聚合物纳米复合材料结晶行为研究进展

综述了聚合物/粘土纳米复合材料及聚合物/刚性纳米粒子复合材料中基体树脂的结晶行为,并分析了纳米粒子影响聚合物结晶过程的机理。     

滑石粉、碳酸钙填充聚丙烯复合材料等温结晶行为的研究

用熔融共混法分别制备了聚丙烯(PP)/滑石粉、PP/碳酸钙(CaCO3)复合材料,用差示扫描量热法考察了PP及其复合材料的等温结晶过程,并用Avrami方程对纯PP及PP/滑石粉、PP/CaCO3复合材料的等温结晶动力学行为进行了分析。结果表明,PP、PP/滑石粉及PP/CaCO3复合材料的Avrami指数均小于2.3,存在均相成核和异相成核双重成核机理,且其结晶速率常数和结晶速率均随着结晶温度的升高而减小;在该体系中,滑石粉对基体PP有明显的异相成核作用,使PP的结晶速率加快、结晶时间缩短;而CaCO3则没有明显的异相成核作用。     

滑石粉、碳酸钙填充聚丙烯复合材料等温结晶行为的对比研究

用熔融共混法分别制备了聚丙烯（PP）/滑石粉、PP/碳酸钙(CaCO3)复合材料,用差示扫描量热法(DSC)考察了PP及其复合材料的等温结晶过程,并用Avrami方程对纯PP及PP/滑石粉、PP/CaCO3复合材料的等温结晶动力学行为进行了分析。结果表明,PP、PP/滑石粉及PP/CaCO3复合材料的Avrami指数均小于2.3,存在均相成核和异相成核双重成核机理,且其结晶速率常数和结晶速率均随着结晶温度的升高而减小;在该体系中,滑石粉对基体PP有明显的异相成核作用,使PP的结晶速率加快、结晶时间缩短;而CaCO3则没有明显的异相成核作用。     

聚合物纳米复合材料结品行为研究综述

综述了国内外聚合物纳米复合材料结晶行为的最新研究进展.其聚合物基体主要包括有聚丙烯、尼龙、聚苯乙烯、聚对苯二甲酸乙二醇酯和聚乙烯等;填充的纳米粒子主要有CaCO3、有机蒙脱土、黏土和SiO2等.同时,总结了研究聚合物纳米复合材料结晶行为的理论模型.对聚合物纳米复合材料结晶行为的研究进行了展望.     

聚丙烯/海泡石复合材料的等温结晶行为

采用熔融共混的方法制备聚丙烯（PP）/海泡石复合材料,通过示差扫描量热仪和偏光显微镜研究有机化改性海泡石填充PP复合材料在不同温度下的等温结晶行为,考察海泡石对PP结晶行为的影响,采用Avrami方程处理等温结晶过程,并计算结晶动力学参数。结果表明,海泡石的加入使复合材料的结晶时间缩短,结晶度增大;随着结晶温度的升高,各体系的结晶速率下降,结晶速率常数n、K降低,并且随着结晶温度（Tc）的升高,半结晶时间（t1/2）增大;在同一结晶温度（Tc）下,海泡石的加入提高了基体的结晶速率,加快了PP的异相成核过程,使得PP球晶尺寸减小。     

热致液晶聚合物增强PP/mPE原位复合材料的研究

采用热致液晶聚合物（TLCP）对PP及PP/mPE共混物进行增强，制得PP／TLCP和PP／mPE／TLCP原位复合材料。探讨了TLCP对复合材料拉伸性能、低温冲击性能和加工流变行为的影响。结果表明，加入15％的TLCP可以显著提高PP和PP／mPE的刚性，改善加工流动性。但由于体系的相容性较差，基体的拉伸强度有所降低，低温冲击韧性也有显著的降低。     

