Binders and Bonding Mechanism for RHF Briquette ... - J-Stage

1781 © 2014 ISIJ

ISIJ International, Vol. 54 (2014), No. 8, pp. 1781–1789

Binders and Bonding Mechanism for RHF Briquette Made from Blast Furnace Dust

Hongliang HAN,1)* Dongping DUAN1) and Peng YUAN2)

1) Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing,100190 China.2) College of Metallurgy and Energy Resources, Hebei United University, Tangshan, Hebei, 063009 China.

(Received on March 12, 2014; accepted on May 2, 2014)

Blast furnace dust is a kind of solid waste that produced in the process of iron smelting and it containslarge amount of Fe and non-ferrous metal elements. It’s not only a very good Fe-contained resource, butalso a very important non-ferrous metal resource. Application of blast furnace dust to RHF (Rotary HearthFurnace) briquette is an effective and comprehensive utilization method. However the strength of the bri-quettes is low, therefore the application of binder to the briquette should be developed. In this study,physical and chemical characteristics of blast furnace dust were investigated firstly. And the experimentsof different binder used in the briquettes were studied. Then the bonding mechanisms of binders werediscussed. The experiment results showed that different binder has different bonding mechanism of thebriquettes. According to the application effect of binders, it should be priority to use the compositebinder, and the excellent collocation pattern is starch binder together with silicon-containing binder, suchas sodium silicate.

KEY WORDS: Rotary Hearth Furnace; agglomeration; carbon composite briquette; blast furnace dust;strength; bonding mechanisms.

1. Introduction

Blast furnace dust is a kind of solid waste generated in theprocess of blast furnace ironmaking. It’s treated as a kind ofprecious secondary resources, because its main componentsare C, Fe and a spot of recyclable non-ferrous metal ele-ments, such as Zn, Pb, K, Na, etc.1,2) However it is harmfulto human health, because it is characterized by easily float-ing in the air, due to its small particle size and low density.Therefore, the comprehensive utilization of blast furnacedust, not only has the good economic benefits, but also hasthe considerable social and environmental benefits.3)

At present, most of companies utilize blast furnace dustdirectly or indirectly through mineral processing such assintering process, in order to recycle the iron and carbon init. However, some companies sent it to cement plant asingredient or directly store it. These methods can’t obtainthe purpose of reasonable use of blast furnace dust resourc-es.4,5) Considering the cyclic economy, the blast furnace dustshould be regarded as precious secondary resources and gotfully comprehensive utilization and recycling.6) Applicationof blast furnace dust to RHF (Rotary Hearth Furnace) bri-quette is an effective and comprehensive utilization meth-od,7,8) however, RHF has a high standard of the materialstrength, a series of treatments such as drying, burden dis-tribution and discharging is necessary, the strength of mate-

rial in each part affect the smooth and efficient productionof RHF.9,10) Therefore, adding suitable binder to improvestrength of the briquettes is a key issue.

But there are less studies on binder that is suitable forblast furnace dust in China and abroad, and some researcheson binder in metallurgical field mostly focused on the ironore concentrate briquettes.11–13) Binder used in briquettingprocess can be divided into inorganic binder, organic binderand compound binder, and all of them have respectiveadvantages and disadvantages:14) (1) The inorganic bindersuch as bentonite has a long history and mature experienceof using it, and it has significant effect on the performanceof briquettes, however, due to it’s many impurities, theappropriate control of supplying amount is necessary, suchas the 1.5%–2.0% mass fraction of bentonite is appropriate.(2) Adding organic binder will not increase the content ofharmful elements in the briquettes, but its performance athigh temperature is poor, which has a great influence on thedecrepitation temperature of briquettes, and its price is high.(3) The use of compound binder can reduce the supplyingamount of inorganic binder, reduce the cost of briquettes,improve the quality of briquettes, and get better performanceof briquettes. Therefore, considering the development direc-tion of binder, organic binder15) andorganic-inorganiccompound binder16) has become the focus of research anddevelopment.

