Dissolution kinetics of fluorapatite in the hydrochloric acid solution

A thermochemical study of hydrochloric acid attack of synthetic fluorapatite was performed by a DRC. The calculated thermogenesis curves show one peak. The plot of the heat quantity as a function of the dissolved mass undergoes only one straight segment, and the thermogenesis curves present a single peak, suggesting the occurrence of a one-step dissolution process. The dissolution kinetics was examined according to the heterogeneous reaction models and showed that the dissolution is controlled by the product layer diffusion process with a reaction rate expressed by the following semiempirical equation; \(\left[ {1 + 2(1 - X) - 3(1 - X)^{{\frac{2}{3}}} } \right] = 3195 \times 10^{ - 2} C^{0.145} \left( {\frac{S}{L}} \right)^{ - 0.628} e^{{ - \frac{2600}{\text T}}} t\). The activation energy was determined as 21.6 ± 1.5 kJ mol^?1     

Analysis of flammability and smoke emission of rigid polyurethane foams modified with nanoparticles and halogen-free fire retardants

Using one-step method, rigid polyurethane foams were made, modified with developed fire retardant systems containing halogen-free flame retardants and nanofillers in the form of multi-walled carbon nanotubes or nanoscale titanium dioxide. The materials were subjected to a test using a cone calorimeter and smoke-generating chamber, and selected samples were further analyzed via thermogravimetry and oxygen index. Moreover, the products of thermal degradation of selected samples were identified using gas chromatography with mass spectrometer. Conducted flammability tests confirmed the presence of a synergistic effect between the used nanofillers and halogen-free flame retardants. It has been observed that the carbonized layer, the formation of which favored the presence of nanoadditives, inhibits the combustion process. Furthermore, nanofillers influenced favorably reduction in the amount and the number of occurring products of thermal degradation.     

Thermal degradation kinetics and reaction models of 1,3,5-triamino-2,4,6-trinitrobenzene-based plastic-bonded explosives containing fluoropolymer matrices

In this article, thermal degradation behavior of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB)-based plastic-bonded explosives (PBXs) bonded with a different fluoropolymer matrices namely indigenous poly(vinylidene fluoride-chlorotrifluoroethylene) (FKM), FK 800, fluoroplastic F-32L and fluororubber SKF 32 was investigated through non-isothermal thermogravimetric analysis (TG) technique under nitrogen atmosphere. It was observed that the mass loss of PBXs containing FKM and FK 800 matrices occurred in three steps. The mass loss of PBXs containing fluoroplastic F-32L and fluororubber SKF 32 occurred in two steps. Kinetics were investigated through non-isothermal TG at different heating rates for the first step of degradation by means of model-free Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunose (KAS) methods. The activation energies calculated by applying FWO method are in good agreement and very close to those obtained by KAS method. The results revealed that the effect of the polymer matrices on the thermal degradation reaction of TATB was significantly observed especially different outcomes of kinetic parameters. The reaction models for degradation were also studied by Criado method. The reaction models are probably best described by the power law and diffusion models.     

Effect of nanoclay and barium sulfate nanoparticles on the thermal and morphological properties of polyvinylidene fluoride nanocomposites

