Evolved Gas Analysis by Mass Spectrometry

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Evolved Gas Analysis by Mass SpectrometryS. Materazzia; S. Vecchiob

a Department of Chemistry, “Sapienza” Università di Roma, Rome, Italy b Department of ChemicalEngineering (I.C.M.A.), “Sapienza” Università di Roma, Rome, Italy

Accepted uncorrected manuscript posted online: 09 March 2011

Online publication date: 15 April 2011

To cite this Article Materazzi, S. and Vecchio, S.(2011) 'Evolved Gas Analysis by Mass Spectrometry', AppliedSpectroscopy Reviews, 46: 4, 261 — 340, doi: 10.1080/05704928.2011.565533, First posted on: 09 March 2011 (iFirst)To link to this Article: DOI: 10.1080/05704928.2011.565533URL: http://dx.doi.org/10.1080/05704928.2011.565533

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Applied Spectroscopy Reviews, 46:261–340, 2011Copyright © Taylor & Francis Group, LLCISSN: 0570-4928 print / 1520-569X onlineDOI: 10.1080/05704928.2011.565533

Evolved Gas Analysis by Mass Spectrometry

S. MATERAZZI1 AND S. VECCHIO2

1Department of Chemistry, “Sapienza” Universita di Roma, Rome, Italy2Department of Chemical Engineering (I.C.M.A.), “Sapienza” Universita diRoma, Rome, Italy

Abstract: The analytical applications of the evolved gas analyses (EGAs) performedby mass spectrometry for the period extending from 2005 to 2010 are collected in thisreview. By EGA, the nature of volatile products released by a substance subjected to acontrolled temperature program are determined on-line, with the possibility to prove asupposed reaction either under isothermal or under heating conditions.

Keywords: Evolved gas analysis, TGA–MS, EGA

Introduction

Several analytical instruments (like pyrolyzers, thermobalances, differential thermal analyz-ers or calorimeters, or sometimes even simply temperature-controlled reactors) are on-linecoupled to mass spectrometers to perform evolved gas analysis (EGA) because the possi-bility to on-line detect the nature of the released gases or vapors has became fundamentalto prove a supposed reaction, either under isothermal or under heating conditions.

The history of the EGA–Fourier transform infrared (FTIR) and EGA–mass spectrom-etry (MS) hyphenated techniques from the first attempts to 2004 was previously reported[1–6]. A recent review collected the 2005–2009 EGA-FTIR applications [7].

In this review, the applications of the evolved gas analysis performed by mass spec-trometry for the period extending from 2005 to 2010 are proposed. Many examples arereported from the literature, and often the references are obtained from the journals that spe-cialize in thermal analysis. However, the number of publications on hyphenated techniquescontinues to grow in areas of specific applications; as a consequence, it is not unusual foran article on the topic to appear in an unfamiliar journal or a trade-specific publication.

Sometimes articles regarding EGA may be difficult to locate. As a result, certain im-portant articles may were overlooked: the authors apologize for any inadvertent omissions.

Applications

EGA-MS Technique Improvements

The use of MS in the identification of evolved gaseous species in thermogravimetric (TG)experiments is well established. The mass spectrometer can be attached directly to the outgas

Address correspondence to S. Materazzi, Department of Chemistry, “Sapienza” Universita diRoma, p.le A. Moro 5, 00185 Rome, Italy. E-mail: [email protected]

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262 S. Materazzi and S. Vecchio

port of the thermogravimetric instrument. Mass spectrometers have the ability to detectspecies to 1 ppm or better, and the detection is done in real time as the thermogravimetricanalysis (TGA) scans. Typically, the mass spectrometer is used for identification only.However, there are situations where it would be desirable to quantify the MS data. Forexample, when two or more species are evolved during a weight transition, the total weightloss is known from the TGA, but the weights for the individual components are unknown.Calibration techniques for quantifying MS data are already well established. Following oneof these techniques, in 2005 Slough [8] showed that trend data from a mass spectrometercan be used to approximate the amount of material evolved for low m/z ratio species such aswater and carbon dioxide. The process involves first calibrating the system using a samplethat only gives off the gaseous species of interest. Multiple runs at different initial weightsprovide the data for the calibration. A correlation between mass loss as measured by theTGA and ion current increase as measured by the MS was then constructed. In his study,Slough showed that the technique is applied not only to overlapping transitions but also tothe quantification of reaction products from gases released during a TGA experiment [8].

A new EGA-MS instrument was presented in 2005 by Tsugoshi and coworkers; a com-bination of skimmer interface with no change of evolved gaseous species and ion attach-ment mass spectrometry (IAMS) with no fragmentation during the ionization was success-fully developed. In its application in the characterization of evolved gaseous species frompolyvinylacetate (PVA) as firing process of alumina ceramics binder, the method indicateddetection of gaseous species that have not been detected with pyrolysis (Py)-GC-MS [9].

In thermoanalytical investigations the determination of the composition of the evolvedgases is very important, especially when investigating decomposition processes or gas–solidreactions occurring in multicomponent systems. The potential of simultaneous techniquesenabling the qualitative analysis of evolved species, such as TG-MS or TG-FTIR, wasfurther improved by the introduction of pulse thermal analysis. Eigenmann and coworkersstudied the influence of several experimental parameters that may affect the quantification ofFTIR signals using a combined thermal analysis (TA)-FTIR-MS system. Parameters studiedincluded sample mass (1–400 mg), carrier gas flow rate (25–200 mL min−1), resolution ofthe FTIR spectrometer (1–32 cm−1), and location of injection of the calibrating gas. MSanalysis, which was not significantly affected by the experimental conditions, was used asa reference for assessing the accuracy of quantification by FTIR [10, 11].

In an academic publication, Fiorini demonstrated that coupling a mass spectrometer toa thermal analysis instrument provides a wealth of information to complement the outputof the analyzer. Gases evolved from the sample during heating can be identified by the MSand fragments matched to events such as weight loss. Moreover, data gathered by such ahyphenated system may be used to study the kinetics of thermal degradation of polymersto help evaluate the quality of raw material used in processing [12].

Tsugoshi et al. enhanced the application of EGA-MS with a skimmer interface andIAMS. It could detect characteristic species evolved by the pyrolysis of the organic additives,according to the instrumental advantages such as the transmission of the gaseous specieswith no transformation by the skimmer interface and complete soft ionization for gaseousspecies by the IAMS technique. Further, the pyrolysis behavior of blended polymers as abinder could be monitored individually as EGA curves of characteristic species evolved bythe pyrolyses [13–15].

A new method called TG-bridge–mass spectrometry was presented by Tzamtzis andcoworkers for the on-line monitoring of pine needle combustion emissions in a common labfurnace. The TG-bridge system was developed in-house as a TG-MS interface for TG-MSanalysis. In this work, TG-bridge was used for direct sampling of the combustion emissions


Evolved Gas Analysis by Mass Spectrometry 263

from the inside of the furnace and transferring them into the MS without disturbing thesubpressure conditions inside the MS ion source. The effect of a long-term fire retardanton the emissions produced during the combustion of pine needles was tested in the lab forfuture application in the field. It was shown that in treated samples, increased evolution ofammonia and aromatic compounds took place compared to untreated samples. Maximumconcentrations of specific compounds, such as benzene and toluene, evolved during thecombustion experiments in the furnace, were determined [16].

Property values of powdered certified reference materials (CRMs) are very oftenrelated to dry mass. The dry mass is indirectly determined by measuring the moisturecontent of the sample. The most commonly used methods are the drying oven method andthe Karl Fischer titration (KFT) method. It is well known that these two methods may givedifferent values for the moisture/water content. With this aim, thermogravimetry was used tosimulate the drying oven method and to investigate the reasons for the differences betweenboth moisture/water content determination methods. A mass spectrometer coupled to athermobalance (TG-MS) added further useful information regarding the release of volatilesubstances and the decomposition of the material during the drying process [17].

The 2006 ASTM proceedings included applications of thermal analysis to house-hold waste; quantitative mass measurements from mass spectrometer trend data in a TG-MS system; separation of overlapping processes from TGA data and verification EGA;characterization of modified carbon nanotubes by TG-MS and Py-GC-MS; characteriza-tion of epoxy curing units by high heating rates differential scanning calorimetry (DSC);photothermal microspectroscopy, a new method for infrared analysis; a thermal analysismethod for measuring polymer flammability; and fast scan differential scanning calorime-try, which distinguishes melting, melting degradation–sublimation, and thermal stability ofdrugs [18].

The use of mass spectrometry in the identification of evolved gaseous species inthermogravimetric experiments allows detecting species to 1 ppm or better, and the detectionis done in real time as the TGA scans. In situations where it would be desirable to quantifythe mass spectrometric data—for example, when two or more species are evolved duringa weight transition and the weights for the individual components are unknown—a 2007study showed that trend data from a mass spectrometer can be used to approximate theamount of material evolved for low m/e ratio species such as water and carbon dioxide [19].

Thermogravimetric analysis combined with evolved gas analysis is often used to studythermal decomposition of organic polymers. Frequently, results are used to determinedecomposition mechanisms and to develop rate expressions for a variety of applications,which include hazard analyses. Although some current TGA instruments operate withcontrolled heating rates as high as 500◦C/min, most experiments are done at much lowerheating rates of about 5 to 50◦C/min to minimize temperature gradients in the sample.The intended applications, such as hazard analyses involving fire environments, for rateexpressions developed from TGA experiments often involve heating rates much greater than50◦C/min. Erickson demonstrated that the heating rate can affect polymer decompositionby altering relative rates at which competing decomposition reactions occur [20].

In their review, Leszczynska and Pielichowski presented examples of applications ofDSC, modulated temperature differential scanning calorimetry (MT-DSC), dynamic me-chanical thermal analysis (DMA), thermal mechanical analysis (TMA), TG, and thermo-analytical methods coupled with Fourier transformation infrared spectroscopy (TG-FTIR)and mass spectroscopy (TG-MS) in characterization of nanocomposite materials. The com-plex behavior of different polymeric matrices upon modification with montmorillonite wasbriefly discussed [21].



Lewicki and coworkers developed a novel evolved gas analysis technique, subambientthermal volatilization analysis (SATVA), and its application in characterizing key analytespecies from conservation artifacts. In this work SATVA was applied to the study of volatilesevolution processes occurring in a number of model conservation artifacts. The evolution ofvolatile species from cured formaldehyde resin, leather, and metallic artifacts was studied bySATVA. The specific analytes making up the total quantity of evolved material in each casewere separated and identified using subambient differential distillation and a combinationof on-line mass spectrometry, gas-phase IR spectroscopy, and GC-MS. The data gatheredwere used to provide information on both the degradation processes occurring within theartifacts and the environmental history of the artifacts themselves [22].

For the first time, a novel single-photon ionization–mass spectrometry (SPI-MS) tech-nique was employed in conjunction with thermogravimetry. The coupling was achieved withan improved heated interface and adjacent transfer capillary between TG and ion sourceof a quadrupole mass spectrometer. The feasibility of this approach was proven by inves-tigating semivolatile substances such as long-chain alkanes, polymers, polymer mixtures,and blends. Mass spectra with almost no fragmentation were obtained, and quantificationof selected substances was achieved. Polymer mixtures could be distinguished by their SPImass spectra, and the effect of premixing of polymers was accessed. It was shown that itsunique attributes render the TA-SPI-MS method a promising new tool for quantitative andqualitative evaluation of complex organic thermal degradation products [23].

It is a practice to analyze the gaseous products evolving from thermal analysis by massspectrometry using electron impact ionization (EI). For complex mixtures, in particular,fragmentation can be reduced using the so-called soft ionization techniques. SPI using anelectron beam pumped excimer lamps (EBEL) emitting vacuum ultraviolet (VUV) light(126 nm) was employed by Geissler et al. to propose a TA system coupled to an EBEL-SPI–orthogonal acceleration time-of-flight mass spectrometer (oaTOFMS). The systemused a heated transfer capillary in order to detect semivolatile organic substances fromthe gas flow of a thermobalance with high temporal resolution in measurements on crudeoils of different origins. In-depth analysis demonstrated that it is possible to tell differentcrude oil samples apart on the basis of temperature resolved mass spectra gained from thedescribed setup. The gases that evolve during thermal analysis can be analyzed withoutlosing molecular information using mass spectrometry with a soft ionization technique, suchas SPI [24]. Various novel techniques were applied to the study of polyolefin materials. Inaddition to fast scanning, hyper DSC and DSC-Raman, TG-GC-MS was shown to allowlooking at degradation products and additives from polyethylene samples in great detail[25–28].

A well-established IAMS was combined with an in-house single-atom infrared imagefurnace (IIF). In addition to the detection of many chemical species at atmospheric pressure,including free radical intermediates, the ion attachment mass spectrometer can also be usedfor the analysis of products emanating from temperature-programmed pyrolysis. The per-formance and applicability of the IIF-IAMS was illustrated with poly(tetrafluoroethylene)(PTFE) samples. A brief comparison with a conventional pyrolysis GC-MS system wasalso given [29].

Thermally evolved gas analysis (TEGA), one of several instruments on board thePhoenix lander, performed differential scanning calorimetry and evolved gas analysis ofsoil samples and ice collected from the surface and subsurface at a northern landing site onMars. TEGA is a combination of a high-temperature furnace and a mass spectrometer thatwas used to analyze samples delivered to the instrument via a robotic arm. The sampleswere heated at a programmed ramp rate up to 1000◦C. The power required for heating



can be carefully and continuously monitored by scanning calorimetry. The evolved gasesgenerated during the process can be analyzed with the evolved gas analyzer (a magneticsector mass spectrometer) in order to determine the composition of gases released as afunction of temperature [30].

A novel microkinetic analyzer (MFBK) for fluidized bed gas–solid reactions wasdeveloped and reported by Yu et al. With this MFBK analyzer, the reaction rate and kineticparameters can be deduced via measuring the time-dependent composition changes of itsevolved gas. The use of a microfluidized bed reactor is expected to enable the on-line feed ofparticle reactant based on a pulse solid conveying mechanics and the effective suppressionof external gas diffusion in the reactor. This MFBK analyzer was evaluated through thedecomposition of CaCO3 powder [31].

Alcolea et al. reported the application of a thermogravimetric analyzer coupled to amass spectrometer to research the influence of heating rate and sample mass on the responseof the detector. That response was examined by means of a particular efflorescence takenfrom an acid mine drainage environment. This mixture of weathered products was mainlycomposed of secondary sulfate minerals, which are formed in evaporation conditions, thatappear as efflorescence salts. Thermogravimetry coupled to mass spectrometry was used toanalyze the three main loss steps that happen when this combination of minerals is heatedfrom 30 to 1100◦C [32]. Takahashi and coworkers designed a simple EGA system to actas a sampler between solid samples at atmospheric pressure and the high vacuum insidea mass spectrometer. The newly designed stainless steel system was shown to be simple,small, and rugged and fulfilled all the basic requirements for EGA [33].

Applications to Polymers

To improve the performance of stationary and automotive fuel cells, it is desirable tooperate them at higher temperatures than currently possible for existing proton-exchangemembranes (PEMs). Most current membrane materials based on perfluorinated or aro-matic acid polymers, however, display proton conductivities that dramatically decreaseabove 80◦C, due to dehydration of the membrane. The membranes are prepared by us-ing block copolymer species to direct the structures of network-forming silica, whichis cast, calcined, and grafted with active species to yield inorganic membranes with in-terconnected mesostructured channels. TGA-MS analyses established that hydration ca-pacity and water retention of the functionalized membranes are significantly improved,compared to commercially available Nafion 117 membranes [34]. Study of the thermaldecomposition of well-characterized poly(ethylene oxide) (PEO) under nonoxidative con-ditions was conducted by TG in both dynamic and isothermal mode and by thermo-gravimetry coupled on-line with infrared spectroscopy or mass spectrometry. Analysisof the evolution of low-molecular-weight decomposition products by TG-FTIR and TG-MS techniques showed that main decomposition products were ethyl alcohol, methylalcohol, alkenes, noncyclic ethers (ethoxymethane, ethoxyetane, and methoxymethane),formaldehyde, acetic aldehyde, ethylene oxide, water, CO, and CO2 [35]. Color generationin blends of poly(ethylene terephthalate) and poly(m-xylylene adipamide) (PET/MXD6)were studied by Bandi et al. Several techniques, including TGA-MS, proton and car-bon nuclear magnetic resonance (NMR), and matrix assisted laser desorption ionization(MALDI-MS), were used to characterize reaction products that result in the observedcolor generation; both the polymer system and model compounds were used to understandthe underlying chemistry [36]. Pyrolysis and fire behavior of high-impact polystyrene(HIPS) containing red phosphorus and melamine polyphosphate were investigated.



The thermal and thermooxidative decomposition were characterized using thermogravime-try coupled with FTIR and MS, respectively. The fire behavior was monitored with a conecalorimeter using different external heat fluxes and determining the limiting oxygen index(LOI). Red phosphorus reduced the heat release in HIPS due to radical trapping in the gasphase. The reduction in effective heat of combustion was accompanied by an increase ofincomplete combustion products such as smoke and carbon monoxide [37]. The whole pro-cess of thermal decomposition of (2,2′,4,4′,6,6′) hexanitro-stilbene (HNS) was investigatedby Chen and coworkers by using TG-MS and in situ thermolysis rapid-scan FTIR coupledtechniques. Kinetic parameters of the thermal decomposition of HNS were obtained anda possible decomposition mechanism was suggested [38]. A fixed bed reactor connectedto a mass spectrometer was used to carry out a qualitative study of the evolution of thegases evolved in the pyrolysis of two commercial ethylene-vinyl acetate copolymers. Thecatalyst used was MCM-41 prepared by a two-step sol-gel method, in acid medium, atroom temperature. Pure copolymer samples and mixtures of copolymer with around 10%of MCM-41 catalyst were pyrolyzed in an He atmosphere at a heating rate of 10 K/min.Once the less volatile compounds condensed, the gas evolved was analyzed by MS. Thestudy of the total ion current (TIC) curves as well as the evolution with time of the ionsselected as representative of several compounds or groups of compounds confirmed theexistence of the two reaction steps suggested in the cited bibliography for the second stageof poly(ethylene-co-vinyl acetate) (EVA) pyrolysis: cracking of the polyethylene domainsand cracking of the polyene domains, both domain types resulting from the first decompo-sition stage. On the other hand, the analysis and comparison of the evolution of the intensityof current corresponding to the selected mass ions in the thermal and catalytic processesshowed that the gas evolved always contained a higher amount of olefines than alkanes andthat greater conversion to gaseous products was obtained in the presence of the catalyst [39].Structural and thermal analyses of a polythiophene–polyacrylonitrile (PTh-PAN) sample,prepared by electrochemical polymerization of thiophene onto a poly(acrylonitrile) coatedanode, were performed by a direct insertion probe pyrolysis mass spectrometry technique.The evolution profiles of PTh-based products from PTh-PAN showed nearly identical trendswith those recorded during the pyrolysis of pure PTh. However, when PAN-based productswere considered, contrary to the trends observed for pure PAN, evolution of HCN and thedegradation products due to the homolytic cleavages of the polymer backbone continuedthroughout the pyrolysis, indicating a significant increase in their production even at thefinal stages of pyrolysis [40].

The thermal pyrolysis of wood-derived rayon fiber was studied from ambient temper-ature up to 800◦C by TG-MS coupled analysis in an inert environment. Gases and tarryvolatile products formed from the pyrolysis of wood-derived rayon fiber were monitoredby MS. Water (m/z 18) was the predominant ion observed, followed by CO (m/z 28), CO2

(m/z 44), and CH4 (m/z 16). The MS signals showed that the tarry volatiles were composedof a variety of compounds [41].

A detailed evaluation of the events that occur during the heating of organic–inorganichybrid solids obtained by the sol-gel method was established. The correlation of manycharacterization techniques, in particular TG-MS analysis associated with specific alkox-ide structural units, provided some explanations in terms of a set of mechanisms [42].Homogeneous TiO2 gel powders were prepared by hydrolysis and condensation of tita-nium (IV) isopropoxide with HCl or SnCl2 catalysts by working under reduced pressureor in air. Thermal analyses including hyphenated TG-MS were carried out to quantify theresidual organic components in the crude TiO2 gels and to obtain stoichiometric formulasto describe their chemical compositions [43].



The first example of a highly ordered periodic mesoporous thiophene-bridgedorganosilica with large pores was reported by Morell et al. The analysis of the TG-MSdata demonstrated a relatively high thermal stability (up to 400◦C in air) of the mesoporousorganosilica before a decomposition of the organic moieties [44].

Synchrotron-based extended X-ray absorption fine structure spectroscopy (EXAFS),X-ray diffraction at room and high temperature, thermal analyses combined with massspectrometry of evolved gas, and chemical analyses contributed to assess the influenceof mercury on montmorillonite and vermiculite layers [45]. The series of LiMn2O4-ySy

spinels was obtained by the sol-gel method followed by the calcination at 300◦C. TheTGA measurements with simultaneous EGA-MS showed evolution of oxygen in the sametemperature range as in the case of Li1-xMn2–2xO4 samples obtained and calcined in thesame way, which may suggest the elimination of the cationic defects and the improvementof the crystal structure [46].

The thermal stability of some known (bromomethylated, carboxylated, brominated,nitrated) and novel (tertiary amine) polysulfone derivatives were studied and the thermal de-composition products were identified by various coupled mass spectrometric methods. Fromthese data, the possible decomposition mechanism was deduced [47]. A new original methodof poly(aspartic acid) synthesis in a microwave radiation field was developed. The synthe-ses were carried out mainly without the catalyst using two different monomers, asparticacid and maleic acid ammonium salt. The products were characterized using spectroscopictechniques (infrared spectroscopy, proton nuclear magnetic resonance), gel permeationchromatography, and thermoanalytical coupled methods, like thermogravimetry coupledwith infrared spectroscopy or with mass spectrometry [48]. Poly(phenyleneethynylene)s(PPEs) capable of reacting with thiol-containing molecules were designed and synthesizedwith number-average molecular weights ranging from 8,000 to 11,000. The PPEs containpendent-masked maleimide units available to participate in conjugate additions and Diels-Alder chemistries after being thermally activated. If the maleimide group is left unmaskedduring palladium-catalyzed cross-coupling polymerization, it leads to side reactions andthe production of only short-chain oligomers. Reversible Diels-Alder reactions between themaleimides and furan were determined to be very effective in producing a masked Michaelacceptor that can be unveiled after polymerization under relatively mild thermal conditions.Cycloreversion to the maleimide was monitored by TGA, TGA-MS, IR, and NMR [49].By combining the results of TG-MS, FTIR, and 13C NMR, Ozaki et al. proposed a mech-anism for the pyrolysis of poly-p-phenylene butadiyne, including the cross-link formationby a Diels-Alder–type reaction between the terminal acetylene and the diene structure.Diacetylene and phenyl groups facilitated the reaction by increasing the mobility due to thepartial fusion and the presence of the terminal acetylene groups [50]. The HCl scavengingeffect of particulate fillers such as Red Mud (RM), CaCO3, and dolomite on the thermaldegradation of poly(vinyl chloride) (PVC) was investigated by TG-MS. It was found that,in the presence of carbonates, the peak temperature of dehydrochlorination was shifted toa higher temperature and the rate of mass loss was decreased, whereas in the presence ofRM, FeCl3 was formed and dehydrochlorination of PVC was accelerated, but the seconddecomposition step of PVC was retarded. Benzene is the hindered product of the reactionby the acid scavenger additives and retarded by RM, evolution of benzene and other aro-matics being shifted to higher temperatures [51]. The evaporation–grinding MALDI-TOFMS sample preparation method and EGA-GC-MS were used to study the cyclodehydrationof polybenzoxazole and poly(benzoxazoleamide) precursors. Precursor fibers were heatedfrom 100 to 300◦C while evolved gases were monitored by GC-MS; after each heating,samples were removed for MALDI-TOF-MS analysis. Changes observed in MALDI-TOF



mass spectra result from cyclodehydration, along with end group and structure modifica-tions (due to decarboxylation and branching). EGA-GC-MS by thermogravimetry indicatedmass loss (from chain rupture) and evolution of low mass material, which led to branching.Results from this study indicate that a combination of MALDI-TOF-MS and EGA-GC-MShas great potential for examination of thermal, chemical, and photodegradation pathwaysof high-molecular-weight condensation polymers [52]. The influence of reprocessing andthermooxidative aging on the degradation behavior of a commercial poly(oxymethylene)(POM) copolymer was studied by means of thermogravimetric analysis with the simultane-ous monitoring of the evolved gases with a mass spectrometer coupled to the TGA-furnaceoutlet. The mass spectra showed that the main degradation product was formaldehydeand that in air further formation of water was detectable. In a nitrogen atmosphere agedspecimens emitted small amounts of carbon dioxide at the beginning of the mass loss[53]. A novel preceramic polymer suitable for forming an SiBCN ceramic was synthesizedby hydroboration reaction of 1,3,5-trivinyl-1,3,5-trimethyl-cyclotrisilazane with boranedimethylsulphide. The obtained polymer denoted as poly (borosilazane) was characterizedby FTIR and NMR spectroscopy and its thermal stability was studied by thermal gravimetricanalysis in combination with in situ mass spectrometry (TG-MS). The polymer-to-ceramictransformation was achieved at 1050◦C in an inert argon atmosphere yielding black andX-ray amorphous SiBCN ceramics thermally stable up to 1800◦C. Using the dip-coatingtechnique, an SiBCN ceramic thin film was formed on a porous alumina substrate. N2 sorp-tion isotherm analysis revealed that the thin film contained a small amount of microporesof about 0.6 nm in diameter, as well as mesopores between 2.7 and 6 nm in size. Thetotal pore volume was found to be about three orders of magnitude smaller than that of ahydrogen permselective amorphous silica membrane derived from polysilazane. These re-sults indicated potential application of the SiBCN thin film as a molecular sieve membranesuitable for high-temperature separation of small gas molecules like hydrogen below 0.3nm in size [54]. The thermal degradation process of ethoxylated bisphenol A (BPA) andoxyalkylenated 2,6-toluenediamine-based polyurethane (PU) foams blown with pentaneand flame retarded by a novel NaH2PO4 and NaHSO4 intumescent system (5:3, w/w) wasstudied by thermogravimetry coupled with mass spectrometry, thermogravimetry coupledwith Fourier transform infrared spectroscopy, pyrolysis–gas chromatography coupled withmass spectrometry, and diffuse reflectance Fourier transform spectroscopy methods. It wasfound that an NaH2PO4/NaHSO4 system is active both at the initiation stage of PU decom-position and it catalyzes cross-linking reactions that lead to enhanced char formation duringdegradation; both effects contribute to the overall flame retardation effect [55–57]. Thermaldegradation experiments were performed in order to study the kinetics of the decomposi-tion of polychloroprene. Some of the experiments were partially conducted in isothermalconditions in order to cover a wider range of operating conditions. Two different reactionmodels were proposed, one for pyrolysis and another one for combustion, which proved toappropriately simulate the experimental results at all the heating rates simultaneously [58].The degradation processes initiated by thermomechanical and thermooxidative loadingas well as exposure to ultraviolet irradiation weathering were examined in commerciallyavailable semicrystalline polyoxymethylene (POM), using predominantly thermoanalyticalmethods. TGA was used to observe stabilizer consumption and further degradation, whereasinvestigations of melt-flow index and molar mass showed effects correlated to late-termchanges of the molar mass distribution. MS-EGA investigations identified formaldehydeand carbon dioxide as the main degradation products [59–61].

