聚氯乙烯/多壁碳纳米管复合材料的热降解研究

采用熔融共混法制备了聚氯乙烯/多壁碳纳米管(PVC/MWCNT)复合材料,利用热失重法研究了MWCNT对PVC热降解及热寿命的影响,采用Kissinger法和Friedman法计算了复合材料的热降解动力学参数。结果表明,添加MWCNT后,复合材料的初始降解温度T0和最大热失重速率温度Tm较纯PVC均有提高,含量4%时,T0和Tm分别提高了18.9℃和22.76℃。Kissinger法计算的活化能随MWCNT含量增加呈先增大后减小趋势,在含量4%时复合材料两个失重阶段分别提高了82.23 kJ/mol和18.54 kJ/mol,Friedman法计算得到的活化能变化趋势与Kissinger法一致。     

聚丙烯/纳米金刚石复合材料热降解动力学研究

用熔融共混法制备了纳米金刚石（Nano-diamond）/聚丙烯复合材料,利用热重分析（TGA）法研究了复合材料的热降解动力学,并采用Flynn-Wall-Ozawa,Friedman和Kissinger三种方法计算了共混物的热降解反应活化能(Ea)。结果表明,复合材料呈现单一阶段的降解过程,Nano-diamond有助于提高材料的热稳定性。复合材料的热稳定性随Nano-diamond含量的增加先增大后减小,当其含量为3%时,复合材料的热稳定性最好,热降解反应的Ea提高了5-30 kJ/mol。     

HIPS/MWCNT和HIPS/GE复合材料的动态热力学性能及热降解动力学研究北大核心

利用熔融共混法制备了高抗冲聚苯乙烯(HIPS)/多壁碳纳米管(MWCNT)和HIPS/石墨烯(GE)复合材料,测试了其力学性能和动态力学性能,利用热重法研究了复合材料在氮气和氧气中的热降解行为,并采用Kissinger和Friedman两种方法计算了热降解动力学参数。结果表明:与GE相比,MWCNT对HIPS力学性能有较大的提升作用,拉伸强度和冲击强度分别提高了26.6%,74.6%;HIPS/MWCNT复合材料的储能模量和玻璃化转变温度较纯HIPS有一定提高;GE对HIPS动态力学性能没有明显影响;加入MWCNT能有效延缓HIPS的热降解过程,提高HIPS的高温热稳定性;GE对HIPS热降解的影响不显著;Kissinger和Friedman两种方法计算得到的降解活化能变化趋势一致。     

石墨烯/PMMA和多壁碳纳米管/PMMA复合材料的热降解动力学研究

利用热重法研究了石墨烯(GE)和多壁碳纳米管(MWCNTs)对聚甲基丙烯酸甲酯(PMMA)热稳定性的影响,并采用Kissinger法、Friedman法和Coats-Redfern法计算了复合材料的热降解动力学参数。结果表明:PMMA的热失重包含两个失重阶段,添加GE和MWCNTs并没有改变PMMA的热失重历程,但是T0、Tm和Tp均随MWCNTs含量的增加呈先增大后减小的趋势,添加量为3%时达到最大,分别较纯PMMA提高了57.23、14.13和20.55℃,而GE的添加没有明显提高PMMA的热稳定性。三种计算方法得到的复合材料的热降解活化能(Ea)随填料含量增加变化趋势一致,在MWCNTs含量为3%、GE含量为4%时,Ea值分别达到最大值,Friedman法计算的PMMA的反应级数为1.6,GE/PMMA复合材料的平均反应级数为1.9,MWCNTs/PMMA复合材料的平均反应级数为1.5。     

