODRÍGUEZ DE RIVERA1, 2, MIRIAM RODRÍGUEZ DE RIVERA1,

FABIOLA SOCORRO1, GUSTAVO MARRERO CALLICÓ2, AND MANUEL RO-DRÍGUEZ DE RIVERA1

1University of Las Palmas de Gran Canaria, Department of Physics

2University of Las Palmas de Gran Canaria, Institute for Applied Microelectronics (IUMA) *Corresponding author: [email protected]

Keywords: direct calorimetry; medical calorimetry; skin heat loss; skin thermal properties; heat capacity; thermal physiology

Measurement of the heat capacity of human tissues is mainly performed by in vitro procedures, generally using differential scanning calorimetry (DSC) [1]. In vivo measurement of this property is an underexplored field. A recent work has characterized the heat capacity by measuring the thermal diffusivity of the skin [2]. However, there are no instruments capable of directly measuring skin heat capacity in vivo. The developed sensor measures the heat flux of a localized skin area of 4 cm2, and is able to determine the heat capacity of the skin area where the measure-ment is made. The sensor consists of a thermopile equipped with a programmable thermostat. The principle of operation consists of a linear variation of the tempera-ture of the sensor thermostat, while the device is applied to the skin. To relate the heat capacity of the skin with the signals provided by the sensor, a two-body RC model is considered. Using this device, the skin has been characterized under dif-ferent conditions. The heat capacity of skin varies between 2.4 and 3.7 JK-1g-1. This magnitude is different in each zone and depends on several factors. The most de-termining factor is the degree of hydration. This sensor can be a versatile and use-ful tool in the field of physiology.

References [1] Myron L. Cohen. Measurement of the thermal properties of human skin. A review. Journal of In-

vestigative Dermatology, 69 (3), 333-338, 1977. [2] Webb, R.C, et al. Thermal Transport Characteristics of Human Skin Measured in Vivo Using

Ultrathin Conformal Arrays of Thermal Sensors and Actuators. PloS One, , 10 (2), e0118131, 2015


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A modular system of chemical reactors for work in a cascade system with analytical capabilities online - MATRIX 9 HAAS concept

T. BURDA, P. GRUSZKA, K. ŁAPIŃSKI, M. RUCIŃSKA, R. TOMIKOWSKA, R. TO-

MIKOWSKI, M. SIEDLECKI, M. STASZAK

1HAAS, Research and Development Department * e-mail: [email protected]

Keywords: chemical reactors, multicomponent groups of substrates, online analysis, simultaneous techniques

Concept of modular system chemical reactors that can operate in a cascade or in any configuration depending on the current demand for a given research process will be presented. Aspects of research works aimed at developing individual techno-logical solutions and verifying the operation of the reactors in conditions correspond-ing to their intended use shows opportunities and risks. Temperature control leading to the range of informations about exo and endothermal character of chemical pro-cesses are subject of testing. Effects changes of thermal properties creates require-ments of process engineering, especially for high pressure requirements.

The way in which the reagents are mixed can have a big impact on the yield and range of products formed in multiple rapid chemical reactions. Understanding this phenomenon enables chemists to carry out reactions more selectively for better uti-lization of raw materials, and for simplification product handling and separation [1].

Matrix 9 chemical reactors with analytical options are designed to be a unique system for multidimensional chemical processes, i.e. possible to be carried out in different standard volumes and at different time intervals, as well as in a parallel way to increase the efficiency of research.

References [1] J. Bałdyga, J.R. Bourne, w: „ Turbulent Mixing and Chemical Reactions”, J. Wiley (ed), 1999.

Project in progress: "Development of a modular system of chemical reactors for work in a cascade system and in any configuration, for conducting chemical processes of multicomponent groups of substrates with online analytical capabilities" POIR.01.01.01-00-1481 / 19-00, received funding from Program 1.1 .1. Intelligent Development Operational Program 2014-2020.


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STA thermal analysis for selected explosives using RealView® technique for octogen and hexogen

K. ŁAPIŃSKI¹, A. ORZECHOWSKI2, D. POWAŁA2, R. TOMIKOWSKA¹

1HAAS, Research and Development Department 2 Military Institute of Armament Technology

* e-mail: [email protected] Keywords: thermal analysis with image and color analysis, explosives, simultane-ous thermal analysis

Thermal analysis is one of the analytical techniques that is increasingly used in the analysis of explosives. Especially the possibility of working with small weights for safety reasons, as well as the possibility of recording an image during the meas-urement, assigning images to specific points on the DSC or TGA curve, and meas-urement video - significantly expand the scope of information provided by classic thermal measurements. Various kinds of physical and chemical phenomena, as a function of the ambient temperature, may cause its uncontrolled decomposition. This is one of the important reasons for the safety of, especially long-term stored explo-sives, for which thermal analysis is a technique necessary for characterization.

There has been following compounds using TGA and DSC with image capture and color analysis HITACHI HAAS tested:

1. Octogen HMX is a solid, crystalline body, it occurs in four polymorphic crys-tal forms: alpha, beta, gamma, delta, with different physical properties.

2. Hexogen RDX is currently the most important high-performance explosive. It is relatively insensitive and stable.

Tests were performed using a simultaneous HITACHI (HAAS) STA 7300 ther-mal analyzer for HMX and STA 7200 with RealView - an online image recording camera for RDX.

In the analysis of HMX and RDX explosives decomposition in two stages (melt-ing-decomposition) has been observed.

Changing the parameters of the analysis results in significant changes in the re-sults, for example: an increase in the heating rate causes a shift towards higher tem-peratures.

TGA ug and DSC mW curve for RDX and images before changes (1), during melting (2,3), sec-

ond transformation (4.5) and after second transformation (6) References Application Notes HITACHI High-Tech Analytical Science. Material Safety Data Sheets RDX Material Safety Data Sheets HMX

ANALIZA TERMICZNA STA DLA WYBRANYCH MATERIAŁÓW WYBUCHOWYCH PRZY JEDNOCZESNYM UŻYCIU TECHNIKI REAL VIEW DLA OKTOGENU I HEKSOGENU

Krzysztof Łapiński1, Andrzej Orzechowski2, Dorota Powała2, Rafał Tomikowski1, Róża Tomikowska11Dział Anal iz

HAAS, ul. Bratkowa 9, 60-175 Poznań,2 WOJSKOWY INSTYTUT TECHNICZNY UZBROJENIA, ul. Prymasa Stefana Wyszyńskiego 7; 05-220 Zielonka

HAAS i WITU

Analiza termiczna jest jedną z technik analitycznych, która coraz szerzej jest stosowana w analizie materiałów wybuchowych. Szczególnie możliwość pracy z niewielkimi naważkami zewzględów bezpieczeństwa a także możliwość rejestracji obrazu w czasie pomiaru i przyporządkowania zdjęć danym punktom na krzywej DSC lub TGA jak również rejestracji videoznacznie poszerzają zakres informacji dostarczanych przez klasyczne pomiary termiczne. Materiały zarówno w postaci indywiduów chemicznych, jak również mieszanin kilkusubstancji charakteryzują się różnym poziomem wrażliwości na bodźce termiczne. Różnego rodzaju zjawiska fizyczne i chemiczne, w funkcji temperatury otoczenia mogą powodowaćjego niekontrolowany rozkład. To jeden z istotnych powodów z uwagi na bezpieczeństwo, zwłaszcza przechowywanych przez długi okres czasu materiałów wybuchowych, dla któregoanaliza termiczna jest techniką niezbędną do ich charakterystyki.

WNIOSKI

Analiza STA pozwala na dokładne wyznaczenie temperatur charakterystycznych, uzyskane wyniki są oczywiście zależne od warunków prowadzenia pomiaru (prędkości ogrzewania,masy próbki, rodzaju naczynka, rodzaju gazu nośnego). Pomiar względem materiału wzorcowego pozwala określić w sposób dokładny temperatury charakterystyczne i w ten sposóbokreślić stabilność termiczną badanego MW. Dla optymalnego doboru warunków pomiaru dla danego materiału należy wykonać kilka prób dla różnych naważek oraz pozostałychparametrów analizy.

WŁAŚCIWOŚCI BADANYCH MATERIAŁÓWPrzebadano termicznie:- Oktogen HMX jest ciałem stałym, krystalicznym, występuje w czterech

polimorficznych postaciach krystalicznych: alfa, beta, gama, delta, o odmiennychwłaściwościach fizycznych. Znaczenie praktyczne ma tylko odmiana beta oktogenu,stabilna w temperaturze pokojowej. HMX charakteryzuje się wysokątermostabilnością. Zastosowanie oktogenu w mieszaninach wybuchowych wpływana zwiększenie prędkości detonacji, kruszności i termostabilności.

- Heksogen RDX jest obecnie najważniejszym materiałem wybuchowym o wysokichparametrach detonacyjnych stosowanym w wyrobach wojskowych. Jest stosunkowoniewrażliwy, stabilny i niedrogi. Stosowany jest głównie w formie prasowanej dowyrobu ładunków kumulacyjnych, detonatorów, w formie plastycznej do ładunkówelastycznych i plastycznych oraz w formie odlewanej z TNT lub odpowiednimiciekłymi polimerami do wyrobu amunicji, min, torped itp.

ANALIZA STA (TGA i DSC) Z REAL VIEW DLA RDX


PODSUMOWANIE

Wykorzystanie analizy termicznej pozwala w prosty i bezpieczny sposób określićstabilność termiczną materiału wybuchowego, jego czystość, jak równieżkompatybilność z innymi składnikami w przypadku mieszanin wybuchowych. Zaletą tejtechniki jest wykorzystywanie niewielkich ilości materiału, rzędu kilku miligramów, co wznaczący sposób zwiększa bezpieczeństwo samej pracy z materiałem wybuchowym.Nowoczesne analizatory termiczne umożliwiają wykorzystanie różnego rodzaju technikipomiarowych jednocześnie np. analizy DTA-TGA lub DSC-TGA co w znaczący sposóbzwiększa wszechstronność realizowanego pomiaru.

Tzw. „temperatura onest rozkładu” – jest to istotny parametr wskazujący temperaturę, wktórej rozpoczyna się rozkład materiałów wybuchowych. Przesuniecie tej wartości wkierunku niższych temperatur w stosunku do materiału wzorcowego świadczy ozmniejszeniu stabilności materiału co jest bardzo istotne z punktu widzeniabezpieczeństwa. Temperatura maksimum piku rozkładu – jest to temperaturacharakterystyczna dla każdego materiału wskazująca punkt w którym proces przebiegaz największą szybkością.W analizie materiałów wybuchowych rozkładających się dwuetapowo (topnienie-rozkład) dla uzyskania właściwego jej efektu analizę należy prowadzić w naczynkach hermetycznych.Zmiana parametrów analizy skutkuje znaczącymi zmianami wyników dla przykładu: wzrost prędkości ogrzewania powoduje przesuniecie w kierunku wyższych temperatur.

LITERATURA

1. Nota aplikacyjna Hitachi High-Tech Science Corporation2. Karty charakterystyki materiałowej RDX3. Karty charakterystyki materiałowej HMX

ANALIZA STA (TGA i DSC) DLA HMX

ZESTAW DO JEDNOCZESNEJ ANALIZY TERMICZNEJ STA i REAL VIEW

Wszystkie próbki badano w zbliżonych warunkach :Zakres temperatur : 30 - 400 °CSzybkość ogrzewania : 5 °C/min i 10 °C/min Atmosfera: azot 100 ml/minWielkość naważki: ok 0,3 – 2,5 mg


Rys. 2. Przebieg krzywej TGA ug i DSC mW dla RDX i zdjęcia przed przemianami (1), w trakcie topnienia (2,3), drugiej przemiany (4,5) i po drugiej przemianie (6)

I. Naważka ok. 1 mg - temperatura topnienia ok. 202,3 st C.II. Ciepło przemiany plasuje się na poziomie ok. 103 mJ/mg.III. Pik drugiej przemiany – ok. 348 mJ/mg.

Badania wykonano stosując jednoczesny analizator termiczny STA 7300 Hitachi High-Tech Science Corporation (HAAS) dla HMX i STA 7200 z RealView – kamerą rejestrującą obraz online dla RDX

Rys. 1 Zestaw do analizy termicznej - jednoczesny analizator termiczny STA 7300 Hitachi High-Tech Science Corporation (HAAS) , STA 7200 z RealView

Rys. 4. Przebieg krzywej TGA ug i DSC mW dla RDX

I. Naważka ok. 1,8 mg, ogrzewanie 10 st C/min - temperatura topnienia ok. 202,9 st C,Naważka ok. 2 mg – ogrzewanie 10 st C/min - temperatura topnienia ok. 202,8 st C.

II. Ciepło przemiany plasuje się na poziomie odpowiednio ok. 109 mJ/mg i 106 mJ/mg.III. Pik drugiej przemiany odpowiednio – ok. 610 mJ/mg i 762 mJ/mg.

Rys. 5. Przebieg krzywej TGA ug i DSC mW dla HMX

(1) (2) (3)

(4) (5) (6)

Rys. 3. Przebieg krzywej TGA ug i DSC mW dla RDX

I. Naważka ok. 2,1 mg, ogrzewanie 10 st C/min - temperatura topnienia ok. 202,4 st C.II. Ciepło przemiany plasuje się na poziomie ok. 99 mJ/mg.III. Pik drugiej przemiany – ok. 719 mJ/mg.

I. Naważka ok. 0,3 mg, ogrzewanie 5 st C/min - temperatura przemiany ok. 279,2 st C,Naważka ok. 1,5 mg – ogrzewanie 10 st C/min - temperatura przemiany ok. 280,7 st C.

II. Ciepło przemiany plasuje się na poziomie odpowiednio ok. 1207 mJ/mg i 683 mJ/mg.

Time min26,0025,0024,0023,0022,0021,0020,0019,0018,0017,0016,0015,0014,0013,0012,0011,0010,009,008,007,006,005,004,003,002,00

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Module: STA7300Sample Name: RS-RDX VSample Weight: 1,025 mgReference Name: emptyReference Weight: 0,000 mg

Comment:Operator: DPGas1: azotPan: Al-openNaczynko ca≥kowicie otwart, kalibracja 10 K /min. wykonana przez dostawcÍ

Temperature Program: Cel Cel Cel/min min s1* 30 300 10 0 0,5

Subtract Correction Count: 0 Count

1,034mg

19,43min202,3Cel1,003mW

-348mJ/mg

103mJ/mg

Time min26,0025,0024,0023,0022,0021,0020,0019,0018,0017,0016,0015,0014,0013,0012,0011,0010,009,008,007,006,005,004,003,002,00

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Comment:Operator: DPGas1: azotPan: Al-openNaczynko ca≥kowicie otwart, kalibracja 10 K /min.



2,143mg

19,38min202,4Cel1,88mW

99,0mJ/mg

-719mJ/mg

Time min27,0026,0025,0024,0023,0022,0021,0020,0019,0018,0017,0016,0015,0014,0013,0012,0011,0010,009,008,007,006,005,004,003,002,001,00

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Comment:Operator: DPGas1: azotPan: Al-openNaczynko ca≥kowicie otwart, kalibracja 10 K /min. 100 ml/min



1,832mg

109mJ/mg

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19,03min202,9Cel2,64mW

Time min26,0024,0022,0020,0018,0016,0014,0012,0010,008,006,004,002,000,00

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18,94min202,8Cel2,28mW


Comment:Operator: DPGas1: azotPan: Al-openNaczynko otwarte, kalibracja 10 K /min. 100 ml/min



Time min56,0054,0052,0050,0048,0046,0044,0042,0040,0038,0036,0034,0032,0030,0028,0026,0024,0022,0020,00

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51,26min279,2Cel-0,545mW

-1207mJ/mg

Module: STA7200Sample Name: HMXSample Weight: 0,315 mgReference Name: emptyReference Weight: 0,000 mg

Comment:Operator: DPGas1: azotPan: AlNaczynko - Al odkrytePrzep≥yw gazu - 200 ml/min



Time min30,0029,0028,0027,0026,0025,0024,0023,0022,0021,00

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min

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26,79min280,7Cel2,40mW

-683mJ/mg

Module: STA7300Sample Name: HMX-kryst.Sample Weight: 1,530 mgReference Name: emptyReference Weight: 0,000 mg

Comment:Operator: DPGas1: azotPan: Al-openNaczynko - Al




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SESSION 3:

INORGANIC MATERIALS

Investigation of the hydration of Dyckerhoff G-Oil Cement and its blends by Calorimetry and Thermal methods

M. PALOUa, b, E. KUZIELOVÁa, b, R. NOVOTNÝc, M. ŽEMLIČKAa, J.

ČAPČIANSKAa, J. DRAGOMIROVÁa

aSlovak Academy of Sciences, Dúbravská cesta 9, SK–845 03 Bratislava, Slovak Republic bSlovak University of Technology, Radlinského 9, SK–812 37 Bratislava, Slovak Republic

cBrno University of Technology, Purkyňova 118, CZ–612 00 Brno, Czech Republic [email protected]

Keywords: G-Oil Cement, hydration, thermal analysis, activation energy

Dyckerhoff G-Oil Cement is a specific class of binders used as zonal isolation ma-terial in hydrocarbon and geothermal wells. It is a best candidate to all underground repositorie constructions, where temperatures and humidity are elevated. Although the primary study on Dyckerhoff G-Oil Cement was focused on its hydration reac-tions in hydrothermal environments, the present investigation was undertaken with the objective of developing heavyweight concrete for a possible underground ap-plication for the storage of radioactive waste. Heavyweight concrete has a strong capacity in absorbing gamma rays and in slowing down fast neutrons. To this pro-pose, the hydration of Dyckerhoff G-Oil Cement and its blends at different substi-tution levels were studied at 25°C, 40°C, 50°C, 60°C and 80°C using conduction calorimter and TGA/DSC technique in order to characterize the products of hydra-tion, pozzolanic reactions and carbonation of the smples. Figures 1 and 2 depict the heat flow and overall cumulative hydration heat respectively of samples at two extreme temperatures 25°C and 80°C. Apparent activation energy using Arrhenius equation was calculated for each reac-tion represented by peaks at curve of heat flow of hydration based on five different temperatures.

𝑘(𝑇) = 𝐴𝑒𝑥𝑝 − (1),

where k is the temperature-sensitive rate or rate constant, A is a pre-exponential constant sometimes called the attempt frequency, R is the ideal gas constant (8.314 J/ (mol K); T is the absolute temperature (K); Ea is the activation energy (J/mol). It is evident that the hydration is influenced by the substitution level and tempera-tures. The value of Ea decreases with the decrease in the content of Dyckerhoff G-Oil Cement, but Ea of the second peak is greater than that of the first. It indicates a relatively strong barrier to overcome for the second reaction of C3A.


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0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75

0

1

2

3

He

at F

low

/mW

g-1

Time/h

Dyck100 Dyck95 Dyck90 Dyck85 Dyck80 Dyck75 Dyck70 Dyck65

exo^ 25 °C

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0

25

50

75

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125

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200

225

250

27525 °C

Hea

t/J

g-1

Time/h


Fig.1 The hydration heat release curves of Dyckerhoff Cement and its Blends at

25℃: (a) heat flow; (b) cumulative heat.

0 5 10 15 20 250

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32580 °C

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Fig.2 The hydration heat release curves of Dyckerhoff Cement Blends at 80℃: (a)

heat flow; (b) cumulative heat. The determination of hydration products and pozzolanic activity is mainly based on the TG/DTG curves at four temperature intervals. The dehydration of C–S–H and ettringite takes place at the temperature range 100–140°C following by thermal decomposition of C–A–S–H products at 140–420 and then CH at 420–500 °C. 600–1000 °C corresponds to the decomposition of different kind of carbonated cal-cium. The formation of C-S-H is retarded at high temperatures which support the formation of C-A-S-H, release and consumption of CH in pozzolanic reaction and overall carbonation.

Conclusion Though the Dyckerhoff G-Oil Cement is intended for application in Oil well or geothermal well with temperature higher than 120 °C, its hydration at normal con-ditions is governed by the same principles as Ordinary Portland Cement. The prod-ucts of hydration are similar and stable up to 80 °C at least. These preliminary re-sults are hopeful in the development of heavyweight concrete for an eventual ap-plication in underground depository. ACKNOWLEDGEMENTS This work was supported by courtesy of APVV-19-0490, APVV-15-0631, Slovak Grant Agency VEGA No. 2/0032/21 and 2/0017/21, and The Czech Science Foundation No. GA19-16646S. Also, authors express their thankful to V4–Kórea Joint Research Program on Chemistry and Chemical Engineering under the auspices of Slovak Academy of Sciences.


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Kinetics of Thermally Induced Aragonite–Calcite Transformation in

Biomineralized Calcium Carbonates

TAIGA TONE1, NOBUYOSHI KOGA¹*

1Hiroshima University, Graduate School of Humanities and Social Sciences, Division of Educational

Sciences, Department of Science Education


Keywords: aragonite–calcite transformation, thermal dehydration of included water,

kinetic constraint

Calcium carbonate is a natural resource, which has been used as a raw material

in materials science and engineering for various purposes. In addition to the calcium

carbonate minerals, biomineralized calcium carbonates can be the potential re-

sources. For discovering the further applications, characteristics of the biomineral-

ized calcium carbonate should be revealed in detail including its thermal behavior

[1]. The biomineralized calcium carbonates are composed of calcite or aragonite

phase, in which aragonite transforms to calcite during heating before its thermal de-

composition. The thermally induced aragonite–calcite transformation in biomineral-

ized aragonite occurs in overlapping with the thermal dehydration of included water

[2-4]. Kinetic constraints for the aragonite–calcite transformation caused by the con-

tribution of the thermal dehydration of included water are topics to be revealed.

In this presentation, the thermally induced aragonite–calcite transformation of a

biomineralized aragonite (Euplica scripta) is subjected to reveal the kinetic behavior

in relation to the thermal dehydration of included water. The thermal dehydration of

included water characterized by a multistep process was traced using TG and ana-

lyzed kinetically. The high temperature XRD and FT-IR spectroscopy were used to

collect the kinetic data for the thermally induced aragonite–calcite transformation.

The kinetic correlations between the aragonite–calcite transformation and each reac-

tion step of the thermal dehydration of included water were investigated by compar-

ing the kinetic results. The findings for Euplica scripta are also compared with our

previous results for coral [3] and freshwater pearl [4].

References

[1] Y. Tsuboi, N. Koga. Thermal decomposition of biomineralized calcium carbonate: correlation be-

tween the thermal behavior and structural characteristics of avian eggshell. ACS Sustain. Chem.

Eng. 6:5283–5295, 2018.

[2] N. Koga, D. Kasahara, T. Kimura. Aragonite crystal growth and solid-state aragonite–calcite trans-

formation: A physico–geometrical relationship via thermal dehydration of included water. Cryst.

Growth Des. 13:2238–2246, 2013.

[3] N. Koga, K. Nishikawa. Mutual relationship between solid-state aragonite–calcite transformation

and thermal dehydration of included water in coral aragonite. Cryst. Growth Des. 14:879–887,

2014.

[4] T. Tone, N. Koga. Thermally induced aragonite–calcite transformation in freshwater pearl: A mu-

tual relation with the thermal dehydration of included water. ACS Omega. 6: in press, 2021.


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Thermal behaviour of ceramic bodies based on Estonian clay from Arumetsa deposit with oil shale ash or/and clinker dust additives

TIIT KALJUVEE1*, IGOR ŠTUBŇA2, TOMAŠ HÚLAN2, MAI UIBU, MARVE

EINARD1, RAINER TRAKSMAA1, MART VILJUS1, JEKATERINA JEFIMOVA3, ANDRES TRIKKEL1

1Tallinn University of Technology, Laboratory of Inorganic Materials

2Constantine the Philosopher University, Department of Physics 3University of Tartu, Estonian Marine Institute

*[email protected] Keywords: clay, clinker dust, FTIR, kinetics, oil shale ash, TG-DTA-MS, TMA

Thermal behaviour of green clay samples from Arumetsa and Füzérradvány de-posits (Hungary), and the influence of two new type of Estonian oil shale (OS) ashes or/and cement by-pass dust (clinker dust) additives on it were the objectives of this study. The ashes were from circulated fluidized bed combustion of OS at Auvere Power Plant (at temperatures 750-830°C, fly ash), and from pulverized firing at Eesti Power Plant (1200-1400°C, DeSOx ash). Clinker dust was obtained from Kunda Nordic Cement Factory (Estonia). Composition of clay with 40% of previously fired at 1050°C clay (grog) was used as the base material. In the blends studied the grog was on the level of 50% or it was entirely replaced with OS ash or/and clinker dust. Experiments were carried out under non-isothermal condition up to 1050°C using a Setaram Setsys 1750 thermoanalyzer coupled with Pfeiffer Omnistar Spectrometer at different heating rates in an oxidizing atmosphere. The differential isoconversional method of Friedman was applied to calculate the kinetic parameters. The results of thermal analysis of clays and blends up to 200-250°C indicated the emission of physically bound water. At temperatures from 200-250°C to 550-600°C the emission of water is caused by oxidation of organic matter and dehydroxylation of different clay minerals like illite, illite-smectite, mica and kaolin. From blends, in addition, also from decomposition of portlandite contained in ashes and clinker dust. The emission of CO2 at these temperatures is a result of oxidation of organic matter contained in the clays. In temperature range from 550-600°C to 800-900°C the mass loss is caused by continuing dehydroxylation processes in clay minerals, but, mainly, by decomposition of carbonates contained in OS ashes and clinker dust. These pro-cesses are accompanied by contraction and expansion of ceramic bodies with corre-sponding changes in SSA and porosity values of the samples. Therefore, the decomposition of clays takes place in one step, blends in two steps: at first, mainly, dehydroxylation of clay minerals occurs, and then decomposition of carbonates. The value of activation energy E along the reaction progress α varied for Arumetsa and illitic clay between 75-182 and 9-206 kJ mol-1, respectively. For the first step of blends based on Arumetsa and illitic clay the value of activation energy varied between 14-193 and 5-205 kJ mol-1, and for the second step between 15-390 and 135-235 kJ mol-1, respectively.


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Characteristics of hydrothermally obtained

Na3RE(PO4)2 phosphates, where RE=La, Ce, Nd, Gd or Er

ALEKSANDRA J. PELCZARSKA*, IRENA SZCZYGIEŁ

Wroclaw University of Economics and Business,

Department of Inorganic Chemistry, Faculty of Production Engineering


Keywords: thermal transitions, rare earth phosphates, hydrothermal method

The doped with active RE3+

Na3RE(PO4)2 compounds show good lumines-

cence in the visible range of light after excitation by UV radiation. This feature

is a primary property for using the phosphates in white LEDs construction.

The group of phosphates is characterized by rich polymorphism, which affects their

luminescent properties [1, 2]. The most popular synthesis method of the com-

pounds is a long-term sintering of substrates, which leads to obtaining of high-

temperature polymorphic forms of Na3RE(PO4)2, mostly orthorhombic one. Our

aim was to propose an alternative method of Na3RE(PO4)2 synthesis (where RE:

La, Ce, Nd, Gd or Er) and to study a transformation path of the phosphates

with changing temperature.

The phosphates of the Na3RE(PO4)2 composition (where RE: La, Ce, Nd, Gd

or Er) were obtained by precipitation from sols under hydrothermal conditions.

Chemical composition of dried powders was checked by ICP/OES method,

it proved the expected Na:RE:P molar ratio, i.e. 3:1:2. Morphology of the phos-

phates under study was visualized by SEM technique. The powders consisted

of non-agglomerated grains with the size of several microns. Polymorphism

of the obtained powders was investigated by XRD and TG/DSC methods.

The crystalline structure of dried powders is trigonal with the S.G. P m1

and it changes under heating. For the first time we have observed a monoclinic

structure of Na3Er(PO4)2, which is similar to that of Na3Y(PO4)2 [3]. Eventually,

we determined onset temperatures of the Na3RE(PO4)2 structural transitions,

as well as their structure present in the appropriate temperature ranges.

References

[1] A. Matraszek, P. Godlewska, L. Macalik, K. Hermanowicz, J. Hanuza, I. Szczygieł. Optical and

thermal characterization of microcrystalline Na3RE(PO4)2:Yb orthophosphates synthesized by

Pechini method (RE= Y, La, Gd). J. Alloys Compd. 619:275-283, 2015.

[2] P. Godlewska, A. Matraszek, L. Macalik, K. Hermanowicz, M. Ptak, P.E. Tomaszewski,

J. Hanuza, I. Szczygieł. Spectroscopic and structural properties of Na3RE(PO4)2:Yb orthophos-

phates synthesised by hydrothermal method (RE = Y, Gd). J. Alloys Compd. 628:199-207, 2015.

[3] A. Matraszek, I. Szczygieł, B. Szczygieł. Hydrothermal synthesis and characterization

of Na3Y(PO4)2 phosphate. J. Alloys Compd. 612:411-417, 2014.


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Verifying studies of V2O5–NiO and V2O5–SrO binary oxide systems

MONIKA BOSACKA*, ELŻBIETA FILIPEK, ANNA BLONSKA-TABERO,

AGNIESZKA PROKOP

West Pomeranian University of Technology, Szczecin, Faculty of Chemical Technology

and Engineering, Department of Inorganic and Analytical Chemistry,


Keywords: binary oxide system, phase equilibria, XRD, DTA-TG, vanadates(V)

of metals(II)

The two-component V2O5–SrO and V2O5–NiO systems have been the subjects of

extensive research for many years, primarily in terms of catalytic, electrical, optical

and magnetic properties of new materials based on strontium or nickel vanadates.

Among the various host materials, strontium vanadates, for example Sr3V2O8 and

Sr2V2O7, have been proved to be good candidates for the luminescent hosts [1].

Nevertheless, the literature data on the vanadates formed in these systems and their

thermal stability are often fragmentary and contradictory.

For the research in this work, samples were prepared from V2O5 and SrCO3 or

2NiCO3·3Ni(OH)2·4H2O as the precursors of SrO or NiO, respectively. The synthe-

ses of samples representing V2O5–NiO and V2O5–SrO systems were conducted by

the conventional calcining method in the temperature range from 450 to 1000°C in

20 or 24 h stages. The results of the research carried out using the XRD, DTA-TG,

IR, UV-Vis (DRS) and SEM methods allowed not only to verify the literature data

on the title systems, but also to supplement them. It has been shown, inter alia, that

in the V2O5–SrO system four strontium vanadates(V) are formed, i.e. Sr(VO3)2,

Sr2V2O7, Sr3(VO4)2 and Sr4V2O9. It was also established that the polymorphic trans-

formation of Sr(VO3)2 is enantiotropic and takes place at 530°C. Formation of

SrV12O30, Sr6V2O11, Sr16V18O61, SrV4O11, SrV6O16, Sr6V14O41 and Sr2V6O17, men-

tioned in literature [2, 3], has been not stated during the conducted investigations.

In the second part of this work, a phase diagram of the V2O5–NiO system was

constructed based on the results of XRD and DTA-TG tests of samples in equilib-

rium state. This diagram differs significantly from its two known versions and is

similar to the third version shown in paper [4].

References:

[1] Z. Zhou, N. Wang, N. Zhou, Z. He, S. Liu, Y. Liu, Z. Tian, Z. Mao, H.T. Hintzen. High colour

purity single-phased full colour emitting white LED phosphor Sr2V2O7: Eu3+. J. Phys. D: Appl.

Phys. 46: 1–6, 2013.

[2] A. A. Fotiev, V. A. Makarov. Crystal optics of strontium vanadates and phase diagram of V2O5‒

SrO system. Sov. Phys. Cryst. 14: 621–623, 1970.

[3] A. A. Fotiev, G.V. Bazuev. Phase relations in the La2O3–V2O5–SrO system. Zh. Neorg. Khim.

29:1337–1340, 1984.

[4] V. L. Kozhevnikov, M. L. Kotik, S. M. Cheshnitskii, L.V. Zolotukhina, L. L. Surat, T. P. Sirina, A.

A. Fotiev. Phase relations in the NiO–V2O5 system. Zh. Neorg. Khim. 32: 2322–2324, 1987.


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Recommendations and guidelines for safety evaluation of ammonium

nitrate systems with the use of thermal analysis

MACIEJ KANIEWSKI ¹*, JÓZEF HOFFMANN ¹ 1Wroclaw University of Science and Technology, Faculty of Chemistry


Keywords: thermal analysis, ammonium nitrate, methodology recommendations,

thermal stability, safety evaluation

Ammonium nitrate has been a cause of numerous disasters occurring through-

out the world. It is mainly used as a novel propellant, explosives component for

mining and irreplaceable fertilizer. The thermal stability of ammonium nitrate is

heavily influenced by multiple factors, e. g. temperature, pressure or presence of

impurities in the system. It is widely studied by multiple research groups and pro-

duced by many manufacturers, however its regulations are still lacking in both

USA and Europe. Thermal analysis is the prevalent method used to assess safety

and thermal stability of samples containing ammonium nitrate in most scientific

papers, yet there are no specific guidelines to be followed, resulting in inconsistent

experiments and conclusions in many studies [1-3].

This work presents an advanced elaboration on suggested proper methodology

and various aspects of thermal analysis of systems containing ammonium nitrate.

Parameters of analysis are discussed, including heating rate, atmosphere, sample

preparation, mass and heat transfer conditions and heating program type. Conclu-

sions and proposed methodology are supported by performed experiments and lit-

erature references, highlighting extreme cases, meaningful differences between

obtained results and the evolution of methodology used in studies of ammonium

nitrate. Characteristic values, derived from performed analyses, that are typically

used to define thermal stability and safety of ammonium nitrate systems, are com-

pared and their possible, correct use is considered with examples given [4,5].

The study underlines the importance of safety assessment of ammonium ni-

trate systems and should provide useful guidelines for both inexperienced and well-

versed scientists on how to create an optimal research plan and interpret obtained

results.

References

[1] D.J. Frurip, T. Elwell, Effective use of differential scanning calorimetry in reactive chemicals

hazard evaluation, Process Saf. Prog. 26(1):51-58, 2007.

[2] H. Cao, L. Jiang, Q. Duan, D. Zhang, H. Chen, J. Sun, An experimental and theoretical study of

optimized selection and model reconstruction for ammonium nitrate pyrolysis, J. Hazard. Mater.

354:539-547, 2019.

[3] Z. Han, S. Sachdeva, M. Papadaki, M.S. Mannan, Calorimetry studies of ammonium nitrate -

Effect of inhibitors, confinement, and heating rate, J. Loss Prev. Process Ind. 38:234-242, 2015.

[4] V. Babrauskas, D. Leggett, Thermal decomposition of ammonium nitrate, Fire Mater. 44:250-

268, 2020.

[5] H. Cao, X. Li, K. Jin, Q. Duan, H. Chai, J. Sun, Experimental and theoretical study of the effect of

typical halides on thermal decomposition products and energy release of ammonium nitrate

based on microcalorimetry and FTIR, Chem. Eng. J. 410:128405, 2021.


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Mn-Al-X alloys: thermal analysis and hard magnetic L10 phase

J.J. SUÑOL¹*, W. BEN MBAREK1, J. DAZA1, J. SAURINA1, L. ESCODA1

1GRMT University of Girona, Department of Physics.

*Corresponding author: [email protected] Keywords: Inorganic materials, DSC, magnetic materials, thermal treatment.

The phase diagram of managanese-aluminium based alloys show several crys-

tallographic phases. The permanent magnet phase is the L10 tetragonal one. Unfor-tunately, this phase is metastable and should be formed after controlled annealing of a hexagonal phase obtained from a quenched in high temperature hexagonal ε parent phase. The addition of a third alement (1 to 5 at.%) shift the transition temperatures and can help to the thermal stabilization of the tetragonal phase [1].

