A re-investigation of the thermal decomposition of ammonium paratungstate

The thermal decomposition of monoclinic ammonium paratungstate (APT) and amorphous ammonium metatungstate (AMT) has been studied over the temperature range 20 to 500° C using thermogravimetry, evolved gas analysis, X-ray diffraction analysis, differential thermal analysis and scanning electron microscopy. A mechanism of decomposition which postulates the formation and subsequent decomposition of various lower ratio tungstates is proposed and substantiated by the experimental data.     

Thermal decomposition of the ammonium zinc acetate citrate precursor for aqueous chemical solution deposition of ZnO

The thermal decomposition of an aqueous chemical solution deposition Zn²⁺-precursor is studied by HT-DRIFT (high temperature diffuse reflectance infrared Fourier transform spectroscopy), on-line coupled TGA-EGA (thermogravimetric analysis - evolved gas analysis by Fourier transform infrared spectroscopy (FTIR) and mass spectrometry (MS)), and HT-XRD (high temperature X-ray diffraction). Using these complementary techniques, it is found that the -hydroxyl group of the citrate ligand plays a significant role in the decomposition pathway of the ammonium zinc acetate citrate precursor. TEM (transmission electron microscopy) shows that crystalline ZnO (zincite) is formed at 390°C, after dehydroxylation of the -hydroxyl group and subsequent decarboxylation of the Zn²⁺-precursor complex. Before total calcination, ZnO particles are already formed and a residual organic backbone thereby remains. The results obtained by these complementary techniques clearly indicate the importance of thermal analysis in the preparation of ceramics through chemical solution deposition.     

Production of strontium-substituted lanthanum manganite perovskite powder by the amorphous citrate process

The amorphous citrate process has been used to produce Mn₂O₃, Mn₃O₄, LaMnO₃, SrMnO₃ and strontium-substituted LaMnO₃. The citrate-nitrate gels were dehydrated at 70 C to yield solid precursor materials. The decomposition/oxidation of the precursors have been studied using thermogravimetry and evolved gas analysis. The products of decomposition have been characterized by X-ray diffraction analysis, scanning electron microscopy and, in the case of the strontium-substituted LaMnO₃, by analytical electron microscopy. The surface area and residual carbon content of the strontium-substituted LaMnO₃ have been determined as a function of the decomposition/oxidation temperature. Both the process yield and compositional homogeneity of the strontium-substituted LaMnO₃ have been shown to increase as the decomposition temperature increases. The residual carbon content has been shown to decrease as decomposition temperature increases. However, the surface areas of the powders decrease significantly as decomposition temperature increases. Consequently, it is evident that there is a conflict in the experimental conditions required for optimum yield, homogeneity and residual carbon content compared to those required for maximum surface area.     

Thermal polycondensation of ammonium paratungstate, (NH4)10[W12O40(OH)2].4H2O

Connected with the examination of the thermal polycondensation of ammonium paratungstate pentahydrate the chemical and morphological properties of intermediate phases formed during the thermal decomposition of APT have been investigated. We have studied the pH and the turbidity of the aqueous solutions of the intermediate phases, the solubility of the phases, and their rehydratation capability as well as the morphology of the crystallite granules and the grain size distribution. These properties of the original APT have been related to the same properties of the products of decomposition formed between different temperature ranges. The results obtained show unambiguously that each of the above mentioned properties suddenly changes in the temperature range 225 to 250°C. This temperature range coincides with the formation temperature of a new phase called APT II. The most probable formula of APT II is (NH₄)₈ [H₂W₁₃O₄₃(OH)₂]·H₂O.     

Synthesis, characterization and catalytic activity of CdO nanocrystals

In this paper, we report the synthesis of nanocrystalline cadmium oxide (CdO) and its characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Its catalytic activity was investigated on the thermal decomposition of 1,2,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), ammonium perchlorate (AP), hydroxyl terminated polybutadiene (HTPB) and composite solid propellants (CSPs) using thermogravimetric analysis (TG), simultaneous thermogravimerty and differential scanning calorimetry (TG-DSC) and ignition delay measurements. Kinetics of thermal decomposition of AP + CdO has also been investigated using model free (isoconversional) and model-fitting approaches which have been applied to data for isothermal TG decomposition. All these studies show enhancement in the rate of decomposition of AP, HTPB and CSPs but no effect on HMX. The burning rate of CSPs has also been found to be increased with CdO nanocrystals.     

