聚乳酸/环氧基笼型倍半硅氧烷纳米复合材料的流变性能研究

采用毛细管流变仪分析了熔融共混法制备的聚乳酸/环氧基笼型倍半硅氧烷(PLA/EVOS)纳米复合材料的流变行为。结果表明:PLA/EVOS纳米复合材料为假塑性流体,呈现出切力变稀的特征;随着温度的升高,复合材料的非牛顿指数有所提高;随着EVOS含量的增加,复合材料的非牛顿指数先升后降,而稠度和表观黏度先减小后增大;复合材料熔体的黏流活化能相对较低,仅为12~35 kJ/mol。     

Study on Thermal Properties and Crystallization Behavior of Blends of Poly(phenylene sulfide)/Poly(ether imide)

The thermal behavior of poly(phenylene sulfide) (PPS) blends with poly(ether imide) (PEI) was studied by differential scanning calorimeter (DSC). The crystallization temperature of PPS in blends shifted from 216.8°C to 226.4°C upon addition of 20–70% PEI contents. The heat of crystallization remained unchanged with less than 50% PEI in blends, whereas the heat of fusion decreased with increasing PEI content. The isothermal crystallization indicated that incorporating PEI would accelerate the crystallization rate of PPS. The activation energy of crystallization increased with addition of PEI. The equilibrium melting point of PPS/PEI blends was not changed with compositions.     

Study on the Crystallization Kinetic and Characterization of Poly(lactic acid) and Poly(vinyl alcohol) Blends

In this study, poly(lactic acid) (PLA) and poly(vinyl alcohol) (PVA) blends, with PLA/PVA mass ratios of 100/0, 90/10, 80/20, 70/30, 60/40, 50/50, and 40/60, were prepared by means of the melt blending method. The result of torque measurements and thermal gravimtric analysis tests showed that the addition of PLA can decrease the melt viscosity of PVA and that the second degradation step of PVA nearly disappeared for the PLA₈₀/PVA₂₀ blend. The absorbance peaks of the carbonyl group and the hydroxyl group in the Fourier transform infrared spectra of PLA/PVA blends had significant shifts to lower wave numbers, indicating that there were interactions between these two groups. Combined with the result of the differential scanning calorimetry curves, this interaction would be favorable for improving miscibility. The X-ray diffraction patterns and the polarized light microscope (PLM) micrographs showed that PVA can serve as a nucleating agent to promote the crystallization of PLA in PLA/PVA blends. Moreover, the PLA₈₀/PVA₂₀ blend gave the highest growth rate of PLA spherulite.     

聚乳酸结晶的研究进展

综述了自合成以来聚乳酸（PLA）结晶行为研究的主要成果，介绍了PLA的α、β、γ三种晶型结构参数及不同晶型晶体的形成条件，以及PLA球晶、单晶、孪晶、微纤晶和串晶等结晶形态及其形成条件。此外，还介绍了PLA在不同条件下的结晶行为，着重阐述了分子结构、第二组分及温度场、应力场以及辐照等外部因素对其结晶行为的影响。     

PLA/T-ZnOw等温冷结晶及熔融行为的研究

采用熔融共混法制备了PLA/T-ZnOw复合物。用差示扫描量热仪（DSC）研究了PLA/T-ZnOw的等温冷结晶及其熔融行为,Avrami方程分析表明,Avrami方程能很好的描述PLA/T-ZnOw的等温冷结晶过程,Avrami指数n值在1.78~3.10之间,表明PLA/T-ZnOw是以二维盘状生长和三维球晶生长并存的球状晶体。偏光显微镜观察结果显示,随着T-ZnOw的加入,PLA球晶尺寸变小,数目增多,说明T-ZnOw促进了PLA的成核但未提高其结晶速度。     

Poly(lactic acid)/montmorillonite blown films: Crystallization,mechanics, and permeation