In this work, small amount of Co, Cu or C are added to Mn and Al powders to produce the desired tetragonal phase by mechanical alloying after heat treatments. The analysis of the DSC thermoanalytycal curves show that the solid-state transfor-mation from the hexagonal phase to the tetragonal varies between 500 and 580ºC depending on the alloy. In the literature, temperatures between 480 and 550ºC have been mesaured [2-3]. Likewise, we detect that the ferromagnetic τ-phase was formed via a two step process; metastable B19 ordering within the parent ε-phase (ε →ε’) followed by a displacive or martensitic shear transformation (ε’ →τ) [3]. Likewise, the addition of a magnetic element improves the magnetic behavior of the alloy. One of the technological problems to be avoived is the decomposition of the alloy into non-magnetic γ-Al8Mn5and β-Mn phases. Furthermore, we also analyse by thermal analysis the effect of ambient aging on the heat treated alloys.

References [1] E. Fazakas, L.K. Varga, F. Mazaleyrat. Preparation of nanocrystalline Mn-Al-C magnets by melt

spinning and subsequent heat treatments. Journal of Alloys and Compounds 611-613, 434-435. 2007.

[2] C.Chen, Z.W. Liu, X.C. Zhong, H.Y. Yu, W.Q. Qui, D.C. Zheng, R.V: Ramanujan. Structure and hard magnetic properties of Mn-Al alloys of Mn-Al alloys with C, B and/or RE addition. The 7th National conference on Functional Materials and Applications, 1212-1215, 2010.

[3] A.M. Genc, O. Acar, S. Turan, I. Kalay, U. Savaci, Y.E. Kalay. Investigation on phase selection hierarchy in Mn-Al alloys. Intermetallics 115, 236-249, 2019.


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Decomposition of a metastable supersaturated solid solution of Cu-Fe-

based immiscible alloys prepared by mechanical alloying

O. ADAM¹*, V. JAN¹

1Institute of Materials Science and Engineering, Faculty of Mechanical Engineering, Brno University

of Technology

*Corresponding author: Ondrej Adam, e-mail: [email protected]

Keywords: thermal analysis, immiscible alloys, mechanical alloying

In the last years, significant attention has been paid to Cu-Fe-based immiscible

alloys that show the ability to overcome strength-ductility trade-off due to their dual-

phase microstructure. Currently, most bulk immiscible alloys are produced by cast-

ing although this method requires several additional steps to obtain high-perfor-

mance materials. However, powder metallurgy could provide an easier way how to

produce immiscible alloys with comparable or even better mechanical properties. It

was shown that despite the positive enthalpy of mixing of Cu and Fe, it is possible

to create a single-phase microstructure consisting of a supersaturated solid solution

by mechanical alloying. At elevated temperatures, this supersaturated solid solution

decomposes into a fine dual-phase microstructure.

In this work, powders with the chemical composition of Cu50Fe50 and

Cu50(FeCo)50 were prepared by mechanical alloying. The kinetics of decomposition

of the supersaturated solid solution was evaluated by differential scanning calorim-

etry. Activation energy values were determined by the Kissinger method and the

effect of cobalt on the activation energy and mechanism of decomposition of super-

saturated solid solution were evaluated.


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Silica/quercetin hybrid materials synthesized by sol-gel method.

Thermal, morphology and antibacterial investigation

M. CATAURO¹*, A. D’ANGELO¹, M. FIORENTINO¹, G. GULLIFA2, R. RISOLUTI2,

S. VECCHIO CIPRIOTI3

1University of Campania, Department of Engineering

2Sapienza University of Rome, Department of Chemistry 3Sapienza University of Rome, Department of Basic and Applied Sciences for Engineering

*Corresponding author: e-mail: michelina [email protected]

Keywords: sol-gel particles, quercetin, ceramics, thermal analysis, FTIR, SEM, an-

tibacterial properties

The sol–gel method is widely used to synthesize organic/inorganic hybrid ma-

terials because of the low processing temperature and pressure, versatility and flex-

ibility. In the present study, SiO2 (S) matrix entrapped different amounts of quercetin

(Q), namely, 5, 10, 15, and 20 wt% [1]. A detailed characterization focused on re-

vealing the nature of the bonds between the inorganic and organic components was

performed by Fourier-Transform Infrared (FTIR) spectroscopy.

Silica/quercetin (SQ) hybrid materials showed an increase in the mass loss per-

centages of the first decomposition step with increasing the amount of Q, thus sug-

gesting the incorporation of Q in the hybrid materials and a stabilization of the struc-

ture by hydrogen bonds. The DTG peak temperature of the second heating experi-

ment was found to shift toward lower temperature and the amount of water reversibly

bound to the materials with increasing the amount of Q in the hybrid.

The morphology of the SQ hybrids investigated by Scanning Electron Micros-

copy coupled with Energy Dispersive X-Ray Spectroscopy (SEM/EDS) confirmed

a regular size distribution of the particles and a homogeneous distribution of querce-

tin in the silica matrix in the suitable expected ratio.

Furthermore, the SEM images confirmed the absence of contaminants during

the sol-gel synthesis. Finally, the antibacterial properties of the SQ hybrid materials

were tested using four (two Gram-positive and two Gram-negative) bacteria strains.

The results demonstrated that they can be proposed as valuable antibacterial

agents against Escherichia coli and Pseudomonas aeruginosa as Gram-negative bac-

teria and Staphylococcus aureus and Enterococcus faecalis as Gram-positive for

amounts above 50 mg.

References

[1] M. Catauro, F. Papale, F. Bollino, S. Piccolella, S. Marciano, P. Nocera, S. Pacifico. Silica/quercetin

sol–gel hybrids as antioxidant dental implant materials. Sci. Technol. Advanced Mater. 16:3,

2015.


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Thermal analysis of materials based on calcium sulfate derived from

various sources

AGNIESZKA MYKA¹*, RENATA ŁYSZCZEK2, ANNA ZDUNEK1,

PIOTR RUSEK1

1Łukasiewicz Research Network – New Chemical Syntheses Institute, Fertilizer Department

2 Department of General and Coordination Chemistry and Crystallography, Faculty of Chemistry,

Institute of Sciences, Maria Curie-Skłodowska University in Lublin


Keywords: thermal analysis, natural gypsum, FGDG, phosphogypsum, anhydrite

There are four different types of calcium sulfate crystalline phases present at

room temperature [1]. Phase naturally occurring is mineral - gypsum

(CaSO4·2H2O). There are also chemical industry sources of gypsum. One of them

is by-product derived from the flue gas desulfurization process in coal - fired pow-

er plants (FGD gypsum) [2]. The second one is the form of hydrated calcium sul-

fate called phosphogypsum. Its presence is connected with the production of ex-

tractive orthophosphoric acid, the basic phosphorus raw material [3]. Other forms

of calcium sulfate are hemihydrate (CaSO4·1/2 H2O) – partially dehydrated gypsum,

soluble anhydrite (CaSO4 III) and insoluble anhydrite (CaSO4 II).

In nitrogen fertilizer industry anhydrite is used as filling material in the produc-

tion of nitrogen - calcium fertilizers with added sulphur. There were also investiga-

tions on preparations of urea adducts (as raw materials were tested phoshogypsum

and chemically pure compounds of calcium sulfate) [4].

The paper focused on thermal analysis of materials based on calcium sulfate de-

rived from various sources (natural gypsum, anhydrite, FGDG, phoshogypsum,

synthetic building plaster). The aim of these investigations was evaluation of per-

spectives of using FGD gypsum as a potential raw material in the fertilizer indus-

try, in comparison with currently used and other available raw materials based on

calcium sulphate.

Measurements were performed with simultaneous TG/DSC analysis with the

use of a thermal analyzer STA 449 F3 coupled with mass spectrometer QMS 403 D

(Netzsch) in dynamic atmosphere of nitrogen and synthetic air at a flow rate of 50

cm3 min-1. The FTIR spectra of volatile products of the investigated materials de-

composition were recorded on the Nicolet 6700 spectrophotometer coupled with

Q5000 (TA) thermal analyzer in nitrogen atmosphere. References

[1] A. De Korte. Hydration and thermal decomposition of cement/calcium- sulphate based materials https://www.researchgate.net/publication/277955228_Hydration_and_thermal_decomposition_

of_cementcalcium_sulphate_based_materials 7.05.201

[3] Y.Chernysh, O. Yakhnenko, V. Chubur, H. Roubik, Phosphogypsum Recykling: A Review of

environmental Issues, current trends and prospects. Appl.Sci 2021, 11,1575.

[3] N..H. Koralegedara, P. X. Pinto, D. D. Dionysiou, S. R. Al- Abed, Recent advaces in flue das

desulfurization gypsum processes and applications – A review, Journal of Environmental Man-

agement 251 (2019) 109572.

[4] P. Malinowski, A. Biskupski, J. Głowiński, Preparation methods of calcium sulphate and urea

adduct, Polish Journal of Chemical Technology, 9, 4, 111-114, 2007.


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https://www.researchgate.net/publication/277955228_Hydration_and_thermal_decomposition_of_cementcalcium_sulphate_based_materials%207.05.201

https://www.researchgate.net/publication/277955228_Hydration_and_thermal_decomposition_of_cementcalcium_sulphate_based_materials%207.05.201

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Properties of cobalt doped SrTiO3 derived from two methods: Pechini

method and citrate-combustion method

ADRIAN MIZERA¹*, RADOSŁAW LACH 1, EWA DROŻDŻ1

1AGH University of Science and Technology, Faculty of Materials Science and Ceramics


Keywords: Pechini synthesis, DC measurements, perovskite materials

Two series of cobalt doped (2, 6, 10 mol. %) strontium titanates were obtained

from two different wet chemical methods: citrate-combustion method and modified

Pechini method. The modification consisted of replacing the commonly used in

Pechini method α-hydroxyalcohol (e.g. ethylene glycol) to the polymer - poly (vi-

nyl alcohol) (PVA).

All samples were calcined at 900 ℃ for 3h. After cooling, the powders were

used to form pellets by uniaxial pressing and next were sintered at 1300 ℃. Both

powders and sinters produced from powders were studied by XRD method to de-

termine phase composition, average crystallite size and unit cell parameter (only

for sinters).

All powder samples were tested by temperature-programmed reduction and

oxidation (TPR/TPOx) in order to evaluate and compare their ability to participate

in redox reactions. Sintered pellets were used to measure electric properties (con-

ductivity and Seebeck coefficient) using direct current method (DC). Based on re-

sults from the DC method and the geometry of the pellets, the activation energies

of the conductivities were calculated.

All powder samples derived from the modified Pechini method were single

phased. In case of citrate-combustion method, the presence of additional phases

such as TiO2 or Ruddlesden-Popper phases was confirmed using XRD method.

However, during thermal treatment (mainly sintering), additional phases undergo a

conversion to tausonite as a result of diffusion and solid-phase reactions. The TPR

profiles of powders derived from Pechini method are different than those of pow-

ders from the citrate method, and the reduction peaks shifted towards lower tem-

peratures (compared to the citrate method). In the case of direct current measure-

ments, a difference was also observed in the properties of materials obtained by the

two methods.

AM has been partly supported by the EU Project POWR.03.02.00-00-I004/16


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The synthesis and properties of materials in CaxSr1-xTiO3 system

PAULINA GWÓŹDŹ¹*, AGNIESZKA ŁĄCZ¹, MAGDALENA SZUMERA¹,

EWA DROŻDŻ¹



Keywords: SrTiO3 – CaTiO3 system, electrical properties, SOFC anode material

Strontium titanate and calcium titanate are materials belonging to the represent-

atives of compounds with a perovskite-type structure (with the general formula

ABO3). Their electrical properties can be modified by appropriate doping. This fact

makes it possible to use doped - SrTiO3 and doped - CaTiO3, among others as anodes

in solid oxide fuel cells (SOFCs). A series of materials based on a mixed system with

a general formula CaxSr1-xTiO3 (where x = 0,0; 0,2; 0,4; 0,6; 0,8; 1,0) were synthe-

sised by sol – gel method. The conditions of thermal treatment and calcination were

determined based on the TG/DSC analysis (Fig. 1). Based on these results, the ma-

terials were dried at 220 °C for 18 hours and calcined at 900 °C for 3 hours.

Fig. 1. TG/DSC curves for CaxSr1-xTiO3 precursors mixture.

For each of the samples,

the DSC measurements

results showed complex

peaks related to the de-

composition and/or

combustion of nitrate

groups, organic tita-

nium precursor, organic

modifiers and complex-

ing agents introduced

into the system during

synthesis. Additionally,

oxidation of carbon res-

idue can be seen (550 –

600 °C).

The obtained materials were investigated for their structural, redox, thermal and

electrical properties. The main aim of the work was to investigate the electrical prop-

erties of the materials after doping. One of the elements of the research are chemical

stability tests which can verify of potential applications of these materilas in specific

atmospheres.

Acknowledgements

The work is financed from the subsidy no. 16.16.160.557 of the Polish Ministry of Science and Educa-

tion.


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Influence of temperature on formation of precursor for cuspidine

A. GINEIKA*, K. BALTAKYS

Kaunas University of Technology, Faculty of Chemical Technology,

Department of Silicate Technology, Radvilenu pl. 19, LT–50270 Kaunas, Lithuania


Keywords: cuspidine, thermal ana cuspidine, thermal anlysis, hydrothermal syn-

thesis lysis, hydrothermal synthesis

Cuspidine Ca4Si2O7F2 is a fluorine bearing calcium silicate, which may form

hydrothermally or in the melts if CaO, SiO2 and F– are available [1,2]. Recent re-

search has shown that the mineral is a major phase not only in fluoride glasses but

also in synthesis products if fluoride-rich silica-gel waste is used for production of

calcium silicates [3]. Crystalline cuspidine forms in the system even if slight

amount of F– ions are present in the mixture. It was also determined that the miner-

al participates in carbonation curing process and reacts with CO2 similarly to fluo-

ride-free calcium silicates forming calcium carbonate and releasing amorphous sil-

ica in addition to calcium fluoride. As the latter is denser and harder than calcite it

may contribute to strength gain of the formed samples [4]. However, the literature

about formation of precursor of cuspidine during hydrothermal synthesis and its

recrystallization into cuspidine is very sparse

The aim of this work was to investigate the influence of temperature on the

hydrothermal synthesis of the precursor for cuspidine during and its further crystal-

lization during calcination.

The hydrothermal synthesis was carried out in stirred suspensions in the tem-

perature range of 95-200 °C for 4-12 h using reagent grade CaO, SiO2·nH2O and

CaF2. The molar composition of the mixture corresponded to the formula of cus-

pidine Ca4Si2O7F2 or 3CaO·2SiO2·CaF2. The obtained precursors were calcined in

the temperature range of 300-1100 °C to investigate the crystallinity of cuspidine.

The obtained results were analysed using XRD, STA and FT-IR.

It was determined that precursors contained low-crystalline cuspidine with var-

ious calcium silicate hydrates (1.13 nm tobermorite and xonotlite) while some of

CaF2 remained unreacted. However, calcined samples consisted mostly of cus-

pidine with admixtures of wollastonite. With the increment of temperature, the

crystallinity of cuspidine increased.

References

[1] A. Iljina et al. The stability of formed CaF2 and its influence on the thermal behavior of C–S–H in

CaO–silica gel waste-H2O system. J. Therm. Anal. Calorim. 127(1):221–228, 2017.

[2] M.–D. Seo et al. Non-isothermal melt crystallization of cuspidine in CaO–SiO2–CaF2 based

glasses. J. Non–Cryst. Solids. 412:58–65, 2015.

[3] V. Rudelis et al. The Prospective Approach for the Reduction of Fluoride Ions Mobility in Indus-

trial Waste by Creating Products of Commercial Value. Sustainability. 11(3):634, 2019

[4] A. Gineika et al. Synthesis of wollastonite from AlF3-rich silica gel and its hardening in the CO2

atmosphere. Sci. Rep. 9(1):1–10, 2019.


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New solid solution and phase equilibria in the subsolidus area

of the three-component CuO–V2O5–Ta2O5 oxide system

GRAŻYNA DĄBROWSKA*, ELŻBIETA FILIPEK, PIOTR TABERO

1West Pomeranian University of Technology, Faculty of Chemical Technology and Engineering,

Department of Inorganic and Analytical Chemistry,


Keywords: phase equilibrium, solid solution, CuO–V2O5–Ta2O5 system, DTA-TG

The three-component system of metal oxides CuO–V2O5–Ta2O5 has not been sub-

ject of research so far. A large variety of properties of the oxides that build this sys-

tem, as well as the compounds formed in its lateral systems, i.e. CuTa2O6 and

CuV2O6 make them interesting for technical applications. The CuV2O6 compound is

a promising cathode material for lithium batteries [1, 2]. In turn, CuTa2O6 improves

the piezoelectric properties of ceramics used in the production of transformers, trans-

ducers, ultrasonic motors and surface acoustic wave devices [3].

The research on the three-component system of CuO–V2O5–Ta2O5 oxides began

with examining one of its cross-sections, i.e. the CuTa2O6–CuV2O6 system. In the

first stage of the research, the synthesis of CuV2O6 and CuTa2O6 compounds was

carried out using CuO p.a.. (Aldrich, USA), V2O5 p.a. (POCh, Gliwice) and Ta2O5

p.a. (Aldrich, USA) as substrates. From the obtained phases, 10 samples were pre-

pared in such a way that their compositions represented the whole components con-

centration range of the investigated system. The mixtures of reagents, after homog-

enization, were subjected to staged heating, depending on their composition, at tem-

peratures in the range of 500-900°C. The phase compositions of the samples, after

successive stages of heating, were determined on the basis of the results of the XRD

investigations. The thermal stability of the formed phases was determined by per-

forming the DTA-TG analysis. After the last stage of heating all the compounds were

subjected to examination by IR and UV-Vis methods.

The results of the conducted research allow us to state that in the ternary system

of CuO–V2O5–Ta2O5 oxides, a previously unknown substitutional solid solution with

a limited homogeneity range is formed. As part of the presented work, the types of

coexisting phases in the CuO–V2O5–Ta2O5 system in equilibrium in the solid state

were also determined and on this basis it was divided into 8 partial subsystems. In

this part of the research, the temperature ranges of the coexistence of individual

phases in separate partial subsystems were also determined.

References:

[1] T. Hillel, Y. Ein-Eli. Copper vanadate as promising high voltage cathodes for Li thermal batteries.

J. Powder Sources. 229: 112–116,2013.

[2] X. Cao, J. Xie, H. Zhan, Y. Zhou. Synthesis of CuV2O6 as a cathode material for rechargeable

lithium batteries from V2O5 gel. Mater. Chem. Phys. 98:71–75, 2006.

[3] S.L.Yang, Ch.Ch. Tsai, Ch.S. Hong, S.Y.Chu. Effects of sintering aid CuTa2O6 on piezoelectric and

dielectric properties of sodium potassium niobate ceramics. Mater. Res. Bull. 47:998–1003, 2012


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Effect of added P2O5 on the thermal stability of Li2O.2 SiO2 glass

evaluated by the induction period of crystallization

K. MORICOVÁ¹*, P. ŠIMON², R. JANÍK1, J. KRAXNER3, J. PAGÁČOVÁ1,

M. PAJTÁŠOVÁ1

1 Department of Material Technologies and Environment, Faculty of Industrial Technologies, Trenčín

University of A. Dubček, SK-020 01 Púchov 2 Institute of Physical Chemistry and Chemical Physic, Faculty of Chemical and Food Technology,

Slovak University of Technology, SK-812 37 Bratislava

3 Centre for Fuctional and Surface Funcionalized Glass, Trenčín University of A. Dubček,

SK-911 50 Trenčín


Keywords: induction period, activation energy, characteristic temperature, glass

To evaluate the thermal stability of lithiumsilicate glasses with P2O5 against

crystallization criterions based on characteristic temperatures, activation energy and

the length of induction period of crystallization is suggested. Three glasses with the

composition of Li2O.2SiO2, Li2O.2SiO2.0,05P2O5 and Li2O.2SiO2.0,1P2O5 were

preared and the validity of criterion was tested by applying it to these glasses.

It was found that the thermal stability of oxide glasses decreases with increas-

ing P2O5 content as the most stable and therefore proved essential system

Li2O. 2SiO2.

References

[1] K. A Cheng. Criterion for evaluating the thermal stability of glasses. J. Therm. Anal. and Calorim.

103:8272-8276, 1999.

[2] P. Šimon. Isoconversional methods. Fundamentals, meaning and application. J. Therm. Anal. and

Calorim. 76:123-132, 2004.

[3] G. Madhurambal, P. Ramasamy et al. Thermal properties, induction period, interfacial energy and

nucleation parameters of sopution grow benzophenone. J. Therm. Anal. and Calorim. 90:673-679,

2007.


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SESSION 4:

POLYMERS

AND ORGANIC COMPOUNDS

Analyses of non-isothermal polymer crystallization at constant scan rates based on the Avrami and Ozawa models

AKIHIKO TODA

Hiroshima University, Graduate School of Advanced Science and Engineering, Japan

e-mail: [email protected] Keywords: Non-isothermal crystallization; Avrami and Ozawa models; polymer;

Analysis methods are presented for the non-isothermal kinetics of nucleation

and growth processes of polymer spherulites on the basis of the Avrami and Ozawa models.

1) The Avrami model suggests the expression of crystallinity 𝜙 1 exp 𝜙

with an extended volume 𝜙 which is expressed as 𝜙 𝑁 𝑔 𝐺 𝑇 𝑠 d𝑠 for athermal heterogeneous nuclei 𝑁 and crystal growth rate 𝐺. It can be shown that

the integration over the crystallization peak has the approximate form of 𝐺d𝑠𝐺/ 𝛽𝑓 for a constant scan rate 𝛽 with 𝐺 ∝ 𝑒 and the temperature derivative

𝑓 . For the expression 𝐺 ∝ exp 𝐴/∆𝑇 of a nucleation-controlled growth, it means the following approximate relationships;

∆ peak≅ 𝐺 𝑇peak 𝑁 𝑔 / /𝐴

∆ half≅ 𝐺 𝑇half

/ /𝐴

where ∆𝑇x 𝑇 𝑇x represents the degree of supercooling at the x peak, half crystallization temperature for crystallization on cooling from the melt. Therefore, the left-hand-side of the expressions can be the measure of crystal growth rate in the same way as the peak and half times under isothermal conditions.

2) The expression of the Ozawa model can be expressed as 𝜙 𝑇,𝛽 1exp ln2 𝛽 𝑇 /𝛽 , which represents the 𝛽 dependence of 𝜙 at a certain temperature 𝑇 in the original Ozawa model. Because 𝛽 𝑇 at 𝜙 1/2 is a function of temperature 𝑇, this expression can also be regarded as the 𝑇 depend-ence of 𝜙 at a certain fixed cooling rate 𝛽. Here, 𝛽 𝑇 is the inverse function of 𝑇 𝛽 that represents the temperature 𝑇 at 𝜙 1/2 by a fixed cooling rate 𝛽, which can be determined experimentally. Hence, as a reinterpretation of the Ozawa method, the continuous curve of the double logarithmic plot of log ln 1𝜙 𝑇,𝛽 vs log 𝛽 𝑇 at a fixed 𝛽 can be utilized for the determination of the Ozawa (Avrami) index 𝑛.

The applicability of both was experimentally examined for the spherulitic crystalli-zation of polymers.


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Development and characterization

of lignin-based self-healing bio-aromatic networks

MARLIES THYS1,2, NIKO VAN DEN BRANDE1, RICHARD VENDAMME2,

GUY VAN ASSCHE1*

1 Vrije Universiteit Brussel (VUB), Research group of Physical Chemistry and Polymer Science

2Flemish Institute for Technological Research (VITO)


Keywords: thermal analysis, self-healing polymers, lignin

Driven by the need to develop more sustainable materials, the biopolymer in-

dustry has been growing rapidly in recent years. This can be mainly attributed to the

increasing production capacity of a variety of aliphatic bio-based thermoplastic pol-

ymers, such as polylactic acid [1]. In contrast, the development of bio-aromatic ther-

moplastics, rubbers, and thermosets from sustainable resources is lagging behind. As

a biogenic by-product of the paper and pulp industry, lignin is a promising aromatic

resource that could provide for interesting properties when integrated into polymers,

resins, or composites [2,3]. However, these materials are often limited in their recy-

cling possibilities, which restricts the development of highly sustainable materials.

This work aims at developing lignin-based self-healing networks using the

thermo-reversible Diels-Alder reaction between furan and maleimide groups. To cre-

ate highly crosslinked thermoreversible networks, furan-modified lignin and a furan-

bearing Jeffamine (F5000) were reacted with a bismaleimide (DPBM). To gain in-

sight in their structure-property relations, the obtained networks were analysed using

a broad range of thermal analysis and other characterization techniques: modulated

temperature differential scanning calorimetry, thermogravimetric analysis, dynamic

mechanical analysis, dynamic rheometry, and tensile testing. The networks showed

a substantial increase in mechanical properties by introducing furan-functionalized

lignin: going from a Young's modulus of 13 MPa for the reference network up to

425 MPa for a 29 wt% lignin-containing network. Moreover, their healing capacity

and processing opportunities were repeatedly tested, showing reproducibly promis-

ing results.

References

[1] P. Skoczinski, R. Chinthapalli, M. Carus, W. Baltus, D. de Guzman, H. Käb, A. Raschka, J. Ra-

venstijn, “Bio-based Building Blocks and Polymers – Global Capacities, Production and Trends

2019 – 2024”, nova-Institut GmbH, (2020)

[2] P. Ortiz, R. Vendamme, W. Eevers, Molecules, 25 (2020) 1158, 11 p.

[3] R. Vendamme, J.B. de Bueren, J. Gracia-Vitoria, F. Isnard, M.M. Mulunda, P. Ortiz, M. Wadekar,

K. Vanbroekhoven, C. Wegmann, R. Buser, F. Heroguel, J.S. Luterbacher, W. Eevers, Biom-

acromolecules, 21(10) (2020) 4135-4148


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On the extedability of ISO 11358-2 obtaining activation energy of thermal degradation of polymer

MASAYUKI ITO

Toyo gakugei University, Wasa University Faculty of science and technology*Corresponding author: e-mail: [email protected]

Keywords: thermogravimetric analysis, ISO 11358-2, Efect of antioxidant reagent, plyethylene, Friedman plot, induction period of oxydation

1. Material: The sample used was linear low density polyethylene (LLDPE). 3.0phr of dicumyl peroxide and the different concentration of the antioxidant reagent

(4,4’ thio bis-(3-methyl-6-tert-buthyl phenol) was blended by using mixing roll. With heat press, the crosslinked sheets of about 0.15 mm thick were prepared.2. Thermogravimetric measurement: The measurement of TG curve was meas-ured under air flow. The heating rates were from 0.1 K/min to 5.0 K/min. The fo-cused weight retained on TG curve was 96%, 92%, 88 %, 84% and 80 %.3. Result: The weight of LLDPE was increased in the early stage of TG curves.After that, the weight started to decrease. Table 1 shows activation energy obtained using the analytical methods for TG curve. Freidman plot [1] was not applicable for the samples which contain the higher concentration of antioxidant reagent. The analytical method of ISO [2] showed parallel lines on "Heating rate versus the re-ciprocal of the absolute temperature" when the antioxidant reagent was not added to this commercial grade LLDPE. But, when the antioxidant reagent was added, the slope of the lines depended on the selected weight % of TG curve. The ratio of the lowest and the highest value of activation energy was 1:1.5. On the other hand, OIT on TG curves gave almost the same values, not being influenced by the con-centration of the reagent as shown in Table 1.Table 1. Activation energy (kJ/mol) of LLDPE containing different concentration

of antioxidant reagent obtained with various methods Method Concentration of antioxidant reagent/phr

0.0 0.33 0.065 0.0125 0.25

ISO11358-2 97.1-112 71.7-110 70.4-118 77.4-120 78.9-121Friedman plot 70.3-94.7 54.8-65.3 - - -OIT on TG curve*1) 140 157 160 163 153

*1) The values were calculated from the slope of logarithm of heating rate and the reciprocal of the absolute temperature from which the weight started to in-crease on TG curve.

References[1] H. L. Friedman, J.Polymer SCi., 6C, 175 (1965)[2] ISO-11358-2 p4


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Investigation on the depolymerization behavior of natural rubber in the

hydrothermal gasification with ReaxFF simulation and DFT compu-

tation

SHAOQIANG NIE1,2, MEIQIAN CHEN1,2*





Abstract：Massive amounts of used tires are currently produced in the world,

which brings great challenges to the disposal and recycling of waste tires. The de-

polymerization behavior of natural rubber during hydrothermal gasification was

evaluated based on ReaxFF molecular dynamics simulation. The depolymerization

process and reaction pathway of natural rubber in supercritical water were revealed.

The energy barrier for each reaction pathway was determined by density functional

theory (DFT), and the effect of water as catalyst on the depolymerization of natural

rubber was analyzed. The monomers on the non-end chain of natural rubber were

broken into 5-carbon monomer molecules. The molecules on the end chain reacted

with water to generate acrylols, methyl radicals and 6-carbon molecules, which

then reacted further. The final products included formaldehyde, methanol, ethylene,

vinyl alcohol, acetylene, hydrogen and so on. In the hydrothermal gasification of

natural rubber, water acted as a reactant and a catalyst. The present work could at-

tribute to a theoretical support for further identifiction of the hydrothermal gasifica-

tion of natural rubber.

Keywords: Hydrothermal gasification, Natural rubber, ReaxFF molecular dynam-

ics, DFT


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Bio-based polyester polyols and their usage for thermoplastic polyure-

thane elastomers synthesis – thermal stability and selected properties

PAULINA PARCHETA-SZWINDOWSKA¹*, EWA GŁOWIŃSKA¹, JANUSZ DATTA¹*

1Department of the Polymers Technology, Chemistry Faculty, Gdansk University of Technology,

Narutowicza St. 11/12, 80-233 Gdansk

*E-mail: [email protected] / [email protected]

Keywords: thermal analysis, polyester polyols, thermoplastic polyurethane elasto-

mers

The synthesis of polyols from renewable substances as an alternative for petro-

chemical-based polyols plays important matter in the polyurethane industry. The bi-

otechnological process for non-food corn crops residues fermentation allows obtain-

ing compounds for bio-based polyols synthesis. The various type of the impurities

which occurrence at the bio-based substrates compared to corresponding petrochem-

ical-based substrates for polyols synthesis can lead to the different reaction mecha-

nism and in the sequel – different product properties. So, it is necessary to find the

contaminants impact on the synthesis pathways [1].

The polyols with 100 % of bio-carbon content were synthesized with the use of

bio-based succinic acid (bio-SA) and the bio-based 1,3-propanediol (bio-PDO). The

bio-based polyols were synthesised with the planned chemical structure, average

molecular weight and functionality with indicate its possibility to polyurethane ma-

terials synthesis [2]. The results indicated that the novel polyester polyols revealed

similar properties to the commercially used petrochemical-based counterpart. Pre-

pared polyester polyols were used for the synthesis of novel bio-based thermoplastic

polyurethane elastomers (bio-TPU). Selected properties of bio-TPU were investi-

gated [3].

References

[1] P. Parcheta, J. Datta. Environmental impact and industrial development of biorenewable resources

for polyurethanes. Critical Reviews in Environmental Science and Technology. 47:1986-2016.

[2] P. Parcheta, I. Koltsov, J.Datta. Fully bio-based poly(propylene succinate) synthesis and investiga-

tion of thermal degradation kinetics with released gases analysis. Polymer Degradation and Sta-

bility. 151:90-99, 2018

[3] P. Parcheta, E. Głowińska, J. Datta. Effect of bio-based components on the chemical structure, ther-

mal stability and mechanical properties of green thermoplastic polyurethane elastomers. Euro-

pean Polymer Journal. 123:1-10, 2020


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Thermal stability of bio-based polyols obtained by biomass

liquefaction

ADAM OLSZEWSKI1*

, PAULINA KOSMELA1, ŁUKASZ PISZCZYK

1

1Department of Polymer Technology, Chemical Faculty, G. Narutowicza St. 11/12, Gdansk Univer-

sity of Technology, 80-233 Gdansk, Poland; *Corresponding author: e-mail: [email protected]

Keywords: Thermal stability, Bio-polyol, biomass liquefaction

The rapid industrialization and unsustainable resource management is associ-

ated with depletion of fossil fuel and negative environmental impacts such as global warming. Therefore, the development of innovative technologies that will help in the

replacement of petroleum-based products has attracted considerable attention from

scientists. One of the possible solutions of this problem could be the introduction of renewable sources of chemical intermediates. An interesting source of such products

can be agricultural and forestry wastes, which can be directly converted to high-

value end products using thermochemical conversion technologies which include:

pyrolysis, gasification, liquefaction, combustion, carbonization, and co-firing [1,2]. Among these methods, the most interesting for this research is the liquefaction of

biomass, which relies on turning the whole biomass into liquid by a solvolysis reac-

tion of the biomass with a suitable solvent and catalyst. As a result of this process, a valuable polyol can be obtained. These polyols can be used as substitutes for petro-

chemical polyols in the production of polyurethane foams, resins, composites, and

adhesives [3,4].

In several studies bio-polyols obtained during biomass liquefaction are mainly characterized by Fourier transform infrared spectroscopy (FT-IR), rheological stud-

ies, hydroxyl value, and biomass conversion. Although this approach is interesting,

it fails to account for the thermal stability of the obtained compounds. Knowledge on the thermal stability of biopolyols is needed for better characterization of the

chemical structure and mechanisms of thermal degradation of these compounds. The

aim of this work is to broaden our knowledge of thermal properties of bio-based polyols. The properties of bio-polyols have been determined by thermogravimetric

analysis (TGA) and differential scanning calorimetry (DSC).

References [1] M. Patel, X. Zhang, A. Kumar, Techno-economic and life cycle assessment on lignocellulosic biomass thermochemical conversion technologies: A review, Renew. Sustain. Energy Rev. 53 (2016) 1486–1499. [2] C. Song, C. Zhang, S. Zhang, H. Lin, Y. Kim, M. Ramakrishnan, Y. Du, Y. Zhang, H. Zheng,

, Thermochemical liquefaction of agricultural and forestry wastes into biofuels and oBarcel aDami

chemicals from circular economy perspectives, Sci. Total Environ. 749 (2020) 141972. [3] J. Akhtar, N.A.S. Amin, A review on process conditions for optimum bio-oil yield in hydrothermal liquefaction of biomass, Renew. Sustain. Energy Rev. 15 (2011) 1615–1624. [4] H.J. Huang, X.Z. Yuan, Recent progress in the direct liquefaction of typical biomass, Prog. Energy Combust. Sci. 49 (2015) 59–80.


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Thermal properties of polysaccharide-crosslinked polyurethane compo-

sites modified with hydroxyapatite and graphene oxide

PATRYCJA DOMALIK-PYZIK*, KAROLINA KOSOWSKA, MARTYNA HUNGER,

KINGA PIELICHOWSKA

AGH University of Science and Technology, Faculty of Materials Science and Ceramics,

Department of Biomaterials and Composites


Keywords: thermal analysis, polyurethanes, hydroxyapatite, graphene oxide

Polysaccharides consist of carbohydrate repeating units linked together with

glycosidic bonds. As biopolymers, they offer innate favourable biological features,

what makes them promising materials for many biomedical applications. When re-

acted with polyfunctional isocyanates, they can form polyurethanes (PUs). One of

the most characteristic features of PUs are repeating units of hard and soft segments.

By playing with those building blocks and chemical composition, properties of PUs

can be tailored to specific demands and even more versatile with PUs-based compo-

sites.

In our study, highly porous PU scaffolds were synthesized using a one step bulk

polymerization method. Chitosan (CS) or hyaluronic acid (HA) were employed as

cross-linkers. The synthesis was carried out using poly(ethylene glycol) and poly(ε-

caprolactone) with a molar ratio of 1:3 as soft segments, 1,4-butanediol as chain

extender and 4,4'- diphenylmethane diisocyanate. Composite systems were modified

with nanohydroxyapatite (HAp) and/or graphene oxide (GO).

