Thermoanalytical study of the formation of compounds in the PbO−MO (M=Ca,Sr, Ca+Sr) system

In order to clarify the effect of PbO addition on the formation steps of the superconducting phases in the system Bi₂O₃?SrO?CaO?CuO, a study of solid-state reactions under non-isothermal conditions, in the PbO?MO (M=Ca, Sr, Ca+Sr) system has been carried out. Results suggest that the reactivity of the components in the system containing PbO and CaO is much higher than in the system containing SrO. The Ca₂PbO₄ compound is formed first even in the system whereM=Ca+Sr. It is confirmed that Ca₂PbO₄ systems containing PbO.     

Thermogravimetric study of the nonstoichiometric regions in the Y-Ba-Cu-O system

The paper presents the results of studies on thermal reduction and oxidation of the nonstoichiometric phases from the Y-Ba-Cu-O in air.The thermogravimetric (TG, DTA) experiments were performed in air in order to establish the ranges of stoichiometry and temperature of oxidation and reduction of YBa₂Cu₃O_x, YBa₄Cu₃O_x, YBa₅Cu₂O_x and Y₃Ba₈CusO_x.It has been found, that at 950°C in air there are four oxygen deficient ternary cuprates: YBa₂Cu₃O_6.02, YBa₄Cu₃O_8.01, YBa₅Cu₂O_8.35, Y₃Ba₈Cu₅O_16.45 and stoichiometric Y₂BaCuO₅. When these nonstoichiometric cuprates are cooled slowly to room temperature in air they oxidize to the following compositions: YBa₂Cu₃O_6.98, YBa₄Cu₃O_8.97, Y₃Ba₈Cu₅O₁₈ and YBa₅Cu₂O_8.97.This work has been supported by the CPBR 6.6.64 research programme.     

The ternary system propyl propanoate+ hexane+chlorobenzene at 298.15 k

Differential thermal analysis shows many interesting properties that allow for prompt finding the place (p,T) and characteristics (endothermic, exothermic) of a phase transition or chemical reaction. In application to reactive sintering under active gas atmosphere at high pressure despite of numerous technical problems encountered during DTA measurements we found its unique possibilities. That allows for quantitative estimation of nitrogen involved in reaction of phase transition from the hexagonal phase to the cubic phase of MoN, and vice versa, in high gas pressure condition. DTA high gas pressure measurement system has the maximum operate temperature 2000°Cat pressure 2 GPa. This revised version was published online in August 2006 with corrections to the Cover Date.     

Studying the ash behaviour of agricultural residues using thermal analysis

In this paper, the ash behaviour of some typical Mediterranean agricultural residues, such as peach stones, cotton gin wastes and grape residues is studied via simultaneous, (DTA/TG), thermal analysis methods. Furthermore, the effect of various pre-treatment techniques, such as fractionation and leaching, on the ash behaviour of the specific residues is also studied. Fractionation improves some of the main biomass properties such as calorific value, volatiles and ash content but deteriorates significantly the ash chemical composition of the remaining ash fraction. Leaching improves both the main properties of the treated biomass samples and the chemical composition of the remaining ash fraction, while the combination of the two pre-treatment methods results in a merge of their main advantages leading to an even larger improvement of the ash thermal behaviour. This revised version was published online in July 2006 with corrections to the Cover Date.     

Investigations on the ternary system Ag-P-S and thermal behaviour of the compounds

Parts of the ternary system Ag-P-S were investigated by DTA- and X-ray measurements. The quasibinary section of Ag₂S-P₄ S₁₀ is described. The thermal behaviour and X-ray diffraction patterns of Ag₇PS₆, Ag₃PS₄, Ag₇P₃S₁₁, Ag₄P₂S₇ and Ag₂P₂S₆ were studied. DTA-diagrams and X-ray powder data are given.

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Zusammenfassung Mittels DIA- und Röntgendiffraktionsmessungen wurden Teile des Dreikomponentensystemes Ag-p-s untersucht. Es wird der quasibinäre Schnitt von Ag₂S-P₄ S₁₀ beschrieben. Weiterhin wurden das thermische Verhalten und die Röntgenbeugungsbilder von Ag₇PS₆, Ag₃PS₄, Ag₇P₃S₁₁, Ag₄P₂S₇ und Ag₂P₂S₆ untersucht. DTA-Diagramme und Röntgen-Pulverdaten werden gegeben.

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Ag-P-S. Ag₂S-P₄S_IO. $ Ag₇PS₆, Ag₃Ps₄, Ag₇P₃S_II, Ag₄P₂S₇ Ag₂P₂S₆. .