The study focuses on the development and characterization of poly(lactic acid) (PLA)/montmorillonite (clay) nanocomposite films. Samples of 0%, 1%, 3%, and 6% (by weight) clay were shear‐mixed, melt‐blended, and blown‐film processed. Afterward, the effects of clay on the kinetics of cold‐crystallization, mechanical properties, and the oxygen barriers are investigated using differential scanning calorimetry, dynamic mechanical analyzer, and permeation tester, respectively. Through the traditional Avrami analysis, clay is found to accelerate the crystallization process with a higher crystallization rate constant. The Avrami exponent obtained for composites is higher than the neat PLA although all samples show a decreased Avrami exponent with increase of the crystallization temperature. At the same time, the clay exhibits reinforcement effects on the glassy modulus of the composites and influences the cold‐crystallization event, similar to the calorimetric results. In addition, the oxygen permeation slightly decreases on adding the clay. With 3% clay concentration, the permeation coefficient is reduced by 24%. The implication of the results is discussed in the article. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45260.     

Nonisothermal Crystallization and Melting Behavior of EVA/OMWNTs Nanocomposites

EVA/OMWNTs nanocomposites have been successfully prepared by a simple melt compounding method. The nonisothermal crystallization behaviors of the EVA/OMWNTs nanocomposites are strongly dependent on the degree of crystallinity (X_c), peak crystallization temperature (T_p), half-time of crystallization (t_1/2), and Avrami exponent (n) on the OMWNTs content and cooling rate. The dependence of the crystallization activity energy on the extent of relative crystallization for the plain EVA and the EVA/OMWNTs nanocomposites shows that ΔE increases with the increase in the relative degree of crystallinity below about 5%, and the ΔE decreased when the relative degree of crystallinity was greater than about 5%.     

增塑剂对生物降解塑料聚乳酸结晶形态的影响

采用熔融共混方法制备了聚乙二醇(PEG)和聚乳(酸PLA)的共混物,并借助差示扫描量热仪和广角X射线衍射仪研究了在80~140℃等温结晶时PEG对PLA结晶形态和熔融行为的影响。结果表明:100℃以上时PLA的结晶度随结晶温度的升高逐渐增加;100℃以下时PLA的结晶度随PEG含量的增加逐渐增大。110℃以下时,晶面间距随结晶温度的升高和PEG含量的增加而逐渐减小;110℃以上时,晶面间距保持不变;当加入15%的PEG时PLA的晶面间距不受结晶温度的影响结,晶生成的是稳定的α晶。     

亚磷酸三苯酯对聚乳酸结晶性能的影响

采用偏光显微镜和差示扫描量热仪分别对亚磷酸三苯酯（TPP）扩链聚乳酸（PLA）的结晶形态和结晶过程进行表征,并采用莫至深法对PLA的结晶动力学过程进行研究。结果表明,TPP的扩链引入并没有改变PLA的结晶形态,仍然保持为球状晶体;TPP的引入大大提高了PLA的结晶能力,使其冷结晶温度（Tcc）从115.4 ℃降低到102.8 ℃,相对结晶度从30.2 %提高到34.9 %;莫至深法适合PLA结晶动力学过程的研究,TPP的引入使得PLA的F(T)值大大降低。     

聚乳酸/乙烯-醋酸乙烯酯共聚物/碳酸钙复合材料的性能研究

采用熔融共混法制备了聚乳酸/乙烯-醋酸乙烯酯共聚物/碳酸钙（PLA/EVA/CaCO3）复合材料,利用差示扫描量热仪、X射线衍射仪、偏光显微镜、扫描电子显微镜、力学性能测试和热变形温度测试等手段,研究了EVA和CaCO3对复合材料的结晶性能、断面形貌、力学性能和耐热性能的影响。结果表明,EVA 具有增韧作用,但降低了复合材料的强度和耐热性;而CaCO3可以提高复合材料的强度、韧性、结晶性能和耐热性能;CaCO3与EVA的加入对PLA有协同增韧作用,且不改变PLA的晶型;当PLA/EVA=90/10,加入10 %（质量分数,下同）的CaCO3时,复合材料有最佳的综合性能。     