Differential scanning calorimetry (DSC) and thermogravimetry (TG) were ap-

plied to assess how the polysaccharides used and the addition of HAp and/or GO

affected the thermal properties of PUs. DSC results showed that CS effectively cross-

linked the network, hindering crystallization ability and thus creating stiff, cross-

linked structure resulting from intermolecular hydrogen bonding between polysac-

charide chains and PU. Introduction of bioceramic nanoparticles led to the decrease

of polymer chain mobility and the increase in the segment stiffness, observed as the

increase of the soft segments glass transition tmeperature. It suggests possible inter-

action between polar groups of HAp and PU matrix. HAp acted also as a plastifier,

decreasing glass transition temperature of the hard segments. The results of GO ad-

dition were opposite. GO nanosheets may interact with CS, decreasing the number

of available functional groups, hence reducing cross-linking rate what was observed

as the negative change in the soft segments glass transition temperature – for the GO

composite it was 14 ℃ lower as compared to the reference PU sample.

The obtained PU_chitosan and PU_hyaluronic acid composites are interesting

materials for biomedical applications.

Acknowledgments

This research was funded by the National Sciene Centre (UMO-2016/22/E/ST8/00048) and the Na-

tional Centre for Research and Development, Poland (STRATEGMED3/303570/7/NCBR/2017).


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Thermal properties and fire behavior of polyisocyanurate foams

MONIKA BORUCKA¹*, KAMILA MIZERA¹, MACIEJ CELIŃSKI¹, KAMILA

SAŁASIŃSKA¹, AGNIESZKA GAJEK¹

1Central Institute for Labour Protection - National Research Institute (CIOP-PIB), Czerniakowska 16,

00-701 Warsaw, Poland;


Keywords: thermal anlysis, polyisocyanurate foams, burning behavior, combus-

tion products

The polyisocyanurate foams (PIR) are used as thermally insulating materials in

construction, roofing, district heating and in cooling applications. PIR structures do

not melt due to crosslinking. They have the superior thermal stability and fire retard-

ance compared to conventional polyurethane foams and other thermally insulating

materials [1, 2]. However during thermal degradation and combustion, PIR form

carbon monoxide, hydrogen cyanide, isocyanates and other toxic products [3].

In this study, the thermal characteristic of the polyisocyanurate foams were ex-

amined by the cone calorimeter (ISO 5660-1) and by simultaneous thermal analysis

(STA) that combines thermogravimetry (TG) and differential scanning calorimetry

(DSC). Moreover burning behavior and combustion products from selected materials

have been investigated in diffrent fire scenarios in the the steady-state tube furnace

(ISO 19701) coupled with Gasmet DX-4000 analyser.

All tested materials were characterised by the three-step degradation that started

at about 150ºC. The PIR material tests with 350°C furnace temperature did not show

flaming combustion and can be regarded as regular oxidative pyrolysis tests. The

tests in 700°C furnace temperature (and high ventilation) and in 825°C furnace tem-

perature (and low ventilation) showed steady flaming behavior. The most hazardous

products emitted during the combustion of polyisocyanurate foams were carbon ox-

ides and hydrogen cyanide.

References

[1] J. Lenz, D. Pospiech, M. Paven, R.W. Albach, B. Voit, Influence of the catalyst concentration on

the chemical structure, the physical properties and the fire behavior of rigid polyisocyanurate

foams. Polym. Degrad. Stabil. 177:109-168, 2020.

[2] . K. Chen, Ch. Tian, Sh. Liang, X. Zhao, X. Wang, Effect of stoichiometry on the thermal stability

and flame retardation of polyisocyanurate foams modified with epoxy resin. Polym. Degrad. Stabil.

150:105-113, 2018.

[3] A.A. Stec, T.R. Hull, Assessment of the fire toxicity of building insulation materials. Energ. Build-

ings. 43:498-506, 2011.


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Water in non-isocynate based, POSS-containing, poly(hydroxy ure-

thanes). Effects on glass transition.

KONSTANTINOS N. RAFTOPOULOS 1*, CARLOS BUJALANCE CALDUCH 1,2, IZABELA ŁUKASZEWSKA1, PIOTR STACHAK1, EDYTA HEBDA1, SEBASTIAN

LALIK3, MONIKA MARZEC3, AND KRZYSZTOF PIELICHOWSKI1

1Cracow University of Technology, Department of Chemistry and Technology of Polymers

2Universitat Politècnica de Valencia (UPV), Departamento de Ingeniería Química y Nuclear 3Institute of Physics, Jagiellonian University


Keywords: polyurethane, POSS, hydration, glass transition, molecular dynamics

Polyurethanes serve well in a very broad spectrum of applications, due to the

versatility of their synthesis and the easy tailoring of their properties. However,

diisocyanates used in their synthesis pose health and environmental hazards. For this

reason, non-isocyanate routes for their synthesis are explored [1].

In this work we employ the reaction between cyclic carbonate and amine groups

to synthesize a polyurethane network. The system is modified by polyhedral oligo-

meric silsesquioxane (POSS). POSS consists of a cubic siliceous core, with organic

side groups, which –upon proper functionalization– allow these large organic-inor-

ganic hybrid molecules to become part of the chemical structure itself. Here we use

moieties with one and three epoxy rings which act as chain terminating groups and

“heavy” chemical crosslinks, respectively.

Interestingly, the employed synthetis route introduces a hydroxyl group pendent

on the chain, close to the urethane link. As a result, the resulting materials are very

hydrophilic. Here, we study in detail the absorption of water as a fuction of environ-

mental humidity. We also explore the effects of absorbed water and POSS on the

calorimetric and dynamic glass transition.

We find that the unmodified matrix absorbs up to an impressive 60% of water

(at relative humidity 98%), which leads to an acceleration of dynamics and subse-

quently to a reduction of glass transition temperature by up to approximately 80 K.

POSS accelerates mobility when introduced as chain ends “loosening” the network,

or decelerates mobility when introduced as “heavy” chemical crosslinks, stiffening

it. POSS also inhibits water absorption to some extent, also dependent on the topol-

ogy, thus reducing plasticization. Hence POSS proves to be a suitable additive for

tailoring physical properties of poly(hydroxyl urethanes).

Acknowledment

This research was funded by the National Research Center in Poland (Narodowe

Centrum Nauki, NCN), under contract number 2017/27/B/ST8/01584.

Reference

[1] H. Khatoon, S. Iqbal, M. Irfanc, et al, A review on the production, properties and applications of

non-isocyanate polyurethane: A greener perspective, Prog Org Coat, 154:106124, 2021.


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Physical aging in the constrained amorphous fractions of polylactide

N. DELPOUVE, X. MONNIER, A. SAITER–FOURCIN, E. DARGENT

Normandie Univ, UNIROUEN Normandie, INSA Rouen, CNRS,

Groupe de Physique des Matériaux – 76800 St Etienne du Rouvray

Keywords: Fast Scanning Calorimetry, glass transition, structural relaxation, PLA

During the structural relaxation, or physical aging, the out–of–equilibrium glass

minimizes its thermodynamic quantities, such as enthalpy and specific volume, to

approach equilibrium. In glassy polymers, this phenomenon can negatively affect

the dimensional stability during storage, resulting in the degradation of mechanical

and barrier properties, as examples. Reducing the relaxation kinetics thanks to ther-

mal and thermo–mechanical treatments can therefore be of interest for industrials.

Our study focuses on the impact of several processing conditions on the physical

aging of poly (lactic acid) (PLA). PLA is today the most produced biodegradable

and biobased polymer, mainly for packaging applications or bioresorbable devices.

However, its brittleness is generally considered as a limiting factor for its large–scale

commercialization, this feature being aggravated under physical aging.

Fast scanning calorimetry (FSC) is a powerful tool to investigate physical aging.

In this technique, a low mass sample (about ten to hundred nanograms), is heated up

and cooled down at rates in the order of thousand Kelvins per second. FSC can pro-

vide glasses with high level of enthalpy or specific volume. Moreover, physical ag-

ing can also be investigated at temperatures higher than in standard DSC conditions,

due to the shift of the glass transition to higher temperatures when increasing the

cooling rate. Besides, the structural relaxation can be tracked in accelerated condi-

tions since the ratio surface/volume is significantly increased.

Our results show that quiescently crystallized PLAs, following a three–phase

model, exhibit different relaxation kinetics depending on their respective contents of

mobile (MAF) and rigid (RAF) amorphous fractions. At low aging temperatures,

MAF and RAF exhibit the same structural relaxation rate. However, in the aging

temperature domain close to the glass transition, the structural relaxation occurs

faster in the MAF, showing the sensitivity of the physical aging to the crystallization

conditions, either favouring or inhibiting the RAF formation [1]. An even more im-

portant slowing down of the relaxation kinetics can be obtained when the amorphous

phase mobility is hindered by the orientation of the macromolecules, even in the

absence of crystalline phase [2]. It is assumed that the constraining of the amorphous

phase is a reliable procedure to limit the physical aging impact.

References

[1] X. Monnier, et al. Distinct dynamics of structural relaxation in the amorphous phase of poly(L-

lactic acid) revealed by quiescent crystallization, Soft Matter, 16: 3224-3233, 2020

[2] X. Monnier, et al.. Reduced physical aging rates of polylactide in polystyrene/polylactide multilayer

films from fast scanning calorimetry, Polymer, 150:1–9, 2018.


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Development of the state diagrams of PBTTT and a novel PBTTT de-

rivative in combination with PC61BM for organic near-infrared cav-

ity photodetectors

ZHEN LIU1, JOCHEN VANDERSPIKKEN2,3, KRISTIEN VAN DER FLAAS4, MOUNA

HAMID4, BART GODERIS4, KOEN VANDEWAL2,3, WOUTER MAES2,3, GUY

VAN ASSCHE1, BRUNO VAN MELE1, NIKO VAN DEN BRANDE1*

1Vrije Universiteit Brussel, Physical Chemistry and Polymer Science

2Hasselt University, Institute for Materials Research (IMO-IMOMEC) 3imec, Associated Laboratory IMOMEC

4KU Leuven, Polymer Chemistry and Materials Division


Keywords: conjugated polymers, state diagram, cocrystal, eutectic, rapid heat-cool

DSC, synchrotron XRD

In organic cavity-based near-infrared (NIR) photodetectors, the formation of an

intermolecular charge transfer (CT) state at the interface between the donor and the

acceptor plays a crucial role in the device performance. For this particular applica-

tion, a high interfacial contact area is required, as it results in relatively strong CT

absorption [1]. A benchmark system, PBTTT:PC61BM, is selected because the inter-

calation of the fullerene acceptor between the side chains of the polymer donor max-

imizes the PBTTT:PC61BM contact [2]. A novel PBTTT derivative with alternating

alkyl and alkoxy substituents was developed to further lower the energy gap between

the HOMO of the donor and the LUMO of PC61BM, and therefore extend the CT

absorption of the device more into the NIR.

In this research, the benchmark donor material PBTTT and the novel alkoxy-

alkyl-PBTTT polymer, as well as their blends with PC61BM, are studied by Rapid

Heat-Cool DSC (RHC). RHC allows a relatively wide range of heating and cooling

rates up to 2000 K/min, thanks to its unique infrared furnace design and small sample

size (ca. 250 µg). Using this technique, the state diagram of alkoxy-alkyl-

PBTTT:PC61BM is constructed for the first time. The comparison with the bench-

mark system regarding the state diagrams and their complex thermal behaviour, in-

cluding cocrystal formation and eutectic transitions, is discussed with the help of

synchrotron XRD results.

References

[1] B. Siegmund, A. Mischok, J. Benduhn, O. Zeika, S. Ullbrich, F. Nehm, M. Böhm, D. Spoltore, H.

Fröb, C. Körner, K. Leo, K. Vandewal. Organic narrowband near-infrared photodetectors based

on intermolecular charge-transfer absorption. Nat. Commun. 8:15421, 2017.

[2] A. C. Mayer, M. F. Toney, S. R. Scully, J. Rivnay, C. J. Brabec, M. Scharber, M. Koppe, M. Heeney,

I. McCulloch, M. D, McGehee. Bimolecular crystal of fullerenes in conjugated polymers and the

implications of molecular mixing for solar cells. Adv. Funct. Mater. 19:1173-1179, 2009.


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Diffusion-controlled self-healing of reversible Diels-Alder networks

JESSICA MANGIALETTO*, DOROTHEE EHRHARDT, AUDREY CUVELLIER,

ROBRECHT VERHELLE, JOOST BRANCART, GUY VAN ASSCHE, HUBERT RA-

HIER, NIKO VAN DEN BRANDE, BRUNO VAN MELE

Vrije Universiteit Brussel, Faculty of Engineering, Physical Chemistry and Polymer Science (FYSC)


Keywords: reversible thermosets, self-healing, TTT/CHT diagram, chip calorimetry

Intrinsic self-healing polymer networks were developed based on dynamic co-

valent bonding by means of thermoreversible Diels-Alder (DA) cycloadditions. The

DA bonds are preferentially broken in case of damage, but also reversibly reform,

leading to a repeatable healing cycle and an increased lifetime for many applications,

such as sustainable coatings [1], [2]. However, thermo-mechanical robustness is re-

quiring a network in the (partially) vitrified state, with a sufficiently high Tg.

This work focuses on the effect of vitrification on DA reaction kinetics, using

fully reversible model systems of furan and maleimide compounds. In bulk, using

(MT)DSC, vitrification is followed through (non-)isothermal heat capacity measure-

ments, while non-isothermal microcalorimetry provides heat flow information.

These results are used to optimize the parameters of a kinetic model, considering

the DA endo−exo stereochemistry. In addition, dynamic rheometry allows the con-

struction of time-temperature-transformation (TTT) and continuous-heating-trans-

formation (CHT) diagrams for both reversible elastomers and thermosets [3]. A

double asymptotic behavior of the isoconversion lines is revealed, and also two

subsequent gelation/degelation events can occur during non-isothermal curing.

This bulk study was extended towards thin films through AC chip calorimetry,

yielding preliminary results to compare vitrification in bulk and thin layers.

This work is the first systematic study of diffusion-controlled reversible DA

network formation. The DA reaction was proven to proceed in diffusion-controlled

conditions, allowing self-healing in mobility-restricted applications [2], [4].

References

[1] M. M. Diaz, J. Brancart, G. Van Assche, and B. Van Mele, Room-temperature versus heating-me-

diated healing of a Diels-Alder crosslinked polymer network, Polymer, vol. 153, no. April, pp. 453–

463, 2018.

[2] D. Ehrhardt, J. Mangialetto, J. Bertouille, K. Van Durme, B. Van Mele, and N. Van den Brande,

Self-healing in mobility-restricted conditions maintaining mechanical robustness: furan-maleimide

Diels-Alder cycloadditions in polymer networks for ambient applications, Polymers, vol. 12, no. 11,

pp. 2543–2566, 2020.

[3] J. Mangialetto, R. Verhelle, G. Van Assche, N. Van den Brande, and B. Van Mele, Time-Tempera-

ture-Transformation, Temperature-conversion-Transformation, and Continuous-Heating-Transfor-

mation diagram of reversible polymer networks, Macromolecules, vol. 54, no. 1, pp. 412–425, 2021.

[4] J. Mangialetto et al., Diffusion- And Mobility-Controlled Self-Healing Polymer Networks with Dy-

namic Covalent Bonding, Macromolecules, vol. 52, no. 21, pp. 8440–8452, 2019.


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DSC study on the influence of PET microplastics on abiotic processes in

soil

JAKUB FOJT*, PAVLA DENKOVÁ, JIŘÍ KUČERÍK

1Brno University of Technology, Faculty of Chemistry


Keywords: Microplastics, Soil, DSC, PET, Soil organic matter

The ecotoxicological and health adverse effects of microplastics are examined worldwide, however only few studies focuses on impact of these particles on abiotic

properties of soil organic matter (SOM) [1]. Disruption of soil physical and chemical

structure not only can endanger soil organisms, but it also can lower the agricultural crop yields and landscape water reserves [2]. Selected abiotic soil indicators were

determined for soil contaminated with PET microplastics to evaluate their effect on

soil quality. The peat was chosen as a model soil due to the high content of SOM. Prior to the measurement, the peat was wetted and dried under three different relative

humidities to assure the conditions variability typical for arid areas. Differential

Scanning Calorimetry (DSC) was used to measure evaporation enthalpy of water

from soil, stability of water molecule bridges stability (WaMB) and lipids melting enthalpy. Also, water holding capacity was determined.

We have found that PET microplastics decrease evaporation enthalpy (strength

of water binding) and soil lipids crystallites melting enthalpy (i.e. their concentra-tion) for each relative humidity, WaMB and water holding capacity of SOM were

different for each humidity. These results implicate that conventional microplastics

change the SOM supramolecular structure and negatively effect the interaction be-tween water and soil, which may have an adverse effect on retention of water in

landscape.

Acknowledgement:

The financial support of projects FCH-S-21-7398 and Kvalitní interní granty VUT EF19_073/0016948 of Ministry of Education, Youth and Sports are acknowl-

edged.

References

[1] de Souza Machado AA, Kloas W, Zarfl C, Hempel S, Rillig MC. 2018. Microplastics as an emerging threat to terrestrial ecosystems. Global Change Biology 24:1405-1416.

[2] Komendová R, Žídek J, Berka M, Jemelková M, Řezáčová V, Conte P, Kučerík J. 2019. Small-sized platinum nanoparticles in soil organic matter: Influence on water holding capacity, evapora-tion and structural rigidity. Science of The Total Environment 694.


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Impact of silane and siloxane on the Portland cement hydration

KALINA GRABOWSKA¹*, ALICJA WIECZOREK1, MARCIN KONIORCZYK1

1Lodz University of Technology, Faculty of Civil Engineering, Architecture and Environmental Engi-

neering, Department of Building Materials Physics and Sustainable Design *Corresponding author: e-mail: [email protected]

Keywords: Thermal analysis, Portland cement hydration, organosilicon com-

pounds, silane, siloxane, internal hydrophobization

Admixtures based on organosilicon compounds, such as silanes and siloxanes,

are used for internal protection against detrimental effects of water and moisture.

Internal hydrophobization by means of organosilicon compounds can significantly

improve durability of cement-based materials by increasing their water resistance

and thus extend the application areas. But the process of internal hydrophobization

consist of chemical reactions between Portland cement phases and silicon-based

compounds.

In our study, we investigated the impact of organosilicon compounds such as

triethoxysilane (OTES) and poly(dimethylsiloxane) (PDMS) on the Portland cement

hydration and thus on subsequent properties of cement mortar. The isothermal calo-

rimetry was used to measure the heat of cement hydration. By differential thermal

analysis (DTA) and thermogravimetry (TG) the thermal decomposition of cement

paste was investigated. The differential scanning calorimetry (DSC) technique was

helpful in determining the capillary and gel pores content in the cement paste. The

microstructure of hardened cement paste was also analyzed by mercury intrusion

porosimetry (MIP). The preliminary study has shown that organosilicon compounds

interact with Portland cement. The decrease in heat of cement hydration was notice-

able for cement paste with silane. But, on the other hand, the DTA-TG analysis did

not indicate significant differences during thermal decomposition. The most im-

portant difference was noticeable for the amount of chemically bounded and physi-

cally adsorbed water in cement paste. The amount of physiosorbed water was higher

for paste with siloxane and lower in case of cement paste with silane than for refer-

ence sample. In case of chemically bounded water its amount was insignificantly

lower for silane sample and noticeable decreased for siloxane one. DSC analysis

showed that the organosilicon admixtures might lead to the decreasing in amount of

capillary pores and increasing in amount of gel pores. MIP measurements demon-

strated significant differences in differential pore volume distribution for siloxane

sample by increasing it.

Our research indicates that organosilicon compounds used for internal hydro-

phobization interact with Portland cement, which might lead to changes in properties

of the final product. Our results may have particular significance during selecting a

hydrophobic silicon-based compound for the hydrophobization of cement-based

building materials.


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Characterizing the thermal phase behaviour of fipronil

DENNIS S. MOYO1,2, ANTONIO B. MAPOSSA2,3, MARIA ATANASOVA3,

WALTER W. FOCKE2,3*, ELIZABET M. VAN DER MERWE1,

FREDERICK P. MALAN1, MELANIE RADEMEYER1

1University of Pretoria, Department of Chemistry

2University of Pretoria, UP Institute for Sustainable Malaria Control & MRC Collaborating Centre for

Malaria Research

3University of Pretoria, Institute of Applied Materials


Keywords: polymorphs, pseudomorphs, recrystallization, thermal analysis, insecticide

Fipronil is a broad spectrum, low application rate insecticide that belongs to a class

of chemicals known as phenylpyrazoles. It is mostly used for controlling pest

organisms of numerous animals and crops such as fleas, weevils, ants, ticks, ants,

rootworms, mosquitoes, and termites. When preparing and formulating a large-scale

market compound such as fipronil, it is of utmost importance to know if alternate

crystalline modifications (polymorphs or solvate pseudo-polymorphs) of the

compound exist, how they can be obtained, and what their characteristic properties are.

Polymorphs of one compound may have contrasting properties, for instance melting

point, colour, degradation stability, crystal size, mechanical and optical properties, and

solubility.

The present study was undertaken to identify crystalline polymorphs, solvate

pseudomorphs and amorphous forms of fipronil that arise as a result of recrystallization

of fipronil.

Analysis by DSC, TGA, single-crystal XRD and powder XRD demonstrated that

recrystallisation of fipronil from organic solvents such as acetonitrile, acetone, ethyl

acetate yielded fipronil hemi-solvates. TGA analysis shows the solvents are liberated

well before 150 C. Thereafter, DSC analysis shows two sharp melting endotherms

located at onset temperatures of ca. 194 C and 204 C. The relative proportions of the

enthalpy’s associated with the two melting events varies depending on the nature of the

starting material (e.g. solvent used for recrystallization) and its previous thermal

history. However, the combined enthalpy measured for the two melting events remains

approximately constant suggesting that these events may be associated with the

presence of separate crystalline phases. Single-crystal XRD and powder XRD analysis

of the samples studied support the thermal observations.


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Enthalpy relaxation kinetics of epoxy systems

B. QUELENNEC1, N. DELPOUVE1, R. DELANNOY2, E. RICHAUD2, L. DELBREILH1

1 Normandie Univ, UNIROUEN Normandie, INSA Rouen, CNRS, GPM, France

2 PIMM, CNAM, CNRS UMR 8006, Arts et Métiers-ParisTech, France

*Corresponding authors: [email protected]; [email protected]

Keywords: Fast Scanning Calorimetry, physical aging, epoxy

The glassy state results from the inability of the liquid to equilibrate in the time

allowed by the cooling rate. It is described as a disordered non-equilibrium state with

the possibility of evolving over time towards an equilibrium state. This evolution is

called physical ageing. This phenomenon can be observed by measuring the relaxa-

tion enthalpy using calorimetry. The study of physical ageing is a major challenge

for understanding the structural relaxation process influence on physical properties.

Indeed, in the glassy state, there are divergent points of view, particularly as to the

nature of the movements by which physical ageing takes place [1][2].

The development of fast scanning calorimetry (FSC) has increased scientists'

interest in the study of the glassy state and physical ageing. This technique allows

samples of considerably smaller mass, a few nanograms, than standard differential

scanning calorimetry (DSC), a few miligrams, to be cooled to thousands of Kelvin

per second. The result is an acceleration of the physical ageing kinetics, which there-

fore becomes easier to follow in its entirety.

This work investigated the physical ageing by FSC of two epoxy resins with

different cross-linking densities. Each system was aged for 10 minutes over a wide

range of temperatures to observe the enthalpy recovery profile. From this profile, the

enthalpy relaxation was probed from 0 to 1000 minutes at different distances from

the glass transition. For each system, two enthalpy recovery kinetics are observed:

one close to the glass transition, the other in the far glassy region. In addition, the

enthalpy recovery kinetics vary with network density for equivalent distances to

equilibrium.

References

[1] D. Cangialosi, et al. Physical aging in polymers and polymer nanocomposites: recent results and

open questions, Soft Matter, 9: 8619, 2013

[2] G. B. McKenna. 50th Anniversary Perspective: Challenges in the Dynamics and Kinetics of Glass-

Forming Polymers, Macromolecules, 50:6333–6361, 2017.

Acknowledgements

The authors would like to thank the Agence Nationale de la Recherche for the financial support of the

ANR DUREVE project.


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Thermal properties of active polyacrylate-based packaging

JELENA M. TANASIĆ1*, TAMARA D. ERCEG1, MARIJA G. KOSTIĆ1, IVAN KRAKOVSKY2, IVAN S. RISTIĆ1

1University of Novi Sad, Faculty of Technology Novi Sad, Novi Sad, Serbia

2Charrles University of Prague, Prague, Czeck Republic *Corresponding author: e-mail: [email protected]

Keywords: active packaging, polyacrylates, thermal properties, conductive proper-ties

Packaging is a very important part in the process of handling and transporting prod-ucts to end consumers. It is responsible and extremely important for maintaining the quality of production from the output of the production plant to the consumer. In the last couple of years, research has been developing precisely towards the process of packaging development, by moving towards active packaging that would, in addition to adequate product protection, provide adequate information to the customer about the validity of the product, through sensors in the packaging itself. In this paper, the synthesis of nanocomposites based on acrylate, which can be used as a coating for packaging paper, is made. The polyacrylate was synthesized by emulsion polymeri-zation of methyl methacrylate and butyl acrylate with an initiator concentration in the range of 0.3% by weight at 70 ° C. Carbon nanotubes were used as a filler to obtain conductive coatings. The concentration of nanoparticles ranged from 0.5% to 2% by weight of the polymer. These emulsions are applied on paper and crosslinking at a slightly elevated temperature - 40 ° C, or under UV light. Emulsions, which are applied on paper in one and two layers and crosslinked at 40 ° C and under the action of UV light, give coatings on paper of uniform structure, resistant to water and oils. FTIR spectroscopy was used to confirm the struc-ture of the obtained acrylic films. The influence of nanofiller concentration on thermal properties was investigated, by DSC an TG analyses since for use in packaging it is of exceptional importance ther-mal properties, mechanical properties and conductivity of the samples are investiga-tion. Conductivity measurements confirmed that this coating on paper can be used for conduc-tive packaging coatings. References [1] L. Wang, W. Dong, Y. Xu, Synthesis and characterization of hydroxypropyl methylcellulose and ethyl acrylate graft copolymers, Carbohydrate Polymers, Vol.(2007) 626‒636. [2] H. Zhang,R. V. D. Linde, Atom tansfer radical polymerization of n-butyl acrylate catalyzed by CuBr/N-(n-hexyl)-2-pyridylmethanimine, Polymer Chemistry, Vol. 40 (2002) 3549‒3561. [3] J. Kumaki, A. Watanabe, Morphology control through hierarchical phase separation in Langmuir monolayers of poly(methyl methacrylate)-b-poly(n-butyl acrylate), Journal of Colloid and Interface Science, Vol. 486(2017) 316‒324.


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Determination of thermal properties of new biopolyols obtained via

biomass liquefaction

ADAM OLSZEWSKI1*

, PAULINA KOSMELA1, ŁUKASZ PISZCZYK

1

1Department of Polymer Technology, Chemical Faculty, G. Narutowicza St. 11/12, Gdansk Univer-

sity of Technology, 80-233 Gdansk, Poland; *Corresponding author: e-mail: [email protected]

Keywords: Bio-polyol, biomass liquefaction, thermal degradation

Unsustainable development is associated and the lack of appropriate waste

management methods are leading to depletion of fossil fuel and negative environ-mental impacts such as global warming. For this reason, the development of novel

technologies that will reduce negative impact on the environment has attracted con-

siderable attention from scientists. One of the proposed solutions of this problem could be the development of processes for chemical intermediates synthesis. An in-

teresting source of such products can be agricultural and forestry wastes, which can

be directly converted to high-value end products using thermochemical conversion

technologies which include: pyrolysis, gasification, liquefaction, combustion, car-bonization, and co-firing [1,2]. Among these methods, biomass liquefaction biomass

is one of most promising methos for polyols production. This method relies on turn-

ing the whole biomass into liquid by a solvolysis reaction of the biomass with a suitable solvent and catalyst [3,4].

To date, research on biomass liquefaction products has mostly focused on Fou-

rier transform infrared spectroscopy (FT-IR), rheological studies, hydroxyl value,

and biomass conversion. Although this approach is interesting, it fails to account for the thermal stability of the obtained compounds. Knowledge on the thermal stability

of biopolyols is needed for better characterization of chemical structure, and mech-

anisms of thermal degradation of bio-polyols. The main aim of this research is to broaden our knowledge about thermal degradation of novel polyols. The properties

of bio-polyols have been determined by thermogravimetric analysis (TGA) and dif-

ferential scanning calorimetry (DSC).

References [1] M. Patel, X. Zhang, A. Kumar, Techno-economic and life cycle assessment on lignocellulosic biomass thermochemical conversion technologies: A review, Renew. Sustain. Energy Rev. 53 (2016) 1486–1499. [2] C. Song, C. Zhang, S. Zhang, H. Lin, Y. Kim, M. Ramakrishnan, Y. Du, Y. Zhang, H. Zheng,

tion of agricultural and forestry wastes into biofuels and , Thermochemical liquefacoBarcel aDamichemicals from circular economy perspectives, Sci. Total Environ. 749 (2020) 141972. [3] J. Akhtar, N.A.S. Amin, A review on process conditions for optimum bio-oil yield in hydrothermal liquefaction of biomass, Renew. Sustain. Energy Rev. 15 (2011) 1615–1624.

[4] H.J. Huang, X.Z. Yuan, Recent progress in the direct liquefaction of typical biomass, Prog. Energy Combust. Sci. 49 (2015) 59–80.


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The thermal properties of polyoxymethylene modified

with functionalized hydroxyapatite

KRZYSZTOF WALASEK, PIOTR SZATKOWSKI, KINGA PIELICHOWSKA*

AGH University of Science and Technology, Faculty of Materials Science and Ceramic

Al. Mickiewicza 30, 30-059 Kraków


Keywords: thermal analysis, polyoxymethylene, functionalized hydroxyapatite

Acetal copolymers are a group of thermoplastics that are polymerization prod-

ucts of aldehydes, most often formaldehyde, with cyclic ethers. The best known is

polyoxymethylene (POM). POM is distinguished by advantageous performance

properties, including high mechanical strength, stiffness, hardness, resistance to

abrasive wear, low water absorption, good chemical resistance, ease of processing

and many others. The serious problem, especially during the processing of acetal

polymers, is their poor resistance at high temperatures. In our previous research it

has been found that incorporation of stoichiometric nanohydroxyapatite (HAp) leads

to dramatic decreasing POM thermal stability due to the presence of acid and basic

active sites in HAp structure [1].

In this study we modified HAp by grafting poly(ethylene glycol) (PEG) to HAp

hydroxyl groups by using 1,6-hexamethylene diisocyanate as a coupling agent. The

obtained functionalized HAp-g-PEG has been incorporated to POM matrix using

melt processing methods [2].Thermogravimetric analysis exhibited significant im-

provement in the POM thermal stability after icorporation od HAp-g-PEG. Based on

TG results in dynamic mode thermal degradation kinetics has been calculated using

Friedman and nonlinear regression methods. The obtained results show an increase

in the activation energy of thermal degradation for POM/HAp-g-PEG composites

compared to neat POM. Additionally, based on DSC data from isothermal measure-

ments, kinetic parameters of the POM crystallization process in the presence of HAp-

g-PEG have been calculated. The obtained result show that HAp-g-PEG act as nu-

cleating agent during POM crystallization.

Acknowledgments

Authors are grateful to the Polish National Science Centre for financial support under the Contract

No. UMO-2016/21/B/ST8/00449.

References

1. Lüftl, S., V.P. M, and S. Chandran, Polyoxymethylene Handbook: Structure,

Properties, Applications and their Nanocomposites. Polymer Science and Plastics

Engineering. 2014: Wiley.

2. Pielichowska, K., K. Król, and T.M. Majka, Polyoxymethylene-copolymer based

composites with PEG-grafted hydroxyapatite with improved thermal stability.

Thermochimica Acta, 2016. 633: p. 98-107.


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Influence of chemically modified cellulose on properties natural rubber

composites.

P. RYBIŃSKI 1*, B. SYREK

1

1 The Jan Kochanowski University, Institute of Chemistry.


Keywords: Chemical modification, cereal straw, natural rubber, flammability,

thermal properties, natural rubber.

Legal regulations towards the reuse and recycling rules as well as reduction

costs production caused that the manufacture of polymeric bio-composites

growing rapidly all over the world. In general to the production of bio-

composites are used natural polymers and fillers e.g. in the form of fibres.

The properties of natural fibres may differ significantly from conventional

carbon, glass or polymeric, synthetic fibres. Their characteristic depends on

the age of the plant, place of origin or initial preparation. These factors also

determine the chemical composition of natural fibres.

Elastomeric materials (elastomers) are very rare used to produce polymeric

bio-composites. Natural rubber (NR), the main representative of the elasto-

mer group, may be considered as a polymer matrix for the naturally derived

fibre-filled composites.

Natural fibers are hydrophilic and what is important they are characterized

by low resistance on the action of fire. Most of the polymers used to pro-

duce natural fibre polymeric composites, including elastomers, are hydro-

phobic, which leads to the problem of poor wettability of the fibres. An in-

crease in the interfacial (fibre-polymer) interaction can be obtained by the

chemical modification of fibres. Three different phosphor-organic com-

pounds were used to modify the lignocellulose filler: Tris (1,3-

dichloroisopropyl) phosphate, cresyl diphenyl phosphate and triaryl phos-

phate isopropylated. The influence of the conducted modification on the

morphology and structure particles was studied with the use of microscope

technique. Influence of chemical modification on the properties filled com-

posites was determined on the basis of rheometric characteristics, cross-link

density, mechanical and thermal properties, as well as flammability tests.

Resistance obtained composites on the action of fire was also studied from

the point of view synergism action of ammonium polyphosphate or mela-

mine polyphosphate with cereal straw as donor of carbon.


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Synthesis and thermal resistance of POSS filled non-isocyanate polyu-

rethane (NIPU) composite materials

PIOTR STACHAK¹*, IZABELA ŁUKASZEWSKA¹, EDYTA HEBDA¹, KRZYSZTOF

PIELICHOWSKI¹

1Cracow University of Technology, Department of Polymer Chemistry and Technology


Keywords: thermal analysis, non-isocyanate polyurethanes, NIPU, composites

Traditionally, polyurethanes are synthesized in the reaction of polyols and

diisocyanates. Although it is possible to obtain polyols from natural sources, diiso-

cyanates are labeled as hazardous and toxic [1]. NIPU modified with POSS parti-cles show promise in the field of novel nanocomposite materials, as their properties are enhanced in terms of thermal and mechanical performance [2].

The synthesis of non-isocyanate polyurethane composites modified with POSS particles (GlycidylIsobutyl POSS and TriglycidylIsobutyl POSS), as well as their thermal characterization is described in this work. Matrices were obtained from

carbonate (TMP TRI Carbonate SP-3-00-003) and amine (polypropylene oxide-based polyether diamine Jeffamine D-400 and alkyl diamine Priamine 1074) raw materials. Two-stage process was employed. The first stage consisted of prepoly-

mer synthesis in the presence of a catalysts (TBD, TBAB, TBAI) in a solvent (DMAC), via the reaction between carbonate and amine (2:1 ratio of reactive groups). POSS particles were added in this stage as well (15 wt%). Chain extension

reaction was carried out in the second stage, by the addition of DAB. The mixture was finally transferred into polypropylene molds and placed in an oven (100ºC) for

curing and solvent removal. Thermogravimetric analysis was performed using a Netzsch TG 209 thermal

analyzer, with a heating rate of 10°C/min in air atmosphere. The samples obtained

with Jeffamine D-400 were less thermally stable than their counterparts based on

Priamine 1074, which is attributed to the role of diamine’s structure in NIPU du-

ring decomposition. NIPU matrices showed contradicting trends in terms of chang-

ing their thermal stability upon modification with POSS. Both types of POSS en-

hanced resistance to thermal degradation of less thermally stable NIPU matrix.

