Thermal Stability and Decomposition Kinetics of Poly(Methacryloyloxyethyl Trimethyl Ammonium Chloride-Co-Acrylamide)

Abstract

Poly(methacryloyloxyethyl trimethyl ammonium chloride-co-acrylamide) (P(DMC-AM)), is widely used for various applications under a wide range of conditions. In this work the thermal stabilities and decomposition kinetics of P(DMC-AM) with various intrinsic viscosities, synthesized in our laboratory, were studied by thermogravimetric analysis (TGA) at various heating rates, 5, 10, 20 and 40?K/min, and differential scanning calorimetry (DSC) at 10?K/min, all under a dynamic nitrogen atmosphere. The kinetic parameters were calculated using a model fitting method (Coats–Redfern, CR) and two model–free methods (Kissinger–Akahira–Sunose, KAS and Flynn–Wall-Ozawa, FWO). The result showed that all samples exhibited three steps of mass loss, one for the elimination of the adsorbed water and organic solvents and two for the thermal decomposition of P(DMC-AM). The first decomposition stage for the three samples was in the range of 5% to 45%, the second decomposition stage in the range of 65% to 95% and with 55% conversion separating the first and second decomposition stages. The E values increased with the increasing intrinsic viscosity of the samples. Hence, P(DMC-AM) had good thermal stability and the higher the molecular weight, the better the thermal stability was.     

地开石热分解过程及非等温动力学研究

用傅利叶变换红外光谱仪研究了湖南晨溪地开石热分解前后的红外光谱,加热反应后原矿粉红外光谱在3620.73、3695.34cm-1处的地开石羟基伸缩振动吸收峰和在916.06、1009.33cm-1处的羟基弯曲振动吸收峰都消失,表明其质量失重为羟基脱水.在298～1123K,用TG DTA综合分析仪研究了地开石在程序升温下的热分解行为.结果表明,在600～1000K,其质量损失为13.7%,与理论计算的脱水量相近.根据TG DTG曲线上的基础数据,联合运用积分法(Coats Redfern方程、HM方程、MKN方程)和微分法(Achar方程)对地开石脱水反应过程进行了非等温动力学研究,结果显示,地开石热分解反应的机理函数为F2,求得反应的动力学参数:反应级数为2.1,表观活化能为131.62kJ/mol,指前因子为108.3s-1.作为一种验证方法,使用Ozawa方程对不同升温速率TG曲线上相同分解率处的绝对温度进行线性回归分析,求出的表观活化能值为133.07kJ/mol,此值不仅与上述各种方法的表观活化能值相近,也与确定机理函数时的表观活化能值相近.说明实验求得的动力学参数在很大程度上是可靠的.     

聚-α-甲基苯乙烯热降解动力学研究

利用热分析技术(TG/DTG)对聚--甲基苯乙烯(PAMS)在氮气气氛下以不同升温速率为条件进行热降解动力学研究。研究结果表明:PAMS的热降解步骤为一步反应,在升温速率为10 ℃/min时,主要失重温度区间为302～343 ℃,热失重速率最大时温度为325 ℃。在同一温度下,随着升温速率的不断提高,主要降解温度向高温区移动。采用了Kissinger,Flynn-Wall-Ozawa及Coats-Redfern方法研究其动力学参数,确定了PAMS的降解活化能在160～220 kJ/mol之间、反应级数为一级。     

Characteristics and Kinetics of Thermal Degradation of Fluoroether Rubber

An advanced, heat-resistant fluoroether rubber (FM-20) was subjected to dynamic thermogravimetric analysis (TGA) in the air atmosphere. The results suggested that its thermal degradation process can be divided into two parts. As the heating rate increased, the initial decomposition temperature and degradation temperature would move to higher ranges. The apparent activation energy of thermal decomposition, calculated by the Kissinger, Friedman and Flynn-Wall-Ozawa methods were 209, 240, and 211kJ/mol, respectively. Furthermore, the probable thermal degradation mechanism was also analyzed by the Coats-Redfern method. As a result, the most reasonable thermal degradation mechanism of FM-20 was g (α) = α^3/2     

钾基CO2吸收剂再生反应特性

通过热重分析试验研究了钾基 CO2 吸收剂的再生反应特性.深入分析了气氛、分解终温和升温速率对再生转化率和分解反应速率的影响.通过热分析方法求取了反应动力学参数.研究发现,其分解终温最佳值为 200℃;CO2 和H2O 在分解终温较低时对反应过程的影响较大;升温速率对反应的影响程度在其高于 10℃/min 后明显减弱;KHCO3分解反应的表观活化能为 90～120 kJ/mol.本文为干法 K2CO3/KHCO3 循环脱除 CO2 的研究提供了一定的基础数据.     

