Non-isothermal crystallization kinetics of Ti<Subscript>20</Subscript>Zr<Subscript>20</Subscript>Hf<Subscript>20</Subscript>Be<Subscript>20</Subscript>(Cu<Subscript>50</Subscript>Ni<Subscript>50</Subscript>)<Subscript>20</Subscript> high-entropy bulk metallic glass

The crystallization transformation kinetics of Ti₂₀Zr₂₀Hf₂₀Be₂₀(Cu₅₀Ni₅₀)₂₀ high-entropy bulk metallic glass under non-isothermal conditions are investigated using differential scanning calorimetry. The alloy shows two distinct crystallization events. The activation energies of the crystallization events are determined using Kissinger, Ozawa and Augis–Bennett methodologies. Further, we observe that similar values are obtained using the three equations. The activation energy of the initial crystallization event is observed to be slightly small as compared to that of the second event. This implies that the initial crystallization event may have been easier to be occurred. The local activation energy (E(x)) maximizes in the initial stage of crystallization and keeps dropping in subsequent crystallization process. The non-isothermal crystallization kinetics are further analyzed using the modified Johnson–Mehl–Avrami (JMA) equation. Further, the Avrami exponent values are observed to be 1.5 < n(x) < 2.5 for approximately the entire period of the initial crystallization event and for most instances (0.1 < x < 0.6) of the second crystallization event, which implies that the mechanism of crystallization is significantly controlled by diffusion-controlled two- and three-dimensional growth along with a decreasing nucleation rate.     

Analysis and perspectives concerning CO<Subscript>2</Subscript> chemisorption on lithium ceramics using thermal analysis

CO₂ removal from flue gas has been proposed as one of the most reliable solutions to mitigate global greenhouse emissions. Lithium ceramics are among several materials that have potential applications in CO₂ removal. Lithium ceramics are able to chemisorb CO₂ in a wide temperature range, presenting several interesting properties. All lithium ceramics present a similar CO₂ chemisorption reaction mechanism that has been described at the micrometric scale. However, there are several issues that have not been fully elucidated. The aim of this study is to re-analyze different experiments related to the CO₂ chemisorption on lithium ceramics and to propose how different factors control this process. This study focuses on diffusion controlled CO₂ chemisorption, which has been shown to be the limiting step of the CO₂ chemisorption process. Diffusion controlled CO₂ chemisorption appears to be mainly influenced by the chemical composition of a product’s external shell.     

Pressurized CO<Subscript>2</Subscript>-enhanced gasification of coal

Carbon dioxide was considered as a co-gasifying agent in a coal gasification reactor. The work presented herein describes the simulation results for the process and the experimental data on coal char gasification with CO₂ addition as the rate-controlling step for the entire process. To study the potentially beneficial effect of the introduction of CO₂ into the gasification system, several simulations were conducted using the commercial process simulation software ChemCAD 6.3^®. The results of a Gibbs equilibrium reactor were evaluated. The Boudouard reaction is a critical path for the development of this process, and the kinetics were studied experimentally. Four chars derived from the pyrolysis of Polish coals of different origins were selected for the experiments. The kinetic characteristics of this system were examined using a custom-designed pressurized fixed-bed reactor. To determine the effect of pressure on the gasification rate, several preliminary studies on the gasification of coal chars were performed isothermally at the temperature of 950 °C and pressures of 1, 10, and 20 bars. In contrast to the thermodynamic calculations, the experimental data revealed that increasing the CO₂ pressure leads to a higher reaction rate for medium-rank coal chars and low-rank lignite coal char, resulting in higher efficiency for carbon monoxide production. The pressure influences the reactivity more strongly when varied from 1 to 10 bars; a further increase in pressure affects the rate almost insignificantly. The observed behavior representing the changes in carbon conversion degree during gasification is satisfactorily described by the grain model.     

