纳米金属粉对高氯酸铵热分解动力学的影响

用TG和DSC研究了普通级和纳米级的铝、镍金属粉对普通高氯酸铵热分解特性的影响 .结果表明 ,普通级和纳米级铝粉对普通高氯酸铵热分解几乎没有影响 ,纳米镍粉对普通高氯酸铵的热分解 ,特别是高温阶段的促进作用最明显 .这种促进作用随着纳米镍粉含量的减少而逐渐减弱 .利用Coats Redfern积分法计算了超细高氯酸铵热分解的动力学参数 ,结果显示纳米镍粉使超细高氯酸铵热分解的表观活化能从 15 7.9kJ/mol下降为134.9kJ/mol,而其热分解的机理函数都同属于“成核和核成长”的Avrami Erofeev方程系列的函数 ,同时还探讨了纳米镍粉对高氯酸铵热分解促进作用的机理 .     

3,7-二硝基亚氨基-2,4-二氮杂双环[3,3,0]辛烷的放热分解反应动力学

在程序升温条件下 ,用DSC研究了标题化合物的放热分解反应动力学 .用线性最小二乘法、迭代法以及二分法与最小二乘法相结合的方法 ,以积分方程、微分方程和放热速率方程拟合DSC数据 .在逻辑选择建立了微分和积分机理函数的最可几一般表达式后 ,用放热速率方程得到相应的表观活化能 (Ea)、指前因子 (A)和反应级数 (n)的值 .结果表明 :该反应的微分形式的经验动力学模式函数、Ea 和A值分别为 (1-α) 0 .44、2 30 .4kJ/mol和 10 18.16s-1.借助加热速率和所得动力学参数值 ,提出了标题化合物放热分解反应的动力学方程 .该化合物的热爆炸临界温度为 30 2 .6℃ .上述动力学参数对分析、评价标题化合物的稳定性和热变化规律十分有用 .     

β-CD/1-MCP包结物热分解反应机理及动力学

用溶液法制备了β-CD与1-MCP的包结物,并借助于热分析和X射线粉末衍射法证实了包结物的存在,采用Satava-Sestak法,并结合Ozawa法和Kissinger法,推断出可能的热分解反应机理,获得了热分解反应的动力学参数。结果表明：β-CD与1-MCP包结物热分解反应在170～180℃出现失重,其机理为一维随机成核和随后生长反应,反应机理函数为2／3级反应,其降解反应的活化能为102.14 kJ／mol,指前因子值为3.63×10~(10)s~(-1)。较低的表观活化能说明了β-CD与1-MCP之间没有形成强烈的化学键。     

微型流化床-快速过程红外热分析仪对CaCO_3热分解的动力学研究

本文使用程序升温热重分析仪和自主开发的微型流化床(MFB)一快速过程红外(IR)热分析仪进行CaCO_3热分解动力学的实验研究。通过MFB-IR系统实验获得的碳酸钙分解活化能为107.7 kJ/mol,处于文献报道的范围之内;反应动力学模型符合形核与成长(n=2/3)模型。当转化率小于30%时,通过MFB-IR系统获得的CaCO_3分解活化能与热重较一致,但在转化率大于30%情况下,MFB-IR中获得的分解活化能随转化率的变化比热重分析所得活化能变化明显。同时,其活化能数值小于通过热重分析仪实验获得的数值。     

聚甲基丙烯酸甲酯热氧化降解的化学动力学研究

使用质谱、热分析手段研究了PMMA热解反应 .结果表明 ,在氮气中 ,PMMA -CH =CH2 有两个失重阶段 ,分别对应于主链末端双键引发的断链和主链无规则断链反应 ,转折点的失重率约为 2 6 % .其中 ,第一阶段的失重速率受扩散过程控制 ,平均表观活化能E为 15 8.5kJ/mol,lnA为 2 7.6 9;第二失重阶段为 1.5级化学反应 ,平均表观活化能E为 2 14 .79kJ/mol,lnA为 4 0 .4 6 .在空气中 ,PMMA也有两个失重阶段 ,反应机理为 1级化学反应 ,转折点处的失重率约为 70 % .其中在第一失重阶段平均表观活化能E为 130 .32kJ/mol,lnA为 2 4 .81,在此阶段中 ,过氧化基团的分解反应对PMMA的失重速率有重要影响 ;在空气中第二失重阶段平均表观活化能E为 78.2 5kJ/mol,lnA为 13.97.     

溴酸钾氧化甲基红褪色分光光度法的动力学

依据褪色分光光度法对BrO3--甲基红-NaCl体系进行了研究,实验表明,在518nm为最大吸收波长下,测定了该反应的动力学参数,确定了反应速率方程式,得知该反应的总反应级数为2.5级,表观活化能为55.82k J/mol,活化能为66.87kJ/mol,实验还测定了其他离子对该反应的催化作用,达到了预期的结果.     