However, the effect of using these binders to produce thebriquettes made from blast furnace dust and quality assess-ment for production should be further discussion through

* Corresponding author: E-mail: [email protected]: http://dx.doi.org/10.2355/isijinternational.54.1781

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ISIJ International, Vol. 54 (2014), No. 8

experimental studies.In this study, the properties of blast furnace dust and bind-

ers have been investigated firstly. Based on which, theexperiments of the briquettes added binders were studiedthrough measuring the strength of green briquettes, driedbriquettes and briquettes after roasting. Then the bondingmechanisms of binders were discussed. This study will pro-vide theoretical and technical basis on economical and ratio-nal use of blast furnace dust.

2. Materials and Methods

2.1. Experiment Materials2.1.1. Blast Furnace Dust

Blast furnace dust used in the experiment were from aChinese steel plant. The chemical composition and mineralcomponent measured by X-ray diffraction of blast furnacedust is shown in Table 1 and Fig. 1, respectively. The par-ticle size is shown in Table 2. The blast furnace dust notonly contains T.Fe and C, but also contains some Zn, Pb, K,Na, etc. The content of Zn has reached more than 13%. Theparticle size of blast furnace dust is relatively fine, mass%of the dust under –200 mesh reached 62.75% and the aver-age particle size is 0.103 mm. In addition, the carbon con-tent is 32.21%, the carbon/oxygen is 1.8, and the carboncontent is extremely excess. Based on this, in order to makefull use of excess carbon in the blast furnace dust, 20% ofiron oxide should be added into the briquettes, and the car-bon/oxygen ratio is regulated to 1.2.

2.1.2. BinderIn order to detect the bonding properties of different bind-

er in the briquettes, three kinds of binders were used in thisstudyas shown in Table 3.

2.2. Experiment Methods2.2.1. Preparation of Briquettes

The flow chart of test process is shown in Fig. 2.At first, in order to remove the water in the materials,

blast furnace dust should be dried in an oven as seen in Fig.3(a) under the condition of 105°C for 12 h. After drying,blast furnace dust were mixed with a selected binder, ironoxide and water, then charged into the horizontal twinrolerforming machine (as seen in Fig. 3(b)) with the pressure as

Table 1. Chemical composition of the blast furnace dust used inthis study.

Component TFe MgO Al2O3 Zn Pb K Na C

(mass%) 32.54 1.31 1.78 13.02 0.84 0.52 0.21 32.21

Fig. 1. XRD patterns of blast furnace dust.

Table 2. Particle size of blast furnace dust.

Particle size (mesh) –200 100–200 +100 Average size

(mass%) 62.75 4.68 32.57 0.103 mm

Table 3. Category of binder.

Category Sample

Inorganic binder Bentonite Sodium silicate

Organic binder Corn starch Silicone resin Epoxy resin

Compound binder Composed of two binders at least

Fig. 2. The flow chart of test process.

Fig. 3. Photos of apparatus used in this study. a) drying oven b)horizontal twinroler forming machine c) high temperatureelectric resistance furnace d) compressive strength testapparatus.


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20 MPa. Diameter of formed briquettes was 30 mm. Finally,the green briquettes were dried in an ovenas seen in Fig. 3(a)at 200°C for 60 min for the next experimental process.

Roasting experiments were conducted in a high tempera-ture electric resistance furnace as seen in Fig. 3(c). Temper-ature was measured with a Pt-Pt/Rh thermocouple, whichwas placed inside the furnace. Dried briquettes were put intothe furnace and the experiment was started. When tempera-ture had reached the design value, the experiment finished.After finishing roasting process, roasted briquettes were nat-urally cooled to room temperature.

2.2.2. Testing of Mechanical Strength of BriquettesMechanical strength consists with compressive strength

of briquettes and falling strength of green and dried bri-quettes, twenty briquettes were used for testing the mechan-ical strength in each test. The value for mechanical strengthof every briquettes was recorded and used for average value.Compressive strength was measured by compressivestrength test apparatus as seen in Fig. 3(d). Falling strengthwas measured through counting the drop number. The bri-quettes were dropped on the 10 mm thickness steel platefrom the height of 0.5 m repeatedly, when crack or burstgenerated after drop, drop number is then obtained as thefalling strength.