Kinetic model of the oxidation of ZrSi<Subscript>2</Subscript> powders

The oxidation kinetics of Zr-disilicide (ZrSi₂) powders up to temperatures of 1550°C were studied in flowing air using non-isothermal and isothermal thermogravimetric (TG) analysis. During the oxidation process two main thermal events were detected. The first stage of the oxidation reaction leads to the formation of elemental silicon as an intermediate reaction product. Upon further temperature increase the newly formed silicon is oxidized. Completely oxidized ZrSi₂ samples consist of ZrSiO₄, amorphous and crystalline SiO₂ as well as some residual ZrO₂. The experimental TG data were analysed with a model-fitting kinetic method. The gas-solid reaction is complex and can best be fitted with a multi-step reaction scheme consisting of branching reactions based on 3D diffusion mechanisms and a fractal order reaction.     

Influence of the atmosphere on the thermal decomposition kinetics of the CaCO<Subscript>3</Subscript> content of PFBC coal flying ash

The thermal decomposition behavior of hard coal fly ash (HCA2), obtained from the combustion of an Australian hard coal in thermoelectric power plants, in different atmospheres (air, N₂ and N₂-H₂ mixture), was studied using thermogravimetry (TG), infrared-evolved gas analysis (IR-EGA), differential scanning calorimetry (DSC) and thermodilatometry (DIL) techniques. It was found that changing of the applied atmosphere affects the carbon content of the ash which results in different thermal decomposition behaviors. In air, the carbon content was oxidized to carbon dioxide before the decomposition of carbonate. In N₂ or in N₂-H₂ atmospheres, the carbon content acts as a spacer causing a fewer points of contact between calcium carbonate particles, thus increasing the interface area which results in a decrease of the carbonate decomposition temperature. Following the carbonate decomposition, the iron oxide content of the ash undergoes a reductive decomposition reaction with the unburned carbon. This oxidation-reduction reaction was found to be fast and go to completion in presence of the N₂-H₂ mixture than in the pure nitrogen atmosphere due to the reducing effect of the hydrogen. The kinetics of the carbonate decomposition step, in air and N₂-H₂ mixture was performed under non-isothermal conditions using different integral methods of analysis. The dynamic TG curves obeyed the Avrami-Erofeev equation (A₂) in air, and phase boundary controlled reaction equation (R₂) in N₂-H₂ mixture. The change in the reaction mechanism and the difference in the calculated values of activation parameters with the change of the atmosphere were discussed in view of effect of the atmosphere on the carbon content of the ash.     

Non-isothermal two-membrane reactors for reversible gas phase reactions

The performance of a non-isothermal two-membrane reactor for reversible chemical reactions in gas phase has been analyzed by numerical simulation. The analyzed reactions were of the form: aA = bB + cC. Two membranes, that are permeable to all the components of the reaction mixture, are supposed to be the most permeable to one of the two reaction products, satisfying the condition of reverse products permselectivities. The reactant is taken to be the slowest permeating component. A negative temperature influence on the permeabilities of components has been assumed. Co-current plug flow pattern has been accepted. It has been shown that it is possible to enhance reactant conversion above that of a conventional reactor for both endothermic and exothermic reversible reactions, including adiabatic and non-adiabatic case. By using a two-membrane reactor, considerable lowering of feed temperatures is enabled for an endothermic reaction. For endothermic reactions, there is the optimum feed temperature, whereas for exothermic reactions, the higher the temperature, the lower is the attained conversion. In reactor design, the optimal external heat exchange for both endothermic and exothermic reactions can be determinated.     

