Thermal stability of Ag-exchanged clinoptilolite rich mineral

Thermal stability of clinoptilolite rich mineral from Western Anatolia, Turkey and its Ag-exchange forms was investigated. Parent mineral of different sizes were heated up to 1000°C with heating rate of 2 and 10°C min^-1 using differential thermal analyzer (DTA) and thermogravimetric analyzer (TG). Ag exchange was conducted both in conventional constant temperature waterbath and microwave at 40, 60 and 80°C. The exchanged minerals were then characteized by scanning electron microscopy (SEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), DTA and TG. The particle size and heating rate do not have significant effect on the thermal behavior of the parent mineral and no structural changes were observed with Ag exchange, only decomposition temperature was lowered. It was finally concluded that, Ag-exchanged clinoptilolite rich minerals were less thermally stable compared to parent mineral that does not affect their use for possible applications.     

Thermal diffusivity and electrical conductivity of electropolymerized polypyrrole films

This article presents measurement of thermal diffusivity and electrical conductivity of polypyrrole films prepared by electropolymerization. Thermal diffusivity was measured by laser radiometry (former flash radiometry). Electrical conductivity was determined by a conventional four-probe method. Increase of thermal diffusivity is observed when increasing the supporting electrolyte concentration, which is also shared with the increase of electrical conductivity. Both thermal diffusivity and electrical conductivity significantly depended on the types of counter anion incorporating into polymer bulk. Thermal diffusivity of polypyrrole film is larger than that for common nonelectrical conductive polymers. Temperature profile of thermal diffusivity for as-grown polypyrrole films shows that thermal diffusivity increases with increasing temperature (first running profile), whereas remeasured temperature profile of thermal diffusivity (second or third running profiles) shows the decrease of thermal diffusivity with increasing temperature. Electrical conductivity monotonically increases until the significant decrease of it occurs at the temperature above 130°C. Investigation of these temperature profiles of thermal diffusivity and electrical conductivity has been made by corresponding to thermal analysis data. © 1994 John Wiley & Sons, Inc.     

Effect of grinding on thermal reactivity of ceramic clay minerals

The effect of grinding on thermal behavior of pyrophyllite and talc as commonly used ceramic clay minerals was investigated by DTA, TG, emanation thermal analysis (ETA), B.E.T. surface area (s.a.) measurements, X-ray diffraction (XRD) and scanning electron microscopy (SEM). A vibratory mill was used in this study, grinding time was 5 min. It was found that the grinding caused an increase in surface area and a grain size reduction of the samples. From TG and DTA results it followed that grinding caused a decrease of the temperature at which the structure bound OH groups released. The formation of high temperature phases was enhanced with the ground samples. For the ground talc sample the crystallization of non-crystalline phase into orthorhombic enstatite was observed in the range of 800°C. For ground pyrophyllite a certain agglomeration of grains was observed in the range above 950°C. Moreover, for both clays the ETA characterized a closing up of subsurface irregularities caused by grinding as a decrease of the emanation rate in the range 250–400°C. The comparison of thermal analysis results with the results of other methods made it possible to better understand the effect of grinding on the ceramic clays.     

Effects of vapor‐phase‐formaldehyde treatments on thermal conductivity and diffusivity of ramie fibers in the range of low temperature

To understand the influence to thermal conductivity by bridging in the polymer fibers, the thermal conductivity, and thermal diffusivity of ramie fiber and those bridged by formaldehyde (HCHO) using vapor‐phase method (VP‐HCHO treatment) were investigated in the lower temperature range. The thermal conductivities of ramie fiber with and without VP‐HCHO treatments decreased with decreasing temperature. Thermal diffusivities of ramie fiber with and without VP‐HCHO treatments were almost constant in the temperature range of 250–50 K, and increased by decreasing temperature below 50 K. Thermal conductivity and thermal diffusivity of ramie fiber decreased by VP‐HCHO treatment. The crystallinities and orientation angles of ramie fibers with and without VP‐HCHO treatment were measured using solid state NMR and X‐ray diffraction. These were almost independent of VP‐HCHO treatment. Although tensile modulus decreased slightly by VP‐HCHO treatment, the decrease could not explain the decrease in thermal conductivity and diffusivity with decreasing sound velocity. The decrease of the thermal diffusivity and thermal conductivity by VP‐HCHO treatment suggested the possibility of the reduction of the mean free path of phonon by HCHO in VP‐HCHO treated ramie fiber. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2754–2766, 2005     