2.2.3. Observation of Binders BehaviorIn order to identify the binding mechanism of different

binders, the behavior of binders in the heating process hasbeen observed by optical microscope. The drying oven hasbeen used for heating process in the lower temperaturerange (<200°C), and the high temperature electric resistancefurnace has been used for heating process in the relativelyhigher temperature range (>200°C). The photographs ofbinders behavior in different stages were obtained by usingan image analysis system. These results will be useful tomaster the bonding properties of binders at different temper-atures, and guide the determination of the collocation pat-tern.

3. Results and Discussion

3.1. Strength of Blast Furnace Dust Briquettes withSingle Binder

Bentonite, sodium silicate, corn starch, silicone resin, andepoxy resin were blended by 3% addition ratio respectivelywith blast furnace dust and iron oxide. Strength of the greenbriquettes, dried briquettes and the briquettes after roastingat high temperature were measured. The comparison ofcompressive strength of the briquettes at room temperature,200°C and 1 000°C is shown in Fig. 4, and the fallingstrength of the briquettes at room temperature and 200°C isshown in Fig. 5, The comparison of compressive strength ofthe briquettes after roasting at 1 100°C, 1 200°C and1 250°C is shown in Fig. 6.

From the result of the experiment, the falling strength andcompressive strength of the briquettes without binder arevery poor, so does the compressive strength of briquettesafter roasting at high temperatures, which can not meet therequirement of production (The requirement of productionare as follows: falling strength is above 3 times, compres-

sive strength of green and dried briquette is above 40 N, andthe compressive strength of roasted briquette is about1 800 N). However, the strength of the briquettes can beimproved by using every binder.

At room temperature, the compressive strength of the bri-quettes used binder is more than 40 N and the fallingstrength is more than 4 times. The adhesive effect of corn

Fig. 4. The influence of single binder addition to the briquettes oncompressive strength at different temperatures.

Fig. 5. The influence of single binder addition to the briquettes onfalling strength at different temperatures.

Fig. 6. The influence of single binder addition on compressivestrength of roasted briquettes at different temperatures.

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starch is relatively better, the compressive strength and fall-ing strength indices are 72 N and 5.9 times, which is theresult from good viscosity of corn starch. It makes the blastfurnace dust particles bonding closer, so the strength is rel-atively high. Silicone resin and epoxy resin have a relativelysmall improvement of the strength of the green briquettes,and the effect of the epoxy resin is relatively better. Theimprovement of strength is mainly result from the goodbonding strength of the two kinds of resin binder. The effectof bentonite and sodium silicate for strength of the bri-quettes is not obvious, this is mainly determined by theproperties of the binders and the blast furnace dust.

When the temperature reaches 200°C, water evaporates,bonding properties of organic matter decreases, and thecompressive strength and falling strength of the briquettesis generally lower, considering the adhesive effect, the bestis starch, then is epoxy resin, and the silicon-containingbinder has a relatively small effect.

Above 1 100°C, the reduction reaction of iron oxidesstarted, the metallization rate of the briquette increased, andthe strength increased. Adding bentonite, silicone resin andsodium silicate binder can get a relatively high strength ofthe briquettes, which resulted from the framework role ofsilicon. Sodium silicate can promote the reduction of bri-quettes, so the strength of the briquettes is higher than oth-ers. The corn starch and epoxy resin have the property ofhigh temperature volatile, which makes the strength of thebriquettes is relatively low. Although using the single bindercan enhance the compressive strength of the roasting bri-quettes, the strength is lower than 1 800 N, and it is hard tomeet the production requirement.

Therefore, different binders play the different role, starchbinders can improve the low temperature strength of the bri-quettes, the silicon-containing binders can improve the hightemperature strength of the briquettes, in order to make fulluse of the advantages of all kinds of binder, the starch bind-ers should be used accompanying with silicon-containingbinder to develop the appropriate compound binder.

3.2. Strength of Blast Furnace Dust Briquettes withCompound Binder

In order to make surfficient use the characteristics of eachbinder, bentonite, sodium silicate, corn starch and siliconeresin were choosen to combine compound binder,17) and theinfluence on the strength of the briquettes were studied. Thepercentage of compound binder is 3%, There combinationsof compound binders were made as fallows.