生物油及其重质组分的热解动力学研究

采用热重分析法对生物油及其三种重质组分模型化合物的热解特性进行了对比研究,并对动力学参数进行了求解.结果表明:生物油的热解包括挥发组分的蒸发及重质组分的裂解两个阶段,反应级数都是4级,活化能分别为29～36kJ/mol及13～19 kJ/mol;三种重质组分模型化合物中左旋葡聚糖也存在两个失重区间,反应级数分别为1和2,且表观活化能最高;3,4二甲氧基苯甲醛和丁香酚则只有一个失重区间,且相应的反应级数分别为0.8和0.5,表观活化能也依次降低.     

对甲基苯磺酰化丝氨酸Nd(Ⅲ)配合物的合成、表征及热分解反应动力学

合成了对甲基苯磺酰化丝氨酸配体(L)和对甲基苯磺酰化丝氨酸Nd(Ⅲ)配合物。通过元素分析、热分析、红外光谱、紫外光谱和摩尔电导等分析技术,确定配合物的组成为NdL3。用非等温热重分析方法研究了Nd(Ⅲ)配合物的热分解反应动力学,分解反应一步进行,其分解的动力学方程为dα/dt=Aexp(-Ea/RT)(1-α)2,并计算出了该步热分解的活化熵ΔS#、活化吉布斯自由能ΔG#和活化焓ΔH#分别为-86.7674J/mol.K、219.3884kJ/mol、170.9938kJ/mol。     

水合乙酸锌脱水反应的动力学

用等温热重法和非等温热重法研究了Zn(CH3COO) 2·2H2 O的脱水反应 .在 61.1、62 .8、66.2、69.9℃下的等温热重数据 ,由等转化率下的lnt=E/RT +ln[g(α) /A]进行拟合 ,确定了活化能的大小 ;升温速率为 10℃ /min的非等温热重曲线显示 ,Zn(CH3COO) 2·2H2 O的脱水反应发生在 71～ 10 2℃间 ,其数据通过Doyle Zsako法进行拟合 ,以线性相关系数为判据 ,并结合等温热分析拟合结果 ,得到该脱水反应的积分动力学模式函数g(α) =[-ln( 1-α) ]2 / 3、活化能E =10 0 .8kJ/mol、指前因子ln(A/s-1) =3 6.0 9、动力学补偿效应方程为lnA =0 .3 3 3 9E + 2 .0 10 .     

Structural Characterization and Thermal Properties of 1-Amino-1-ethylamino-2,2-dinitroethylene

1,1-二氨基-2,2-二硝基乙烯(FOX-7)和乙胺水溶液在92 oC下反应合成出了一种新型含能材料1-氨基-1-乙氨基-2,2-二硝基乙烯(AEFOX-7). 利用理论计算方法研究了AEFOX-7的分子结构、红外吸收和核磁共振化学位移. 用DSC和TG/DTG研究了AEFOX-7的热行为. 其热行为可分为一个熔化过程和一个紧接的剧烈放热分解过程. 热分解反应的放热焓、表观活化能和指前因子分别为：374.88,169.7 kJ/mol和1019.24 s^-1, 热爆炸的临界温度 是145.2 oC. 采用微量热法和理论计算方法研究了AEFOX-7的比热容,298.15 K时为214.50 J/(mol K).     

基于ReaxFF模拟的正戊烷热分解机理研究

采用密度泛函理论和ReaxFF力场对正戊烷的热分解机理进行研究,分析了热分解的起始反应路径、温度对热分解的影响,并对正戊烷热分解进行了一级动力学研究。结果表明正戊烷热分解的起始反应主要分为两类:一类为碳碳单键断裂,另一类为碳氢键断裂,其中C2-C3键断裂是主要的起始反应路径。正戊烷热分解的主要产物为氢气、甲烷、乙烷、乙烯、乙炔、丙烷和丙烯。经过一级动力学计算得到表观活化能和指前因子分别为224.4 kJ·mol^-1和3.1324×10^14 s^-1。     

A thermal and electrochemical properties research on gel polymer electrolyte membrane of lithium ion battery

N-methyl-N-propyl-piperidin-bis(trifluoromethylsulfonyl)imide/bis(trifluoromethylsulfonyl) imide lithium base/polymethyl methacrylate(PP₁₃TFSI/LiTFSI/PMMA) gel polymer electrolyte (GPE) membrane was prepared by in situ polymerization. The physical and chemical properties were comprehensively discussed. The decomposition characteristics were emphasized by thermogravimetric (TG-DTG) method in the nitrogen atmosphere at the different heating rates of 5, 10, 15 and 20 °C min⁻¹, respectively. The activation energy was calculated with the iso-conversional methods of Ozawa and Kissinger, Friedman, respectively, and the Coats-Redfern methods were adopted to employ the detailed mechanism of the electrolyte membrane. The equation f(α)=3/2[(1−α)^1/3−1] was quite an appropriate kinetic mechanisms to describe the thermal decomposition process with an activation energy (E_α) of 184 kJ/mol and a pre-exponential factor (A) of 1.894×10¹¹ were obtained.     

