Thermal Analysis and X-ray Diffraction of Synthesis of Scheelite

Scheelite (calcium tungstate)is the product of one of the processing methods of wolframite by its roasting with calcium oxide or limestone or its fusion with calcium chloride, followed by acid processing of calcium tungstate with the formation of tungstic acid. Scheelite occurs in contact metamorphic deposits, hydrothermal veins and pegmatites. The present work illustrates a thermal analysis study of synthesis of scheelite by sintering of wolframite with calcite and sintering of tungsten oxide with calcite or calcium oxide using a derivatograph. The reaction products were identified microscopically and by using a Siemens Crystalloflex diffractometer. The DTA curve of sintering of wolframite with calcite shows the beginning of the reaction at 560°C with the formation of scheelite. The intensive formation of scheelite is represented by the medium and wide endothermic peak at 740°C. This is followed directly by a large and sharp endothermic peak at 860°C, representing the dissociation of unreacted calcite. The DTA curve of tungsten trioxide shows three thermal effects. The sharp exothermic peak at 320°C represents the oxidation of tungsten oxide content of lower valency. The endothermic peaks at 750 and 1090°C are related to polymorphic changes of tungsten trioxide. The beginning of its sublimation is observed at temperature higher than 800°C. The DTA curves of sintering of tungsten trioxide with calcite or calcium oxide indicate that the intensive formation of scheelite takes place by endothermic reactions at 660 and 545°C respectively. The medium and small endothermic peaks at 520 and 730°Con the DTA curve of tungsten trioxide with calcium oxide represent the dehydration of calcium oxide and the loss of carbon dioxide due to some carbonatization of calcium oxide with carbon dioxide from air, respectively. The produced scheelite is colorless in thin sections, has distinct cleavage (101), crystallizes in the tetragonal system in the form of tabular crystals and is optically positive. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal analysis of synthesis of wulfenite

A derivatograph was used in a thermal analysis study of the synthesis of wulfenite (lead molybdate) by the sintering of cerussite or lead oxide with molybdite. The reaction products were identified microscopically and by using a Siemens crystalloflex diffractometer. The DTA curves of mixtures of cerussite with molybdite show first the characteristic peaks of cerussite. The sharp endothermic peak at 300°C reflects the dehydration of hydrocerussite associated with cerussite. The endothermic peak at 350°C indicates the first step of cerussite decomposition, into PbO·PbCO₃, and that at 400°C indicates the second step of its decomposition, into lead oxide. The formation of wulfenite takes place at 520°C in an exothermic reaction. The medium endothermic peaks at 880 and 955°C reflect the melting and volatilization of unreacted lead and molybdenum oxides. The DTA curve of sintering of molybdite with lead oxide reveals the formation of wulfenite at 500°C. The melting and volatilization of unreacted lead and molybdenum oxides appear in only one large and sharp endothermic peak at 980°C.The resulting wulfenite is pale-yellow in thin section, and crystallizes in the tetragonal system, in the form of square tabular crystals, with distinct (011) cleavage.     

Thermal Analysis and X-Ray Diffraction of Roasting of Egyptian Molybdenite

Molybdenite is the main ore mineral for the molybdenum industry and the production of molybdenum. The industrial processing of molybdenite is based on its oxidized roasting to technical grade molybdenum oxide, followed by its purification by distillation or its ammonia leaching.The present work reports a thermal analysis study of the oxidized roasting of Egyptian molybdenite, using a derivatograph. The reaction products were identified microscopically and by using a Siemens Crystalloflex diffractometer.The DTA curves of the roasting of molybdenite show that its oxidation begins at 360–370°C, as indicated by the small exothermic peak at such temperatures. This is followed immediately by a large, wide exothermic peak with maximum at 510–520°C, representing the intensive oxidation of molybdenite. The medium endothermic peak at 795–800°C reflects the melting and sublimation of molybdenum oxide. The vigourous vaporization of molybdenum oxide and its boiling are associated with the large, sharp endothermic peak at 1150°C. This is accompanied by a large loss in mass (TG).The study includes calculation of the thermodynamic constants and the kinetics of the reaction of oxidation of molybdenite.The oxidized roasting of molybdenite results in the production of molybdenum oxide, which is the essential starting material of the molybdenum industry. The molybdenum oxide produced has the molybdite structure and crystallizes in the orthorhombic system in the form of elongated, thin, light-green crystals.This revised version was published online in November 2005 with corrections to the Cover Date.     

