A kinetic study of the thermal decomposition process of potassium metabisulfite: Estimation of distributed reactivity model

The thermal decomposition kinetics of potassium metabisulfite was studied by thermogravimetric (TG) and differential thermogravimetric (DTG) techniques using non-isothermal experiments. The apparent activation energy (E_a) is determined using the differential (Friedman) isoconversional method. The results of the Friedman's isoconversional analysis of the TG data suggests that the investigated decomposition process follows a single-step reaction and the observed apparent activation energy was determined as 122.4±2.1 kJ mol⁻¹. A kinetic rate equation was derived for the decomposition process of potassium metabisulfite with contracting area model, f(α)=2(1−α)^1/2, which is established using the Malek's kinetic procedure. The value of pre-exponential factor (A) is also evaluated and was found to be A=1.37×10¹² min⁻¹. By applying the Miura's procedure the distributed reactivity model (DRM) for investigated decomposition process was established. From the dependence α versus E_a, the experimental distribution curve of apparent activation energies, f(E_a), was estimated. By applying the non-linear least-squares analysis, it was found that the Gaussian distribution model (with distribution parameters E₀=121.3 kJ mol⁻¹ and σ=1.5 kJ mol⁻¹) represents the best reactivity model for describing the investigated process. Using the Miura's method, the A values were estimated at five different heating rates and the average A values are plotted against E_a. The linear relationship between the A and E_a values was established (compensation effect). Also, it was concluded that the E_a values calculated by the Friedman's method and estimated distribution curve, f(E_a), are correct even in the case when the investigated decomposition process occurs through the single-step reaction mechanism.     

Isothermal reduction kinetics of nickel oxide using hydrogen: Conventional and Weibull kinetic analysis

The powder sample of nickel oxide was synthesized by sol-gel procedure. The isothermal reduction of nickel oxide using hydrogen was investigated by thermogravimetric analysis at five operating temperatures: 245, 255, 265, 275 and 300 °C. The kinetic triplet (E_a, A and f(α)) was determined using conventional and Weibull kinetic analysis. Both the kinetically procedures show that the reduction process considered can be explained with a two-step kinetic model. It is established that at lower temperatures (245 °C?T?255 °C), the reduction process considered is governed by two-parameter Šesták-Berggren autocatalytic model (first step) and at higher temperatures (T?265 °C), the reduction process is governed by Fn reaction model with different values of parameter n (second step). In this paper, the complex manner of dependence of the Weibull shape parameter (β) on temperature is established. With alterations of Weibull shape parameter from lower temperatures (β>1) to higher temperatures (β<1), it was concluded that isothermal reduction process of NiO using hydrogen can be described by a multistep reaction mechanism. These results are confirmed by the evaluated density distribution functions (ddf) of apparent activation energies (E_a), which show variations in basic characteristics at lower and higher operating temperature regions. Also, in this paper, it was shown that the shape parameter (β) of Weibull distribution function can represent the behaviour index, which indicates the kinetic pattern of the mechanism controlling the process studied.     

玻璃纤维/环氧树脂复合材料热分解动力学参数的确定

采用热重分析仪对空气和氮气气氛中的玻璃纤维增强环氧树脂基复合材料进行热分析,得到该材料在空气气氛中的烧蚀热为3125～3440J/g,而在氮气气氛中并未出现明显的氧化放热峰。基于阿伦纽斯形式的多步分解模型和直接解法,计算了该材料在空气气氛中的热分解动力学参数。分析表明:阿伦纽斯形式的多步分解模型能够较好地描述该材料的热分解过程;直接解法适用于计算复合材料的热分解动力学参数;确立的热分解动力学参数是正确有效的。     

Theoretical kinetic study on the decomposition of 1,5‐diaminotetrazole

1,5‐Daminotetrazole (DAT) is of much interest because of the practical significance and the diversity of characteristics. The study on the decomposition pathway and the kinetics of DAT has been performed based on the quantum chemistry theory. The minimum energy path (MEP) calculation has shown that NH₂N₃ and NH₂CN are the initially detected products of DAT. And the structures of reactant, products and transition state were optimized with MP2 methods using 6‐311G** basis sets, and the energies were refined using CCSD(T)/6‐311G** levels of theory. The calculated rate constants were obtained using the conventional transition‐state theory (TST) and the canonical variational transition‐state theory (CVT) methods. The calculation results indicated that the energy barrier of decomposition reaction is 47.98 kcal mol^?1 and the variational effect is small. In addition, the rate constants and the Arrhenius experience formula of DAT decomposition have been obtained between 200 and 2500 K temperature regions. The fitted three‐parameter expressions calculated using the TST and CVT methods are (TST) and (CVT). This work may provide the theoretical support for further experimental synthesis and testing. Copyright © 2015 John Wiley & Sons, Ltd.     

A Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA) study of oleate adsorbed on magnetite nano-particle surface

Magnetite nano-particles were coated with sodium oleate and the spectral behaviour of the coating layer was studied by FTIR spectroscopy after the particles had been heated in air and argon. Magnetite was synthesized by controlled co-precipitation and subsequently coated with sodium oleate. Thermal analysis in combination with mass spectroscopy was carried out to support the FTIR spectroscopic interpretations, but also to monitor the decomposition and surface reaction of oleate adsorbed on the magnetite surface. It was deduced from FTIR and TGA results that the oleate molecules are bonded to iron atoms by a bidentate mononuclear complex and form essentially a single layer with a distance between oleate molecules of ∼36 Å². It was shown by IR as well as Raman spectroscopy that oleic acid, when heated in air, undergoes decomposition implying that new carbon-oxygen bonds are formed. Heating the iron oxide-oleate system in air also implies oxidation of the double bond at the C:9 position of the alkyl chain and formation of intermediate oxygen-rich molecules. An enthalpy change of ΔH = 49.86 J/g was obtained for oleate desorption/decomposition at ∼350 °C under argon atmosphere and a carbonaceous graphitic species resulted from this decomposition.     

高温下HBT晶体热分解过程的理论模拟

基于自洽电荷密度泛函紧束缚(SCC-DFTB)方法研究了富氮含能材料5, 5’-双四唑肼(C₂H₄N₁₀, HBT)晶体在高温下的热分解反应过程.结果表明,结构优化参数与实验误差在5%以内.在2000 K, 2500 K,和3000 K不同温度下,HBT晶体热分解路径和产物表现出相似性.通过过渡态理论和分子动力学两种方法,研究了分解反应C₂H₄N₁₀→C₂H₃N₇+HN₃,发现HBT晶体分解产物中存在叠氮酸(HN₃)分子,化学反应势垒高度为222.85 kJ·mol^-1.研究结果为进一步理解高温下HBT晶体热分解特征提供理论参考.     

玻璃纤维/环氧树脂复合材料热分解动力学参数的确定

采用热重分析仪对空气和氮气气氛中的玻璃纤维增强环氧树脂基复合材料进行热分析,得到该材料在空气气氛中的烧蚀热为3 125～3 440 J/g,而在氮气气氛中并未出现明显的氧化放热峰。基于阿伦纽斯形式的多步分解模型和直接解法,计算了该材料在空气气氛中的热分解动力学参数。分析表明：阿伦纽斯形式的多步分解模型能够较好地描述该材料的热分解过程;直接解法适用于计算复合材料的热分解动力学参数;确立的热分解动力学参数是正确有效的。     

Phase-field study of spinodal decomposition under effect of grain boundary

Grain boundary directed spinodal decomposition has a substantial effect on the microstructure evolution and properties of polycrystalline alloys. The morphological selection mechanism of spinodal decomposition at grain boundaries is a major challenge to reveal, and remains elusive so far. In this work, the effect of grain boundaries on spinodal decomposition is investigated by using the phase-field model. The simulation results indicate that the spinodal morphology at the grain boundary is anisotropic bicontinuous microstructures different from the isotropic continuous microstructures of spinodal decomposition in the bulk phase. Moreover, at grain boundaries with higher energy, the decomposed phases are alternating α/β layers that are parallel to the grain boundary. On the contrary, alternating α/β layers are perpendicular to the grain boundary.     

Experimental study of thermal oxidation of nanoscale alloys of aluminium and zinc (nAlZn)

Aluminium-based alloys have wide applications but little is known about the thermal-chemical kinetics of nanoalloys. This work investigated the thermal oxidation of Zn and Al nanoalloys (nAlZn) with a BET equivalent diameter of 141 nm through the simultaneous TGA/DSC method. The thermal analysis was combined with elemental, morphology and crystalline structure analysis to elucidate the reaction mechanisms. It was found that the complete oxidation of nAlZn in air can be characterised by a three-stage process, including two endothermic and three exothermic reactions. With the help of ex-situ XRD, different reaction pathways were proposed for different stages, forming the end products of ZnO and ZnAl₂O₄. The reactivity comparison between Al and nAlZn suggested that different criteria should be used for different applications.     