The mechanisms of the preparation of rayon-based carbon fibers with an(NH4)2SO4/NH4Cl/organosilicon composite catalyst system were studied. The thermal



behaviors of rayon fibers that were treated with different catalysts were studied by TG-MSand the surface of treated rayon fibers was studied by scanning electron microscopy (SEM)analysis. Resulting data showed that the composite catalyst-treated rayon fibers underwentpyrolysis under lower temperatures and in a wider range of temperatures. Rayon-basedcarbon fibers prepared with different catalyst systems showed different mechanical prop-erties. The presence of (NH4)2SO4/NH4Cl/organosilicon increased the production of H2O,CO2, and CO and decreased the production of tar, aldehyde, furan, and phenol deriva-tives [62]. The pyrolysis characteristics of PVC were systematically investigated usinga Netzschne TG thermobalance coupled to a quadrupole mass spectrometer. The gasesevolved during thermogravimetric analysis monitored the relative intensity of HCl, C6H6,light hydrocarbon, and chlorine-containing gases. The formation of these gases can beexplained by considering these reactions: dehydrochlorination, intramolecular cyclization,and the addition of HCl to unsaturated hydrocarbons [63]. Poly(m-phenylene isophthala-mine) (PMIA) and poly(p-phenylene terphthalamine) (PPTA) are among the most importanthigh-temperature-resistant aramid fibers. The pyrolysis behaviors of these two fibers underinert gases were studied using Py-GC-MS and thermogravimetric analysis coupled withmass spectrometry [64].

Photoionization mass spectrometry (PIMS) with a vacuum ultraviolet (VUV) lightsource provides an efficient and fragmentation-free method for the soft ionization of gaseouscompounds, in order to facilitate an understanding of thermal decomposition behavior andchemical composition of polymeric materials. PIMS was applied to an evolved gas analysissystem equipped with a skimmer interface that is constituted based upon a jet separatorprinciple between a vacuum MS chamber and an atmospheric sample chamber in a fur-nace. A photoionization source with a deuterium lamp was closely installed to the vacuumionization chamber of a mass spectrometer to improve the ionization efficiency. The ther-mal decomposition of typical polymers in an inert gas atmosphere was investigated byEGA-PIMS and the resulting PI mass spectrum was characterized satisfactorily by onlythe parent ions with no contribution as a result of fragmentation during the ionization.The results suggested that the EGA-PIMS was an especially powerful and desirable in situthermal analysis method for polymeric materials that evolve organic gases simultaneouslyand concurrently. The combination of EGA equipped with a skimmer interface with nochange of evolved gaseous species and PIMS with fragmentation-free during the ionizationwas described briefly, and the effective results were presented by comparison with EGAusing conventional electron impact ionization mass spectrometry [65]. Thermal decompo-sition products of polyamide-6,6 (PA-6,6) and acrylonitrile-butadiene-styrene copolymer(ABS) were converted over Y zeolites at above the temperature of thermal decomposition ofthese polymers. Selected TG-MS ion curves of polymer and zeolite mixtures indicated thechanges due to the catalytic conversion of the thermally produced products in to compoundsof high volatility [66]. Mass spectra of the thermal decomposition of polychloroprene (PCP)revealed that HCl is mainly produced in the first and second stages. Chlorinated organiccompounds such as 2-chloro-1,3-butadiene and chlorobenzene are produced in the secondstage. Aromatics, particularly the polycyclic compounds such as naphthalene, are producedin the third and fourth stages. In addition, the effect of temperature on the dehydrochlori-nation of PCP during isothermal degradation was examined. Among select temperatures,the degree of dehydrochlorination of PCP was the highest at 500◦C. It is more difficult torecycle the Cl in PCP as HCl compared to the Cl in PVC due to the production of chlorinatedorganic compounds [67]. Kwon and Castaldi characterized the thermal decomposition ofstyrene–butadiene rubber (SBR) using thermogravimetric analysis on-line coupled to aGC-MS and investigated the formation and ultimate fate of chemical species produced



during gasification of SBR. The results indicated polycyclic aromatic hydrocarbon (PAH)formation at a relatively lower temperature as compared to conventional fuel, such as coaland diesel. The PAH sequence is not simply the construction of larger PAHs from smallerones to achieve the complex polymer structures. It is possible to generate large PAHmolecules while circumventing the typical construction pathway [68]. The thermal degra-dation mechanism of poly(vinyl acetate) (PVAc) and (EVA) copolymers was investigatedwith solid-state NMR, thermogravimetry coupled with mass spectrometry, and differen-tial thermal analysis by Rimez et al. [69, 70]. The influence of TiO2 nanoparticles on thethermal degradation of poly(methyl methacrylate) (PMMA) was investigated by Laachachiand coworkers [71]. The thermal degradation behaviors of polymeric fibers were studiedusing Py-GC-MS, thermogravimetric analysis coupled with differential thermoanalysis andmass spectrometry (TGA-DTA-MS), and thermogravimetric analysis coupled with Fouriertransform infrared spectroscopy (TGA-DTA-FTIR). Py-GC-MS affords the advantages ofdetecting temporary thermal stability and volatile fragments, and the rupture process ofmolecular chains can be recorded. TGA-DTA-FTIR and TGA-DTA-MS undertake the con-tinuous heated processes, and the thermal properties and volatiles illustrate the chemicalreactions involving scission and recomposition [72–74].

Some properties of perfluorosulfonated ionomer membranes contaminated by a se-ries of 10 counterions were investigated by FTIR, TG-MS, and DMA and distinctiveparameters were extracted and regarded as a function of the cation properties. Thermalstability analyses also pointed out the influence of each cation parameter on the polymerdegradation process [75]. Main chain anionic polymers with lithium cations, which havetetrakis(ethyleneboryl)borate as repeating units, were prepared by Cakmak and coworkersand the ionic conductivities were determined [76]. In order to improve PVC’s thermalstability, a poly(vinyl butyral) (PVB) matrix and calcium carbonate nanoparticles were in-corporated into plasticized PVC. Thermal properties of these composites were investigatedby TGA coupled with MS and FTIR. This approach highlighted the efficiency of bothPVB and CaCO3 as HCl scavengers [77]. A process for generating hydrogen gas fromPE by milling and heating with Ni-doped layered double hydroxide (LDH), which wasalso prepared by a mechanochemical route of two-step milling operation, was reported byTongamp et al. Characterizations by a set of analytical methods of X-ray diffraction (XRD),TG-MS, and GC were performed on the milled and heated samples to monitor the process.Gaseous products obtained during heating mainly consisted of H2, CH4, and CO, CO2 withH2 concentration over 80% [78, 79]. Thermal degradation and stabilization of two kindsof polyacrylonitrile (PAN) fibers were investigated by a combination of spectroscopic andthermoanalytical techniques. The two types of samples produced different ring structuresin the thermal degradation and stabilization process, as evidenced by results from tensiletests, TG-MS, and thermal shrinkage behavior analyses [80].

In order to improve PVC’s thermal stability, a PVB matrix and calcium carbonatenanoparticles were incorporated into plasticized PVC. Thermal properties of these com-posites were investigated by TG-MS and this approach highlighted the efficiency of bothPVB and CaCO3 as HCl scavengers by postponing both the onset degradation tempera-ture and the HCl release [81]. The thermal degradation of an amphiphilic block copoly-mer poly(ethylene)-b-poly(ethylene oxide)-carboxylic acid terminated and its salt obtainedas intermediary product from chemical oxidation of the end group of poly(ethylene)-b-poly(ethylene oxide) (PE-b-80%PEO) was studied using a TG-MS coupled system. Theisothermal fragmentation of PE-b-80%PEO-CH2COOH showed a more complex fragmen-tation pattern than PE-b-80%PEO due to the simultaneous occurrence of the polyetherblock and the carboxylic end group fragmentations [82]. Combustion and smoke emission



properties of PVC compounds, modified with copper (II), molybdenum, and zinc oxides,were studied using a cone calorimeter, LOI, and TG-MS. Results showed that the metaloxides had a very significant effect on the combustion and smoke suppression properties ofthe PVC compounds. The results also confirmed the anticipation mechanisms of the dehy-drochlorination reactions, reductive coupling, and elimination of benzene resulting from thepresence of copper (II), molybdenum, and zinc, indicated by the increasing content of post-combustion char residue and the significant reduction in benzene production, indicated bythe MS measurements performed [83, 84]. Pore surface engineering of mesoporous materi-als is fundamental for the development of highly selective sorbents, solid catalysts, or drugdelivery systems. Tailored mesoporous amine-functionalized polymer–silica compositeswere synthesized using a two-step mesopore surface-confined polymerization technique:a functional polymer, polychloromethylstyrene (PCMS), was first introduced as a uniformcoating on the mesopore surface of mesoscopically ordered silica; then selected amines, asmodel functions, were attached to the polymer surface by nucleophilic substitution, gener-ating a variety of nanoporous amino–polymer–silica composites. From the results obtainedby several techniques including EGA-MS, it appeared that the preparation method shouldbe highly flexible and appropriate to enable modulation of location and distribution ofvarious functional groups within mesopores [85]. The effect of chloride ions on photoox-idation of propylene on a TiO2 semiconductor was investigated. The experimental resultsshowed that the activity of Cl−/TiO2 catalysts increased as heat-treated temperature de-creased. The adsorbed species on the TiO2 surface before and after reaction were analyzedby X-ray photoelectron spectroscopy and evolved gas analysis with mass spectrometry thatconfirmed chlorine absorbed on the surface [86]. A novel semi-interpenetrating polymernetwork membrane was prepared to improve the proton selectivity of perfluorosulfonicacid membrane. TG-MS results allowed describing its physicochemical properties, indi-cating that the introduction of the cross-linked PVP mainly affects the configuration of theNafion side chains and thus indirectly influences the formation and interconnection of ionclusters [87]. EGA-MS was applied to investigate the thermal stability of an MDI-basedpolyurethane elastomer [88]. A two-step process to generate H2 gas (by milling polystyreneor poly(vinyl alcohol), followed by heating of the milled product in the second step) wasperformed by Tongamp et al. Analysis of the gaseous products by TG-MS and GC showedthat CO2 gas was fixed as CaCO3 at temperatures between 350 to 600◦C, allowing genera-tion of H2 gas [89]. A process to produce hydrogen from polyethylene [-CH2-]n (PE) wasdeveloped by milling with Ca(OH)2 and Ni(OH)2 followed by heating the milled product.Characterizations by a set of analytical methods of XRD, FTIR, TG-MS, and GC wereperformed on the milled and heated samples to monitor the process. Gaseous compositionsfrom the milled samples varied depending on the added molar ratio of calcium hydroxide.The process offers a novel approach to treat waste plastic by transforming it into hydrogen[90].

Applications to Inorganics

Copper complexes [91], as well as new mixed-ligand complexes of d-electron metals(M(II) = Mn, Ni, Cu) with 2,2′-bipyridine (2-bpy) and mono- or dichloroacetates, wereprepared as crystalline solids. During heating in air, complexes decompose via differentintermediate products to metal oxides. A coupled TG-MS system was used to analyze theprincipal volatile thermal decomposition (or fragmentation) products of 2,2′-bipyridine-chloroacetato complexes [92].



Zinc (II) complexes with commercial auxin herbicides were prepared and charac-terized. The formulae of the resulting solid complexes were established and the thermaldecomposition of these complexes in air was studied by TG, DTG, DTA, and TG-MSmethods with simultaneous analysis of the solid and gaseous products [93].

Copper–zinc nanocomposites were prepared by thermolysis of copper–zinc cyanidesunder mild conditions. Two different routes were used for the preparation of the cyanidecomplex: a batch precipitation method and the continuous overflow precipitation method.The thermolysis of the cyanides was studied in situ by thermogravimetry coupled withinfrared spectroscopy and by thermogravimetry coupled with mass spectroscopy [94]. IR,far-IR, Raman, and Mossbauer spectra were utilized to identify a new compound consistingof a tetrachloroferrate (III) anion and a tetrabutylammonium cation [(C4H9)4N][FeCl4]. Itsdegradation was studied by thermal analysis using TG, TG-MS, DTG, and DTA, as wellas DSC techniques. The discussion was focused on processes proceeding during the firststep of the thermal decomposition [95]. From a previously assumed decomposition stage of[Co(NH3)6]2(C2O2)3·4H2O (HACOT) under different atmospheres (inert, oxidizing, andreducing), the gaseous products of the decomposition were qualitatively and quantitativelyanalyzed. It was confirmed that the gaseous products of HACOT decomposition under thestudied atmospheres were H2O (stage I) and NH3 and CO2 (stage II). The main gaseousproducts in the third stage in argon and hydrogen (20 vol% H2/Ar) were CO and CO2,whereas in air (20 vol% O2/Ar) only CO2 was identified. The studies of the multistage de-composition of HACOT, additionally complicated by many secondary reactions, requiredapplication of the hyphenated TA-MS or TA-FTIR techniques combined with pulse thermalanalysis (PTA), allowing quantification of the spectroscopic signals and investigation ofgas–solid and gas–gas reactions in situ [96]. The molecule 1,1′-bi-2-naphthol (BINOL)was reported to have a propensity for supramolecular, hydrogen-bonded strand formationwhen crystallized with its deprotonated form. The strand adapts from racemic rac-BINOL toenantiomeric S-BINOL and from di- to monocationic metal ions but keeps the overall strandfeature. The applications of simultaneous DTA-TG-MS showed that the EtOH, MeOH, andH2O solvent of crystallization together with the NH3 ligands can be removed before the BI-NOL moieties [97]. An acetonitrile complex 1 of composition [Mn(NCCH3)6][B(C6F5)4]2

was grafted onto Na-AlMCM-41/48 and H-AlMCM-41/48 by ion exchange. A metal load-ing of 0.25–0.6 wt% was achieved; the grafting of complex 1 was found to yield higherloading on Na-AlMCM-41/48 compared to H-AlMCM-41/48. FTIR, EPR, TG-MS, andelemental analyses confirmed the successful grafting of the Mn(II) complex in the chan-nels of the mesoporous materials, retaining the octahedral nitrile environment around theMn2+ cation. The obtained materials can be applied as heterogeneous initiators for thepolymerization of isobutene [98].

Qiu and coworkers synthesized yttrium aluminum garnet (YAG) powders by a sol-gelcombustion process from a mixed solution containing aluminum and yttrium nitrates. Thethermal behavior of the precursor was determined by DSC-TG-MS techniques [99]. TG-MS studies were proposed by Zhang et al. [100] and Zhao and Liu [101] to characterizethe thermophysical and thermochemical behavior of coated composite particles.

Phase-pure lanthanum-substituted bismuth titanate was prepared by an aqueoussolution-gel route by Hardy et al. In this route aqueous precursors were synthesized bystabilization of the metal ion in the aqueous medium through complexation with strongelectron donor ligands. The precursors were transformed to phase-pure oxides by heat treat-ment in an appropriate dynamic atmosphere. The decomposition reactions of the gels werestudied by means of several hyphenated thermal analysis techniques, including thermo-gravimetry coupled on-line to FTIR or MS and high-temperature diffuse reflectance infrared



spectrometry by Fourier transform. Phase segregation during gel calcination was correlatedto the oxygen partial pressure. An explanation for this phenomenon was suggested basedon thermal analysis [102]. A chiral menthyl cyclopentadienyl molybdenum tricarbonylchloro complex was synthesized; tested as catalyst for the epoxidation of cis-cyclooctene,styrene, and trans-methylstyrene in the presence of tert-butyl hydroperoxide using chloro-form as solvent; and immobilized on mesoporous MCM-41 and MCM-48 surfaces leadingto grafted materials. The presence of the organometallic complexes in the materials wasconfirmed by several spectroscopic techniques and by TG-MS. AM-41CpMoChi and AM-48CpMoChi were also tested as epoxidation catalysts, including leaching experiments, andthe reuse of the grafted materials for several runs [103]. Wyrzykowski et al. studied thethermal decomposition of a compound consisting of a tetrachloroferrate (III) anion and aquinolinium cation, of general formula [QH][FeCl4], by using TG-FTIR, TG-MS, DTA,and DTG techniques [104]. A copper complex with weakly coordinating anions was graftedonto the surface of mesoporous SBA-15 molecular sieves through an aminosilane linker.The nature of the support after the grafting was examined by powder XRD, transmissionelectron microscopy (TEM), and N2 adsorption–desorption analysis. Elemental analysis,FTIR, TG-MS, and MAS-NMR studies confirmed the successful grafting of the complexeson the surface. The grafted material was applied as catalysts for aldehyde olefination. Sameexperiments were carried out with ruthenium complexes [105–108]. Citronellol and cit-ronellyl acetate were entrapped with cyclodextrin (CD). Evolved gas detection and TG-MScoupling was applied to prove the actual inclusion complex formation between monoterpensand CDs [109]. A new sodium lanthanum phosphate thiosulfate compound was character-ized by thermal analysis (DSC, TG-MS), vibrational spectroscopy (FTIR and Raman),and energy-dispersive spectroscopy (EDS). Thermal analysis showed that the compoundwas not stable at elevated temperatures in air, displaying two irreversible thermal events[110]. Bretos et al. described calcium-modified lead titanate (PCT) precursor solutionswith different amounts of Ca2+ substituting Pb2+ prepared for the first time by an entirelyaqueous solution-gel route. The use of water as a nonhazardous and inexpensive solvent,together with the easy handling of the technique, were shown as the major advantages of thismethod. A stable citrato-peroxo complex of Ti(IV) was synthesized first and subsequentlycombined with the reagents (citrates) in the desired molar ratio to obtain the aqueous precur-sor solutions. Gels were obtained from these solutions and subjected to thermogravimetricanalysis coupled on-line to Fourier transform infrared (TGA-FTIR) and mass spectroscopy(TGA-MS) techniques [111]. New mixed-ligand complexes containing bipyridine isomersand lactates were obtained and characterized by elemental analysis, IR, conductivity, andmagnetic measurements, and the thermal behavior of all compounds was studied by thermalanalysis in air. A coupled TG-MS system was used to analyze the principal volatile productsof thermolysis and fragmentation processes of Cu(II) compounds in air and argon [112,113]. Hydrolysis and condensation under acidic conditions of bis(triprop-1-ynylstannyl)p-phenylene, p-xylene, or butylene precursors yielded bridged polystannoxanes in the formof xerogels after being dried under reduced pressure. Thermal treatment of the xerogels inair at 400–500◦C resulted in nanocrystalline nanoporous cassiterite tin dioxide materials,thoroughly characterized by elemental analysis, FTIR, TGA-MS, and powder XRD [114].

Novel mixed-ligand complexes of yttrium and light lanthanides with 4,4′-bipyridineand dichloroacetates were prepared and the thermal properties in the solid state were studiedby coupled TG-MS system to determine the main decomposition (or fragmentation) prod-ucts evolved during pyrolysis [115]. A water-soluble citratoperoxo-Ti(IV) complex wassynthesized and the chemical reactions that occurred during the different synthesis stepswere studied. The thermooxidative decomposition pathway of the crystalline complex and



the gel to the metal oxide was described based on in situ thermal analysis techniques com-bined with Fourier transform infrared and mass spectrometry, diffuse reflection infraredby Fourier transform, as well as high-temperature X-ray diffraction. The study offers afundamental understanding of the behavior of the aqueous solution gel Ti(IV) precursor,which is applicable in the preparation of all kinds of multimetal oxide systems containingTi(IV) ions [116]. Barium strontium titanate with a Ba:Sr ratio of 50:50 was prepared usinga modified polymeric precursor method, which proved to be cost-effective because neithermoisture sensitive materials nor costly starting materials were used for the preparation.The reaction pathway, temperature of decomposition of the precursor, and temperature offormation of the oxide were found using the data from the EGA-TGA-MS coupled in-strument [117]. Mixed cadmium (II) complexes with o-aminobenzoic acid and imidazoleswere synthesized and characterized by spectroscopic techniques and the thermal behav-ior of compounds was investigated by a coupled TG-MS system to analyze the principalvolatile products of the complexes. Thermal decomposition pathways were postulated forsynthesized complexes [118]. Two Ru(II) salen complexes grafted on poly(4-vinylpyridine)were synthesized and characterized. Immobilization of both Ru(II) salen complexes on thepolymer increased their thermal stability as demonstrated by TG-MS analysis. The graftedmaterials were applied as catalysts for the olefination of various aldehydes at 60◦C underan inert gas atmosphere, showing comparable yields as their homogeneous congeners andhigh trans-selectivities. The ruthenium (II) compound with a larger salen ligand showeda better recyclability and selectivity than the derivative with the smaller ligand [119].Transition metal (M)-ethylenediaminetetraacetate (EDTA) complexes were intercalated inlayered double hydroxides (LDHs) by a hydrothermal method using MgAl-NO3LDH as theprecursor. The evolution of the interlayer arrangement of [M(edta)]2 in LDHs with increas-ing temperature was studied by variable-temperature in situ XRD measurements, variable-temperature in situ FTIR, and combined thermogravimetric analysis and mass spectrometry[120]. New tetrachloro- and tetrabromo-ferrates (III) were synthesized and the differencesin their physicochemical properties were highlighted using TG-MS and DSC [121, 122].The thermal decomposition of ammonium paratungstate tetrahydrate was followed by on-line evolved gas analysis directly up to 900◦C. A previously unexplained exothermic heateffect, detected at 700–750◦C, on the basis of H2O and NH3 evolution curves and XRDpatterns, was assigned to the formation and crystallization heat of WO2.72/W18O49 fromWO2.9/W20O58 tungsten-oxide and residual ammonium tungsten bronze [123].

New mixed ligand complexes of Zn(II) and Cd(II) with some bipyridine isomers andpropionates were prepared in a pure solid state. A coupled TG-MS system was used toanalyze the principal volatile products of thermal decomposition or fragmentation [124].SnO2 and SnO2/Co-porphyrin solids were prepared and hydrolyzed to sol. The thermalbehavior of samples obtained at 110◦C was studied in the 20–600◦C interval by ther-mal analysis coupled with mass spectrometry for identification of released species [125].The thermal decomposition of ammonium paratungstate tetrahydrate in air to tungstentrioxide, WO3, was investigated under nonisothermal conditions using thermal analysiscoupled on-line by a Skimmer R© system to a quadrupole mass spectrometer for evolvedgas analysis [126]. Inclusion complexes of Lippia sidoides essential oil and cyclodex-trin were obtained by a slurry method and its solid powdered form was prepared usingspray drying. Thermoanalytical techniques (TG, EGD, TG-MS) were used to support theformation of inclusion complex and to examine their physicochemical properties after ac-celerated storage conditions [127]. Huang and coworkers investigated a thermochemicalhole burning (THB) effect on a charge transfer (CT) complex, triethylammonium bis-7,7,8,8-tetracyanoquinodimethane [TEA(TCNQ)2], in an ultrahigh vacuum (UHV) system.



