Thermal Decomposition of Polynitro Compounds under Nonisothermal Conditions

The effect of chemical structure on the thermal stability of multifunctional gem-trinitro compounds is studied. The characteristic temperatures and activation parameters of the thermal decomposition are determined. Depending on the structure of the compounds, the decomposition rate changes by more than two orders of magnitude, which is due not only to the effect of substituents but also to the different mechanisms of the rate-determining stage of the process. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 1, pp. 73–77, January–February, 2006.     

Investigation on Decomposition Kinetic and Thermal Stability of Metallocene Catalysts

Data on thermal stability of metallocene catalysts such as bis(n-butyl cyclopentadienyl) zirconium dichloride and bis(t-butyl cyclopentadienyl) zirconium dichloride is required because of their application in high temperature polymerization process. In the present study, the thermal stability of the bis(n-butyl cyclopentadienyl) zirconium dichloride and bis(t-butyl cyclopentadienyl) zirconium dichloride was determined by differential scanning calorimetry (DSC) and simultaneous thermogravimetry-differential thermal analysis (TG-DTA) techniques. The results of TG analysis revealed that the main thermal degradation for the bis(n-butyl cyclopentadienyl) zirconium dichloride and bis(t-butyl cyclopentadienyl) zirconium dichloride occurs in the temperature ranges of 194–360 °C and 195–350 °C, respectively. On the other hand, TG-DTA analysis indicated that bis(n-butyl cyclopentadienyl) zirconium dichloride melts (about 98.7 °C) before it decomposes. However, the thermal decomposition of the bis(t-butyl cyclopentadienyl) zirconium dichloride was started simultaneously with its melting. Also, the kinetic parameters such as activation energy and frequency factor for both compounds were obtained from the DSC data by non-isothermal methods proposed by Kissinger and Ozawa. Based on the values of activation energy obtained by Kissinger and Ozawa methods, the following order for the thermal stability was noticed: bis(t-butyl cyclopentadienyl) zirconium dichloride >bis(n-butyl cyclopentadienyl) zirconium dichloride. Finally, the values of ΔS^#, ΔH^# and ΔG^# of their decomposition reaction were calculated.     

Specific features of thermal decomposition of ammonium perchlorate subjected to γ radiation

Results of studying thermal decomposition of ammonium perchlorate (AP) samples in the original form and after irradiation by γ-quanta of ⁶⁰Co by methods of differential scanning calorimetry and dynamic thermogravimetry with heating rates b = 0.1–0.3 K/sec are described. Irradiation is performed in air at a temperature of 298 ± 2 K and a dose rate of ≈0.2 Gy/sec in the range of absorbed doses D = 0–150 kGy. Preliminary irradiation is demonstrated to lead to substantial transformations of the pattern of thermal decomposition of ammonium perchlorate in the dynamic regime of heating: the single-stage process of decomposition of non-irradiated samples proceeding at b = 0.107 K/sec in the temperature range of 625 to 743 K is replaced by a multistage process. At D = 150 kGy, exothermal transformations accompanied by noticeable losses of sample mass are observed starting from 473 K. Within experimental errors, the total thermal effect of AP decomposition is found to be independent of the absorbed dose and amounts to −1150 kJ/kg on the average. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 6, pp. 69–74, November–December, 2007.     

邻苯二甲酸镁的流变相合成及其热稳定性研究

用流变相反应法合成了二水邻苯二甲酸镁。通过元素分析、X-射线粉末衍射、红外光谱确定了它的组成和晶体结构,它为层状结构,属单斜晶系。用TG和DTA研究了它在氮气中的热稳定性,并用GC—MS、XRD表征了热分解产物。二水邻苯二甲酸镁在氮气中热分解分为两步：先失去两个结晶水,最终产物为氧化镁。生成的气相凝聚物成分比较复杂,主要是二苯甲酮、蒽醌。     

The thermal activation of propyl groups on Pt(111)

The thermal chemistry of 1‐ and 2‐propyl moieties on Pt(111) was studied by using temperature‐programmed desorption (TPD) and reflection–absorption infrared spectroscopy (RAIRS). The propyl intermediates were prepared via thermal activation of the C–I bond of 1‐ and 2‐iodopropane adsorbed precursors, respectively. It was determined that the subsequent thermal activation of those propyl groups results in a competition between reductive elimination to propane, β‐hydride elimination to propene, and complete decomposition to propylidyne (and eventually to hydrogen and surface carbon). It was found that while the 2‐propyl intermediate favors propene production, 1‐propyl also yields significant amounts of propane. The formation of propene via β‐hydride elimination was identified by isotopic labeling TPD experiments, and directly about 200 K by RAIRS. Coadsorption experiments with hydrogen and deuterium were used to characterize hydrogenation and H–D reactions. All possible propene and propane isotopomers are formed from both 1‐ or 2‐iodopropane on the D/Pt(111) surface, indicating that exchange is likely to occur via a cyclic propyl–propene–propyl mechanism involving the formation of both 1‐ and 2‐propyl intermediates. Relative rates for 1‐ versus 2‐propyl conversion were estimated. This revised version was published online in August 2006 with corrections to the Cover Date.     