However, thermal stability of more thermally resistant NIPU matrix lowered after

incorporation of either type of POSS nanoparticles.

Acknowledgments

This research was funded by the Polish National Science Centre (Narodowe Centrum Nauki, NCN),

under contract number 2017/27/B/ST8/01584.

References

[1] A. Cornille et al. A perspective approach to sustainable routes for non-isocyanate polyurethanes. European Polymer Journal 87:535–552, 2017.

[2] G. Liu. et al. Synthesis and properties of POSS-containing gallic acid-based nonisocyanate polyu-rethanes coatings. Polymer Degradation and Stability 121:247–252, 2015.


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Thermal properties of polyurethanes modified with starch and hydroxyapatite for medical applications

P. SZATKOWSKI*, K. ORDON, K. PIELICHOWSKA

AGH University of Science and Technology, Faculty of Materials Science and Ceramics

*Corresponding author: e-mail:[email protected] Keywords: thermal analysis, polyurethanes, biomaterials

Among natural polymers, starch is getting an increasing attention due to its nat-ural abundance, biodegradation and low price. Starch is a relatively cheap biopoly-mer and has several advantages, such as biodegradability, biocompatibility and good solubility. The benefits of starch make it a promising raw material in the develop-ment of biodegradable plastics. Due to the presence of large number of hydroxyl groups, starch can be readily combined with other polymers to obtain materials with improved structural and mechanical characteristics [1]. It has been demonstrated that blending of starch with polyurethanes (PURs) can lead to improvements in me-chanical properties of the resultant materials [1-4]. Both the starch and PUR compo-nents play an essential role in controlling the physicochemical properties of the final biocomposites [1, 4].

Starch and hydroxyapatite modified PURs were synthesized by a two-step polymerization reaction between prepolymer and chain extenders at different weight ratio (1,3-propanediol/starch). In order to improve the bioactivity and mechanical properties of the biomaterial, hydroxyapatite was applied as a filler. The obtained PURs were studied by thermogravimetry (TG/DTG), differential scanning calorim-etry (DSC), multi-frequency TMDSC and dynamic mechanical analysis (DMA). The structure of obtained materials was studied by Fourier transformed infrared spectroscopy (FTIR). The observed enhancements in the thermal stability of PURs modified with starch and hydroxyapatite were caused by formation of a cross-linked structure.

Authors are grateful to the Polish National Science Centre for financial support under

the Contract No. UMO-2016/22/E/ST8/00048. References [1] N. L. Tai, M. Ghasemlou, R. Adhikari, B. Adhikari. Starch-based isocyanate- and non-isocyanate

polyurethane hybrids: A review on synthesis, performance and biodegradation. Carbohydrate Polymers. 265: 118029, 2021.

[2] S.S. Chee , M. Jawaid , M. Sultan , O.Y. Alothman , L.C. Abdullah. Accelerated weathering and soil burial effects on colour, biodegradability and thermal properties of bamboo/kenaf/epoxy hy-brid composites. Polymer Testing. 79: 106054, 2019.

[3] K.Ordon, M. Szlachta, P. Szatkowski, K. Pielichowska. Examining the effect of starch and hydrox-yapatite crosslinking on the thermal properties of polyurethane-based biomaterials. Thermo-chimica Acta. 682: 178414, 2019.

[4] M. Ghasemlou, F. Daver, E.P. Ivonova, R. Brkljaca, B. Adhikari. Assessment of interfacial interac-tions between starch and non-isocyanate polyurethanes in their hybrids. Carbohydrate Polymers. 246: 116656, 2020.


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Preparation and thermal properties of a-PHA/PHB blends.

EWA M. SZEFER1*, TOMASZ M. MAJKA1, ADAM SZELIGOWSKI2, OLGA ZA-

STAWNY2, MACIEJ GUZIK2, KRZYSZTOF PIELICHOWSKI1


2 Jerzy Haber Institute of Catalysis and Surface Chemistry Polish Academy of Sciences


Keywords: polyhydroxyalkanoates, a-PHA/PHB, blends, thermal properties

The biodegradable plastics such as poly(3-hydroxyalkanoates) (PHAs) have

attracted considerable research interest recently [1]. In our work the amorphous

PHA:polyhydroxybutyrate (aPHA:PHB) blends were fabricated in two steps: in the

first stage solvent casting method was applied - dissolving the components in chlo-

roform at 55°C and pouring out of the solution. A series of blends was obtained:

60:40%w. aPHA:PHB (60:40); 70:30%w. aPHA:PHB (70:30); 90:10%w. aPHA:PHB

(90:10). The second step was extrusion of the mixtures previously obtained by sol-

vent casting with the mini-extruder. The obtained blends were then tested by ther-

mal analysis methods (TG and DSC) and SEM analysis.

For blends of biopolymers, the thermogravimetric measurements were made in

both inert and oxidizing atmospheres. The reference sample PHB_100 showed the

highest thermal stability under oxidative conditions at the maximum decomposition

at a temperature of about 295℃. On the other hand, the least stable material turned

out to be the PHA_100 sample, for which the DTG curve under the conditions of

an oxidizing atmosphere revealed the second stage of decomposition at a tempera-

ture of about 509℃.

The results of the differential scanning calorimetry analysis allowed to calcu-

lated the degree of crystallinity (xc) for the obtained aPHA/PHB blends. The refer-

ence sample PHB_100 with a value of 38.83% had the highest degree of crystal-

linity among the tested samples. This material showed high brittleness, which may

have been caused by low nucleation density, whereby large spherulites caused

large interspherulite cracks. The blend with the lowest PHB content were charac-

terized by the lowest degree of crystallinity, i.e. the blend with the mass ratio

aPHA:PHB 90:10. Moreover, the analysis showed the decreasing dependence of

the glass transition temperature with the decrease of the amorphous phase content

in the blend. The glass transition temperature for pure aPHA was -55℃ while for

the 90:10 sample it was -58℃.

Acknowledgements: This work was performed under TechMatStrateg program, project No.

TECHMATSTRATEG2/407507/1/NCBR/2019.

References

[1] S. Hong, H. Hsu, M. Ye. Thermal properties and applications of low molecular weight polyhy-

droxybutyrate. Journal of Thermal Analysis and Calorimetry 111, 2: 1243–1250, 2013.


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Reversible bio-aromatic elastomers: Combining lignin with Diels-Alder

chemistry

M. THYS¹,²*, G. VAN ASSCHE¹, R. VENDAMME² AND N. VAN DEN BRANDE¹

1Vrije Universiteit Brussel (VUB), Physical Chemistry and Polymer Science (FYSC)

2Flemish Institute for Technological Research (VITO)


Keywords: Diels-Alder, Lignin, Bio-polymers

The growing awareness of society towards major environmental challenges

pushes the polymer industry to develop greener and more sustainable products. A

way to realize this is to by the replacement of fossil-based building blocks by bio-

based alternatives. Lignin is a promising bio-aromatic resource that could provide

for interesting properties when integrated into polymer resins, or composites. How-

ever, these materials are often limited in their recycling possibilities which restricts

the development of highly sustainable materials. These limitations can be mediat-

ed by the incorporation of reversible covalent bonds.

In this work, self-healable and processable lignin-based elastomers were de-

veloped relying on the thermo-reversible Diels-Alder reaction. An EMK (ethyl me-

thyl ketone) extracted Kraft lignin was modified with furan moieties and inte-

grated in an optimized Diels-Alder formulation based on a furan-modified Jeffam-

ine (F5000) and 1,1'-(methylenedi-4,1-phenylene)bismaleimide (DPBM). Increas-

ing amounts of lignin were added in order to tune the mechanical properties of the

obtained elastomers. The integration of lignin significantly improved the thermal

and mechanical properties of the networks as measured by thermogravimetric anal-

ysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis

(DMA), rheology and stress-strain curves. Moreover, the healing efficiency and

processing opportunities were repeatedly tested and showed promising recycling

and end-of-life options.


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Thermal analysis of novel lanthanide coordination polymers based on

the 2,4-quinolinedicarboxylate linker

RENATA ŁYSZCZEK, DMYTRO VLASYUK

1Maria Curie-Skłodowska University in Lublin, Faculty of Chemistry, Institute of Chemical Sciences,

Department of General and Coordination Chemistry and Crystallography


Keywords: thermal analysis, lanthanides, coordination polymers.

Coordination polymers (CPs) are regarded as very attractive class of inor-

ganic-organic materials due to their promising applications in many fields like:

storage and separation of gases and small molecules, environmental protection for

removal of toxic ions and compounds, chemical sensing, catalysis, biomedicine

and many others [1, 2]. These crystalline metal complexes are constructed from

metal ions or cluster and multidentate bridging ligands such as polycarboxylates.

Building blocks form infinitive one-, two- or three-dimensional polymeric struc-

tures which are very often characterized by the network of pores or channels which

make them new generation of porous materials. The coordination polymers based

on the lanthanides offer not only unusual architectures due to high and variable

coordination number but also unique magnetic and luminescence properties which

make them desirable multifunctional modern compounds [3].

The aim of this work was to demonstrate structural and thermal properties of

novel coordination polymers built up from selected lanthanide ions and 2,4-

quinolinedicarboxylate linker. This ligand is regarded not only as perfect bridging

ligand but also chelating agent what strongly effects its coordination ability. The

investigated complexes were prepared under hydrothermal conditions. The influ-

ence of temperature on final solid products was also determined. The composition

and structural properties were determined by means of following methods: elemen-

tal analysis, ATR-FTIR, PXRD, XRF and XPS. The metal complexes formation

process was additionally studied in-situ with FTIR device. Thermal behaviour of

the obtained lanthanide complexes was investigated by TG-DSC methods in air

while volatile products of decomposition were identified based on the coupled TG-

FTIR technique. These complexes were investigated in detail as luminescent

dopants in hybrid materials based on the polymeric matrices.

References

[1] P. Silva, S. M. F. Vilela, J. P. C. Tome, F. A. Almeida Paz. Multifunctional metal–organic frame-

works: from academia to industrial applications. Chem. Soc. Rev. 44:6774-6803, 2015.

[2] Ch. Janiak, J. K. Vieth. MOFs, MILs and more: concepts, properties and applications for porous

coordination networks (PCNs). New J. Chem. 34:2366-2388, 2010.

[3] W. P. Lustig, J.Li. Luminescent metal–organic frameworks and coordination polymers as alterna-

tive phosphors for energy efficient lighting devices. Coord. Chem. Rev. 373: 116–147, 2018.


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Influence of the bio-based hard segments structure on the thermal, vis-

coelastic and mechanical properties of thermoplastic polyurethane

elastomers

EWA GŁOWIŃSKA¹*, PAULINA PARCHETA-SZWINDOWSKA, JOANNA NIESIO-

BĘDZKA ¹, JANUSZ DATTA¹*

1Department of the Polymers Technology, Chemistry Faculty, Gdansk University of Technology,

Narutowicza St. 11/12, 80-233 Gdansk

*E-mail: ewa.glowinska.pg.edu.pl / [email protected]

Keywords: thermal anlysis, thermoplastic polyurethane elastomers, bio-based hard

segments

Thermoplastic polyurethanes elastomers (TPU) are obtained in the polyaddition

process with the usage of compounds with active hydrogen atom (such polyols

or/and diols) and compounds with isocyanate groups (di- and polyisocyanates).

These polymers are built from hard (HS) and soft segments (SS). The structure of

hard segments influences on mechanical properties, hardness or thermal stability,

while the SS are responsible for such properties like elasticity or hydrolytic and ox-

idative resistance. Increasingly for TPU preparation monomers derived from plants

sources (e.g. vegetable oils or corn) are used.

In this work we investigated the influence of bio-based monomers (created the

hard segments of novel bio-TPUs) on the thermal, viscoelastic and mechanical prop-

erties. Bio-TPUs obtained by two-step method with the use of partially bio-based

diisocyanate, petrochemical-based diisocyanates, bioglycols and selected polyols.

Series of bio-TPUs materials different in molar ratio of isocyanate to hydroxyl

groups were obtained and tested. The thermal stability was determined by TGA, vis-

coelastic properties were investigated by DMA, while mechanical properties in ten-

sile test. In general it was found that the bio-TPUs contained high amount of green

carbon characterized good thermal stability. DMA results indicated on low glass

temperature of soft degments in all prepared bio-TPUs. Depends on the amount of

bio-based monomers in the structure of bio-TPUs the mechanical properites are

changed in board range.

References

[1] E. Głowińska, P. Parcheta, P. Kasprzyk, J. Datta. Chapter: Polyisocyanates from Sustainable Re-

sources// Polyurethane Chemistry: Renewable Polyols and Isocyanates. American Chemical So-

ciety, Pittsburg, 2021.

[2] E. Głowińska, P. Kasprzyk, J. Datta. The Green Approach to the Synthesis of Bio-Based Thermo-

plastic Polyurethane Elastomers with Partially Bio-Based Hard Blocks. Materials. 14:2334,

2021.

[3] E. Głowińska, P. Kasprzyk, J. Datta. Eco-friendly Route for Thermoplastic Polyurethane Elasto-

mers with Bio-based Hard Segments Composed of Bio-glycol and Mixtures of Aromatic–Ali-

phatic and Aliphatic–Aliphatic Diisocyanate. Journal Of Polymers And The Environment, DOI: 10.1007/s10924-020-01992-5, 2021.


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The thermal properties of polyurethanes modified

with functionalized hydroxyapatite

MONIKA SZLACHTA, KINGA PIELICHOWSKA*


Al. Mickiewicza 30, 30-059 Kraków


Keywords: thermal analysis, polyurethanes, hydroxyapatite

The polyurethanes are copolymers of altered arrangement of soft and hard seg-

ments. The soft segments are obtained from the polyol, which impacts on elastomeric

properties of the polymer. The hard segments consist of the urethane linkages. In the

case of the urethane hydrogen bonds, the two segments indicate the ability to the

phase separation. The mechanical and physical properties of polyurethane strongly

depend on hard segments content [1]. One of the problems that are often related to

hydroxyapatite as an additive to the polymer is its poor dispersion in an organic ma-

trix. The surface modification of hydroxyapatite using macrochains improves the

miscibility between organic and inorganic phases [2].

A series of polyurethane materials were prepared with poly(-caprolactone) diol

(PCL) as a polyol, 1,5-pentanediol as chain extender, 1,6-hexamethylene diisocya-

nate (HDI) and chitosan. The series with a different molar ratio of grafted hydroxy-

apatite was prepared. The functionalization of the hydroxyapatite was obtained by

the grafting of poly(ethylene glycol) 2000 to the hydroxyapatite particles by covalent

bonding with 1,6-hexamethylene diisocyanate. Data concerning the morphology and

structure of polyurethane samples were obtained by analyzing their thermal proper-

ties using differential scanning calorimetry (DSC). The differentiation of the extent

of phase transitions associated with the melting point and glass transition tempera-

ture of hard and soft segments confirmed their block structure. Thermal degradation

was studied by thermogravimetry (TG). The chemical structure of synthesized pol-

ymers was confirmed by infrared spectroscopy (FTIR). The samples were character-

ized by scanning electron microscopy (SEM) and EDX analysis.

Acknowledgments

Authors are grateful to the Polish National Science Centre for financial support under the Contract

No. UMO-2016/22/E/ST8/00048. M.Sz. has been partly supported by the EU Project POWR.03.02.00-

00-I004/16.

References

1. Rahman, M.M., H.-D. Kim, and W.-K. Lee, Properties of Waterborne Polyurethane

Adhesives: Effect of Chain Extender and Polyol Content. Journal of Adhesion Science and

Technology, 2009. 23(1): p. 177-193.

2. Włodarczyk, B., et al., Synthesis of hydroxyapatite particles with in situ immobilized

ATRP initiator. Polymer, 2015. 72: p. 348-355.


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Thermal analysis of PHBV/CNC nanocomposites - the effect of biofiller

and its modification with succinic anhydride.

EWA M. SZEFER1*, AGNIESZKA LESZCZYŃSKA1, KRZYSZTOF PIELICHOWSKI1



Keywords: thermal analysis, cellulose nanocrystals, CNC, PHBV, nanocompo-

sites.

Bionanocomposites are an increasing attention due to their advantageous

properties, easy acces to raw materials and the possibility of biodegradation after

service life [1].

An example is the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)

composite with a filler in the form of cellulose nanocrystals (CNC), in which both

the polymer and the filler are of natural origin. The problem that occurs during

processing is the incompatibility of cellulose nanocrystals with hydrophobic poly-

mer matrix. Hence, cellulose nanocrystals are often modified to improve the better

interaction between the matrix and filler.

The work presents the preparation of cellulose nanocrystals by acid hydrolysis

reaction using phosphoric acid (V) and their surface modification by esterification

with succinic anhydride. Composites with PHBV were made using hydrolysed cel-

lulose nanocrystals and modified cellulose nanocrystals. The influence of the filler

type on the mechanical and thermal parameters was evaluated by TG, DSC and

DMA tests.

The samples were subjected to thermal stress relief by DSC to check the effect

on phase transition temperatures and the content of the crystalline phase. Moreo-

ver, selected samples were subjected to the process of thermal relaxation. Thanks

to this treatment, the melting point increased by approx. 5℃ for PHBV composite

with 1% wt. of CNC modified with succinic anhydride. The highest value of the

degree of crystallinity was calculated also for this sample. It was investigated that

thermal relaxation causes an increase in the degree of crystallinity by an average of

about 2% due to recrystallization and relaxation of stresses resulting from pro-

cessing.

The DMA analysis allowed to examine the strength properties of the obtained

materials. The loss modulus was increased for nanocomposites with cellulose

nanocrystals, especially for nanocomposites with 1% wt. modified CNC in the

temperature region below the PHBV glass transition. Such an addition of nanofiller

improves the materials damping ability and its mechanical strength by almost

900 MPa at 20 ℃ in relation to the pristine polymer. This proves that the surface

esterification improves the compatibility of the nanofiller with the PHBV matrix.

References

[1] Kurcok P., Kawalec M., Sobota M., Michalak M., Kwiecień M., Jurczyk S. Polihydroksyalkania-

ny – zastosowanie i recykling. Polimery 62, 5: 364-370, 2017.

[2] …..


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Thermal and mechanical properties of PU-based biocomposites modified with natural cellulose additives

P. SZATKOWSKI¹*, A. LACH¹, K. PIELICHOWSKA1


*Corresponding author: e-mail: [email protected] Keywords: thermal analysis, polyurethanes, cellulose

Polyurethanes (PUs) are linear or crosslinked synthetic polymers that contain

the repeated urethane group [-C-CO-NH-] in their main chain. PUs can be synthe-sized via the polyaddition process of di- or triisocyanates with polyols and hydroxy-terminated chain extenders. The structure of polyurethanes consists of two types of segments called soft and hard segments. The ratio between these segments can be controlled during the manufacturing process. Polyurethanes can be chemically mod-ified in a wide spectrum by using various chain extenders and croos-linking agents.

One of the examples of chain extenders/crosslinkers used in the PUs synthesis are polysaccharides. By incorporating them into PU, the crosslinked biocomposite can be obtained with advantageous mechanical and thermal properties.

Polysaccharides as natural materials are gaining more and more attention now-adays, mostly due to economical and environmental benefits. Natural modifiers are commonly available for a relatively low price. In addition, biocomposites are the solution to the problem of excessive waste and their use leads to independence from non-renewable fossil resources. One of the abundant examples of polysaccharides is cellulose which can be found in natural plant fibers [1,2].

This research is focused on the manufacturing and determination of mechanical and thermal properties of PU-based biocomposites. As additives, natural materials - pineapple leaf fibers and microcrystalline cellulose, were chosen.

The results of mechanical tests showed that both pineapple leaf fibers and mi-crocrystalline cellulose worsened the tensile strength of the material. A different ef-fect of fillers on Young's modulus of biocomposites was observed. The presence of natural modifiers had a positive effect on the thermal properties of the polyurethane matrix. However, it was observed that the fibers containing lignin did not provide the thermal stability enhancements in the fabricated biocomposites.

Authors are grateful to the Polish National Science Centre for financial support under

the Contract No. UMO-2016/22/E/ST8/00048. References [1] Vivek, S., Kanthavel, K., Torris, A. et al. Effect of Bio-filler on Hybrid Sisal-Banana-Kenaf-Flax

Based Epoxy Composites: A Statistical Correlation on Flexural Strength. J Bionic Eng 17, 1263–1271 2020.

[2] Balla, V. K., Kate, K. H., Satyavolu, J., Singh, P., Tadimeti J. G. D. Additive manufacturing of natural fiber reinforced polymer composites, processing and prospects. Composites Part B: En-gineering, 2019, 174, 106956, 2019.


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Glass transition temperature changes of plasma modified polymer films

R. JANÍK1*, M. KOHUTIAR2, M. PAJTÁŠOVÁ1, K. MORICOVÁ1

1Faculty of Industrial Technologies in Púchov,

Alexander Dubček University of Trenčín, Slovak Republic 2Faculty of Special Technology,

Alexander Dubček University of Trenčín, Slovak Republic


Keywords: dynamic mechanical analysis, polymer foil, glass transition

temperatures, DCSBD plasma discharge

Dynamic mechanical analysis is a sensitive and accurate thermal method for mate-

rial testing. This analysis is widely used, e.g., in the study of nanocomposites [1]

but also viscoelastic materials in the form of foam [2] or film/foil [3, 4]. The pre-

sent study observes changes in the polymer film after its exposure to a low-

temperature DCSBD plasma discharge type. The study presents new information

obtained from the plasma-chemical modification process of a polymer film, ob-

tained with a wide variability of this modification. The plasma-chemical treatment

process of a material is considered to be a process that modifies the materials sur-

faces but based on the change in the range of the glass transition temperature, it can

be determined that this modification also caused changes in the material itself.

References

[1] A. Leszczynska, K. Pielichowski. Application of thermal analysis methods for characterization

of polymer/montmorillonite nanocomposites. J Therm Anal Calorim 93, 677–687 (2008). [2] G.Z. Papageorgiou, A. Palani, D. Gilliopoulos, et al. Mechanical properties and crystallization

of high-density polyethylene composites with mesostructured cellular silica foam. J Therm Anal

Calorim 113, 1651–1665 (2013).

[3] M. Teixeira, I. Del Hoyo, F. Wandrowelsti, et al. Evaluation of thermal degradation in isotactic

polypropylene films used in power capacitors. J Therm Anal Calorim 130, 997–1002 (2017).

[4] A.N. Frone, D.M. Panaitescu, I. Chiulan, et al. Thermal and mechanical behavior of biode-

gradable polyester films containing cellulose nanofibers. J Therm Anal Calorim 138, 2387–

2398 (2019).


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SESSION 5:

MATERIALS SCIENCE

AND ENERGY


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Assessment on the thermal and moisture migration of sand-based ma-

terials coupled with different additives

BIN LIANG1,2, MEIQIAN CHEN1,2*, JUNLI GUN1,2





The thermal and moisture diffusion and soil water diffusivity in sand-based

backfill materials were evaluated. Compared with sand, the thermal conductivity of

the sand/kaolin and sand/kaolin/graphite blends (5% blending percentage each) with

10% moisture content increased by 9 and 17%, respectively. The average values for

the soil water diffusivity of the sand/kaolin and sand/kaolin/graphite blends reduced

by 68 and 84%, respectively, compared with the sand. Based on the unsteady heat

conduction differential equation, the average apparent thermal diffusivity of the

sand/kaolin blend increased by 7% compared with the sand, and that for the sand/ka-

olin blend rose by 173% with adding the graphite. The main moisture effect range

of in sand/kaolin blend was about 2/5 of the sand. The thermal diffusion in sand was

prompted by kaolin additive, which could be further highly improved after adding

graphite. Kaolin and graphite could be available additives against the moisture mi-

gration in the sand-based backfill material.

Keywords: thermal and moisture diffusion, soil water diffusivity, apparent thermal

diffusivity, sand, kaolin


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Effect of gamma radiation and thermal ageing on the residual stability

of polyethylene cable insulation

ZUZANA CIBULKOVÁ¹*, ANNA VYKYDALOVÁ1, PETER ŠIMON1, TIBOR DUBAJ1

1Slovak University of Technology, Faculty of Chemical and Food Technology


Keywords: residual stability, ageing, radiation, polyethylene

Materials such as polymers are commonly used in specific environments, for

example in nuclear power plants, where they are most often affected by radiation

and higher temperatures. Thus, their stability should be tested to assess their life-

time under these specific conditions [1]. Thermooxidative degradation of polymers

usually occurs in two steps: induction period (IP) and oxidation itself [2]. The end

of the IP is characterized by a sudden change of material properties. Therefore, the

length of the IP is frequently considered as a measure of the material stability [2].

Since the oxidation is an exothermic process, methods of thermal analysis can be

used for its study.

In this work, the stability of cable insulation made of low density polyethylene

with catalyst masterbatch after gamma radiation, thermal ageing and their combi-

nation using non-isothermal DSC measurements has been studied. The kinetic pa-

rameters describing the induction period were obtained from the dependence of the

onset oxidation temperature on the heating rates using isoconversional analysis

with the Berthelot-Hood temperature function. From the kinetic parameters the

lengths of IPs and subsequently the residual stabilities have been calculated.

Acknowledgement

Financial support from the Slovak Research and Development Agency (APVV-15-

0124) is gratefully acknowledged.

References

[1] V. Plaček, B. Bartoníček. The dose rate effect and the homogeneity of radio-oxidation of plastics.

Nucl. Instrum. Methods Phys. Res. B, 185: 355–359, 2001.

[2] P. Šimon. Induction periods: Theory and applications. J. Therm. Anal. Calorim. 84:263-27, 2006.


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Pyrrolidinium-based ionanofluids of substantially improved

thermal conductivity and thermal stability

JUSTYNA DZIADOSZ1, BERTRAND JÓŹWIAK2, GRZEGORZ DZIDO3, EDWARD

ZORĘBSKI1, KRZYSZTOF CWYNAR1, ADRIAN GOLBA1, ŁUKASZ SCHELLER1,

ANNA KOLANOWSKA2, RAFAŁ JĘDRYSIAK2, HEATHER F. GREER4,

SŁAWOMIR BONCEL2*, MARZENA DZIDA1*

1University of Silesia in Katowice, Institute of Chemistry

2Silesian University of Technology, Department of Organic Chemistry, Bioorganic

Chemistry and Biotechnology 3Silesian University of Technology, Department of Chemical and Process Engineering

4University of Cambridge, Department of Chemistry

*Corresponding authors: e-mails: [email protected], [email protected]

Keywords: ionanofluids, thermal conductivity, thermal stability

The ionanofluids (INFs) as the stable dispersions of nanoparticles in ionic liq-

uids [1] are characterized by improved thermal conductivity, high thermal stability,

and non-flammability. Therefore, they can be tested as potential working fluids in

novel electronic, heating, and cooling devices, along with coating materials.

This work focuses on proving the influence of different length to diameter ra-

tio (aspect ratio) of multi-walled carbon nanotubes (MWCNTs) on thermal conduc-

tivity and thermal stability of INFs by testing systems composed of selected

MWCNTs with aspect ratio of 150 and 11000 and 1-butyl-1-methylpyrrolidinium

bis(trifluoromethylsulfonyl)imide [C4C1pyr][NTf2]. Moreover, we have experimen-

tally determined the actual thickness of interfacial nanolayer in INFs by applying

the unique transmission electron cryomicroscopy (cryo-TEM).

This research shows that the addition of 1 wt% MWCNTs with aspect ratio of

150 and 11000 into the [C4C1pyr][NTf2] leads, as previously [2], to moderate and

substantial increase of thermal conductivity by 14.2% and 40.8% at 298.15 K, re-

spectively. The over one year sedimentation stability of INFs at different tempera-

ture conditions (295.15 K and 353.15 K), as well as the high decomposition offset

temperatures, were also detected.

This work was financially supported by the National Science Centre (Poland)

Grant No. 2017/27/B/ST4/02748. HFG thanks the EPSRC Underpinning Multi-

User Equipment Call (EP/P030467/1) for funding the TEM.

References

[1] A. P. C. Ribeiro, M. J. V. Lourenço, C. A. Nieto de Castro. Thermal Conductivity of Ionanofluids.

17th Symposium on Thermophysical Properties, Boulder, USA, 2009.

[2] B. Jozwiak, G. Dzido, E. Zorebski, A. Kolanowska, R. Jedrysiak, J. Dziadosz, M. Libera,

S. Boncel, M. Dzida. Remarkable Thermal Conductivity Enhancement in Carbon-Based

Ionanofluids: Effect of Nanoparticle Morphology. ACS Appl. Mat. Interf. 12:38113–38123, 2020.


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Crystal-chemical and thermal properties of decorative cement composites

V. PETKOVA1*, V. STOYANOV2,3, B. KOSTOVA4, VL. KOSTOV-KYTIN1,

AL. KALINKIN5, I. ZVEREVA6, Y. TZVETANOVA1

1Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, 2University of Structural Engineering and Architrcture (VSU) „Lyuben Karavelov“,

3Academy of the Faculty of Fire safety and civil protection, 4New Bulgarian University, Department of Natural Sciences,

5Tananaev Institute of Chemistry and Technology of Rare Elements and Mineral Raw Materials, Kola Science Centre of the Russian Academy of Sciences,

6Center for Thermal Analysis and Calorimetry, Research Park, St. Petersburg State University, *Corresponding author: e-mail: [email protected]

Keywords: Portland cement, marble powder, zeolite, crystal and thermal properties

The advanced tendencies in building materials development are related to the

design of cement composites with a reduced amount of Portland cement, contrib-uting reduced CO2 emissions, sustainable development of used non-renewal raw ma-terials, and decreased energy consumption. This work deals with water cured for 28 and 120 days cement composites: Sample A (reference) - white Portland cement and cement replacement material - marble powder; Sample B - white Portland cement, marble powder and zeolite as an additive; Sample C - of the same composition with polycarboxylate-based water reducer.

By powder X-ray diffraction and FTIR spectroscopy, the redistribution of CO3

2-, SO42-, SiO4

4-, AlO45-, and OH- (as O-H bond in structural OH- anions and O-

H bond belonging to crystal bonded water molecules) from raw minerals to newly formed minerals have been studied, and the scheme of samples hydration has been defined. By thermal analysis, the ranges of sample decomposition mechanism were distinct: dehydration, dehydroxylation, decarbonation, and desulphuration. Using mass spectroscopic analysis of evolving gases during thermal analysis, the reaction mechanism of samples thermal decomposition has been determined. These results have both practical (architecture and construction) and fundamental (study of archae-ological artifacts as ancient mortars) applications.

Funding.This work was supported by the Operational Program "Science and Education for In-

telligent Growth", co-financed by the European Union through the European Structural and Investment Funds under grant BG05M2OP001-1.001-0008 of National Centre for Mechatronics and Clean Tech-nology (V.P. and Vl. K.-K.), by the Bulgarian Science Research Found under grant KP-06-N39/9 (B.K.,V.S.) and by the Bulgarian Science Research Found under grant KP-06-N39/9 (B.K., V.S.).

Acknowledgements.The authors acknowledge the technical support from the project PERIMED BG05M2OP001-1.002-0005 /29.03.2018 (2018–2023), of the Department of Natural Sciences, Labor-atory of Geology -BF at NBU (B.K.) and of Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences (K2-V.P., Vl.K.-K., Y. Tz.).


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The effect of nano additives on calcium aluminate cement hydration

and structure formation of binder

R.BORIS1*, V. ANTONOVIČ1, J. MALAIŠKIENĖ1, R. STONYS1

1Vilnius Gediminas Technical University, Institute of Building Materials


Keywords: thermal anlysis, calcium aluminate cement (CAC), hydration, nano ad-

ditives, calorimetry, microstructure, XRD

In this work, the hydration of calcium aluminate cement (CAC, Al2O3>70%)

binder mixtures with nano additives (0%, 0.1% and 0.2%) of nano silica (NS) and

nano cones (NC), when W/CAC=1 was investigated. The methods of calorimetry,

thermal analysis, X-ray diffraction (XRD) and scanning electron microscopy (SEM)

were used. SEM and XRD analysis tests were also carried out for binder after it

thermal treatment at the temperatures of 800°C and 1000°C. NS was found to short-

ens the induction period of the CAC hydration and accelerates the time of the sec-

ondary heat release effect, especially in specimens with the highest content of NS.

An incorporation of NC (up to 0.2%) slowing down the hydration process. Addition,

it has been found that after 3 days of hydration were formed such crystalline hydra-

tion products: C2AH8, CAH10 and AH3 hydrate is formed in the CAC binder with

nano additives. Compared with the control group, the peak heights of hydrates and

cement minerals differed. However, the SEM results obtained show differences in

the effect of NS and NC on the formation of the structure of binder during its hard-

ening and after thermal treatment in high temperatures. Significant changes in CAC

binder microstructure caused by the added 0,2% of the NS and NC additives. The

results of XRD analysis showed that, after thermal treatment at the temperature of

1000°C the reactions in solid state materials proceed and as a result the intensity of

the diffraction maximum of mineral C12A7 are increasing in CAC binder with NC,

while those of minerals – CA and CA2 are decreasing.


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Thermoregulating gypsums by using NPCM slurry.

DANIEL LÓPEZ PEDRAJAS¹*, ANA M. BORREGUERO SIMÓN¹, I. GARRIDO

SÁENZ2, M. JIMÉNEZ VÁZQUEZ, F. J. RAMOS MELLADO¹, J. F. RODRÍGUEZ

ROMERO¹, M. CARMONA FRANCO¹

1University of Castilla-La Mancha, Deparment of Chemical Engineering, Institute of Chemical and

Environmental Technology. Ciudad Real, Spain. 2University of Castilla-La Mancha, Deparment of Applied Mechanics and Engineering Projects,

School of Architecture. Toledo, Spain.


Keywords: PCM, slurry, nanocapsule, gypsum, thermal properties, mechanical

properties, physical properties

The high and quick growing energy demand in the world can result in depletion

of resources, supply difficulties and destructive environmental impacts, all these

facts are promoting the development and use of sustainable enery resources. Solar

power is considered one of the most promising renewable energy due to its zero cost,

abundance, and lack of emissions [1]. However, the intermittency of the solar energy

is an important limitation that forces to storage it in order to achieve a constant sup-

ply. Latent heat storage (LHS) is once of the promising thermal energy storage tech-

nologies for building applications. The materials used for the LHS are known as

phase change materials (PCMs) [2]. In recent years, the efforts are focused on ob-

taining submicron- and nanocapsules of PCM (NPCM), since the smaller the cap-

sules, the higher the surface area, improving the heat transfer.

In view of the foregoing, a highly concentrated NPCM slurry (NPCS) was de-

veloped and applied to obtain gypsum composites with thermoregulating properties.

The NPCS presented low viscosity (62.4 mP s-1 at 20 ºC and 680 s-1 of share rate),

high solid concentration (38.5 %) and stability and long-term shelf life (- 53.5 mV

of potential Z). The NPCM had a poly(styrene-divinylbenzene) shell and wax Ru-

bitherm®RT27 (RT27) core and presented a dn0.5 = 78.7 nm and dv0.5 = 117.7 nm

with 99.5 J g-1 of latent heat. This translates in a PCM content of 59.1 % in the NPCM

and reaction yield towards capsules of 95.8 %.

Gypsum composites made of NPCM/hemihydrate with mass ratios ranging from

0 to 0.41 have been produced from the NPCM. This addition reduced the mechanical

properties, and the apparent and real density of the materials. Nevertheless, the ther-

mal properties of the gypsum improved with the addition of the NPCM. The

NPCM/gypsum composite presented a considerably larger accumulative energy

(around 45 J g-1) in comparison with gypsum blocks (around 17 J g-1), achieving an

increment in the thermal storage capacity from 1.1 to 3.6 J g-1 ºC-1 without any in-

crease in the thermal conductivity with the NPCM. References

[1] V. Siva Reddy, S. C. Kaushik, K. R. Rnajan, S. K. Tyagi. State-of-the-art of solar thermal power

plants – A review. Renew. Sustain. Energy Rev. 27:258-273, 2013.