聚丙烯/碱式硫酸镁晶须复合材料等温结晶动力学研究

采用月桂酸(LA)对碱式硫酸镁晶须(MOSw)进行改性,将改性产物LA-MOSw与聚丙烯(PP)熔融共混制成复合材料。利用差示扫描量热法(DSC)考察了纯PP及PP/MOSw、PP/LA-MOSw复合材料的等温结晶行为,并进一步通过Avrami方程计算得到相关等温结晶动力学参数。结果表明:在相同结晶温度下,PP/LAMOSw复合材料具有较短的半结晶时间(t_(1/2))及较小的Avrami指数(n),说明加入LA-MOSw能促进PP基体结晶,生成更多二维盘状结晶;但MOSw的加入则会抑制PP的结晶,而诱导生成更多的三维球状结晶。Arrhenius方程及Hoffman-Lauritzen模型分析结果表明,LA-MOSw促进PP结晶的原因主要在于LAMOSw的引入降低了PP基体的结晶活化能(ΔE)与成核参数(K_t),使PP基体成核结晶变得更加容易。     

聚合物纳米复合材料结晶行为研究综述

综述了国内外聚合物纳米复合材料结晶行为的最新研究进展。其聚合物基体主要包括有聚丙烯、尼龙、聚苯乙烯、聚对苯二甲酸乙二醇酯和聚乙烯等；填充的纳米粒子主要有：CaCO3、有机蒙脱土、黏土和SiO2等。同时，总结了研究聚合物纳米复合材料结晶行为的理论模型。对聚合物纳米复合材料结晶行为的研究进行了展望。     

PP/EPDM/纳米TiO_2复合材料的制备与热性能

采用熔融共混法制备了PP/EPDM/纳米TiO_2复合材料,并对其结晶行为和热稳定性进行了研究。通过Jeziorny法和莫志深模型对复合材料的非等温结晶动力学进行表征,并利用Kissinger法和Friedman法计算结晶活化能。结果表明,三元乙丙橡胶(EPDM)包裹在纳米TiO_2表面所形成的核壳结构虽然延缓了复合体系的结晶过程,但并没有影响PP基体的结晶能力。纳米TiO_2作为导热填料使复合材料的特征温度T_(5%)、T_(10%)、T_(max)比PP分别提高了33.34、21.55、7.92℃,说明纳米TiO_2能够增强体系的热导率,增加内部的热传导作用,从而有效地提高了基体的热稳定性。     

SEBS-g-MAH对聚丙烯/氢氧化镁纳米复合材料微观结构与流变性能的影响

以马来酸酐接枝的SEBS(SEBS-g-MAH)作为界面改性剂制备了PP/SEBS-g-MAH/氢氧化镁(MH)纳米复合材料,采用SEM、DSC和毛细管流变仪研究了SEBS-g-MAH对复合材料的微观结构、结晶行为和流动性能的影响。结果表明,SEBS-g-MAH的加入充当了MH粒子与PP基体的界面层,提高了纳米MH粒子在PP中的均匀分散性,改善了两者的界面相互作用和PP/MH复合体系的流动性能。     

PP/纳米SiO2复合材料的非等温结晶动力学

采用差示扫描量热法研究了聚丙烯（PP）/纳米SiO2复合材料的非等温结晶动力学,研究了纳米粒子的成核活性及复合材料的结晶有效能垒。研究结果表明,纳米SiO2起到异相成核的作用,使PP的结晶峰温升高,结晶总速率增大;增容剂马来酸酐接枝聚丙烯(PP-g-MAH)提高了纳米SiO2的成核活性;添加纳米SiO2使复合材料的结晶有效能垒降低,PP-g-MAH使复合材料的结晶有效能垒增大,但低于纯PP的结晶有效能垒。     

The effects of MWCNT length on the mechanical,crystallization and electromagnetic interference shielding effectiveness of PP/MWCNT composites