Effect of the modifier ion on the properties of MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript> and ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> pigments

Magnesium and zinc ferrites have been prepared by the polymeric precursor method. The organic material decomposition was studied by thermogravimetry (TG) and differential thermal analysis (DTA). The variation of crystalline phases and particle morphology with calcination temperature were investigated using X-ray diffraction (XRD) and scanning electronic microscopy (SEM), respectively. The colors of the ferrites were evaluated using colorimetry. Magnesium ferrite crystallizes above 800°C, presenting a yellow- orange color with a reflectance peak at the 600–650 nm range, while zinc ferrite crystallizes at 600°C, with a reflectance peak between 650–700 nm, corresponding to the red-brick color.     

Thermal study of calcium silicate material synthesized with solid wastes

This work focuses on the thermal characterization of a calcium silicate-based material synthesized with different solid wastes (chamotte and marble) for use as thermal insulation material. Thermal and structural changes occurring during heating were accompanied by differential thermal analysis, thermogravimetric analysis, dilatometric analysis, open photoacoustic cell technique, X-ray diffraction (XRD), and scanning electron microscopy. An endothermic event at 823.2 °C was interpreted as decomposition of carbonates. An exothermic event around 900 °C is associated with the crystallization of calcium silicate phases mainly wollastonite. The themophysical properties of the calcium silicate-based material (thermal diffusivity, thermal conductivity, specific thermal capacity, and thermal effusivity) are influenced by the synthesis temperature. The thermal analysis results agree well with the XRD. The calcium silicate pieces presented low thermal conductivity values (0.227?0.376 W m^?1 K^?1). These results suggest that the calcium silicate-based materials produced essentially with chamotte and marble wastes has high potential to be used as thermal insulation construction material.     

Thermal conductivity and thermal diffusivity of poly(acrylic acid) by transient hot wire technique

The paper describes a new transient hot wire instrument which employs 25.4 μm diameter tantalum wire with an insulating tantalum pentoxide coating. This hot-wire cell with a thin insulating layer is suitable for measurement of the thermal conductivity and the thermal diffusivity of electrically conducting and polar liquids. This instrument has been used for experimental measurement of the thermal conductivity and the thermal diffusivity of poly(acrylic acid) solution (50 mass%) in the temperature range of 299 to 368 K at atmospheric pressure. The thermal conductivity data is estimated to be accurate within ±4%. Thermal diffusivity measurements have a much higher uncertainty (±30%) and need further refinement.     

A comparative study on the thermal decomposition of some transition metal carboxylates

Thermal decomposition of transition metal malonates, MCH₂C₂O₄?xH₂O and transition metal succinates, M(CH₂)₂C₂O₄?xH₂O (M=Mn, Fe, Co, Ni, Cu, Zn) has been studied employing TG, DTG, DTA, XRD, SEM, IR and Mössbauer spectroscopic techniques. After dehydration, the anhydrous metal malonates and succinates decompose directly to their respective metal oxides in the temperature ranges 310–400 and 400–525°C, respectively. The oxides obtained have been found to be nanosized. The thermal stability of succinates have been found to be higher than that of the respective malonates.     