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.     

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。     

Thermal Properties of Carboxymethylcellulose and Methyl Methacrylate Graft Copolymers

Carboxymethyl cellulose and methyl methacrylate graft copolymers (CMC-g-PMMA) were synthesized by using potassium persulphate (KPS) as initiator. These graft copolymers were characterized by Fourier transform infrared spectra (FTIR), thermogravimetric analyses (TGA), and differential scanning calorimeter analyses (DSC). In addition, the nonisothermal thermal decomposition kinetics of copolymers was studied. The experimental results indicated that in the temperature range from 300°C to 450°C, the copolymer had a mass loss. The activation energy was 41.96 kJ/mol, and the logarithm of the Arrhenius coefficient (lnA) was 17.31.     

Thermal Degradation Kinetics of Plasticized Poly (Vinyl Chloride) with Six Different Plasticizers

Plasticized PVC formulated with different kinds of normally used plasticizers, including bis(2-ethylhexyl) phthalate (DOP), dioctyl terephthalate (DOTP), acetyl tri-n-butyl citrate (ATBC), acetyl trioctyl citrate (ATOC), trioctyl trimellitate (TOTM), and a new vegetable devived plasticizer, isosorbide ester (ID-37), were prepared by a melt blending method. The effect of plasticizer on the thermal degradation behavior of plasticized PVC was investigated by thermal gravimetric analysis (TGA). The activation energies were calculated by three well known methods, developed by Flynn-Wall-Ozawa (FWO), Friedman and Kissinger, respectively. The TGA conducted in N₂ atmosphere showed that the type of plasticizer had an obvious influence on the thermal stability of plasticized PVC. It was found that the peak temperatures (T_P) of the thermal degradation processes shifted to higher temperature with the increase of the heating rate, with two processes being shown. The activation energy of the first thermal decomposition process (E₁), calculated by the Kissinger method, was between 118 and 130 kJ/mol, while the activation energy of the second thermal decomposition process (E₂) was between 261 and 305 kJ/mol, except 499 kJ/mol for the PVC/TOTM formulation. The corresponding values of E₁ and E₂ obtained by the Flynn-Wall-Ozawa method were similar to the above data. E of the sample with TOTM also showed a higher value than the others; the results demonstrated that the PVC plasticized with TOTM was more thermally stable than with the others. The activation energies for certain conversion degrees were calculated by the Friedman method and the FWO method. The value of activation energy for 20%, 50%, and 80% conversion calculated by the Friedman method, exhibited an apparent difference from that calculated by the Flynn-Wall-Ozawa method; the results showed that the value of E obtained by the Friedman method was much more reasonable than that obtained by the Flynn-Wall-Ozawa method.     

Kinetics Study on Thermal Decomposition of Polyepoxyphenylsilsesquioxane/Epoxy Resin Systems

The thermal decomposition kinetics of epoxy resin (EP) containing polyepoxyphenylsilsesquioxane (PEPSQ) was studied by thermogravimetric analysis (TGA) in a nitrogen atmosphere. Kissinger and Flynn–Wall–Ozawa methods were both used to analyze the thermal decomposition process under nonisothermal conditions. The results showed that a slight increase of activation energy was observed in the presence of PEPSQ, which indicated that the addition of PEPSQ retarded the thermal decomposition of EP. The Flynn–Wall–Ozawa method further revealed that PEPSQ significantly increased the activation energy of the whole EP thermal decomposition, especially in the final stage of the thermal decomposition process, which is attributed to the PEPSQ stabilizing the char layer and improving the flame retardancy of EP.     