Simulation approach to decomposition kinetics and thermal hazards of hexamethylenetetramine

The thermal stability of HMT under dynamic, isothermal and adiabatic conditions was investigated using differential scanning calorimeter (DSC) and accelerating rate calorimeter (ARC), respectively. It is found from the dynamic DSC results that the exothermic decomposition reaction appears immediately after endothermic peak, a coupling phenomenon of heat absorption and generation, and the endothermic peak and exothermic peak were indentified at about 277–289 and 279–296 °C (T_peak) with the heating rates 1, 2, 4 and 8 °C min⁻¹. The ARC results reveal that the initial decomposition temperature of HMT is about 236.55 °C, and the total gas production in decomposition process is 6.9 mol kg⁻¹. Based on the isothermal DSC and ARC data, some kinetic parameters have been determined using thermal safety software. The simulation results show that the exothermic decomposition process of HMT can be expressed by an autocatalytic reaction mechanism. There is also a good agreement between the kinetic model and kinetic parameters simulated based on the isothermal DSC and ARC data. Thermal hazards of HMT can be evaluated by carrying out thermal explosion simulations, which were based on kinetic models (Isothermal DSC and ARC) to predict several thermal hazard indicators, such as T_D24, T_D8, TCL, SADT, ET and CT so that we can optimize the conditions of transportation and storage for chemical, also minimizing industrial disasters.

     

Thermal analysis of polyesters containing oxirane groups

The preliminary studies of the thermal behaviour of polyester obtained in polycondensation process of cyclohex-4-ene-1,2-dicarboxylic anhydride and ethylene glycol and its new epoxidized form have been performed. The thermal characterization of initial polyester and its completely oxidized form was done by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TG). The non-isothermal DSC was applied to determine the influence of time and the temperature on the chemical modification of initial polyester using 38-40% solution of peracetic acid. On the basis of DSC profiles it has been found that the endothermic transition, due to the degradation process of initial polyester was characteristic feature under controlled heating program. The two characteristic transitions for the new epoxidized polyester, the exothermic peak corresponded to the thermal crosslinking of epoxidized polyester (322.8–336.4°C) and the endothermic decomposition peak of the cured material (363.8–388.9°C) were observed. The peak maximum temperatures (Tmax) and the heat of cross-linking reaction (ΔH_c) for epoxypolyester prepared at 20–60°C under 1–4 h were evaluated. The Tmax1 were almost independent from epoxidation conditions, while, the values of ΔH_c were dependent from conditions of synthesis. The ΔH_c values of this process decreased when time of oxidation increased. The highest values of ΔH_c at 40°C were obtained. Additionally, TG experiments confirmed two separated degradation steps of the new epoxidized polyester indicating the ester (370–380°C) and ether (450–460°C) bond breakdown.     

3,6-双(1-氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪银盐的热分解反应动力学及热安全性

利用两步合成法,得到标题化合物3,6-双(1-氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz)银盐（Ag2(BTATz)·2H2O）,并用元素分析、X荧光和红外光谱分析对其进行了结构表征。 采用DSC和TG-DTG技术对化合物进行热分解行为及非等温热分解动力学研究。 结果表明,其热分解过程是由1个吸热阶段和2个放热阶段组成,主放热阶段的非等温热分解反应动力学方程为:dα/dt=1014.29×{3(1-α)[-ln(1-α)]1/4/4}exp(-2.10×104/T)。 计算得到化合物的自加速分解温度(TSADT)、热爆炸临界温度(Tb)、热点火温度(TTIT)和绝热至爆时间（tTIAD）分别为517.10 K、580.12 K、531.00 K和90.32 s ,以此来评价其热安全性。     

Oxygen adsorption characteristics on hybrid carbon and boron‐nitride nanotubes

In this work, first‐principles density functional theory (DFT) is used to predict oxygen adsorption on two types of hybrid carbon and boron‐nitride nanotubes (CBNNTs), zigzag (8,0), and armchair (6,6). Although the chemisorption of O₂ on CBNNT(6,6) is calculated to be a thermodynamically unfavorable process, the binding of O₂ on CBNNT(8,0) is found to be an exothermic process and can form both chemisorbed and physisorbed complexes. The CBNNT(8,0) has very different O₂ adsorption properties compared with pristine carbon nanotubes (CNTs) and boron‐nitride nanotube (BNNTs). For example, O₂ chemisorption is significantly enhanced on CBNNTs, and O₂ physisorption complexes also show stronger binding, as compared to pristine CNTs or BNNTs. Furthermore, it is found that the O₂ adsorption is able to increase the conductivity of CBNNTs. Overall, these properties suggest that the CBNNT hybrid nanotubes may be useful as a gas sensor or as a catalyst for the oxygen reduction reaction. © 2014 Wiley Periodicals, Inc.     