The parallel TG-MS analysis allowed a detailed understanding of the thermochemical de-composition reaction [128]. Thermal decomposition of tetraethylammonium tetrachloro-,bromotrichloro-, and tribromochloroferrates was reported by Wyrzykowsky and coworkers[129]. Copper (I) carboxylates films were characterized by SEM, TG-MS, and energy-dispersive X-ray (EDX) studies. Pure layers were obtained with copper particles of size200–780 nm [130]. The thermal decomposition of ammonium 3-nitro-1,2,4-triazol-5-onatemonohydrate was studied by coupling thermal analysis and mass spectrometry and bythe combination technique of in situ thermolysis cell with rapid-scan FTIR spectroscopy.The results showed that there are two endothermic steps and one exothermic step in thedecomposition process. The detected gas products consisted of NH3, H2O, N2, CO2, CO,and NO2 [131]. The thermal decomposition of a series of thiourea compounds was stud-ied by thermogravimetry, mass spectrometry, nuclear magnetic resonance, and elementalanalysis. The combined use of MS and TG in the analysis of these compounds has allowedcharacterization of the fragmentation pattern, which was the objective of this research. Thegaseous products, volatile condensed products, and solid residues were identified by NMRand MS. Based on the product of thermal decomposition, the mechanism of thermal decom-position was derived [132]. Metal acetylacetonates are coordination compounds containingbidentate ligands that, due to their intrinsic properties, are extensively used as precursorsboth for solution and vapor deposition of oxide thin films. The cerium oxide (ceria) filmshave received a great deal of interest due to their special optical and electrical properties.The thermal decomposition of cerium (III) acetylacetonate hydrate in dynamical argon at-mosphere and in static air was studied by simultaneous DTA-TG-MS, which is a powerfultool to analyze the complicated successive and superposed reactions accompanying theformation of the intermediate decomposition products to give the final cerium oxide [133].The thermal decomposition of tetraethylammonium complexes was studied by TG-MSand X-ray diffractometry by Stycze and coworkers [134, 135]. The thermal degradation ofthe solid monomeric Na[FeEDTA(H2O)]·2H2O complex was studied in air by simultane-ous thermogravimetry and differential thermal analysis coupled on-line with a quadrupolemass spectrometer for evolved gas analysis. The solid products were also analyzed byMossbauer spectroscopy. A four-step decomposition was observed until 500◦C, involvingfirst the release of two molecules of crystal lattice water and then one coordinated watermolecule and above 200◦C, the release of CO2 as a result of degradation of a carboxylatearm of the EDTA ligand. While releasing CO2, reduction of the ferric iron to ferrous ironwas observed by Mossbauer spectroscopy [136]. New mixed-ligand complexes of Gd(III),Tb(III), Ho(III), and Tm(III) with 4,4′-bipyridine and dichloroacetates were prepared andcharacterized by Czakis-Sulikowska et al. The thermal properties of complexes were in-vestigated and the principal volatile products of pyrolytic decomposition were detectedby a coupled TG-MS system [137]. Madarasz and coworkers proposed several papers oncomplexes characterized by EGA by both in situ TG-EGA-FTIR and TG-DTA-EGA-MS[138–140]. Acik et al. studied the thermal decomposition of dried crystalline powder ob-tained from titanium (IV) bis(acetylacetonate) diisopropoxide. The thermal behavior andthe decomposition steps were monitored by simultaneous EGA-FTIR and EGA-MS mea-surements and the results were compared with those of amorphous powder obtained bygelling of acetylacetonate-modified titanium (IV) tetra-isopropoxide [141]. The thermalbehaviors of three zinc (II) benzoate complex compounds (two new with caffeine and urea)were characterized by evolved gas analysis with mass spectrometry detection. Temperatureintervals of the stability of the compounds as well as the mechanisms of their thermal degra-dation were determined. The evolved gas analysis allowed determination of intermediateproducts of thermal degradation and temperature ranges of their evolution from the samples



[142]. The systems NixMn1-xC2O4·2H2O (x = 0.11, 0.34) were characterized by severaltechniques including EGA-MS [143]. New Co(II) and Cd(II) complexes with nonsteroidalanti-inflammatory drugs were isolated and investigated by Kafarska et al. The complexeswere characterized by spectroscopy and thermoanalytical techniques. A coupled TG-MSsystem was used to detect the principal volatile products of thermolysis and fragmentationprocesses [144]. Thermal properties of five divalent ruthenium precursors with three typesof structures were examined. Evolved gas analysis, as a result of TG-MS analyses, showedthat 2,4-dimethyl-1,3-pentadiene (DMPD) is a thermolysis product of Ru(DMPD)(EtCp),though no thermolysis products of Ru(EtCp)2 were observed. These results showed that thevolatility and decomposition temperature of a divalent ruthenium precursor can be designedby adjusting the precursor’s structure [145]. Mixed zinc (II) and cadmium (II) complexeswith o-hydroxybenzoic acid or o-aminobenzoic acid and 2-methylimidazole were synthe-sized and characterized. A coupled TG-MS system was used to analyze the principal volatileproducts of complexes and to postulate the thermal decomposition pathways [146]. Ther-mal decomposition of compounds consisting of tetrahalogenomanganese (II) anions and atetrabutylammonium cation was studied by DSC, TG-FTIR, TG-MS, and DTA techniques[147]. Copper (I) halide complexes were prepared by Aslanidis and coworkers and their pho-toluminescence and thermal properties were investigated. A simultaneous TG-DTG-DTAtechnique, coupled with MS for the analysis of the gaseous decomposition products, wasused for two complexes to determine their thermal degradation, which was found to be verycomplicated [148]. Synthesis, characterization, and thermal behavior (in addition to evolvedgas analysis by mass spectrometry) of fluorinated salicylaldehyde Schiff base derivatives(salen) and their complexes with copper (II) were reported by Avsar et al. [149]. The co-ordination behavior and the thermolysis of some rare-earth complexes with 4,4′-bipyridineand di- or trichloroacetates was reported by Czylkowska and Markiewicz [150]. Materazziand coworkers studied the crystal structure and the thermal decomposition of cobalt (II) andnickel (II) complexes with 2,2′-bis-(4,5-dimethylimidazole) [151] and of Mn(II) complexesof bis(1-methylimidazol-2-yl)ketone [152]. A free-base tetraphenyl porphyrin (TPP) andits corresponding metalloporphyrins (MTPPs) where M = Co, Fe, and Sn was synthesizedand characterized. MTPPs were subjected to TG-EGA-MS analysis for the detailed infor-mation about evolved gases at their corresponding decomposition temperatures to predictthe probable mechanism for ring opening of the macromolecular porphyrins [153]. Thelow-temperature heat capacities and thermodynamic properties of Mn3(HEDTA)2·10H2Owere also reported [154]. The decomposition of iridium acetylacetonate impregnated onamorphous silica–alumina was investigated by combined TG-DTA-MS [155]. A thermaland kinetic investigation by simultaneous TG-DTG-DTA coupled with MS of lanthanidecomplexes of 3-methoxy-salicylaldehyde was published by Papadopoulos et al. [156]. Athermoanalytical investigation of tris(ethylenediamine)nickel (II) oxalate and sulfate com-plexes by TG-MS and TR-XRD studies was reported by Rejitha and Mathew [157].

A new precursor molecule for chemical modification of oxide surfaces was synthesizedin three steps from tricyclohexyltin hydride. The so-modified powders were thoroughlycharacterized using several techniques, including TGA-MS [158]. A homogeneous ZrO2

gel was obtained by hydrolysis–condensation of zirconium (IV) n-propoxide previouslyreacted with acetic acid. Thermogravimetric and differential thermal analysis coupled withmass spectrometric measurements was carried out in order to identify and quantify theorganic products released during the ZrO2 gel pyrolysis. The TG-MS semi-quantitativeanalysis of the main released species allowed describing the chemical rearrangement oc-curring in the solid during heating and determination of the chemical composition ofthe initial gel [159]. The thermal behavior of a formamide-intercalated mechanochemically



activated (dry-ground) kaolinite was investigated by TG-MS and diffuse reflectance Fouriertransform infrared spectroscopy (DRIFT). After the removal of adsorbed and interca-lated formamide, a third type of bonded reagent was identified in the temperature range230–350◦C decomposing in situ to CO and NH3 [160].

Samples of electrolytic manganese dioxide were chemically reduced using 2-propanolunder reflux (82◦C) for 1-, 2-, 3-, 6-, and 24-h intervals. XRD analysis showed that theMnO2 structure was preserved although the lattice dimensions were observed to increasewith increasing degree of reduction to accommodate the intercalation of protons. Three re-gions of decomposition in the range of 50–1000◦C were observed using TG-MS and wereaccounted for as water removal below 390◦C, reduction of MnO2 to Mn2O3 between 400and 600◦C, and Mn2O3 to Mn3O4 between 600 and 1000◦C. [161]. The low-temperatureformation of crystalline zinc oxide via thermal decomposition of zinc acetylacetonatemonohydrate was studied by humidity-controlled thermal analysis. The thermal decom-position was investigated by sample-controlled thermogravimetry (SCTG), TG-MS, andsimultaneous XRD-DSC [162]. The thermal decomposition of solid samples of iron (VI)mixed oxides in an inert atmosphere was examined by Madarasz et al. using simultaneousthermogravimetry and differential thermal analysis, in combination with in situ analysisof the evolved gases by on-line coupled mass spectrometry (EGA-MS). The final decom-position products were characterized by 57Fe Mossbauer spectroscopy. Water moleculeswere released first, followed by a distinct decomposition step with an endothermic DTApeak corresponding to the evolution of molecular oxygen as confirmed by EGA-MS. Thedecomposition product of K2FeO4 at 250◦C was determined as Fe(III) species in the formof KFeO2 [163]. Sn, Sn-Sb, Ti, Zr, Fe, Ce, and In oxides were prepared as nanometricpowders by the hydrolytic route, starting from their ordinary salts or alkoxides, in the pres-ence of 5% w/v starch as a nonionic stabilizer of crystallization nuclei versus coalescenceand flocculation. The nanoparticle features of prepared oxides resulted from experimen-tal evidence based on X-ray diffractometry, transmission electron microscopy, differentialthermal analysis–thermogravimetry coupled to mass spectrometry, specific surface areaand porosity of samples obtained by curing in the 80–600◦C interval [164]. A sol-gelmethod followed by calcination at temperatures of 300–900◦C was used to obtain a seriesof LiMn2O4 samples with varying amounts of chemical and structural defects while pre-serving a constant Li:Mn atomic ratio. The physicochemical and structural properties of thesamples were characterized by XRD, TG-MS, DSC, and Raman spectroscopy techniques[165]. Sodium methoxide and sodium ethoxide were synthesized by Chandran et al., andtheir thermal decomposition and reaction kinetics were investigated under nonisothermaland isothermal conditions. Kinetics of decomposition in each run was evaluated from thedynamic TGA and MS data obtained from a thermogravimetric analyzer coupled with amass spectrometer-based evolved gas analyzer. The evolved gases were found to be a mix-ture of saturated and unsaturated hydrocarbons [166]. The adsorption of CO on hydratedRu/Al2O3 oxides produced absorbance features that were red-shifted by 50–116 cm−1 fromthose seen in the absence of water. Temperature-programmed desorption done with TGA-MS indicated three different high-temperature CO2 desorption peaks. These peaks weremost likely the result of the oxidation of adsorbed CO reacting with surface adsorbed waterand/or the disproportionation of CO [167]. Soon and coworkers studied the kinetics of theformation of iron oxide nanocrystals obtained from the solution-phase thermal decomposi-tion of iron-oleate complex via the heating-up process. To obtain detailed information on thethermal decomposition process and the formation of iron oxide nanocrystals in the solution,a thermogravimetric–mass spectrometric analysis and in situ magnetic measurements usinga SQUID detector were performed. The TG-MS results showed that iron-oleate complex



was decomposed at around 320◦C. [168]. Cathode materials Li[CoxMn1-x]O2 for lithiumsecondary batteries were prepared by a new route, a precursor method of layered doublehydroxides (LDHs). In situ high-temperature X-ray diffraction and thermogravimetric anal-ysis coupled with mass spectrometry were used to monitor the structural transformationduring the reaction of CoMn LDHs and LiOH·H2O [169]. Mesoporous CeO2 was synthe-sized by using CMK-3 carbon as a structure matrix. Spectroscopic techniques and TG-MSanalysis were used for their characterization. Methanol decomposition to hydrogen, CO,and methane was used as a catalytic test reaction. The synthesis of CeO2 from Ce(NO3)3

within the pores of the carbon matrix and the subsequent thermal combustion of the carbonwas monitored by thermal analysis. Catalytic tests revealed that the activity of the meso-porous products in methanol decomposition was substantially higher than for a nonporoussample [170]. Cryptomelane-type manganese oxides were synthesized, characterized, andtested in the total oxidation of volatile organic compounds and CO oxidation. The struc-tural, compositional, morphological, acid-base, physisorptive–chemisorptive, and thermalstability properties (especially the reversible evolution of lattice oxygen) were studied in de-tail using several techniques; among them, temperature-programmed decomposition–massspectroscopy (TPD-MS), and TGA-DSC allowed kinetic and mechanistic suggestions forthe catalytic function [171]. The formation of nanosized hexagonal tungsten oxide (h-WO3)during the annealing of hexagonal ammonium tungsten bronze was investigated by TG-DTA-MS, XRD, SEM, Raman, X-ray photoelectron spectroscopy (XPS), and 1H-MASNMR analyses [172, 173]. The as-prepared cobalt oxide (assigned as CoOx) was obtainedby precipitation–oxidation from aqueous cobalt nitrate solution using sodium hydroxide andoxidation with hydrogen peroxide. Phase transformation, structural properties, and redoxproperties were characterized by TG-MS, XRD, IR, Raman spectroscopy, and temperature-programmed decomposition–reduction (TPD-TPR) [174]. A series of ZnO/Al2O3 mixedoxide samples with varying Zn/Al ratio was prepared by Miao et al. Samples were investi-gated in the state after drying and calcination by several techniques like X-ray diffraction,solid-state 27A1 magic-angle spinning nuclear magnetic resonance spectroscopy, transmis-sion electron microscopy, and thermogravimetry coupled with evolved gas analysis. Allresults indicated the substitution of Al ions for Zn ions in zinc oxide of zinc-rich samples[175]. Pasierb et al. investigated the influence of titanium and yttrium dopants on selectedBa(Ce1-xTix)1-yYyO3 compounds. Initially, thermal analysis was used for optimization ofpreparation conditions. Subsequently, DTA-TG-MS hyphenated techniques were appliedfor evaluation of the stability of prepared materials in the presence of CO2 [176]. Polyani-line/NiO (PANI/NiO) composites were synthesized by in situ polymerization in the presenceof HCl (as dopant). In addition to the thermal stability, TG-MS curves indicated that theproducts for oxidative degradation of both the PANI and PANI/NiO composite were H2O,CO2, NO, and NO2 [177]. Nanoscaled indium tin oxide (ITO) was prepared via an electro-chemical method in an aqueous system containing ammonium acetate as conductive salt.As an intermediate product of the synthesis, nanocrystalline In(OH)3 was obtained, whichserved as a precursor for the subsequent calcinations accompanied by tin doping resultingin ITO powders with various tin concentrations. Its phase transitions and the reductionbehavior of hydroxide to oxide were investigated by high-temperature X-ray diffraction,TG-DSC-MS, high-resolution transmission electron microscopy (HRTEM), and SEM anal-ysis [178]. In this study, p-type ZnO films with excellent electrical properties were preparedby ultrasonic spray pyrolysis (USP) combined with a N-Al codoping technique. The influ-ence of the substrate temperature and annealing temperature on electrical properties of ZnOfilms was investigated. The growth and doping process of ZnO films was explored by si-multaneous TG-DSC-MS measurements [179]. High-purity single-crystal ZnO nanowires



were synthesized by the thermal decomposition of zinc acetate dihydrate at 300◦C in air for3 h without a catalyst. The characterization by TG-DSC-MS determined the thermal de-composition and crystallization temperature. Results revealed that the ZnO nanowires wereproduced through a dehydration, vaporization–decomposition, and deposition–formationprocess, which differs from the common vapor–liquid–solid (VLS) mechanism [180]. Thecatalytic effect of nickel oxide on thermal decomposition of nitrocellulose (NC) was in-vestigated via a TG-MS coupled technique, and the residue of NC with 20% NiO reactedin tubular furnace was analyzed by XRD. TG-MS analysis showed that adding 2% NiO toNC accelerated the thermal decomposition process and promoted the generation of gaseousproducts [181]. A thermal treatment of Co3O4-type spinel phases, synthesized by electroox-idation of CoO powder in a mixed alkaline electrolyte (KOH, LiOH, NaOH), was shown tohave an important influence on the electronic conductivity properties of the materials. Thethermal treatment, followed by in situ X-ray diffraction, TGA-MS, and electronic conduc-tivity measurements induced a water release, coupled with an increase of the Co/O atomicratio and a structural reorganization. The resulting cationic redistribution within the spinelframework entailed an increase of the Co4+ amount in the [Co2O4] network and thereforeof the electronic conductivity (by three orders of magnitude) [182]. Nanocrystalline mag-nesium aluminate spinel (MgAl2O4) was synthesized using metal nitrates, citric acid, andammonium solutions by Saberi and coworkers. The precursor and the calcined powdersat different temperatures were characterized by X-ray diffraction, thermal analysis, andmicroscopy (SEM, TEM). The combustion mechanism was studied by a quadrupole massspectrometry coupled to thermal analysis (STA-QMS) [183]. Evidence for the existence ofprimitive life forms such as lichens and fungi can be based upon the formation of oxalates.These oxalates form as a film-like deposit on rocks and other host matrices. High-resolutionthermogravimetry coupled to evolved gas mass spectrometry showed the decomposition ofwheatleyite at 255◦C [184]. The same approach was used to study the thermal decomposi-tion of a synthetic aurichalcite with varying copper–zinc ratios from 0.1:0.9 to 0.5:0.5. Thethermal decomposition of aurichalcite offers a method of preparing metal oxides mixedat the molecular level, making the thermally activated aurichalcites suitable for use ascatalysts [185]. Thermogravimetric analysis of synthetic smithsonite and hydrozincite, twosecondary minerals of zinc, was used to determine their relative thermal stability. Hot-stageRaman spectroscopy confirmed the decomposition temperature range of both smithsoniteand hydrozincite [186]. The formation of cadmium sulfide (CdS), a semiconductor used foroptoelectronic devices, in the interlayer space of montmorillonite by solid–solid reactionsbetween Cd(II)-montmorillonite and sodium sulfide at room temperature was investigated.The reaction was followed by XRD and TG-MS analysis of the products [187]. The totalspecific surface area (TSSA) and smectitic layer charge (Qs) calculated from the structuralformulae and unit-cell dimensions of 12 pure smectite samples were used as a referencein the design and evaluation of TSSA and Qs measurement techniques based on cationexchange capacity (CEC). The TG-MS technique was used to study the release of waterfrom smectite on heating and to introduce a correction for the water amount remaining inthe smectite after heating to 110◦C, because the sample weight at this temperature was usedroutinely as a reference in CEC and ethylene glycol monoethyl ether (EGME) sorption mea-surements [188]. Calcination is the last process step of the sulfate method for productionof titanium dioxide. The chemical reactions that occur during calcination were analyzed bymeans of simultaneous DTA-TG-MS-measurements in order to provide a five-step reactionschematic, and the corresponding enthalpies of reaction were determined calorimetricallyby means of the reversed drop method. The developed schematic is suitable for processmodeling purposes [189]. Synthesis and structural characterization of the first LiFeO2



compound with tetrahedrally coordinated Fe3+ (used as a positive intercalation electrode ina lithium cell) was reported by Armstrong et al. By combining results from several electro-analytical techniques and TG-MS, it was suggested that intercalation–deintercalation wasaccompanied by the exchange of Li+ by H+ [190]. The properties and especially the ther-mal stability of NH4

+ in a nanodrop of water encapsulated into a structurally well-definedporous molybdenum oxide–based nanocontainer was studied with thermoanalytical meth-ods (TG-MS, DTA, DTG) to give new insights into the behavior of electrolytes underconfined conditions [191]. The stability of the solid oxide fuel cell (SOFC) cathode ma-terial Ba0.5Sr0.5Co0.8Fe0.2O3 in CO2-containing atmospheres was investigated by precisionthermogravimetry and mass spectrometry as a function of temperature [192]. The thermalstability of a charged graphite electrode was studied by TG-DTA-MS. The study indicatedthat the exothermic reactions at around 285◦C should be accompanied by the generation ofmethane. When charged electrode powders coexisted with electrolyte solution in a hermeticpan, the heat values at around 285◦C varied in an apparently complicated way depending onthe ratio of charged electrode powder to an electrolyte. These phenomena were discussedquantitatively by considering the amount of lithium ions in charged graphite powder anda coexisting electrolyte. These results suggested that the exothermic reactions at around285◦C can be attributed to the reductive decomposition of SEI by charged graphite [193].

Fluorinated transition aluminas with a hexagonal platelet shape were synthesized underair; they were thermally stable up to 1000◦C and exhibited a weight loss with volumereduction at 1150◦C caused by fluorine departure corresponding to a phase transitiontoward corundum alumina. The different characterizations performed in this study werestructural (XRD), chemical (TGA-MS and microprobe analysis), and morphological (SEM,TEM and dilatometry) [194].

LDHs calcined at different temperatures (denoted as CLDH) were demonstrated to re-cover their original layered structure in the presence of appropriate anions. In light of this so-called memory effect, removal studies of fluoride from aqueous solution by calcined Mg-Al-CO3-LDH were carried out. The LDH calcined at 500◦C had the highest capacity of removalof fluoride ion, because of retention of its intrinsic structure. The results of X-ray diffrac-tion, FTIR, and TG-MS demonstrated that the adsorption phenomenon was accompanied byrehydration with concomitant uptake of fluoride ions to rebuild the initial layered structure[195, 196]. Ceria powders were synthesized via a combustion technique using two kinds ofstarting materials: urea as a fuel and ceric ammonium nitrate as both the source of cerium ionand an oxidizer. The thermal decomposition and combustion process of the reactant mix-ture were investigated using thermogravimetry, differential scanning calorimetry, and massspectrometry techniques simultaneously. Based on the results of thermal analysis, a possi-ble mechanism concerning the combustion reaction was proposed [197]. Nanocrystallineceria was synthesized by a nonhydrolytic method using organic solvent and precipitant.The effect of the source compound on final nanocrystalline powder was investigated. Thecerium nitrate hexahydrate was subjected to different vacuum-thermal treatments to obtain acerium source compound having a different extent of water of crystallization. The nanoceriasynthesized from these compounds was characterized by TGA-MS, XRD, HR-TEM, andatomic force microscopy (AFM) [198]. Supramolecular 2,3- and 2,5-pyridinedicarboxylate(PDC)-intercalated ZnAl-layered double hydroxides (2,3- and 2,5-PDC-ZnAl-LDHs) wereprepared and their thermal decomposition processes were studied by the use of in situ high-temperature XRD and the combined technique of TG-DTA-MS. The same investigationwas performed on the supramolecular 2,3-pyridinedicarboxylate-intercalated NiAl-layereddouble hydroxides (2,3-pyridinedicarboxylate-NiAl-LDHs) [199, 200]. Nanosized ZnSwas synthesized in the interlayer galleries of Mg-Al LDHs. The thermal decomposition



process of the hybrid material was characterized by in situ high-temperature powder XRDand TG-DTA-MS [201]. CLDH as a potential adsorbent to remove iodide contaminantswas investigated in batch mode. The uptake capacity of calcined LDH was higher thanthat of LDHs as a precursor, due to their different mechanism that is supported by XRDand TG-MS measurements [202]. Lv used MgAl-CO3 CLDH to remove fluoride with thereconstruction of their original layered structure in the presence of appropriate anions.The data of fluoride removal fitted well into the linearly transformed Langmuir prediction.The mechanism of defluoridation was confirmed by powder X-ray diffraction and TG-MS[203]. The nickel (II) citrate complex anion was intercalated into the interlayer galleriesof an LDH host by a process involving ion exchange. The powder XRD pattern confirmedthat the layered structure was maintained and the thermal decomposition process of thecomplex anion-intercalated material was characterized by TG-DTA also coupled to MS[204]. Two commercially available nanosized TiO2 colloids and their suspensions in TritonX-100 were precipitated and dried carefully. The solids obtained were studied up to 500◦Cby simultaneous thermogravimetric and differential thermal analysis on-line coupled withquadrupole mass spectrometer for analysis of evolved gases in flowing air, nitrogen, and he-lium atmospheres in order to check and model pyrolytic processes taking place at elevatedtemperature ranges of porous TiO2 layer fabrication techniques [205]. Thermal decom-position of precursor xerogels for TiO2, obtained by gelling of acetylacetonate-modifiedtitanium (IV) tetraisopropoxide, was monitored by simultaneous TG-DTA-EGA-MS andEGA-FTIR measurements. EGA by FTIR and MS revealed release of H2O below 120◦C,followed by evolution of acetone and acetic acid between approximately 100 and 320◦Cand that of CO2 up to 560◦C [206]. An aqueous solution-gel route was developed for thepreparation of TiO2 by TruiJen et al. To gain insight into the behavior of the precursorduring thermal treatment, the thermal decomposition mechanism was studied by TGA-MS,and the gel structure and changes in the solid upon heating were studied by means ofFTIR [207–210]. X-ray powder diffraction (XRPD) was combined with TG-MS analysisto study and compare the phase transformations, thermal stability, and microstructural andstructural changes of two cobalt-containing nitrate-based LDHs upon heating in a con-trolled inert atmosphere of nitrogen. The correlation of XRPD data with those from theTG-MS analyses gave information about the transformation mechanisms [211]. A funda-mental investigation on the uptake of bromide ion from contaminated water by calcined anduncalcined MgAl-CO3 LDHs was conducted in batch mode. The uptake capacity of CLDHwas higher than that of uncalcined LDHs, due to their different mechanisms, which wereconfirmed by powder X-ray diffraction, FTIR spectroscopy, and TG-MS measurements[212]. Ferritic steels in steam turbines for the power industry operate without coatingsin the temperature range of 590–600◦C, whereas for higher operation temperatures thesubstrate has to be replaced or coated; otherwise, the ferritic substrate at a temperature of650◦C develops thick oxide scales that promote sudden turbine blade failure. To this end,TG-MS experiments were conducted in a closed steam loop in order to obtain informationabout the oxyhydroxides formation as reaction between coatings and steam. From thoseresults the role of the different coating element was established and optimized for thecoating durability. An oxidation mechanism based on the TG-MS results was also given[213]. The mechanism and kinetics of thermal decomposition of Ni/Al LDH nitrate werestudied by coupled TG-DTA-MS and the results proved that the thermal decomposition ofNiAl-LDH proceeds in three individual processes; that is, removal of the physisorbed andinterlayer water, dehydroxylation of the layers, and decomposition of the interlayer nitrateions (denitration) [214]. Zn/Al LDHs were intercalated with the anionic antihypertensivedrugs enalpril, lisinopril, captopril, and ramipril by using a coprecipitation or ion-exchange



technique. TG-MS analyses suggested that it is possible that the intercalated guests, ar-ranged with a monolayer in the interlayer, show lesser repulsive forces and strong affinitywith the LDH layers [215]. The influences of atmospheric CO2 and H2O on the kineticsof the thermal decomposition of zinc carbonate hydroxide were investigated by meansof controlled rate evolved gas analysis (CREGA). Although CO2 and H2O were evolvedsimultaneously in a single mass-loss step of the thermal decomposition, different effects ofthose evolved gases on the kinetic rate behavior were observed [216]. Modified magnesiumhydroxide was prepared by a precipitation method. It was shown that the flame-retardantefficiencies were very low when the polymer composites only contained magnesium hy-droxide [217]. The Ni/Al nitrate form LDHs were successfully synthesized at atmosphericcondition by chemical precipitation and hydrothermal methods through pH control. Sam-ples obtained at various pH conditions were characterized by several techniques includingEGA-MS analysis [218]. Cu-Zn-Mn-Fe-Al LDHs with Cu:Zn:Mn:Fe:Al atomic ratios of1:1:0:0:1, 1:1:1:0.3:0.7, and 1:0.7:0.3:0.3:0.7 in a synthesis mixture were prepared by co-precipitation under controlled conditions of temperature and pH. The decomposition of theprecursors at 500◦C in air to obtain mixed oxides was monitored by TG-DTA-MS [219,220]. The mechanism of the thermal decomposition of tetramethyl ammonium hydroxidepentahydrate was studied using DSC, TG, and EGA because of the importance of relatedions in anion exchange membranes for fuel cells. The products of the reaction (trimethylamine, methanol, and dimethyl ether) and the relative ratio of the products were determinedby how much water remained in the sample as it decomposed [221].