     

Investigation of refractory oxides by high-temperature DTA

Aim of this work in connection with the development of materials in the periclase-forsterite-zirconia system was the determination of melting temperature and melting enthalpy of refractory compounds. The possibility of determination of the melting and solidification of minor phases in refractory materials should be proved.The forsterite melting enthalpy was determined equal 783 J/g with a standard deviation of 22 J/g.The addition of zircon to periclase leads to the formation of an eutectic MgO-ZrO₂-Mg₂SiO₄ melt. 1750°–1755°C was determined as its solidification temperature. Cooling leads to the crystallization of forsterite and cubic-ZrO₂ from the melt.

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Zusammenfassung Ziel dieser Arbeit ist die Bestimmung von Schmelztemperatur und Schmelzenthalpie der feuerfesten Verbindungen in Verbindung mit der Entwicklung von Substanzen im System Periklas-Forsterit-Zirkonerde. Es sollte die Möglichkeit zur Bestimmung von Schmelzen und Erstarren von Minor-Phasen in feuerfesten Substanzen geprüft werden.Die Schmelzenthalpie von Forsterit wurde mit einem Wert von 783 J/g und einer Standarddeviation von 22 J/g ermittelt.Der Zusatz von Zirkonerde zu Periklas führt zur Bildung einer eutektischen MgO-ZrO₂-Mg₂SiO₄-Schmelze, deren Erstarrungstemperatur mit 1750°–1755°C ermittelt wurde. Beim Abkühlen kristallisieren aus der Schmelze Forsterit und kubisches ZrO₂ aus.

     

Devitrification of Nd3+-doped glasses in the akermanite-gehlenite system

The devitrification of glasses in the akermanite-gehlenite system [(C₂Al_2?2yMg_ySi_1+yO₇ (0≤y≤1)] doped with Nd³⁺ (2% mol) has been studied. DTA was used to determine the kinetics of the process. The Avrami law α=1-exp(?kt ⁿ) withn=1 was found to hold for doped gehlenite. For pure gehlenite, parametern was determined to be 1.5. The activation energy of the devitrification process is independent of the presence of neodymium, and it is of the same order of magnitude as that for the viscous flow in molten silicates (ca. 650–750 kJ·mol^?1).     

Fusion temperatures and enthalpies of high-temperature materials determined by differential thermal methods

The temperature and enthalpy of fusion of silver were measured in a differential thermal analyzer with gold and aluminum as reference materials. The measurement procedures and the data calibration (or correction) procedures used successfully in our laboratory for differential scanning calorimetry were applied. The experimental fusion temperature, (1233.9±1.0)K, and enthalpy, (108.4±3.3) J·g⁻¹, are compared with the assigned value of temperature for the IPTS-68 scale, 1235.08 K, and with a value for enthalpy, 110.75 J·g⁻¹. Work done at the National Institute of Standards and Technology. Not subject to copyright.     

The thermal analysis of polymers at high pressures

The extension of two techniques of thermal analysis into the region high pressures (50–100 MPa) are discussed. One is the extension of dilatometry (thus becoming pressure-volume-temperature measurements, PVT). This technique has been well established over the past few years. Some results obtained on typical polymer systems are presented and discussed. The second is the extension of the differential thermal analysis (DTA) principle to high pressures, trying to maintain some of the advantages of the DTA technique when compared to the PVT method, such as small sample size and productivity. DTA determinations of the pressure dependence of the melting points of pure metals and polymers are presented and compared with results from the PVT technique. Satisfactory agreement is obtained. The advantages and limitations of our current high-pressure DTA method are discussed.We gratefully acknowledge the partial financial support of the high-pressure DTA development by Metler Instrumente AG, Switzerland.     

Reinvestigation of system CdO-V<Subscript>2</Subscript>O<Subscript>5</Subscript> in the solid state

As a result of solid-state reactions three cadmium vanadates(V) have been obtained, i.e. CdV₂O₆, Cd₂V₂O₇ and Cd₄V₂O₉. Melting temperature and the product of melting has been determined for Cd4V2O9. Thermal properties of the obtained cadmium vanadates(V) have been reinvestigated. The phase equilibria being established in the CdO-V₂O₅ system over the whole components concentration range up to the solidus line were described.     

High-temperature behaviour of lithium borates:: Part I: Characterization and thermal stability

Nine compounds, namely Li₃BO₃, -Li₄B₂O₅, β-Li₄B₂O₅, Li₆B₄O₉, -LiBO₂, Li₂B₄O₇, Li₃B₇O₁₂, LiB₃O₅ and Li₂B₈O₁₃ in the Li₂O–B₂O₃ system have been synthesized and characterized. The unit-cell parameters, density and solubility in water at room temperature of all the compounds are reported. The densities of the compounds were found to be in the 1.90–2.50 g cm⁻³ range, while their solubility in water at room temperature was in the 0.91–8.64×10⁻² g cm⁻³ range. Determination of the thermal stability of the compounds by quenching and differential thermal analysis (DTA) showed that only -LiBO₂ and Li₂B₄O₇ retained their original symmetry up to their congruent melting at 1121 and 1188 K, respectively, in air.     