The length of multi-walled carbon nanotubes (MWCNT) has an important influence on the properties of polymer/MWCNT composites. This study aims to examine the influence of the length of MWCNT on the mechanical properties, distribution, melting and crystallization behavior, and electromagnetic interference shielding effectiveness (EMI SE) of PP/MWCNT composites. The test results show that MWCNT of a short length contribute to better mechanical properties and have a better dispersion in the matrix. MWCNT also serve as a nucleating agent for PP, thereby increasing the crystallization temperature (T_c). In particular, short MWCNT provide PP/MWCNT composites with a greater degree of cyrstallinity. The conjunction of 8 wt% long MWCNT in PP/MWCNT composites results in an optimal electrical resistivity of 65.02 Ω-cm, and an average EMI SE of ?29.47 dB. The polymer/MWCNT composites have properties that can be adjusted by using different lengths of MWCNT, which is advantageous for application in diverse products.     

PP/PP-g-NH2/纳米SiO2复合材料的非等温结晶

采用示差扫描量热法（DSC）研究了聚丙烯/氨基化聚丙烯/纳米二氧化硅（PP/PP-g-NH₂/SiO₂）复合材料的非等温结晶行为。利用Caze法对结晶动力学进行了分析,Avrami指数n表明纳米SiO₂和PP-g-NH₂的加入改变了PP的结晶成核和生长机理;运用Dobreva法研究了纳米粒子的成核活性,结果表明纳米SiO₂成核活性差,增容剂PP-g-NH₂明显增强其成核活性;采用Friedman法分析了复合材料的结晶有效能垒,研究表明加入纳米SiO₂使PP的结晶有效能垒降低,添加PP-g-NH₂则进一步降低复合体系的结晶有效能垒;当纳米粒子含量为3%时,添加5% PP-g-NH₂能有效提高纳米粒子成核活性,降低复合材料结晶有效能垒。     

Non‐isothermal crystallization kinetics of cork‐polymer composites for injection molding

The non‐isothermal crystallization behavior of cork–polymer composites (CPC) based on polypropylene (PP) matrix was studied. Using differential scanning calorimetry (DSC), the crystallization behavior of CPC with 15 wt % cork powder at different cooling rates (5, 10, 15, and 20 °C/min) was studied. The effect of a coupling agent based on maleic anhydride was also analyzed. A composite (PPg) containing polypropylene grafted maleic anhydride (PPgMA) and PP was prepared for comparison purposes. Crystallization kinetic behavior was studied by Avrami, Ozawa, Liu, and Kissinger methods. The Ozawa method fails to describe the behavior of these composites. Results show that cork powder surface acts as a nucleating agent during non‐isothermal crystallization, while the addition of PPgMA decreases the crystallization rate. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44124.     

PP/PP-g-NH2/纳米SiO2复合材料的非等温结晶

采用示差扫描量热法（DSC）研究了聚丙烯/氨基化聚丙烯/纳米二氧化硅（PP/PP-g-NH₂/SiO₂）复合材料的非等温结晶行为。利用Caze法对结晶动力学进行了分析,Avrami指数n表明纳米SiO₂和PP-g-NH₂的加入改变了PP的结晶成核和生长机理;运用Dobreva法研究了纳米粒子的成核活性,结果表明纳米SiO₂成核活性差,增容剂PP-g-NH₂明显增强其成核活性;采用Friedman法分析了复合材料的结晶有效能垒,研究表明加入纳米SiO₂使PP的结晶有效能垒降低,添加PP-g-NH₂则进一步降低复合体系的结晶有效能垒;当纳米粒子含量为3%时,添加5% PP-g-NH₂能有效提高纳米粒子成核活性,降低复合材料结晶有效能垒。     

Crystallization of different polypropylene matrices in the presence of wood fillers