Pappa and coworkers used thermogravimetry coupled to mass spectrometry to studythe effect of the inorganic salts (NH4)2SO4 and (NH4)2HPO4, active substances of manycommercial forest fire retardants on the pyrolysis of Pinus halepensis needles and their maincomponents (cellulose lignin and extractives). These salts seemed to affect the pyrolysis ofcellulose by significantly increasing the char residue, decreasing the pyrolysis temperature,and changing the composition of the evolved gases; that is, increasing levoglucosenone anddecreasing oxygen-containing volatile products [222]. The thermal decomposition mech-anism of FeSO4·6HO was studied by mass spectroscopy coupled with DTA-TG thermalanalysis under an inert atmosphere [223]. Zinc borohydride Zn(BH4)2 (8.5 wt% theoreticalhydrogen storage capacity) was synthesized by mechanochemical reaction between NaBH4

and ZnCl2 and characterized by XRD and FTIR, and its thermal stability was studied byTG-MS and DSC under flowing argon [224]. Yu and coworkers determined the optimalnitridation conditions of InN by the application of a TG-MS coupled technique for simul-taneous characterization of the changes of mass and determination of the evolved gasesduring the thermal decomposition of InN prepared at different nitridation temperatures.Moreover, pulse thermal analysis (PulseTA) was combined with TG-MS for the quantita-tive calibration of the evolved nitrogen formed during the thermal decomposition of InNsamples [225, 226]. Magnesium alanate Mg(AlH4)2 was synthesized by mechanochem-ically activated metathesis reaction between NaAlH4 and MgCl2 without solvent. Thethermal decomposition behavior of solvent-free Mg(AlH4)2 was analyzed by TG-MS andDSC [227]. The decomposition processes of silver behenate were studied by several tech-niques, including combined TG-DTA-MS. The TG-DTA and the higher temperature IR andXRD measurements indicated that complicated structural changes took place while heatingsilver behenate, but there were two distinct thermal transitions. The combined TG-MSanalysis showed that the gas products of the thermal decomposition of silver behenate werecarbon dioxide, water, hydrogen, acetylene, and some small-molecule alkenes [228]. Con-ductive polyaniline salts were synthesized by an inverted emulsion polymerization methodand were characterized by EGA-MS analysis and XPS methods. The various characteristic



fragments evolved during the thermal degradation of polyaniline were identified. The weightloss of dopants as well as sodium lauryl sulfate decomposition were identified at differenttemperatures from TGA-MS analysis [229]. A new strategy was introduced to decomposeKNO3 and generate strong basic sites at a temperature as low as 723 K. The redox in-teraction between loaded KNO3 and methanol was proved to account for the generationof basic sites on KNO3/NaY composites and the interaction pathway was proposed byevacuated FTIR and TG-MS. In comparison with the conventional thermal approach, theredox process could also suppress the release of NOx from KNO3 decomposition accordingto the results of the colorimetric method and TG-MS [230]. Sodium carbonate, a primaryinorganic standard of volumetric analysis, was certified in different countries by using dif-ferent drying conditions. The drying conditions for reference materials have a significanteffect on the titration results due to changes in the acidimetric factor. The drying conditionsfor sodium carbonate were investigated by TG-MS by heating from room temperature to700◦C. The study concluded that suitable drying conditions were between 200 and 400◦C,with the optimum approximately around 300◦C for 2 h [231]. A gas-tight thermal analysissystem was connected to an isotope ratio mass spectrometer via an interface containing anoxidizing furnace, water trap, and gas-sampling valve. Using this system, 13C was mea-sured for CO2 derived from the thermal decomposition of carbonate and oxalate mineralsand organic materials at temperatures that correspond to different decomposition events.Thermogravimetry–isotope ratio mass spectrometry (TG-IRMS) is ideal for materials andsamples for which it is not possible to use other isotopic measurement techniques; forexample, because of sample heterogeneity [232]. Debris samples from braking tests carriedout with carbon–carbon discs, mounted in a reduced-scale bench, were studied by X-raydiffraction, EGA-MS, and N2 physisorption at −196◦C. Debris samples from both materi-als were similar, essentially amorphous, and contained up to 10% of oxygen. However, acareful examination of the experimental results clearly showed some differences depend-ing on the starting materials [233]. (3-Triethoxysilylpropyl)succinic anhydride (TESP-SA)is an organofunctional silicon compound that can be converted into a polysilsesquioxanewhen it is hydrolyzed and subsequently subjected to a condensation reaction at elevatedtemperatures (>160◦C). If this process is performed without sodium hypophosphite (SHP),a hard solid material is obtained. In contrast, the condensation reaction of TESP-SA in con-junction with SHP resulted in the formation of a foamed, brittle material with closed macrocells. The foam was obtained and characterized by Schramm and coworkers by means ofvarious analytical methods (FTIR, 29Si MAS-NMR, XRD, TG-MS, SEM) [234]. A newmaterial constituted by cerium dioxide highly dispersed on activated carbon (CeO2/AC) wasprepared by an impregnation method using cerium (III) nitrate as CeO2 precursor. In orderto evaluate the degree of ceria dispersion on the carbon support, CeO2/AC was character-ized by a number of techniques including evolved gas analysis by mass spectrometry. Theanalysis of the decomposition process under inert atmosphere indicated that cerium nitratedecomposes at 440–460 K, with the evolution of NO. Furthermore, this process producedan additional oxidation of the carbon surface (with evolution of N2O) and the subsequentonset of new oxygen surface groups, detected by means of temperature-programmed des-orption [235]. BN-NHx samples were synthesized by ball milling hexagonal boron nitride(h-BN) under hydrogen and/or ammonia atmosphere firstly. Then, the BN-NHx sampleswere ball milled with lithium hydride under a hydrogen atmosphere to synthesize Li-BN-Hcomposites. XRD, FTIR, and TG-MS were used to investigate the microstructure and gasdesorption properties of samples [236]. A novel CO2 capturer with a high efficiency wasfabricated through dispersing the amine mixture of tetraethylenepentamine (TEPA) anddiethanolamine (DEA) or glycerol within the as-synthesized mesoporous silica SBA-15.



The influence of the hydroxyl group on the CO2 adsorption capacity of the composite wasinvestigated by using CO2-TPD and TG-MS techniques. It was demonstrated that the useof this mixed amine (TEPA and DEA) modified as-synthesized SBA-15 as CO2 capturernot only saved the energy for removal of template but also cut down the cost in the prepa-ration and regeneration of CO2 capturer, which is critical in CO2 separation and capture[237]. Inorganic gels were prepared from aqueous solutions of zirconium dinitrate oxide,ammonium metatungstate, and citric acid in the pH range 1.1–10. The thermal behaviorof these precursor gels and the oxide phase evolution were studied by thermal analysisand EGA-MS [238]. High-temperature X-ray diffraction, absorption–reflection infraredspectrometry, and thermal analysis coupled on-line to mass spectrometry were applied tocitratoperoxo precursor gels and films of (Bi,Nd)4Ti 3O12 (BNdT). A slow heating rateresulted in secondary phases and a high rate yielded phase-pure layered perovskite BNdT.Comparison of the evolved gas profiles from the bulk gel and thin film showed completedecomposition of the film at lower temperature than expected from thermogravimetric andevolved gas analysis of the bulk gel. Thermal methods adapted to thin films therefore arecrucial for understanding and controlling the oxide formation in the film [239]. The promot-ing effect of ceria in the electrocatalytic activity of rhodium for ethanol electrooxidationin alkali media was studied. Rh/C, CeO2/C, and RhCeO2/C catalysts were synthesized andcharacterized by TG-MS, electrochemistry, and spectroscopic techniques [240]. TPD-MSwas utilized for the study of the thermal dehydration and decomposition of copper selenatepentahydrate. The results suggested that the dehydration is a three-step process reachingcompletion at 300◦C. The decomposition process, far more complicated and consistingof several successive steps, via several unstable intermediates up to the conversion of theremaining copper monoxide into dicopper monoxide was accompanied by oxygen emis-sion [241]. The phase compositions of hydrided Ti-Cr-V hydrogen storage alloys wereexamined by X-ray diffraction and TG-DTA-MS coupled analysis. The aim was to studythe dependence of hydrogen desorption characteristics with temperature and the states ofreleased hydrogen (inspected by mass spectrometry) [242]. To understand the influence ofthe physical properties of carbon on the thermal decomposition behavior of ammoniumnitrate and carbon mixtures, analyses using several techniques including EGA-MS werecarried out. Mass spectra of decomposition gases for ammonium nitrate and activated car-bon or graphite mixtures showed different patterns when scanning by TGA, but they showedsimilar spectra when instantaneous heating with a flash pyrolyzer was performed. It wasconcluded that ammonium nitrate mixed with carbon of low crystallinity showed violentreactions after melting, whereas when mixed with carbon of high crystallinity it showedthe same behavior as if it were pure [243]. Thermal analysis coupled to mass spectrometryfor evolved gas analysis was applied to hydrotalcites containing carbonate prepared by co-precipitation and with varying divalent–trivalent cation ratios. The thermal decompositionof carbonate hydrotalcites, consisting of two decomposition steps between 300 and 400◦C,was attributed to the simultaneous dehydroxylation and decarbonation of the hydrotalcitelattice [244]. Szilagyi and coworkers discussed the changes in the structure and thermalreduction of nanosized hexagonal ammonium tungsten bronze (HATB), which were causedby K+ ion exchange (doping). After the reaction, from the hexagonal channels less NH3

evolved, which also supported the incorporation of K+ ions into the hexagonal channels[245, 246]. The crystal and molecular structures of p-dimethylaminobenzaldehyde semicar-bazone and p-dimethylaminobenzaldehyde semicarbazone hydrochloride were determinedand their thermal behaviors were characterized by thermogravimetric analysis in conjunc-tion with evolved gases in the air atmosphere [247]. Samples of an organic–inorganic hybridwere prepared by solvolysis and polycondensation in formic acid of tetraethoxysilane and



diethylbenzyl phosphonate, simultaneous with the oxidative polymerization of aniline. Twosignificant thermal events were established by evolved gas analysis: the elimination fromthe polymeric matrix of low mass molecules and the thermooxidative degradation of theorganic part of the matrix [248]. The transformation of organic and inorganic sulfur duringpyrolysis of a western Australian lignite was studied using several complementary tech-niques. TGA-MS studies of the raw lignite showed that SO2 is the dominant sulfur-bearinggas evolved during the pyrolysis of the raw lignite. The effect of inherent and added inorgan-ics was studied by comparing the amounts of various forms of sulfur retained in the chars ofthe raw lignite, the acid-washed lignite, and the acid-washed lignite doped with sodium andkaolinite following pyrolysis in a fixed-bed reactor in nitrogen [249]. In situ catalytic ther-mal decomposition of ammonium perchlorate was investigated. The EGA results showedthat the new ecological nanocobalt oxide exhibited better catalytic performance in thermaldecomposition of ammonium perchlorate [250–252]. Detailed investigation on the thermalbehavior of hexaamminenickel (II) chloride and hexaamminenickel(II) bromide was car-ried out by means of simultaneous TG-DTA coupled on-line with mass spectroscopy andtemperature-resolved X-ray diffraction [253]. The decomposition process of Y(BH4)3− (anovel highly efficient hydrogen storage material) in a mixture with LiCl was investigatedwith MS-EGA [254]. The interaction between uranyl nitrate hexahydrate (UNH) and ru-bidium nitrate in solid state at elevated temperatures was studied for several compositionsusing simultaneous thermal analysis techniques (TG-DTA-EGA), X-ray diffraction, andIR spectral measurements [255]. The interaction between uranyl nitrate hexahydrate andrubidium nitrate in solid state at elevated temperatures was studied for several compositionsusing simultaneous EGA-MS, X-ray diffraction, and IR spectral measurements [256]. Twotypes of semiconductor particles, ZnS and CdS, were formed in the interlayer spaces ofmontmorillonite by solid–solid reactions. The formation of the intercalation compoundswas confirmed by powder XRD and TG-MS [257]. Li and Cheng reported an investigationon the thermal stability of nitroguanidine by TG-DSC-MS-FTIR and multivariate nonlinearregression [258]. A thorough analytical study on the thermal decomposition evolution ofthe metal-trifluoroacetate precursor toward high-performance YBa2Cu3O7 superconduct-ing films was presented by Llordas et al. Evolved gas analysis by Fourier transform infraredspectroscopy and mass spectrometry was performed to determine the complete chemicaldecomposition reaction of the metal-trifluoroacetate precursors [259]. To understand anovel process for preparation of calcium carbide from pulverized feedstocks, the reactionsbetween a coke and various calcium compounds were examined in a TG-MS system upto 1850◦C [260]. The evolved gas analysis during the thermal decomposition and crystal-lization of precursor sol for preparing oxidation resistant coatings on intermetallic TiAlwas reported by Tian et al. [261]. The catalytic effect on the thermal decomposition of thepropellant TEGDN-NC was studied via a thermogravimetry–mass spectrometry coupledtechnique: the results showed that adding 2% NiC2O4· 2H2O can accelerate the thermal de-composition of TEGDN-NC propellant and accelerate the generation of gaseous products[262]. Direct nitrous oxide decomposition with a cobalt oxide catalyst was investigatedby Wilczkowska et al. [263] and the thermal decomposition of citric acid and trans- andcis-aconitic acid was studied by Wyrzykowski et al. [264]. Urazole [265] and a guanidinenitrate mixture with 1,2,4-triazole-3-one, which have the potential to be used as alternativegas-generating agents, were characterized to obtain a better understanding of the thermaldecomposition properties [266, 267]. Reinvestigation of dehydration and dehydroxylationof hydrotalcite-like compounds through combined TG-DTA-MS analyses was proposed byZhang et al. [268]. The thermal decomposition of hydrotalcites with chromate, molybdate,and sulfate in the interlayer, liebigite, and jarosites was studied using thermogravimetric



analysis coupled to a mass spectrometer to measure the gas evolution [269–271]. Ni-Znferrite with the chemical formula of Ni0.5Zn0.5Fe2O4 was synthesized in an amount of 100 gper batch by means of a modified combustion synthesis method using glycine and metal(Ni, Zn, and Fe) nitrates as reactants. By directly mixing and thoroughly dehydrating, aflammable precursor with good homogeneity can be obtained. Once ignited in the air at roomtemperature, it underwent a combustion process, and with a large amount of gas smoke, avoluminous loose product was yielded. The results revealed that the nanocrystalline Ni-Znferrite powders were directly formed after combustion and that the product’s propertiesshowed good reproducibility. The thermal decomposition and combustion process of theprecursor were investigated using TG-DSC-MS techniques simultaneously. Based on theexperimental results of evolved gas analysis, a possible reaction mechanism as well as asuggestion for improving the method was proposed [272].

Sidewall functionalization of carbon nanotubes via various dissolving metal reductionmethods was reported by Borondics and coworkers. The thermal stabilities and chemicalcompositions were determined by TG-MS. Characteristic decomposition peaks, observedin the range of 350–600◦C, suggested the formation of covalent derivatives upon functional-ization [273]. TG-DSC-MS coupled techniques were used to make a simultaneous charac-terization study for the thermal decomposition process of the carbon nanotube (CNT)/SiO2

precursor powders prepared by rapid sol-gel method [274]. Multiwalled carbon nanotube(MWCNT) samples were obtained by purification and ball-milling of an MWCNT samplesynthesized by catalytic chemical vapor decomposition. These samples were oxidized withKMnO4-H2SO4 solution. A heat treatment was employed to decompose the oxygenatedgroups created by the oxidation treatment [275]. Evolved gas analysis techniques and Py-GC-MS were used to study modified single-wall carbon nanotubes (SWNTs). Increasedweight loss was exhibited in the modified SWNTs below 800◦C, which was attributed to theaddition of methoxide introduced during the modification [276]. Iodinated single-walledcarbon nanotubes, with iodine covalently bound to the nanotube surface, were synthe-sized and fully characterized using XPS, Raman spectroscopy, UV-Vis-NIR spectroscopy,and hyphenated thermogravimetric analysis–mass spectrometry [277, 278]. Random andaligned MWCNTs were modified by Diels-Alder [4+2] cycloaddition, Sandmeyer reaction,and catalytic oxidation. The properties of MWCNTs were studied by several techniques,including TG-MS. The presence of the modifying groups and their fragments from thefunctionalized MWCNTs was demonstrated by TG-MS. Due to the high thermal stabilityof modified MWCNTs, the functionalized derivatives are applicable in several industrialfields [279]. Preliminary results of Raman spectroscopy are presented on in situ growth ofcarbon nanotubes in a cyclic voltammetry device (CVD)-cell that is optionally coupled toa mass spectrometer. The system allowed analyzing the differences in the content of thetypes of carbon nanotubes in the sample during the processes after 2, 5, 10, 15, 20, and30 min. The evolved gases in the throughput synthesis were analyzed in the MS mode[280]. For practical applications, the surface of porous carbon materials usually needs to bemodified/tailored according to specific requirements; for instance, in order to improve theirhydrophilicity or their interaction with catalytic species. Bazula et al. reported a detailedstudy on surface and structure modification of ordered mesoporous carbons (OMCs) via aliquid-phase chemical oxidation approach. The physical parameters as well as the chemicalnature of the modifications were investigated with low-temperature nitrogen adsorption,FTIR, EGA-MS, TEM, XPS, and XRD analysis [281]. Multiwalled carbon nanotubes mod-ified by cyclodextrin were synthesized in order to provide a theoretical basis for developinggas sensors for NO detection. NO adsorption–desorption was detected by TG-MS, and themechanism of NO adsorption was discussed on the basis of the results that demonstrated that



the small tip of cone-shaped cyclodextrin reacts with walls of MWCNTs, and cyclodextrinlocated on MWCNTs inside or outside has strong interactions, acting as hydrogen bondingand binds each other layer by layer [282]. A high-purity SWCNT sample was subjectedto a rapid functionalization reaction that attached butyric acid moieties to the nanotubesidewalls. Resultant IR-MS-EGA data were easily utilized to identify the desorption of thebutyric acid groups across a narrow temperature range and allowed calculating the degreeof substitution of the attached acid groups within the nanotube backbone [283]. Functional-ization of single-walled carbon nanotubes via atom-transfer radical addition in the presenceof copper (I/II) redox systems allowed covalent attachment of a variety of different groupssuch as carboxylate and aryl [284].

Noble metal nanoparticles (NPs) prepared by a surfactant-free single-phase solutionmethod were proposed to contain fewer ionic contaminants than similar NPs prepared bya two-phase method. To determine a possible contamination of Au and Pd NPs preparedby a surfactant-free single-phase method with Li2CO3 and other Li salts, high-temperaturethermogravimetric analysis coupled with mass spectrometry up to 1100◦C was employed.Assignment of the different weight-loss events was supported by MS analysis of the evolvedgases. TGA-MS also revealed the presence of larger amounts of oxidized sulfur speciesin the Pd NPs [285]. Silica@copper (SiO2@Cu) core-shell nanoparticles were synthesizedand characterized by XRD, TEM, AFM, XPS, UV-Vis, TG-MS, and ICP-AES techniques tocheck their use as catalysts for the conjugate addition of amines to unsaturated compoundsin water. Furthermore, it was demonstrated that the catalyst works well for hetero-Michaeladdition reactions of heteroatom nucleophiles such as thiols to unsaturated compounds.Because the reaction is performed in water, it allows for easy recycling of the catalyst withconsistent activity [286]. The direct UV irradiation of nanoparticulate TiO2 films depositedby the “doctor-blade” technique led to nanoporous and nanocrystalline anatase layers onvarious kinds of substrates as evidenced by various characterization techniques (MET,SEM, XRD, TGA-MS, and N2 sorption measurements) [287]. Cimitan et al. preparedindium- and gallium-doped ZnO nanoparticles by a hydrothermal reaction in ethanol andmethoxyethanol and reported a comprehensive study of the preparation process, includinga thorough investigation by TG-FTIR and TG-MS of the thermal-purification procedure.Reported data indicated that the use of methoxyethanol as a solvent allows an enhancedcontrol of nanoparticle size and favors dopant incorporation into zinc oxide [288]. Palla-dium nanoparticles were prepared by a single-phase reduction of palladium acetate in thepresence of different organic thiol ligands. Sizes, size distributions, and crystallinity of thePd-NPs were determined by HRTEM and powder X-ray diffraction, and EGA by mass spec-trometry was employed to measure their organic ligand-to-palladium ratios and to quantifycontaminants [289]. The nanophase of Ga2O3 has potentially important applications in pho-tocatalysis. Srihari and coworkers reported the nanophase synthesis of both the metastableand stable Ga2O3 and demonstrated that it is possible to prepare a continuously varyingmixture. MS-EGA and FTIR studies showed the presence of physisorbed H2O moleculesand chemisorbed -(OH) ions bonded to active surface states and accounts predominantlyfor the observed weight loss [290]. The catalytic effect of NiO nanoparticles on the thermaldecomposition of double-base propellant composed of nitrocellulose (NC) and triethyleneglycol dinitrate (TEGDN) was investigated by MS-EGA. The catalytic mechanism was alsodiscussed [291]. Copper (II) oxide nanoparticles were incorporated into the pore system ofmesoporous carbon CMK-3 by a facile method, forming the composite Cu/CMK-3. Resultsshowed that Cu/CMK-3 preserved the ordered mesoporous structure of CMK-3 and copper(II) oxide was dispersed within the CMK-3 channels as small nanoparticles. A combinedTG-MS characterization allowed investigation of the catalytic activity and ignition behavior



of Cu/CMK-3. Results showed that CuO is the active component during the catalytic dryoxidization of phenol [292]. The initial nickel sulfide precipitated in normal Earth surfaceaqueous environments is nanoparticulate hydrated NiS. The water content was determinedby EGA-MS analysis and the chemical composition was determined by inductively cou-pled plasma–optical emission spectrometer (ICP-OES). TG-MS results suggested that thewater is an integral part of the shell layer configuration analogous to the intralayer H2O ofsome clays. The results also suggested that this phase determines the aqueous solubility ofnickel in low-temperature sulfidic systems and provides a novel route for the nucleation andgrowth of nickel sulfides in aqueous solutions [293]. The thermal decomposition behavior of(Bi2O3)0,75(Dy2O3)0,25 nanocrystalline solid electrolyte and its precursor were investigatedby Li et al. using X-ray diffractometry and TG-MS analysis [294]. A starch suspension wasproved to be a useful matrix for the hydrolytic route to metal oxide nanoparticles, due toits size-stabilization effect, working also at high temperatures. To understand the type ofinteraction between the organic part and the oxide particles, various parameters were testedthrough X-ray diffraction, transmission electron microscopy, solid-state nuclear magneticresonance, and TG-MS analyses of the obtained SnO2 nanopowders [295, 296].