Effect of Al content on impact resistance behavior of Al-Ti-B4C composite fabricated under air atmosphere

Reaction behavior, mechanical property and impact resistance of TiC-TiB₂/Al composite reacted from Al-Ti-B₄C system with various Al content via combination method of combustion synthesis and hot pressed sintering under air was investigated. Al content was the key point to the variation of mechanical property and impact resistance. Increasing Al content could increase the density, strength and toughness of the composite. Due to exorbitant ceramic content, 10 wt.% and 20 wt.% Al-Ti-B₄C composites exhibited poor molding ability and machinability. Flexural strength, fracture toughness, compressive strength and impact toughness of 30–50 wt.% Al-Ti-B₄C composite were higher than those of Al matrix. The intergranular fracture dispersed and defused impact load and restricted crack extension, enhancing the impact resistance of the composite. The composite with 50 wt.% Al content owned highest mechanical properties and impact resistance. The results were useful for the application of TiC-TiB₂/Al composite in impact resistance field of ceramic reinforced Al matrix composite.     

A mechanistic study on kinetic compensation effect during low-temperature oxidation of coal chars

This paper provides mechanistic insights into the low-temperature oxidation of a range of carbon materials (graphite, a sub-bituminous coal char, and a brown coal char). Kinetic analysis was carried out on oxidation of the chars, prepared from fast-heating pyrolysis, under chemical-reaction-controlled regime. FT-Raman spectroscopic analysis was adopted to provide direct structural information on the carbon structure of reacting carbon materials throughout oxidation. The results demonstrate the significance of selective oxidation under the conditions, and parallel to this, the kinetic compensation effect of carbon oxidation reaction throughout conversion for all samples. Supported by the results from FT-Raman spectroscopy, the kinetic compensation effect seems to be a result of the selective oxidation of these carbon materials with heterogeneous carbon structures. Oxidation of all samples, with or without catalysts, appears to be similar in terms of the ‘nature’ of carbon structural condensation during low-temperature oxidation, suggesting a similar increase in apparent active sites population with respect to increase of apparent energy barrier. Under the current experimental conditions, a general kinetic compensation effect correlation has been deduced for various materials, requiring only the initial char kinetic parameters. The inherent inorganic species in chars also seem to alter the ‘degree/extent’ of carbon structural condensation as results of selective oxidation. In this case, the use of the compensation effect correlation will require more information on the catalysis during oxidation, apart from the initial char kinetic parameters.     

Structures of CoAl(1 1 1) surface: A first principles study

The structures of the CoAl(1 1 1) surface are studied by first principles calculations. Our calculations show that the surface layer is always occupied by pure Al for all concentrations studied here, which indicates the dominant role of the Al segregation tendency. This is different from the CoAl(0 0 1) surface, where a number of Co anti-sites are found on the top most layer. The calculated surface phase diagram of ground states shows that there are three stable structures. The diffusion barriers of the metastable structure evolving to the stable structure are also calculated. The high diffusion barrier can explain the appearance of metastable structures at low temperature in experiment.     

A study of the activation energy of thermal decomposition of irradiated polymers

The ion irradiation of polymeric solids induces numerous modifications in the polymer properties thus increasing their applicability in various fields. The present work looks into the aspect of thermal modifications induced in the irradiated polymers. The kinetics of thermal decomposition of polymers is investigated by using the thermogravimetric (TG) technique. It has been observed that the degradation of polymers is a multi-step process that involves sequential and competing processes, and obeys the Arrhenius kinetics which allows us to connect the rate constant with the absolute temperature and the activation energy. The activation energy of thermal decomposition has been calculated from the TG curves, and its variation with different irradiation doses has been derived.     

A wire microcalorimetric study of catalytic ignition of methane–air mixtures over palladium oxide

Catalytic ignition and heat release of methane oxidation over a Pd wire covered with a 1–2 μm PdO surface layer were investigated by wire microcalorimetry over the temperature range of 600–770 K and pressure range of 0.5–4 atm. Ignition temperatures and heat release rates for different methane concentrations (1–4 vol.% in dry air) were determined, showing that the ignition temperatures decrease with increasing the methane concentration and increasing ambient pressure. At total pressure of 1 atm and 2% methane concentration, the global activation energy for the catalytic reaction is 21.5 ± 0.9 kcal/mol and 14.3 ± 0.2 kcal/mol in the temperature ranges of 600–670 K and 670–770 K, respectively. The reaction order for methane is 0.9 ± 0.1 over the temperature range of 630–770 K.     