[2] A. M. Khudhair, M. M. Farid. A review on energy conservation in building applications with ther-

mal storage by latent heat using phase change mateirals. Energy Convers. Manag. 45:263-275. 2004.


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Tuning the CO2 adsorption properties by using different adsorbents

I.BEURROIES¹*, G. LANDETTA AVELLENA², L . EL HANACHE,

1Aix Marseille Universié, CNRS, MADIREL,


Keywords: microcalorimetry, adsorption, hydrophobicity

The consumption of fossil fuels has caused catastrophic climatic effects on the whole

planet since, CO2, one of the main greenhouse gases, is produced during combustion

processes. Thus, adsorption on porous materials may be a good alternative for

storage and recovery of CO2. However, this process is often limited by the presence

of water vapor in the gas streams leading to a decrease in the adsorption capacities

in the porous material.

In this study, we were interested in controlling the hydrophobicity of porous

adsorbents used for CO2 capture to optimize the competition with H2O adsorption.

In order to promote CO2 adsorption, H2O adsorption should be limited and moreover

it is possible to take advantage of the displacement by H2O molecules for rising CO2

recovery.

This study focuses on the main families of adsorbents such as zeolites, mesoporous

silicas, activated carbons and MOFs. The textural characterization of these materials

is carried out by various techniques such as nitrogen absorption manometry,

thermogravimetric analysis among others. In order to assess the performance of these

different materials, CO2 adsorption manometry coupled with Tian Calvet

microcalorimetry makes it possible to determine the amount of CO2 adsorbed and

the energies involved during adsorption.

The study first focuses on an activated carbon which is a microporous and

hydrophobic material. The adsorption results are valuable in terms of CO2 adsorption

capacities and the enthalpy of adsorption profile indicates that the adsorption takes

place in an quite energetically homogeneous manner over the entire surface. At the

same time, water adsorption experiments have shown that water is less adsorbed than

CO2 at low vapor pressures but then CO2 might be displaced at higher relative pressures.

Similar experiments are carried out on ZIF-8, an hydrophobic Metal Organic

Framework with a zeolitic microporous structure, and on mixtures with activated

carbon. The results highlight the possibility to modulate the competition between

water and CO2 and to facilitate the desorption of CO2.

The perspective is to ensure a good capture of CO2 from the polluted atmosphere and

then improve the regeneration of the adsorbent while recovering the CO2 which

constitutes a new source of energy.


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Microcalorimetric study on compounds of the MgO-Al2O3, CaO-MgO-

Al2O3 and CaO-MgO-Al2O3-SiO2 systems hydration in the aspect of

smart refractory castable matrix

KARINA WARMUZ¹*, JAKUB RAMULT¹, DOMINIKA MADEJ1

1AGH University of Science and Technology,

Faculty of Materials Science and Ceramics,

Department of Ceramics and Refractories

al. Mickiewicza 30, 30-059 Kraków

* Corresponding author: e-mail: [email protected]

Keywords: Thermal analysis, Microcalorimetry, Hydraulic binder, Hydration of

reactive nano- or micro-powders

Hydraulically bound refractory castables, which are used to perform monolith-

ic linings in thermal devices in the steel industry and others, are playing an increas-

ingly important role in the refractory industry. Innovative refractory materials are

developed in accordance with the idea of sustainable development, especially in

terms of designing and obtaining a refractory material that will be an alternative to

the currently produced shaped corundum-spinel refractories, in which the ceramic

structure is formed during the firing of the material.

In recent years, low-cement, ultra-low-cement and no-cement castables have

been dynamically developed and widely used in the refractory industry. Designing

the castable matrix through the reduction in the amount of calcium aluminate ce-

ments (CACs) and introducing the deflocculants and/or magnesium oxide lead to

improve the selected properties. Additionally, hydration of the reactive Al2O3 and

MgO leads to obtain magnesium aluminate hydrates (MAH phase; M=MgO,

A=Al2O3, H=H2O) which at elevated temperature convert to MgAl2O4, providing

the strong ceramic bonding also. Due to this facts, it essential to conduct research

on the hydration of smart binders which can be used in refractory industry.

The aim of this work was to examine hydration behavior of binders composed

of CAC with and without deflocculants or magnesium oxide and the hydratable

micro- or nano-powders of MgO and Al2O3 as cementitious systems for refractory

castables. The hydration behavior of each binders was investigated and compared

using heat flow calorimetry, DTA-TG-EGA(MS), XRD and FT-IR.

Acknowledgements

This study was partially supported by The National Centre for Research and De-

velopment within the framework of LIDER VIII project

No.LIDER/5/0034/L8/16/NCBR/2017 and Initiative for Excellence – Research

University - project entitled " Modelling of the properties of refractory corundum

castables in the aspect of castable ceramic bond modification with compounds with

a specific thermal expansion coefficient "


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Structural and Thermal characterization of Late Antiquity mortars

from the area of Gorno Novo Selo village, Bulgaria

B. KOSTOVA1, V. PETKOVA2*, V. STOYANOV3,4, B. DUMANOV5, B. ZLATEVA6

1New Bulgarian University, Department of Natural Sciences,

2“Acad. Iv. Kostov” Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, 3University of Structural Engineering and Architrcture „Lyuben Karavelov“

4Academy of the Faculty of Fire Safety and Civil Protection, 5New Bulgarian University, Department of Archaeology,

6University of Sofia, Faculty of Chemistry and Pharmacy, Department of Analytical Chemistry


Keywords: late antiquity mortar, archaeological chemistry, Thermal analysis

The structural and thermal characterization of ancient mortar presents new

knowledge for the surrounding environment and production technology.

This research aims to provide data about the raw materials used and techniques

of production applied. The investigated sample is from the Late Antiquity fortified

settlement near Gorno Novo Selo village (Bulgaria). The determination of structural

and thermal characterization of mortar was made by Thermal analysis, X-Ray Fluo-

rescent analysis (XRF), powder X-ray diffractometry (PXRD), and Fourier Trans-

form infrared spectroscopy (FTIR). The phase composition is of quartz, calcite, mus-

covite, and albite. Their thermal decomposition has been detected in the temperature

intervals RT-300°C and 700-900°C. Using thermal analysis has been determined the

most significant characteristic of the mortar (binder component) - hydraulicity index.

The obtained data are of fundamental importance (new knowledge about the

mentioned archeological period) and practical application (restoration).

Funding. This work was supported by the Operational Program "Science and Education for

Intelligent Growth", co-financed by the European Union through the European Structural and Invest-

ment Funds under grant BG05M2OP001-1.001-0008 of National Centre for Mechatronics and Clean

Technology (V.P.), by the Bulgarian Science Research Found under grant KP-06-N39/9 (B.K., V.S.,

B.D., B.Z.-R.)

Acknowledgements. The authors acknowledge the technical support from the project PERIMED

BG05M2OP001-1.002-0005 /29.03.2018 (2018–2023), of the Department of Natural Sciences, Labor-

atory of Geology - BF at NBU (B.K.) and of Institute of Mineralogy and Crystallography, Bulgarian

Academy of Sciences (K2-V.P.).


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Thermal analysis as a tool to compare the effect of mineral additions on

the calcium aluminate cement conversion

M. NOWACKA¹, B. PACEWSKA¹*

1Warsaw University of Technology, Faculty of Civil Engineering, Mechanics and Petrochemistry,

Institute of Chemistry, Łukasiewicza 17 St., 09-400 Plock, Poland


Keywords: thermal anlysis, calcium aluminate cement, aluminosilicate addition,

hydration, conversion

Among many available investigation techniques of materials and processes the

thermal analysis including thermogravimetry/differential thermogravimetric analy-

sis (DTG), differential thermal analysis (DTA) and differential scanning calorime-

try (DSC) is a very usuful and a popular method to qualitative and quantitative re-

search of building materials [1].

In this work the TG/DTG method was applied to compare the effect of two

kinds of mineral addition on the calcium aluminate cement conversion over time at

different temperatures. The transformation of thermodynamically metastable hy-

drates of calcium aluminate to stable hydrogarnet in presence of two structurally

different aluminosilicates in comparison to reference sample of neat cement paste

was estimated by the calculation way presented in our previous work [2].

Based on the obtained results it was found that both the aluminosilicates can

reduce the conversion degree however the active effect of the studied additions on

the conversion of calcium aluminate cement is strictly temperature-dependent and

some differences between the influence of these aluminosilicates occur [3].

References

[1] V.S. Ramachandran, R.M. Paroli, J.J. Beaudoin, A.H. Delgado. Handbook of thermal analysis of

construction materials. Noyes Publications, William Andrew Publishing, New York 2002.

[2] B. Pacewska, M. Nowacka. Studies of conversion progress of calcium aluminate cement hydrates

by thermal analysis method, J Therm Anal Calorim. 117:653–660, 2014.

[3] M. Nowacka, PhD thesis, Warsaw University of Technology, Faculty of Chemistry, Warsaw 2015

(in Polish).


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Multicomponent Portland-cement based compositions for geothermal

wells

E. KUZIELOVÁ1,2*, M. SLANÝ1,3, M. ŽEMLIČKA1, M.T. PALOU1,2

1Institute of Construction and Architecture, Slovak Academy of Sciences

2Faculty of Chemical and Food Technology, Slovak University of Technology 3Institute of Inorganic Chemistry, Slovak Academy of Sciences


Keywords: thermal anlysis, FTIR, XRD, geothermal wells, silica fume,

metakaolin, blast furnace slag

Two or three additives (silica fume, metakaolin, granulated blast furnace slag)

in the total amount of 30 mass% were used for partial substitution of Portland

cement class G and submitted to hydrothermal treatment at 150 °C and 18 MPa for

7 days. A combination of thermogravimetric, X-ray diffraction, and Fourier

transform infrared analyses in the mid-IR region was used to overcome the

shortcomings of individual techniques for the investigation of high-temperature

phase formation. Morphology of developed crystalline phases was studied by

scanning electron microscopy and compressive strength measurements were per-

formed to assess the mechanical properties.

The phase composition of the samples after hydrothermal treatment as well as

their mechanical properties depended on the amount and properties of the used

additives. In the samples prepared without their addition, the transformation of

primary hydration products to α-C2SH was determined, which led to the lowest

values of compressive strength. On the contrary, the highest amount of thermally

stable amorphous C-S-H and C-A-S-H phases was formed owing to the synergic

effect of silica fume and metakaolin. Following the higher quantity of Al3+ and

hydrothermal conditions, hydrogrossular phases, hibschite and katoite, were

formed. The decrease of the CaO/SiO2 ratio resulted in the formation of thermally

stable tobermorite. In the case of partial cement substitution by slag, its lower reac-

tivity led to the formation of the lower amount of stable hydration products, which

partially transformed to α-C2SH. The values of compressive strength of corre-

sponding samples therefore decreased.


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Composite rigid polyurethane foams modified with fluidized-bed combustion fly ash and microspheres as potential thermal insulating

materials ANNA MAGIERA¹*, MONIKA KUŹNIA1, BEATA ZYGMUNT-KOWALSKA1, PIOTR

SZATKOWSKI2, MAGDALENA ZIĄBKA3, WOJCIECH JERZAK1

1AGH University of Science and Technology, Faculty of Metals Engineering and Industrial Computer

Science, Department of Heat Engineering and Environment Protection

2AGH University of Science and Technology, Faculty of Materials Science and Ceramics, Depart-ment of Biomaterials and Composites

3AGH University of Science and Technology, Faculty of Materials Science and Ceramics, Depart-ment of Ceramics and Refractories

*Corresponding author: e-mail: [email protected] Keywords: rigid polyurethane foam, fly ash, microspheres, composite materials

One of the most popular and commonly used polymeric material is rigid poly-

urethane foam (RPUF). It is used mainly in building and construction industry, due to its low thermal conductivity. Its good performance properties i.e. low apparent density, chemical resistance, good thermal and mechanical characteristics [1-3], resulted in more widespread usage of RPUF in other industries.

In this study composite RPUF were prepared, using two types of fillers: fly ash (FA) from fluidized bed combustion (FBC), and microspheres (M) which were the separated fraction of FA. Conventional FA is often used in different industrial ap-plications but most of FA from FBC remains unused. Microspheres represent val-ued performance properties, including low density, thermal and mechanical stabil-ity, hydrophobicity. Considering all this, FA and M consist a cheap, potential filler and flame-retardant in RPUF production. This work described influence of afore-mentioned fillers, and their concentration, on RPUF physical and performance properties. Composite RPUF characteristics, which were under investigation, were: polyurethane cellular structure, mechanical properties, thermal properties and thermal stability. Acknowledgements This work was supported by the Ministry of Science and Higher Education, Poland [grant AGH-UST no 16.16.110.663].

References [1] Y. Zhou, R. Bu, L. Yi, J. Sun. Heat transfer mechanism of concurrent flame spread over rigid

polyurethane foam: effect of ambient pressure and inclined angle. Int. J. Therm. Sci. 155: 106403, 2020.

[2] M. Stanzione, V. Russo, M. Oliviero, L. Verdolotti, A. Sorrentino, M. Di Serio, R. Tesser, S. Iannace, M. Lavorgna. Synthesis and characterization of sustainable polyurethane foams based on polyhydroxyls with different terminal groups. Polymer 149:134–145, 2018.

[3] J. Pagacz, E. Heb da, S. Michałowski, J. Ozimek, D. Sternik, K. Pielichowski. Polyurethane foams chemically reinforced with poss—thermal degradation studies. Thermochim. Acta 642:95–104, 2016.


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Hydration heat of white cement

JANA ČEPČIANSKA, JANETTE DRAGOMIROVÁ1, EVA KUZIELOVÁ1,2, MARTIN PALOU1,2, MATÚŠ ŽEMLIČKA1 AND RADOSLAV NOVOTNÝ3

1Institute of Construction and Architecture, Slovak Academy of Sciences, Dúbravská cesta 9, SK–845 03 Bratislava, Slovak Republic.

2Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, SK–812 37 Bratislava, Slovak Republic.

3Materials Research Centre, Faculty of Chemistry, Brno University of Technology, Purkyňova 118, CZ–612 00 Brno, Czech Republic.

[email protected]

Keywords: Self-Compacting mortars, White cement, Supplementary cementitious materials, hydration, rheology

The hydration of White Cement Composites (White Cement-Blast Furnace Slag, White Cement-Ground Limestone, and White Cement-Blast Furnace Slag- Ground Limestone) was investigated by conduction calorimeter and thermogravimetric analysis to design Self-Compacting Mortars (SCM). White Portland cement was replaced by supplementary cementitious materials at different seven substitution levels from 5% to 35% with each increment of 5. When the level of substitution is up to 25 %, the composites undergo the hydration behaviors similar to those of OPC. At level substitution of 30-35 %, a third peak, which intensity depends on substitution level appears. The Self-Compacting mortars were developed using White Cement (WC) and two composites ternary system (WC-BFS-GL) at ratios 65:5:20 and 65:20:25. Fresh properties of SCM were investigated using Slump-flow test and V-funnel to determine flowability and viscosity (assessed by rate of flow) of binders according to the European Guidelines for Self-Compacting Concrete [1]. Conclusion

The hydration of White cement and its composites was studied through conduction calorimeter and thermogravimetric analysis. Finely Ground Limestone and Blast Furnace Slag with the same substitution levels have similar influence on the hydration of white cement. Self-Compacting mortars of viscosity class VF2 was prepared. Mechanical and physical properties are related to the material composition. ACKNOWLEDGEMENTS This work was supported by courtesy of APVV-19-0490, APVV-15-0631, Slovak Grant Agency VEGA No. 2/0032/21 and 2/0017/21, and The Czech Science Foundation No. GA19-16646S. Also, authors express their thankful to APVV SK-KR-18-0006. References [1] The European Guidelines for Self-Compacting Concrete Specification, Production and Use.2005:

80;129–137.


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Mechanical activation of fly ash-cement mixtures

IWONA WILIŃSKA¹*, BARBARA PACEWSKA1, ANDRZEJ OSTROWSKI2

1 Warsaw University of Technology, Faculty of Civil Engineering, Mechanics and Petrochemistry

2 Warsaw University of Technology, Faculty of Chemistry *Corresponding author: e-mail: [email protected]

Keywords: cement, fly ash, high volume fly ash binders, activation, hydration

It is well known that cement industry emits large amounts of CO2, thus reduction

of cement clinker production and replacing cement with another alternative binder

are highly desirable. One of the possibility to make cement production more envi-

ronmentally friendly is using fly ash as cement component. Fly ash exhibits poz-

zolanic activity. It means that it can react with Ca(OH)2 in the presence of water,

forming phases having binding properties: C-S-H and C-A-S-H (abbreviations used

in cement chemistry: C – CaO, S – SiO2, A – Al2O3, H – H2O). The more fly ash is

used, the lower is the amount of cement clinker in the mixture and the more eco-

friendly the binder can be. However, the more fly ash, the lower is the amount of

Ca(OH)2 needed for pozzolanic reaction, the slower is the hardening, the later is the

initial setting time and the compressive strength development is slower. As a result,

without taking action to improve the properties of the very high volume fly ash mix-

tures, their practical application is very limited and they cannot replace cement.

There are different methods of activation of the high volume fly ash systems [1].

Mechanical activation is one of them. Interesting results were obtained by grinding

the mix containing fly ash and Portland cement [1,2]. Research results of chemical

activation by Na2SO4 and Ca(OH)2 were discussed recently in the paper [3].

The aim of this work is to investigate mechanical activation of fly ash-cement

mixtures containing 80wt.% of fly ash and 20wt.% of Portland cement. The influ-

ence of the time of grinding on intensity of hydration processes and structure of

hardened material will be discussed.

References

[1] I. Wilińska, B. Pacewska, Influence of selected activating methods on hydration processes of mix-

tures containing high and very high amount of fly ash. A review. J. Therm. Anal. Calorim., 133:823–843, 2018.

[2] I. Wilińska, B. Pacewska, Zastosowanie kalorymetrii we wstępnych badaniach aktywowanych mie-

szanek popiołowo-cementowych. Przemysł Chemiczny, 96:761–765, 2017.

[3] I. Wilińska, B. Pacewska, A. Ostrowski, Investigation of different ways of activation of fly ash–cement mixtures. Part 1. Chemical activation by Na2SO4 and Ca(OH)2. J. Therm. Anal. Calorim.,

138:4203–4213, 2019.


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Thermoluminescence properties of CeO2 doped borosilicate glass

SZYMON ŚWIONTEK¹*, MARCIN ŚRODA¹


*Corresponding author: e-mail: [email protected] Keywords: borosilicate glass, glass-ceramics, thermoluminescence (TL), thermal stability, high-energy radiation

The aim of the study was to develop a new BaO-B2O3 glass and glass-

ceramics with CeO2 dopant and to characterize a volume effect of cerium ions on the thermal stability and luminescence properties [1]. The effect of SiO2 con-tent on the efficiency of the thermoluminescence process was investigated. The study revealed that up to 20 mol% SiO2 no phase separation appears due to the high content of Ba and Ce modifiers [2]. The results confirm that the gradual in-troduction of SiO2 into the borate glass lowers the efficiency of the lumines-cence processes [3]. However, it enhances the thermal stability and reduces ΔH of crystallization. As a result, the glass-ceramics exhibited the thermolumines-cence (TL) efficiency which is comparable with commercial crystalline materi-als [4].

Acknowledgements This research has been supported by the EU Project POWR.03.02.00-00-I004/16 and financed by the Polish Ministry of Science and Education – the subsidy no 16.16.160.557. References [1] M. Środa, S. Świontek, W. Gieszczyk, P. Bilski, The effect of CeO2 on the thermal stability, struc-ture and thermoluminescence and optically stimulated luminescence properties of barium borate glass, Journal of Non-Crystalline Solids 517 (2019) 61-69. [2] S. Świontek, J. Adamczyk, M. Środa, P. Bilski, Optically active borate glasses doped with cerium in the range of high-energy radiation, Ceramic Materials 70 (2018) 116-121. [3] S. Świontek, M. Środa, The effect of SiO2 on the thermal stability and thermoluminescence prop-erties of barium-cerium borate glass and glass-ceramics, Journal of Non-Crystalline Solids 559 (2021) 120708. [4] M. Środa, S. Świontek, W. Gieszczyk, P. Bilski, The effect of lithium fluoride on the thermal sta-bility and thermoluminescence properties of borosilicate glass and glass-ceramics, Journal of the European Ceramic Society 40 (2020) 472–479.


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Near surface viscosity in amorphous chalcogenides

MICHAELA VČELÁKOVÁ¹*, MICHAL KURKA2, KAREL PÁLKA3,

JAROSLAV BARTÁK4, PAVLA HONCOVÁ1

1University of Pardubice, Faculty of Chemical Technology, Department of Inorganic Technology

2University of Pardubice, Faculty of Chemical Technology, Center of Materials and Nanotechnolo-

gies – CEMNAT 3University of Pardubice, Faculty of Chemical Technology, Department of General and Inorganic

Chemistry 4University of Pardubice, Faculty of Chemical Technology, Department of Physical chemistry


Keywords: amorphous chalcogenides, AFM, nanoindentation, thin films, viscosity

The contribution is focus on the near surface viscosity study of glass-forming

chalcogenides in the form of bulk samples and thin films. Different experimental

methods are used to provide reliable data for comparison of the bulk and near-surface

viscosity in the amorphous materials.

One of the possible method is to measure the grating of micro- and nano-struc-

tures imprinted on the surface of the studied material. This method is based on the

principle of pressing the appropriate structure into the surface of the sample. The

change in structure due to annealing, caused by the movement of structural units,

indicates the so-called "surface grating decay”. This flow is most often investigated

using atomic force microscopy. By suitable setting of experimental conditions, in-

formation on surface self-diffusion can also be obtained. This method is also appli-

cable to bulk samples. Another suitable method is nanoindentation.

During nanoindentation, a defined force is applied to a small tip of a defined

shape. By this force, the tip is pressed into the surface of the sample. After penetra-

tion of the indenter into the body, the force load can be released immediately or kept

constant for a certain time. During the measurement, information such as load and

penetration depth is recorded over time. These values are plotted in the graph most

often in the form of load-displacement. According to the slope of the curve when the

force is released, information about the material can be derived, such as the Young's

modulus or the hardness of the material. From the dependence of the square of the

penetration depth on the time, it is possible to determine the viscosity value.

Acknowledgements

This work was supported by the Czech Science Foundation (Grant no. 20-02183Y), by the Min-

istry of Education, Youth and Sports of the Czech Republic (Grant no. LM2018103), and by the Uni-

versity of Pardubice (Grant no. SGS_2021_006).


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The influence of MgO and CaO on the thermal characteristics of sulfur-

bearng silicate-phosphate glasses

A. BEREZICKA¹*, J. SUŁOWSKA1, M. SZUMERA1



Keywords: silicate-phosphate glasses, glass transition, glass crystallization, sulfur

Although belonging to the group of bioactive materials silicate-phosphate

glasses are primarily known for their medical applications in bone regenerative ther-

apies, the lesser-known fact is that such materials may function as controlled release

rate ecological fertilisers of composition selected accordingly to actual plant require-

ments. With the aim of addressing progressive sulfur deficiency in soils, as the sub-

ject of present study, glasses from SiO2-P2O5-K2O-MgO-CaO-SO3 system, modified

by addition of increasing amounts of sulfur, have been selected. Materials were pre-

pared via conventional melt-quenching technique, after which the amorphous nature

of samples was verified by XRD method, while the content of the amorphous phase

was found by applying the internal Al2O3 standard.. It has been found that SO3 in the

0.5–5 mol% content impacted the glass-forming nature of silicate-phosphate glasses

in the studied system as with the increase in amount of sulfur the general tendency

of material to undergo crystallization also increased. DSC method allowed to deter-

mine characteristic parameters (𝑇𝑔, 𝑇𝑐, ∆𝑐𝑃, ∆𝐻) for obtained materials, calculate

values of their thermal stability and establish the influence of sulfur on the course of

phase transitions during thermal treatment of tested glasses. The analysis of resulting

DSC curves of glasses containing more than 3 mol% of SO3 allowed also to reveal a

sharp endothermic effect occurred at temperature of approximately 575°C, the origin

of which was related to the polymorphic transformation of potassium sulphate.

Given that there is an analogy between the structure of domains present in glassy

material and the structure of its devitrificate [1], studied materials were also sub-

jected to the process of induced crystallization, followed by identification of result-

ing crystalline products (XRD). In order to reveal the precise amounts of crystalline

phase, developed during thermal treatment of samples, Rietveld analysis was ap-

plied. Additionally, homogeneity of the glasses was determined by elemental map-

ping at the micro-structural level by SEM-EDS analysis whilst the structure of

glasses was characterized by spectroscopic techniques (Raman, DRIFTS).

Since very little has been published on the impact of sulfur on thermal behavior

of silicate-phosphate melts, obtained results substantially contribute to the

knowledge of sulfur-bearing glasses and may constitute valuable guideline for opti-

mizing their formulation in applications as ecological fertilizers.

References

[1] M. Sitarz, M. Szumera. Crystallization of silico-phosphate glasses, Journal of Thermal Analysis

and Calorimetry, 91:255-260, 2008.

This work was financed by the National Science Centre, Poland, project number 2018/31/D/ST8/03148


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Thermal stability and thermoluminescence properties

of hybrid materials with modified zinc phthalocyanine

BARBARA POPANDA1*, JAROSŁAW GROLIK

2, MARCIN ŚRODA1

1 AGH University of Science and Technology, Faculty of Engineering Materials and Ceramics,

Department of Glass Technology and Amorphous Coatings,

al. A. Mickiewicza 30, 30-059 Kraków, Poland 2 Jagiellonian University in Kraków, Faculty of Chemistry, Gronostajowa 2, 30-387 Kraków, Poland


Keywords: ORMOSIL, zinc phthalocyanine, thermal stability, optical properties,

thermoluminescence

Hybrid organic-inorganic composites are interesting materials for their wide

range of applications [1]. We studied hybrid materials with optical active dopants

for thier optoelectronic properties [2]. In this work, unsubstituted commercial zinc

phthalocyanine and its derivative containing axial siloxane substituent were intro-

duced into modified inorganic-organic silica matrix (ORMISIL). The materials

have been fabricated using the sol-gel method. Various paths of synthesis including

protic and aprotic solvents, different catalysts, on-stage and a two-stage sol-gel

process (acid-base conditions) were studied. The thermal stability of obtained ma-

terials was analyzed by TG/DSC method. Optically stimulated luminescence and

thermoluminescence have been corelated with the process of sol-gel synthesis.

Acknowledgments. This work was supported from the subsidy of the Ministry

of Education and Science for the AGH University of Science and Technology in

Kraków (Project No 16.16.160.557).

References

[1] S. Parola, B. Julián-López, L.D. Carlos, C. Sanchez. Optical Properties of Hybrid Organic-

Inorganic Materials and their Applications. Adv. Funct. Mater. 2016, 26, 36, 6506-6544

[2] B. Popanda, M. Środa, K. Cholewa-Kowalska. Effect of Solvent and Catalyst Types on Stability

and Properties of Zinc Phthalocyanine in the Organic–Inorganic Hybrid Materials. Crystals

2021, 11(6), 592, https://doi.org/10.3390/cryst11060592.


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Thermal and thermoluminescence properties of fluorophosphate glass

SZYMON ŚWIONTEK¹*, MARCIN ŚRODA¹


*Corresponding author: e-mail: [email protected] Keywords: fluorophosphate glass, glass-ceramics, thermoluminescence (TL), thermal stability, high-energy radiation

The fluorophosphate glass and glass-ceramics from the LiF-P2O5 system are

developed. The effect of LiF admixture on the thermal stability of the glass as well as the thermoluminescence (TL) properties such as glow curves shape are studied [1]. The results show that the increase of lithium fluoride content in the fluoro-phosphate glass causes efficiency enhancement of the thermoluminescence signal [2]. Additionally, the process of controlled crystallization of the fluorophosphate glasses can lead again to increased intensity of the TL process [3]. The glass-ceramics with 50 mol% LiF reveals similar level of TL signal to commercially used doped LiF material and can be considered as active material for alpha and beta radiation detectors [4].

Acknowledgements This work was supported from the subsidy of the Ministry of Education and Science for the AGH University of Science and Technology in Kraków (Project No 16.16.160.557). This research has been supported by the EU Project POWR.03.02.00-00-I004/16 and financed by the Polish Ministry of Science and Education – the subsidy no 16.16.160.557. References [1] M. I. Teixeira, G. M. Ferraz, L. V. E. Caldas, Thermal treatments to minimize fading effects of colored glass radiation detectors, Nuclear Instruments and Methods in Physics Research B 263 (2007) 67–71. [2] Y. O. Salem, A. Nourreddine, Z. El Bitar, N. Arbor, O. Bolusset, Beta energy dependence of the Ag-doped phosphate glass detector response, Radiation Measurements 126 (2019), 106136. [3] K. Martell, C. Law, Y. Hasan, A. Taggar, E. Leung, Using infrared depth-sensing technology to improve the brachytherapy operating room experience, Brachytherapy 19 (2020) 323–327. [4] B. Rogers, J. Lawrence, J. Chmura, E. Ehler, C. Ferreira, Dosimetric characterization of a novel 90Y source for use in the conformal superficial brachytherapy device, Physica Medica 72 (2020) 52–59.


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Thermal analysis of Fe rich and (Mn,Fe)2P based ferromagnetic alloys and composites

J.J. SUÑOL¹*, W. BEN MBAREK1, J. DAZA1, J. SAURINA1, L. ESCODA1

1GRMT University of Girona, Department of Physics.

*Corresponding author: [email protected] Keywords: Materials science, DSC, magnetic materials, DTMA, composites.

The aim of this work is to analyze the feasibility of producing composites with

soft ferromagnetic, Fe rich and (Mn,Fe)2P, alloys as a reinforcement of a polymer matrix. These alloys are candidates for applications as: a) magnetic sensors or actuators, b) magnetic materials to be integrated in magnetic refrigeration devices (alternative to conventional refrigeration). The magnetic, mechanical and/or thermal properties of both the composite and the alloy itself that acts as a reinforcing material have been determined. DTMA, DSC and XRD analyzes have been performed to determine the different properties of both: composites and ferromagnetic alloys. Thermal analysis techniques are used in the characterization of these alloys and composites to determine their characteristic temperatures (including magnetic or structural transformations), as well as their thermal stability. On the other hand, thermodynamic parameters can be determined. The analysis of the produced alloys shows that their structure and properties are similar to those of alloys of similar composition [1,2]. SEM observations of the composites have also been made.

Experimental tests have been performed with RS 816 epoxy resin matrix composites. The reinforcement is in the form of microwire, ribbon flake or powder. One of the main problems is the control of parameters such as the percentage of reinforcement in volume and its homogeneous distribution in the sample. Analysis by DTMA shows in some composites a slight variation between 245 and 265 K, probably due to the magnetic transformation. SEM micrographs confirms a good adhesion between matrix and reinforcement and a tendency of the reinforcement to agglomeration.

References [1] R. Ameur, M. Cheminghi, T. Bachaga, L. Escoda, M. Khitouni, J.J. Suñol. Martensitic

transformation and crystalline structure of Ni50Mn50-xSnx melt-spun Heusler alloys. Crystals, 10, 853, 2020.

[2] S. Alleg, T. Chabi, N. Bensebaa, J. Saurina, L.E scoda, E.K. Hlil. Investigation on the critical behaviour, magnetocaloric effect and hyperfine structure in th Fe72Nb8B20 powders. Materials 13, 4476, 2020.


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Thermal hazard evaluation and kinetic analysis

of barium titanate/polymer composites

YUKA SAKAE¹*, EIKO HIGASHI², YASUTOMO KOBAYASHI3, KATSUMI KATOH2

1Graduate School of Engineering, Fukuoka University

2Faculty of Engineering, Fukuoka University 3Murata Manufacturing Co., Ltd.


Keywords: thermal analysis, ceramics, capacitor, hazard evaluation

With the miniaturisation of electronic devices, finer powders are being used as

raw materials in the electronics industry, which may increase thermal hazards such

as unexpected heat generation in the manufacturing process [1]. In this study, the

thermal hazard properties of BaTiO3/polymer composite powder used as a raw ma-

terial for monolithic ceramic chip capacitors were evaluated using differential scan-

ning calorimetry (DSC). The measurements were conducted in an air or N2 atmos-

phere at a heating rate of 1–10 K/min using an open aluminium crucible with ap-

proximately 10 mg of each sample. Three types of sample were employed in this

study: BaTiO3 with 1 wt% of polymer (BaTiO3 (1%)), that with 3 wt% of polymer

(BaTiO3 (3%)), and BaTiO3 containing 3 wt% of polymer whose surface was rich in

Ti (Ti-rich BaTiO3). The results of DSC showed that in BaTiO3 (1%) and (3%), an

exothermic peak was observed around 330°C in the air atmosphere whereas no heat

release was observed in the N2 atmosphere. Moreover, the heat amount almost dou-

bled as the polymer amount was increased from 1% to 3%, indicating that the exo-

thermic peaks were derived from oxidation reactions of polymer. In Ti-rich BaTiO3,

two exothermic peaks were observed at 180 and 330°C, lower than those of the other

samples. Acting as catalyst, Ti possibly accelerated the polymer oxidation. The ther-

mal hazard in the industrial drying process of these samples was predicted by ana-

lysing the obtained DSC data with the Friedman kinetic method [2] using AKTS-

Thermal Safety Software [3]. The result suggested that whereas BaTiO3 (1%) and

(3%) did not release heat for at least two days, Ti-rich BaTiO3 would release reaction

heat immediately after storage at the process temperature of 100°C. We will conduct

further studies to confirm the accuracy of this prediction by scaling up the experi-

ments.

References

[1] H. Matsumoto. Japan Society for Safety Engineering, 48(3), 185–190, 2009.

[2] H. L. Friedman. J. Polymer Sci. Part C, 6, 95–183, 1963.

[3] AKTS-Thermal Safety Software. https://www.akts.com/


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The synthesis and properties of materials in SrTi1-xCuxO3 system

PAULINA GWÓŹDŹ¹*, AGNIESZKA ŁĄCZ¹, ADRIAN MIZERA¹, EWA DROŻDŻ¹



Keywords: Cu – doped SrTiO3, redox properties, perovskite structure

In recent years significant growth of the interest of researchers in perovskite –

type structure materials can be noticed. This is due to the fact that appropriate doping

can modify their functional properties, such as electrical, optical and/or catalytic. It

expands the area of these materials’ potential applications, among others, in modern

technologies in the field of energy storage and conversion, for example in fuel cells.

One of the representatives of this type of materials is doped strontium titanate. The

introduction of copper into the structure of strontium titanate should modify its elec-

trical properties, as copper introduced into Ti position is an acceptor dopant. More-

over, an influence of Cu on the catalytic activity can be postulated.

The aim of this work was to introduce Cu into the strontium titanate structure in

order to obtain a material which will finally contain a small amount of copper in

relation to the conventionally used catalysts and at the same time will show appro-

priate catalytic activity. The materials were synthesized by the sol-gel method to

obtain various Cu concentrations - 1, 2 or 5 mol.% relative to Ti in the systems.

Materials in the form of powder were examined for structural (XRD analysis), mi-

crostructural (SEM combined with EDS method) and redox (TPR/TPOx measure-

ments) properties. The major phase indicated by XRD analysis was tausonite but

some amount of Ruddlesden-Popper (RP) phases was also observed. Moreover,

XRD results did not show the presence of copper(II) oxide as a separate phase, but

for materials with higher copper content, the presence of strontium cuprate phases

(SrCuO2, Sr2CuO3) was confirmed. The TPR results showed the presence of two

ranges of reduction corresponding to two types of copper with different reduction

abilities - copper as a separate CuO phase (low-temperature range) and copper intro-

duced into tausonite structure and/or in the R-P phases structure (high-temperature

range). The obtained reduction profiles confirm the high redox potential of the tested

system for all the assumed material compositions.