Pure and Sn-doped In2O3 nanopowders were synthesized by a starch-aided sol-gelprocess. A detailed characterization by means of TEM and HRTEM, TG-MS, XRD, and119Sn solid-state NMR analysis was carried out. The behavior of the resistive gas sensorsbased on the synthesized nanopowders in the monitoring of carbon monoxide for auto-motive applications was evaluated, and the good sensing behavior of these samples wasassociated with their special features such as very small grains and high oxygen vacan-cies due to the peculiar reductive character of starch pyrolysis [297]. Eu3+-doped Lu2O3

phosphor nanopowders were also synthesized by a coprecipitation process with NH3·H2O,NH4HCO3, and the mixed solution as the precipitants, respectively. The effects of precip-itants on microstructures and properties of the obtained nanopowders were investigatedby a study of the decomposition behavior by means of DTA-TG-MS and FTIR spectra[298]. Thermal decomposition of amorphous precursors for sulfur-doped titania (S:TiO2)nanopowders, prepared by controlled sol-gel hydrolysis–condensation of titanium (IV)tetrabutoxide and thiourea in aqueous butanol, was studied in situ up to 850◦C in flowingair by simultaneous thermogravimetric and differential thermal analysis coupled on-linewith quadrupole mass spectrometry [299, 300]. Sodium potassium niobate powders wereproduced successfully using a Pechini sol-gel method modified with a novel niobiumprecursor. The decomposition of the gels produced by this method was observed withthermogravimetric analysis and evolved gas analysis by mass spectrometry. The effect ofdifferent heat treatments of the equimolar gel was studied and correlated to particle prop-erties and phase development. The resultant calcined powders were nanosized and singlephase with some residual organic material and water. The effect of varying the compositionbetween sodium niobate and potassium niobate was also studied and correlated to particlesize and phase development [301].

The rotor–stator phases of fullerenes with cubane, a new family of heteromolecularcrystals, was described: cubane (C8H8), the stator component of these materials, is a highlystrained molecule that decomposes to higher stability C8H8 hydrocarbons at 200◦C, and theresulting material is a random copolymer, percolating in the primitive cubic sublattices of theparent crystals. The polymerization was followed by HPLC, IR, and UV-VIS spectroscopy,and the thermal stability was determined by TG-MS analysis. The polymers were stableup to 400◦C, when they started to decompose while preserving their crystalline appearance[302]. The synthesis of oxidized water-soluble fullerenes, prepared by chemically inducedaerobic oxidation, yielded functionalized carbon cluster structures, which were oxidized



by the covalent insertion of different oxygen units. The presence of these groups, which areusually neglected and underestimated, was thoroughly investigated by several concurrentspectral and chemical methods, including EGA by MS spectrometry, which provided adefinitive set of consistent evidence, indicating for the first time the direct linkage ofcarboxylic groups on water-soluble fullerenes prepared in this manner [303]. Test resultsfor the applicability of TG-MS techniques to ascertain an average number of exohedralchemical attachments in a new class of fullerene dyads consisting of multiple hemi-orthoesters onto fullerenol was presented by Singh and Goswami [304].

Ethylene molecules are considered to oligomerize in the interlayer nano-space ofternary graphite intercalation compounds (GICs), CsC24(C2H4)x; however, the mechanismand the degree of oligomerization have not yet been clarified. In the present study, thereleased gases from CsC24(C2H4)1.4 at high temperatures were investigated. The detectionof alkanes (C3–C20) by TG-MS analysis in both the trap and direct modes supported theexistence of the oligomers in the nano-space. Other gases such as water vapor, methane,etc., were also detected [305]. The thermal reactions of a lithiated graphite anode in LiPF6-ethylene carbonate (EC)-dimethyl carbonate (DMC) in the temperature range 40–320◦Cwere investigated. EGA-MS during thermal reactions detected a small exothermic peakaround 140◦C due to CO2 evolution, which suggested partial destruction of the SEI formedon the graphite and/or decomposition of the electrolyte through the SEI. In addition, the mainexothermic reaction above 280◦C, which was associated with simultaneous evolution ofC2H4O, was caused by direct reaction of the lithiated graphite with solvent [306, 307]. Car-bon felt (CF)- and activated carbon (AC)-based electrodes for sodium polysulfide–bromineredox flow battery (PSB) were prepared and compared with a laboratory-scale PSB flow cellin terms of structure and application performances. Catalyst coating, discharge behavioranalysis, and thermogravimetric analysis coupled to mass spectrometry were carried out tomake out the different dominant factor in the application performances of the two materials[308]. Chiang and Hsu studied expandable graphite, grafted using a coupling agent to forma covalent bonding between organic and inorganic phases, increasing the compatibility be-tween the fillers and polymer, and thereby enhancing the thermal stability of the composites.TG-MS allowed demonstrating that functionalized expandable graphite can improve thethermal stability of composites and increase the flame retardancy [309]. Cyclopentadienylruthenium phosphane and carbene complexes were grafted on the surface of mesoporousSBA-15 molecular sieves through an aminosilane linker. Several techniques, includingTG-MS, confirmed the successful grafting of the complexes on the surface. The graftedmaterials were applied for catalytic aldehyde olefination and cyclopropanation [310].

The thermal evolution process of RuO2-IrO2-SnO2 mixed-oxide thin films of varyingnoble metal contents was investigated under in situ conditions by TG-MS, infrared emissionspectroscopy, and cyclic voltammetry. The detected chlorine evolution took place in a singlestep between 320 and 500◦C accompanied with the decomposition of the acetate ligand[311].

Iron-incorporated zeolites were successfully synthesized at a low temperature bychoosing appropriate starting materials. The ammonia and water desorption profiles werecompared for Fe-free and 22.7% Fe-zeolites ion-exchanged for NH4

+ by means of TG-MS and DSC. The ammonia desorption peak temperatures considerably shifted towardlower temperatures by the introduction of Fe, suggesting decreased solid acidity [312].The formation ratio of zeolite faujasite (FAU)/Linde type A (LTA) was shown to be con-trolled in the presence of an organic structure-directing agent (SDA), tetramethylammoniumcation (TMA+), by tuning synthesis parameters. The local environments and amounts ofTMA+ in FAU and LTA were determined by thermogravimetric analysis coupled to mass



spectroscopy [313]. Pb(OH)2 was previously proposed as an intermediate in the synthesisof PMN [Pb(Mg1/3Nb2/3)O3] and PMN-PT [0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3]. CoupledTG-MS of the precursor revealed that the intermediate was Pb6O5(NO3)2, not Pb(OH)2,because the evolved gas was nitric oxide and oxygen, not water [314]. EGA-MS, emana-tion thermal analysis (ETA), DTA, TG, and XRD were used to investigate the formationof perovskite-type lanthanum ruthenates on heating their hydroxide precursor in argonfrom 20 to 1200◦C. The mass loss corresponding to the release of water and CO2 fromthe precursor was determined by TG-EGA-MS. The obtained information on formationof phases and their transformation was shown to be useful for optimizing their synthesisprotocols for achieving the desired physical properties and to estimate the thermal stabilityof these materials to be used as catalysts [315]. The thermal behavior of montmorilloniteand organically modified montmorillonite, both treated with heavy metal cations [Cu(II),Cd(II) and Hg(II)], was characterized via thermal analyses combined with evolved speciesgas mass spectrometry and X-ray diffraction at in situ controlled temperature (HTXRD).The reactions involving Cu(II)- and Cd(II)-montmorillonite samples were demonstrated tobe mostly related to H2O and OH loss [316]. Adsorption of Na-nitrosonornicotine (NNN),one of the tobacco-specific nitrosamines (TSNA), in various zeolites with different poresize and acid-basicity was studied by in situ infrared technique. The bulky NNN can betrapped by zeolite KA through inserting the N-NO group into the narrow channel resultingfrom the strong adsorbate–adsorbent interaction. TG-MS coupled analysis was carried outto recognize the products of NNN degraded in zeolite. NNN cannot desorb from zeoliteonce trapped in the channel of adsorbent but only degraded to less carcinogenic fragments,which is profitable for removal of this carcinogen in the environment and protection ofpublic health [317]. To develop a new trapper of nitrosamines with high efficiency, cobaltoxide–incorporated zeolite NaY samples were prepared by different methods and character-ized. As revealed by EGA results, cobalt-modified zeolite NaY had high activity to catalyzethe degradation of NPYR at relatively low temperature [318]. Inorganic–organic layeredhybrid materials based on kaolinite were prepared from dehydrated potassium acetate inter-calated through the guest-displacement reaction with ethylene glycol and glycerol. Thesematerials were characterized and their behavior upon heating was investigated using X-ray diffraction, diffuse reflectance Fourier transform infrared spectroscopy, and combinedthermogravimetry and differential scanning calorimetry coupled with mass spectroscopy[319]. Kameda and coworkers prepared a chloride ion-intercalated hydrotalcite-like com-pound (Cl-HT) in a coprecipitation reaction and investigated its thermal properties usingsimultaneous TG-MS [320].

Amorphous piezoelectric polyimides were synthesized and characterized to analyzetheir utility for high-temperature applications by Gonzalo et al. The studied polyimidesdiffered in the position of the dipolar groups -CN in the aromatic ring and in the number ofthese groups in the repetitive unit. The imidization degree was studied by coupled TG-MSand the thermal properties by differential scanning calorimetry. The piezoelectric behaviorwas analyzed from remnant polarization measurements [321].

Lithium borohydride is a promising candidate for hydrogen storage and fuel cell appli-cation due to its high hydrogen content. The effect of various oxides on the dehydrogenationof LiBH4 was investigated. The EGA-MS results showed that the LiBH4/oxide mixtureswere able to dehydrogenate at much lower temperatures [322, 323]. In order to reducethe use of fossil energies, the development of new technologies, such as those concerningfuel cells, is required. Borohydride materials, like ammonia borane, seem to present aninteresting solution to the problem of hydrogen release, because a high percentage caneasily be released by moderate heating. Understanding and controlling the behavior of



ammonia borane would allow the development of a safe, lightweight, and compact hy-drogen storage system. Helary et al. reported on the thermal decompositions of ammoniaborane doped with various percentages of ammonium nitrate. The detection of releasedhydrogen was examined by evolved gas analysis on a thermogravimetric analyzer coupledto a mass spectrometer [324].

A series of organic silica–Nafion composite membranes was prepared by using organicsilane coupling agents (SCA) bearing different hydrophilic functional groups. The physic-ochemical properties of the composite membranes were characterized by electrochemicaltechniques, SEM, diffuse-reflection FTIR spectroscopy, wide-angle XRD, and TG-MS.The results clearly demonstrated that the diffusion of methanol and protons through themembrane can be controlled by adjusting the functional groups on the organic silica [325].The thermal decomposable species in the solid electrolyte interphase film on Cr2O3 powderanode at different lithiated and delithiated states in the first cycle were analyzed by massspectrometry evolved gas analysis [326].

Solvent-free high-temperature oxidations of rare earth metals with the heterocyclepyrazole as well as in low- to noncoordinating solvents were investigated to isolate inter-mediate stages between monomeric and polymeric pyrazolates of the lanthanides. Reactionconditions were tuned according to simultaneous DTA-TG and temperature-dependentXRPD experiments on known monomeric and polymeric pyrazolates, which gave rise tothe idea that further structure intermediates could be isolated. According to simultaneousDTA-TG-MS investigations, the condensation process can be identified with the release ofpyrazole molecules [327]. A coupled TG-MS system was used to monitor principal volatilefragments evolved during the pyrolysis of a carboxylic coordination polymer of samarium(III) [328].

Volatile species released during the initial stages of oxidation of a P92 ferritic steel,with and without an aluminized coating, at 650◦C in Ar+20%H2O for 150 h were studiedin order to obtain information about the oxyhydroxides formation as a reaction betweencoatings and steam. From those results, the role of the different coating elements couldbe established and optimized for the coating durability. An oxidation mechanism based onthe TG-MS results was given [329]. A gas-phase nitridation procedure was investigatedby Ajikumar and coworkers by using a home-assembled EGA-MS system to enhancethe high-temperature hardness and wear resistance of electroplated chromium on AISI316 LN austenitic stainless steel [330]. The steels with chromium contents between 9and 12 wt% were used for power plants with advanced steam oxidation conditions. Al-Hf protective coatings, deposited by CVD-FBR on ferritic steel HCM-12A followed bya diffusion heat treatment, have shown to be protective at 650◦C under steam for at least3,000 h of laboratory steam exposure under atmospheric pressure. TG-MS experiments wereconducted in a closed steam loop in order to obtain information about the oxyhydroxidesformation as reaction between coatings and steam. From those results the role of thedifferent coating elements was established and optimized for the coating durability. Anoxidation mechanism based on the TG-MS results was given [331]. The oxidation behaviorof P91 steel with and without Al-CVD-FBR coating was investigated by means of massspectrometry evolved gas analysis during TG measurements. TG-MS experiments wereconducted in a closed steam loop in order to obtain information about the oxyhydroxidesformation as reaction between coatings and steam. From those results the role of thecoating element could be established and optimized for the coating durability [332]. Thedetermination of the surface oxide layer composition is vital to facilitate the adjustment ofthe sintering conditions for sufficient removal of the surface oxides for providing strongmetal bonding between the metal particles during sintering. To systematically investigate the



composition, morphology, and thickness of the surface oxide, the influence of manganesecontent on the surface products composition in the case of water atomized steel powderwas evaluated. Analysis of the powder surfaces by X-ray photoelectron spectroscopy andhigh-resolution scanning electron microscopy in combination with X-ray microanalysisshowed that powder particles in all cases were covered by a heterogeneous oxide layer.The help of thermal analysis coupled with mass spectrometry allowed investigation ofthe sintering and degassing behavior of three different stages of a carbothermal reductionprocess. Their correlation with surface oxides composition was established during sinteringin argon [333].

Bai and coworkers reported the thermal performance of metallurgical coke and the gasevolution under methane studied by TG-MS to understand the interaction between methaneand metallurgical coke. No weight gain and methane decomposition reaction occurred inthe absence of metallurgical coke in the reactor, indicating that the metallurgical coke hadsome catalytic effects on the decomposition of methane. The weight loss at the initialstage was mainly caused by the evolution of CO2 and H2O, and the weight gain of cokeabove 800◦C was due to the carbon formation on the coke by the CH4 decomposition torelease H2. The experimental conditions and the quality of the coke had great effects onmethane decomposition [334].

In order to increase the understanding of the pyrolysis mechanism, FTIR and TG-MS were used to study the pyrolysis behavior of furfural–acetone resin used for newcarbon materials. The curing and carbonization mechanisms of furfural–acetone resin weremainly investigated; structural changes and volatile products evolved during pyrolysis wereanalyzed [335, 336].

An aqueous solution-gel route was developed for the preparation of the ferroelec-tric material strontium bismuth niobate (SrBi2Nb2O9). Starting from aqueous bismuthand strontium acetate solutions and an aqueous peroxo-citrato-Nb precursor solution, thismethod offerred a low-cost and environmentally friendly alternative to the conventional sol-gel techniques. The thermal decomposition mechanism of the precursor gel was studied:weight loss and evolved gases were characterized by hyphenated TGA-MS and TGA-FTIR[337].

New mixed-metal organic frameworks (MOFs) assembled from Y(III), Na(I), and chi-ral flexible-achiral rigid dicarboxylates were reported and characterized by Amghouz andcoworkers [338]. Fu et al. studied the structures and magnetic properties of synthetizedMn(II), Co(II), and Ni(II) metal–organic frameworks constructed from 1,3,5-benzenetricarboxylate and formate ligands [339], Li- and Co-based metal–organic frame-works were studied by Jiang et al. [340–342], and Mg- or Cu-based MOFs were charac-terized by Song et al. [343–345]. Thermogravimetry–differential thermal analysis coupledwith mass spectroscopy showed the release of NH3 in metal–aluminum amides [346].

For the quantitative analyses of evolved CO2 and H2O during the thermal decomposi-tion of solids, calibration curves, that is, the amounts of evolved gases vs. the correspondingpeak areas of mass chromatograms measured by TG-MS, were plotted as referenced bythe reaction stoichiometry of the thermal decomposition of sodium hydrogencarbonateNaHCO3. The accuracy and reliability of the quantitative analyses of the evolved carbondioxide and water based on the calibration curves were evaluated by applying the calibrationcurves to the mass chromatograms for the thermal decompositions of copper (II) and zinccarbonate hydroxides. It was indicated from the observed ratio of evolved gases that thecompositions of copper (II) and zinc carbonate hydroxides examined in this study corre-sponded to mineral malachite and hydrozincate, respectively. The reliability of the presentanalytical procedure was confirmed by the fairly good agreement of the mass fraction of



the evolved gases calculated from the analytical values with the total mass loss during thethermal decompositions measured by TG [347]. An instrument of controlled rate evolvedgas analysis (CREGA) coupled with TG-DTA was constructed for analyzing the influencesof product gases on the kinetics and mechanism of the thermal decomposition of solidsthat produce more than one gaseous products at the same stage of reaction. The thermaldecomposition of synthetic malachite was subjected to the measurements of CREGA-TGunder controlled concentrations of H2O and CO2 in the reaction atmosphere with taking intoaccount the self-generated water and carbon dioxide during the course of the reaction. Theusefulness of the CREGA-TG technique for measuring the kinetic rate data for the thermaldecomposition of solids was demonstrated in the study by emphasizing the importance ofquantitative control of self-generated reaction atmosphere [348].

Die-cast magnesium is increasingly used for automotive applications and consumerelectronics. For protective and decorative purposes it is coated. When the end-of-life goodsare processed, considerable amounts of coated magnesium scrap are created. Currently thisscrap is not recycled, leaving a scrap source unused. To close the magnesium utilizationcycle the influence of coatings on the remelting process will be determined. As a first step,thermal decoating of scrap prior to melting was investigated. Three different coated die-cast objects were decoated in air and argon using a thermogravimetric furnace with on-linemass spectrometry [349]. A batch of five formulations of novel brake friction materialswas tested for light rail transit (LRT) applications. The LRT braking system operatesat elevated temperatures and may reach an upper extreme of 900◦C. TGA-MS evidence(m/z 2 and 44) was detected in all samples at critical temperature zones correspondingto substantial weight loss, denoting the probable evolution of compounds consisting ofhydrogen, helium, carbon dioxide, nitrogen oxide, and propane that are related to thephysical–chemical reaction involved [350].

The drying conditions for primary standards of volumetric analysis have a significanteffect on the titration results due to changes in the purity, stability, and homogeneity. Ami-dosulfuric acid, a strong acid used as a reference material for volumetric analysis in Japan,was dried in a vacuum desiccator or heated at different temperatures and then measuredby Karl-Fischer titration, thermogravimetry–mass spectroscopy–ion chromatography andcoulometric titration. The optimum drying conditions were at 50◦C for 24 h with crushing[351].

The gas-phase catalytic hydrodechlorination (HDC) of mono- and di-chlorobenzenesover unsupported and silica-supported Mo carbide (Mo2C) was presented by de LucesConsuegra and coworkers as a viable means of detoxifying Cl-containing gas streamsfor the recovery/reuse of valuable chemical feedstock. The action of Mo2C/SiO2 wascompared with MoO3/SiO2 and Ni/SiO2 (an established HDC catalyst). The pre- and post-HDC catalyst samples were characterized by several techniques, including hyphenatedTG-MS [352]. The two polymorph forms of synthetic hopeite, zinc phosphate tetrahydrates(ZPT), were synthesized by hydrothermal crystallization from aqueous solution at 20 and90◦C, respectively. Aside from their subtitle crystallographic differences originating from aunique hydrogen bonding pattern, their thermodynamic interrelation was fully investigatedby means of XRD and EGA-MS [353].

The natural antibacterial agent allyl isothiocyanate (AITC) encapsulated in CD haspreviously been evaluated as a slow-release additive in polylactide-co-polycaprolactone(PLA-PCL) films designed for use in cheese packaging. Thermogravimetric analysis in tan-dem with mass spectrometry was used to explore the thermal properties of CD-encapsulatedALTC complexes as well as those of PLA-PCL films containing these complexes. The re-sults showed that CD complex of AITC would be preferred in situations where adequate



long-term controlled release of ALTC from polymer films is required as, for example, inthe case of active packaging applications [354].

Identification and monitoring of gaseous species released during thermal decomposi-tion of pure thiourea, (NH2)2C = S, in argon, helium, and air atmospheres were carried outby both on-line coupled TG-FTIR and simultaneous TG-DTA-MS apparatuses manufac-tured by TA Instruments (New Castle, DE). In both inert atmospheres and air between 182and 240◦C the main gaseous products of thiourea are ammonia and carbon disulfide, whereasin flowing air, sulfur dioxide, and carbonyl sulfide as gas-phase oxidation products of CS2

and hydrogen cyanide also occur, which were detected by both FTIR spectroscopic and massspectrometric EGA methods [355]. Thermally evolved gases from [Mg(H2O)6](NO3)2 re-leased in flowing air and nitrogen atmosphere were analyzed and monitored by simultaneousthermogravimetry and differential thermal analysis coupled on-line with mass spectrom-etry and with an FTIR spectroscopic gas cell up to 700◦C [356]. Two evaporite mineralsfrom the El Jaroso Ravine, Spain, were analyzed by thermogravimetry coupled with anevolved gas mass spectrometer and X-ray diffraction. Results proved that the evaporiteminerals were a mixture of sulfates including the minerals magnesiocopiapite, coquimbite,and possibly alunogen. Thermal decomposition of the unoxidized samples confirmed, bymass spectrometric results, adsorbed water, interstitial water, and chemically bonded water.By comparison of the patterns of halotrichite and jarosite it was shown that the El Jarososamples were mineral sulfates and not halotrichite or jarosite [357]. Starting from a novelwater-based Zr(IV)-peroxo-citrato solution, an entirely aqueous solution-gel synthesis ofPb(Zr0.53Ti0.47)O3 (PZT) was carried out. By combining complementary thermal analy-sis techniques such as HT-DRIFT, TGA-MS, and DTA information on the decompositionmechanism of the PZT gel was gained. Single-phase perovskite PZT, however, was obtainedat lower temperature (−610◦C) when a 16% lead excess was applied [358].

Mary et al. reported the chemical functionalization of porous silicon (PS) by trimethy-lammoniumpropyl bromide and alkylsulfonic acid groups for microsystem components.PS was prepared by electrochemical etching of a p-type silicon wafer. Samples of PS werefirst thermally oxidized at 300◦C and densified at 500 or 700◦C under an inert atmosphere.The samples were studied by FTIR and TPD-MS [359].