Carbonate release from carbonated hydroxyapatite in the wide temperature rage

Synthetic carbonated apatite ceramics are considered as promising alternative to auto- and allograft materials for bone substitute. The aim of this study was to investigate the thermal stability of an AB-type carbonated apatite in the wide temperature range. The data on the thermal stability have to allow the conditions of the sintering of the ceramics to be controlled. Initial carbonated apatite powders were prepared by interaction between calcium oxide and ammonium hydrogen phosphate with addition of ammonium carbonate. Decomposition process was monitored by infra red spectroscopy, weight loss and X-ray diffraction of solid, and by infra red analysis of condensed gas phase resulted from the thermal decomposition of the sample in equilibrium conditions. Features of carbon monoxide and carbon dioxide release were revealed. The synthesized AB-type carbonated apatite is started to decompose at about 400°C releasing mainly carbon dioxide, but retained some carbonate groups and apatite structure at the temperature 1100°C useful to prepare porous carbonate-apatite ceramics intended for bone tissue engineering scaffolds.     

Extrapure WO<Subscript>3</Subscript> for the preparation of CdWO<Subscript>4</Subscript> single crystals

A process has been developed for the preparation of extrapure WO suitable for crystal growth. The method involves thermal decomposition of ammonium paratungstate (APT) powder at 230–250° C, resulting in the formation of soluble ammonium metatungstate (AMT). The AMT solution is then purified and hydrolyzed. The resultant purified APT is converted to WO₃. The reaction yield is at a level of 95%. The contents of metallic impurities, especially those of polyvalent impurities (Fe, Mn, Cu, Pb, V, Cr, and others), capable of influencing the optical properties of crystals, was comparable to their detection limit: 10^?6 to 10^?5 wt %. The purification process was tested using a pilot-scale system. The purity was confirmed by the synthesis of high-quality CdWO₄ crystals.     

Some new aspects of the phase diagram of the NH 4 + /H+-W-O system

The phase composition of partially-reduced products of ammonium paratungstate (APT) was investigated. The samples were prepared by reducing the APT in a H₂ + N₂/129 volume ratio/atomosphere in the temperature range 610 to 860 K, and studied by means of chemical analysis, by X-ray diffraction analysis and by thermoanalytical methods. The reduction products can be described by the general formula of M _xWO_3–y+x/2 where M can be either H⁺ and/or NH ₄ ⁺ . Products considered as tungsten bronzes (TB) can be formed in a fairly narrow temperature range. Another product, the so-called decomposed APT (DAPT) is a mixture of bronzes and of some other compounds characterized by y/2 and considered as some intermediate phases between TB and tungstates.     

Preparation of CdS coatings on the inner surface of silica aerogels by single-source metal-organic chemical vapor deposition at atmospheric pressure

CdS coatings are deposited on the external and inner surfaces of silica aerogels with a single-source metal-organic chemical vapor deposition method at atmospheric pressure. Thermogravimetry analysis and differential scanning calorimetry experiments are used to investigate the thermal behavior of silica aerogels, and the sample treated at 500 °C for 120 min has been found to possess the lowest density. The densities and morphologies of the silica aerogels under the different treatment temperatures are also studied. The CdS coatings are deposited on the inner surface of the silica aerogels with a 4 l/min flow of Ar gas. The procedure for the preparation of the CdS coatings on the inner surface is reported in details. The surface morphologies of the CdS-coated silica aerogels are analyzed by scanning electron microscopy. The results of the energy dispersive X-ray spectroscopy and X-ray diffraction analysis demonstrate that the CdS coatings are composed of cadmium and sulphur with an approximately atomic ratio of 1:1, and they are hexagonal structures.     

The controlled reduction of copper tungstate in H2O/H2 mixtures

The controlled reductions of copper tungstate, copper tungstate plus blue tungsten oxide and CuO plus WO₃ have been studied at temperatures of 500, 600 and 700C using H₂/H₂O mixtures in a glass thermobalance. The copper-tungsten oxide composite powder products have been characterized by X-ray diffraction analysis and scanning electron microscopy. The morphologies of the copper-tungsten oxide products have been related to the morphologies of copper-tungsten powders obtained by dry hydrogen reduction. It is shown that widely varying copper-tungsten oxide morphologies may be obtained as precursors for metal powder production by control of the H₂/H₂O ratio in the reducing gas mixture.     