Additionally, the obtained powders were sintered in air atmosphere at 1200°C

and next obtained pellets were subjected to the same tests as the powder materials.

The analysis of materials after sintering indicated that high-temperature treatment

(1200°C) led to the removal of some of the copper from the perovskite crystal struc-

ture.

Acknowledgements

The work is financed from the subsidy no. 16.16.160.557 of the Polish Ministry of Science and Educa-

tion


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Structural and redox properties of cobalt doped strontium titanates

ADRIAN MIZERA¹*, EWA DROŻDŻ1



Keywords: perovskites, TPR-H2, wet chemical synthesis

A series cobalt doped strontium titanates were synthesized using modified

Pechini method with citric acid and poly(vinyl alcohol) (PVA). The samples were

calcined in several different temperatures (700, 800, 900℃) and phase composition

were checked by XRD method. In order to compare the reducibility of as prepared

materials, a series of temperature-programmed reduction and oxidation

(TPR/TPOx) measurements were performed and correlated with average crystallite

size and specific surface area (BET). The mictrostructure of obtained powders was

observed under SEM.

The results of TPR/TPOx measurements show that doping the SrTiO3 perov-

skite structure results in an increase in reducibility of the materials, even for sam-

ples calcined at 900℃. Except for the first sample doped with 2 mol. % of Co, the

others begin to reduce at lower temperatures compared to pure Co3O4 (Fig.1). In-

troduction of cobalt was confirmed by XRD which shows only SrTiO3 crystal

phase without separate Ti or Co oxides.

Figure 1. TPR-H2 profiles for series of doped with Co strontium titanates calcined at

900℃ for 3h

Cobalt was introduced completely into perovskite crystal lattice which pro-

vides homogenous distribution of Co cations in materials volume. Such high re-

ducilibity combined with high open porosity and structural defects (from doping

the Ti-sublattice with aliovalent Co metal) have great impact in case of potential

applications of doped SrTiO3 materials e.g. in catalytis (Fisher-Tropsh process or

NH-SCO – selective catalytic reduction) or materials for SOFC anodes.

AM has been partly supported by the EU Project POWR.03.02.00-00-I004/16


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Characterization of alumina synthesized by combustion method

from aluminum nitrate mixed with various fuel components

MINAMI OTA¹, EIKO HIGASHI², TOMOYA ISHIKAWA3, KATSUMI KATOH²*

1Fukuoka University, Graduate School of Engineering

2Fukuoka University, Faculty of Engineering 3Kayaku Japan Co.,Ltd.


Keywords: thermal analysis, combustion synthesis

Alumina (Al2O3) is used in various applications, such as refractories and semi-

conductors, due to its high heat resistance and electrical insulation properties. Vari-

ous methods have been adopted to synthesize alumina with different properties. In

this study, we used combustion synthesis [1] to obtain α-alumina from different mix-

tures of an oxidizer (aluminum nitrate nonahydrate) and a fuel (one of carboxyme-

thyl cellulose ammonium; guanidine nitrate; glycine; and urea). The thermal behav-

ior of the prepared samples was observed by differential thermal analysis (DTA).

The samples were also heated in a muffle furnace at 900 °C and 1150 °C, and their

combustion residues were analyzed by scanning electron microscopy (SEM) and X-

ray diffraction (XRD). The thermal analysis of pure aluminum nitrate revealed that

it melted at 73 °C and endothermically decomposed around 150 °C. In the mixtures

of aluminum nitrate, exothermic peaks were observed around 160 °C. In particular,

the mixture containing glycine had a sharp exothermic peak at 220 °C, suggesting it

reacts violently. After heating at 1150 °C in a muffle furnace, α-alumina formed in

all the samples. Interestingly, only the mixture of aluminum nitrate containing urea

showed signs of the formation of α-alumina after heating at 900 °C, whereas the

other samples formed γ-alumina, which is a precursor of α-alumina, at the same heat-

ing temperature. This indicated that when using urea as a fuel, α-alumina may form

at a lower temperature. All the samples after heating at 900 °C had particle sizes of

about 10 µm, and they aggregated after heating at 1150 °C regardless of the fuel.

References

[1] K. Frikha et al., Comptes Rendus Chimie, 22, 206-219 (2019).


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Investigation of the stability test method for nitric acid esters

using detector tube

AYANE HABA¹*, EIKO HIGASHI², KEN OKADA3, KATSUMI KATOH2

1 Graduate School of Engineering, Fukuoka University

2 Faculty of Engineering, Fukuoka University 3 Research Institute of Science for Safety and Sustainability, AIST


Keywords: nitrocellulose, spontaneous ignition, Methyl Violet test, stability test

Nitrocellulose (NC) used as a main ingredient of propellants is prone to self-

decomposition at room temperature which can lead to spontaneous ignition during

the storage process. It is considered that the decomposition is related to NOx gener-

ated from the thermal dissociation and hydrolysis of ONO2 group in NC [1]. There-

fore, to prevent the spontaneous ignition, the stability of the NC-based propellants

needs to be evaluated by measuring the NOx release amount. As a stability test, the

Methyl Violet (MV) test detecting NOx generated from NC heated at 134.5°C using

a test paper is commonly used [2]. However, since this test has to deal with explo-

sives on a gram scale heated at a high temperature, it is concerned about safety issues

during the test implementation. Therefore, in this study, we proposed a test method

measuring NOx released from a 100 mg sample heated at 134.5°C using detector

tubes. The schematic diagram of the experiment is shown in Figure 1. The experi-

ment procedure is as follows: a glass vessel with the sample was isothermally heated

at 134.5°C; after heating for 1 h, 1 L of air was allowed to flow into the glass vessel

using a syringe; the outlet gas was collected into a sampling bag and its NOx con-

centration was observed by the detector tube (No. 11S, GASTEC). Four types of

NC-based propellants were subjected to this detector tube test. In addition, to inves-

tigate the accuracy of the test results, it was compared with the results of the MV test

following the UN standard [2] and the calorimetry (C80 calorimeter manufactured

by SETARAM) under a 134.5°C isothermal condition in an O2 atmosphere, con-

ducted with the same four samples. As the

result, the NOx generation amount meas-

ured by the detector tube test was correlated

with the stability evaluated by the MV test

and the induction time of the exothermic

peak measured by the calorimetry. There-

fore, there is a possibility that the detector

tube test enables reproduction of the MV

test results, and measuring the thermal haz-

ard of NC-based propellants.

References

[1] K.Katoh,et al., Thermochim. Acta, 431:161, 2005

[2] UNITED NATIONS, ST/SG/AC.10/11/rev.7/A10.3, 2019

Figure 1 The schematic diagram

of the detector tube test.


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A thermodynamic approach to investigate the drug loading into mi-

croporous materials

LORENZO LISUZZO, GIUSEPPE CAVALLARO, STEFANA MILIOTO, GIUSEPPE

LAZZARA Dipartimento di Fisica e Chimica, Università degli Studi di Palermo, Viale delle Scienze, pad. 17,

90128 Palermo, Italy.

*Corresponding author: Giuseppe Lazzara e-mail: [email protected]

Keywords: halloysite, nanotubes, sustained release, clay nanoparticles, drug load-

ing, Knudsen thermogravimetry.

Halloysite nanotubes are emerging and promising hollow tubular nanocontain-

ers for loading biologically active compounds that undergo to a sustained or trig-

gered release. The nanotubes lumen is suitable for being loaded with molecules ve-

hiculated in a proper solvent media. In this work, we exploited different protocols

that provided not only a control in the loading efficiency but also on the release ki-

netics [1,2]. To highlight the crucial role of the hollow tubular morphology, kaolin-

ite, with a layered structure and identical chemical surface features of halloysite, was

investigated for comparison. The thermodynamic description of the ethanol and wa-

ter confinement into halloysite was correlated to the effects of the pressure condi-

tions in the experimental protocol for halloysite loading by using Knudsen thermo-

gravimetry. Loading and release of model drugs will be investigated.

This work represents a thermodynamic look at the development of nanotubular

carriers with tunable release feature based on the loading protocol and drug locali-

zation into the carrier.

References

[1] Lisuzzo, L.; Cavallaro, G.; Milioto, S.; Lazzara, G. Halloysite Nanotubes Filled with Salicylic Acid

and Sodium Diclofenac: Effects of Vacuum Pumping on Loading and Release Properties. Journal

of Nanostructure in Chemistry 2021, doi:10.1007/s40097-021-00391-z.

[2] Lisuzzo, L.; Cavallaro, G.; Pasbakhsh, P.; Milioto, S.; Lazzara, G. Why Does Vacuum Drive to the

Loading of Halloysite Nanotubes? The Key Role of Water Confinement. Journal of Colloid and

Interface Science 2019, 547, 361–369.


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Isobaric heat capacity of cyano-based ionanofluids

KRZYSZTOF CWYNAR1, JUSTYNA DZIADOSZ1, PAWEŁ GANCARZ1, EDWARD

ZORĘBSKI1, ADRIAN GOLBA1, BERTRAND JÓŹWIAK2, GRZEGORZ DZIDO3,

ANNA KOLANOWSKA2, RAFAŁ JĘDRYSIAK2, HEATHER F. GREER4,

SŁAWOMIR BONCEL2*, MARZENA DZIDA1*

1University of Silesia in Katowice, Institute of Chemistry

2Silesian University of Technology, Department of Organic Chemistry, Bioorganic

Chemistry and Biotechnology 3Silesian University of Technology, Department of Chemical and Process Engineering

4University of Cambridge, Department of Chemistry

*Corresponding authors: e-mails: [email protected], [email protected]

Keywords: ionanofluids, thermal conductivity, thermal stability

The ionanofluids (INFs) composed of multi-walled carbon nanotubes

(MWCNTs) and ionic liquids characterize improved thermal conductivity [1,2]. By

contrast the influence of carbon nanoparticles on the isobaric heat capacity of INFs

is not pronounced. Therefore, this work is aimed to study the effect of the function-

alization of MWCNTs on the isobaric heat capacity of the INFs. The INFs com-

posed of 1-ethyl-3-methylimidazolium thiocyanate [EMIM][SCN] and polyeth-

ylene glycol-functionalized MWCNTs (MWCNT-PEG) with average length 250

µm, mean diameter 45 nm, functionalization levels: 0.90 mmol·g-1; carbon chain-

functionalized MWCNTs (MWCNT-C18) average length 250 µm, mean diameter

45 nm, functionalization levels: 0.50 mmol·g-1; and carboxyl-functionalized

MWCNTs (MWCNT-COOH) with average length <500 µm, mean diameter 50

nm, COOH content: 1.00 mmol·g-1, OH content: 0.40 mmol·g-1 have been studied.

This research shows that the addition of 0.5 wt% MWCNT-COOH and 1 wt%

MWCNT-PEG into the [EMIM][SCN] leads to increase of isobaric heat capacity

by 3.1% and 2.6% at 323 K, respectively. While, even 2.5 wt% MWCNT-C18 does

not change the isobaric heat capacity of INF. It therefore seems that functionaliza-

tion of MWCNTs with polar groups may be a good way to obtain a real increase in

the isobaric heat capacity.

This work was financially supported by the National Science Centre (Poland)

Grant No. 2017/27/B/ST4/02748.

References

[1] A. P. C. Ribeiro, M. J. V. Lourenço, C. A. Nieto de Castro. Thermal Conductivity of Ionanofluids.

17th Symposium on Thermophysical Properties, Boulder, USA, 2009.

[2] B. Jozwiak, G. Dzido, E. Zorebski, A. Kolanowska, R. Jedrysiak, J. Dziadosz, M. Libera,

S. Boncel, M. Dzida. Remarkable Thermal Conductivity Enhancement in Carbon-Based

Ionanofluids: Effect of Nanoparticle Morphology. ACS Appl. Mat. Interf. 12:38113–38123, 2020.


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Design and properties of polyurethane-based hydrogels for biomedical aplication

JELENA M. TANASIĆ1*, URSZULA KLEKOTKA2, BEATA KALSKA-SZOSTKO2,

IVAN KRAKOVSKY3, TAMARA D. ERCEG1, IVAN S. RISTIĆ1

1University of Novi Sad, Faculty of Technology Novi Sad, Novi Sad, Serbia

2University of Bialystok, Institute of Chemistry, Bialystok, Poland 3Charrles University of Prague, Prague, Czeck Republic *Corresponding author: e-mail: [email protected]

Keywords: polyurethane hydrogels, thermal properties, morphological properties, carbon nanotubes, regenerative medicine

Hydrogels are ideal for use in regenerative medicine. Polyurethane is a material that is known for its stable structure and good mechanical properties, but also for its hydrophobicity and insolubility in water. However, the properties of polyure-thane can be modified by incorporating hydrophilic soft segments (such as poly (ethylene oxide) (PEO)) into the structure of the polyurethane to increase their hydrophilicity. In this work, polyurethane hydrogels were synthesized from 2.7 functional isocya-nates, poly (ethylene oxide) molecular weights of 6000 and 10000 g/mol, with thean appropriate amount of catalyst, dibutyltin dilaurate, are polymerized in tetrahydro-furan as a solvent. Nanostructured polyurethane hydrogels were made by addition of carbon nanotubes as a filler. Quantities of carbon nanotubes in amounts of 1wt%-5wt% were added to the polyurethane matrix, by mixing with diisocyanate and dyol prior polymerization. The structure of the samples was examined by infrared spec-troscopy with Fourier transformation, thermal properties were examined by diffe-rential scanning calorimetry and thermogravimetry. The morphological properties of the samples and the distribution of nanoparticles in the structure were examined by scanning electron microscopy. The FTIR results show that the reaction of the NCO group is complete and a quantitative reaction is achieved, the DSC results show that the melting temperature varies depending on the molecular weight of used PEO and the amount of PEO. The results of the TGA analysis show that the temperature of the PU degradation increases with the change of the polyol component. The swelling ratio of polyurethane hydrogels was between 320 and 1200%. The results, apart from microscopy, show that when CNTs are added, there is a more uniform distribution of pore size in the samples

References [1]Frydrych М., Román S., Green N. H., MacNeil S., Chen B., Thermoresponsive, stretchable, biode-gradable and biocompatible poly(glycerol sebacate)-based polyurethane hydrogels, Polymer Chemi-stry, 6, 2015, 7974–7987 [2]Gennen S., Grignard B., Thomassin J-M., Gilbert B., Vertruyen B., Jerome C., Detrembleur C., Polyhydroxyurethane hydrogels: Synthesis and Characterizations, European Polymer Journal, 84, 2016, 849–862


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Thermal characteristics and combustion reactivity of coronavirus face masks using TG-DTG-MS analysis

NEBOJŠA G. MANIĆ¹*, BOJAN Ž. JANKOVIĆ², DRAGOSLAVA D. STOJILJKOVIĆ¹,

PANAGIOTIS N. ANGELOPOULOS3, VLADIMIR V. JOVANOVIĆ¹, MILOŠ B. RADOJEVIĆ¹

1University of Belgrade Faculty of Mechanical Engineering, Fuel and Combustion Laboratory

2University of Belgrade, Department of Physical Chemistry, Vinča Institute of Nuclear Sciences - Na-tional Institute of thе Republic of Serbia

3National Technical University of Athens, School of Mining and Metallurgical Engineering *Corresponding author: [email protected]

Keywords: coronavirus face mask, TG-DTG-MS, combustion, thermal analysis properties, heating rate

The presented paper deals with the influence of heating rate on combustion char-

acteristics (reactivity and reactivity evaluation, ignition index (Di), burn-out index (Df), combustion performance index (S), and combustion stability index (RW)) of protective coronavirus face masks. Two types of commonly used face masks in dif-ferent state (new and exploited) were investigated by TG-DTG analysis in air atmos-phere, directly coupled with mass spectrometry (MS). Based on experimental results, the impact of ultimate and proximate analysis data on the evolved gas analysis (EGA) was disscused in detail. Also, the derived values from thermoanalytical data were compared with literature, related to individual constitutive face mask materials. According to the performed research, it was established that different maximal reac-tion rate values at various heating rates indicate the complex nature of coronavirus face mask thermo-oxidative degradation, which is stimulated with carbon oxidation reactions and volatile matter (VM) release. By detailed analysis of obtained TG-DTG profiles, it was established that process takes place through multiple-step path-ways, due to many vigorous radical reactions, causes by polymers degradation. The performed research was done to evaluate the possible utilization of coronavirus waste to energy production and sustainable pandemic environmental risk reduction.


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Characterization of the Forest Residues Combustion by

Thermogravimetric Analysis

JOÃO SILVA1,2*, SENHORINHA TEIXEIRA 2, BERNHARD PETERS 3, AND JOSÉ TEI-

XEIRA 1

1MEtRICs Research Centre, University of Minho, Guimarães, Portugal

2ALGORITMI Research Centre, University of Minho, Guimarães, Portugal

3University of Luxembourg, Faculty of Science and Technology, and communication


Keywords: biomass, combustion, thermogravimetric analysis

To improve the biomass combustion process, it is fundamental to understand

and analyze the influence of the main parameters on the conversion process. Conse-

quently, the development of experimental research is fundamental to obtain reliable

details of the combustion developments in a biomass particle. In this sense, this work

presents the thermogravimetric study of the main forest residues used in a biomass

power plant in Portugal.

Initially, biomass samples were collected, prepared, and characterized through

proximate and ultimate analysis. The collection was framed by the range of resources

used in a representative biomass power plant and considering the main forest species

in Portugal. Eucalyptus, pine, and acacia are extensively used in Portugal as fuel for

power generation. Furthermore, since Portugal is a reference in modern olive pro-

duction, and it is expected that during the next decade to be the third largest producer

of olive oil in the world, olive tree pruning appears to be a very interesting alternative

for power generation. Therefore, these four distinct fuels were collected to study

their combustion behavior. Then, the raw materials were milled into powdered sam-

ples and sieved to obtain particles with only 125-250 µm. Subsequently, a simulta-

neous TGA-DSC equipment, TA INSTRUMENTS SDT 2960, was used to carry out

the TGA experiments in an oxidative atmosphere. Samples with around 10 mg were

used and, in each experiment, they were subjected to a thermal decomposition from

ambient temperature up to 900°C at low and high heating rates. The low heating rates

were applied to avoid transport effects and to ensure that reaction is temperature

dependent only, and therefore, the experiments are performed in a pure kinetic re-

gime. Finally, using the thermogravimetric and derivative thermogravimetric curves,

the major characteristic temperatures, and some important indexes were calculated

to fully characterize the combustion behavior of the selected fuels.

Although the experiments were performed with laboratory equipment, it was

allowed to investigate and understand transport phenomena at the particle level with

different operating conditions. This is an important task that delivers a meaningful

and trustworthy conclusion that will benefit the community of researchers and engi-

neers. Furthermore, this work is essential to develop a numerical model of biomass

combustion systems since experiments can be conducted in a controlled environ-

ment, and repeatable conditions, providing precise measurements for different fuels

and ambient conditions, to quantify the influence of different key parameters. In the

future, this study will be very useful to study and optimize the combustion in indus-

trial grate-fired boilers regarding its efficiency.


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Dynamic mechanical characteristic of epoxy-based composites with carbon foam microparticles and graphene nanoplatelets as fillers

K. OLSZOWSKA1, A. KOBYLIUKH1, M. GODZIERZ1, J. MYALSKI2,

S. PUSZ1, U. SZELUGA1

1 Centre of Polymer and Carbon Materials, Polish Academy of Sciences, Zabrze 2 Silesian University of Technology, Department of Materials Science and Metallurgy


Keywords: dynamic mechanical analysis, polymer-carbon composites, carbon foam, graphene structures

One of the main goals of modern science of polymer-based materials is devel-opment of new multifunctional composites with significantly improved mechani-cal, thermal and electrical properties, and, at the same time, relatively low density, meeting the expectations of present-day applications. Application of carbon foams (CFs) with specific structure and properties as a particulate filler of epoxy matrix gives the opportunity to develop new multiphase composite materials [1,2]. They are easy to process and are characterized by good thermal stability, tribological properties, and ability to absorb different types of energy while maintaining high hardness and relatively low density, compared to pure epoxy matrix. Although me-chanical strength of composites with CF microparticles deteriorates but it can be improved by introduction of additional nanofiller into polymer matrix to produce hybrid composites [3].

Thus the main purpose of this work is to determine the effect of CF grains, applied separately and together with graphene nanoplatelets as a second nanofiller, on interac-tions between polymer matrix andfiller’s particles, and consequently on properties of polymer-carbon composites. The CF used as composite filler was prepared by self-foaming of epoxy/novolac precursor and followed by carbonization to obtain a stable carbon skeleton [1]. The CF grain fraction below 315 m was used. Graphene nano-platelets were distributed in epoxy resin using ultasonication procedure before intro-ducing CF particles. Morphology of composites with CF particles and graphene struc-tures were characterized by scanning electron and optical microscopy techniques. The effect of micro-and nano-sized fillers on the mechanical characteristic of epoxy com-posites was studied using dynamical mechanical thermal analysis (DMA). It is ex-pected that CF particles simultaneousy applied with graphene nanoplatelets will have a positive effect on mechanical and thermal parameters (dynamic moduli, glass transition temperature, thermal stability) of epoxy composites. References

[1] U. Szeluga, S. Pusz, et al. Carbon foam based on epoxy/novolac precursor as porous micro-filler of epoxy composites. Compos. Part A Appl. Sci. Manuf. 105, 28-39, 2018.

[2] U. Szeluga, K. Olszowska, et al. Effect of grain fractions of crushed carbon foam on morphology and thermomechanical and tribological properties of random epoxy-carbon composites. Wear 466–467, 203558, 2021.

[3] U. Szeluga, B. Kumanek, B. Trzebicka. Synergy in hybrid polymer/nanocarbon composites. A review. Compos. Part A Appl. Sci. Manuf. 73, 204-231, 2015.


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SESSION 6:

LIFE SCIENCE

Hierarchy of interactions dictating the thermodynamics

of cell membrane lipid bilayers: a calorimetric route

FRANCESCA SAITTA*, MARCO SIGNORELLI, DIMITRIOS FESSAS

Università degli Studi di Milano, Department of Food, Environmental and Nutritional Sciences

(DeFENS)


Keywords: model membranes, DSC, free fatty acids, type 2 diabetes mellitus

Cells and vesicles functionalities, as well as membrane proteins one, are strictly

correlated to membrane lipid composition because of its influence on membrane

thermodynamic stability [1]. In this frame, a stepwise study of vesicles with different

morphology and lipid composition was performed through high-sensitivity differen-

tial scanning calorimetry at physiological pH with the purpose of comprehending the

role played by some of the main factors that contribute to the thermodynamic stabil-

ity of cell membranes. The phospholipid bilayer of Insulin Secretory Granules

(ISGs), vesicles located in the pancreatic Langerhans β-cells and which are respon-

sible for insulin and amylin storage and secretion in response to nutrient intake, was

considered as reference system.

The cross-study of single-component and binary systems composed by different

phospholipids allowed the dissection of the roles played by curvature, phospholipid

headgroups and tails on the thermotropic behaviour of cell membranes [2]. There-

fore, a hierarchy of contribution to the overall thermodynamic stability of mem-

branes was depicted as membrane curvature < phospholipid headgroup < phospho-

lipid tail < phospholipid unsaturation. The following inclusion of sphingomyelins

and lysophosphatidylcholines together with a more complete fatty acids distribution

allowed the achievement of a high-complexity fourteen-components model mem-

brane that reflected the 80% of ISG’s phospholipids. The inclusion of cholesterol

was finally considered for the achievement of the final ISG-like membrane [3].

Furthermore, the effect of several Free Fatty Acids (FFAs), whose levels are

recurrently altered in diabetic and/or obese subjects, on the thermodynamic stability

of selected membranes was investigated. The results highlighted strong stabilizing

effects on the membranes as well as pronounced phase segregations in the case of

saturated acids, moderate stabilizing effects for a trans-unsaturated FFA, whereas

opposite effects were observed in the case of cis-unsaturated ones [2,3].

References

[1] W. Zhang et al. Reversible Topological Organization within a Polytopic Membrane Protein Is Gov-

erned by a Change in Membrane Phospholipid Composition. J. Biol. Chem. 278: 50128, 2003.

[2] F. Saitta et al. Dissecting the effects of free fatty acids on the thermodynamic stability of complex

model membranes mimicking insulin secretory granules. Colloids Surf B Biointerfaces. 176: 167-

175, 2019. [3] F. Saitta et al. Hierarchy of interactions dictating the thermodynamics of real cell membranes:

Following the insulin secretory granules paradigm up to fifteen-components vesicles. Colloids

Surf B Biointerfaces. 186: 110715, 2020.


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Non-isothermal cold-crystallization and physical stability of quench-

cooled carbamazepine

A. DOŁĘGA¹*, E. JUSZYŃSKA-GAŁĄZKA1, A. DEPTUCH

1, S. BARAN

2,

P.M. ZIELIŃSKI1

1Institute of Nuclear Physics Polish Academy of Sciences

2M. Smoluchowski Institute of Physics, Jagiellonian University


Keywords: cold-crystallization, DSC, FTIR, X-ray, pharmaceuticals

Cold-crystallization is a phenomenon observed e.g. during heating glassy sam-

ple above glass transition temperature. Such a situation is in some cases undesira-

ble – e.g. for amorphous pharmaceuticals, which are better soluble in glassy state

than in the crystalline one. Physical stability of the amorphous drug is necessary

during manufacturing and storage time. An in-depth knowledge of kinetics of cold-

crystallization is needed to properly design non-crystalline pharmaceuticals.

Carbamazepine (CBZ) – an antiepileptic drug – is an example of poorly water

soluble active pharmaceutical ingredient (API). Many attempts are made to obtain

its non-crystalline, better soluble form. Quench-cooling is one of the methods ena-

bling amorphisation of CBZ. Our studies had shown, that at least 100 K min-1

cool-

ing rate is needed to avoid crystallization and to get glassy sample [1].

X-ray measurements prove that for quench-cooled CBZ stored at room tem-

perature, nucleation starts after ~7 hours, whereas for that stored at refrigerator

temperature – after ~8 hours. However, for sample stored at 278 K process of crys-

tal growth is considerably slowed down when compared to the sample stored at

298 K. Due to that, at 278 K quench-cooled CBZ can be still considered as an

amorphous one even 7 weeks after preparation, which is not the case for sample

stored at 298 K.

Extended to the glassy state Adam-Gibbs equation enables estimation of the

physical stability of API from non-isothermal DSC measurements. It can be shown,

that estimated stability of quench-cooled CBZ from this equation is ~7 h for the

sample stored at 298 K and ~17 days for the sample stored at 278 K.

FTIR measurements show that meaningful changes in vibrational dynamics

take place when phase transitions of quench-cooled CBZ occur. Glass softening is

the most pronounced phase transition when it comes to the changes in dynamics,

whereas cold-crystallization and melting are less pronounced, but still visible.

References

[1] A. Dołęga, E. Juszyńska-Gałązka, A. Deptuch. S. Baran, P. M. Zieliński. Non-isothermal cold-

crystallization and physical stability of glassy carbamazepine studied by X-ray diffraction, DSC

and FT-IR spectroscopy. Thermochim. Acta 2021 (under review).

Acknowledgments

AD has been partly supported by the EU Project POWR.03.02.00-00-I004/16


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Isothermal and non-isothermal assessment of thermo-oxidative stability

of Camelina sativa L. seed oils from different varieties

MAHBUBA ISLAM1, MAŁGORZATA MUZOLF-PANEK1, EMILIA FORNAL2,

JOLANTA TOMASZEWSKA-GRAS1*

1 Poznań University of Life Sciences, Department of Food Quality and Safety Management,

2Medical University of Lublin, Department of Pathophysiology, Faculty of Medicine


Keywords: Camelina oil, Oxidative stability, Differential scanning calorimetry

(DSC), OIT, Antioxidative activity, DPPH.

There is a growing interest worldwide about the use of camelina oil for food as

well as for biofuel purposes. For both of these applications, oxidative stability is

important feature of the oil. Therefore, the aim of this work was to test the resistance

to oxidation of three different varieties of camelina oil by means of isothermal and

non-isothermal DSC technique. For isothermal DSC analysis different temperatures

were tested (120, 140, 160 °C) and in non-isothermal mode different scanning rates

(2, 5, 10 °Cmin -1) were used. To support the DSC data, chemical analyzes were also

performed i.e. fatty acid composition, peroxide value (PV), p-anisidine value (pAV),

acid value (AV) and antioxidative activity (DPPH).

The results indicated that for all camelina varieties oxidation induction time

(OIT) decreased with the increase of temperature in average from 69.83 min for 120

°C to 5.13 min for 160 °C. For non-isothermal DSC analysis the temperatures (Ton)

increased with the increase of heating rates from 153.34 °C for 2 °Cmin-1 to 180.57

°C for 10 °Cmin-1. Parameters of DSC oxidative stability i.e. OIT (determined for

120, 140, 160 °C) as well as Ton values (obtained by scanning rate 5 and 10 °Cmin-

1) were positively correlated with saturated fatty acids content (C16:0, C18:0) and

DPPH values. In turn they were negatively correlated with polyunsaturated fatty ac-

ids content (C18:3, C20:3). In the case of slow heating rate 2°Cmin-1 values of Ton

were not significantly correlated with the content of fatty acids and DPPH. Principle

Component Analysis (PCA) enabled discrimination of samples in terms of different

varieties and also revealed strong correlation between fatty acids content, all meas-

ured DSC parameters and DPPH.

Funding:

This research was funded by NATIONAL SCIENCE CENTRE, POLAND, grant number:

2018/31/B/NZ9/02762.


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DSC study on the hydrated hydroxyethyl cellulose (HEC)

matrix compared to other non-ionic, water-soluble

cellulose polysaccharides

PRZEMYSLAW TALIK¹*

1Jagiellonian University Medical College, Pharmaceutical Faculty,

Department of Inorganic and Analytical Chemistry


Keywords: DSC, hydroxyethyl cellulose, HEC, hydrated polysaccharides

Hydroxyethyl cellulose (HEC) is a non-ionic, water-soluble cellulose ether de-

rivative (Figure 1). It is an unscented, tasteless, and non-toxic white to light-yellow

polymer that readily dissolves in hot and cold water, however is insoluble in most

organic solvents. HEC is widely explored in oral drug delivery systems in pharmacy.

Accordingly, the influence of conformations and its interactions with drugs or ex-

cipients is of scientific and practical interest of many research groups. As for the

other hydrophilic polysaccharides, it is believed that HEC and water interactions are

related to hydrogen bonding. However, it was demonstrated [1-3] that hydrogen

bond bound water is only one of the various physical states in the polymer, because

formation of “nanocavities” have also a great ability in changing the polymer me-

chanical and chemical properties.

This type of research may contribute to better understanding of both highly and

poorly soluble drug release from tablet formulations and their dissolution behaviour.

Fig. 1 Structure of investigated molecule of hydroxyethyl cellulose HEC.

References

[1] P. Talik, U. Hubicka. J. Therm. Anal. Calorim. 132(1):445-451, 2017.

[2] P. Talik, J. Piotrowska, U. Hubicka. AAPS PharmSciTech. 20:187, 2019.

[3] GL. Liu, KD. Yao. Polymer. 42:3943-7, 2001.


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Effect of methylcellulose and hydroxypropyl methylcellulose on reduc-

tion of acetaminophen crystallinity

EDYTA LEYK¹, MAREK WESOLOWSKI¹*

1Medical University of Gdansk, Faculty of Pharmacy, Department of Analytical Chemistry

Gen. Hallera 107, 80-416 Gdansk, Poland


Keywords: DSC, FT-IR, Raman spectroscopy, acetaminophen, cellulose deriva-

tives

Excipients, known also as auxiliary substances, are widely used in the pharma-

ceutical technology to manufacture solid dosage forms. Proper selection of excipi-

ents allows to obtain safe, effective and stable drug products with optimal bioavail-

ability. There are many groups of excipients, which differ in their functionalities in

drug products such as uncoated or coated tablets, tablets with controlled release,

granulates, and others. One of the most used group of excipients in the solid dosage

formulation are cellulose derivatives. Individual representatives of this group differ

in their physicochemical properties, and therefore, they can be applied in scientific

research and pharmaceutical industry for different purposes.

Acetaminophen belongs to the analgesics and antipyretics drug class. This ac-

tive pharmaceutical substance has three polymorphic forms (stable form I and two

metastable forms II and III) [1]. Since methylcellulose and hydroxypropyl methyl-

cellulose are commonly used excipients to manufacture the acetaminophen solid

dosage formulations, the aim of this study was to assess to what extent both poly-

meric excipients can affect on the crystallinity reduction of acetaminophen. To

solve this problem, differential scanning calorimetry (DSC), Fourier transform in-

frared (FT-IR) and Raman spectroscopy were used. Physical mixtures of active

substance containing 10, 30, 50, 70 and 90% of polymeric excipient were prepared

by gentle homogenization of both ingredients using a mortar and a pestle or a cellu-

loid card. A linear correlation between the heat of fusion of acetaminophen (form I)

and its content in the mixtures revealed a proportional loss of acetaminophen crys-

tallinity in the mixtures examined. This effect was greater for pestle-homogenized

mixtures than for those homogenized with celluloid card. Furthermore, the reduc-

tion of crystallinity was greater for mixtures with hydroxypropyl methylcellulose

than for those with methylcellulose. Using the DSC heating-cooling-reheating program,

formation of a metastable form of acetaminophen has also been observed for mix-

tures containing 90% of the active substance. Moreover, the findings of the FTIR

and Raman spectroscopy measurements confirmed that there are no chemical or

physical interactions between the active substance and polymeric excipients.

References

[1] S. Gaisford, A. B. M. Buanz, N. Jethwa. Characterisation of paracetamol form III with rapid-

heating DSC. J. Pharm. Biomed. Anal. 53:366–370, 2010.


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Thermal study of cotton candy using differential scanning calorimetry

YUKIO TERASHIMA*

Naruto University of Education


Keywords: cotton candy, sucrose, amorphous or crystal, DSC

Thermal stability of food materials is so important for food processing and stor-

age, and it strongly depends on the physical states, i.e., amorphous or crystalline states. Sugar is one of the most familiar ingredients in daily foods, and it is also used

for a wide variety of confections. Cotton candy is a spun sugar sweet which resem-bles cotton. The candy is made by heating and liquefying sugar, spinning it centrif-ugally through minute holes. In this process, the melted sugar rapidly cools and re-solidifies into fine strands.

The physical state of cotton candy was found to be strongly affected by the tem-perature and the relative humidity during cooking by powder X-ray diffraction meas-urement [1]. In contrast, detailed differential scanning calorimetry (DSC) for cotton

candy have not been conducted systematically so far, and its physical states and ther-mal properties are not fully understood.

This study aims to reveal the DSC profile of cotton candy and to understand its thermal characteristics. First, we made a cotton candy from granular sucrose sugar for foods in normal air using a commercial cotton-candy machine. We carried out DSC measurements for the handmade cotton candy and for its original sucrose to determine the physical state of usual cotton candy, namely, crystalline or amorphous

states, in terms of calorimetry. As a result, the cotton candy indicated some thermal anomalies which are not found for the crystalline sucrose. We found that the normal cotton candy is a crystal containing a little amorphous part.

Fresh cotton candy is expected to absorb moisture easily and to transform hy-drates rapidly in normal humid air. In dry nitrogen atmosphere, however, such mois-ture absorption and transformation can be difficult to occur, and more glassy sucrose formed by quenching can maintain in cotton candy. To test effects of outer atmos-phere on the physical properties of fresh cotton candy, we carried out DSC measure-

ments for cotton candy made in dry N2 atmosphere and compared with the results for one made in normal air mentioned above. As a result, the multi-step glass transi-tions of sucrose were observed clearly only for the cotton candy made in dry N2 gas. We found that the fresh cotton candy made in dry N2 atmosphere contains more glassy structure than usual one made in the air.