Influence of γ-irradiation on the non-isothermal decomposition of calcium-gadolinium oxalate

Thermal decomposition of co-precipitated unirradiated and irradiated Ca-Gd oxalate has been studied by adopting differential thermal analysis (DTA) and thermogravimetric (TG) techniques. The reaction occurs through two stages corresponding to the decomposition of gadolinium oxalate (Gd-Ox) followed by that of calcium oxalate (Ca-Ox). The kinetic parameters for both the stages are calculated by using solid state reaction models and Coats-Redfern's equation. The co-precipitation as well as irradiation alter the DTA peak temperatures and the kinetic parameters of Ca-Ox. The decomposition of Gd-Ox follows the two dimensional Contracting area ( R 2 ) mechanism, while that of Ca-Ox follows the Avrami-Erofeev ( A 2 ) mechanism ( n =2), which are also exhibited by the co-precipitated and irradiated samples. Co-precipitation decreases the energy of activation and the pre-exponential factor of the individual components but the reverse phenomenon takes place upon irradiation of the co-precipitate. The mechanisms underlying the phenomena are explored.     

Influence of Ca2+ or Na+ extraframework cations on the thermal dehydration and related kinetic performance of LSX zeolite

Nitrogen adsorption performances of low-silica type X zeolites (LSX) containing Na⁺ or Ca²⁺ ions were studied and compared with Li⁺ ion, and their structural and thermal properties were investigated using various characterizations (XRD, TG-DTG, BET, XPS, SEM, TEM, and EDX with elemental mapping techniques). The kinetics of their thermal dehydration and decomposition was studied using thermogravimetry at three rates (5, 10, and 15 K/min) of linear increase of temperature under non-isothermal heating. Two model free procedures named, Kissinger, and Flynn–Wall–Ozawa (iso-conversional) and one model fitting method called Coats–Redfern based on single TG curves, as well as 41 mechanism functions were used. The kinetic parameters (apparent activation energy E, pre-exponential factor A and model) of the three phases for each sample obtained from the non-isothermal methods were then compared with the results from iso-conversional methods this showed that they strongly depend on the selection of appropriate mechanism function and the corresponding kinetic model from the perspective of crystal structure used. The results demonstrated that the E value obtained at low temperature was lower than that at high temperature, implying that the dehydration process of physisorbed water belongs to diffusion-based control, while decomposition of bonded water (chemisorbed) belongs to kinetic-based control at high temperature. These comparisons allow us to underline the strong effect of cations in association with water and their distribution in the micropores of LSX on the N₂ adsorption performance.     

A Kinetic Study on the Thermal Degradation of Polypropylene/Attapulgite Nanocomposites

In this work, a polypropylene (PP)/attapulgite nanocomposite was prepared via melt blending using a novel organically modified attapulgite (OATP). The thermal stability of PP/clay nanocomposites compared to pure PP was examined in nitrogen using a kinetic analysis. The kinetic parameters, including reaction order and activation energy (A and E _a) of the degradation process were determined by applying the Flynn‐Wall‐Ozawa method using derivative thermogravimetric (DTG) curves. At the same time, the effect of organic attapulgite on thermal decomposition of polypropylene matrix was analyzed. As a result, PP/OATP nanocomposites have slightly higher degradation temperature than that of the pure PP. The values of the reaction order of PP and PP/OATP nanocomposites are close to 1 in the nonisothermal degradation process. The activation energies of PP/OATP nanocomposites also increase slightly compared to the pure PP, thus it is suggested that the org‐attapulgite has little effect on the thermal stability of the pure PP.     

GAP和GAP/B的红外光谱和热分析研究

采用傅里叶红外光谱测试(FTIR)、热重法(TG)和微商热重法(DTG)研究了GAP和GAP处理硼的样品(GAP/B)在空气和氮气两种环境中的热分解。结果表明：GAP在约170 ℃开始发生叠氮基消除反应,250 ℃左右结束,GAP骨架的解聚反应延后了40 ℃左右;硼(B)改变了GAP的热分解过程,GAP/B在55～70 ℃开始分解,明显提前于GAP本身,而且,叠氮基的消除反应与GAP骨架的解聚反应几乎同时发生。基于Kissinger热分析数据处理方法,对GAP和GAP/B两种体系在叠氮基消除阶段的热分解动力学进行了研究,结果发现在空气环境中,两种体系的活化能E的数值均较低,较易于发生反应,这是由于GAP与空气中的氧发生有氧热解所致。