LDPE及LDPE/TiO_2纳米复合材料的熔限及等温结晶研究

采用熔融共混法制备了LDPE／TiO2纳米复合材料,以膨胀计对LDPE及LDPE／TiO2复合材料的熔点、熔限及等温结晶进行了研究。结果表明：膨胀计可用于LDPE及LDPE／TiO2纳米复合材料熔点及熔限的测试：与LDPE相比,LDPE／TiO2复合体系的半结晶期及AVrami指数较小,表明TiO2粒子对LDPE的结晶具有明显的异相成核作用;而Avrrdmi指数为非整数,且Avrami作图直线的最后部分与实验点的偏离,则表明LDPE及LDPE／TiO2纳米复合材料的等温结晶过程比Avrami方程要复杂得多。     

聚乳酸/环氧基笼型倍半硅氧烷纳米复合材料的制备与性能研究

采用熔融共混法制备了聚乳酸/环氧基笼型倍半硅氧烷(PLA/EVOS)纳米复合材料,利用动态热机械分析(DMA)、热失重分析(TGA)和扫描电子显微镜(SEM)等表征和分析了材料的性能与结构。结果表明:EVOS的加入显著提高了材料的拉伸性能和储能模量,但对玻璃化转变温度和热分解温度无明显影响;当EVOS质量含量为0.5%时,纳米复合材料的断裂伸长率和储能模量达到最大值,分别为2.23%和7 352 MPa。     

聚乳酸/聚(已二酸-对苯二甲酸丁二酯)共混物的非等温结晶动力学

采用熔融挤出法制备了聚乳酸/聚(已二酸-对苯二甲酸丁二酯)共混物。利用差示扫描量热仪研究了聚乳酸及其共混体系的非等温结晶过程。用经Jeziorny修正的Avrami方程和Mo法对其非等温结晶动力学进行了分析。结果表明:Avrami方程和Mo法都适用于处理聚乳酸及其共混体系的非等温结晶过程,共混物的结晶速率大于聚乳酸的结晶速率。此外,用Huffman-Lauritzen理论计算了非等温结晶的结晶活化能,发现共混体系的结晶活化能绝对值小于聚乳酸。     

Poly(lactic acid)/carbon nanotube nanocomposites with integrated degradation sensing

For the first time, an in-situ degradation monitoring system for biodegradable polymers is reported in present work. The proposed concept is based on a conductive biodegradable polymer composite, where carbon nanotubes (CNTs) are incorporated in poly(lactic acid) (PLA) in order to develop an intelligent biocomposite system that can sense biodegradation. Changes in electrical resistivity of the PLA/CNT nanocomposites were successfully correlated with degradation levels of the biopolymer. PLA/CNT nanocomposites demonstrated excellent degradation sensing abilities at CNT concentrations around the percolation threshold, with resistivity changes of about four orders of magnitude with biodegradation. In contrast to many other stimuli, biodegradation resulted in a reduction in resistivity due to an increased CNT network density after partial removal of the amorphous phase of the polymer matrix.     

Isothermal crystallization kinetics and spherulite morphologies of poly(lactic acid)/ethylene acrylate copolymer blends

Isothermal crystallization kinetics and spherulite morphologies of partially immiscible blends of poly(lactic acid) (PLA) and ethylene acrylate copolymer (EAC) were investigated by differential scanning calorimetry (DSC) and polarized optical microscopy. The DSC data obtained was analyzed using the Avrami equation. Crystallization kinetics of PLA from the melt was strongly influenced by the blend composition and the crystallization temperature. At a given crystallization temperature, the overall crystallization rate value was greater in the blends than in PLA suggesting that the presence of EAC enhanced crystallization of PLA. Polarized optical micrographs showed that the crystallization of PLA initially took place at the PLA/EAC interface. At high EAC content (>1 wt %), EAC domains acted as hindrance to crystallization reducing the overall crystallization rate of PLA in the blends. Based on the DSC analysis, the crystallization rate was maximum when PLA blend with 1 wt % EAC was isothermally crystallized at 103 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45487.     