References

[1] T.P. Labuza, P.S. Labuza. Influence of temperature and relative humidity on the physical states of

cotton candy. J. Food Processing and Preservation. 28:274-287, 2004.


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Assessment of bioactivity of isolates from various coffee extracts di-

gesed “in vitro” as inhibitors of MAO-A responsible

for the deamination of serotonin. JOANNA GRZELCZYK¹*, GRAŻYNA BUDRYN1, DOMINK SZWAJGIER2

1Institute of Food Technology and Analysis, Lodz University of Technology,

2Department of Biotechnology, Microbiology and Human Nutrition, University of Life Sciences in

Lublin


Keywords: ITC, MAO-A, coffee, 5-HT

Monoamine oxidase A (MAO-A) is the main enzyme responsible for the

degradation of neurotransmitters by oxidative deamination including the removal of

the amine functional group from serotonin (5-HT) in the central nervous system

(CNS). The use of MAO-A inhibitors contributes to increased levels of biogenic

amines in the brain and re-uptake of 5-HT. Maintaining the proper level of serotonin

in the center nervous system prevents the development of depression,

improves mood by reducing nervousness, motor perception and contributes to the

prevention of obesity by decreasing appetite for high carbohydrate products, and

prevent to metabolic diseases such as diabetes. Potential selective serotonin reuptake

inhibitors are coffee bioactive compounds.

The aim of the study was to assess the affinity for MAO-A of isolated

fractions of bioactive components from coffees after "in vitro" digestion and the en-

zyme inhibition efficiency by digested isolates. The analysis was conducted by

isometrmal titration calorimetry (ITC). The digestion of fractioned coffee extracts

from green, light and dark roasted bean was carried out in a simulated digestive sys-

tem, reproducing physiological processes of the gastrointestinal tract (the stomach,

small and large intestine) optionally with a presence of selected probiotic

bacteria strains. The evaluation of MAO-A inhibition was assessed for hydrolyzed

fractions of coffee extracts taken after digestion and performed using an isothermal

titration calorimetry that allowed to determine the most effective coffee extract lim-

iting the enzyme activity that protects 5-TH from deamination.

The studies have shown that after digestion the highest bioavailability of com-

pounds with high affinity for MAO-A had the isolates from green coffee of high

concentration of monochlorogenic acids. Our analysis has shown that coffee isolates

have high potential of MAO-A enzyme activity inhibition, which may support

the protection of serotonin. The research was funded by National Centre of Science

(project No. UMO-2018/2019/N/NZ9/01160).

References

[1] Palacios J. M., Pazos A., Hoyer D. A short history of the 5-HT2C receptor: from the choroid plexus

to depression, obesity and addiction treatment. Psychopharmacology. 234:1395-1418, 2017.

[2] Huang, C.; Hui-Da, G.J.X.; Wangb, C.H.; Leia, X.; Hua, J.F. Discovery, synthesis, biological eval-

uation and molecular docking study of(R)-5-methylmellein and its analogs as selective mono-

amine oxidase Ainhibitors. Bioorg. Med. Chem. 27:2027-2040, 2019.


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Physicochemical nature of sodium dodecyl sulfate interactions with

bovine serum albumin revealed by interdisciplinary approaches

O. GRABOWSKA, M. M. KOGUT, K. ŻAMOJĆ, A. TESMAR, K. CHMUR,

S. A. SAMSONOV, J. MAKOWSKA,

D. WYRZYKOWSKI*, L. CHMURZYŃSKI

Faculty of Chemistry, University of Gdańsk,


Keywords: sodium dodecyl sulfate, bovine serum albumin, thermodynamic pa-

rameters, molecular dynamics

To rigorously characterize the interactions of sodium dodecyl sulfate (SDS)

with bovine serum albumin (BSA) a set of experimental methods, namely isother-

mal titration calorimetry, conductometric titration, steady-state fluorescence spec-

troscopy, differential scanning calorimetry and circular dichroism spectroscopy,

supported by in silico analysis have been applied. The influence of pH and temper-

ature on the binding mode has been revealed. At a low molar ratio of SDS to BSA

up to ca. 16:1, there are at least two structurally distinct binding sites in BSA. The

formation of SDS-BSA complexes is an enthalpy-driven process in which the van

der Waals interactions play a crucial role. The first binding site, located close to the

Trp-134 residue within the sub-domain IA, is pH-independent and binds two mole-

cules of SDS per one molecule of BSA whereas the total number of SDS molecules

bound to the second site of albumin is affected by temperature and pH . The satura-

tion of the first binding site of BSA (ca. 0.009 mg of SDS per 1 mg of BSA) is suf-

ficient to thermally stabilize the helical conformation of BSA. The presented re-

sults have important structural and thermodynamic implications to understand the

influence of a widely used anionic surfactant on globular protein functionality in

modern branches of chemistry [1,2].

References

[1] M. Aguirre-Ramírez, H. Silva-Jiménez, I. M. Banat, M. A. Díaz De Rienzo. Surfactants: physico-

chemical interactions with biological macromolecules. Biotechnol. Lett. 43:523–535, 2021.

[2] D. Otzen. Protein-surfactant interactions: A tale of many states. Biochim. Biophyis. Acta

1814:562-591, 2011.


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DSC monitoring of the direct and delayed effects of ionising radiationon human blood serum solutions

AGNIESZKA KIEŁBOŃ ¹*, ANNA MICHNIK¹, KINGA POLACZEK – GRELIK2,EWA SADOWSKA - KRĘPA3

1Faculty of Science and Technology, Institute of Biomedical Engineering, The Silesian Centre forEducation and Interdisciplinary Research, University of Silesia in Katowice

2NU-Med Cancer Diagnosis and Treatment Centre Katowice, University Clinical Center to them.prof. K. Gibiński of the Medical University of Silesia in Katowice

3The Jerzy Kukuczka Academy of Physical Education in Katowice, Institute of Sport Sciences*Corresponding author: [email protected]

Keywords: human blood serum, DSC, ionizing radiation effects

Changes in the biological structure of protein and its stability after exposure toionizing radiation are one of the fundamental issues of radiobiology. The dose de-pendent effects of radiation have a great importance in medical treatment. Thechosen dose values in the order of several to several dozen Gy are widely used inradiotherapeutic applications either as a fractional or as a total treatment dose.

The aim of this study was to observe, how the in vitro exposition to severaldoses of ionizing radiation (in the range 5 – 120 Gy) affects DSC profile of humanblood serum thermal denaturation. Not only the direct effects of radiation exposurewere tracked, but also its long-term effects during an aging of serum solutions.

The serum samples obtained from healthy volunteers were diluted 20-fold indegassed redistilled water. The measurements were made using VP-DSC (Mi-croCal). Each sample was scanned twice in the temperature range 20 – 100 ºC, 1 ºCper min. All serum samples were measured weekly up to 3 weeks post exposure toobserve an aging process of solutions. The in vitro exposition process was conduc-ted using two kinds of ionizing radiation – neutrons and X rays. The Californ-252radioisotope was used as a neutron source and at time of the experiment the sourceactivity was approximately 65 do 58 MBq (mean energy of neutrons 2.35 MeV).The X – rays were produced by linear accelerator working at the nominal potentialof 6 MV. The control group of samples always remained under the same conditionsas the irradiated group (except for the irradiation process). This procedure allowedthe comparison of the differences between the aging process of the control and theirradiated sample taking place in cooling conditions, about 4 °C.

The direct influence of ionising radiation on serum solutions was observed inDSC profiles of samples exposed to 5 Gy neutron radiation while the effect of Xrays was only visible at doses above 30 Gy. A clear tendency for the serum solu-tions to age faster as a result of their irradiation has been observed. These resultsare in agreement with what we observed in a previous research regarding X-rayand neutron radiation effects on human blood serum using lower doses of radiation.The current results show the dependence of the aging acceleration on the radiationdose.


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Thermogravimetry analysis of bioadsorbents from coffee grounds for

CO2 capture MARCELINA SOŁTYSIK¹*, IZABELA MAJCHRZAK-KUCĘBA1,

DARIUSZ WAWRZYŃCZAK1

1 Czestochowa University of Technology, Faculty of Infrastructure and Environment, Department of

Advanced Energy Technologies, Dabrowskiego Street 73, 42-201

Czestochowa, Poland


Keywords: bioadsorbents, CO2 capture, coffee grounds

The world is facing a growing problem of increasing waste. According to a

World Bank report, 2.01 billion tons of waste were produced in 2016. This amount

may increase to 3.4 billion tons already in 2050 if the growing trend remains un-

changed [1]. One of them is coffee grounds - one hundred and twenty thousand tons

of this coffee waste ends up in landfills [2]. The appropriate processing of coffee

grounds gives the possibility to receive bioadsorbent with optimal properties in terms

of microstructure and surface area for efficient carbon dioxide adsorption. The one-

step carbonization process with simultaneous activation of coffee substrate allows

obtaining microporous adsorbent structures.

This paper presents the potential of bioadsorbent prepared from coffee grounds

for carbon capture dioxide.

The possibility for its application for carbon dioxide capture was determined

by thermogravimetry analysis. Thermal stability tests were performed for all sam-

ples. The determination of the sorption capacity was performed by temperature-pro-

grammed adsorption under condition of dilute 16% CO2 and pure (99,999%) CO2.

The final step of the thermogravimetric tests was to determine the stability of

the obtained adsorbents in the results of several cycles of adsorption/regeneration of

carbon dioxide, thanks to the TG-Vacuum. This system allowed the investigation of

the cycling capability of the adsorbent in a vacuum regeneration system.

References

[1] Kaza, Silpa, et al. What a waste 2.0: a global snapshot of solid waste management to 2050. World

Bank Publications, 2018.

[2] https://naukawpolsce.pap.pl/aktualnosci/news%2C80573%2Cogien-w-kominku-dzieki-fusom-z-

kawy.html (Access to the website on 6.05.2021.)


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Tetraphenylborate ions as modulators of binding interactions of

sodium dodecyl sulfate with bovine serum albumin

O. GRABOWSKA, K. CHMUR, J. MAKOWSKA, K. ŻAMOJĆ, A. TESMAR,

D. WYRZYKOWSKI*, L. CHMURZYŃSKI

Faculty of Chemistry, University of Gdańsk,


Keywords: tetraphenylborate, sodium dodecyl sulfate, bovine serum albumin,

thermodynamic parameters

In this contribution the binding interactions of sodium dodecyl sulfate (SDS)

with bovine serum albumin (BSA) saturated with tetraphenylborate ions, [BPh4]-,

in 10 mM cacodylate buffer (pH 7, T = 298.15 K) were investigated using a set of

experimental methods, namely isothermal titration calorimetry, differential scan-

ning calorimetry, fluorescence spectroscopy and circular dichroism spectroscopy.

Experimental data revealed that BSA has two binding sites capable to bind

[BPh4]- anions. The first site of BSA binds two [BPh4]

- ions followed by the satura-

tion of the second site by four tetraphenylborate anions. The binding of the anions

in the first site of BSA is an enthalpy driven process in which the charge – charge

type or/and van der Waals interactions are engaged in the formation of the {BSA-

([BPh4]-)2} complex. On the other, thermodynamic parameters (|ΔH(ITC)2| <

|TΔS(ITC)2|) point the fact that hydrophobic interactions involved in binding events

in the second site, play a pivotal role in the stabilization of the resulting

{([BPh4]-)2-BSA-([BPh4]

-)4} complex. Previous studies revealed that in the absence

of [BPh4]- in the system albumin binds two and five molecules of SDS per one

molecule of BSA in the first and the second site, respectively.

In this study, we have found that in the presence of tetraphenylborate anions

only one binding site of BSA becomes saturated with 4 – 5 molecules of SDS.

Thus, it can be concluded that both [BPh4]- and SDS are bound to the same “first”

binding site of BSA. Upon saturation of the "first" site, the investigated compounds

reveal affinity to different sites of the protein. Due to high amounts of albumin (ca.

40 μM) in cell culture media used in cytotoxicity assays [1], the described phe-

nomenon of the blocking the BSA binding sites can be applied in biological studies

for preventing the albumin - tested drug interactions.

Furthermore, the thermal stability of the investigated BSA/SDS/[BPh4]- com-

plexes as well as the conformational changes of the protein on account of the bind-

ing events were accessed and discussed over the 298.15 – 363.15 K temperature

range based on DSC and CD measurements.

References

[1] J.C. Pessoa, I. Correia. Misinterpretations in evaluating interactions of vanadium complexes with

proteins and other biological targets. Inorganics. 9:17, 2021.


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Evaluation of the thermal stability of bioactive compounds in coffee

beans.

JOANNA GRZELCZYK¹*, GRAŻYNA BUDRYN², PETR FIURASEK2, ASHOK

KAKKAR2

1Institute of Food Technology and Analysis, Lodz University of Technology

2Department of Chemistry, McGill University


Keywords: thermal anlysis, coffee, stability

Coffee is one of the food products with the highest content of polyphenols,

which is significantly changed during roasting. During the coffee roasting process,

coffee beans experience weight loss and volume increase, change in color as well

as chemical composition, structural and phase transitions. All these changes affect

quality and stability of coffee beans. During coffee roasting new compounds are

created responsible for the aroma, color and flavor of coffee beans and finally

brews. However, under the influence of exothermic reaction, decomposition of pro-

teins, polysaccharides, trigonelline, chlorogenic acid and caffeine occurs.

The main aim of this research was to evaluate the thermal behavior of the

green, light and dark roasted beans. We carried out tests of ground and freeze-dried

coffee two types: Coffea arabica L. (Arabica) and Coffea canephora L. (Robusta)

with different roasting levels. A detailed evaluation of the thermal stability of bio-

active compounds in coffee was carried out using techniques including thermo-

gravimetric analysis (TGA), differential scanning colorimetry (DSC) and Fourier

transform infrared spectroscopy (FT-IR).

The study showed that the coffee roasting process should be carried out at

temperatures below 250 °C, to preserve the highest quality and high concentrations

of bioactive compounds. Green coffee was found to be the most stable as a poten-

tial additive of thermally processed food, because it has a high content of thermo-

stable caffeine and caffeic acid. On the other hand the ideal re-heat treatment for

coffee extracts was found to be up to 130 °C, where we found high level concentra-

tion of bioactive compounds. The use of low temperatures helps prevent degrada-

tion of valuable coffee compounds, and it allows them to be used in the design of

foods with health-promoting properties. The work is the result of the research pro-

ject No. RNN/WFS/22/2018 financed by The Own Scholarship Fund of TUL.

References

[1] Lee SJ, Kim MK, Lee KG. Effect of reversed coffee grinding and roasting process on physico-

chemical properties including volatile compound profiles. Innov Food Sciemegr. 44:97-102,

2017.

[2] Parniakov O, Bals O, Barba FJ, Mykhailyk V, Lebovka N, Vorobiev E. Application of differential

scanning calorimetry to estimate quality and nutritional properties of food products. Crit Rev

Food Sci. 58:362-285, 2018.

[3] Roos YH. Thermal analysis, state transitions and food quality. J Therm Anal Calorim. 71:193-

199, 2003.


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SESSION 7:

V4 8 & CCTA14

Surface mobility and crystal growth in Se95Te5 amorphous material

JAROSLAV BARTÁK¹*, SIMONA MARTINKOVÁ¹, MICHAL KURKA2,

MICHAELA VČELÁKOVÁ3

1University of Pardubice, Faculty of Chemical Technology, Department of Physical chemistry

2University of Pardubice, Faculty of Chemical Technology, Center of Materials and Nanotechnolo-

gies – CEMNAT 3University of Pardubice, Faculty of Chemical Technology, Department of Inorganic Technology


Keywords: crystal growth, viscosity, thin films, chalcogenide glass

This contribution is focused on the crystal growth in bulk glasses and thin films

of Se95Te5 with respect to the mobility of structural units in volume and at the sur-

face [1]. The surface crystal growth in Se95Te5 thin films was followed down to the

glass transition temperature and below, evincing a similar behavior to that occurring

in organic molecular glasses [2], and showing the possible transition from diffusion-

controlled to diffusion-less crystal growth [3].

Furthermore, the surface mobility was studied by following the smoothing pro-

cess of a sinusoidal periodic grating embossed onto the surfaces of bulk and thin film

samples [4]. The smoothing occurred by viscous flow providing the near-surface

viscosity data of the studied material, which were used to describe the crystal growth

in a wide temperature region. Analysis of the relationship between crystal growth

rate and viscosity revealed significant decoupling concerning the surface crystal

growth showing similar behavior observed in amorphous selenium [5, 6]. This was

attributed to the fast crystal growth induced by high surface mobility, as described

by the surface diffusion coefficient.

Acknowledgements

This work was supported by the Czech Science Foundation (Grant no. 20-02183Y) and by the

Ministry of Education, Youth and Sports of the Czech Republic (Grant no. LM2018103).

References

[1] S. Martinková, D. Valdés, S. Slang, K. Pálka, J. Barták. Relationship between crystal growth and

surface/volume mobilities in Se95Te5 bulk glasses and thin films. Acta Mater.

https://doi.org/10.1016/j.actamat.2021.116953, 2021

[2] Q. Shi, T. Cai. Fast Crystal Growth of Amorphous Griseofulvin: Relations between Bulk and Sur-

face Growth Modes. Cryst. Growth Des. 16:3279-3286, 2016.

[3] Y. Sun, H. Xi, S. Chen, M.D. Ediger, L. Yu. Crystallization near Glass Transition: Transition from

Diffusion-Controlled to Diffusionless Crystal Growth Studied with Seven Polymorphs. J. Phys.

Chem. B 112:5594-5601, 2008.

[4] W.W. Mullins. Flattening of a nearly plane solid surface due to capillarity. J. Appl. Phys., 30 (1959)

77-83.

[5] J. Barták, J. Málek, K. Bagchi, M.D. Ediger, Y. Li, L. Yu. Surface mobility in amorphous selenium

and comparison with organic molecular glasses. J. Chem. Phys.154: 074703-1-6, 2021.

[6] J. Barták, D. Valdés, J. Málek, V. Podzemná, S. Slang, K. Pálka. Comparison of Lateral Crystal

Growth in Selenium Thin Films and Surface of Bulk Samples. Cryst. Growth Des. 18:4103-4110,

2018.


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Application of thermal analysis in the study of photochemically active

kaolinite surfaces

KRISTÓF J*, HORVÁTH E, ZSIRKA B, VÁGVÖLGYI V

University of Pannonia

Faculty of Engineering, Veszprém, Hungary


Keywords: kaolinite, photocatalysis, TPD, TGA

Photocatalytically active sites on a kaolinite mineral surface can be prepared by

thermal and acidic treatment as well as via mechanochemical means. Acid

treatment of the surface results in the formation of coordinated water, which –

due to the wide range of bonding strengths- is liberated between 300 and 400 ºC

upon heating. Temperature Programmed Desorption (TPD) is a commonly used

technique for the quantitative determination of surface bonding sites with acid-

ic/basic character. In the case of kaolinite, however, morphological changes re-

sult in H-bonds of varying energy. In additon, in the vicinity of defect sites and

along broken edges the bonding of Eigen/Zundel-type water occurs with a wide

energy range. Partial dehydroxylation around and above 400 ºC represents an

additional error. Therefore, the proper selection of the sample pre-treatment

temperature is of utmost importance.

The amount of water liberated between 300-400 °C (determined by TGA) was 0.2

%, depending on the type of heating (linear or CRTA). At the same time, under

isothermal heating at 400 °C (for 30-180 min) the water loss is 5-15%. It means

that the amount of water is comparable to that of the test gases causing signifi-

cant measurement errors. Therefore, TPD should be used very carefully. When

defect sites are prepared either with acidic treatment or heating to increase pho-

tochemical activity, the population and/or the strength of H-bonds is reduced

due to steric hindrance leading to the reduction of the measurement error. The

temperature and time of heat treatment should be determined by the TG/DTG

method.

With the parallel use of 1H MAS NMR and inverse gas chromatography (IGC)

specific ((H-bonds, Broensted acid/base character) and non-specific ((Lewis)

sites can be distinguished. It was proved that the ratio of the two types of bond-

ing sites can influence the photochemical activity and can lead to the proper

planning of the catalyst surface.

References

[1] V. Vágvölgyi, K. Győrfi, B. Zsirka, E. Horváth, J. Kristóf. The role of thermal analysis in the

study of high iron-content kaolinite-based photocatalyst. J. Therm. Anal. Calorim. 2020. DOI:

10:1007/s10973-020-09350-2


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Polymorphism of Na3RE(PO4)2 compounds – a review of available data

IRENA SZCZYGIEŁ*, ALEKSANDRA J. PELCZARSKA

Wroclaw University of Economics and Business,

Department of Inorganic Chemistry, Faculty of Production Engineering


Keywords: phase transitions, rare earth orthophosphates, crystal structure

Doped double phosphates of sodium and rare earth elements (RE) with

the general formula Na3RE(PO4)2 have been extensively studied in recent decades

for their optical and structural properties. These compounds can crystallize in sev-

eral types of structures derived from those of glaserite. Since binary Na and RE

orthophosphates are promising phosphors emitting tunable or white light, they can

be applied as white LEDs components. Unfortunately, optical properties

of Na3RE(PO4)2 are affected by their exact structure, which can change from trigo-

nal to monoclinic and is dependent not only on RE3+ radii but also on synthesis

method and sintering temperature. Due to the multitude of Na3RE(PO4)2 structures,

the use of a different temperature regime during their synthesis may lead to obtain-

ing different polymorphs of the same compound and thus to a different assessment

of their physicochemical properties.

Until now there is a scarce data on Na3RE(PO4)2 polymorphism and the phos-

phates structure-temperature dependence. Therefore, we have made an attempt

to systematize the data on the relationship between the type of synthesis and

the crystallographic structure of Na3RE(PO4)2. The temperatures of polymorphic

transitions have been compared with the available literature data.


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Some recommendation for the treatment of thermoanalytical kinetic

data

PETER ŠIMON,*, ZUZANA CIBULKOVÁ, TIBOR DUBAJ

Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology in Bratislava


Keywords: thermal analysis, kinetics, model-free methods, general rate equation

Condensed state processes are extensively studied by thermoanalytical tech-

niques. Mechanisms of these processes are very often unknown or too complicated

to be characterised by a simple kinetic model. They tend to occur in multiple steps

that have different rates. To describe their kinetics, the methods based on the sin-

gle-step approximation are mostly applied [1]:

( ) ( )d

fd

k Tt

=

(1)

Eq.(1) is called the general rate equation, where k(T) is the temperature

function and f(α) is the conversion function. Among the methods based on Eq.(1),

the isoconversional (or model-free) ones are most popular, mainly in evaluation of

the experimental results measured under linear heating rate.

The isoconversional methods can be divided into integral, incremental and dif-

ferential ones. The best values of kinetic parameters can be obtained by the incre-

mental methods. Application of non-Arrhenian temperature functions will be

demonstrated. Mainly the application of Berthelot-Hood temperature function re-

moves the problems with evaluation of the temperature integral where this can be

obtained in a closed form. Use of integral isoconversional methods should be

avoided since they provide mathematically incorrect results in the case of activa-

tion energy depending on conversion.

The temperature and conversion functions are just mathematical tools for the

description of kinetic data. The parameters occurring in these functions may not

have any clear physical meaning in general. Hence, conclusions on the kinetics of

the process under study should not be drawn from the values of individual kinetic

parameters (e.g., activation energy); they should be drawn from the experimentally

accessible quantities such as reaction rate, isoconversional time, temperature, etc.

This paper offers an alternative view on the thermoanalytical kinetics than that

published in [2]. Acknowledgement – This paper was supported by the Slovak Research and Developent Agency, pro-

ject No. APVV-15-0124.

References

[1] P. Šimon. Considerations on the single/step kinetics approximation. J.Therm.Anal.Calorim. 82:

651-657, 2005.

[2] S. Vyazovkin, A. K. Burnham, J. M. Criado, L. A. Pérez-Maqueda, C. Popescu, N. Sbirrazzuoli.


analysis data. Thermochim. Acta 520: 1–19, 2011.


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50th Anniversary of the Establishment of Czech Group

for Thermal Analysis

PETRA ŠULCOVÁ*

Faculty of Chemical Technology, University of Pardubice, Studentská 573,

532 10 Pardubice, Czech Republic


Keywords: thermal analysis, Czech Group for Thermal Analysis

The Czech Group for Thermal Analysis (CGTA) has been founded in 1972

being inspired by the foundation of International Confederation for Thermal

Analysis in Aberdeen in 1965 (ICTAC from 1992). CGTA is a collective member

of ICTAC. First chairman was Dr. Karel Habersberger (Inst. Chem. Technol.,

Prague) followed by Assoc. Prof. Vladimír Balek (Nuclear Res. Inst. Řež). One of

the founders and eminent personage professor Jaroslav Šesták served many years

as the head of CGTA and national representative at ICTAC. Since 2008 professor

Petra Šulcová is the head of CGTA and professor Jiří Málek (University of

Pardubice) was national representative at ICTAC (University of Pardubice) from

2010 to 2020. Since 2020, this position has been held by Dr. Jaroslav Barták.

Organization of workshops and meetings focused on theoretical aspects and

instrumentation of thermal analysis as well as the methods of evaluation of

thermoanalytical data is one of the main activities of CGTA. Among the main

achievements of these activities certainly belongs the Czech and Slovak thermal

analysis terminology as well as the standardization tests for calibration of thermal

analysis instruments that took place in university and Academy of Sciences

laboratories and research institutions in Czechia and Slovakia.

In 2010 CGTA has organized the session of Thermal Analysis and Calorimetry

within the 62nd annual meeting of Czech Chemical Society that has been

historically first joint meeting of thermal analyst from Slovakia and Czechia within

the framework of annual meetings of chemical societies. According to the

participants it has been a successful event that significantly improved mutual

exchange of experiences and helped to establish new contacts within the different

laboratories. The section of Thermal Analysis is also part of the program at the

Congress every two years (64th in Olomouc, 2012; 66th in Ostrava; 68th in Prague,

2016; 70th in Zlín, 2018 and 72nd in Prague, 2020). This tradition will be maintained

in the future.

The CGTA also participated in organization of Joint Czech-Hungarian-Polish-

Slovak Conference on Thermal Analysis (1st Joint meeting has been organized by

Hungarian Thermal Analysis Group, 2nd under auspices of Polish Society of

Calorimetry and Thermal Analysis, 3rd being organized by Slovak Working Group

on Thermal Analysis and Calorimetry). The Joint conference in 2013 was

organized by CGTA in Pardubice, Czech Republic.

More information about the current and future activities of the Czech Group

for Thermal Analysis can be found at: www.thermal-analysis.cz.


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Current state of thermal analysis and calorimetry in Hungary

KRISTÓF J1*, LIPTAY G2

1University of Pannonia, Veszprém, Hungary

2Budapest University of Technology and Economics


Keywords: thermal analysis and calorimetry in Hungary

Thermal analysis has long been one of the most important research fields in Hungary. Start-

ing with the development of the Derivatograph in the early 1960s, Hungarian thermoan-

alysts have gained international reputation and contributed significantly to the develop-

ment of several different areas of science and technology.

The ICTAC Conference in 1974 organized in Budapest (chaired by Ferenc Paulik) with

more than 600 participants from 30 countries was a real breakthrough bringing together

– for the first time - scientists from all parts of a politically divided World.

The Atlas of Thermoanalytical Curves edited by G. Liptay in five volumes (between 1971

and 1976) compiled in international collaboration was an important step from a practical

aspect to help practicing thermoanalysts. Also, the book Who is Who in Thermal Analy-

sis and Calorimetry (edited by G. Liptay and J. Simon in 2004 and by I.M. Szilágyi and

G. Liptay in 2014) helped bring together the members of the community in a more per-

sonal way.

The most significant research teams are working in Budapest (Budapest University of

Technology and Economics; Loránd Eötvös University; Chemical Research Center of

the Hungarian Academy of Sciences), Veszprém (University of Pannonia), Szeged

(University of Szeged) and Pécs (University of Pécs).

Among the most important research topics are the study of drugs and pharmaceutical mate-

rials, biological systems and medical applications, nano-powders and surface-modified

materials, biomass utilization and analysis, polymers and polymer composites, minerals

and clay organo-complexes.

The most recent results are discussed at regular meetings (twice a year) organized jointly by

the Working Committee for Thermal Analysis and Calorimetry (established in 1973) and

the Thermoanalytical Branch of the Hungarian Chemical Society (founded in 1967)

providing a forum for researchers, academics and expert from the industry.

The most important recent event was the organization of the 2nd Journal of Thermal Analy-

sis and Calorimetry Conference organized together with the 7th Joint Czech-Hungarian-

Polish-Slovakian Conference on Thermal Analysis and Calorimetry (JTACC+V4) be-

tween June 18-21, 2019 in Budapest. This unique event was devoted to the celebration

of the 50th anniversary of the foundation (by Judit Simon) of the most popular thermo-

analytical journal, the Journal of Thermal Analysis and Calorimetry (current impact

factor is 4,626).

References

[1] G. Liptay, Thermal analysis in Hungary (in Hungarian), Magyar Kémikusok Lapja, 12:397-403,

2015.

[2] P. Šulcova, J. Sestak, A. Menyhard, G. Liptay, Some historical aspects of thermal analysis on the

mid-European territory. J. Thermal Analysis and Calorimetry 120(1): 239-254, 2015.


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The Polish Society of Calorimetry and Thermal Analysis - Scientific and Educational Activities

IWONA WILIŃSKA2, EDYTA HEBDA1, BARBARA PACEWSKA2,

KRZYSZTOF PIELICHOWSKI1*

1Cracow University of Technology, Department of Chemistry and Technology of Polymers, Faculty

of Chemical Engineering and Technology 2 Warsaw University of Technology, Faculty of Civil Engineering, Mechanics and Petrochemistry,

Institute of Chemistry

*Corresponding author: e-mail: [email protected] Keywords: PTKAT, thermal analysis, calorimetry, schools of thermal analysis

The Polish Society of Calorimetry and Thermal Analysis memorial of Wojciech Świętosławski (PTKAT) was established in 1985 on the initiative of prof. Wojciech Zielenkiewicz. The aim of the Society is to promote and develop calorimetry, ther-mochemistry and thermal analysis by organizing conferences, scientific meetings and training courses, to conduct publishing activities and to cooperate with foreign scientific societies.

Since 2004 PTKAT has been affiliated with International Confederation for Ther-mal Analysis and Calorimetry (ICTAC). Prof. Andrzej Małecki was President of IC-TAC (2012-2014).

PTKAT appreciates contribution of distinguished researchers to development of thermal and calorimetric methods granting Honorary Membership and Medal me-morial of W. Świętosławski. PTKAT also awards a prize for young scientists for their achievements in calorimetry and thermal analysis. Some of PTKAT members won prestigious international awards in recognition of their activities in this field.

Every three years, the Society's conferences (Conferences on Calorimetry and Thermal Analysis – CCTA) are held in Zakopane. The conferences are also an op-portunity to organize bi- or multilateral international events.

PTKAT also co-organizes other scientific meetings taking place in Poland, e.g. International Seminar on Thermal Analysis and Calorimetry to the memory of Prof. St. Bretsznajder, in Plock.

Since 1996 PTKAT has been organizing Schools of Thermal Analysis (SAT) aimed at familiarizing participants with research methods, possibilities of using re-search equipment and the interpretation of measurement results.

The Society is also involved in other scientific events co-organized with cooper-ation of foreign societies, for example: Joint Czech-Hungarian-Polish-Slovakian Thermoanalytical Conference (since 2007).

It should be emphasized that two important conferences at international level were co-organized by PTKAT. In 2006 – 9th European Symposium on Thermal Analysis and Calorimetry ESTAC 9 in Cracow. Then, ICTAC authorities awarded the Society with the organization of the ICTAC Congress - ICTAC-17 - in 2021 also in Cracow.


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Past and present of the Slovak Group of Thermal Analysis and

Calorimetry

PETER ŠIMON*, EVA SMRČKOVÁ

Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava


Keywords: Slovak group of thermal analysis and calorimetry, history, present

Founders of the Scientific Group for Thermal Analysis (SGTA), affiliated at the

Slovak Chemical Society, were Matej Vaniš and Vladimír Fajnor in 1972. The Sci-

entific Group was headed by Matej Vaniš until 1994. Within 1994-1998, the head

of SGTA was Vladimír Fajnor. Since 1998, SGTA is chaired by Peter Šimon.

The history of the Slovak thermal analysis is bound with the history of the Czech

thermoanalytical group since we formed practically one group. The division of the

Czechoslovak hermoanalytical group took place after splitting Czechoslovakia into

two states, Czech Republic and Slovakia (1 January 1993). However, splitting of

the state did not affect the excellent relations between Czech and Slovak thermoan-

alysts; by contrast, it seems that the collaboration became even more intense. Until

1993, SGTA was a member of ICTAC as a part of the Czechoslovak thermoanalyt-

ical group. In 1999, SGTA rejoined ICTAC and the Scientific Group of Thermal

Analysis was renamed into Slovak Group of Thermal Analysis and Calorimetry

(SGTAC).

In 1985, Czechoslovak Thermoanalytical Group was entitled to organize the

congress of ICTA-8. SGTAC organized a series of conferences on thermal analysis

called TERMANAL (17 conferences). In 2007, heads of thermoanalytical groups

of Czech Republic, Hungary, Poland and Slovakia (P. Šulcová, Cs. Novák, B.

Paczewska and P. Šimon) agreed to merge the domestical conferences into a single

international Czech-Hungarian-Polish-Slovak (V4) Conference on Thermal Analy-

sis and Calorimetry (7 conferences up to now).

Activities of SGTAC can be summarized as: organization of conferences, sup-

port of collaboration, educational activities, consultation activities, organization of

Summer school on thermal analysis and calorimetry (19 courses up to now) and

international relations. We have very close relations mainly with the Czech, Hun-

garian, Polish, Italian and Greek thermoanalytical groups; however, we keep con-

tacts also with other thermoanalytical groups and we are open for any type of col-

laboration.

Acknowledgement – This paper was supported by the Slovak Research and Developent Agency, pro-

ject No. APVV-15-0124.


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SPONSOR LECTURES

Thermal Analysis Milestones in Rigaku Corporation

LANI LLEGO CELIZ¹*, TADASHI ARII1

1Application Laboratory, SBU: Thermal Analysis, Thermal Analysis Division, Rigaku Corporation

3-9-12 Matsubara-cho, Akishima-shi, Tokyo 196-8666 Japan

*Corresponding author: e-mail: [email protected] Keywords: thermal analysis, sample observation thermal analysis, hyphenated in-strumentation STA-MS, -FTIR, polymer, food, pharmaceuticals, other materials

Thermal analysis is an extensively applied technique in understanding the ther-

mal behavior of a material. Rigaku Corporation has been in the forefront in the deve-lopment and manufacturing of thermal analyzers for nearly seven decades. In 1957, Rigaku announced Japan’s first automatic recording thermal analyzer “Thermoflex series” and has developed the world’s first thermal balance based on the differential principle in 1981. Since then, Rigaku has a long history in providing cutting edge technology from general-purpose thermal analyzers to hyphenated instrumentations such as STA-MS/FTIR, XRD-DSC, thermal analysis in humidity controlled at-mosphere and sample controlled thermal analysis. Significant milestones in the hi-story of thermal analysis in Rigaku Corporation up to the recently developed thermal analyzers with sample observation capability and other attachments that are essential to your needs will be presented during the sponsor lecture.