Other Applications

The pyrolysis of waste sludges was investigated using thermogravimetry–mass spectrom-etry and a fixed-bed reactor. Two types of sludge were used, namely, mixed sludge and oilsludge. In TGA-MS measurements, two degradation steps were observed. Degradation oforganic structures in sludge took place in the first step, and inorganic materials in sludgewere mainly decomposed in a second step above 500◦C [360]. To demonstrate the advancedincineration technology, which was adapted to process the selected solid waste, TG-FTIR-MS offers structural identification of compounds evolved during combustion processes[361]. Kinetic analysis of pyrolysis and gasification processes of sewage sludge from twodifferent wastewater treatment plants was reported. Experiments were performed in TG-MS system under nonisothermal conditions. Based on DTG curves, the comparison of thesludge samples was made. Kinetic parameters of main reaction groups were determinedusing the Kissinger method [362]. The pyrolysis of an urban plant sewage sludge carriedout under He atmosphere was studied by TG-MS and TG-GC-MS analyses. The sludgewas thermally degraded and water, carbon mono- and di-oxide, and several hydrocarbons(up to C5, both saturated and unsaturated) were the major detected species. Minor amountsof pollutant species, such as cyano-compounds, were also detected [363]. Combustion and



pyrolysis of anaerobic digested sewage sludge and undigested sewage sludge was investi-gated under air and nitrogen atmospheres and the results showed that the combustion andpyrolysis processes could be divided into three stages: volatilization of water, decompo-sition of organic substances, and decomposition of inorganic substances. At temperaturesfrom 300 to 350◦C, the decomposition of organic substances of the undigested sludgewas more significant than that of the anaerobic digested sludge during both combustionand pyrolysis processes. The results showed that H2, CH4, C2H6, C4H10, and C7H8 weredetected and the amount of the organic gases emitted from the anaerobic digested sludgewas smaller than that from undigested sludge [364]. TG-FTIR-MS was shown to offerstructural identification of compounds evolved during thermal processes when burninghousehold waste. The results helped to evaluate the chemical pathway for the degradationreactions by determining the decomposition products. The measured results also providedsome insight into burning household waste as an energy source in large-scale incinerators[365, 366]. Treatments alternative to landfilling take into account reconstruction and reuseof the tires or the matter and/or energy recovery by means of thermal treatment processes(incineration, gasification, and pyrolysis). Experimental tests were reported for the study oftire waste pyrolysis, conducted by means of thermogravimetric analysis of the material andthe simultaneous determination, through FTIR and MS, of the decomposition products. Theanalysis of the volatile fraction allowed isolating, within the thermograms, the evolution ofproducts referable to specific tire components and therefore it suggested the application ofa multicomponent decomposition model [367]. The high-temperature thermal destructionof poultry derived wastes (e.g., manure and bedding) for energy recovery is viable in Aus-tralia when considering resource availability and equivalent commercial-scale experiencein the UK. Florin et al. identified and examined the opportunities and risks associated withcommon thermal destruction techniques, including volume of waste, costs, technologicalrisks, and environmental impacts. Typical poultry waste streams were characterized basedon compositional analysis, thermodynamic equilibrium modeling, and TG-MS. Based onliterature data, cost estimates for generic poultry waste-fired power plants were presentedwith throughputs of 2 and 8 tonnes/h [368]. The decreasing costs and increasing availabilityof electronic products of all kinds, including mobile phones, audio and video equipment,and personal computers and their accessories, coupled with advances in technology thatrapidly make these products obsolete, foretell a growing disposal problem. The materialsstudied by Molto and his group were a mobile phone (printed circuit board + casing)and printed circuit boards alone. Pyrolysis and combustion runs at 500◦C in a horizontallaboratory furnace were performed, and the analyses of the gas and semivolatile fractions(including dioxins and furans and dioxin-like PCBs) were critically discussed in order toestablish the level of pollutant in the samples themselves. TG-MS experiments allowedbetter determination of the thermal decomposition of electronic wastes and identificationof some compounds emitted during the controlled heating of these materials [369]. A newaluminum polynuclear crystalline species, obtained from aluminum waste cans treated withHCl solution in strong acid media, was synthesized and characterized followed by an agingperiod. Thermal characterization of the compound was performed by evolved gas analy-sis coupled to simultaneous TGA-DSC [370]. The pyrolysis thermal treatment of severalwastes such as polymers, sewage sludge, tires, and waste wood as spruce sawdust andthe successive stabilization of the pyrolysis residue was investigated from analytical andenergetic points of view. A schematic energetic analysis was proposed implementing the py-rolysis stage with a vitrification process in order to obtain, in particular for sewage sludgeresidue, an environmentally friendly product for use as raw material in industry [371].The pyridine vapor adsorption behavior and its influence on suppressing low-temperature



cross-linking reactions during slow pyrolysis of lignite was reported [372]. A large datapool of mechanically and biologically treated municipal solid waste originating from dif-ferent Austrian treatment plants was investigated using simultaneous thermal analysis thatcomprised mass spectrometry evolved gas analysis [373]. Wastewater sewage sludge wascopyrolyzed with a well-characterized clay sample in order to evaluate possible advantagesin the thermal disposal process of solid waste. Characterization of the copyrolysis processwas carried out both by TG-MS analysis and by reactor tests, using a lab-scale batch reac-tor equipped with a gas chromatograph for analysis of the evolved gas phase. Due to thepresence of clay, two main effects were observed: the clay surface catalyzed the pyrolysisreaction of the sludge and the release of water from the clay enhanced gasification of part ofcarbon residue of the organic component of sludge following pyrolysis [374]. The EGA-MSstudy of some ferrocene derivatives with liquid crystal properties was aimed at evaluatingthe relationship between structure–thermostability–degradation mechanisms, leading to in-formation about their applications, processing parameters, and industrial waste recyclingprocedures [375].

The properties and quality of silicate glasses strongly depend on the amount of residualdissolved gases. Thus, the knowledge of the quantitative content of different volatile com-ponents is of great relevance within the technical production line. Until now no availabletechnique has provided simultaneous and quantitative information on different gases in asingle run. Schaps and coworkers developed a new technique to detect the most commonvolatiles (H2O, CO2, SO2, O2, and N2) simultaneously and quantitatively in silicate glasseswith the help of a modified TG-MS system. One characteristic feature of this new methodwas the direct coupling of a thermobalance and a mass spectrometer without the use ofany capillary or skimmer system [376]. By thermogravimetric analysis coupled with massspectrometry, Latournerie et al. followed the thermal behavior of silicon oxycarbide glasses(Si/C/O) of various compositions from 1000 to 1500◦C. Based on these results and chemi-cal analysis data, they established the main reactions that occur during the decompositionof the oxycarbide glasses [377].

To understand the rates of turnover of soil carbon, and hence interactions between soilcarbon pools and atmospheric CO2 levels, it is essential to be able to quantify and char-acterize soil organic matter and mineral hosts for C. Thermal analysis is uniquely suitedto this task, because different C compounds decompose during a heating cycle at differenttemperatures. In air (80% He or N2, 20% O2), relatively labile cellulosic material decom-poses between 300 and 350◦C and more refractory lignin and related materials decomposebetween 400 and 650◦C. Calcite and other common soil carbonate minerals decompose at750–900◦C. Using thermal analysis connected to a quadrupole mass spectrometer and toan isotope ratio mass spectrometer, it is possible to simultaneously determine mass lossduring combustion, evolved gas molecular compositions, and carbon isotope ratios forevolved CO2 [378]. Evaporation of primary tar during fossil fuel pyrolysis is one of theprocesses that can influence yield and composition of pyrolysis products. Oja illustratedthe volatility of oil shale primary pyrolysis tars, with the focus on the less volatile heavyend of the tar. Several different experimental methods were employed to study tar vapor-ization and the relationships between tar volatility and tar characteristics such as molecularweight distribution and molecular heterogeneity. Elemental and infrared analysis, TG-MS,and field ionization mass spectrometry (FIMS) were used for tar characterization in thisinvestigation [379]. The analysis of biomass tar by 1H NMR, FTIR, TOF-MS, GC-MS,and TG-MS indicated that it is different from tar or pitch from fossil fuels because of theremarkable oxygen content in biomass tar, originating from the botanical precursor, and itconsists basically of phenols with one to three aromatic rings [380].



A thermogravimetric analysis system was interfaced to a mass spectrometry detec-tor to investigate the thermal evolution of decomposition products from microorganisms.Traditionally, TGA-MS has been used to investigate the thermal parameters and chemicalcomposition of materials such as the coal and lignin energy producing compounds and awide range of technical organic polymers. The relative weight loss of biochemical speciesand compounds in bacteria from the TGA system allowed a comparison to the relativeamounts of the same substances in bacteria from conventional microbiological extractionand isolation techniques. MS is shown to produce information-rich total ion chromatogramprofiles of thermal products from biochemical standards and microorganisms. The TGAcurve provides a degree of resolution, because the bacterial biochemical substances andcomponents partition in a temporal fashion. Standard biochemical substances such as dipi-colinic acid, polyhydroxybutyric acid, and peptidoglycan are produced in the same generaltemperature region in the TG profile, and the compounds have similar mass spectra com-pared to those from microorganisms. Characterization of microorganisms was possibleby the relation of their thermal events and extracted mass spectra to those of low- andhigh-mass model biochemical compounds [381].

Cyclodextrins and their inclusion complexes were investigated with a TG-MS com-bined thermoanalytical technique in order to get information about their fragmentationbehavior. By comparison of the TG-DTA curves, a different thermal behavior was foundfor each of the native and chemically modified cyclodextrins [382].

Arenillas and coworkers, using simultaneous TG-MS analysis, studied the release ofvarious nitrogen compounds during pyrolysis of different-rank coals. In addition, a seriesof coal chars with different burn-off degrees was obtained in a bench-scale fluidized bedreactor, using the same parent coal. The evolution of gaseous compounds arising fromthe thermal treatment of the partially burned chars was studied in the TG-MS system. Itwas found that the different chemical structures of the chars exerted some influence onthe evolution of the gaseous compounds during the devolatilization process [383]. Theevolution characteristic of sulfur-containing gases released from the pyrolysis of Yanzhoucoal macerals was on-line analyzed using MS. The forms of sulfur in vitrinite and inerti-nite were systematically investigated based on the evolution behaviors of sulfur-containinggases [384]. Plastic wastes of different structures and origins (agriculture, municipal, elec-tronic, automobile) were proposed as minor components of coal blends for metallurgicalcoke manufacture in order to contribute to the protection of the environment and naturalresources. Because an adequate development of coal fluidity in high-temperature carboniza-tion is a prerequisite for producing a graphitizable carbon material of high quality, Viveroand coworkers investigated the role of high density polyethylene (HDPE), polypropylene(PP), PET and a mixture containing these three thermoplastics in the formation of semi-cokes, an intermediate carbon material in the transformation of coal to coke. These plasticwastes blended with a bituminous coal in amounts of 1, 2, and 5 wt% caused a decrease incoal fluidity as measured by the Gieseler plastometer, and the extent of the reduction wasdependent on the amount, the structure, and the thermal behavior of the plastic waste added.Model hydrocarbons were used to explain the differences in the fluidity of the blends withHDPE and PP. Evidence of the incorporation of HDPE into the carbon matrix of semicokescomes from diffuse reflectance infrared spectroscopy and scanning electron microscopyas well as from the study of the evolution of volatile products in the post-plastic stage ofcoal by thermogravimetry coupled to mass spectrometry [385]. Model compounds, witha controlled heteroatoms content and well-defined functionalities, were used to study therelease of nitrogen compounds from char combustion. In the present work, the mechanismsinvolved in NO-char heterogeneous reduction were studied with a synthetic coal (SC) char



as carbon source. Another synthetic char (SN) without any nitrogen in its composition wasalso employed in these studies. TPR tests with a gas mixture of 400 ppm NO in argon andwith isotopically labeled nitric oxide, 15NO (500 ppm 15NO in argon), were carried out.The gases produced were quantitatively determined by means of MS and FTIR analyzers.Under the conditions of this work the main products of the NO-C reaction were found tobe N2 and CO2. The main path of the reaction involved the formation of surface nitrogencompounds that afterwards reacted with nitrogen from the reactive gas to form N2. It wasobserved that fuel-N also participated in the overall heterogeneous reduction reaction, al-though to a lesser extent [386]. Combustion tests were performed by TG-MS to improvethe biodesulfurization of a semi-anthracite by packed-column leaching by reducing theinsoluble sulfate on the coal surface and to determine whether after the combustion oftreated and untreated coal, sulphate sulfur was transformed completely into sulfur diox-ide or part remained in the ashes without reacting [387]. To combust coal together witha small percentage (<10%) of sewage sludge may be an option for the management ofthese wastes. Combustion of two different sewage sludges, one semianthracite coal, andseveral sludge-coal blends (containing different dried mass percentage of each of the twosewage sludges) was studied by simultaneous TG-MS dynamic runs carried out at 5◦Cmin−1 in the temperature range 100–800◦C. No interactions were observed between coaland sludge during the blends combustion [388]. The pyrolysis characteristics of maceralsseparated from Chinese Shenmu coal were systematically investigated using a pressurizedthermobalance coupled with a mass spectrometer under 0.1 MPa of Ar and H2, heating rateof 10◦C/min, and final temperature of 900◦C. The results showed that vitrinite always hada higher volatile matter yield, larger maximum rate of weight loss, and lower temperatureof the maximum rate of weight loss than inertinite. Inertinite showed a high response to theexternal hydrogen, especially at a higher temperature. The gases evolved during thermo-gravimetric analysis of macerals were analyzed on-line by mass spectrometry. The contentof all gases evolved from vitrinite was higher than those from inertinite in both atmospheres.The evolution curves also revealed the different structural characteristics among vitrinite,inertinite, and the parent coal [389]. TG-MS analysis was applied to simulating the cokingprocess with five coal samples. Three types of methane emission existing in coal pyroly-sis were, respectively, the emission of methane adsorbed in coal and generation from therupture of aliphatic linkages and condensation of aromatic hydrocarbon [390]. The opensystem pyrolysis characteristics of seven low-rank coals and the evolution kinetics of H2

and its relation to the first coalification jump were determined using a thermogravimetricanalyzer coupled to a quadrupole mass spectrometer. Results showed that both the coalpyrolysis characteristics and the evolution kinetics of H2 were strongly related to the firstcoalification jump [322]. Open system pyrolysis modeling of immature Huolinhe lignitewas carried out and an on-line curve for the methane generation rate was obtained using athermogravimetric analyzer coupled to a quadrupole mass spectrometer [323]. Simultane-ous TG-MS was used to investigate the pyrolysis behavior of coal tar and the instantaneousevolution characteristics of gaseous products, and the pyroletic reaction mechanism of coaltar was inferred by the double extrapolated method [391].

LDH-supported nanoplatinum (0) and nanopalladium (0) catalysts were prepared by asimple ion exchange technique and subsequent reduction with hydrazine hydrate and usedfor the allylation of aldehydes to give moderate to good yields of homoallylic alcohols.Detailed mechanistic studies of LDH-Pd(0)-catalyzed allylation using XPS and TGA-MSrevealed that a monoallyl-palladium complex was the key intermediate for the catalyticcycle [392]. It was found that air exposure suppressed the subsequent reduction behaviorbefore a Fe-Mn-Cu-K/SiO2. Fischer-Tropsch synthesis (FTS) catalyst was loaded in the



reactor. Thermogravimetry and mass spectrometry analysis, in situ DRIFT analysis, CO2

TPD, in situ syngas reduction, and Mossbauer spectroscopy were used to reveal the intrinsicrelationship between air exposure and reduction behavior of catalysts [393]. Microstruc-tural characteristics of the copper phase in Cu/ZnO catalysts for methanol steam reforming(MSR) were investigated as a function of aging of the precipitated hydroxycarbonates duringcatalyst preparation. The bulk structure of active catalysts under MSR reaction conditionswas determined by in situ XRD and in situ X-ray absorption spectroscopy (XAS) combinedwith on-line mass spectrometry [394]. Vaccaro studied the performances of a catalyst forsoot combustion under reducing and oxidizing environments to draw indications on the cat-alytic mechanism and the implications of the sulfation process [395]. The H2 reactivity ofcarbon-related phases in a slurry-bubble column using FT catalysts was studied by Gruverand coworkers using TGA-MS techniques. Though hydrogen treatment is quite effective atremoving paraffinic wax components at relatively low temperature, about 250◦C, a fractionof the carbon was resistant to hydrogen even at 350◦C. This fraction of the carbon in used FTcatalysts increases as on-stream time increases. Regenerating the catalyst with a procedurethat includes an oxidation step removes much of this residual carbon [396]. Titania-basedphotocatalytic materials were prepared by a sol-gel method using Fe3+ and polyethyleneg-lycol (PEG600) as additives. Thermogravimetry, differential thermal analysis, and evolvedgas analysis with MS detection were used to elucidate processes that take place during heat-ing of Fe3+-containing titania gels [397]. Ru-containing hydroxyapatite (HAp) catalystswere developed for the oxidation of alcohols with molecular oxygen in an organic solvent.Various methods were used for characterization of these catalysts, including XPS, DRIFTspectroscopy, ICP-OES, XRD, thermogravimetry combined with mass spectroscopy (pulsethermal analysis), and nitrogen adsorption [398]. The NOx storage behavior of a seriesof Pt-Ba/Al2O3 catalysts, prepared by wet impregnation of Pt/Al2O3 with Ba(Ac)2, wasinvestigated. The catalysts with Ba loadings in the range 4.5–28 wt% were calcined at500◦C in air and subsequently exposed to NO pulses in 5 vol% O2/He atmosphere. Cata-lysts were characterized by means of thermogravimetry combined with mass spectroscopyand XRD before and after exposure to NO pulses. Characterization of the calcined cat-alysts corroborated the existence of three Ba-containing phases, which were discerniblebased on their different thermal stabilities: BaO, LT-BaCO3, and HT-BaCO3. Characteri-zation after NOx exposure showed that the different Ba-containing phases present in thecatalysts possessed different reactivities for barium nitrate formation, depending on theirinterfacial contact. The different Ba(NO3)2 species produced upon NOx exposure couldbe distinguished based on their thermal stability. The study revealed that during the NOx

storage process a new thermally instable BaCO3 phase formed by reaction of evolved CO2

with active BaO [399]. A series of Pt-Ba/Al2O3 catalysts with Ba loadings in the range of4.5–33 wt% was prepared using a two-nozzle flame-spray pyrolysis method. The structuralproperties and activities of these catalysts in NOx storage-reduction (NSR) were comparedto corresponding standard Pt-Ba/Al2O3 catalysts prepared conventionally via wet impreg-nation. The catalysts were characterized by XRD, TEM, ESI, DRIFT, TG-MS, TPRD, andgas adsorption [400]. Nylon et al. showed the most relevant results obtained during a jointacademic and industrial effort to develop new effective catalysts for upgrading light cycleoil (LCO) into a high-quality diesel-blending component. Bench-scale atmospheric pres-sure screening with indan over 12 different Pt-Ir-based ring-opening catalysts prepared bythe incipient wetness technique showed that the relative amount of iridium and the choiceof support material were factors that mainly influenced the activity but also the initial andfinal product distribution. Moreover, temperature programmed oxidation (TPO)-TG-MSanalyses of the spent catalysts revealed that for ceria-based catalysts there is a correlation



between the amount of iridium, the amount of coke deposits, and the resulting catalyticactivity: increasing the iridium load results in less carbonaceous deposits and hence highercatalytic activity due to the intrinsic hydrogenolysis–hydrogenation properties of iridiumthat effectively destroy coke precursors [401]. Mesoporous sulfated zirconia catalysts wereprepared and tested for the acylation of anisole with benzoic anhydride. All samples werecharacterized by N2 physisorption, ion chromatography, and thermal analysis coupled withMS analysis of evolved gases. TG-DSC-EGA analysis allowed observation of all phenom-ena related to the calcination process and better understanding of the catalyst behavior[402]. Radivojevia and coworkers explored methods to prepare platinum on silica catalystusing temperatures as low as possible. Therefore, thermal stability in both oxidizing andreducing atmosphere of eight different precursors was studied with thermogravimetric anal-yses. Based on these data, the precursors were tested to prepare silica-supported catalysts,resulting in a relationship between the thermal stability of the precursors and the proceduresof impregnation, reduction, and calcination with the final dispersion on silica [403]. Thedurability of PEM fuel cell materials, essential to application longevity, was explored byBaturina and coworkers to detect the limits of thermal stability of platinum/Vulcan XC72 catalysts and a 46 wt% Pt/Vulcan XC 72/Nafion catalyst layer by thermogravimetricanalysis in air. The products of decomposition were analyzed with TGA coupled withmass spectrometry. Low-temperature (100–200◦C) carbon combustion in the presence ofplatinum was confirmed, and the high precision and sensitivity of TGA allowed the differ-entiation of two oxidative-mass loss regimes for 46% Pt/C. As a result of the above studies itwas found that TGA-MS analysis is convenient for the determination of Pt wt% in catalyst-coated membranes [404]. Direct oxidation of benzene to phenol over Fe-ZSM-5 catalystwas chosen as a model reaction to characterize the influence of microwave irradiationon adsorption/desorption processes during heterogeneously catalyzed reactions. The directoxidation of benzene was investigated under different reaction conditions (temperature, res-idence time, reactant concentrations) and microwave power in a specially designed reactor.The results obtained by additional microwave radiation were compared to those obtained byconventional heating under similar reaction conditions. In addition, ex situ TG-MS analyseswere conducted to study the sorption behavior. Extensive investigations were carried out todetermine adsorption–desorption effects (benzene, phenol, and a mixture of both) and thecoking behavior under microwave conditions [405]. A K/Al2O3 catalyst was prepared usingthe wet impregnation method with K2CO3 as a precursor salt. During the activation process,a clear interaction between potassium carbonate-derived species and the support took place,resulting in the formation of K aluminate-like species, as observed by evolved gas analysisby mass spectrometry and infrared spectroscopy [406]. A Pt/Al2O3 catalyst prepared byincipient wetness impregnation was used as a diesel oxidation model catalyst and tested inthe simultaneous total oxidation of CO and C3H6. Sulfur incorporation by wet impregnationresulted in deactivation of the Pt/Al2O3 catalyst in both oxidation reactions. Characteri-zation of the catalysts by evolved gas analysis by mass spectrometry and several otherspectroscopic techniques demonstrated that the formation of aluminum sulfate modifiedthe acidic properties of the support and the electronic properties of the platinum particles[407]. Granados et al. studied activated CaO as a catalyst in the production of biodiesel bytransesterification of triglycerides with methanol. Three basic aspects were investigated: therole of H2O and CO2 in the deterioration of the catalytic performance by contact with roomair, the stability of the catalyst by reutilization in successive runs, and the heterogeneouscharacter of the catalytic reaction. Characterization by X-ray diffraction and evolved gasanalysis by mass spectrometry during heating the sample under programmed temperature,X-ray photoelectron, and FTIR spectroscopies allowed concluding that CaO was rapidly



hydrated and carbonated by contact with room air [408]. A series of acid-activated claycatalysts was prepared from a purified bentonite, rich in structural iron. The ability ofthe activated samples to convert limonene to p-cymene was evaluated using a reactiontime of 15 min at 80◦C. TG-MS analysis of acid activated samples, saturated with cyclo-hexylamine, reflected the dehydrogenation capabilities of the catalysts [409]. Rutheniumcatalysts modified by selenium are of interest as a methanol-insensitive oxygen reductioncatalyst in a polymer electrolyte membrane fuel cell for mobile application. To elucidate thestructural and chemical features of unsupported and carbon-supported ruthenium nanopar-ticles prepared by thermolysis of Ru3(CO)12 in an organic solvent with and without thepresence of dissolved selenium, different bulk and surface sensitive methods, includingthermogravimetry coupled with mass spectrometry, were performed. After heat treatmentat 900◦C under vacuum, organic residues and ruthenium oxides could be removed [410].The proton conductors Sr3CaZr0.5Ta1.5O8.75, BaCe0.9Y0.1O2.95, and Ba3Ca1.18Nb1.82O8.73

were shown to be active heterogeneous catalysts for the reverse water gas shift (RWGS)reaction. Catalytic characterization was conducted in a quartz fixed-bed reactor with a silicafritted disk and monitored by a gas chromatograph. X-ray diffraction and TGA coupled toMS were used to characterize samples before and after catalytic tests [411]. The catalyticactivities of strontium-substituted perovskite catalysts for NO reduction were studied, fur-ther improved by incorporation of Pt outside and inside the perovskite lattice structure.Catalyst evaluations were carried out using thermogravimetric analysis coupled with massspectra [412]. The effect of sulfate doping of titania in promoting activity and selectivityof MoOx/TiO2 catalysts for the cyclohexane photooxidative dehydrogenation was investi-gated in a gas–solid fluidized bed reactor. The catalysts were characterized by spectroscopy,thermogravimetric analysis coupled with mass spectroscopy, and mass titration [413]. Stud-ies were conducted by Peng and coworkers to demonstrate the preparation of an anatasetitanium dioxide (TiO2) nanosheet with active sites along (101) planes of anatase, by aChimie-Douce method. Commercial TiO2 powder was refluxed in air atmosphere at 423 Kfor 24–72 h, suspended in 15 M NaOH(aq), to conduct the study. The isolated solid wasrinsed with deionized water and dried at 343 K to give product A. Energy-dispersive X-rayspectroscopy and thermogravimetric analysis, along with mass spectroscopy, were also usedto study the chemical composition of the as-prepared samples [414, 415]. Decompositionof an amorphous precursor for S-doped titania (TiO2) nanopowders, prepared by controlledsol-gel hydrolysis–condensation of titanium (IV) tetraisopropoxide and thiourea in aqueousisopropanol, was studied up to 800◦C in flowing air by simultaneous thermogravimetricand differential thermal analysis coupled on-line with quadrupole mass spectrometry andFTIR spectrometric gas cell for analysis of gases and their evolution dynamics (by evolvedgas analysis) in order to explore and model thermal annealing processes of fabrication tech-niques leading to S:TiO2 photocatalysts with photocatalytic activities under visible light[416]. Kang et al. focused on improvement of the photocatalytic activity of an N-doped TiO2

(reference sample) by its grinding in solvent [417]. Structural modifications of Cu/ZnO cat-alysts for MSR as a function of precipitate aging in catalysts preparation processes wasinvestigated comparatively by Muhamad and coworkers. A pronounced effect of aging wasfound for aged HC precipitates, whereas no significant effect of aging was observed foraged HN solids. The bulk structure of the Cu/ZnO catalysts was investigated by meansof TG-MS, in situ XRD, and 63Cu NMR [418]. In situ amino acid surface-modified TiO2

nanoparticle syntheses were performed by a simple one-pot hydrolysis of heteroleptic tita-nium alkoxide in water with NnBu4Br. This process allowed precise control of the surfacegrafting rate by varying the amount of precursors and provided highly functionalized nano-materials. Their compositions and microstructures were determined by several techniques,



including TGA-MS [419]. By a TG-MS study, Sietsma and coworkers proved how nitricoxide affects the decomposition of supported nickel nitrate to arrive at highly dispersedcatalysts [420]. A CuZnAl slurry catalyst was prepared directly from a solution of metalsalts by an entirely liquid-phase method. Results by TG-MS analysis showed that the intro-duction of CO2 into the heat-treatment atmosphere made it easier to reduce the catalyst. Thecatalysts performed best when the heat-treatment atmosphere contained 50% CO2 [421].A series of mixed-linker metal–organic frameworks (MIXMOFs) of the general formulaZn4O(BDC)x(ABDC)3-x was synthesized and tested as catalyst in the reaction of propyleneoxide (PO) and carbon dioxide. X-ray diffraction and TG-MS analysis revealed that thepure MIXMOF materials could be obtained up to an ABDC loading of 40%. The potentialapplication for catalytic purposes in the temperature range at least up to 300◦C was provenby using the synthesis of propylene carbonate (PC) from propylene oxide and carbon diox-ide as a test reaction [422]. Pyrolysis of iron phthalocyanine–phenolic resin (FePc-PhRs)and phthtalocyanine–phenolic resin (Pc-PhRs) was studied to clarify the effect of Fe duringthe preparation of carbon alloy cathode catalysts. FePc-PhRs pyrolyzed at 600◦C showedthe best electrocatalytic activity for oxygen reduction. The results of TG-DTA-MS and IRsuggested that Fe increases the nitrogen content of the catalysts by enhancing the interac-tion of phthalocyanine moiety and phenolic resin [423]. Rubio-Caballero et al. investigatedthe use of calcined calcium zincate as solid base catalyst for the methanolysis of sun-flower oil to FAME (biodiesel). The precursor and catalyst were characterized by XRD,XPS, SEM, EGA-MS, FTIR, and N2 adsorption [424]. Commercial hopcalite calcined atdifferent temperatures and hopcalite modified with noble metals (Pt, Pd, and Au) were stud-ied in oxidation of thiophene. Surface and bulk properties of catalysts were studied usingtemperature-programmed reduction, X-ray diffraction, and TG-DTA-MS. It was shown thatcalcined samples displayed higher activity in comparison with commercial untreated hop-calite; however, a lower temperature of calcination was favorable [425]. Well-characterizedAu nanoparticles were deposited on commercial TiO2 (P25, Degussa, Hanau–Wolfgang,Germany) and analyzed by means of scanning transmission electron microscopy (STEM)and thermogravimetry coupled with mass spectrometry [426]. A study on catalysts madeup by single-step flame-spray pyrolysis of Pd on different supports (Al2O3, SiO2, ZrO2,TiO2, MgAl2O4 and CeO2) was reported by the same group [427].

