含CL-20的改性双基推进剂的热行为及非等温反应动力学

用DSC和TG方法研究了含六硝基六氮杂异伍兹烷(CL-20)的改性双基推进剂在常压(0.1 MPa)和高压(4和7 MPa)下的热行为和高压下的热分解反应动力学. 结果表明, 该推进剂常压下DSC曲线有3个放热峰, 相应TG曲线有3个失重过程; 而高压下DSC曲线只有一个放热峰, 高压下放热峰的峰温随加热速率增大而升高. 高压下该推进剂放热分解反应机理和反应动力学参数受测试环境压强影响较弱, 反应机理是随机成核和随后生长, 放热分解反应的动力学方程可以表示为, 4 MPa时, dα/dt=1014.5(1-α)[-ln(1-α)]1/3e-17981.7/T; 7 MPa时, dα/dt=1014.7(1-α)·[-ln(1-α)]1/3e-18138.1/T.     

十二烷基氯化吡啶合成工艺的热危险性研究

利用全自动反应量热仪(RC1mx)、差示扫描量热仪(DSC)和绝热加速量热仪(ARC)检测十二烷基氯化吡啶合成反应的反应热、最大反应温度及热稳定性，依据绝热温升(ΔT_ad)、最大反应速率到达时间为24 h的温度(T_D24)和失控体系可能达到的最高温度(MTSR)等温度参数对工艺危险性进行评估。结果显示，ΔT_ad为276.2 K,T_D24为290℃，MTSR为165.6℃。经过研究反应温度和吡啶滴加时间，确认了145℃是合理的反应温度。如果缩短吡啶滴加时间会导致物料累积，影响反应转化率，增加危险性。     

阿司匹林的热解机理及热动力学研究

在用热重法研究了阿司匹林的热稳定性实验的基础上,通过量子化学方法(ab initio DFT)计算了阿司匹林分子的键级,据此计算结果提出了阿司匹林的热解机理,按此机理得到的理论计算值与实验结果一致;运用Freeman-Carroll、Kissinger和Ozawa三种方法分别计算了阿司匹林的热解动力学参数:活化能(E)、反应级数(n)和指前因子(A),其热解动力学方程为: dα/dt=4.74×1011[exp(－(100.34±5.18)×103/RT)](1－α)2.8±0.3;用差示扫描量热法测定的该物质的熔点、摩尔熔化焓和摩尔熔化熵分别为(409.19 ± 0.22) K、(29.17 ± 0.41) kJ•mol-1和(71.09±1.06) J•mol-1•K-1.     

热重-差示扫描量热法研究金属铝盐与载体的相互作用

通过浸渍法将相同负载量的不同类型的金属铝盐负载在介孔分子筛HMS内外表面,用热重-差示扫描量热(TG-DSC)法研究了金属铝盐热性质的变化。将负载型金属铝盐干燥、焙烧,得到负载型催化剂Al2O3/HMS样品,用X射线衍射(XRD)、N2吸附-脱附等手段对样品进行了介孔结构表征,并初步考察了催化剂上烷基化反应的活性。实验结果表明:负载金属盐的起始分解温度均高于金属盐,证明了金属盐与载体之间有相互作用。Al2O3/HMS催化剂在对苯二酚烷基化反应中表现出不同的催化活性。这种催化活性的高低与催化剂比表面积、孔容的大小没有相应的顺变关系,与负载金属盐与载体的相互作用有关,相互作用越弱,催化剂在烷基化反应中表现出的催化活性越高。     

高分子片状板材热分析测试影响因素的研究

研究了高分子片状板材的取样位置、样品尺寸、升温速率、热历史及气流速率对DSC及(或)TGA测试结果的影响,简要分析了各因素影响测试结果的原因。结果表明,升温速率对测试结果影响很大,热历史对测试结果有一定影响,取样位置及一定范围内的样品尺寸对测试结果影响不大,气流速率对测试结果影响较微。     

热爆合成三铝化钛复杂反应动力学的差示扫描量热法

用Friedman法研究了非等温DSC条件下热爆合成反应Ti 3Al→TiAl3的复杂反应动力学。根据表观激活能（Ea）随转化率（α）的变化关系，识别出该反应至少包含3个Ea值分别为109、175和89kJ/mol的子过程。通过与Ti-Al二元系的反应和互扩散激活能的比较，提出了可能的复杂反应动力学机制。     

陆英提取物乌索酸的热分析研究

用差示扫描量热法(DSC)和热重-微分热重法(TG-DTG)对静态空气气氛的乌索酸进行了热分析研究,为热分析鉴别乌索酸提供了实验依据.结果表明,加热到251℃时质量损失约3.31%,251～341 ℃时质量损失约68.09%,341～464 ℃时质量损失约27.70%,到464℃时质量仅余约0.90%.在158、311、415℃分别有3个放热峰.     