高氯酸羟胺热分解动力学

引言 高氯酸羟胺(HAP)是一种用于推进技术领域的新型高能氧化剂,在高性能推进系统中具有极为重要的价值[1～3].     

Thermal Behaviors of Ferrocenyl-Terminated Hyperbranched Polyester

The first to the fourth generation (G1–G4) of ferrocenyl-terminated hyperbranched polyesters (HBPE-CP-Fe) were successfully synthesized by esterification between ferrocene carboxylic and hyperbranched polyester(HBPE).The molecular structures of HBPE-CP-Fe were characterized by FTIR, ¹H NMR and ¹³C NMR techniques. The thermal properties and the structure of thermal decomposition segments were investigated by thermal gravimetry (TG)-derivative thermal gravimetry (DTG), differential scanning calorimetry (DSC), FTIR and element analysis techniques. G1–G4 HBPE-CP-Fe are more thermally stable than G1–G4 HBPE and the incorporation of ferrocene could efficiently improve the thermal stability of HBPE. The thermal degradation of HBPE-CP-Fe is multi-stage process between 240 and 500 °C and the mass loss of the HBPE-CP-Fe seems to stop further at the temprerature above 500 °C with the final weight losing rate of 78.6%. The left residua is carbon and iron elements. A possible thermolysis mechanism is proposed as that the thermal decomposition might contain some complicated subsequent reactions including the scission of weak links of ester bands, the formation of intermediate composites and the degradation of the ferrocene.     

Ferrocene End-Cap Hyperbranched Poly (amine-ester): Structure and Catalytic Performance for Thermal Decomposition of Ammonium Perchlorate

Second to fourth generation (G2–G4) ferrocene end-cap hyperbranched poly (amine-ester) (HPAE-CP-Fe) was successfully synthesized by esterification of ferrocenecarboxylic acid and hyperbranched poly (amine-ester) (HPAE). The ¹H-NMR, ¹³C-NMR, FTIR, and mass spectra confirmed the structure of HPAE-CP-Fe and provided evidence of the successful modification of ferrocene to HPAE. The thermal behavior and catalytic performance for thermal decomposition of ammonium perchlorate (AP) were investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC). Activation energy and kinetic parameters were computed by the Kissinger method. The results indicated that HPAE-CP-Fe was more thermally stable than pure HPAE and that the ferrocenyl groups could efficiently improve the thermal stability of HPAE. Low- and high-temperature exothermic peaks of AP decreased with the addition of G2–G4 HPAE-CP-Fe into AP. Catalytic reactions were characterized by decreased activation energy and increased rate constant for thermal decomposition. An efficient catalytic effect of HPAE-CP-Fe on the thermal degradation of AP was observed. A possible catalytic mechanism was proposed where the electron transfer from Fe²⁺ to Fe³⁺ in ferrocene oxidized by AP accelerated the decomposition reaction under 300 °C. The formation of iron clusters with large surface areas may cause the rupture of the chemical bond in AP at high temperature.     

载体活性炭的热分析动力学研究

以热重分析为手段,考察了活性炭的热分解性能。采用多个升温速率法,获得热重(TG)和微分热重(DTG)曲线。采用等转化率法对实验数据进行了处理,求出其动力学参数。结果表明,随着升温速率的增大,TG曲线的失重反应起始温度及DTG曲线的峰温向高温方向漂移,出现温度滞后现象。根据采集的实验数据,将ln(βddαT)对Tl作图所拟合的直线的线性关系良好,根据直线斜率值求得的活化能E=96.59 kJ/mol。以ln[A.(1-α)n]对ln(1-α)作图得到一条直线,根据直线的斜率和截距可分别求得该反应在设定f(α)=(1-α)n形式下的n=3.585,A=40 189.859 84。     