Analysis of glass fiber reinforced cement composites and their thermal and hygric material parameters

Methods of thermal analysis are employed in a study of the high-temperature properties of three different types of glass fiber reinforced cement composites together with the measurements of their thermal and hygric parameters. First, basic TG and DTG measurements are carried out to get the first insight into the high-temperature behavior of the analyzed materials. Then, mercury porosimetry and scanning electron microscopy of specimens subjected to the temperatures of 600 and 800°C are performed and compared to the reference specimens not exposed to any thermal load. Finally, measurements of thermal and hygric parameters of the studied materials are done and matched with the results of the material characterization experiments. Three main effects are found to influence the thermal and hygric properties of the analyzed materials. The first is the decomposition of the cement matrix, which is clearly a negative factor. The second is the positive effect of the presence of fibers that could partially keep the cement matrix together even after significant decomposition of cement hydration products. The third important factor affecting the thermal and hygric properties is the composition of the particular materials. The application of vermiculite aggregates instead of sand is found to be clearly positive because of its porous character leading to the bulk density decrease without worsening the other properties. Also, wollastonite aggregates are a better choice than sand because of its fibrous character that could partially magnify the effect of fiber reinforcement. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal behaviour of synthetic pyroaurite-like anionic clay

Thermal behaviour of synthetic pyroaurite-like anionic clay with molar ratio Mg/Fe=2 was studied in the range of 60-1100°C during heating in air. TG/DTA coupled with evolved gas analysis, emanation thermal analysis (ETA), surface area measurements, XRD, IR and Mössbauer spectroscopy were used. Microstructure changes characterized by ETA were in a good agreement with the results of surface area measurements and other methods. After the thermal decomposition of the pyroaurite-like anionic clay, which took place mainly up to 400°C, a predominantly amorphous mixture of oxides is formed. A gradual crystallization of MgO (periclase) and Fe₂O₃ (maghemite) was observed at 400-700°C by XRD. The MgFe₂O₄ spinel and periclase were detected at 800-1100°C. The spinel formation was also confirmed by Mössbauer spectroscopy.     

Thermal anomaly in LiKSO4 crystals in the temperature range 300–800 K

Thermal analysis, DTA, TG, TMA and DSC were performed on LiKSO₄ in the temperature range 300 to 800 K, using a Heraeus TA 500 thermal analyser. The thermal expansion coefficients measured along the three fundamental crystallogrpahic axes, together with the specific heatC _p, show anomalous behaviour around the phase transition temperature of these crystals atT _c=705 K. Anisotropy in the thermal expansion coefficient as well as endothermic peaks aroundT _c were also observed, while no loss of weight was detected. The temperature-dependence of the thermal conductivity of LiKSO₄ crystals has been estimated, using the temperature-variation of the thermal diffusivity.     

Investigations on growth, thermal, electrical, and etching studies of KCl-doped triglycine sulfate single crystals

Single crystals of pure triglycine sulfate (TGS) and potassium chloride (KCl)-doped TGS with different concentrations (0.2, 0.4, 0.6, and 1?mol%) were grown from aqueous solutions by natural evaporation process at room temperature. Thermal stability of the grown crystals was investigated by differential thermal analysis (DTA) and thermogravimetric (TG) studies. DTA curve shows a lower decomposition temperature for KCl-doped TGS crystal than that of pure TGS crystal. The dielectric properties of pure TGS and KCl-doped TGS crystals were performed in the frequency range of 1?C500?kHz at 30?°C and this study showed that the dielectric constant was increased due to KCl concentration. DC electrical conductivity measurements were made in the temperature range from 35 to 100?°C and showed that the DC conductivity was increased with the increase of temperature as well as doping concentrations of KCl. The etching feature of the surface of the grown crystals was studied in water etchant.     