A: corn starch (2/3) + silicone resin (1/3)B: corn starch (2/3) + sodium silicon (1/3)C: corn starch (1/3) + sodium silicon (1/3) + bentonite (1/3)The compressive strength of the briquettes added com-

pound binder at room temperature, 200°C and 1 000°C isshown in Fig. 7, the falling strength of the briquettes atroom temperature and 200°C is shown in Fig. 8, the com-pressive strength of the briquettes at 1 100°C, 1 200°C and1 250°C is shown in Fig. 9. The experimental samples areindicated by the English letters thatrepresent the compoundbinder.

From the experimental results, the compound binder caneffectively improve the strength of the briquettes.

At room temperature, the compressive strength of the bri-

quettes added compound binder is more than 55 N, and fall-ing strength is more than 5.3 times, especially the briquettesadded compound binder of corn starch and silicone resin,whose compressive strength is 66 N and falling strength is5.8 times.

After drying at 200°C, because of water evaporates andlow bonding properties of the carbon, the falling strength

Fig. 7. The influence of compound binder addition to briquettes oncompressive strength at different temperatures.

Fig. 8. The influence of compound binder addtion to briquettes onfalling strength at different tempertures.

Fig. 9. The influence of compound binder addition on compressivestrength of roasted briquettes at different temperatures.


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and compressive strength of the briquettes decrease, thecompressive strength of the briquettes added compoundbinder is more than 54 N, and the falling strength is morethan 2.9 times.

Under the condition of high temperature, the frameworkrole of silicon-containing compound binder is obvious,which makes the strength of the briquettes greatly improved,especially the compressive strength of the briquettes addedcorn starch and silicone resin or sodium silicate compoundbinder has been improved relatively larger, the strength isabout 2 000 N. This is because the iron oxide in the bri-quettes have been reduced in great quantities at the hightemperature, the connection between the particles becomesthe connection between the metal iron or iron whisker, andsilicone resin has excellent bonding strength and superiorthermal oxidation stability and the effect of the silica frame-work, which makes the briquettes added silicone resin-containing compound binder obtain a higher compresivestrength. At the same time, sodium silicate promotes thereduction, so the carbon-containing briquettes added sodiumsilicon-containing compound binder gets high metallizationrate, the compressive strength of the briquettes is relativelyhigh due to the close bond between the metal irons.

In a word, strength of the briquettes added compoundbinder is greatly improved. But the price of bentonite andsodium silicate is relatively low, and the price of siliconeresin is relatively high. Considering economy and strengthof the briquettes, the excellent collocation pattern is the cornstarch and sodium silicate.

3.3. Strength of Blast Furnace Dust Briquettes withDifferent Binder Proportion

The different binder proportion affected strength of thebriquettes. the appropriate proportion of corn starch andsodium silicate compound binder has been studied throughthe determination of strength. And results were shown inTable 4.

From the experimental results, the compressive strengthand falling strength of the briquettes increase with increas-ing the binder proportion. When the binder proportion ismore than 2%, the comprehensive strength of greenbriquettes is above 54 N, and the falling strength of greenbriquettes is above 5.5 times; After drying, the briquettescomprehensive strength is above 46 N, falling strength isabove 3.1 times, and strength at high temperature reaches1 796 N, and all of these has met the mentioned requirementof production. Therefore, the appropriate proportion of cornstarch and sodium silicate compound binder is 2%.

3.4. The Bonding Mechanism of BindersAccording to the experiments results, different binders

have different function. The binders, such as corn starch andepoxy resin, can improve the strength of the briquettes atlow temperature, and the silicon-containing binder canimprove strength of the briquettes at high temperature.Based on these facts, the two better binders selected in thisstudy are sodium silicate and corn starch, and the bondingmechanisms are investigated.

3.4.1. The Mechanism of Sodium Silicate Addition1) The Mechanism of Enhancement of Solid Phase BondingThe general chemical formula of sodium silicate is

Na2O·mSiO2·nH2O, where m is called the modulus,18) themolar ratio of SiO2 to Na2O, n means moisture content ofsodium silicate. In this study, m=2.3, n=9.