Formation of mullite,topaz and corundum

The influence of aluminium fluoride on the thermal behavior of quartz and the formation of topaz, mullite and corundum have been examined in the present work using the derivatograph. The products of sintering were identified microscopically and by using a Siemens Crystalloflex diffractometer. The DTA curves indicate the formation of topaz at 760°C and the formation of mullite at 1000°C using the theoretical amount of aluminium fluoride. The reaction between quartz and aluminium fluoride takes place in two distinct steps using 50% excess of aluminium fluoride. The first is marked by a large endothermic peak at 780°C, representing the formation of topaz and the second by a sharp endothermic peak at 960°C, representing its subsequent dissociation with the formation of corundum or alpha-aluminium oxide.     

Thermal behaviour of lignins extracted from different raw materials

The thermal degradation of lignins extracted from bagasse, rice straw, corn stalk and cotton stalk, have been investigated using the techniques of thermogravimetric analysis (TG) and differential thermal analysis (DTA), between room temperature and 600°C. The actual pyrolysis of all samples starts above 200°C and is slow. The results calculated from TG curves indicated that the activation energy, Efor thermal degradation for different lignins lies in the range 7.949–8.087 kJ mol^?1. The DTA of all studied lignins showed an endothermic tendency around 100°C. In the active pyrolysis temperature range, thermal degradation occurred via two exothermic process at about 320 and 480°C, and a large endothermic pyrolysis region between 375 and 450°C. The first exothermic peak represents the main oxidation and decomposition reaction, the endothermic effect represents completion of the decomposition and the final exothermic peak represents charring.     

Ethylenebisdithiocarbamate fungicides

DTA curves were run for the ethylenebisdithiocarbamate fungicides maneb, mancozeb and zineb in a nitrogen atmosphere. Zineb produces a curve quite different from the others, with weak endothermic peaks at 166°C, 252°C and 293°C. Maneb and mancozeb have a relatively strong endothermic peak at 185–190°C corresponding to carbon disulphide evolution and a weaker endothemic peak at 290°C corresponding to hydrogen sulphide evolution. Maneb samples and some mancozeb samples also had a minor endothermic peak at 235°C, but this peak was lost after solvent extraction, which proved that it was due to an impurity or impurities. Elemental sulphur was found in the extract and on mixing sulphur with mancozeb, the peak at 235°C made its appearance. There is no distinguishing feature between the DTA curves for maneb and mancozeb. The shapes of the curves are, within experimental limits, indistinguishable, which means that the temperatures and energies of decomposition are the same. The chemist is left with the question whether differences in structure between maneb and mancozeb should lead to different DTA curves.     

Physico-chemical behaviour of the carbonate rocks of Western Son Valley Region,India

The techniques of DTA and TG were employed to study the thermal characteristics of unfossiliferous carbonate litho-units, viz. Fawn dolomitic limestone (microdolsparite) and Rohtas limestone (micrite) belonging to the Vindhyan Supergroup (PreCambrian) of India. The DTA of Fawn dolomitic limestone displayed two successive endothermic peaks at 725° and 860° whereas only one endothermic change at 910° was recorded in the DTA curve of Rohtas limestone. It was confirmed by chemical analyses, TG, IR and X-ray diffraction studies that the two peaks in the first case are due to dissociation of CO₂ from magnesium and calcium lattice positions, while the sole peak in the second case is due to complete decarbonation. A tentative correlation between the thermal characteristics and structural changes of these carbonate rocks at various transition temperatures is presented.     