热降解动力学方法研究ABS的降解机理

在空气气氛下,采用热重分析(TGA)研究了不同升温速率下丙烯腈-丁二烯-苯乙烯共聚物（ABS）的热降解过程,分别使用Flynn-Wall-Ozawa法和Kissinger法对降解过程进行动力学分析。结果表明,ABS降解包含2个阶段,350~450 ℃之间发生降解反应,同时伴有交联反应,降解活化能（Ea）在200 kJ/mol左右,转化率在80 %~90 %时发生炭化反应,Ea提高到262.81 kJ/mol;500~600 ℃之间是残炭的氧化,Ea降低到130 kJ/mol左右,炭层稳定性较差。ABS的降解过程反应级数为0.946,降解受到随机成核与生长机理控制,降解在ABS基体内进行,而不是表面,所以降解气体燃烧不完全,易产生黑烟和熔融滴落。     

生物基聚对苯二甲酸丙二醇酯的非等温热降解动力学研究

通过热重分析手段,以非等温法研究了生物基聚对苯二甲酸丙二醇酯(PTT)以及经溶解沉淀法提纯处理后的生物基PTT在氮气气氛下的热降解过程,采用Kissinger法、Friedman法、Flynn-Wall-Ozawa法、Criado法、Coast-Redfern法对生物基PTT的非等温热降解动力学进行了分析。结果表明:溶解沉淀法提纯生物基PTT对其热稳定性有一定提升,采用Kissinger法、Friedman法、Flynn-Wall-Ozawa法求取了生物基PTT的热降解活化能为172.85～191.59 kJ/mol,相比文献报道的石油基PTT的206～267 kJ/mol要低;由Criado法和Coast-Redfern法明确了生物基PTT的热降解动力学机理函数为一级反应函数;溶解沉淀法提纯处理不会影响生物基PTT的机理函数。     

热塑性木薯淀粉/SiO_2复合材料的热降解动力学

通过熔融共混法制备热塑性木薯淀粉(TPS)/二氧化硅(SiO_2)复合材料,利用热失重分析(TG)方法研究TPS/SiO_2复合材料的热降解温度及热降解动力学。结果表明,随着升温速率增加或加入SiO_2后,TPS/SiO_2复合材料的热降解温度增加。利用Kissinger方法对TPS/SiO_2复合材料热降解动力学进行研究,发现未添加SiO_2时TPS热降解活化能为206.90 kJ/mol;当添加2份SiO_2时,TPS/SiO_2复合材料热降解活化能提高到223.41kJ/mol;添加亲水SiO_2后TPS/SiO_2复合材料的热降解活化能高于添加疏水SiO_2的。采用Flynn-Wall-Ozawa方法发现,随着SiO_2的加入,TPS/SiO_2复合材料的热降解活化能增加。     

酚酞聚芳醚砜/灌流硅胶微球复合材料的耐热性能研究

利用热重分析仪对PES-C/PSM复合材料的耐热性能进行分析,并以Kissinger法研究其热分解动力学,计算热分解表观活化能Ea。结果表明,在空气氛下复合材料的热分解温度随PSM含量的增大而升高,且当PSM的含量提高至1.0%,复合材料的热分解结束温度提高了41.29℃。复合材料的表观热降解活化能随PSM含量的增加而增大,与纯PES-C(Ea_(PES-C)=241 kJ/mol)相比,当PSM含量为1.0%时,PES-C/PSM复合材料的活化能为264.76 kJ/mol,较纯PES-C提高了9.86%。     

PP/POSS纳米复合材料热氧化稳定性

采用熔融物理共混和熔融反应共混两种方法制备了聚丙烯(PP)/八乙烯基笼型硅倍半氧烷(OV-POSS)纳米复合材料,并用热重分析对两种方法制备的复合材料热氧化稳定性进行分析和比较。结果表明,在OV-POSS含量同为2%(质量分数)时,物理共混复合材料的热氧化稳定性要优于反应共混复合材料,且物理共混复合材料的热氧化稳定性随着OV-POSS含量的增加而提高。为进一步评估OV-POSS对物理共混复合材料热氧化性能的影响,利用Kissinger法和Flynn-Wall-Ozawa方法从热氧化降解动力学的角度对复合材料表观活化能(E_a)进行了研究。研究表明,OV-POSS可以明显提高复合材料的E_a,含5%(质量分数)OV-POSS的物理共混复合材料的E_a为92.48 kJ/mol(Kissinger法)和97.53 kJ/mol(Flynn-Wall-Ozawa法),而纯PP的E_a仅为67.79 kJ/mol以及61.81 kJ/mol。     