Hydrothermal synthesis and gas sensing properties of different titanate nanostructures

Anatase TiO₂ nanoparticles and other three different morphologies of titanate nanostructures such as nanotubes, nanosheets and nanowires were successfully prepared by hydrothermal method. The structures and morphologies of the final products were characterized with field-emission scanning electron microscopy (FE-SEM). Phase analysis was carried out using X-ray diffraction (XRD). A novel formation mechanism from anatase TiO₂ nanoparticles to titanate nanowires is proposed based on FE-SEM. The gas sensing properties to ethanol were also investigated. The results indicate that nanotubes, nanosheets, nanowires show much less resistance and larger response than nanoparticles.     

Thermogravimetry-evolved gas analysis-mass spectrometry system for materials research

Thermal analysis is a widely used analytical technique for materials research. However, thermal analysis with simultaneous evolved gas analysis describes the thermal event more precisely and completely. Among various gas analytical techniques, mass spectrometry has many advantages. Hence, an ultra high vacuum (UHV) compatible mass spectrometry based evolved gas analysis (EGA-MS) system has been developed. This system consists of a measurement chamber housing a mass spectrometer, spinning rotor gauge and vacuum gauges coupled to a high vacuum, high temperature reaction chamber. A commercial thermogravimetric analyser (TGA: TG + DTA) is interfaced to it. Additional mass flow based gas/vapour delivery system and calibration gas inlets have been added to make it a versatile TGA-EGA-MS facility. This system which gives complete information on weight change, heat change, nature and content of evolved gases is being used for (i) temperature programmed decomposition (TPD), (ii) synthesis of nanocrystalline materials, (iii) gas-solid interactions and (iv) analysis of gas mixtures. The TPD of various inorganic oxyanion solids are studied and reaction intermediates/products are analysed off-line. The dynamic operating conditions are found to yield nanocrystalline products in many cases. This paper essentially describes design features involved in coupling the existing EGA-MS system to TGA, associated fluid handling systems, the system calibration procedures and results on temperature programmed decomposition. In addition, synthesis of a few nanocrystalline oxides by vacuum thermal decomposition, gas analysis and potential use of this facility as controlled atmosphere exposure facility for studying gas-solid interactions are also described.     

Preparation of Mn2SnO4 nanoparticles as the anode material for lithium secondary battery

The ultrafine Mn₂SnO₄ nanoparticles with diameters of 5-10 nm have been prepared by thermal decomposition of precursor MnSn(OH)₆. The MnSn(OH)₆ nanoparticles precursor was synthesized by a hydrothermal microemulsion method. X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy and electron diffraction have been employed to characterize the crystal structures and morphologies of the as-prepared samples. High-resolution transmission electron microscopy observations revealed that the as-synthesized nanoparticles were single crystals. The thermal characterization was studied by differential thermal analysis and thermogravimetry analysis measurements. Electrochemical test showed that the Mn₂SnO₄ nanoparticles exhibited a high initial charge-discharge capacity of 1320 mAh/g.     

Meso/macroporous γ-Al2O3 fabricated by thermal decomposition of nanorods ammonium aluminium carbonate hydroxide

Through exploring the reaction parameters during the synthesis of the AACH, rod-like ammonium aluminium carbonate hydroxide (AACH) with high crystallinity has been successfully prepared via a facile hydrothermal method. The synthesis parameters like time, the molar ratio of NH₄HCO₃/Al and the properties of starting materials were systematically investigated. The structure was characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), IR and transmission electron microscopy (TEM). The experimental results display that the obtained γ-Al₂O₃ materials possess meso/macroporosity and large pore volume, which are mainly attributed to the removal of gas molecules during the decomposition of AACH. Moreover, using the rod-like AACH as precursor, γ-Al₂O₃ nanorods were obtained via a low-temperature thermal decomposition method.     