Thermal study of vermiculites and mica-vermiculite interstratifications

Simultaneous DTA-TG has been carried out on a set of natural vermiculite samples. Based on their dehydration behaviour the samples can be divided in two groups: (a) those with DTA endothermic peak temperatures at 140°–150°C and 240°–270°C (pure vermiculties) and (b) those with peak temperatures at 95°–115°C (vermiculite with mica or mica-vermiculite interstratifications). The low temperature at which the endothermic effect in group (b) appears is discussed on the basis of dilution due to the inert layers of mica, differences in chemical composition, and lowering of interlamellar water bond energy.     

Time and temperature-based study for the production of high T C phase by sol-gel technique in Pb-bscco system

The high T_C superconducting phase Bi₂Sr₂Ca₂Cu₃Ox (2223) in the Pb-BSCCO system has been produced by EDTA-gel processing using nitrate solutions. The precursor has heated in two stages, at 300 and 800°C each for 2 h, to avoid the burning of the important species involved in the final product. The effects of time (6 to 48 h) and temperature (845 and 855°C) on the formation of the 2223 phase have been studied by sintering the samples in air. Thermal analysis (TG/DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and a vibrating sample magnetometer (VSM) have been employed to investigate the powder produced at different stages of decomposition, oxidation and formation of sintered materials from the powders. The volume-fraction of the 2223 phase at 845°C increases with time, the maximum value of the 2223 phase was obtained at 120 h. It has been observed that the formation of the high T_C phase is remarkably enhanced at the temperature of the endothermic peak of the DTA curve. The best result has been obtained in the sample sintered for 24 h at the temperature 855°C (endothermic peak). This also indicated that at 855°C, the large volume-fraction of 2223 phase with T_C 113 K grew in short time and as the sintering time increased, it decomposed into the Bi₂Sr₂CaCu₂Ox (2212) phase and other phases.     

Thermal transformations of red wall tile pastes

This work focuses on the thermal and mineralogical transformations of red wall tile pastes. The pastes contain different amounts of calcareous and are prepared with Brazilian raw materials. Thermal transformations are evaluated by TG, DTG and DTA, dilatometric analysis, and X-ray diffraction. Four endothermic transformations were identified and interpreted as the release of physically adsorbed water, dehydration of hydroxides, dehydroxylation of kaolinite, and decomposition of carbonate. An exothermic transformation within the 925–950°C range is associated to crystallization of new phases such as calcium aluminosilicates and mullite. TG measurements indicate that the total mass loss of the pastes is dependent on the amount of calcareous addition. Dilatometric analysis indicates the onset of sintering at around 900°C, leading to shrinkage of the pellets. The thermal analysis results agree well with the X-ray diffraction.     

Research on historical bricks from a Baroque Church

Baroque bricks were investigated by DTA, TG, EGA, TDA, and XRD. The analyses showed that the brick consisted of dehydroxylated illite, quartz, and calcite. Dehydroxylation as a consequence of the former rehydroxylation was not found probably because of protection of the bricks by plaster. Between the temperatures 600 and 800 °C, (a) intensive mass loss in TG, (b) endothermic minimum in DTA, (c) intensive escape of CO₂ in EGA, and (d) contraction of the sample in TDA were observed. All these events belong to decomposition of calcite. As follows from these results, the maximum firing temperature was about 700 °C. The bricks have relatively high porosity ~43 % and specific surface area ~18.6 m² g^?1.     

Thermal analysis of eugenol,isoeugenol and their benzoic acid esters

Eugenol and isoeugenol were investigated by means of thermal analysis. It was observed that eugenol and isoeugenol have one characteristic endothermic effect at 260° and 290°C, respectively, and two exothermic effects in the temperature intervals 270°–590°C. The DTA curves of the benzoyl esters of eugenol and isoeugenol begin with endothermic effects at 70° and 95°C, respectively, which coincide with the melting points of these compounds.     