Appropriate sodium silicate and water are blended toblast furnace dust, a layer of sodium silicate bond film willbe formed on the blast furnace dust particles surface19)

(silicate bond film), and the blast furnace dust particles areconnected by this film, which improves strength of the bri-quettes at room temperature. However, the amounts of sodi-um silicate are relatively small, the bond film is very thin,and the range of the increased strength is also relativelysmall. With the increase of temperature, sodium silicatecondensation20) and water evaporation, sodium silicate sep-arates out the silica acid gel after dewatering and hardeningas shown in Fig. 10.

Newborn gel particles have intensive activity, they willenter the briquettes and block capillary pores inside the bri-quettes, and the connection between blast furnace dust par-ticles is enhanced by the silica acid gel particles. However,the briquettes lose water after being heated, and the cohesivestrength between carbon particles has decreased, which lead

Table 4. Strength of blast furnace dust briquettes with different binder proportion.

Binderproportion

Room temperature 200°C Compressive strength/N

Compressivestrength/N

Falling strength/times

Compressivestrength/N

Falling strength/times 1 000°C 1 100°C 1 200°C 1 250°C

1% 49 5.3 44 2.7 51 286 779 1 295

2% 54 5.5 46 3.1 66 338 1 053 1 796

3% 60 5.5 55 3.4 78 484 1 187 1 958

4% 67 5.7 62 3.7 102 521 1 272 2 018

5% 72 6.0 69 4.0 134 572 1 315 2 072

Fig. 10. Schematic diagram of gel particle formation.18)

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to the loose of briquette structure, and a relatively smallrange of the strength increase. Even the strength of bri-quettes is lower than the strength at room temperature asshown in Fig. 11.

More Si–OH bonds exist in the silica acid gel, with highertemperature, dehydration and condensation take placebetween Si–OH bonds, and form a reticular formation of Si–O–Si bond, which is a three-dimensional structure of thecuring system with excellent water resistance.21) Curingreaction under the condition of heating is as follows:

... (1)

NSi(OH)4→[Si(OH)4]m→ ..... (2)

Si–O–Si bonds generated between silica acid gel particlesafter the curing reaction have the effect of connection bridge(negative ion connection bridge), connect the gel particlesand mineral particles into a complex reticular formation,make the structure of briquette more compact, thus improvethe strength of briquettes. Under the condition of high tem-perature, silica acid gel can be dried, and K, Na, Pb, Zn andother elements in the briquettes volatilized, but strength ofthe briquettes also be improved because of the existence ofhigh temperature resisting silicon and its reticular formationas shown in Figs. 12 and 13.

2) The Mechanism of Promotion of ReductionSodium silicate is comprised of ionic compound, and the

sodium ions have good hydrophilicity. Therefore the sodiumions will leave the original position when contact with aque-ous solution, and the water molecules take the originalplace, and the displacement reaction starts. In weak alkalineenvironment, sodium silicate forms bond film of silicic acid[nSi (OH)4], thus sodium ions can promote the curing ofsodium silicate.

In the process of briquettes reduction, due to a small sizeof the sodium ion, the free sodium ions can easily spread tothe blast furnace dust particles and enter into the lattice ofFe3O4, and the amount of sodium ions will be increased

Na O nSiO n H O NaOH nSi OH2 2 2 42 1 2⋅ + + → +( ) ( )

Fig. 11. Structure of sodium silicate.

Fig. 12. Change of sodium silicate in bonding process.

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when FexO generates in the reduction process.22) In this pro-cess, the sodium ions can greatly promote the spread of ironions inside the blast furnace dust, which promotes the twotransformation reactions, such as Fe3O4→FexO andFexO→Fe. With the progress of reduction reaction, the num-ber of sodium ions entered into the lattice is growing, so thereduction process of FexO→Fe is promoted more greatly.

The metallization rate of the briquettes with sodium sili-cate as binder and without sodium silicate after roasting athigh temperature is shown in Table 5.

From the experimental results, sodium silicate is conduc-tive to the promotion of metallization rate of the briquettes.Compared with the pallets without sodium silicate, the met-allization rate increased by 4.6%. In addition, more ironoxide was reduced to metallic iron due to the increase ofmetallization rate, so does the strength of briquettes.