Thermal Decomposition Kinetics of Triethylene Glycol Dinitrate

Introduction Triethylene glycol dinitrate (TEGDN) is a novel en-ergetic material containing two groups of NO2, which can be used as an energetic plasticizer ingredient in propellants because of its excellent proformance.1 It exhibits lower impact sensitivity, better thermostability, weaker poisonousness and volatility, and stronger effec-tiveness of plasticizing cellulose nitrate than nitroglyc-erine (NG). As a new plasticizer TEGDN has good ap-plication prospects in the near future. The…     

差示扫描量热研究水稻线粒体能量释放动力学

线粒体是细胞的一个重要的亚细胞器．它通过呼吸作用为细胞各项活动提供能量，有细胞'动力戒'之称．生物摄取的食物通过代谢分解形成小分子产物之后，被输送至线粒体，经过氧化作用将其中贮存的能量逐步释放出来，并转化为三磷酸腺苦（ATP）以供生命机体各种活动的需要，因而它     

联苯聚醚醚酮酮的结晶动力学的研究

通过ｄｓｃ 方法对新型聚芳醚酮联苯聚醚醚酮酮（ＰＥＥＫＤＫ） 的等温及非等温熔融结晶动力学进行了研究,运用Ａｖｒａｍｉ 方程分析了其等温结晶行为,求得了等温结晶活化能,平衡熔点,成核参数,并与其它聚芳醚酮类聚合物进行了比较。同时,对ＰＥＥＫＤＫ的非等温结晶动力学也进行了研究。     

Non-isothermal Kinetic Study of the Heterogeneous Thermal Decomposition of a Mannich Compound

The authors present data concerning the evaluation of kinetic parameters of the decomposition of a Mannich compound by using the classical method of constant heating rate thermal analysis and the new one of controlled rate thermal analysis (CRTA). The data processed using the CRTA method allow to obtain more reliable kinetic parameters according to the proposed reaction mechanism. This revised version was published online in July 2006 with corrections to the Cover Date.     

Isothermal and nonisothermal crystallization kinetics of irradiated nylon 1212

The crystallization behavior of nylon 1212, irradiated at ⁶⁰Co γ‐rays (50 kGy), was studied by a rheometer, polarized optical microscopy (POM), and differential scanning calorimeter (DSC). The results showed that irradiated nylon 1212 samples exhibited abnormal crystallization behavior during the crystallization process: The Avrami exponent n was calculated and was found to be in the range from 2.06–2.41 for isothermal crystallization, and from 2.67–4.91 for nonisothermal crystallization; the spherulite morphology also changed largely by polarized optical microscopy (POM); the crystallization activation energy ΔE for isothermal and nonisothermal crystallization process of irradiated nylon 1212 are determined to be 57.4 kJ/mol and 78.65 kJ/mol, respectively, which are lower than that of nonirradiated nylon 1212. At the same time, a new method by a combination of the Avrami and Ozawa equations was successfully applied to analyze the noncrystallization process of irradiated nylon 1212. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2326–2333, 2005     

Thermal and Kinetic Studies on the Stability of Some Ureido-Sulfonamide Derivatives

The kinetic and thermal behaviour of the following compounds: R-HN-CO-NH-(CH₂)_n-C₆H₄-SO₂NH₂ where R=3,4-dichlorophenyl, phenyl, cyclohexyl; n=0, 1, 2 were studied by TG and DTA techniques. The compounds decompose in many steps; the last one corresponding to the burning of H₂N–S–C₆H₄–C₆H₄–S–NH₂ occurs with comparable reaction rates. This revised version was published online in August 2006 with corrections to the Cover Date.     

消旋卡多曲在空气中的热分解动力学

用热分析(TG/DTA/DSC)技术研究了消旋卡多曲(C₂₁H₂₁NO₄S)在空气中的热分解过程. 热分析结果表明, 消旋卡多曲在空气中一步分解, 其熔点为77.4 ℃. 用Friedman法, Flynn-Wall-Ozawa (FWO)法和ASTM E698法求取了分解过程的活化能E, 并通过多元线性回归法给出了可能的机理函数.     