DTA study of the chlorination of fly ash and bauxite in the presence of carbon

The chlorination processes of fly ash and bauxite in the presence of carbon were studied by means of a gas-flow type DTA, X-ray analysis and SEM observation, and the reactivity of Al-compounds as their constituents was compared. In the case of fly ash, the exothermic peak due to the formation of AlCl₃ (mainly) and FeCl₃ appeared at about 790–920°C. The reactivity of Al estimated from the DTA peak temperature depended on the particle size, carbon content and preparation temperature of fly ash, and was much lower than that of bauxite. Fractional conversion of Al was about 60–70%, when fly ash (?300 mesh) was heated up to 900°C in Cl₂ at 5°C min^?1 of heating rate. In the case of bauxite, two exothermic peaks due to the chlorination of Fe and Al appeared at about 270 and 490°C, respectively. The chlorination of Al was completed at 550°C under the above conditions.     

A comparative study of the dehydroxylation process in untreated and hydrazine-deintercalated dickite

A dickite from Tarifa (Spain) was used to study the influence of the intercalation and the later deintercalation of hydrazine on the dehydroxylation process. The dehydroxylation of the untreated dickite occurs through three overlapping endothermic stages whose DTA peaks are centred at 586, 657 and 676°C. These endothermic effects correspond, respectively, to the loss of the inner-surface, the inner hydroxyl groups, and the loss of the water molecules, product of dehydroxylation process, which has been trapped in the framework of the dehydroxylated dickite. The intercalation of hydrazine in the interlayer space of dickite and the later deintercalation affect the dehydroxylation process. It occurs through only two endothermic stages which DTA peaks are centred at 575 and 650°C. The first corresponds to the simultaneous loss of both the inner and the inner-surface hydroxyl groups, whereas the second one is analogous to that at 676°C observed in the DTA curve of untreated dickite. These effects appear shifted to lower temperatures compared to those observed in the untreated dickite.     

Curing mechanism for phenol—formaldehyde resins

A pressure DTA method was used to study the curing of resins. The hardening of novolacs by hexamine was studied at pressures up to 5000 kg/cm². The application of the pressure DTA method to the thermal curing of some dioxymethylated para-substituted phenols indicates that the endothermic peak observed at about 75°C at ambient pressure is due to the superposition of two peaks due to melting of the substance and formation of ester bonds.     

A novel process for making alkaline iron oxide nanoparticles by a solvo thermal approach

In the present work alkaline iron oxide nanoparticles are synthesized by a novel solvo thermal approach and characterized exhaustively by various complementary techniques. Field emission scanning electron microscopy (FESEM) studies reveal that the size of nanoparticles is in the range of 31.5 nm to 96.9 nm. Energy-dispersive X-ray spectroscopy spectral analysis reveals the presence of oxygen, carbon, iron, and sodium. The X-ray diffraction studies confirm the formation of tetragonal NaFeO₂ as the major phase along with orthorhombic NaFeO₂·H₂O and rhombohedral FeCO₃ (siderite) as the minor phases. Fourier transform infrared spectroscopy exhibits peaks due to the stretching and bending vibrations of O-H, C=O, CH₃-N, CH₃, C-H, C-N, and Fe-O groups. Differential scanning calorimetry (DSC) results display an endothermic peak at 100.85°C and a very small endothermic peak at 791.56°C with 819.73 mJ and 349.28 mJ energies respectively. These DSC peaks can be correlated with thermal gravimetric analysis (TGA) peaks representing 31.04% weight loss and 7.70% weight loss respectively in the sample at around 160°C and 980°C respectively.     