The thermal, morphological and optical studies of BaSO₄ and MMT (nanoclay) embedded in PVDF were investigated. Nanocomposites samples of PVDF–BaSO₄–MMT were prepared by varying the loadings (1–4 mass%) in case of BaSO₄ and MMT nanomaterials, respectively. Polyvinylidene fluoride–barium sulfate-montmorillonite (PVDF–BaSO₄–MMT) nanocomposites were prepared by solvent-mixing technique. Nanoparticles were synthesized by in situ deposition technique with the help of nonionic polymeric surfactant, and the particle size of nanoparticles was recognized by scanning electron microscopy (SEM) analysis which confirms that the particle has diameter of 80–90 nm. As prepared, nanocomposites films (thickness, 25 μm) were characterized by Fourier transform infrared microscopy (FTIR), SEM and electron diffraction spectroscopy (EDS). FTIR shows that all the chemical constituents were present in the nanocomposites, whereas SEM analysis suggested that the nanofillers dispersed well in polymer matrix and EDS showed the elemental composition of nanocomposite samples. Thermal properties of nanocomposites were studied by using TG/DTA/DTG. TG/DTA studies showed decomposition temperature of pure PVDF is 473.5 °C. The decomposition temperature (T _d) of nanocomposites was increased by 93 °C in case of nanocomposites with addition of both BaSO₄ and MMT nanomaterials. The difference in the thermal degradation temperature was found to be 1.2% higher in case of addition of BaSO₄ nanoparticle as compared to nanoclay. The obtained transparent nanocomposite films were characterized by using UV–Vis spectrophotometer which shows that transparencies of nanocomposites are maintained in visible region, the intensity of absorption band in UV region is increased with the addition of BaSO₄ nanoparticles, while in case of addition of nanoclay the UV region does not show drastic changes. Addition of both nanoparticle and nanoclay shows higher absorption in comparison with the individual samples. But further, doubling the amount of nanoparticle and nanoclay shows decrease in UV absorption. Overall, the results of thermal studies show that the incorporation of BaSO₄ and MMT could significantly improve the thermal properties of nanocomposites.     

Hydrotalcite-derived Co-containing mixed metal oxide catalysts for methanol incineration

The Co–Mg–Al mixed metal oxides were prepared by calcination of co-precipitated hydrotalcite-like precursors at various temperatures (600–800 °C), characterised with respect to chemical (AAS) and phase (XRD) composition, textural parameters (BET), form and aggregation of cobalt species (UV–vis-DRS) and their redox properties (H₂-TPR, cyclic voltammetry). Moreover, the process of thermal decomposition of hydrotalcite-like materials to mixed metal oxide systems was studied by thermogravimetric method combined with the analysis of gaseous decomposition products by mass spectrometry. Calcined hydrotalcite-like materials were tested as catalysts for methanol incineration. Catalytic performance of the oxides depended on cobalt content, Mg/Al ratio and calcination temperature. The catalysts with lower cobalt content, higher Mg/Al ratio and calcined at lower temperatures (600 or 700 °C) were less effective in the process of methanol incineration. In a series of the studied catalysts, the best results, with respect to high catalytic activity and selectivity to CO₂, were obtained for the mixed oxide with Co:Mg:Al molar ratio of 10:57:33 calcined at 800 °C. High activity of this catalyst was likely connected with the presence of a Co–Mg–Al spinel-type phases, containing easy reducible Co³⁺ cations, formed during high-temperature treatment of the hydrotalcite-like precursor.     

Review of heat transport properties of solar heat transfer fluids

The present article reviews the test techniques for some of the important heat transport properties of oils such as viscosity, density, specific heat capacity and thermal conductivity mainly used for characterization of heat transfer fluids. It can be seen that while density of oils can be tested at higher temperatures, the other heat transport properties of oils like viscosity, specific heat capacity and thermal conductivity have a limitation of being tested at low temperatures below 100–150 °C. While quite a few number of researchers have reported evaluation of heat transfer properties like specific heat capacity and thermal conductivity of oils by different methods, there remains a huge scope of debate and discussions on the repeatability and reproducibility of such tests, especially in case of oils used in high-temperature applications. A lot of insight has been gathered with respect to testing of thermal conductivity of oils, and several common test methods have been compared with each other. Lastly, two mathematical models, reported in the literature in open domain, have been reviewed and compared with each other. If the oils are to be used at elevated temperatures, like heat transfer fluids used in concentrated solar power generation where temperatures go as high as 400 °C and beyond, there is an urgent need to standardize a laboratory test method for performance evaluation of heat transport properties, which can help in formulating new generation oils based on novel chemistries and technologies like nanofluids, synthetic oils of novel chemistries, molten salts and molten metals.     