原位漫反射红外光谱研究升温速率对HMX炸药热分解过程的影响

原位红外光谱法是一种新兴的动态研究方法。该方法具有原位实时监控和红外光谱精确分析物质化学结构的优点,能够实时跟踪材料在不同温度下的化学变化,测定材料的微观结构与温度的关系。采用原位漫反射红外光谱研究了炸药1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷(HMX)分别在每min 5, 10, 20和40 ℃四种不同升温速率下的热分解行为。研究结果表明：在5 ℃·min-1升温速率下,断裂的HMX环发生分子内结合,在10, 20和40 ℃·min-1升温速率下,断裂的HMX发生分子间成环,形成稳定的八元环结构。随着温度的升高,C—N键的断裂数率远高于N—N键的断裂速率。随着升温速率的增加,C—N键的起始分解温度增加,表明增加升温速率会引起HMX分解的滞后。检测到HMX的分解所释放出CO₂, N₂O, CO, NO, HCHO, HONO, NO₂和HCN共八种气体,升温速率的变化未改变HMX的分解机理。     

Thermal Decomposition Behavior of a Heterocyclic Aramid Fiber

Heterocyclic aramid fibers are one of the high-performance fibers with excellent mechanical and thermal properties. In this article, the thermal decomposition behaviors of a type of the fibers were studied in nitrogen and air by pyrolysis/gas chromatography–mass spectrometry (Py/GC-MS), thermal gravimetric analysis–differential thermal analysis/Fourier transform infrared spectroscopy (TGA-DTA/FTIR), and thermal gravimetric analysis–differential thermal analysis/mass spectrometry (TGA-DTA/MS). The results showed that under nitrogen atmosphere, the thermal decomposition mainly happened between 520°C and 580°C, the temperature of the maximum weight loss rate was 550°C, and the weight remaining at 800°C was 58%. HCN, NH₃, NO₂, NO, CO₂, CO, H₂O, and some other compounds containing benzene rings were detected by the TGA-DTA/FTIR. Among these released chemicals, the intensity of the absorption peak assigned to CO₂ was the strongest. These chemicals were also identified by the TGA-DTA/MS. The Py-GC/MS analysis revealed that the number of chromatographic peaks increased with the increase of temperature. Most of the pyrolysis products were produced between 550°C and 600°C, which represented the major pyrolysis process. Moreover, the detection of benzene ring containing compound fragments reflected the process of the molecular chain scission. In air atmosphere, the thermal decomposition mainly happened between 500°C and 680°C. The maximum weight loss rate was observed at 600°C, and almost 100% weight was lost at 900°C. NH₃, NO₂, CO₂, and H₂O were detected by the TGA-DTA/MS, and the ion current intensity of CO₂ was again the strongest with a strong oxidation reaction at around 670°C. It was speculated that the thermal decomposition began with the breaking of the bonds between PPTA (poly-p-phenylene terephthalamide) blocks and heterocyclic blocks at high temperature. Then, with the increase of temperature, the chemical bonds inside the PPTA blocks and heterocyclic blocks were broken. In this process, free radicals that led to restructuring and new breakages to produce micromolecular products were introduced.     

On the Thermal Degradation of a Novel Epoxy-Based Nanocomposite Cured With Tryptophan as an Environment-Friendly Curing Agent

The thermal degradation kinetics of diglycidyl ether of bisphenol-A (DGEBA) cured with tryptophan (Trp) in the presence of silica nanoparticles (SiNP) was investigated by thermogravimetry analysis. The activation energies of the solid-state decomposition process were evaluated using the advanced isoconversional method. The dependence of conversion (degradation) on the temperature and activation energy was determined allowing the calculation of master plots. The experimental master plots agreed with the first-order (F1) kinetic function for both neat epoxy and nanocomposite in the conversion range of 0.45–0.85. Using the kinetic model and the calculated kinetic parameters, the times at half conversion (α = 0.5) were computed for different degradation temperatures. The kinetic analysis showed that the degradation rate of the epoxy nanocomposite was lower than that of the neat epoxy for conversions between 0.45 and 0.85. Therefore, we concluded that adding SiNP to DGEBA/Trp can improve the thermal stability in the conversion range of 0.45–0.85.     