Influence of hydrothermal curing regimes on the hydration of fiber-reinforced cement composites

Simultaneous thermal analysis (DTA and TG) was applied to two fiber-reinforced cement composites cured in autoclave at 0.3, 1.2, and 2.0 MPa for 24, 72, and 168 h. Mercury intrusion porosimeter (MIP) and scanning electronic microscope (SEM) were used to complete the investigations. Thermal analysis was used to identify temperature ranges of thermal decomposition of cured samples and to characterize the nature of hydrate products. Also, fractured surface and surface microstructure were investigated by means of SEM. Based on the results of thermal analysis, three processes occurred during hydrothermal curing. The first one consists of primary hydration reaction leading to the formation of C–S–H, C₃AH₆, and AH₃. The second one is the process characterized by partial decomposition or interaction of primary products to form secondary products (C₂ASH₈, C₃AH_1.5). The last one is the carbonation of some hydrate products. Hydrothermal pressure can enhance the compressive strength, but can also cause its depletion over time. The MIP study has revealed an existence of bimodal pore size distribution that the characteristic depends on the hydrothermal curing conditions.     

Synthesis and thermal decomposition of ditetrazol-5-ylamine

Ditetrazol-5-ylamine (DTA) was synthesized from cyanuric chloride in four steps. The thermal decomposition of DTA in the solid state was studied by thermogravimetry, volumetry, mass spectrometry, IR spectroscopy, and calorimetry. Under isothermal conditions at 200–242 °C, thermal decomposition obeys the first order autocatalytic kinetics. The kinetic and activation parameters of DTA decomposition were determined. The composition of gaseous reaction products and the structure of condensed residue were studied. The thermal effect of thermal DTA decomposition is 281.4 kJ mol⁻¹. The nitrogen content in a mixture of gaseous products formed by the reaction in a temperature interval of 200–242 °C exceeds 97 vol.%. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1660–1664, July, 2005.     

A study of sulphonated and oxidized coals by thermal analysis

Earthy and xylytic brown coals from Poland have been sulphonated with 98% sulfuric acid at temperatures of 60°, 90° and 140°C. The main exothemic peak shifts to higher temperatures with increase in sulphonation reaction temperature whereas overall weight loss to 1000°C decreases. DTA curves of earthy and xylytic coals sulphonated at higher temperatures are similar, even though DTA curves of the unmodified coals differ appreciably. Thermal decomposition of earthy coal oxidized by nitric acid follows a different pattern. Nitric acid causes oxidation and depolymerization of the organic components and this is reflected in the shapes of DTA and TG curves of oxidized coals. As the nitric acid concentration and reaction temperature increase, the main exothermic peak shifts to lower temperatures (from 330°C for basic coal to 270°C for coal oxidized with 30 and 50% nitric acid). The weight loss is higher for oxidized coal than for coal unmodified by nitric acid.     

Defect mode and crystal-electric-field effects on the thermal expansion and heat capacity of RB<Subscript>50</Subscript> boride

This study aimed to evaluate the suitability of using unfired and fired pumice as cement replacement materials as well as their effect on the thermal resistance of hardened ordinary Portland cement (OPC) pastes. Different OPC–pumice (unfired and fired) blends were prepared by partial replacement of OPC by 0, 10 and 20 of pumice (mass%). The effect of the addition of 1 and 5 % of active alumina on the mechanical properties and thermal resistance of different OPC–pumice (unfired) blends was investigated. The fire resistance test was done by exposing the hardened blended cement cubes to elevated temperatures of 200, 400, 600 and 800 °C for 3 h and allowed them to cool down to room temperature before testing for their mechanical properties. The phase composition and thermal analysis of some selected specimens were investigated by XRD, DSC and DTA/TG techniques. The obtained results indicated that replacing OPC by 10 and 20 % by pumice (unfired and fired) improved its thermal stability at different firing temperatures. The cement blend prepared by replacement of OPC with 10 % pumice showed the highest fire resistance. The addition of 1 and 5 % of alumina (A) to OPC–pumice blends causes a notable improve in their mechanical properties and thermal resistance.     

