Application of thermal analysis to study smelting reduction kinetics

A thermal analysis study on the reduction of iron oxide rich slags under different conditions is presented in this paper. The effects of important process variables such as time, temperature, lime-silica ratio, FeO level in slag etc. are discussed. It is shown that the mechanism of reduction by externally added graphite is different from that by a carbon saturated bath although the activation energy values are similar.     

Characterization of thermal diffusion of polystyrene in binary mixtures of THF/dioxane and THF/cyclohexane

The thermal diffusion coefficient (D_τ) was determined for three polystyrene standards of different molecular masses in binary mixtures of tetrahydrofuran/dioxane and tetrahydrofuran/cyclohexane of various compositions. The D_τ values were obtained by combining retention data from thermal field-flow fractionation measurements with diffusion data from dynamic light scattering experiments. In agreement with earlier work of Schimpf and Giddings, the thermal diffusion coefficient was found to be virtually independent of the molecular mass of the polymers. In the binary mixtures of tetrahydrofuran and dioxane, both good solvents for polystyrene, the D_τ value was approximately equal to the average of the D_τ values in the pure solvents, weighted according to the mole fractions of the solvents in the mixture. However, for polystyrene in binary mixtures of tetrahydrofuran and cyclohexane this linear behavior of the thermal diffusion phenomenon was not observed. The addition of cyclohexane to tetrahydrofuran has initially only a minor effect on the molecular and thermal diffusion coefficients of the polystyrene standards. Because cyclohexane is a theta solvent for polystyrene, the preferential solvation of polystyrene by tetrahydrofuran could be an explanation for these results. © 1996 John Wiley & Sons, Inc.     

Application of thermal analysis to study of phase composition changes in blast furnace sinters

Application of thermal analysis to determine a quantity portion of iron oxides in symmetric blast furnace sinters is presented. In the multicomponent sample, calcium ferrites and many silicate phases beside doped iron oxides phases were observed. The dependence of sinter phase composition from basicity and relation with physicochemical properties is defined.     

Techniques of thermal analysis applied to the study of cultural heritage

It is increasingly important that chemistry reaches people who have not studied directly this field of science but that, daily, have practices where chemistry is involved in various extents. This is what happens, for instance, in the activities related with the study and the preservation of cultural heritage. In this sense, the present work is a short review of the particular case of techniques based on the thermal analysis and calorimetry applied within the context of the characterization of art and archeological objects, exemplified by various case studies, as the characterization of mortars, preparatory grounds, ancient painting materials and drying oils.     

Advances in nano thermal analysis of coatings

This article discusses AFM-based localized thermal analysis of crosslinked polymer coatings based on a recent breakthrough in nanoscale thermal probe technology. The addition of a thermal tip to a conventional AFM adds a new and valuable capability of spatially resolved thermal analysis to the AFM. It is particularly useful for thin films since it enables the measurement of transition temperatures (melting (T _m) or glass (T _g)) on selected regions of the sample aiding in the identification and characterization of phases on the length scales approaching macromolecular dimensions. Examples include the monitoring of the softening point of automotive clearcoat systems, as a function of cure time and cure temperature and characterization of degradation and embrittlement of weathered acrylic-polyurethane coatings. Comparison of nano thermal analysis with bulk DSC and MDSC is made and its inherent advantages over DSC in analyzing surfaces, is demonstrated.     

Differential thermal analysis of montmorillonite

The paper provides an overview of publications on the DTA of montmorillonites (in the temperature range 20–1100°C), starting with the first experiments of Le Chatelier (1887) and ranging up to the present. Consideration is given to the dehydration, dehydroxylation, amorphization and rehydration of montmorillonite (42 references).     

盐酸二甲双胍的毛细管电泳法快速测定

建立了毛细管电泳高频电导法快速测定片剂中盐酸二甲双胍的方法。考察了缓冲溶液、有机溶剂添加剂、毛细管长度以及分离电压和进样条件等因素对分离检测的影响。在最佳条件下5.0 min内即可实现盐酸二甲双胍分离检测,盐酸二甲双胍的线性范围为1.50μg/mL~130μg/mL,检出限为1.0μg/mL。该方法成功地测定了盐酸二甲双胍片剂中的盐酸二甲双胍。     

Calorimetric study and thermal analysis of berberine sulphate

The heat capacities of berberine sulphate [(C₂₀H₁₈NO₄)₂SO₄·3H₂O] were measured from 80 to 390 K by means of an automated adiabatic calorimeter. Smoothed heat capacities, H _T-H _298.15 and S _T-S _298.15 were calculated. The loss of crystalline water started at about 339.3±0.2 K, and its peak temperature was 365.8±0.6 K. The peak temperature of decomposition for berberine sulphate was at about 391.4±0.4 K by DSC curve. TG-DTG analysis of this material was carried out in temperature range from 310 to 970 K. TG and DSC curves show that there is no melting in the whole heating process. This revised version was published online in August 2006 with corrections to the Cover Date.     