The preparation by a solid-solid interaction route of aromatic polyamide materials containing sulphone, ether and ketone linkages

The polycondensation reactions between 4,4-[sulphonyl bis(p-benzoyl)(p-phenyleneoxy)]dibenzoic acid (I) andp-phenylenediamine (II), 1,5-diaminonaphthalene (III), 4,4-sulphonyldianiline (IV), 4,4-diaminodiphenylsulphide (V) 4,4-methylenedianiline (VI) and 4,4-oxydianiline (VII) to form aromatic polyamides containing sulphone, ether and ketone linkages were attempted by a solid-solid interaction route. A stoichiometric 11 molar ratio of solid reactants was dynamically heated directly in a TG/DSC apparatus, and simultaneous TG/FT-IR was performed to interpret the mechanism of reaction. The results suggest that the polycondensation is dependent on the diamine used. The formation of polyamide was successful when I interacted with II, III, VI and VII. The interaction with IV and V was in part successful because partial decarboxylation of the diacid, made unstable by the diamine, occurred before the condensation reaction.     

The structure and thermal behaviour of sodium and potassium multinuclear compounds with hexamethylenetetramine

Sodium and potassium thiocyanate complex compounds of formulae [Na(hmta)(H₂O)₄]₂²⁺·2SCN⁻ (1) and [K₂(hmta)(SCN)₂] _n (2) have been synthesized and characterised by IR spectroscopy, thermogravimetry coupled with differential thermal analysis, elemental analysis and X-ray crystallography. Each sodium and potassium cation is six co-ordinated, the sodium by one monofunctional hmta molecule, three terminal water molecules and two bridging water molecules, and the potassium by two bridging tetrafunctional hmta molecules and four bridging tetrafunctional thiocyanate ions. The coordination polyhedra of the central atoms can be described as distorted tetragonal bipyramids. The complex cations and anions of (1) are interconnected by multiple intramolecular O(water)—H···N(hmta/NCS) and O(water)—H···S hydrogen bonds to the three dimensional net. In each complex cation the intramolecular O–H···O hydrogen bonds link two terminal water molecules bonded to two metal cations. The compound (2) forms the three dimensional hybrid network in which the classical two-dimensional coordination polymers are linked by inorganic SCN⁻ spacers to the third-dimension. Thermal analyses show that the compounds decompose gradually in three (for 1) and two (for 2) steps with formation of Na₂SO₄ and K₂S as the final products, respectively, for 1 and 2.     

Electrochemically driven three-phase interlines into insulator compounds: electroreduction of solid SiO2 in molten CaCl2.

The electrochemical reduction of solid SiO2 (quartz) to Si is studied in molten CaCl2 at 1173 K. Experimental observations are compared and agree well with a novel penetration model in relation with electrochemistry at the dynamic conductor|insulator|electrolyte three-phase interlines. The findings show that the reduction of a cylindrical quartz pellet at certain potentials is mainly determined by the diffusion of the O(2-) ions and also the ohmic polarisation in the reduction-generated porous silicon layer. The reduction rate increases with the overpotential to a maximum after which the process is retarded, most likely due to precipitation of CaO in the reaction region (cathodic passivation). Data are reported on the reduction rate, current efficiency and energy consumption during the electroreduction of quartz under potentiostatic conditions. These theoretical and experimental findings form the basis for an in-depth discussion on the optimisation of the electroreduction method for the production of silicon.     

The thermal decomposition of zirconium oxyhydroxide

The thermal decomposition of zirconium oxyhydroxides prepared by the mixture of aqueous zirconium oxychloride solutions and aqueous solutions of sodium hydroxide or ammonium hydroxide under various conditions has been examined by thermogravimetry, differential thermal analysis, X-ray diffraction study and infrared spectrophotometry. As a result, it is seen that the thermal decomposition of zirconium oxyhydroxide, in which the composition is ZrO_2-x(OH)_2xyH₂O where x2 and 1y<2, proceeds according to the following process:

Application of thermal analysis to the cement industry

Methods involving heat measurements have been applied in the cement industry for a long time. Differential thermal analysis (DTA) is used to explain the clinkering reactions, but it is a dynamic method which thus does not allow measurements and calculations of the thermal balance of the reactions to be made. In contrast, high temperature microcalorimetry may be used to measure the enthalpy of the clinkering reactions of industrial raw materials. Results obtained by using this technique allow us to determine the thermal profile of clinkering reactions in the kiln and to quantify the heat exchange in the solid material during its burning.Low temperature conduction microcalorimetry gives information on the hydration mechanism of the cement pastes. In this paper, we review the applications of thermal analysis in the cement industry paying special attention to new methods such as high temperature microcalorimetry.