多聚甲醛法硼酚醛树脂的热降解动力学

采用热分析技术(TG/DTG)研究了多聚甲醛法合成硼酚醛树脂的热降解性能,利用Friedman法和Flynn-Wall-Ozawa法对其热降解动力学进行了分析,计算出了不同条件下降解过程的活化能Ea。结果表明:树脂的热降解过程分为210～438℃,438～728℃,728～900℃3个阶段,当升温速率为10℃/min时,对应热失重率分别为4.256%,40.326%和23.717%,900℃下静态空气中质量残留31.442%。合成树脂的活化能在各升温速率下的平均值是29.91kJ/mol,反应级数n为2.837。     

Processing and properties of carbon nanotube/poly(methyl methacrylate) composite films

A systematic study of the reinforcement of single‐walled carbon nanotubes (SWNTs), multiwalled carbon nanotubes, and vapor‐grown carbon nanofibers (VGCNFs) in poly(methyl methacrylate) (PMMA) is reported. SWNT/PMMA composite films with various SWNT concentrations (from 0.5 to 50 wt % with respect to the weight of PMMA) were processed from nitromethane. Two types of SWNTs were used: SWNT‐A, which contained 35 wt % metal catalyst, and SWNT‐B, which contained about 2.4 wt % metal catalyst. Properties of different nanotubes containing composites were compared with 15 wt % carbon nanotubes (CNTs). Property enhancement included electrical conductivity, mechanical properties, and solvent resistance. The thermal degradation of PMMA in the presence of CNTs in air and nitrogen environments was studied. No variation in the thermal degradation behavior of PMMA/CNT was observed in nitrogen. The peak degradation temperature increased for the composites in air at low CNT loadings. Dynamic and thermomechanical properties were also studied. At a 35 wt % SWNT loading, a composite film exhibited good mechanical and electrical properties, good chemical resistance, and a very low coefficient of thermal expansion. Property improvements were rationalized in terms of the nanotube surface area. Composite films were also characterized with Raman spectroscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermogravimetric and resistivity study of Ex situ and In situ poly(methyl methacrylate)/carboxylic acid group functionalized multiwall carbon nanotubes composites

Polymer composites based on poly(methyl methacrylate) (PMMA)/carboxylic acid group functionalized multiwall carbon nanotubes (MWCNT) were prepared by the ex situ and in situ techniques with 0.05% loading by weight. Composite films were fabricated by solvent casting method. Electrical conductivity of the composites as well as of the neat PMMA polymer was measured in the temperature range 333 K to 423 K. Neat PMMA samples prepared by the same method showed complete insulating behavior. Ex situ technique leads to a lower value of percolation threshold. Infrared spectroscopy was used to analyze the effect of functionalization of MWCNT on the interfacial bonding of PMMA and MWCNT. Thermogravimetric analysis revealed that the maximum degradation temperature has been shifted to higher region for in situ composites compared to PMMA itself—and the ex situ composites indicated better thermal stability. X‐ray diffraction study of composites also indicates that in situ composites functionalization incorporated MWCNT particles in the polymer chain. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

水性纳米SiO2改性环氧树脂/聚氨酯丙烯酸酯涂料的制备与热性能研究

制备了水性纳米SiO2改性环氧树脂（ER）／聚氨酯丙烯酸酯（PUA）复合涂料,用二苯基碘鎓盐为光引发剂研究了涂料的光-热混杂固化反应、动态力学和热降解过程。结果表明,涂料有良好的光固化性能,光-热混杂固化可进一步提高材料刚性;加入纳米SiO2可提高材料的Tg,硬度达到4H,但在高温下对材料有催化降解作用。用Friedman法研究了材料的热降解活化能Ea,证明当Nano-SiO2含量为4％热降解Ea为45．64kJ／mol,比光固化体系约提高13．60kJ／mol。在非等温条件下材料降解率不高于15％时Ea随α逐渐升高,之后随温度升高而降低。     