Thermal behaviour of ground vermiculite

Thermal behaviour of natural vermiculite (Santa Olalla, Huelva, Spain) was investigated by TG, DTA, emanation thermal analysis (ETA) and high temperature XRD on heating in the temperature range from 30 to 1100°C before and after vibratory mill grinding. Microstructure changes of natural and ground vermiculite samples were characterized by using ETA under in situ conditions of heating. By comparing the ETA and XRD results it was demonstrated that a decrease of radon release rate measured by ETA characterized the decrease in the interlayer spacing of the vermiculite samples that followed the dehydration. Dedicated to the memory of Professor Dr. Ferenc Paulik who passed away on October 12, 2005.     

Effect of iron-containing catalysts on thermal decomposition of cured GAP-AP propellants

The effects of various burning rate catalysts on thermal decomposition of cured glycidyl azide polymer (GAP)-ammonium perchlorate (AP) propellants have been studied by means of thermal analysis and a modified vacuum stability test (MVST). Four types of iron-containing catalysts examined in this paper are catocene, ferrocenecarboxaldehyde (FCA), ferrocene, and ferric oxide. Results of differential thermal analysis (DTA) and thermogravimetric analysis (TG) revealed that the catalysts play an important role in the decomposition of both AP and GAP. The peak decomposition temperature (T _m) of DTA curves and onset decomposition temperature (T _o) of TG patterns considerably shifted to a lower temperature as the concentration of catalysts increased in the propellants. The endothermic temperature of AP, however, is unaffected by the presence of burning rate catalysts in all cases. The activation energy of decomposition of the propellants in range of 80 to 120°C is determined, based on the MVST results.     

Thermal analysis at the evaluation of concrete damage by high temperatures

Summary Concrete damage by high temperatures includes mass loss, strength and modulus reductions and the formation of cracks and large pores. Thermal treatment reduces the amount of chemically bound water in the hydrate phase. With a rise in temperature, the spatial distribution of Ca(OH)₂ crystals becomes more compact; smaller crystals occur in a unit volume of the cement paste. A rise in temperature affects the pore structure by reducing the specific surface of hydration products. Cement paste becomes more heterogeneous in microstructure and coarser in pore structure. Compressive strength is not only significant parameter showing structural integrity of concrete; permeability influences concrete durability as well. To demonstrate this, permeability coefficients at various high temperatures are presented. The key quantitative insight into the hydrate phase behavior is based on thermal analysis results. Thermogravimetric (TG) mass losses are related to the phase changes represented either by DTA or DTG. Based on these, the tests employing TG mass losses and related DTA and DTG curves answer the question if the hydrate phase is present at individual high-temperature levels and what its quantitative state is. Method of thermal analysis is suitable for the interpretation of concrete behavior when subjected to high-temperature attack. Conclusions are drawn about thermal stability and residual properties of concrete specimens made at the construction site of Mochovce nuclear power plant (Slovakia); and subjected to temperatures up to 800°C. Relations among mechanical properties, permeability, pore median radius and bound water content in concrete are discussed and evaluated.     

Synthesis of Ultrafine Cobalt Ferrite by Thermal Decomposition of Citrate Precursor

Ultrafine particle of CoFe2O4 has been synthesized using citrate precursor technique. Thermal decomposition of the citrate precursor, Co3Fe6O4(C6H6O7)8·6H2O, was investigated by TG, DTA and DTG techniques, gas and chemical analyses and was found to decompose in one or two major steps depending on the heating rate in static/flowing air atmosphere. In the lower heating rate (5°C min-1), metastable acetonedicarboxylate complex was isolated with the evolution of CO gas and coordinated water molecule in the temperature range of 120-220°C. Complete decomposition of the citrate network occurs between 220-330°C with the simultaneous evolution of CO2 and acetone. However both these steps appeared as simultaneous and/or single step process (between 120-160°C), when the heating rate is high (10°C min-1 and above). The ultrafine CoFe2O4 particles are observed as the aggregates having surface area 133.8 m2 g-1 composed of 4.8 nm crystallites. The citrate precursor and the decomposed products were characterized by IR, NMR, XRD, SEM and surface area measurements. This revised version was published online in July 2006 with corrections to the Cover Date.