尿素铁(Ⅲ)配合物的有机溶剂法合成及其热分解反应

使用硝酸铁和尿素在乙醇溶剂中合成了尿素铁(Ⅲ)配合物,通过元素分析和红外光谱分析等手段表征其组成为[Fe(CON2H4)6](NO3)3;再采用X射线衍射(XRD)、扫描电镜(SEM)和差热-热重分析(DTA-TG)等手段对所得[Fe(CON2H4)6](NO3)3配合物的热分解反应及其产物进行了研究。结果表明,热分解过程分两步进行,并在空气中200℃热分解后得到γ-Fe2O3纳米粉体。     

Non-isothermal degradation kinetics of poly (2,2′-dihydroxybiphenyl)

Catalytic oxidative polymerization of 2,2′-dihydroxybiphenyl (DHBP) was performed by using Schiff base polymer-Cu (II) complex and hydrogen peroxide as catalyst and oxidant, respectively. According to size exclusion chromatography (SEC) analysis, the number-average molecular weight (M _n), weight-average molecular weight (M _w) and polydispersity index (PDI) values of poly (2,2′-dihydroxybiphenyl) (PDHBP) were found to be 37,500, 90,000 g mol⁻¹ and 2.4, respectively. The thermal degradation kinetics was investigated by thermogravimetric analysis in dynamic nitrogen atmosphere at four different heating rates: 5, 10, 15 and 20 °C min⁻¹. The derivative thermogravimetry curves of PDHBP showed that its thermal degradation process had one weight-loss step. The apparent activation energies of thermal decomposition for PDHBP as determined by Tang, Flynn–Wall–Ozawa (FWO), Kissenger–Akahira–Sunose (KAS), Coats–Redfern (CR) and Invariant kinetic parameter (IKP) methods were 109.1, 109.0, 110.0, 108.4 and 109.8 kJ mol⁻¹, respectively. The mechanism function and pre-exponential factor were determined by master plots and Criado–Malek–Ortega method. The most likely decomposition process was a D _n Deceleration type in terms of the CR, master plots and Criado–Malek–Ortega results.     

间规聚苯乙烯的热分解行为分析

利用热重分析（TG—DTA）法研究了间规聚苯乙烯（sPS）在不同气氛（空气和氮气）下的热分解行为机理。研究表明,sPS在两种气氛下都是只有一个主要的热分解过程。结果表明,用Kissinger最大失重速率法求得空气气氛下的表观活化能为133．86kJ／mol,而在氮气气氛下的表观活化能为158．96kJ／mol;用Ozawa等失重百分率法求得空气气氛（10％～30％的失重率）下的表观活化能为92．05～105．88kJ／mol,而在氮气气氛下的表观活化能为149．00—175．38kJ／mol;sPS的热裂解和热氧分解过程均为一级反应。     

二甲基苯基硅氧基封端聚(二甲基-甲基苯基)硅氧烷共聚物的热分解性能及动力学研究

以1,1,3,3-四甲基二苯基二硅氧烷为封端剂,八甲基环四硅氧烷与甲基苯基环硅氧烷混合物为共聚单体,在阴离子催化剂作用下合成了二甲基苯基硅氧基封端的聚(二甲基-甲基苯基)硅氧烷共聚物。采用非等温TG技术,在惰性气氛和5.0、10.0、15.0和40.0 K min 1线性升温速率条件下,考察了共聚物非等温热降解机理及反应动力学,采用Friedman-Reich-Levi、Flynn-Wall-Ozawa和Kissinger等方法对非等温动力学数据进行分析,所得平均表观活化能分别为113.64、115.69和145.80 kJ mol 1。采用等转化率法确定出共聚物热分解反应符合Avrami-Erofeev方程,反应机理为随机成核和随后生长。采用Crane和Doyle方法研究了不同升温速率对反应级数、活化能和指前因子的影响,结果表明降解反应为一级反应,反应活化能介于152.46~183.13 kJ mol 1之间,指前因子介于4.25×109~4.02×109s 1。同时采用等温TG技术得到失重5%和10%条件下的寿命方程,对共聚物的寿命进行了预测。     

脱氢枞酸在空气中的热分解动力学

采用TG/DTA/DSC热分析技术,在线性升温速率为5、10、15和20 K·min^-1和静态空气条件下,研究了脱氢枞酸在空气气氛中的热分解动力学。由热重/差热法(TG/DTA)得到脱氢枞酸在空气中是一步分解;运用差示扫描量热法(DSC)测定了脱氢枞酸的熔点为445.05K,摩尔熔化焓为19.74 kJ·mol^-1和摩尔熔化熵为44.35J·mol^-1·K^-1;分别利用Kissinger法和Flynn-Wall-Ozawa法对脱氢枞酸非等温热分解数据进行了动力学分析,同时利用Satava-Sestak法研究了脱氢枞酸的热分解机理。结果表明,脱氢枞酸的热分解机理为收缩球状界面反应模型R3,热分解反应的表观活化能为107.89 kJ·mol^-1,指前因子为9.33×10⁸ s^-1)。     