3.4.2. The Mechanism of Corn Starch AdditionThe general chemical formula of corn starch is

[(C6H10O5)n]. And corn starch has semi-crystalline particlestructure, the internal area is non-crystalline area, while theouter area is crystallized area. At the same time, the high rel-ative molecular mass of corn starch and the close reticularformation generated from hydroxyl synthesis by hydrogenbond result in large viscosity.23)

The bonding mechanism of corn starch is shown in Figs.14 and 15. In the mechanical blending process, due to theeffect of mechanical force, the crystal structure of cornstarch has been destroyed. The degree of lattice ordering ofcrystal in crystalline area reduces gradually, which creates agood fluidity of corn starch.

After adding water, corn starch granules swell, and vis-cosity increases, so the briquettes get a high strength at roomtemperature. With an increase of temperature, the lattice ofcorn starch granular in crystalline area is broken gradually,so the non-crystalline area becomes larger. When the tem-

perature reaches gelatinization temperature, corn starchgranules unceasingly expand, the volume can reach severaltimes or dozens of times of the original volume. Due to theexpansion of the particles, the crystal structure disappeared,the volume swelled, corn starch became the translucent andsticky liquid. The gelatinization of starch can produce alarge number of hydrogen bond with high activity, that’s thereason why the water absorption of starch has increasedsince the gelatinization process. In the compound binder ofcorn starch and sodium silicate, hydrogen bonds enter intothe sodium silicate, and accelerate the dehydration conden-sation reaction of sodium silicate, then strength of the bri-quettes improve greatly.

With the temperature rising, the water molecules enterinto the corn starch, combine with starch molecular and startirreversible swell. When the temperature reaches 110°C, thegelatinization complete, the original morphological struc-ture of corn starch granules are broken and the intermolec-ular interaction is weakened, so the compatibility betweenthe corn starch granules and blast furnace dust particlesincrease, density and strength of the briquettes areimproved.

After 200°C corn starch gradually transform into a con-tinuous solid connection bridge, which connected the blastfurnace dust particles closely, and strength of the briquettesincreases. With the temperature rise further, the element Pb,Zn, etc. in the briquettes begins to evaporate, Metallic ironbegins to generate gradually, and holes in briquette surfacebecome larger, the solid connection bridge between blastfurnace dust particles gradually evaporates. When thetemperature above 1 000°C, the solid connection bridge dis-appears gradually and strength of briquettes decreased.Therefore, the corn starch is very hard to improve thestrength of the briquettes at high temperatures.

4. Conclusions

(1) Without binder, the strength of RHF briquette madefrom blast furnace dust both after dried and roasted is verylow, so they can’t meet the requirements of the production,thus the binder for the briquettes need to be developed.

(2) The different binder plays the different role, corn

Fig. 15. Bonding mechanism of Corn Starch.

Table 5. The metallization rate of briquettes.

With sodium silicate Without sodium silicate

metallization rate (%) 78.4 73.8


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starch binders can improve the low temperature strength ofthe briquettes, the silicon-containing binders can improvethe high temperature strength of the briquettes. Therefore,the starch binders should be used accompanying with sili-con-containing binder to develop the appropriate compoundbinder.

(3) The compound binder can make full use of theadvantages of all kinds of binder, consequently it can greatlyimprove the strength of green briquettes, dried briquettesand roasted briquettes. The excellent collocation pattern ofcompound binder is the corn starch and sodium silicate, andthe appropriate proportion is 2%.

(4) At low temperature, sodium silicate generates bondfilm and separates out silica acid gel particles, whichenhances the strength of briquettes. And the gel particlesand blast furnace dust will be connected with each other likereticular formation through the Si–O–Si bonds generatedfrom silica acid gel particles at high temperature, which isthe key of cured bonding effect. Besides, Na+ diffuses intothe crystal lattice of Fe3O4 and improves the reduction pro-cess of iron oxides. Simultaneously, it’s conducive to thefurther increasing of strength of the briquettes.

(5) Corn starch can improve the briquettes strength atroom temperature and the strength after drying because ofthe expansibility after absorbing water, viscosity and com-patibility after gelatinization of corn starch. After 200°Ccorn starch gradually transform into a continuous solid con-nection bridge, which connected the blast furnace dust par-

ticles closely. But when the temperature above 1 000°C, thesolid connection bridge disappears gradually and strength ofthe briquettes decreased.

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