Sintering of kaolinite with ammonium fluoride

The present work represents a study of the influence of ammonium fluoride on the thermal behaviour of kaolinite by using a derivatograph. The sintering of kaolinite with ammonium fluoride was found to be complicated. Different products of sintering are obtained, depending on the temperature and the amount of ammonium fluoride. They were identified microscopically and by using a Siemens Crystalloflex diffratometer. These include an ammonium aluminium fluoride complex, cryptohalite, aluminium fluoride, mullite, topaz and corundum. The DTA curves (using kaolinite and ammonium fluoride mixes of ratio 1:1) indicate the formation of the ammonium aluminum fluoride complex and cryptohalite at 120–280°C and the appearance of aluminium fluoride, topaz and mullite at 640°C. The intensive formation of topaz takes place at 750°C and its subsequent dissociation at 940°C with corundum formation. The very small endothermic peak at 1010°C represents the formation of mullite. In experiments using mixes of kaolinite—ammonium fluoride in the ratios 1:1 and 1:1.3 the end-product of sintering consists of corundum and mullite. When using mixes of the ratio 1:1.7, aluminium fluoride constitutes the main composition of the end-product.     

Identification of some sweetening agents by thermal analysis

The thermal behaviours of some artificial sweetening agents — sodium cyclamate, saccharine and sorbitol — were studied by means of a complex thermal method. The quite different thermal behaviours of the different sweeteners are utilized for their identification. An endothermic peak is seen in the DTA curve at about 386° and 94° for saccharine and sorbitol, respectively, which is not accompanied by a weight loss. In the case of sodium cyclamate a characteristic exothermic peak followed by an endothermic one is detected. A semiquantitative method for the determination of sodium cyclamate is described.     

Thermoanalytical study of organs of spontaneous hypertension rats

The thermal behavior of the kidney, heart and liver of spontaneous hypertension rats (SHR) were studied by thermogravimetry (TG) and differential thermal analysis (DTA). SHR are, by far, the most widely used rat model in the study of heart diseases in mammals, because they develop chronic hypertension, which leads to heart failure during their lives. TG curves showed two steps for all samples: at 800°C less residues remained for an SHR kidney (4.0±1.8%) than for an SHR heart (6.9±0.4) and liver samples (7.5±1.9%). It probably happened due to the presence of inorganic substances such as iron, calcium, magnesium, potassium and sodium. DTA curves depicted three endothermic events for kidney (70, 120 and 310°C), heart (85, 250 and 300°C) and liver samples (70, 250 and 310°C), indicating protein denaturation, as well as protein degradation and fat degradation, respectively. TG/DTG/DTA profiles of organs samples showed peculiarities that permit correlation between them. These methods might serve as a simple alternative to investigations over these vital organs.     

Thermal evolution of a slate

The thermal evolution of a slate rock sample (Berja, Almería, Spain) has been studied. The phase minerals identified in this sample were mica (illite), chlorite (clinochlore) and quartz as major components, with minor microcline, iron oxide and a mixed-layer or interstratified phase (montmorillonite-chlorite). This slate is highly silico-aluminous (48.33 mass% silica, 22.04 mass% alumina), and ca. 20 mass% of other elements, mainly Fe₂O₃ (8.35 mass%), alkaline-earths and alkaline oxides. Two main endothermic DTA effects, centered at 640 and 730°C, were observed. The more important contribution of total mass loss (7.15 mass%) was found between 500–900°C, with two DTG peaks detected at 630 and 725°C. All these effects were associated to the dehydroxylation of structural OH groups of 2:1 layered silicates mixed in the slate. The dehydroxylation of the layered silicates evidenced by dilatometry, produced a rapid increase of expansion between 600–800°C. The thermal evolution of the slate upper 800°C indicated the first sintering effects associated to shrinkage, which is also favoured by its low particle size (average 23 μm) and the presence of a liquid or vitreous phase as increasing the heating temperature. The application of thermal diffractometry to the slate sample allowed to study the formation of dehydroxylated crystalline phases from the layered silicates after heating. At 1000°C, β-quartz, dehydroxylated illite, iron oxide, relicts of microcline and the vitreous phase were present in the sample. All these results are interesting to know the thermal behaviour of a complex mineral mixture as identified in the slate.