聚乙烯醇/蒙脱石纳米复合材料的制备工艺研究

通过正交实验法研究了溶液插层-流延成膜法制备聚乙烯醇/蒙脱石纳米复合材料中制备工艺条件对复合材料结构的影响,确定了最佳的制备方法。对复合材料进行了TEM表征,结果表明:蒙脱石片层均匀的剥离分散在PVA基体中,蒙脱石含量不高于7.5wt%时,形成了剥离型的纳米复合材料;高于10wt%时,形成了剥离型和插层型共存的纳米复合结构。     

Synthesis,Morphology, and Viscoelastic Properties of Polyhedral Oligomeric Silsesquioxane Nanocomposites with Epoxy and Cyanate Ester Matrices

Octaaminophenyl(T₈)POSS [1, (C₆H₄NH₂)₈(SiO_1.5)₈] and dodecaaminophenyl(T₁₂)POSS [2, (C₆H₄NH₂)₁₂(SiO_1.5)₁₂] were synthesized, characterized and then incorporated into two types of thermoset resins: (1) the bisphenol-F-based cyanate ester resin, PT-15, and (2) epoxy (Epon 828, Shell Chemical Corp.)/4,4′-diaminodiphenylmethane (DDM) resin, respectively, to make two series of nanocomposites. The sum of amino groups in both DDM and POSS were held in a 1:1 mole ratio to the epoxy groups. EPON-828/1/DDM and EPON-828/2/DDM composites (78.63/0/21.37, 77.48/5/17.52, 76.34/10/13.66, 74.05/20/5.95 and 72.28/27.72/0 wt/wt/wt compositions for both series) were prepared. PT-15/1 and PT-15/2 composites (99/1, 97/3 and 95/5 wt/wt compositions for both types) were also prepared. These nanocomposites were characterized by transmission electron microscopy (TEM), dynamic mechanical analysis (DMA), solvent extraction and FT-IR. In all systems, POSS 1 and 2 were chemically bound into the resin matrix and phase-separated POSS particle domains were not observed. Incorporation of both 1 and 2 can dramatically elevate the high temperature bending storage moduli, E′, of epoxy resins.     

聚乳酸纳米复合材料流变性能研究进展

综述了各种纳米粒子,包括生物质基纳米粒子、碳基纳米粒子、纳米黏土等对聚乳酸(PLA)在剪切力场作用下的流变性能影响及其各自含量、表面处理和与PLA基体之间相互作用等对其流变性能的影响,并总结了纳米粒子对PLA流变性能的作用机理。     

Water Absorption of Poly(lactic acid) Nanocomposites: Effects of Nanofillers and Maleated Rubbers

Injection-molded poly(lactic acid)/organo-montmorillonite (PLA/OMMT) and poly(lactic acid)/ nano-precipitated calcium carbonate (PLA/NPCC) were exposed to a water absorption test at 30°C for 70 days. The analysis was focused on the water diffusion kinetics and impact strength changes induced by the hydrolysis. The diffusion exponent (n) values of all the PLA samples are less than 0.5, indicating the Fickian diffusion model (case I) is obeyed. Adding nanofillers and maleated rubbers (SEBS-g-MAH or EPR-g-MAH) increased equilibrium moisture content but decreased diffusion coefficient values of PLA. The recoverability and retention-ability of the maleated rubbers toughened PLA/OMMT and PLA/NPCC after water absorption are excellent.     

聚乙烯醇/蒙脱石纳米复合材料的结构与性能

通过溶液插层 流延成膜法,以聚乙烯醇和钠质蒙脱石为原料,制备出了不同蒙脱石含量的聚乙烯醇/蒙脱石纳米复合材料薄膜。用X射线衍射(XRD)、扫描电子显微镜(SEM)、热重分析(TGA)和力学性能测试对复合材料的结构和性能进行了表征。结果表明,聚乙烯醇分子成功进入蒙脱石的层间,实现了在纳米尺度上的复合;蒙脱石含量高于7 5wt%形成插层型的纳米复合材料,低于7 5wt%形成剥离型的纳米复合材料;在SEM图片上还观察到了纳米复合材料的微观结构。纳米复合材料的热稳定性、拉伸强度和直角撕裂强度均比纯聚乙烯醇有很大提高。