溴化轻稀土丙氨酸配合物的热分解动力学

溴化轻稀土丙氨酸配合物的热分解动力学;溴化轻稀土丙氨酸配合物;差示扫描量热法;热分解动力学;分解机理     

Thermal decomposition of glassy poly(di-t-butyl fumarate) as a topochemical reaction

Decomposition of t-butyl carboxylate (TBC) groups in a glassy poly(di-t-butyl fumarate) (PDTBF) at 140–170°C proceeds with a sharp acceleration caused by interchain interaction of TBC and carboxylic groups. According to selective dissolution data, at 70% degree of conversion the reaction system contains both unchanged PDTBF and a final product: poly(fumaric acid). For TBC groups decomposition in di-t-butyl fumarate (DTBF)–styrene copolymers above their T_g an apparent rate constant of autocatalysis increases with the increase of DTBF content in copolymer. Together with previously obtained x-ray data these results lead to conclusions about the topochemical character of the PDTBF decomposition. The mechanism suggested includes thermal decomposition of TBC groups (initiation), autocatalytic growth of spheric clusters up to a critical size (an appearance of primary germs of the new phase), and growth and branching of thread-like germs. A mathematical model based on these assumptions describes quantitatively the kinetic data. © 1993 John Wiley & Sons, Inc.     

Thermal expansivity,volume and the effect of pressure on the isobaric heat capacity of 1-hexanamine from 0.1 to 400 MPa at 303, 353, 403 and 453 K

The thermal expansivity of 1-hexanamine has been determined as a function of pressure up to 400 MPa over the temperature range from 303 to 453 K. Measurements were performed in a pressure-scanning calorimeter by the stepwise technique. The compressibility as a function of pressure at 303 K was determined using the technique described before. The molar volume under atmospheric pressure was determined from the density measurements with a Paar instrument. From both the molar volume as a function of pressure at 303 K and the thermal expansivities the effects of pressure on the isobaric heat capacity were determined over the whole pressure and temperature range under study.

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Zusammenfassung Im Temperaturbereich 303–453 K wurde bis zu einem Druck von 400 MPa die Wärmeausdehnung von 1-Hexanamin als eine Funktion des Druckes ermittelt. Die Messungen wurden in einem Druck-Scanning Kalorimeter durch schrittweises Vorgehen ausgeführt. Unter Anwendung derselben Technik wurde bei 303 K die Kompressibilität als eine Funktion des Druckes ermittelt. Das molare Volumen bei atmosphärischem Druck wurde aus Dichtemessungen mit einem Paar-Instrument bestimmt. Aus dem molaren Volumen als eine Funktion des Druckes bei 303 K und den Wärmeausdehnungen wurde der Einfluß des Druckes auf die isobare Wärmekapazität über den gesamten untersuchten Druck- und Temperaturbereich bestimmt.

     

超细AgO粉末:制备及热分解非等温动力学

采用化学沉淀法,以臭氧为氧化剂制备了超细AgO粉末,并用XRD、XPS、SEM和粒度分析仪对制备的粉末进行了表征,借助热重分析法(TG)和线性升温理论对超细AgO粉末的热分解过程和非等温热分解动力学机理进行了研究。结果表明,制备的AgO属于单斜晶系,形貌为片状,其粒径分布在45～551nm之间,大部分在200nm左右;AgO的热分解分两步,158℃开始分解,放出氧气形成Ag2O,413℃进一步分解形成Ag;其热分解反应服从核生成和核成长为控制步骤的A2机理,热分解表观活化能为90.26kJ·mol-1,反应频率因子为1.64×108s-1。     

水合硼酸锶的制备及脱水热分解动力学

以氯化锶和硼酸氢铵为原料,采用液相沉淀法制备了片状水合硼酸锶（SrB6O10•5H2O）粉体,并用XRD、FT-IR及SEM进行了表征。利用热重分析法对片状纳米硼酸锶粉体的脱水热分解动力学进行了研究,分别采用 Coats- Redfern 方程和 Flynn-Wall-Ozawa（FWO）法对热重分析数据进行了处理和拟合,初步确定了水合硼酸锶的四步脱水过程及相应的热分解反应机理,得到各步反应的表观活化能和指前因子。