Ultrasonic disintegration of tungsten trioxide pseudomorphs after ammonium paratungstate as a route for stable aqueous sols of nanocrystalline WO<Subscript>3</Subscript>

A new facile method is proposed for the preparation of aqueous sols of highly crystalline tungsten trioxide with a particle size of 60–150 nm, containing no organic stabilizers/surfactants. These sols possess high sedimentation stability, which is quite unusual for inorganic colloidal systems containing relatively large particles, with a rather high density (ρ _c(WO₃) = 7.3 g/cm³). The method is based on the thermal decomposition of ammonium paratungstate, followed by dispersing the resulting powders in water under ultrasonic treatment. Thermal decomposition of ammonium paratungstate, and the composition and structure of the resulting tungsten trioxide and its aqueous dispersions, were investigated with thermal analysis combined with the mass spectrometry of gaseous thermolysis products, powder X-ray diffraction, scanning electron microscopy, low-temperature nitrogen adsorption, IR spectroscopy and dynamic light scattering. It has been demonstrated that the high sedimentation stability of WO₃ results from electrostatic stabilization, which might be caused by the formation of tungstic acid on the surface of WO₃ particles when they come into contact with water. The nanocrystalline WO₃ obtained can be used to produce gas sensors for ammonia.     

Influence of Al2O3 support on the thermal decomposition of ammonium metavanadate

The thermal decomposition of ammonium metavanadate (AMV) supported on aluminium oxide was investigated using differential thermal analysis, thermogravimetry, infrared and X-ray diffraction techniques. The results obtained revealed that the decomposition of AMV supported on alumina proceeded in three decomposition stages. Alumina was found to enhance only the decomposition of the intermediate ammonium hexavanadate to produce V₂O₅. In addition, the values of activation energies of the various decomposition stages were accompanied by a significant decrease on decreasing the concentration of AMV. The infrared spectra indicated that the band corresponds to the surface site V=O strongly affected by the presence of Al₂O₃. Finally, an interaction between Al₂O₃ and V₂O₅ occurred at 660 °C giving well-crystallized AlVO₄.     

Facile fabrication of silver nanoplates via a solvothermal method

This paper describes a simple solvothermal route to synthesize silver nanoplates by reduction of silver nitrate (AgNO₃) with N,N-dimethylformamide. In this approach, ferric chloride (FeCl₃) servers as the controlling agent, enabling the control over the concentration of free Ag⁺ ions in the solution. As the concentration of FeCl₃ added to the reaction was increased, the morphologies of silver nanostructures evolved from triangular silver nanoplates to hexagonal silver nanoplates. The structures of these nanoplates were characterized by X-ray diffraction, electron microscopy and electron diffraction. A possible mechanism is proposed to interpret the shape-controlled synthesis of silver nanostructures. Finally, our results suggest that this method provides a convenient way to prepare silver nanostructures with different morphologies.     

Preparation of monodispersed cobalt-boron spherical nanoparticles and their behavior during the catalytic decomposition of hydrous hydrazine

Monodispersed cobalt-boron spherical nanoparticles have been prepared through solution plasma processing in the presence of hexadecyltrimethyl ammonium bromide for the first time. The particle size of cobalt-boron can be adjusted by changing either the plasma time or the concentration of hexadecyltrimethyl ammonium bromide. The samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. During the decomposition of hydrous hydrazine, the obtained monodispersed cobalt-boron spherical nanoparticles exhibit higher catalytic activity and hydrogen selectivity than regular cobalt-boron prepared by direct reduction of Co²⁺ with BH₄⁻. The experimental investigations indicate that hydrous hydrazine along with the monodispersed cobalt-boron spherical nanoparticles may find application in small-scale on-board hydrogen storage and supply.     

Synthesis and gas sensor properties of flower-like 3D ZnO microstructures

Flower-like ZnO 3D microstructures composed of nanorods have been successfully prepared via a facile hydrothermal method using p-nitrobenzoic acid as the structure-directing agent. The structures and morphologies of the final products have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscope (HRTEM). The possible mechanism for the synthesis of the flower-like ZnO microstructures has been proposed primarily. The gas sensitivity of the flower-like ZnO microstructures has been studied to a series of organic vapors at different operation temperatures and vapor concentrations. The results show that the flower-like ZnO microstructures composed of nanorods have good gas sensor properties to ethanol.     

负载型纳米NiO催化高氯酸铵热分解的DSC/TG-MS研究

采用浸渍法制备出纳米NiO/MgO,运用X射线衍射(XRD)、透射电子显微镜(TEM),X射线能谱仪(EDS)等对产物的物相和组成进行了表征,利用DSC/TGMS研究了纳米NiO/MgO对高氯酸按(AP)热分解的催化作用.结果表明,在纳米NiO/Mgo的催化作用下,AP的热分解高温分解峰温度降低92.2℃,表观分解热增...