Diesel soot samples collected on an SiC filter while using an oxidation catalyst ornot were solvent extracted or heat treated under an inert atmosphere. All studied sootswere characterized by XPS, DRIFTS, TGA-MS, Py-GC-MS, and gas sorption. In the firstpart, the obtained results were discussed in order to show the influence of an oxidationcatalyst on some properties of the raw soot materials, such as their soluble organic fraction(SOF) content and composition, surface chemistry, and textural characteristics. Then, it wasshown that the thermal decomposition of SOF adsorbed on the particulate matter led to theformation of a microporous carbonaceous layer under an inert atmosphere at 600◦C [428].The possibilities for thermogravimetric analysis for its use in the quantitative compositionalanalysis of atmospheric gases were discussed by Basalik. The features of TGA-MS includehigh sensitivity, high resolution, and high mechanical specificity. In TGA-MS extremelylow concentrations of evolved gases could be identified and the overlapping weight lossescould be interpreted qualitatively [429].

Refuse-derived fuels (RDF) characterization and pyrolysis behavior, carried out bymeans of thermogravimetric analysis, infrared and mass spectroscopy, were presented.Thermal degradation of RDF takes place through three main mass loss stages; the analysesof evolved gas allow us to discriminate the contributions of the different fractions (paper,LDPE, wood, rubber, etc.) to the global decomposition. Furthermore, TG was used for the



determination of kinetic parameters, using the differential method. In order to set up theconditions of production of a good quality pyrolysis gas, the operating conditions of RDFin a pyrolysis reactor were simulated [430].

Volatile organic compound (VOC) emissions from tobacco (Nicotiana tabacum L.var. Bel W3) plants exposed to ozone (O3) were investigated using proton-transferreaction–mass spectrometry (PTR-MS) and GC-MS to find a quantitative reference forplants responses to O3 stress [431]. Pyrolysis of tobacco, a complex biomass matrix, wasinvestigated to further understand thermal decomposition processes that are accompaniedby evaporation of relatively stable nonpolymeric endogenous compounds. Pyrolysis of twotypes of tobacco, bright and burley, were studied using TG-MS and field ionization massspectrometry analyses. Tobacco contains biopolymers and many nonpolymeric compounds.Unlike many biomass pyrolysis tars derived from wood or cellulose, tobacco pyrolysis tarscan contain significant amounts of high-molecular-weight endogenous constituents such aswaxes and terpenes that are transferred intact. The experiments indicated that the evapora-tion of relatively stable high-molecular-weight species occurred below about 220◦C, gener-ating 300 Da and higher molecular weight products; decomposition of tobacco biopolymerssuch as starch, cellulose, hemicellulose, lignin, and pectin occurred mostly at temperatureshigher than 220◦C, producing species mostly with molecular weight below 300 Da [432].

The devolatilization behavior of pine and beech wood from carpentry residualsand an herbaceous product from an energy crop (artichoke thistle) was investigated bythermogravimetry–mass spectrometry. The effects of three pretreatments, hot-water wash-ing, ethanol extraction, and their combination, were also studied. The results showed that thethermal behavior of wood and thistle were still considerably different after the eliminationof some of the inorganic components; however, the macromolecular components decom-posed at similar temperatures. Because we had a large number of samples and TG-MS data,we employed principal component analysis (PCA) to aid in the evaluation of the resultsand comparison of the samples [433]. A commercial Nordic Spruce wood impregnated bymono-ammonium phosphate (fire retardant) was analyzed by cone calorimetry, representingrealistic fire conditions, and thermogravimetry combined with evolved gas analysis, whichcan be used to determine flammability and degradation properties of materials. The desirewas to correlate the flammability properties measured in the cone calorimeter with thosemeasured or deduced from TGA combined with EGA. The aim of such an achievement wasto allow the design of fire-safe materials by quickly assessing the fire safety of materialsin their earliest milligram formulation and the dependence of their flammability propertieson the molecular structure of the material [434].

The atmospheric pressure (AP)-TPR technique, an approach for organic sulfur spe-ciation, was extended by mass spectral detection. The coupling gave ground for preciseassignment of sulfur compounds in flue gases of lignite lithotypes pyrolyzed in an H2 at-mosphere. A broad range of sulfur compounds was determined; that is, thiols, dimethylsul-fide, dimethyldisulfide, CS2, thiophenes, benzothiophenes, and their alkylated homologues.Certain peculiarities in organic sulfur distribution in lithotypes under study were noticed.Humovitrain was the lithotype with the highest organic sulfur content. A preponderance ofaliphatic sulfur, thiols, and dimethylsulfides was determined for both homogeneous litho-types (xylain and humovitrain). Additionally, thiophenes were identified in humovitrain.For heterogeneous lithotypes, liptain and humoclarain, a dominance of disulfides, and analmost lack of sulfides were observed. This is an indication that with coalification a grad-ual loss of aliphatic sulfur functions has proceeded, where more resistant disulfides sulfurbridges turned out to be present. Thiophenes were the most abundant aromatic structures,dominating in humoclarain. Some amounts of oxidized organic sulfur compounds (1%



up to 4.1% of Sorg) were semi-quantitative determined in lithotypes using AP-TPR-MS[435].

The thermal behavior of bone mineral samples was investigated in the range from 600to 900◦C by X-ray diffraction with line broadening analysis and temperature-programmeddesorption–mass spectrometry. At least two stages of CO3

2− release during the thermalevolution were observed;, each can be attributed to a different type of carbonate locationin the bone mineral. The elimination of CO3

2− occurring without pronounced variationsin the substructural parameters of the biomineral nanocrystals was ascribed to the surfacecarbonate, whereas the elimination of CO3

2− accompanied by the growth of crystals anddisappearance of structural distortions was attributed to the lattice carbonate [436]. Can-cellous bone from patients with osteoarthritis was reported to be undermineralized andthat from patients with osteoporosis is more liable to fracture. Changes in the mineralcomponent might be implicated in these processes. To investigate the thermal stability andthe mineral structure of cancellous bone from femoral heads of patients with either ostheo-porosys (OA) or ostheoarthrite (OP), powdered bone was prepared from femoral heads andcompared with a control group. Composition and thermal stability were determined usinga thermogravimetric analyzer coupled to a mass spectrometer, and it was noted that thethermal stability of the bone matrix, or of the mineral phase alone, was a little altered bydisease, though OA bone contained less mineral than OP or control bone [437].

Languri and Boon studied a 19th-century mummy pigment (Hafkenscheid paint mate-rial collection). It was analyzed by direct temperature-resolved mass spectrometry (DT-MS)and other mass spectrometry–based techniques. Megilp and asphalt (Hafkenscheid collec-tion) reference samples were analyzed under similar conditions [438].

Pyrolysis of biomass composed by birchwood xylan (representing hemicellulose), cel-lulose, lignin, chitin, Baker’s yeasts, and sewage sludge was examined by TG-MS coupledtechniques. Weight changes, pyrolyzand, and pyrolyzate compounds and process rates weredetermined. The TG-MS study did help to establish which of the two, pyrolysis or gasifi-cation, was the more profitable process [439]. Chicken litter disposal is a major economicand pollution concern. Poor waste management practices lead to air and water pollution. Toproduce a useful renewable resource for energy, optimal conditions for combustion werestudied by EGA techniques, including TG-MS and TG-FTIR [440, 441]. Florin and Har-ris reported the consequences of thermodynamic equilibrium for hydrogen generation viasteam gasification of biomass, coupled with in situ carbon dioxide capture. Model predic-tions were compared with an experimental investigation of the pyrolysis of pure celluloseand the reactivity of CaO through multiple CO2 capture and release cycles using a thermo-gravimetric analyzer, coupled with a mass spectrometer. On this basis, the applicability ofthermodynamic equilibrium theory for the identification of optimal operating conditionsfor maximising H2 output and CO2 capture were proved [442]. The pyrolysis behaviors ofrice straw, rice husk, and corncob were investigated by the TG-MS technique, paying closeattention to the gas formation during pyrolysis. The weight decreasing profiles and the gasformation rates were significantly different among the samples although their elementalcompositions were almost the same [443]. Water bamboo husks are the main agriculturalwastes of Taiwan in summer. In his study, Shih investigated the fiber obtained from thewater bamboo husks by CP-MAS, C13 NMR, elemental analysis, and adiabatic calorimetry.Moreover, the pyrolysis behavior of the fiber was studied by TGA, TGA-GC-MS, andPy-GC-MS. The kinetic parameters of the pyrolysis process of the fiber were calculated bythe modified Kilzer-Broido model, Coats and Redfern method, Harcourt and Esson rela-tionship, and Ozawa method, respectively. However, the pyrolysis of the fiber in air is muchmore complicated and the activation energies of pyrolysis are quite different from those



in nitrogen. Based on the TGA-GC-MS and Py-GC-MS study, the decomposed productsfrom the pyrolysis of the fiber are of interest for their potential use as organic resources[444]. Pyrolysis experiments of Enteromorpha clathrata (ENT, a species of seaweed) wereconducted at different heating rates and the results indicated that the nonisothermal massloss process of samples was composed of dehydration, rapid mass loss, slow mass loss,and solid residue decomposition. The devolatilization stage of ENT started earlier than thatof woody biomass because the basic components in seaweed are preferable for pyrolysiscompared to lignocellulosic materials. TG-MS analysis was used for the gaseous productsanalysis during the pyrolysis [445]. The devolatilization behavior of pine and beech woodfrom carpentry residuals, an herbaceous product from an energy plantation (artichoke this-tle), the digestion of waste sludge from a pharmaceutical industry, the digestion of cattlemanure, and the codigestion of a mixture of primary sludge and the organic fraction ofmunicipal solid wastes were investigated by Gomez et al. [446, 447]. Biobleaching studiesusing a laccase mediator system (LMS) were carried out under optimized conditions on twounbleached Eucalyptus globulus kraft pulps, one produced using a conventional method andanother obtained by modified kraft procedure with a high liquor–wood ratio and with blackliquor replacement in the middle of the cooking. The original milled wood sample and thekraft pulps were characterized by Py-GC-MS and TG-MS. Eucalypt wood lignin producesguaiacol and syringol derivatives during pyrolysis. These lignin products can be detectedwith high sensitivity using the selected ion chromatograms even in the bleached pulp oflow lignin content (about 0.5%). The TG-MS results showed that the hemicellulose contentof wood was strongly modified during pulping resulting in higher thermal stability [448].Three samples of biomass including rice straw, corn straw, and corn cob were analyzed byusing a TG-MS analyzer. The effect of oxygen concentration on combustion characteristicswas discussed, and relative weight loss velocity was adopted to describe combustion charac-teristics. Results showed that combustion mode is affected by oxygen concentration. Underdifferent oxygen contents, kinetic compensation relationships werere shown between com-bustion activation energy and a proponent factor [449–451]. Biomass gasification coupledwith in situ CO2 removal using CaO is a promising process for the sustainable production ofH2. Thermodynamic equilibrium modeling predicts biomass conversion to gas containingup to 81.4 vol% H2 (dry basis). However, in practice, discrepancies between theoretical andexperimental results demonstrated the significance of nonequilibrium phenomena. In thiscontext, a simultaneous thermogravimetric–mass spectrometric approach was used to studythe influence of heating rate, CaO loading, evolved gas residence time, and reaction atmo-sphere. The results of this study gave insight into the decomposition mechanisms of biomassin the presence of CaO [452]. Recycled compost leachate (RCL, or euphemistically called“goody water”) can be a potent source of foul odor on mushroom substrate production sitesand contributes to composting smells. A complex mixture of sulfur compounds, fatty acids,and nitrogen-containing compounds is responsible for odor production. Samples collectedfrom compost production sites in Ireland and the UK over a 2-year period were analyzedfor chemical properties and by TG-MS for compositional differences. Results indicatedthat aerated samples had lower values of electrical conductivity, redox potential, and drymatter content than nonaerated samples and that the higher thermal stability of aeratedsamples measured by TGA could be attributed to greater mineralization of the substratedue to aerobic processes. The lower temperatures noted for peak evolution of methane,water, and carbon dioxide from TG-MS analysis suggested that a more energetic processhad occurred in aerated RCL storage facilities, producing greater decomposition of macro-molecules that volatilized at lower temperatures. Chemical composition, thermal stabilityof the freeze-dried leachate, pyrolysis profiles, and relative amounts of pyrofysis products



were all markers of how effective control measures could influence RCL quality [453].The pyrolysis behaviors of several agricultural residues were investigated by measuring theevolving rates of the gaseous products such as H2, CH4, H2O, CO, and CO2 by coupledTG-MS. The catalytic effects of alkali and alkaline earth metals during the pyrolysis wereshown to play a major role in the behavior among the different biomass species [454].Pyrolysis of alternative biomasses, which contribute to the recovery of arid soils and donot compete with alimentary biomass, could increase the use of biomass as feedstock inenergy production facilities [427, 428]. In this sense, in order to optimize this thermalprocess and gain better insight the origin and evolution of the main produced volatiles, non-isothermal thermogravimetry coupled to mass spectrometry was applied for samples of twobiomasses (Leucaena leucocephala [Leucaena] and Chamaecytisus palmensis [Tagasaste]),which find application as energy crops and contribute to soil restoration. Moreover, in orderto simulate the hydrogen signal, the char produced during the volatization process wasconsidered. Taking into account the composition of the samples, the relation between thespecific hydrogen production of the single pseudocomponents (hemicellulose: cellulose:lignin) could be calculated [455]. Font et al. reported kinetic studies by TG-MS for pineneedles and cones [456] and for tomatoes [457] under different operating conditions inorder to observe the evolution of the major compounds and to discuss the information thatcould be obtained. A study of all solid products obtained in corn fiber processing to ethanolwas carried out with TG-MS and Py-GC-MS by Maszaros and coworkers. The thermalbehaviors of corn fiber, destarched corn fiber, various alkali-pretreated fibers, and cornfiber gums were compared, showing that no significant changes occurred after treatmentwith amylolytic enzymes. The results also indicated that the applied analytical methods aresuitable for studying changes in the composition of the variously treated corn fibers [458].The fuel characteristics of two typical seaweeds (Enteromorpha clathrata and Sargassumnatans) were studied by Wang et al. It was found that both the contents of volatile andash were high, and the ash melting characteristics were different. Furthermore, the TG-MSanalysis was used for the gaseous products analysis during the combustion. It provided thefundamental data for the development and utilization of seaweed biomass [459]. Cellulosewas mixed with the hydroxides of lithium and nickel and the mixture was milled, followedby heating to produce hydrogen. Several analytical methods including evolved gas analysisby mass spectrometry were used to characterize the samples. Hydrogen was emitted whenheating the milled sample around 400◦C together with low concentrations of methane, car-bon monoxide, and carbon dioxide. It was understood that an interaction occurs betweencellulose and lithium hydroxide to convert the carbon of cellulose into lithium carbonateand to emit hydrogen correspondingly [460]. An experimental study on NO reduction bybiomass gasification tar was carried out on the flow reaction system. Tar is so complex thattar model compounds were selected to reduce NO. Those model compounds were benzene,toluene, styrene, and phenol. According to TG-MS analyses of pyrolysis and gasification ofrice straw, corn stalk, and corncob, these four compounds are main compositions of biogastar. Experimental results showed that the four model compounds had different effects onNO reduction. The results instructed further research and engineering application of biogasreburning [461]. Composting is a biological process of decomposition of organic materialsin an aerobic environment, which modifies the chemical composition and the thermal be-havior of biomass. During composting, fungi and bacteria promote the decomposition ofhemicellulosic and cellulosic fractions, increasing the lignin proportion. Thermogravimet-ric analysis coupled to mass spectrometry allowed the monitoring of the gas productionduring pyrolysis. Water and carbon oxide MS profiles can be simulated by an optimizedlinear combination of previously calculated DTG curves of pseudocomponents; however,



in order to simulate the hydrogen MS signal, it is necessary to consider the char obtained inthe course of the volatilization process [462]. FTIR and TG-MS analyses were employedto study the organic matter transformation attained under anaerobic digestion of slaughter-house waste and to establish the stability of the digestates obtained when compared withfresh wastes. Digestate samples studied were obtained from successful digestion and failedsystems treating slaughterhouse waste and the organic fraction of municipal solid wastes[463]. The emission factors for 16 U.S. Environmental Protection Agency (EPA) prioritypolycyclic aromatic hydrocarbons (PAHs) from the polylactic acid (PLA) pyrolysis andthe decomposition mechanism were investigated by Chien et al. The fragments and gascompositions using on-line TG-MS were determined. The pyrolysis of PLA is a nonradi-cal, backbiting ester interchange reaction involving the OH chain ends. Depending on thesize of the cyclic transition state, the product can be a lactide molecule, an oligomericring with more than two repeat units, methylketene, or acetaldehyde. Carbon monoxideand methane are contributions from the decomposition of acetaldehyde. From the view-point of air pollution control, the results suggested that pyrolysis seems a better alternativethan combustion for the disposal of waste PLA. Also, because pyrolysis is the first stepfor an incineration process, these results provided important information on the controlof PAHs formation for a commercialized incinerator [464]. The combustion properties ofthree of the UK’s commonly imported biomass fuels for cofiring, which are palm kernelexpellers, shea residue, and waste from olive oil production, were examined. Chars fromthe fuels were prepared and analyzed, and combustion studies were conducted by TGA-MSto determine the conversion of char-nitrogen to different nitrogen-containing species. Ingeneral, the main constituents of their ash fractions were K, Si, Ca, and Mg, resulting inhigh alkali indices, which predicted a large tendency to fouling [465]. In order to graspelm sawdust pyrolysis behavior, slow pyrolysis of elm sawdust was studied by MS-EGA[466]. The thermal decomposition of pellets made from pyrenean oak and olive wastepomace mixed under different proportions was studied by the coupled TG-MS technique:this study allowed the monitoring of the emissions of CO2, SO2, NO, and C6H6, and thedifferences found were related to the chemical composition of the precursors and to thefeatures of their thermal degradation [467]. To improve the understanding of the pyrolysisof species involved in fires of Mediterranean vegetation and to propose a description anda quantification of the gases released during their degradation, TG-MS analyses were per-formed with three Mediterranean species: Cistus creticus, Myrtus communis, and Genistacorsica. A part of the study was devoted to the gas quantification from the results obtainedwith the TG-MS. The results showed variations of the gas composition in function to thetemperature and of the plant species [468].

Biodiesel is a potential renewable and carbon-neutral alternative to fossil fuels, andit is environmentally and economically attractive. Chien and coworkers studied the de-composition kinetics of biodiesel using thermogravimetric analysis in one-stage pyrolysis.Biodiesel can be decomposed at 119–237◦C. Characteristics of diesel and biodiesel and theassociated diesel particulate matter (DPM) emitted from a nonroad diesel generator werealso analyzed. The information from TG-MS was shown to offer a better understandingof the by-product formation mechanisms of biodiesel combustion [469]. Analytical pyrol-ysis was conducted to identify and quantify the major pyrolysis products of a biodieselphenolic urethane binder as a function of temperature. This biodiesel binder was used inU.S. foundries to replace conventional phenolic urethane binders for making sand cores.The evolution profiles of the pyrolysis products during slow pyrolysis were also monitoredvia EGA by mass spectrometry that facilitated a quantification of gaseous pyrolysis prod-ucts of the biodiesel binder as a function of temperature. Pyrolysis of the biodiesel binder



also generated a variety of hazardous air pollutants listed by the U.S. EPA, with benzene,toluene, xylene, phenol, and cresols being the prominent species. A considerable fraction ofthe binder’s released mass did not appear as exhausted volatile carbonaceous species [470].The deactivation of organosulfonic acid-functionalized silica catalysts during biodieselsynthesis was reported by Alba-Rubio et al. The reusability of silica functionalized with4-ethyl-benzene sulfonic acid groups used as catalyst in biodiesel production from sun-flower oil–methanol mixtures was shown. Fresh and used catalysts were characterized bychemical analysis, N2 adsorption–desorption isotherms, infrared spectroscopy, and evolvedgas analysis by mass spectrometry. Leaching of the organosulfonic groups and adsorptionof organic compounds onto the acid sites was detected in the used catalysts [471].

A new borazine derivative was prepared by reacting Cl3Si-CH(CH3)-BCl2 (TSDE)with hexamethyldisilazane (hmds) at ambient conditions. The specially designed moleculeserved as a single-source precursor for the synthesis of a highly durable Si/B/N/C ceramicmaterial via the well-known polymer route. Subsequent thermal degradation of the as-obtained polyborocarbosilazane was monitored by means of DTA-TG-MS up to 1400◦C[472].

Analysis of river, estuary, and marine sediments from the Atlantic coast of Spainusing TG-DSC-QMS-IRMS was used to (a) distinguish bulk chemical hosts for C within asediment and humic acid fraction, (b) track C pools with differing natural C isotope ratios,and (c) observe variation with distance from the coast. This was the first application of sucha novel method to the characterization of organic matter from marine sediments and theircorresponding humic acid fractions. Using thermal analysis, a labile, a recalcitrant, and arefractory carbon pool can be distinguished [473].

By coupling an IRMS and a QMS to a thermal analysis system, Lopez-Capel andcoworkers were able to continuously measure 13C and identify the evolved gases duringthe thermal decomposition of a range of lignocellulosic materials derived from soils and/orplant tissue. Here we describe the application of this approach to characterize wheat strawduring fungal degradation by the oyster mushroom Pleurotus ostreatus [474].

A series of N-substituted Ti isopropoxide precursors was synthesized using three dif-ferent amine-type ligands. The resulting Ti-complexes were characterized by NMR andused to obtain solid precipitates by a reverse microemulsion method. These N-rich solidprecipitates were subjected to three calcination treatments differing in the gas atmosphereallowed to contact the solid, yielding nanosized materials. A thermogravimetric analy-sis of the solid precipitates, combined with a mass spectrometry–infrared study of theevolving gaseous products, was able to show the influence of preparation parameters,for example, Ti-precursor nature and treatment conditions, in the decomposition processof the solid precursors and the formation of the final nanoparticulated solid catalysts[475].

Oriental lacquer is the natural resin obtained by tapping lac trees. It hardens into a toughand insoluble film. The extreme hardness and insolubility are some of the most importantfunctions required for industrial coating materials. Two kinds of oriental lacquer films,traditionally named Kiurushi (raw urushi) and Kuromeurushi, produced by two differentpretreatments were analyzed during hardening with FTIR, TG-DTA-MS, and Py-GC-MSto investigate their functional expression process. The TG-DTA-MS curves clarified thatthe thermal degradation of the lacquer films gradually began at around 200◦C and reachedthe fastest rate at 400–500◦C [476].