光量热法初探甲基橙光催化原位降解过程

通过在室温下还原前驱体制备了Ag@AgCl催化剂, 并利用X射线粉末衍射仪(XRD)和场发射扫描电子显微镜(FE-SEM)对产物进行表征. 设计了新型光化学-微热量系统, 用该系统获得了Ag@AgCl光催化降解甲基橙实时、 在线的热力学和动力学瞬态信息. 研究结果表明, 该降解过程首先经历吸热再迅速进入放热阶段, 最后曲线恒定于一个长的放热平台, 计算得到ab, ac和ad段的热效应分别为-0.2609, 2.5845和40.7289 J, 放热平台cd的平均速率为2.581 mJ/s, 并详细探讨了该过程的微观降解机制.     

[Cu(TO)2(H2O)4](PA)2的制备、结构表征和热分解机理研究

[Cu（TO）2（H2O）4]（PA）2 was prepared by the reaction of aqueous 1,2,4-triazol-5-one （TO） solution with the solution of copper picrate Cu（PA）2 and characterized by elemental analysis, FT IR and X-ray powder diffraction analysis. The title complex has been studied by means of TG-DTG and DSC under conditions of linear temperature increase. The thermal decomposition residues were examined by FT IR analysis. Thermal decomposition mechanism of the title complex was proposed. In the temperature range of 30-680 ℃, the thermal decomposition process was composed of four major stages. The first stage was an endothermic process with the loss of four coordination water molecules. Since the dehydration product was unstable, when it was heated, it would be decomposed much more easily. The second stage was composed of an acute endothermic process and a continued strong exothermic process and the main decomposed residues were CuCO3, Cu（NCO）2 and polymers during this stage. The third stage was a sharp exothermic process, which resulted from the decomposition of the polymer. After the forth stage, the final decomposed residues were certainly copper oxide. The Arrhenius parameters have been also studied on the dehydration process and the first-step exothermic decomposition of [Cu（TO）2（H2O）4]（PA）2 using Kissinger＇s method and Ozawa-Doyle＇s method. The results using both methods were consistent with each other. The Arrhenius equation can be expressed as in k=24.0-179.8 × 10^3/RT for the dehydration process and in k= 16.7-206.0 × 10^3/RT for the first-step exothermic decomposition, on the basis of the average of Ea and In A through the two methods.     

Studies on the kinetics of synthesis of TiC by calciothermic reduction of TiO<Subscript>2</Subscript> in presence of carbon

Reaction kinetics of the formation of TiC by calciothermic reduction of TiO₂ in presence of carbon have been investigated using thermal analysis (TG-DTA) of a powder mixture of TiO₂, Ca, and C in argon atmosphere at different heating rates. Both the reaction initiation and the peak temperatures are found to increase with heating rates. The appearance of exothermic peaks in the DTA plots after Ca melting indicates the reduction of TiO₂ by liquid calcium and formation of TiC by in-situ reaction of Ti with C. The apparent activation energy of the process has been found to be 170.8±0.5 kJ mol^–1.     