The thermal behaviour of high-molecular polyoxyethylene-urea binary mixtures

The thermal behaviour (from 20 to 500°C) of high-molecular polyoxyethylene-urea mixtures which formed a molecular complex was investigated by means of a derivatograph. Under the conditions of the investigation, there were no indications of an interaction between the thermal decomposition products and the initial components, or of new intermediates with a thermostabilizing effect. A linear coorelation was obtained between the mass loss at 250°C and the urea content of the mixture, which may be used to determine the urea content of similar mixtures.     

Application of heat pipe technology in thermal analysis of metals

Summary Thermal analysis has been used in foundry applications to assess the quality of the melt before casting. The high-end thermal analysis techniques such as DSC or DTA are expensive and not suitable for foundry applications. The Computer-Aided Cooling Curve Analysis (CA-CCA) method based on one thermocouple has been widely used as a batch process with poor control over heat extraction and cooling rates during solidification. A heat pipe apparatus has been developed as a thermal analysis tool. The apparatus can assess the melt quality more accurately, as well as, allow for better control of heating and cooling rates. Moreover, the solidification process can be modeled more accurately, and thus the casting parameters affecting the casting quality can be closely simulated and consequently controlled. In this paper the principles of a heat-pipe assisted thermal analysis system are highlighted. The advantages of the new system are described and the possibility of its adoption in melt assessments is discussed.     

Applications of thermal analysis in some solid-state reactions

TG-DTG-DTA has been used to characterize various isomers of CoCl₂·2(CH₃C₆H₄NH₂). Thermal analysis is further used to analyse the binary mixtures of these isomers. DTA recorded after different elapsed times follows the progress of reaction between cobalt chloride and benzocaine where progressively small endotherms are associated with starting materials. The application of thermal analysis to following the solid-solid reactions between metal acetates and 8-hydroxyquinoline was highlighted. The stoichiometry of such reactions was confirmed from the decrease in intensity of an endotherm as one increases the stoichiometry.Thanks are due to Drs. Keshav Chander, K. Kaur, Rajinder Singh and G. S. Chopra for helpful discussions and experimental work.     

Reactivity analysis of ammonium dinitramide binary mixtures based on ab initio calculations and thermal analysis

Ammonium dinitramide (ADN) is a promising high energy oxidizer for rocket propellants because it offers a good oxygen balance and has a significant energy content. As a result, ADN-based energetic ionic liquid propellants (EILPs) have been studied, based on ADN combined with urea and monomethyl ammonium nitrate (MMAN). The thermal decomposition of ADN in the condensed phase affects the combustion of both pure ADN and ADN-based EILPs; thus, it is important to understand the reactions of EILPs in the condensed phase. The present study assessed the reactivity of ADN mixtures in the condensed phase, focussing on hydrogen abstraction reactions with NO₂· formed from the thermal decomposition of ADN. The potential energy surfaces of these reactions were obtained using ab initio calculations. The effects of functional groups and of carbon chain length on hydrogen abstraction by NO₂· were examined. Mixtures of ADN with urea and acetamide (AA) as amide compounds, and with MMAN and monoethanol amine nitrate (MEAN) as nitrate salts, were examined. Thermal analysis was conducted to investigate the properties of these mixtures, using differential scanning calorimetry (DSC). The calculation results shows that AA and MEAN are more reactive with ADN than urea and MMAN, which is supported by the DSC data. Hydrogen abstraction by NO₂· is evidently an important condensed phase reaction in ADN mixtures, and substances having alkyl groups and longer carbon chains are more highly reactive.

     

Quantitative thermogravimetric analysis of binary mixtures

Thermogravimetric analysis is used to determine the amounts of Mg(OH)₂ and Mg(CH₃COO)₂in a mixture thereof. The application and suitability of different analysis methods are discussed. In the first method the mass losses in the temperature ranges as indicated by the decomposition of the pure compounds were used. Results obtained using these temperature ranges were unusable. The percentage mass losses due to the decomposition of Mg(OH)₂ and Mg(CH₃COO)₂ were then determined in a second method using the minimum in the derivative mass vs. temperature curves. The results obtained by this method compared well with the actual values for mixtures containing more than 15% magnesium acetate. The third method employed the total experimental mass loss of both decomposition reactions. The results obtained using this method compared well to the actual values, giving a R ² value of more than 0.99. This method of using the total mass losses can however only be used for binary mixtures that consist only of magnesium hydroxide and magnesium acetate. This revised version was published online in August 2006 with corrections to the Cover Date.     