Influence of wrapping on some properties of MWCNT–PMMA and MWCNT–PE composites

The melt processing technique was used to elaborate composites made with a polymer matrix [polymethylmethacrylate (PMMA) or polyethylene (PE)] and multiwall carbon nanotubes (MWCNT). Nanotubes were wrapped by amphiphilic block copolymer (PE–co-polyethylene oxide) in aqueous solution to facilitate the dispersion and the handling. Morphology and physical properties (thermal, mechanical, electrical, and rheological) of the resulting composites were investigated. The wrapping of MWCNT allowed a good dispersion of these nanoparticules in the polymer matrices. Physical properties such as thermal degradation, mechanical behavior, and conduction are improved. The use of wrapped MWCNT allows to reduce drastically the melt viscosity of the blends of crystalline PE composites whereas it is almost non efficient for amorphous PMMA ones.     

An Innovative Approach to the Synthesis of PMMA/PEG/Nanobifiller Filled Nanocomposites with Enhanced Mechanical and Thermal Properties

A facile route was adopted to blend the matrix. The PMMA/PEG blend was reinforced with three types of nanofillers, i.e., pristine MWCNT (P-CNT), amine functionalized MWCNT (PDA-EA-CNT) and nanobifiller i.e. nanodiamond functional MWCNT (PDA-EA-CNT-ND) to yield three different types of nanocomposites i.e. PMMA/PEG/P-CNT, PMMA/PEG/PDA-EA-CNT and PMMA/PEG/PDA-EA-CNT-ND. These nanocomposites were reinforced with nanofiller loading (1 wt. %, 3 wt. %, 5 wt. %, 10 wt. %, 30 wt. % and 50 wt. %) by solution casting method. Structure of composite and nanofillers was confirmed by FTIR. FESEM imaging revealed that nanocomposites have micro porous morphology. At high magnification, distribution of functionalized CNT/ND appears to be protruding out of the polymeric matrix. The TGA result suggests that the thermal stability of the nanocomposites was enhanced in comparison to PMMA due to grafting of filler molecules with PMMA/PEG macromolecules. The DTG results showed that the bifiller nanocomposites (PMMA/PEG/PDA-EA-CNT-ND) exhibited improved thermal stability with T_max (431^°C) as compared to P-CNT and amine functionalized CNT (PMMA/PEG/PDA-EA-CNT) with T_max of 395^°C and 418^°C respectively. XRD results showed fine interaction between filler and the polymeric matrix. As the filler loading was increased the composites showed pronounced XRD peak at 25.9^°, corresponding to (002) reflection of nanotubes. Significant improvement in the mechanical properties of composites was recorded with the reinforcement of fillers as compared to the neat matrix. The most significant improvement in tensile strength and elastic modulus was observed for the bifiller nanocomposites with 5 wt. % PDA-EA-CNT-ND. They showed a tensile strength and elastic modulus of 29.9 MPa and 1474.31 MPa respectively as compared to amine functionalized CNT with tensile strength (25.7) and elastic modulus (1466.99 MPa)and P-CNT with tensile strength(25 MPa) and elastic modulus (1155.75 MPa).     

Studies on Thermal Degradation of Cellulosic Fibers Treated with Flame Retardants

Hemp fabric, one of the most flammable materials, was treated with compounds containing different kinds of elements that contribute to flame retardation. For a study of flame retardation from the standpoint of thermal degradation, the samples were subjected to thermogravimetry (TG) and differential thermal analysis (DTA) in air from ambient temperature to 600℃. The apparent activation energy (Ea) is evaluated by Broido's method at different stages of thermal degradation to observe the variation of Ea in the process of thermal degradation. Flame retardation of samples was determined by limiting oxygen index (LOI) to find the effects of the different compounds on flammability and the thermal degradation of the hemp fabric. The composition of the chars was studied by the IR spectra to obtain information concerning the thermal degradation mechanism. Compared with flammable hemp, the hemp fabric treated with flame retardants showed a higher LOI but lower Ea and decomposition temperatures, which indicated that some compounds make the hemp fabric decompose at lower temperatures, resulting in less flammable products.     