The increasing global energy crisis and ecological risks in recent years have led to the interest in lignocellulosic fillers reinforced polymer composites. In this study, the nucleation ability of pine wood in polypropylene (PP) matrices was studied by differential scanning calorimetry. PPs with different melt flow index values (in range 3.2–25 g/10 min.) were used as the polymer matrix. Moreover, a new technique of wood treatment using γ‐irradiation was used. The experimental results clearly show that the nucleation activity of the wood particles is strongly dependent on the rheological parameter (e.g., MFI) of PP matrix. The composites containing PP matrix with lower MFI exhibited higher degree of crystal conversion, lower half‐times of crystallization, and higher crystallization temperatures. Moreover, the applied γ‐irradiation of wood resulted in a negative effect on the crystallization rate of PP matrix and a distinct deterioration of the nucleation ability of wood surface. The interesting differences in nucleation activity of wood have been interpreted in the context of polymer chains length and relaxation times during crystallization. This article will spotlight the nucleating efficiency of filler, which is critical in polymer processing e.g., optimization of injection molding cycle time of composite materials. POLYM. COMPOS., 36:1813–1818, 2015. © 2014 Society of Plastics Engineers     

Crystallization behavior of carbon black‐filled polypropylene and polypropylene/epoxy composites

The crystallization behavior of polypropylene (PP)/carbon black (CB) and PP/epoxy/CB composites was studied with differential scanning calorimetry (DSC). The effects of compatibilizer MAH‐g‐PP and dynamic cure on the crystallization behavior are investigated. The nonisothermal crystallization parameters analysis showed that CB particles in the PP/CB composites and the dispersed epoxy particles in the PP/epoxy composites could act as nucleating agents, accelerating the crystallization of the composites. Morphological studies indicated that the incorporation of CB into PP/epoxy resulted in its preferential localization in the epoxy resin phase, changing the spherical epoxy particles into elongated structure, and thus reduced the nucleation effect of epoxy particles. Addition of MAH‐g‐PP significantly decreased the average diameter of epoxy particles in the PP/epoxy and PP/epoxy/CB composites, promoting the crystallization of PP more effectively. The isothermal crystallization kinetics and thermodynamics of the PP/CB and PP/epoxy/CB composites were studied with the Avrami equation and Hoffman theory, respectively. The Avrami exponent and the crystallization rate of the PP/CB composites were higher than those of PP, and the free energy of chain folding for PP crystallization decreased with increasing CB content. Addition of MAH‐g‐PP into the PP/epoxy and PP/epoxy/CB composites increased the crystallization rate of the composites and decreased the chain folding energy significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 104–118, 2006     

Structural properties and mechanical behavior of injection molded composites of polypropylene and sisal fiber

Composites based on isotactic polypropylene (PP) and sisal fiber (SF) were prepared by melt mixing and injection molding. The melt mixing characteristics, thermal properties, morphology, crystalline structure, and mechanical behavior of the PP/SF composites were systematically investigated. The results show that the PP/SF composites can be melt mixed and injection molded under similar conditions as the PP homo‐polymer. For the composites with low sisal fiber content, the fibers act as sites for the nucleation of PP spherulites, and accelerate the crystallization rate and enhance the degree of crystallinity of PP. On the other hand, when the sisal fiber content is high, the fibers hinder the molecular chain motion of PP, and retard the crystallization. The inclusion of sisal fiber induces the formation of β‐form PP crystals in the PP/SF composites and produces little change in the inter‐planar spacing corresponding to the various diffraction peaks of PP. The apparent crystal size as indicated by the several diffraction peaks such as L_(110)α, L_(040)α, L_(130)α and L_(300)β of the α and β‐form crystals tend to increase in the PP/SF composites considerably. These results lead to the increase in the melting temperature of PP. Moreover, the stiffness of the PP/SF composites is improved by the addition of sisal fibers, but their tensile strength decreases because of the poor interfacial bonding. The PP/SF composites are toughened by the sisal fibers due to the formation of β‐form PP crystals and the pull‐out of sisal fibers from the PP matrix, both factors retard crack growth.