Quantitative analysis of binary antioxidant mixtures

Quantitative analysis of individual inhibitors and their binary mixtures has been carried out. It has been established that the effect of binary mixtures (additive, synergistic or antagonistic) depends on the structure, concentration ratios and activity of their components. The conditions of the synergistic effect have been determined.

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Study of soils by thermal analysis

The study of soils is very important in the geological and geological engineering researches. A study of ten samples of soils was carried out by thermal analysis, and X-Ray Fluorescence Spectrometry to understand soil evolution in Angra dos Reis region, Rio de Janeiro State, Brazil. The sample collection sites were chosen based on geological characteristics, the soil layer thickness, the soil composition pattern, and whether or not it was moved either by erosion or by gravitational shifts. Because of the humid tropical climatic condition, natural soils tend to show great thickness of weathered mantles with formation of saprolites and saprolite soils. Kaolinite is an important secondary mineral which can be formed from many different minerals, like k-mica and k-feldspar and can be weathered to gibbsite. The results from TG/DTG and DTA indicated which soils had more weathering, and the same results were obtained by XRF, when silica/aluminum ratios from samples are compared with thermal analysis results.     

Emanation thermal analysis study of a sol-gel precursor for silica-titania waveguides

Emanation Thermal Analysis (ETA) was demonstrated as a tool for the characterization of microstructure changes of a sol-gel precursor for silica-titania layers deposited on the glass plate to be used as planar waveguides. Temperature ranges of 280-330 and 380-500°C, respectively, in which the densification of the layers took place, were determined by ETA under in situ conditions of the sample heating. Results of thermogravimetry were compared with the ETA data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Emanation thermal analysis study of brannerite ceramics for immobilization of hazardous waste

Brannerite based ceramics, designed as a matrix for immobilization of high level radioactive waste (HLW), was investigated from the viewpoint of microstructure changes and atomic transport properties caused by leaching of the ceramics at pH 2 and 11, respectively. Scanning electron microscopy (SEM) and emanation thermal analysis (ETA) techniques were used for this purpose. Surface morphology, microstructure changes and transport properties of both ‘as-leached’ and ‘as-prepared’ samples were compared and the effect of leaching on the thermal behavior of the ceramics samples heated in the temperature range from 20 to 1250°C was characterized. The mobility of radon in the brannerite ceramics was evaluated by mathematical modeling from ETA results. The thermal behavior of the non-leached brannerite ceramics sample and its natural analogue brannerite mineral was compared using the ETA. On leave from the Institute of Chemical Sciences, Faculty of Sciences, P. J. Ŝafárik University, 041 54 Koŝice, Slovak Republic     

Use of emanation thermal analysis to characterize thermal reactivity of brannerite mineral

Emanation thermal analysis (ETA) was used to characterize the thermal reactivity of amorphous brannerite mineral of general formula U_1–xTi_2+xO₆ (locality El Cabril, near Cordoba, Spain). It was demonstrated that on sample heating up to 880°C microstructure changes taking place in the sample were accompanied by the formation of new radon diffusion paths, followed by their closing up during the final transformation of amorphous to crystalline brannerite in the range 900–1020 °C. Relative changes in structure irregularities that served as radon diffusion paths during heating and subsequent cooling of the sample to temperatures of 300, 550, 750, 880, 1020 and 1130°C, respectively, were determined from the ETA results. Mass losses in temperature ranges of 230–315, 570–760 and 840–1040°C were observed by thermogravimetry. Mass spectrometry indicated the release of CO2 mainly due to the decomposition of minor carbon amount in the brannerite mineral sample.     

Thermal analysis of binary liquid crystalline mixtures

Two series of binary mixtures composed of bent shaped and rod like molecules are reported. The first star shaped bent core molecules were synthesized and used as a component of binary mixtures. The chiral rod like compounds having commensurable length with the arms of the bent core compounds have been chosen for these mixtures. The resulted compositions show various thermotropic liquid crystalline phases that are characteristic to both types of liquid crystalline materials. In case of mixing the rod like molecules to the bent core compound the B2, B7 and induced B1 phases have been observed. While using the star-shaped bent core and chiral rod like compounds in mixture, the paraelectric smectic A, ferroelectric smectic C* and orthogonal hexatic smectic B phases were preferred. The appearing mesophases were investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction methods.     

Dynamic thermal analysis of solid-state reactions

There are many reactions of interest in which one or more of the reactants belong to some solid phases. Modern thermoanalytical instruments can conveniently provide reaction kinetic data of high precision and accuracy, from which the underlying activation energyE may be derived in principle. Unfortunately, no best method yet exists for the derivation when the data have been collected with a programmed linear increase in sample temperature, unlike the case of isothermal measurements, which however suffer from experimental limitations [1]. Here we propose a method for extractingE from non-isothermal data, that promises general validity.