The aging characteristics of pyrotechnic compositions are influenced not only bytemperature but by surrounding effects as humidity and vibrations. The thermal stabilityof the pyrotechnic system magnesium–sodium nitrate was investigated by De Klerk and



coworkers. Using MS and FTIR, the evolved gases were analyzed. Only above about170◦C were evolving gases detected (which means that during the first step no gases weredetectable). The detected gas mainly consisted of CO2, CO, and N2O, with smaller amountsof NO2, NO, and possibly HCN. The work gave useful information to consider regardingwhich process does not contribute significantly to the aging of the material at much lowertemperatures of maximum 80◦C, which is of interest in view of the use of the materials[477]. BTAw (bis-(1(2)H-tetrazol-5yl)-amine monohydrate) has recently been consideredfor use as a low-smoke pyrotechnic fuel. Because there is relatively little informationavailable in the literature concerning the thermal properties of BTAw or its precursors,various thermoanalytical experiments were performed on BTAw and BTA (bis-(1(2)H-tetrazol-5yl)-amine) to better characterize the thermal stability and decomposition of thesecompounds. Experiments using simultaneous TG-DTA coupled with FTIR and MS wereperformed on BTAw in both helium and dry and CO2-free air atmospheres, and EGA wasused to determine the gaseous decomposition products [478].

Tunable carbon-coated monoliths as carriers for enzyme adsorption were presented byde Lathouder et al. Depending on enzyme properties and reaction conditions, the carrierwas shown to be adjustable to optimize enzyme loading. Carbon–ceramic composites wereprepared by sucrose carbonization, polyfurfuryl alcohol (PFA) carbonization, and growthof carbon nanofibers (CNFs) over deposited Ni. The composites were applied as a carrierfor a lactase from Aspergillus oryzae. The CNFs proved to be the best carrier with respect toenzyme loading. TGA-MS and XRD analyses confirmed the different effects of air–HNO3

treatment and the Ni removing success from the fiber tips of CNFs by different concentratedacids—nitric acid, hydrochloric acid, and oxalic acid [479].

In view of pharmaceutical applications, the glucocorticoide triamcinolone diacetatewas investigated for polymorphism. In addition to DSC characterizations, when the solventswere removed at higher temperatures using simultaneous differential thermoanalysis andthermogravimetry coupled to mass spectroscopy (DTA-TG-MS), the remaining residueswere amorphous against X-rays because the compound melted directly after desolvation[480].

Thermogravimetry also coupled to mass spectrometry and loss-on-drying methodologywas used to provide residual moisture results for freeze-dried biological products regulatedby the U.S. Food and Drug Administration. Residual moisture specifications must be met inorder to ensure freeze-dried biological product potency and stability throughout the licensedproduct’s shelf life. TG-MS, loss-on-drying, and vapor pressure moisture measurementswere compared for a bacillus calmette guerin (BCG) vaccine [481].

The hyphenated thermal analysis–mass spectrometry technique was applied by Roduitand Odlyha for the investigation of the thermal behavior of reference and aged parchmentsamples. For the parchment samples, whereas the aging almost does not change the kineticsof the decomposition calculated from the DSC data (the influence of aging seems to be toonegligible to be detected), the much more sensitive mass spectrometric technique appliedto the kinetic analysis allowed monitoring of visible changes in the thermal behavior of theparchment samples due to the aging process. The influence of aging was especially visiblewhen the MS signals of water and nitric oxide were applied for the determination of thekinetic parameters [482].

Several straight rubbers (natural rubber and three styrene–butadiene rubbers withdifferent styrene and oil contents and butadiene rubber) were characterized and the influenceof three typical tire additives ZnO, sulfur, and carbon black on the thermal degradation ofthe straight rubbers was determined by TG-MS analysis. Rubber mixtures and tire partswere investigated in the same way by TG-MS and compared. It turned out that the MS



spectra of the volatile pyrolysis products of rubber mixtures could be composed from thespectra of their rubber components [483].

Soft ionization mass spectrometry was used to investigate the oxidative decompositionof an epoxy resin–carbon fiber composite using thermogravimetry coupled with massspectrometry. Through comparison between decomposition in air and in argon, it wasrecognized that the first step of the oxidative decomposition of the epoxy resins was similarto the decomposition in argon. Using soft ionization, the components of the evolved gaseswere identified by mass spectrometry [484]. The microstructure evolution of phenolic fiberscarbonized at different temperatures and the influence of the resulting microstructure on themechanical and electrical behaviors were investigated using a combination of techniquesincluding thermogravimetry coupled to mass spectroscopy by Liu et al. [485].

Silane coating is a metal surface pretreatment introduced as a replacement forchromium treatments. It is supposed to be suited for various metals, including aluminum,steel, and galvanized steel. Good corrosion performance was assigned to these hybridorganic–inorganic thin-film deposition systems. Using thermogravimetric analysis com-bined with mass spectroscopy, the mechanism and kinetics of the curing process wereexplained by De Graeve et al. [486].

The thermal behavior of a sol-gel prepared hybride silica gel (HSiO sample) in the20–1000◦C interval was studied by EGA-MS analyses carried out at various heating rates.Thermogravimetric curve elaboration allowed the determination of the flex temperatures,corresponding to the maximum release rate of gas-evolved compounds, and calculationof the activation energy of the overall process. The mass spectrometric data, registeredin the TG-MS measurements, were treated to discriminate the single reactions accountingfor the release of each compound, among water, dihydrofuran, and various silane- andsiloxane-derived species. These results were used to calculate the comprehensive activationenergy and those of each of the released species [487]. The synthesis of micellar-templatedsilica materials was conducted with different SiO2/CTAB molar ratios for two differentcetyltrimethylammoniumbromide concentrations to examine the structure formation forcubic as well as for hexagonal surfactant arrangement in acidic reaction medium withincreasing silicate excess. Reaction products were analyzed with X-ray diffraction, N2

physisorption, and TG-MS. It was found that an increase of the silicate concentration leadsto the formation of additional silica gel in the resulting MTS material, which causes notonly a decrease of specific surface area and pore volume but also of the mesopore diameter[488]. For modeling the presintering procedures of high-grade alumina ceramic, thermallyevolved gases from alumina–organic binder mixtures released in flowing air were analyzedand monitored by simultaneous TG-DTA-EGA-MS and FTIR spectroscopy. Below 280◦C,elimination of organic vapors was dominant, whereas above 280◦C CO2 was the maindecomposition product, indicating that additional measures are to be taken to complete theburning out of organic vapors released at relatively low temperature in considerable amountduring the presintering process; in addition, relatively high temperatures and long durationsare needed to obtain ceramics free from the residues of the moulding additives [489].

The effect of tetrabromobisphenol A (TBBA), ammonium polyphosphate (APP), andtris(2,4-di-ter-dibuthylphenyl-phosphite) (TBP) flame retardants were examined on thethermal decomposition of polycarbonate by pyrolysis and thermogravimetry, both coupledto a mass spectrometer. The maximal rate of polycarbonate decomposition shifted to aslightly lower temperature in the presence of TBBA. More than 20 bromine-containingproducts were identified among the pyrolysis products of the polycarbonate sample con-taining TBBA flame retardant at 550 and 700◦C. A significant decrease of the total eval-uated volatile compounds was found at 550◦C from the APP blended polycarbonate and



at 700◦C pyrolysis temperature in the presence of both phosphor-containing flame retar-dants investigated [490]. A study (based on TG-MS) on the effects of flame retardantson the thermal decomposition of wood was reported [491]. TBBA is the most commonbrominated fire retardant. A TBBA containing paper-laminated printed circuit board pre-pared from novolac was pyrolyzed by TGA and in a quartz glass reactor between 40 and1000◦C, and the products were on-line detected by MS. Compared to pure TBBA, whichmainly produces brominated phenols, the brominated products enclosed in the char re-leased HBr during the last degradation step as well as during the second step. Most of thebromine left the resin in the form of HBr, with about 14% of the bromine being fixed inbrominated aromatics and less than 2% remaining in the residue [492]. Pyrolysis studiesof reactively flame-retarded methyl methacrylate/diethyl(acryloyloxymethyl)phosphonate(MMA/DEAMP) and methyl methacrylate/diethyl(methacryloyloxymethyl)phosphonate(MMA/DEMMP) copolymers were undertaken with a view to gain information per-tinent to the mechanisms of their flame-retardant behaviors. The homopolymer withand without the additive diethylethylphosphonate was also investigated for comparisonpurposes [493].

Nazara et al. studied the effect of smoke suppressants on flammability and smokeproduction of flame-retarded unsaturated polyester resin nanocomposites using four differ-ent testing regimes representing different fire scenarios. Samples containing zinc borate,zinc stannates, and ammonium polyphosphate with and without nanoclay were analyzedfor smoke generation using cone calorimetry (well-ventilated fire), a tube furnace (fullydeveloped fire), and a smoke density chamber (underventilated fire). Carbon monoxideand carbon dioxide measurements using thermogravimetry–evolved gas analysis, conecalorimetry, and tube furnace have also been analyzed and compared. Results confirmedthat the production of smoke, CO, and CO2 depends upon the smoke suppressants and fireconditions used during testing samples. Finally, the presence of nanoclay in flame-retardedresin showed a significant reduction in smoke formations in both well-ventilated and un-derventilated fire conditions. However, in the presence of smoke suppressants used in thisstudy, the nanoclay was not instrumental in further suppressing smoke formation [494].

The thermal stability of modified (by a one-pot synthesis) and functionalized carbonblack Vulcan XC72R powders and the chemical species liberated upon their heat treatmentin air and nitrogen were investigated by a series of physicochemical techniques. Thecovalent bonding of the organic groups was indirectly evidenced by thermogravimetricanalysis and, when coupled to mass spectrometry, suggested that the 4-nitrophenyl graftedgroups undergo the cleavage of the N-O bond of the nitro group followed by the liberationof NO [495].

The aging effect induced by S-compounds added as odorants in the natural gas net-work over a previously developed catalyst now deposited on an FeCrAl alloy fiber matwas reported by Specchia et al. A generation of catalytic premixed fiber burners for low-environmental-impact natural gas combustion was based on Pd/LaMnO3·2ZrO2 catalyst,where ZrO2 acted as a structural promoter and the noble metal-perovskite synergism was ef-fectively exploited, leading to enhanced performance with respect to noncatalyzed burners.TG-MS was used to characterize the fibers [496].

Senneca and coworkers studied the thermal decomposition under oxidative conditionsof 16 pesticides divided in four groups: pesticides with linear molecules belonging tothe family of aldoxime carbamates; benzimidazolylcarbamates; pyrethroids; and pesticidescontaining one aromatic (heterocyclic in one case) ring within their structure. The exper-imental work consisted of nonisothermal thermogravimetric analysis with 5% oxygen inhelium using a TG-DSC-MS system equipped with a skimmer device that ensures the



simultaneousness of thermogravimetric analysis with the analysis of evolved gas and rulesout the possibility of secondary reactions in the gas phase. Results were analyzed in orderto highlight similarities and differences in the modes of decomposition of pesticides withinand among the four mentioned groups. The influence of oxygen and the yield in gaseousproducts was also addressed [497].

The thermal behavior and composition of extractives of 1-year-old shoots of Robiniapseudoacacia (black locust) was studied. The extractives were eliminated from the woodsamples with Soxhlet extraction using different solvents. The study of the thermal decom-position of the extracted materials was performed with TG-MS. The thermal behavior of theoriginal and extracted wood samples was been investigated with the same thermal methods.The obtained results implied that the extractives decomposed in the same temperature rangeas the natural polymers that make up the cell walls of plants. Although the decompositionpathways of polysaccharides and lignin were not altered by the extractive compounds, theextractives evolved additional products influencing the product distribution of the wholewood samples [498, 499].

The effects of temperature on the stability of a soil humic acid were studied by TPD-MS and in situ DRIFTS. Humic acid samples were studied in the 25–800◦C range, with afocus on thermal–chemical processes up to 250◦C [500].

A novel biomaterial consisting of the biodegradable compounds hydroxyapatite, chi-tosan, and starch was developed by Hoffmann and coworkers. Burn-out experiments carriedout by TG-MS provided the organic–inorganic ratio [501].

The chemical characterization of solid organic residues found in ceramic vessels canprovide archaeologists with valuable information about ancient diets. Although several se-lective analytical techniques were applied to the analysis of specific classes of compounds,such as extractable lipids, waxes, terpenoids, and protein fragments, a nonselective analyt-ical technique is required to characterize and categorize complete solid organic residues.In this study, direct temperature–resolved mass spectrometry (DTMS) was used for thecharacterization of 34 solid residues situated on vessels recovered from an indigenous set-tlement from the Roman period at Uitgeest-Groot Dorregeest (The Netherlands). DTMSanalysis of aliquots gave information about a broad range of organic compounds, such aslipids, polynuclear aromatic hydrocarbons, markers for residual proteins and polysaccha-rides, and newly formed complex condensed polymers. Multivariate analysis of the DTMSspectra identified five different chemotypes: groups of residues with comparable chemicalcharacteristics. The biomolecular origin of each of these chemotypes was identified bycomparison with experimentally charred reference materials. [502]. The deleterious inter-action of some traditional sulfide artists’ pigments and copper ions results in the formationof black copper sulfides, in particular, covellite (CuS), and, hence, the discoloration of valu-able artworks. The interaction of malachite, a source of copper (II) ions, with the pigmentcadmium yellow, a sulfide pigment comprising of a solid solution of cadmium and zincsulfides, was investigated by XRD and TG-MS. XRD showed the presence of the coppersulfide and cadmium carbonate phases, produced by a simple ion-exchange mechanism.TG-MS showed the complexity of the range of metastable phases produced [503].

A challenge for forensic examiners is the aging and characterization of bone fragmentsor decomposed skeletal remains. Due to the sensitivity of thermal methods to morphologicalstates, thermal analysis was selected as a technique that could overcome these difficulties. Inthis preliminary study, TG-MS was applied to the characterization of bone fragments derivedfrom the compact bone of pig rib specimens. TG-MS curves were collected by heatingbone samples to 1000◦C in an argon atmosphere. Under these conditions, both the organic



and inorganic phases decomposed, producing a variety of organic fragments and carbondioxide. Pyrolysis of the organic phase, which is composed predominantly of collagen,occurred, resulting in the observation of ion fragments up to 110 amu. Selected fragmentswere monitored and their observation was discussed in terms of the decomposition of boththe collagen phase and the inorganic carbonated hydroxyapatite phase [504]. In order toinvestigate the potential of thermal analysis for the determination of postmortem age, ribbone specimens were collected from the remains of a number of slaughtered pigs thatwere allowed to decompose in the Australian bush in a controlled site under a range ofconditions for time periods ranging from 1 to 5 years. The bone specimens were cut incross section with the compact bone collected for analysis. TG-MS curves were collectedby heating bone samples to 1100◦C in an argon atmosphere. The TG-MS data showedsignificant differences for the pig bone specimens derived from the different environmentsand showed trends in peak size correlating with age. The reported data suggested thatTG-MS has significant potential for the identification of origin as well as the aging ofskeletal remains in a forensic context [505]. The time profile of VOCs produced during theearly stages of human decomposition was investigated. A human cadaver was placed ina sealed bag at approximately the fourth day after death. Evolved VOCs were monitoredfor 24 h by sampling at different time intervals. VOCs produced were analyzed by TD-GC-MS. Over 30 substances were identified in total. These included mainly aliphaticand aromatic hydrocarbons, oxygenated compounds (alcohols, aldehydes, ketones), andorganic sulfides. The last were the most prominent class of compounds identified. Elevencompounds were present in all of the sampling cycles and constituted a common core. Thefundamental physicochemical properties of the evolved VOCs were used for evaluating theirenvironmental impacts. It appeared that the decay process, which is a dynamic procedure,could provide chemical signals that might be detected and properly evaluated by experts inthe fields of forensic sciences, search and rescue units, and environmental scientists [506].

It was demonstrated that radicals and/or anions can promote chain reactions improvingdesulfurization efficiency in flue gas. Recent studies have evidently shown that speciallysynthesized C12A7 is a prominent source of O−, which was found to be one of the mostactive radicals acting as a potential oxidant in many applications. The resulting products,analyzed by TG-MS and FTIR, proved that the reactivity of C12A7 was lower than CaOsamples because of its low surface area accessibility [507].

Six different samples of oil shale from the United States and Turkey were pyrolyzedin a tubular flow reactor set up with nitrogen sweep under nonisothermal conditions. Oilshale samples were analyzed by proximate and ultimate analyses and TGA-MS. The resultsshowed significant differences in yield and hydrocarbon distribution of the liquid productsbetween the oil shale samples from different regions [508]. Pyrolysis of oil sludge firstby thermogravimetry–mass spectroscopy and then in a horizontal quartz reactor with anelectrical laboratory furnace under different pyrolysis conditions was carried out. TheTG-MS results show that pyrolysis reaction of oil sludge started at a low temperature ofabout 200◦C, and the maximum evolution rate was observed between the temperaturesof 350–500◦C. Three additives used in this work as catalysts did not improve oil productquality markedly in spite of increasing pyrolysis conversion [509].

PET clay nanocomposites were synthesized using two different types of organo-modified clay: Cloisite 10A (a montmorillonite) and Somasif MEE (a synthetic fluoromica).In addition to these organo-modified clays, a nanocomposite using the unmodified clay,Somasif ME100, was prepared. Samples were characterized by TEM, XRD, melt rheology,and TGA-MS, revealing that the Somasif ME100 sample showed a high level of thermal



stability, whereas the organo-modified clay additives exhibited some thermal degradationat the PET processing temperatures [510]. Organic–inorganic nanocomposites were pre-pared using epoxy- and silane-modified isocyanuric acid triglycidyl ester (SM-IATE).Novel epoxy nanocomposites containing silicon, nitrogen, and phosphorus were fabri-cated successfully via the sol-gel method to increase thermal stability and flame-retardantproperties. The epoxy was modified by a coupling agent to improve the compatibility ofthe organic and inorganic phases. TGA-MS analysis showed that hybrids liberated lesstoxic gases than pure epoxy and that the hybrids possessed excellent optical transparencyand could be used in protective coatings [511]. A carrageenan-Pt nanoparticle composite(Cg-Pt) was synthesized and characterized by several spectroscopic techniques and TG-MS analysis. It was revealed that the electrical conductivity of Cg-Pt strongly dependedon relative humidity and exceeded the conductivity of Cg under conditions of high hu-midity [512]. A detailed study about the synthesis, characterization, and properties ofpoly(o-methylaniline)(PoMea)/maghnite nanocomposites was performed by Salavagioneet al. Intercalated morphology was detected by TEM in nanocomposites containing copper-treated maghnite (Magh-Cu), whereas when maghnite treated with strong acids was used(Magh-H), an exfoliated material was obtained. Remarkable differences in the propertiesof the polymers were observed by TG-MS and FTIR, suggesting that the polymer producedwith Magh-H had a higher degree of branching [513].

The effect of a recent vegetation change in central Queensland, Australia, on soilorganic matter (SOM) composition and SOM dynamics was investigated using a novelcoupled TG-DSC-QMS-IRMS system. TG-DSC-QMS-IRMS distinguishes the C isotopecomposition of discrete SOM pools, showing changes in labile, recalcitrant, and refrac-tory carbon in the bulk soil and particle size fractions that track the vegetation changes.Analysis of evolved gases (by QMS) from thermal decomposition, rather than observedweight loss, proved essential in determining the temperature at which SOM decomposes,because smectite and kaolinite clays contribute to observed weight losses [514]. Near-critical and supercritical CO2 was used to facilitate the impregnation of additives, vanillinand l-menthol, into cellulose acetate (CA). It was possible to impregnate up to about 10wt% vanillin or l-menthol into CA fiber as verified by gravimetric, thermogravimetric,and TGA-MS analyses. SEM analysis of the CA fiber showed that the fiber did not un-dergo structural changes during this impregnation process even when the fiber was rapidlydepressurized [515]. Wu et al. analyzed the pyrolysis behaviors of Lyocell fiber, a novelman-made cellulosic fiber, with and without catalyst, using TG-MS coupled technology[516].

Aiming to environmental protection, thermogravimetric analysis was combined withevolved gas analysis with the purpose of simulating the thermal behavior of filter dustsamples under inert (desorption) and de novo test oxidizing conditions. Emphasis was onstudying de novo formation of dioxins, surrogates, and precursors arising from filter dustderived from thermal processes, such as municipal solid waste incineration and metallurgy[517].

A TG-DSC-MS was used to study oxygen carriers for their potential use for theapplication of chemical looping combustion to solid fuels. Reaction rates, changes inreaction rates with repeated oxidation-reductions, exothermic heats during oxidation, andthe effect of changing reduction gas compositions were studied [518].

Organo-acid–activated clays with different surfactant contents were prepared by Kooli.The intercalated used cations adopted different orientations in the interlayer spacing of theacid-activated clays, influencing their thermal stability depending on the amounts takenup, acidity of the clay sheets, and heating temperatures. The thermal stability of these



materials was investigated using TG-MS, followed by in situ X-ray diffraction in a nitrogenatmosphere. The clay sheets affected the decomposition of the surfactants and, as a con-sequence, the thermal stability of the surfactants. TG-MS revealed that different types ofwater molecules were detected during the heating process with additional CO2, alkanes,and alkenes species at temperatures above 200◦C. The interlayer spacing collapsed aftercompleted degradation of the intercalated surfactants [519]. Four Chinese palygorskitesclay minerals were analyzed by Cheng et al. The mass spectrometric curves combinedwith the differential thermogravimetric curves enabled detailed determinations of the maindehydration steps. The results showed that the dehydration occurred in four main steps andthat the temperatures of dehydration of the palygorskite minerals were influenced by thegeological environment and the amount and kind of impurities, including various evolvedgases in the decomposition process because of the different amounts and kind of impurities.It was also found that decarbonization took place at around 600◦C due to the decompositionof calcite and dolomite impurities in these minerals. It was evident by the mass spectro-metric curve that the water was given out from the samples and carbon dioxide originatedfrom the impurity of calcite and dolomite [520]. Malferrari and coworkers described theinfluence of temperature on two Hg(II)-cysteine modified clay minerals with different layercharges (i.e., montmorillonite and vermiculite) by using chemical and thermal analysescoupled with EGA [521]. Two kinds of coal-bearing kaolinite from China were also ana-lyzed and the TG-MS characterization showed a series of steps attributed to the desorptionof water and decarbonization and dehydroxylation processes [522, 523]. EGA-MS was alsoemployed to characterize smectites, layered double hydroxides, and their intercalates withporphyrins [524].

An EGA study applied to biology was reported by Hopf et al. Microbially assisteddissolution of biotite was studied using four environmentally important species (Bacillussubtilis, Shewanella putrefaciens, Streptomyces acisdiscabies, and Schizophyllum com-mune) incubated for 35 days in batch reactors at slightly alkaline pH conditions. Structuraland chemical alterations of biotite were analyzed by a directly evolved gas analysis system(DEGAS) and TEM coupled with electron-energy loss spectroscopy (EELS) and EDXanalysis. The results showed that biotite dissolved incongruently with a preferential releaseof the interlayer cations followed by the octahedral and subsequently the tetrahedral site[525].

The aging-resistance ability of the asphalt is an important factor to the life and qual-ity of asphalt pavement. Through the thin-film oven test on two Tahe asphalts, the in-fluence of aging on road performance of Tahe asphalt was analyzed. Using combinedTG-DSC-MS technology, the volatilization and thermal decomposition course of Taheasphalt was determined and the test results showed that Tahe asphalt had good agingresistance and fatigue abilities. In the performing temperature range, the aging of Tahe as-phalt involves a process consisting of the volatilization and oxidation of light components[526].

Thermal decomposition of RDX-CMDB propellants with composite burning rate cat-alysts were investigated by using on-line TG-DSC-IR-MS techniques. On the basis ofchanges in main gaseous products, the influence of the nano and general catalysts on thecharacteristic values of thermal decomposition was compared and effect mechanism ofcatalysts was discussed. It was shown that effect of nanocatalysts was better than thatof general catalysts [527]. In order to reveal the reasons for pore formation in hydroxyl-terminated polybutadiene–ammonium dinitramide–ammonium perchlorate–aluminum(HTPB/ADN/AP/Al) composite propellants, a series of propellant samples containingADN and triethanolamines was prepared. The components of reacting with ADN and pore



formation were confirmed and the reaction mechanism was analyzed by DSC-TG-IR-MS.Results showed that there were no pores in the propellant samples containing curing agentsbut pores were formed in the samples containing aziridine bonding agents [528].

Thermogravimetric analysis and evolved gas mass spectroscopy were used to studythe kinetics of carbon oxidation from a class-F fly ash. A multiprocess ignition loss schemawas presented wherein carbon combustion was modeled as a series or discrete independentreactions. The detailed combustion kinetics are relevant for the postprocessing of fly ashto produce materials suitable for use as concrete admixtures or in the manufacture ofsintered artificial aggregates or similar densified structures based on fly ash. These includelow-temperature, low-heating-rate processes relative to coal combustion power generationapplications [529].

Latent heat storage systems, using phase change materials (PCMs), present the advan-tage of a high storage density at nearly constant temperature. They offer intrinsic advantagesfor heat storage in combination with steam as a heat transfer fluid. Important applications ofthese storage systems are the areas of solar industrial process heat supply and heat recoveryin industrial batch processes. The thermal behavior of 11 potential storage materials wasstudied by means of TG-DSC-QMS [530].

Printed, thermal, or photochemical sintered silver features were electrically conductiveon glass. Conducted tape tests showed the suitability of the ink particularly for polymersubstrates. TG-MS studies demonstrated a two-step decomposition for the conversion of 3to elemental silver [531, 532].

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Evolved Gas Analysis by Mass Spectrometry

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