Thermal degradation behaviour of multi‐walled carbon nanotube‐reinforced poly(L‐lactide) nanocomposites

BACKGROUND: Polymer/multi‐walled carbon nanotube (MWCNT) composites are one of the most promising alternatives to conventional polymer composites filled with micrometre‐sized fillers. This approach can also be applied for the improvement of mechanical properties and thermal stability of biodegradable aliphatic polyesters, such as poly(L ‐lactide) (PLLA), which have been receiving increasing attention due to environmental concerns. Thermal degradation behaviour provides useful information for the determination of the optimum processing conditions and for identification of potential applications of final products. RESULTS: The PLLA/MWCNT composites investigated showed a higher thermal degradation peak temperature and onset temperature of degradation along with a higher amount of residue at the completion of degradation than neat PLLA. Moreover, PLLA/MWCNT composites with a greater MWCNT content showed higher activation energy of thermal degradation than those with a lower MWCNT loading, which confirmed the positive effect of MWCNT incorporation on the enhancement of PLLA thermal stability. CONCLUSION: This study explored the thermal degradation behaviour of PLLA/MWCNT composites by observing the weight loss, molecular weight and mechanical properties during non‐isothermal and isothermal degradation. The incorporation of MWCNTs into the PLLA matrix enhanced considerably the mechanical properties and thermal stability. Copyright © 2009 Society of Chemical Industry     

Synthesizing multi‐walled carbon nanotube‐polymethyl methacrylate conductive composites and poly(lactic acid) based composites

Multi‐walled carbon nanotube was modified with polymethyl methacrylate (MWCNT‐PMMA) by in situ solution radical polymerization in the presence of 2,2′‐Azobis (isobutyronitrile) as an initiator. The products with different addition of methyl methacrylate (MMA) were pressed into slices to prepare specimens for electrical conductivity testing. It was found that the MWCNT‐PMMA nanocomposites demonstrate excellent electrical conductivity. To investigate the microsphere morphology and the colloidal surfactant of MWCNTs in MWCNT‐PMMA composites, samples were submitted to scanning electron microscopy and transmission electron microscopy. The thermogravimetric analysis of the prepared composites confirmed that MWCNTs as a thermal stabilizer for PMMA, which could have a wide range of potential applications, such as in catalysts, sensors, environmental remediation, and energy storage. Two series of poly(lactic acid) (PLA) based biocomposites with different MMA additions and MWCNT‐PMMA composites contents were prepared with twin‐screw extruding and injection molding. The results show the mechanical properties changed a little with the MMA and MWCNT‐PMMA composites contents increasing, which suggested the well compatibility between MWCNT‐PMMA composites and PLA. POLYM. COMPOS., 37:503–511, 2016. © 2014 Society of Plastics Engineers     

抗氧剂对PMMA树脂热氧化稳定性的影响及动力学分析

采用热重分析,研究了抗氧剂种类及用量对聚甲基丙烯酸甲酯(PMMA)热氧化稳定性的影响,并采用Kis-singer、Flynn-Wall-Ozawa和Flynn法对其热氧化降解行为进行了动力学分析。结果表明,抗氧剂1010、1076、702和BHT的用量为0.5‰时就能够显著提高PMMA热氧化稳定性,使其起始热分解温度提高70℃左右,而抗氧剂用量进一步提高对改善PMMA的热稳定性意义不大;动力学分析表明,抗氧剂的加入能够提高PMMA质量损失率小于30%时的热降解活化能,而热分解后期由于降解温度高于抗氧剂熔点,抗氧剂气化逸出,抗氧剂不能有效提高PMMA后期热降解活化能,未能达到提高PMMA整体热稳定性的目的。