Determination of the thermal modification degree of beech wood using thermogravimetry

Thermal modification is one of the environmental friendly wood preservation technologies. During this process, changes of the main woody cell wall components occur, which lead to improved dimensional stability, lower hygroscopicity and improvement in biological durability. Several chemical reactions which occur during thermal treatment of wood caused changes in wood properties. During TG measurements, thermal decomposition reactions, which was not completed during previous thermal modification process, continued in wood samples, meaning that more thermally treated samples exhibited lower mass losses in a certain or whole temperature range up to 600 °C. Therefore, mass loss, obtained within selected temperature range, could be used as a marker of previous thermal treatment. The aim of the present work is to evaluate suitability of a thermogravimetric method (TG) for determination of a degree of thermal treatment of beech wood. On the basis of thermally untreated sample and those which were thermally modified at 180, 190, 200, 210, 215 and 220 °C in the absence of oxygen, respectively, and with known values of mass loss during the modification processes, several calibration curves were constructed. They represent mass loss in a certain temperature range during TG measurement versus mass loss during previous thermal modification. In a temperature range from 130 to 300 °C and from 130 to 320 °C under nitrogen atmosphere, a linear dependence was observed; correlation coefficients R ² were 0.87 and 0.91, respectively. In wider temperature range and under air atmosphere, lower correlation coefficients were obtained. High correlation coefficient, higher than 0.95, was observed in a temperature range from 25 to 130 °C under both atmospheres. In this region, dehydration due to rehydration of thermally modified samples occurs. The results of this work were compared with those obtained for Norway spruce.     

Effect of Metal Vapours on the Radiation Properties of Thermal Plasmas

In metallurgic applications of thermal plasmas the presence of metal vapour, even in small proportion tends to increase the electron number density and to modify some basic properties such as the electrical conductivity and the radiation emission. In this paper we focus on the influence of these vapours on the radiation properties. After the definition of some necessary and basic functions and laws we briefly present the mechanisms responsible for emission and absorption of radiation in thermal plasmas. Then an important section is devoted to the role of metal vapours on the net emission coefficient which is the most popular parameter used to evaluate the radiation power losses in general models. It is shown that metal vapours increase the emission especially at low and intermediate temperatures (T < 12,000 K) and that their relative influence depends on the nature of the initial gas and of the metal itself. We list a rather important number of references presenting calculation of net emission in various gas–metal mixtures. Finally we show in a last section the influence of metal radiation on general plasma properties such as the energy transfer (other methods than the net emission coefficient), the cooling effect, the global energy balance and the heating of particulates injected in the plasma. The most spectacular effects are the increase of radiation losses in the energy balance and the complex role of the metal in the local cooling of the plasma.     

Hydrogen Peroxide Formation by Electric Discharge with Fine Bubbles

Pulsed discharge plasma is typical oxidation technology for disposing organic compounds in aqueous solutions. When this electrical discharge plasma was applied in water, it may produce hydrogen peroxide (H₂O₂) without any catalyst or chemical agent. In order to increase H₂O₂ production by electrical discharge plasma in water, fine bubbles were introduced into the electrical discharge plasma in this experiment. Bipolar pulsed voltages were applied to cylindrical electrodes in the water while Ar or O₂ bubbles were introduced, generating a pulsed discharge plasma. The introduction of the bubbles seemed to enhance the dissociation of water molecules and increased H₂O₂ formation, especially with O₂ bubbling. Dissolved oxygen in the water contributed to H₂O₂ formation by pulsed discharge plasma with the bubbles, while dissociation of water molecules was the cause of H₂O₂ formation by pulsed discharge plasma without bubbles. More H₂O₂ was formed by pulsed discharge plasma with O₂ bubbles, because the amount of dissolved oxygen in the water increased upon bubbling with O₂.