References: [1] T. Arii. Development of a simultaneous thermogravimetry-differential thermal analysis and pho-

toionization mass spectroscopy instrument. Netsu Sokutei. 38(5):149-156, 2011. [2] R. Matsumoto. et. al. Thermal decomposition and gas release properties of metal chloride-graphite

intercalation compounds prepared utilizing polyimide film-derived graphite sheets. Synthetic Metal. 255:116103. (2019)

[3] J. Rouquerol. Thermal Analysis Sample-controlled techniques. In P. Worsfold, C. Poole, A Towns-hend, M. Miro (Eds.), Encyclopedia of Analytical Science (3rd ed.). 10: 17-32 (2019)

[4] M. Wang. Y. Sawada. K. Saito. et. al. Thermal change of Al13, Tris(8-Hydroxyquinolinato Alumi-num (III) studied by TG and XRD-DSC. J Therm Anal Calorim. 89: 363-366 (2007).

[5] K. Kawano. H. Kosuge. N. Oshima. et. al. Ligand structure effect on a divalent ruthenium precursor for MOCVD. Mater. Res. Soc. Symp. Proc. 1155-C09-11 (2009)

[6] T. Arii. K. Motomura. S. Otake. Evolved gas analysis using photoionization mass spectrometry, EGA-PIMS: Characterization of pyrolysis products from polymers. J. Mass Spectrom. Soc. Jpn. 59: 5-11 (2011).

[7] R. Matsumoto. Y. Oishi and T. Arii. Thermal decomposition of cesium-ethylene-ternary graphite intercalation compounds. Thermochimica Acta. 507-508: 142-145 (2010).

[8] T. Tsugoshi. T. Nagaoka. K. Hino. Et.al. Evolved gas analysis-mass spectrometry using skimmer interface and ion attachment mass spectrometry. J Therm Anal Calorim. 80: 787-789 (2005).

[9] T. Arii. N. Fujii. Controlled-rate thermal analysis. Kinetic study in thermal dehydration of calcium sulfate dihydrate. Journal of Analytical and Applied Pyrolysis. 39: 129-143 (1997).

[10] T. Arii. S. Ichihara. H. Nakagawa. N. Fujii. A kinetic study of the thermal decomposition of poly-esters by controlled-rate thermogravimetry. Thermochemica Acta. 319:139-149 (1998).

[11] T. Arii. A. Kishi. Y. Kobayashi. A new simultaneous apparatus for X-ray diffractometry and dif-ferential scanning calorimetry (XRD-DSC). Thermochimica Acta. 325: 151-156 (1999).


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Introducing the Discovery X3: A revolutionary multi-sample DSC

GRAY SLOUGH¹*, JASON SAIENGA¹

1TA Instruments

*e-mail: [email protected] Keywords: thermal anlysis, X3 DSC, TA Instruments

Demand for high-quality DSC data continues to increase rapidly throughout

many industrial markets. Differential scanning calorimeters (DSCs) are standard instruments used in virtually every state of a materials lifecycle: from raw material research and development through quality control and failure analysis. The devel-opment of new materials typically requires extensive testing with the objective of understanding the material structure-property relationship in relation to material formulations, processing conditions, or simply to help produce better, more suc-cessful products.

Traditional DSCs are limited to analyzing a single sample during an experiment which may, depending upon the method, extend from several minutes to many hours. Temperature modulating DSC (MDSC®) experiments, a unique TA Instru-ments invention which can be used to examine material properties such as heat ca-pacity or explore material stability and compatibility, typically take hours to achieve a result. Innovations that increase productivity and improve the efficiency of testing have the potential to impact important metrics such as time to market or responsiveness to customers, and ultimately, the success of materials research.

This presentation will introduce the newest innovation from TA Instruments: the multi-sample Discovery X3 DSC. This revolutionary multi-sample DSC delivers industry-leading performance for up to three samples simultaneously. The new X3 DSC will not only save valuable research time and lab space by consolidating three instruments and three tests into a single operation, it will open possibilities in DSC testing that a single cell DSC simply can’t match.


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Accelerating Rate Calorimetry (ARC) and Isothermal Calorimetry for

Cycling of Batteries

EKKEHARD FÜGLEIN

NETZSCH-Gerätebau GmbH, Wittelsbacherstraße 42, 95100 Selb, Germany

e-mail: [email protected]

Keywords: adabatic, thermal runaway, thermal hazard screening, charging and dis-

charging, coin cell, battery

Accelerating Rate Calorimetry (ARC) is a method to study worst-case scenarios

and thermal runaway reactions. In contrast to other caloric techniques such as reac-

tion calorimetry, combustion calorimetry or Differential Scanning Calorimetry

(DSC), ARC-type equipment allow for an adiabatic sample environment. Adiaba-

ticity is essential in order to observe the most tremendous reaction progress possible.

Decomposition reactions, which are of particular interest in this context, produce

heat and pressure, since the reactions are usually strongly exothermic and are form-

ing decomposition gases. The adiabatic sample environment is realized inside the

ARC-type calorimeter via a set of heaters surrounding the sample compartment and

via a smart temperature control regime. The first objective is to detect the tempera-

ture at which the self-decomposition of a sample or a sample mixture starts. The

second objective is to avoid any exchange of heat between the sample and the sur-

roundings once the exothermic decomposition reaction has started.

This work presents results of the thermal decomposition of hydrogen peroxide

solutions. A scanning device was used in order to detect whether or not the sample

has a thermal hazard potential and an ARC-type device was employed in order to

carry out tests under adiabatic conditions.

A module dedicated to isothermal cycling of batteries is used to measure the

heat signature of coin cells during charging and discharging. The heat dissipated by

the battery is independently quantified and related to the applied power in order to

calculate the efficiency of the cycling process. Special attention was turned on the

influence of temperature as well as the charge and discharge rate. This information

is helpful for the further development and optimization of battery components.


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RTM6 Epoxy resin: An In-Situ Rheo-Raman Study of Curing Kinetics

and Dynamic Mechanical Analysis (DMA) of the Cured Material

JOSÉ ALBERTO RODRÍGUEZ ¹, AND MATTHIAS WALLUCH 2*

1Affiliation (institution only, see example) 1Anton Paar Germany GmbH, Stuttgart, Germany

2Anton Paar GmbH – Business Area Rheometry, Graz, Austria


Keywords: DMA, Epoxy, Curing, Kinetics, Dynamic Mechanical Analysis

The kinetics of an RMT 6 epoxy resin and the thermo-mechanical properties of

the finally cross-linked product were experimentally studied using an Anton Paar

MCR 702 MultiDrive rheometer. In order to gain insights in the evolution of macro-

scopic rheological properties induced by chemical reactions within the sample ma-

terial, the rheological measurements were coupled with in-situ Raman spectroscopy.

The gelation-kinetics was further evaluated with a so-called Multiwave rheometry

test. Accordingly, the Winter-Chambon criterion was used to determine the sol/gel

transition point [1]. For dynamic mechanical analysis of the cured component a lin-

ear drive module was added to the instrument. The combination of linear drive and

rotational drive in one device allowed the characterization of thermal transitions us-

ing dynamic mechanical analysis (DMA) in two different deformation modes (tor-

sion and bending). Two thermal events could be detected from the DMA test: the

main glass transition temperature and a sub-glass transition of the material [2]. Ad-

ditionally, this unique experimental setup allows determining the complex Young’s

modulus as well as shear modulus using a single specimen in a continuous measure-

ment run over a wide temperature and frequency range. The instrument frame and

air bearings are designed to provide outstandingly low radial and axial compliance

at the same time, thus enabling the measurement of accurate modulus values in all

testing modes.

References

[1] Chambon F and Winter H H (Linear viscoelasticity at the Gel Point of a Crosslinking PDMS

with Imbalanced Stoichiometry. Journal of Rheology, 1987.

[2] Terekhina S, Fouvrya S, Salviaa M, Bulanov I. An indirect method based on fretting tests to

characterize the elastic properties of materials: application to an epoxy resin RTM6 under var-

iable temperature conditions. Wear, 2010.


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New possibilities in HITACHI – HAAS coupling techniques – simultaneous thermal - image, dimensions and color analysis

O. SAVARD¹, R. TOMIKOWSKA²*, R. TOMIKOWSKI2

1HITACHI High Tech Analytical Science

2HAAS, Research and Development Department * e-mail: [email protected]

Keywords: thermal anlysis, RealView®, image analysis, color analysis, simultane-ous techniques,

Differential scanning calorimetry DSC, thermogravimetry TGA, simultaniuos analysis STA (TGA/DSC, TAG/DTA), TMA and DMA are established and trusted methods for material characterization. Today’s advanced material development and quality control requires DSC and other thermal analysis instruments with the ability to detect and resolve thermal events in trace amounts of material within complex compounds.

RealView camera system allows to see the changes in sample in real time down to a temperature of -50 deg C. The high-resolution images collected are linked to precise temperature and time measurement data which are saved to review at any time. Using the NEXTA TA software, the colors using LAB, CMYK and RGB standards can be quantified. Seeing what happens to the sample in real time is inval-uable when researching new materials, troubleshooting or understanding unexpected behavior.[1]

There were comparing tests run with HITACHI analysers for solving materials problems and engineering tasks. Results show how accuracy and baseline stability, as well as cooling performance influence research process.

Baseline stability and accuracy allows to obtain results for demanding research aims. Additionaly simultenious analysis combining thermal analysis with image and color analysis solves uncertainty in cases of unknown effects shown on curves only, and widers amount of informations about the sample.

Pic. 1 Copper sulphate CuSO4 thermal and color analysis by HITACHI NEXTA

STA (TGA/DSC and TGA/DTA) References [1] VISIBLY BETTER, Hitachi Materials on thermal analysis.10026815: 2, 2020.


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THERMAL ANALYSIS WORKSHOP

Thermogravimetry coupled with infrared spectroscopy (TG-FTIR) and mass spectrometry (TG-MS) in materials testing

KINGA PIELICHOWSKA*,


*Corresponding author: e-mail: [email protected] Keywords: thermogravimetry, TG-FTIR, TG-MS, materials

In classical thermogravimetry (TG), the measured parameter is the change in

mass (∆m) of the sample, related to the processes taking place as a result of heat-ing. The sample may be subjected to a linear temperature increase or it may be an-nealed at a specific temperature under isothermal conditions at selected atmosphere (oxidative or non-oxidative). After plotting the dependence of the sample mass as a function of time (t) or temperature (T), a thermogravimetric curve is obtained. On the other hand, by plotting the dependence of the mass change rate (dm/dt) on time or temperature, a differential thermogravimetric curve (DTG) is obtained. The use of the TG method allows for obtaining valuable information on the processes tak-ing place in the tested sample under the influence of temperature, such as degrada-tion or oxidation processes, but it does not provide information on the volatile de-composition products. This information can only be obtained by connecting a thermogravimetric analyzer to a gas analysis system.

One of the most commonly used systems is the combination of thermogravim-etry with infrared spectroscopy (TG-FTIR) and/or mass spectrometry (TG-MS). The gaseous products released under the influence of temperature are transported into the spectroscope/spectrometer and analysed, which allows obtaining infor-mation necessary to identify volatile decomposition products of the tested materi-als, including intermediate products. By identifying the decomposition products, it is possible to conclude about the mechanism of the thermal decomposition process.

The lecture will discuss the theoretical basis of TG, TG-FTIR and TG-MS methods along with practical recommendations on how to perform the thermoana-lytical measurements. Selected examples of the applications of the TG-FTIR and TG-MS methods for the studies of thermally induced processes of various groups of materials, including organic & inorganic compounds, as well as polymers, will be presented and explained. Acknowledgements This work was supported from the subsidy of the Ministry of Education and Science for the AGH University of Science and Technology in Kraków (Project No 16.16.160.557).


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Theory and laboratory practice in Differential Scanning Calorimetry - from simple experiments to specific peak analysis

RANJIT K. VERMA*

University Department of Chemistry, Magadh University, Bodh Gaya-824234, India

* E-mail: [email protected]

Keywords: heat-flux DSC, power-compensated DSC, area under peak, la-boratory practice

Differential Scanning Calorimetry (DSC) may have two configurations viz.

‘heat- flux’ and ‘power-compensated’. A Heat Flux DSC is similar to a conven-tional DTA in instrument design and hence it is sometimes termed as Quantitative DTA. In a Power Compensated DSC, the sample and reference pans are main-tained at the same temperature throughout the scan and the difference in power in-puts into sample and reference is recorded w.r.to the reference temperature. In a DSC, it is convenient to understand phenomena such as glass transition, melting, crystallisation, decomposition, curing etc. using a horizontal base-line that also helps in getting the DSC peak area. The area under peak is directly proportional to the heat evolved (exo) or absorbed (endo) during a thermal event in the sample DSC does also provide data on heat capacity and conductivity. However, before its meaningful use, calibration is indispensable for which standard materials are used. For laboratory practice, some basic experiments such as melting point determina-tion and percentage purity is suggested. An application of using the area under peak for kinetic analysis of a step will be discussed. References [1] R.K.Verma, J.O.Hill, L.Niinisto, S.C. Mojumdar, David D. Kumar. A curriculum framework

for education in Calorimetry. Journal of Materials Education. 88:236–249, 2006. 34:161-174, 2012


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Good laboratory practice in Dynamic Mechanical Analysis

KONSTANTINOS N. RAFTOPOULOS

Department of Chemistry and Technology of Polymers, Cracow University of Technology

*Corresponding author: e-mail: [email protected] Keywords: Dynamic mechanical analysis, relaxation phenomena

Dynamic mechanical analysis (DMA) applies a harmonic stimulus to a materi-

al in the form of a mechanical stress, and monitors the corresponding deformation. That way, viscoelastic properties of materials can be measured as a function of temperature. The frequency of the stimulus can be varied in a relatively broad fre-quency range. That way, we can study in detail relaxation phenomena, including the dynamic glass transition.

In this short tutorial, we will introduce the first principles of the method, and

based on them we will try to find out: how to choose the most appropriate mode for the stimulus i.e. should

we stretch the sample, compress, or bend it? how to prepare the sample, and how to choose the optimal size how to choose the magnitude of the stimulus (or rather the response) how to choose the temperature range how to choose the frequency (or the frequencies) of the experiment

We will also comment briefly on data evaluation, especially when we are in-

terested in the dynamic behaviour of relaxation phenomena.


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Treatment of thermoanalytical kinetic data using the general rate equation

PETER ŠIMON

Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology in Bratislava

*Corresponding author: e-mail: [email protected] Keywords: thermal analysis, kinetics, model-free methods, general rate equation

Condensed state processes are extensively studied by thermoanalytical tech-

niques. Mechanisms of these processes are very often unknown or too complicated to be characterised by a simple kinetic model. They tend to occur in multiple steps that have different rates. To describe their kinetics, the methods based on the sin-gle-step approximation are mostly applied [1]:

(1) Eq.(1) is called the general rate equation, where k(T) is the temperature func-

tion and f(α) is the conversion function. Among the methods based on Eq.(1), the isoconversional (or model-free) ones are most popular, mainly in evaluation of the experimental results measured under linear heating rate.

Evaluation of the kinetic results using Eq.(1) is easy and simple; however, the interpretation of the results obtained may be more difficult. In the presentation, the following items will be touched:

(i) Physical meaning of the general rate equation. (ii) Kinetic hypersurface, the temperature and conversion functions. (iii) Model-fitting and model-free methods. (iv) Division of isoconversional methods. (v) Mathematical incorrectness of integral isoconversional methods. (vi) Physical meaning of parameters occurring in the temperature and con-

version functions. (vii) Modelling of processes using the kinetic parameters from isoconver-

sional methods. (viii) Application of non-Arrhenian temperature functions.

Acknowledgement – This paper was supported by the Slovak Research and Developent Agency, project No. APVV-15-0124. References [1] P. Šimon. Considerations on the single/step kinetics approximation. J.Therm.Anal.Calorim. 82:

651-657, 2005.

df

dk T

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Notions of calorimetry and nanocalorimetry for exploring thermal behavior of polymers in relation to their morphology

ALEXEY P. MELNIKOV¹,*, DIMITRI A. IVANOV¹,²

1Lomonosov Moscow State University, Faculty of Chemistry

2Institut de Science des Matériaux de Mulhouse *Corresponding author: e-mail: [email protected]

Keywords: thermal anlysis, polymers, calorimetry, differential scanning calorime-try, nanocalorimetry

The work focuses on applications of thermal analysis techniques in the field of

polymers, including thermoplastics, thermosets, elastomers etc. To describe ther-mal behavior of polymers in relation to their structure some basics of polymers morphology is overviewed. Important issues as chain conformation, crystallinity and possible morphology are described to introduce people who are not specialists in this field.

With the help of several cases with practical application the processes of glass transition, cold crystallization, metl crystallization, melting and recrystallization were described in terms of thermal analysis techniques. Some particularities as is-sues of thermal history and overcooling were also overviewed. The basics of calo-rimetry were described in the framework of principle of measurements, operation mode, construction principle etc.

Moreover, in the present contribution we describe a relatively new technique for thermal analysis – ultrafast chip calorimetry (nanocalorimetry) [1-2], and the possibilities of its in-situ and ex-situ combination with different methods of struc-tural analysis [3-5]. Acknowledgements: The authors thank Russian Foundation for Basic Research for the financial support (project no. 19-29-12049). References [1] L.H. Allen, G. Ramanath, S.L. Lai, Z. Ma, S. Lee, D.D.J. Allman, K.P. Fuch, 1 000 000 °C/s

thin film electrical heater: In situ resistivity measurements of Al and Ti/Si thin films during ul-tra rapid thermal annealing, Applied Physics Letters. 64(4):417, 1994.

[2] S.L. Lai, L.H. Allen, MEMS-based scanning calorimeter for thermodynamic properties of nanostructures, Microscale Thermophysical Engineering. 2(1):11, 1998.

[3] W.A. Donald, R.D. Leib, J.T. O'Brien, A.I.S. Holm, E.R. Williams, Nanocalorimetry in mass spectrometry: A route to understanding ion and electron solvation, Proceedings of the National Academy of Sciences. 105(47):18102, 2008.

[4] M.D. Grapes, T. LaGrange, K. Woll, B.W. Reed, G.H. Campbell, D. A. LaVan, T.P. Weihs, In situ transmission electron microscopy investigation of the interfacial reaction between Ni and Al during rapid heating in a nanocalorimeter, APL Materials, 11(2):116102, 2014.

[5] A. Melnikov, M. Rosenthal, D. Ivanov, What Thermal Analysis Can Tell Us About Melting of Semicrystalline Polymers: Exploring the General Validity of the Technique, ACS Macro Let-ters. 7(12):1426-1431, 2018.


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LIST OF AUTHORS

A Acheson B. S1_O-02

Alonso A. S2_O-04

Alvear D. S2_O-04

Anfertyev V.A. S2_O-05

Angelopoulos P.N. S5_P-21

Antonovič V. S5_O-06

Arai M. S1_P-11

Arii T. SL-01, S2_O-01, S2_P-01

Ashton G.P. S2_O-06

Atanasova M. S4_O-13

Attri D. S2_O-02

B

Badeen Ch. S1_O-02

Balakirev V.Yu. S2_O-05

Baltakys K. S3_P-07

Bandi T.N. S2_O-02

Baran S. S6_O-02

Barták J. S5_P-08, S7_O-01

Ben Mbarek W. S3_P-01

Berezicka A. S5_P-09

Beurroies I. S5_O-08

Biegun M. S1_P-07

Blanco I. IL-03

Blonska-Tabero A. S3_O-04

Boncel S. S5_O-04, S5_P-19

Boris R. S5_O-06

Borreguero Simón A.M. S5_O-07

Borucka M. S4_O-06

Bosacka M. S3_O-04

Brancart J. S1_O-10, S4_ O-1

Brunetti B. S1_P-01

Budryn G. S6_P-0, S6_P-03

Burda T. S2_P-05

Buzyurov A.V. S1_P-01

C Calduch C.B. S4_O-07

Callicó G.M. S2_P-02, S2_P-04

Čapčianska J. S3_KL-01

Catauro M. S3_P-03

Cavallaro G. S5_P-18

Celiński M. S4_O-06

Celiz L.L. SL-01, S2_O-01, S2_P-01

Čepčianska J. S5_P-05

Chen J.Y. S1_O-04

Chen L.-P. S1_P-16

Chen M. S1_O-08, S4_O-02, S5_O-02

Chen W.-H. S1_P-16

Chernyaeva M.B. S2_O-05

Chmur K. S6_P-04, S6_P-07

Chmurzyński L. S6_P-04, S6_P-07

Cibulková Z. S5_O-03, S7_O-04

Ciccioli A. S1_P-01

Ciprioti S.V. S1_P-01, S3_P-03

Cuvellier A. S4_O-10

Cwynar K. S5_O-04, S5_P-19

D D’angelo A. S3_P-03

Dąbrowska G. S3_P-08

Dalinger I.L. S1_O-06

Dargent E. S4_ O-08

Das S.B. S5_KL-01

Datta J. S4_O-03, S4_P-10

Daza J. S3_P-01, S5_P-1

De Rivera M.R. S2_P-02, S2_P-04

De Rivera P.J.R. S2_P-02, S2_P-04

Delannoy R. S4_O-14

Del-Breilh L. S4_O-14

Delpouve N. S1_O-09, S4_O-08,

S4_O-14,

Denková P. S4_O-11

Deptuch A. S6_O-02

Dessì F. S1_P-15

Ding J. S1_O-04, S2_P-03

Dołęga A. S6_O-02

Domalik-Pyzik P. S4_O-05

Domracheva E.G. S2_O-05

Dragomirová J. S3_KL-01, S5_P-05

Drożdż E. S3_P-05, S3_P-06, S5_P-14,

S5_P-15

Dubaj T. S5_O-03, S7_O-04

Dumanov B. S5_P-01

Dziadosz J. S5_O-04, S5_P-19

Dzida M. S5_O-04, S5_P-19

Dzido G. S5_O-04, S5_P-19

E Ehrhardt D. S4_O-10

Einard M. S3_O-02

El Hanache L. S5_O-08

Erceg T.D. S4_P-01, S5_P-20

Erunov S.V. S2_O-05

Escoda L. S3_P-01, S5_P-12


180

F Favergeon L. IL-01

Ferrara F. S1_P-15

Fessas D. S6_O-01

Filipek E. S3_O-04, S3_P-08

Fiorentino M. S3_P-03

Fiurasek P. S6_P-08

Focke W.W. S4_O-13

Fojt J. S4_O-11

Fornal E. S6_O-03

Franco M.C. S5_O-07

Fu K. S1_O-08

Füglein E. SL_03

G Gajek A. S4_O-06

Gallen R. S2_O-03

Gancarz P. S1_O-03, S1_P-03, S5_P-19

Garrido Sáenz I. S5_O-07

Gibson R. S2_O-03

Gineika A. S3_P-07

Głowińska E. S4_O-03, S4_P-10

Goderis B. S4_O-09

Godzierz M. S5_P-23

Golba A. S5_O-04, S5_P-19

Grabowska K. S4_ O-12

Grabowska O. S6_P-04, S6_P-07

Greer H.F. S5_O-04, S5_P-19

Grolik J. S5_P-10

Gruszka P. S2_P-05

Grzelczyk J. S6_P-03, S6_P-08

Gullifa G. S3_P-03

Gun J. S5_O-02

Guo Z.-C. S1_P-16

Guzik M. S4_P-07

Gwóźdź P. S3_P-06, S5_P-14

H Haba A. S5_P-17

Hadała B. S1_O-11

Hamid M. S4_ O-0

Hara M. S1_P-09

Harding L.P. S2_O-06

Hebda E. S4_ O-07, S4_P-05, S7_P-03

Higashi E. S5_P-13, S5_P-16, S5_P-17

Hirai T. S1_P-10

Hoffmann J. S1_P-07, S3_O-05

Honcová P. S5_P-08

Horváth E. S7_O-02

Hotta M. IL-01, S1_P-12

Húlan T. S3_O-02

Hunger M. S4_ O-05

I Ishikawa T. S5_P-16

Islam M. S6_O-03

Ito M. S4_O-01

Ivanov D.A. WL-05

J Janík R. S3_P-09, S4_P-14

Janković B.Ņ. S1_P-04, S5_P-21

Jędrysiak R. S5_O-04, S5_P-19

Jefimova J. S3_O-02

Jerzak W. S5_P-04

Jiménez Vázquez M. S5_O-07

Jovanović V.V. S5_P-21

Jóźwiak B. S5_O-04, S5_P-19

Jóźwiak M. S1_P-02, S1_P-14

Juszyńska-Gałązka E. S6_O-02

K Kakkar A. S6_P-08

Kalinkin Al. S5_O-05

Kaljuvee T. S3_O-02

Kalska-Szostko B. S5_P-20

Kaniewski M. S1_P-07, S3_O-05

Katoh K. S5_P-13, S5_P-16, S5_P-17

Kesarkar R.S. S2_O-02

Kiełboń A. S6_P-05

Klekotka U. S5_P-20

Klem-Marciniak E. S1_P-07

Kobayashi Y. S5_P-13

Kobyliukh A. S5_P-23

Koga N. IL-01, S1_O-06, S1_P-09,

S1_P-12, S1_P-13, S3_O-01

Kogut M.M. S6_P-04

Kohutiar M. S4_P-14

Kolanowska A. S5_O-04, S5_P-19

Komatina M.S. S1_P-04

Komudzińska M. S1_P-02

Koniorczyk M. S4_O-12

Kosmela P. S4_O-04, S4_P-02

Kosowska K. S4_ O-05

Kostić M.G. S4_P-01

Kostova B. S5_O-05, S5_P-01

Kostov-Kytin Vl. S5_O-05

Kowalkowska A. S1_P-06


181

Krakovsky I. S4_P-01, S5_P-20

Kraxner J. S3_P-09

Kristóf J. S7_O-02, S7_P-02

Królikowska M. S1_P-05, S1_P-08

Kučerík J. S4_ O-11

Kumar N. S5_KL-01

Kumar V. S5_KL-01

Kurka M. S5_P-08, S7_O-01

Kuzielová E. S3_KL-01

Kuzielová E. S5_P-03, S5_P-05

Kuźnia M. S5_P-04

L Lach A. S4_P-13

Lach R. S3_P-05

Łącz A. S3_P-06, S5_P-14

Lalik S. S4_ O-07

Landetta Avellena G. S5_O-08

Lapi A. S1_P-01

Łapiński K. S2_P-05, S2_P-06

Lavoie J. S1_O-02

Lázaro D. S2_O-04

Lázaro M. S2_O-04

Lazzara G. S5_P-18

Leszczyńska A. S4_P-12

Leyk E. S6_P-01

Li H.-B. S1_P-16

Liang B. S5_O-02

Liptay G. S7_P-02

Lisuzzo L. S5_P-18

Liu J. PL-03

Liu L. S2_O-03

Liu Z. S4_O-09

Łukaszewska I. S4_O-07, S4_P-05

Lukyanenko I.A. S2_O-05

Łyszczek R. S3_P-04, S4_P-09

M Madej D. S5_O-09

Maes W. S4_O-09

Magiera A. S1_O-11, S5_P-04

Majchrzak-Kucęba I. S6_P-06

Majka T.M. S4_P-07

Makowska J. S6_P-04, S6_P-07

Malaińkienė J. S5_O-06

Malan F.P. S4_O-13

Mangialetto J. S4_O-10

Manić N.G. S1_P-04, S5_P-21

Mapossa A.B. S4_O-13

Martinková S. S7_O-01

Marzec M. S4_O-07

Mbarek W.B. S5_P-12

Mellado F.J.R. S5_O-07

Melnikov A.P. WL-05

Michnik A. S6_P-05

Mikhaylov A.L. S2_O-05

Milanović M.M. S1_P-04

Milioto S. S5_P-18

Mizera A. S3_P-05, S5_P-14, S5_P-15

Mizera K. S4_O-06

Monnier X. S4_O-08

Monogarov K.A. S1_O-06

Moricová K. S3_P-09, S4_P-14

Morvan A. S1_O-09

Moyo D.S. S4_O-13

Muravyev N.V. S1_O-06, S1_P-09

Mureddu M. S1_P-15

Muzolf-Panek M. S6_O-03

Myalski J. S5_P-23

Myka A. S3_P-04

N Nakatsu R. S1_P-13

Nie S. S4_O-02

Niesio-Będzka J. S4_P-10

Nishimoto Y. S1_P-11

Novotný R. S3_KL-01, S5_P-05

Nowacka M. S5_P-02

O Ogino Y. S1_P-11

Okada K. S5_P-17

Okazaki T. S1_P-09

Olszewski A. S4_O-04, S4_P-02

Olszowska K. S5_P-23

Ondrej A. S3_P-01

Ordon K. S4_P-05

Orsini A. S1_P-15

Orzechowski A. S2_P-06

Ostrowski A. S5_P-06

Ota M. S5_P-16

P Pacewska B. S5_P-02, S5_P-06,

S7_P-03

Pagáčo-Vá J. S3_P-09

Pajtáńová M. S3_P-09, S4_P-14

Pálka K. S5_P-08


182

Palou M. S3_KL-01, S5_P-03, S5_P-05

Pan W.-P. PL-03

Parcheta-Szwindowska P. S4_O-03,

S4_P-10

Parikh K. S2_O-02

Parkes G.M.B. S2_O-06

Pedrajas D.L. S5_O-07

Pelczarska A.J. S3_O-03, S7_O-03

Peters B. S1_O-05, S5_P-22

Petkova V. S5_O-05, S5_P-01

Pettinau A. S1_P-15

Pielichowska K. S4_O-05, S4_P-03,

S4_P-06, S4_P-11, S4_P-13,

WL-01

Pielichowski K. S4_O-07, S4_P-05,

S4_P-07, S4_P-12, S7_P-03

Piszczyk Ł. S4_O-04, S4_P-02

Pivkina A.N. S1_O-06

Pobudkowska A. S1_P-06

Polaczek-Grelik K. S6_P-05

Popanda B. S5_P-10

Pouranick P. S1_O-10

Powała D. S2_P-06

Pripolzin S.I. S2_O-05

Prokop A. S3_O-04

Pusz S. S5_P-23

Q Quelennec B. S4_ O-14

R Rademeyer M. S4_ O-13

Radojević M.B. S5_P-21

Raftopoulos K.N. S4_O-07, WL-03

Rahier H. S4_ O-10

Ram T. S2_O-02

Ramult J. S5_O-09

Richaud E. S4_ O-14

Risoluti R. S3_P-03

Ristić I.S. S4_P-01, S5_P-20

Rodríguez J.A. SL-04

Rodríguez Romero J.F. S5_O-07

Rosa J.N. S1_O-01

Rouquerol J. PL-01

Rovira M.F. S1_O-01

Rucińska M. S2_P-05

Rusek P. S3_P-04

Rybiński P. S4_P-04

S Sadowska-Krępa E. S6_P-05

Saienga J. SL-02

Saiter A. S1_O-09

Saiter–Fourcin A. S4_O-08

Saitta F. S6_O-01

Sakae Y. S5_P-13

Sałasińska K. S4_O-06

Samsonov S.A. S6_P-04

Saurina J. S3_P-01, S5_P-01

Savard O. SL-05

Sbirrazzuoli N. S1_O-07

Scheller Ł. S5_O-04

Schick Ch. S2_KL-01

Sempere M.D. S1_O-01

Sheykov Yu.V. S2_O-05

Shiota K. PL-02

Siedlecki M. S2_P-05

Signorelli M. S6_O-01

Silva J. S1_O-05, S5_P-22

Simmons M. S2_O-03

Ńimon P. S3_P-09, S5_O-03, S7_O-04,

S7_P-04, WL-04

Singh R.K. S5_KL-01

Singh S. S1_O-02

Skonieczny M. S1_P-05

Slaný M. S5_P-03

Śliwińska A. S1_P-06

Slough G. SL-02

Smrčková E. S7_P-04

Socorro F. S2_P-02, S2_P-04

Sołtysik M. S6_P-06

Środa M. S5_P-07, S5_P-10, S5_P-11

Stachak P. S4_O-07, S4_P-05

Staszak M. S2_P-05

Stitt E.H. S2_O-03

Stojiljković D.D. S1_P-04, S5_P-21

Stonys R. S5_O-06

Stoyanov V. S5_O-05, S5_P-01

Ńtubňa I. S3_O-02

Ńulcová P. S7_P-01

Sułowska J. S5_P-09

Suñol J.J. S3_P-01, S5_P-01

Świontek Sz. S5_P-07, S5_P-11

Syrek B. S4_P-04

Szatkowski P. S4_P-03, S4_P-13,

S5_P-04

Szczygieł I. S3_O-03, S7_O-03

Szefer E.M. S4_P-07, S4_P-12

Szeligowski A. S4_P-07


183

Szeluga U. S5_P-23

Szlachta M. S4_P-11

Szumera M. S3_P-06, S5_P-09

Szwajgier D. S6_P-03

T Tabero P. S3_P-08

Talik P. S6_O-04

Tanasić J.M. S4_P-01, S5_P-20

Teixeira J. S1_O-05, S5_P-22

Teixeira S. S1_O-05, S5_P-22

Terashima Y. S1_P-10, S6_P-02

Tesmar A. S6_P-04, S6_P-07

Thys M. S4_KL-02, S4_P-08

Tkaczyk M. S1_P-14

Toda A. S4_KL-01

Tomaszewska-Gras J. S6_O-03

Tomikowska R. SL-05, S2_P-05,

S2_P-06

Tomikowski R. SL-05, S2_P-05

Tone T. IL-01, S1_P-12, S3_O-01

Traksmaa R. S3_O-02

Trikkel A. S3_O-02

Tsuchiya M. S1_P-13

Turcotte R. S1_O-02

Tyczyńska M. S1_P-02, S1_P-14

Tzvetanova Y. S5_O-05

U Uibu M. S3_O-02

Urbaniak R. S1_O-11

V Vágvölgyi V. S7_O-02

Vakhmistrov S.A. S2_O-05

Vaks V.L. S2_O-05

Van Assche G. S1_O-10, S4_KL-02,

S4_O-09, S4_O-10, S4_P-08

Van den Brande N. S4_KL-02, S4_O-09,

S4_O-10, S4_P-08

Van der Merwe E.M. S4_ O-13

Van Mele B. S4_O-10

Vanderspikken J. S4_O-09

Vandewal K. S4_O-09

Varfolomeev M.A. S1_P-01

Včeláková M. S5_P-08, S7_O-01

Vella A. S1_O-09

Vendamme R. S4_KL-02, S4_P-08

Verhelle R. S1_O-10, S4_O-10

Verma L. S5_KL-01

Verma R.K. S5_KL-01, WL-02

Viljus M. S3_O-02

Vit J. S3_P-02

Vlasyuk D. S4_P-09

Vyazovkin S. S1_KL-01

Vykydalová A. S5_O-03

W Walasek K. S4_P-03

Walluch M. SL-04

Wang T. PL-03

Warmuz K. S5_O-09

Wasiak M. S1_P-14

Wawrzyńczak D. S6_P-06

Wesolowski M. IL-02, S6_P-01

Więckowski M.T. S1_P-08

Wieczorek A. S4_O-12

Wilińska I. S5_P-06, S7_P-03

Wu W.-Q. S1_P-16

Wyrzykowski D. S6_P-04, S6_P-07

X Xia Z.-Y. S1_P-16

Xu J. S2_P-03

Xu J.X. S1_O-04

Y Yablokov A.A. S2_O-05

Yamada S. S1_P-13

Ye S. S2_P-03

Ye S.L. S1_O-04

Z Żamojć K. S6_P-04, S6_P-07

Zastawny O. S4_P-07

Zdunek A. S3_P-04

Ņemlička M. S3_KL-01

Ņemlička M. S5_P-03, S5_P-05

Zhao X.-Q. S1_P-16

Ziąbka M. S5_P-04

Zieliński P.M. S6_O-02

Zlateva B. S5_P-01

Zorębski E. S1_O-03, S1_P-03,

S5_O-04, S5_P-19

Zsirka B. S7_O-02

Zvereva I. S5_O-05

Zygmunt-Kowalska B. S5_P-04


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