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Zusammenfassung Seit langer Zeit werden in der Zementindustrie Verfahren mit Wärmemessung angewendet. Zur Erforschung der Verschlackungsreaktionen wird DTA verwendet, was jedoch ein dynamisches Verfahren ist und keine Messungen und Berechnungen bezüglich des thermischen Gleichgewichtes erlaubt. Im Gegensatz dazu kann Hochtemperatur-Mikrokalorimetrie zur Messung der Enthalpie von Verschlackungsreaktionen industrieller Rohstoffe dienen. Mit Hilfe der durch diese Methode erlangten Resultate kann das thermische Profil von Verschlackungsreaktionen im Kiln und der Wärmeaustausch im Festmaterial beim Brennen bestimmt werden.Niedertemperatur-Konduktions-Mikrokalorimetrie liefert Informationen über den Hydratationsmechanismus von Zementleim. Unter spezieller Beachtung neuer Methoden, wie z.B. der Hochtemperatur-Mikrokalorimetrie, wird in diesem Artikel ein Überblick über die Anwendungen der Thermoanalyse in der Zementindustrie gegeben.

     

Unknown thermal properties of ZnSb2O6 and Zn7Sb2O12 compounds

The investigations by XRD, DTA/TG and IR methods show that two compounds: ZnSb₂O₆ and Zn₇Sb₂O₁₂ are formed in the ZnO-α-Sb₂O₄ system in air. Oxygen contained in the air participates in the synthesis of these compounds. ZnSb₂O₆ was observed as an intermediate phase, during the Zn₇Sb₂O₁₂ synthesis. The temperature of the β→α-Zn₇Sb₂O₁₂ transition was fixed at 1225±10°C. The mechanisms of the reactions of ZnSb₂O₆ and Zn₇Sb₂O₁₂ thermal decomposition have been proposed. The IR studies of α and β-Zn₇Sb₂O₁₂ have initially indicated that the structures of both polymorphous forms differ in the reciprocal connection of the SbO₆ and ZnO₆ octahedra and the ZnO₄ tetrahedra.     

Influence of the heating conditions on the thermal and chemical behaviour of solid particles undergoing a fast endothermic decomposition

This paper deals with models describing the thermal and chemical behaviour of solid particles undergoing fast endothermic reactions under the influence of an external heat flux. The heat source temperature is supposed to be constant, to increase with time, or to deliver a simple thermal flash. It is shown that the pyrolysis conditions (reaction temperature, conversion, etc.) depend on the chemical characteristics of the reaction and also to a large extent on the external heating conditions. Relationships are proposed to take into account these parameters. The results are applied to the thermal decomposition of NaHCO₃. The pyrolysis of cellulose is finally chosen in order to show how these operating parameters can also affect the selectivity of a more complex reaction.     

The study of the dehydration and dehydroxylation of smectites by emanation thermal analysis

The dehydration and dehydroxylation of the smectites, beidellite and montmorillonite (dioctahedral) and saponite and laponite (trioctahedral), were investigated by ETA, DTA, TG and X-ray diffractions. There are differences between the behaviors of di- and trioctahedral clays which are due to the differences in the ability of the exchangeable cations to migrate into hexagonal holes of the SiO₄ network and due to the fact that the dehydroxylation and recrystallization of dehydroxylated trioctahedral smectites occur simultaneously, whereas there is a temperature gap of about 300°C between the dehydroxylation and the recrystallization of dioctahedral smectites.Dedicated to Dr. Robert Mackenzie on the occasion of his 75th birthdayThe authors wish to thank Laporte Industries, Inc. UK for the laponite sample.This research was supported under Project No. C12-219, Grant No. HRN5544 G002069, U.S.-IsraelCooperative Development Research Program, Office of the Science Advisor, U.S. Agency for International Development.     

The thermodynamic properties of alkali metal compounds at high temperatures

A research program has been in progress to obtain reliable thermodynamic data on various binary and ternary alkali metal compounds in the temperature range of 300 to 1500 K. To date, heat capacity measurements have been made on cesium and rubidium chromates, dichromates, zirconates, molybdates, dimolybdates, and halides in the temperature range of 300 to 800K. In addition, measurements are planned or are currently in progress on cesium and rubidium chalcogenides, aluminates, uranates, silicates, and several other lithium, sodium, and potassium compounds. The status of the research program is discussed.