High-Pressure Analysis of the Multiple Melting Endotherms of Poly(ethylene succinate) and Poly(butylene succinate)

The origin of the multiple melting peaks in two linear polyesters, poly(ethylene succinate) (PES) and poly(butylene succinate) (PBS), of isothermally crystallized samples was investigated by differential scanning calorimetry (DSC) at atmospheric pressure and high-pressure differential thermal analysis (HP-DTA) at elevated pressures. In PES, the DSC melting curves showed three endothermic peaks at slow heating rates, which decreased to two with increasing heating rates. The HP-DTA curves showed that the area (qualitative) and peak height of the high-temperature peak decreased with increasing pressure and merged with the low-temperature peak at pressures above 450 MPa. This behavior supported the melting, recrystallization, and remelting model for the observed multiple melting endotherms. In PBS, the DSC melting curves were similar to those seen in PES. The HP-DTA curves were also similar to PES up to 400 MPa, but above this pressure the area and the peak height of the high-temperature peak and the temperature difference between the high- and low-temperature peaks remained unchanged. This observation suggested that the two peaks in PBS were due to the melting of two populations of crystals with different lamellar thickness originally present in the sample. The multiple melting behavior in isothermally crystallized PBS is proposed to incorporate both the melting of two populations of crystals and melting, recrystallization, and remelting.     

Synthesis and Thermal Behavior of Silica‐Graft‐Polypropylene Nanocomposites Studied by Step‐Scan DSC and TGA

Silica graft poly(propylene) (silica‐g‐PP) nanocomposites were successfully prepared by radical grafting copolymerization and ring‐opening reaction. Their thermal properties were studied by step‐scan differential scanning calorimetry (SDSC) and thermogravimetric analysis (TGA). The exothermic peaks in the IsoK baseline (C_p,IsoK, nonreversing signal) of SDSC reveal that PP and silica‐g‐PP nanocomposites undergo melting‐recrystallization‐remelting during heating. The peak temperatures of recrystallization and remelting shift upward with the existence of nanoparticles in the PP matrix. The thermal degradation kinetics of silica‐g‐PP nanocomposites were investigated using nonisothermal TGA and the Flynn‐Wall‐Ozawa method. The results indicate that the thermal stability was significantly improved with increasing silica content, mainly because of the physical‐chemical adsorption of the volatile degradation products on the nanoparticles that delays their volatilization during decomposition, and the covalent interaction between nanoparticles and PP chains, which will also reduce the breakage of PP backbone chains.     

石灰石颗粒分解的动力学模型研究

本文应用热重法对石灰石在氮气气氛、不同升温速率下的分解动力学进行了研究,采用普适积分法、微分方程法以及多重速率扫描Kissinger法相结合的方式求解动力学参数,确定反应机理模型。研究结果表明石灰石分解反应符合相边界反应的收缩圆柱体模型,采用三种方式相结合的动力学处理方法可以有效的进行动力学模式函数的选取。     

Effect on thermoluminescence parameters of biotite mineral due to thermal quenching

The Thermally Stimulated Luminescence (TSL) at room temperature X-ray irradiated natural biotite in form of micro-grain powder was studied under various heating rates. TSL peaks showed at temperatures 393 K, 399.6 K, 403.5 K, 404.5 K, 406.9 K at their respective heating rates 2 K/s, 4 K/s, 6 K/s, 8 K/s and 10 K/s. The effect of thermal quenching on thermoluminescence parameters such as peak maximum temperature, peak area, FWHM, geometrical symmetry factor, the activation energy were investigated. From the symmetry factor it is clear that the TL glow curve follows the first order kinetics for the lowest heating rate, but as the heating rate increases it defers from the first order. The activation energies for each heating rates were calculated by using Chen peak shape methods for general order kinetics and found to be decreased for higher heating rates. When activation energy is calculated by variable heating rate method it is observed that the method overestimated the value of activation energy and pre-exponential frequency factor significantly due to thermal quenching.     

0.53 μm毫秒脉冲激光对GaAs热分解损伤特性

针对波长0.53 m的毫秒脉冲激光辐照GaAs的表面热分解损伤问题,建立了二维轴对称热传导模型,在考虑材料的热物性参数随温度变化的基础上,采用有限元法模拟了材料的瞬态温度场,得到了温度场分布特征及其随时间的变化规律,给出了材料表面发生热分解损伤阈值曲线。数值结果表明:毫秒脉冲激光对GaAs作用时,热传导影响着激光作用全过程,对应的损伤机理主要为热损伤;在激光作用下,被作用表面中心处温度最高,并且首先发生热分解损伤;随着作用激光能量密度的增加,GaAs表面发生热分解损伤的时刻不断提前。