Energetic and structural evolution of gold nanowire under heating process: A molecular dynamics study

The energetic and structural evolution of a squared gold nanowire under heating process is investigated via molecular dynamics with many-body potential. The simulations reveal that the nanowire undergoes distinct energetic and structural developments during the following four heating processes: low temperature, melting, breaking and high temperature. The cross-section of nanowire is found to change from a square to a circle shape with rising temperature at first. A neck is then found to be initiated above the overall melting point, followed by the formation of a two- to five-atom-thick chain structure before the breaking of neck. The nanowire transforms to a spherical cluster after the final breaking.     

Kinetic study of isothermal crystallization process of Gd2Ti2O7 precursor's powder prepared through the Pechini synthetic approach

Crystallization process of Gd₂Ti₂O₇ precursor's powder prepared by Pechini-type polymerized complex route has been studied under isothermal experimental conditions in an air atmosphere. It was found that the crystallization proceeds through two-parameter Šesták–Berggren (SB) autocatalytic model, in the operating temperature range of 550 °C≤T≤750 °C. Based on the behavior of SB parameters (M, N), it was found that in the lower operating temperature range, the crystallites with relatively low compactness exist, which probably disclosed low dimensionality of crystal growth from numerous nucleation sites, where the amorphous solid is produced. In the higher operating temperature region (above 750 °C), it was established that a morphological well-defined and high-dimensional particles of the formed pyrochlore phase can be expected. It was found that at T=850 °C, there is a change in the rate-determining reaction step, from autocatalytic into the contracting volume mechanism.     

CuO掺杂C3N对C5F10O分解组分吸附性能的第一性原理研究

全氟五碳酮（C5F10O）作为可替代SF6的新型环保绝缘气体已被投入到实际应用中. 在绝缘设备内部不可避免的会发生局部放电等故障,造成C5F10O绝缘气体分解产生弱绝缘性能甚至剧毒的分解组分,为保证绝缘设备的安全运行,在不影响气敏传感器正常检测绝缘设备内部故障的情况下,需对这些分解组分进行有选择地吸附去除. 新型类石墨烯C3N材料在气体吸附领域具有良好的应用前景,文中基于第一性原理计算了CuO分子掺杂C3N对主要分解组分CF4、C2F6及剧毒产物CF2O、HF的吸附过程,计算并分析了各分解组分吸附时的吸附能、态密度、电荷转移量、差分电荷密度以及不同环境温度下的恢复时间. 结果表明,CuO-C3N对HF表现出良好的吸附性,CF2O次之,但其无法吸附CF4与C2F6,因此CuO-C3N可以作为一种高性能的气体吸附剂对C5F10O绝缘设备内的剧毒分解组分HF进行吸附去除.     

A DFT study of 5-fluorouracil adsorption on the pure and doped BN nanotubes

The electronic and adsorption properties of the pristine, Al-, Ga-, and Ge-doped BN nanotubes interacted with 5-fluorouracil molecule (5-FU) were theoretically investigated in the gas phase using the B3LYP density functional theory (DFT) calculations. It was found that the adsorption behavior of 5FU molecule on the pristine (8, 0) and (5, 5) BNNTs are electrostatic in nature. In contrast, the 5FU molecule (O-side) implies strong adsorption on the metal-doped BNNTs. Our results indicate that the Ga-doped presents high sensitivity and strong adsorption with the 5-FU molecule than the Al- and Ge-doped BNNTs. Therefore, it can be introduced as a carrier for drug delivery applications.     

Extent of coverage of surfaces treated with hydrophobizing microemulsions: A mass spectrometry and contact angle study

Glass surfaces were treated with various hydrophobizing microemulsions (HME) containing mineral seal oil or polyisobutylene as hydrophobes emulsified by dimethyl dicoco ammonium chloride (i.e. mimicking commercial car wash practices) and characterized by mass spectrometry (MS) and contact angle measurements. The cationic emulsifier mediates the anchoring of hydrophobes to the polar glass surface. It is demonstrated that by the use of even very low (0.3-3.0 w%) HME concentrations the surfaces become hydrophobic and repel water even after numerous (∼20) rinsing cycles. According to MS evidence, however, the surfaces are not fully saturated with hydrophobes and the unprotected areas remain vulnerable to environmental damage.     

Analytic treatment of linear and nonlinear Schrödinger equations: A study with homotopy-perturbation and Adomian decomposition methods

In this work, two powerful analytical methods, called homotopy-perturbation method (HPM) and Adomian decomposition method (ADM) are introduced to obtain the exact solutions of linear and nonlinear Schrödinger equations. The main objective is to propose alternative methods of solution, which do not require small parameters and avoid linearization and physically unrealistic assumptions. The results show that these methods are very efficient and convenient and can be applied to a large class of problems. The comparison of the methods shows that although the numerical results of these methods are the same, HPM is much easier, more convenient and efficient than ADM.