Effect of LiPF<Subscript>6</Subscript> on the thermal behaviors of four organic solvents for lithium ion batteries

The thermal behaviors of four organic solvents with/without LiPF₆ were measured by C80 microcalorimeter at a 0.2°C min⁻¹ heating rate. With the addition of 1 M LiPF₆, the ethylene carbonate (EC) and propylene carbonate (PC) show the exothermic peaks at elevated temperature, which lessen their stabilities. The exothermic peak temperatures of EC and PC based LiPF₆ solutions are at 212 and 223°C, respectively, in argon filled vessel. However, two endothermic peak temperatures were detected in diethyl carbonate (DEC) based LiPF₆ solution at 182 and 252.5°C, respectively, in argon filled vessel. Dimethyl carbonate (DMC) based LiPF₆ solution shows two endothermic peak temperatures at 68.5 and 187°C in argon filled vessel at elevated temperature. Consequently, it is concluded that LiPF₆ play a key role in the thermal behavior of its organic solution.     

Physicochemical properties of ceramic tape involving Ca<Subscript>0.05</Subscript> Ba<Subscript>0.95</Subscript> Ce<Subscript>0.9</Subscript>Y<Subscript>0.1</Subscript>O<Subscript>3</Subscript> as an electrolyte designed for electrolyte-supported solid oxide fuel cells (IT-SOFCs)

Energetic materials such as a mixture of guanidine nitrate (GN)/basic copper nitrate (BCN) are used as gas generators in automotive airbag systems. However, at the time of the airbag inflation, the gas generators release toxic combustion gases such as CO, NH₃, and NO_x. In this study, we investigated the combustion and thermal decomposition behaviors of GN/BCN mixture, focusing primarily on their exhaust gas composition. As a result, when the exhaust gas of the combustion under constant pressure in an inert gas stream was analyzed using a detection tube, the amount of NO_x (mainly NO) yielded greater decrease with increasing atmospheric pressure as compared to the amounts of CO and NH₃. Thus, provided GN/BCN is ignited in a closed container, a large amount of NO_x is presumed to have been released during the initial stage of combustion, which yielded comparatively low pressure. Results of the thermogravimetry–differential scanning calorimetry–Fourier transform infrared spectroscopy (TG/DSC/FTIR) indicated that the GN/BCN mixture caused endothermic decomposition at 170 °C and exothermic decomposition at 208 °C, which was accompanied by 66% mass loss. The decomposition gases, CO₂, N₂O, and H₂O, were detected via FTIR spectrum. Because N₂O was not detected in the combustion gas, it was suggested that the detected N₂O was generated at a low temperature and decomposed in high-temperature combustion.     

Principal Limitations in Homogeneous Gas Phase Chemistry in Non-Thermal Plasmas

This study highlights the oxidation of H₂, CH₄, and HCl present in the range of some volume percent in a homogeneous O₂ or air phase in a flow through glass barrier discharge reactor. The oxidation of all three compounds is highly exothermic and exergonic at ambient temperature and proceeds at sufficiently high temperatures as radical chain reaction. The conversion of each compound was below 10% in a non-thermal oxygen plasma under various reaction conditions. Increasing concentrations of H₂ and CH₄ above the lower explosion limit did not lead to higher conversion degrees. It is assumed that only initial radical formation by electron impact dissociation and exothermic steps within the chain process run in a sufficiently fast manner at ambient temperature. For endothermic steps within the radical chain, the necessary activation energy is not available and the chain reaction aborts, most likely, after formation of peroxyl (hydro- or methyl-peroxyl) radicals.     

New view on the oxidation mechanisms of crude oil through combined thermal analysis methods

In the previous study, the oxidation behavior of four Chinese crude oils (Oil 1 to 4) in the presence and absence of rock cuttings was investigated by thermogravimetry/derivative thermogravimetry (TG/DTG) techniques and oxidation tube experiments. The present work investigates the thermal behavior of these oils by combining DTG–DTA method. First, we conducted comparative analysis about mass loss rate from DTG curves and endothermic/exothermic phenomenon from DTA curves attempting to clarify the endothermic or exothermic mechanism in crude oil low-temperature oxidation. Finally, we combined the thermal analysis method with low-temperature oil oxidation tube experiment in porous media to ascertain, whether the two methods are consistent in the aspect of low-temperature oxidation mechanism of crude oil by O₂ consumption rate and CO₂ generating rate (carbon bond stripping reaction rate). Results show that crude oils undergo an endothermic oxidation behavior during low-temperature oxidation stage, suggesting the decomposition of hydrocarbon components. Clay can play a catalytic effect on low-temperature oil oxidation. The results of DTG–DTA tests can also better reflect oil oxidation mechanism under real conditions.     