Thermal decomposition kinetics of an epoxy resin with rubber‐modified curing agent

Thermal decomposition kinetics of diglycidyl ether of bisphenol A (DGEBA)/4,4′‐methylene dianiline (MDA) system with rubber‐modified MDA was studied by the methods of Ozawa, Kissinger, and Friedman, and the kinetic parameters were compared. The thermal decomposition data of the cured epoxy resin were analyzed by thermogravimetric analysis (TGA) at different heating rates. TG curves showed that the thermal decomposition of the epoxy system occurred in one stage regardless of rubber‐modified MDA content. The apparent activation energies for the DGEBA/MDA system with 10 phr of rubber‐modified MDA, as determined by the Ozawa, Kissinger, and Friedman methods, are 184, 182, and 222 kJ/mol, respectively. The thermal stability of the epoxy system increased with the increasing content of rubber‐modified MDA, which has four benzene rings with high thermal resistance due to the resonance structure. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 479–485, 2001     

PET黏合剂及其弹性体热解与推进剂热解相关性研究

采用差示扫描量热/热重(DSC/TG)和裂解气相色谱质谱联用(Py-GC/MS)分析技术研究了PET黏合剂体系、PET/TDI弹性体以及含PET黏合剂体系的简单组分推进剂的热分解特性和热裂解产物状况,探索了PET弹性体的热分解与含PET黏合剂体系的推进剂热解性能之间的相关性.研究结果表明,混合硝酸酯增塑的PET黏合剂体...     

Kinetics of heat release during decomposition of cellulose

The kinetic behavior and temperature dependences of the rate constants for thermal decomposition are determined for cellulose of different biological origins and forms. The possibility of thermal decomposition of cellulose in a combustion regime without oxygen is analyzed. Chernogolovka Institute of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Fizika Goreniya i Vzryva, Vol. 29, No. 6, pp. 49–53, November–December, 1993.     

储能硝酸熔盐的热稳定性分析

研究了商业化储能二元混合硝酸熔盐Solar salt (60% NaNO3?40% KNO3)的热稳定性和恒温热稳定性,采用热重法分析了其热分解温度,通过恒温实验考察了处于开放空气气氛中的NaNO3, KNO3和Solar salt在不同温度下的热稳定性,研究了NaNO3和KNO3在Solar salt高温不稳定性中的作用. 结果表明,大于500℃时温度越高,熔盐越不稳定,相同温度下不稳定程度NaNO3>Solar salt>KNO3. 温度升高,分解产物NO2?平衡含量增大而达到平衡的时间缩短,O2?含量很低. Solar salt中硝酸盐热分解和挥发的质量损失比接近1:1,NaNO3是造成体系热分解的主要原因,而KNO3起到抗挥发的作用.     

加巴喷丁的热分解过程及动力学

采用热重法(TG)和差示扫描量热法(DSC)测定加巴喷丁(GBP)在氮气氛和空气氛中的热分解过程,测定GBP、热分解过程中不同阶段残余物和气化物的红外光谱,探讨GBP的热分解机理.根据不同升温速率下的热重曲线计算GBP热分解反应的动力学参数,采用Dakin方程推算GBP在各种温度下的预期寿命.结果表明,GBP的热分解过...     

Thermogravimetric analysis of longan seed biomass with a two-parallel reactions model

The kinetic analysis of pyrolysis process of longan seed was performed in a thermogravimetric analyzer. All experimental runs were carried out by using an initial sample mass of 15 mg and final temperature of 650 °C under the inert atmosphere of nitrogen. Particle sizes in the range from 0.05–2.1 mm and the heating rates from 5–100 °C/min were employed to investigate their effects on the thermogram and the kinetic parameters. The TG curves generally showed sigmoid shape and displayed one major peak in DTG curve. The main devolatilization of longan seed occurred over the temperature range of 210–330 °C. It was found that heat transfer resistance in a particle could be reduced either by decreasing the size of particle or increasing the heating rate. The thermal decomposition of longan seed could be well described by the two-parallel reactions kinetic model. This analysis of reaction kinetic gave the values of activation energy for the decomposition of the two fractions in the model corresponding closely to those of hemicellulose and lignin.