AIM Study on the Reaction of CH2SH Radical with Fluorine Atom

The reaction of CH2SH radical with fluorine atom was studied at the levels of B3LYP/6-311G(d,p) and MP2(Full)/6-311G(d,p). The computational results show that the reaction has three channels and proceeds by the addition of fluorine atoms on carbon or sulfur sites of CH2SH, forming initial intermediates. The calculated results show that the channel in which fluorine attaches to the carbon atom to form CH2S and HF, is the most likely reaction pathway. Topological analysis of electron density was carried out for the three channels. The change trends of the chemical bonds on the reaction paths were discussed. The energy transition states and the structure transition regions (states) of the three channels were found. The calculated results show that the structure transition regions are broad in unobvious exothermic reactions or unobvious endothermic reactions, and are narrow in obvious exothermic reactions or obvious endothermic reactions.     

Phase transition of RbH<Subscript>2</Subscript>PO<Subscript>4</Subscript> and its composite with SiO<Subscript>2</Subscript> studied by thermal analysis

The phase transition at T _p (~109 °C) of RbH₂PO₄ and its composite with SiO₂ has been investigated by thermal analysis here. In the case of neat RbH₂PO₄, there is a linear relationship between endothermic peak temperature (T _m) and square root of heating rate (Φ ^1/2), from which the onset temperature of phase transition can be determined. Besides, Kissinger method and another calculation method were employed to obtain the activation energy of phase transition. The detailed deduction process was presented in this paper, and the estimated activation energies are E ₁ ≈ 126.3 kJ/mol and E ₂ ≈ 129.2 kJ/mol, respectively. On the other hand, the heterogeneous doping of RbH₂PO₄ with SiO₂ as dopant facilitates its proton conduction and leads to the disappearance of jump in conductivity at T _p. The heats of transition in the composites decrease gradually with increasing the molar fraction of SiO₂ additives. In the cooling process, a new and broad exothermic peak appeared between ~95 and ~110 °C, and its intensity also changes with the SiO₂ amount. These phenomena might be related to the formation of amorphous phase of RbH₂PO₄ on the surface of SiO₂ particles due to the strong interface interaction.     

Laws of selective CO oxidation over a Ru/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst in the surface ignition regime: II. Transition states

The kinetics of selective CO oxidation (or individual CO or H₂ oxidation) over ruthenium catalysts are considerably as affected by the heat released by the reaction and specifics of the interaction of ruthenium with feed oxygen. In a reactor with reduced heat removal (a quartz reactor) under loads of ∼701 g_Cat⁻¹ h⁻¹ and reagent percentages of ∼1 vol % CO, ∼1 vol % O₂, ∼60 vol % H₂, and N₂ to the balance, the reaction can be carried out in the catalyst surface ignition regime. When catalyst temperatures are below ∼200°C, feed oxygen deactivates metallic ruthenium, the degree of deactivation being a function of temperature and treatment time. Accordingly, depending on the parameters of the experiment and the properties of the ruthenium catalyst, various scenarios of the behavior of the catalyst in selective CO oxidation are realized, including both steady and transition states: in a non-isothermal regime, a slow deactivation of the catalyst accompanied by a travel of the reaction zone through the catalyst bed along the reagent flow; activation of the catalyst; or the oscillation regime. The results of this study demonstrate that, for a strongly exothermic reaction (selective CO oxidation, or CO, or H₂ oxidation) occurring inside the catalyst bed, the specifics of the entrance of the reaction into the surface ignition regime and the effects of feed components on the catalyst activity should be taken into account.