PEN／MMT纳米复合材料结晶动力学的研究

采用熔融插层法制备聚2,6-萘二甲酸乙二酯(PEN)/蒙脱土(MMT) 纳米复合材料,用Avrami方程和张志英方法对所得数据进行了等温结晶和非等温结晶动力学的研究.结果表明,在PEN/MMT共混物中由于MMT的加入,降低了PEN/MMT的结晶活化能,导致共混物的结晶速率提高;MMT含量影响共混物的结晶速度,加入少量的MMT可以明显提高共混物的结晶速率;共混物的表面活化能的变化与Avrami方程得出的n值变化相似,MMT的含量影响共混物成核结晶速度.     

Rapid crystallization of poly(ethylene 2,6-naphthalate) via aryl amide derivatives

ABSTRACT

A very small amount of aryl amide derivative (TMB-5) was used for nucleating Poly(ethylene 2,6-naphathalate) (PEN) by melt blending. The crystalline temperature, crystallinity, and nucleation efficiency of the composites were increased as a result of the addition of TMB-5. The half-time of crystallization decreased upon the addition of TMB-5 and the work required in folding polymer chains were reduced simultaneously in the polymer mixtures. The crystal size of the PEN/TMB-5 blends became smaller due to the increase of nucleation sites. The TMB-5 had no effect on the PEN crystal type. TMB-5 slightly increased the impact strength of PEN.     

Studies on the phase structure,mechanical, rheological properties,and nonisothermal crystallization kinetics of the PEN/SCF composites

Short carbon fiber reinforced poly(ethylene 2,6‐naphthalate) composites (PEN/SCF) were prepared by twin‐screw extruder. The structure, mechanical, rheological properties, and nonisothermal crystallization kinetics of the composites were investigated by scanning electron microscope, universal tester, and differential scanning calorimetry. The results suggest that there is better interaction between SCF and PEN matrix, which leads to an increase in the tensile strength, Young's modulus, and impact strength of the composites with proper contents of SCF. Rheological behavior of the PEN/SCF composites melt is complicated, combining a dilate fluid at lower shear rate and a pseudoplastic fluid at higher shear rate. Moreover, the flow activation energy of the composites suggests that the melt with more SCF has higher sensitivity to the processing temperature. In conclusion, the composite with 5–10 wt % content of SCF has better properties. The Avrami equation modified by Jeziorny and Ozawa theory was used, respectively, to fit the primary stage of nonisothermal crystallization of various composites. The Avrami exponents n are evaluated to be 2.6–3.1 for the neat PEN and 3.4–4.8 for PEN/SCF composites, and the SCF served as nucleation agent accelerates the crystallization rate of the composites, and more the content of SCF faster the crystallization rate. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of viscosity ratio on processing and morphology of thermotropic liquid crystal polymer‐reinforced poly(ethylene 2,6‐naphthalate) blends

Thermotropic liquid crystal polymer (TLCP) microfibril‐reinforced poly(ethylene 2,6‐naphthalate) (PEN) composites with various intrinsic viscosities were prepared by a melt compounding method. Polymer composites consisting of bulk cheap polyester with a small amount of expensive TLCP are of interest from a commercial perspective. The TLCP acts as a nucleating agent in the TLCP/PEN composites, enhancing the crystallization of the PEN matrix through heterogeneous nucleation. The structural viscosity index of the TLCP/PEN composites was lower than that of PEN and TLCP, which was attributed to the formation of TLCP fibrillar structures with elongated fibrils in the PEN matrix. The TLCP/PEN composites with higher intrinsic viscosity than the polymer matrix contained these elongated fibrils, and had a TLCP component with a smaller average diameter, and a narrower diameter distribution than TLCP/PEN composites with lower intrinsic viscosity. The higher intrinsic viscosity of the polymer matrix, the higher shear rate and the lower viscosity ratio of TLCP to PEN can all favour TLCP fibrillation in the polymer composites. Copyright © 2006 Society of Chemical Industry     

Effect of hydrogen bonding on the crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)/silica hybrid composites

Biodegradable poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHB-HHx)/hydrophobically modified silica hybrid composites were prepared using simple melt compounding and the effect of hydrogen bonding on their crystallization behavior was observed. The intermolecular hydrogen bonding between PHB-HHx and silica increased gradually with the increase of silica content of the hybrid composites. However, the extent of intermolecular hydrogen bonding was not directly proportional to the silica content. Although, the crystallization rates of the PHB-HHx/silica hybrids decreased as the strength of intermolecular hydrogen bonding increased, the constant value of the Avrami exponent indicates that the presence of silica does not alter the nucleation mechanism or the geometry of the crystal growth of the PHB-HHx hybrids. The calculated crystallization activation energy increased with the addition of silica, suggesting that silica retards the overall crystallization rate of the PHB-HHx hybrid composites as a result of the existence of intermolecular hydrogen bonding. The relationship between the extent of intermolecular hydrogen bond and crystallization rate is described by the empirical second-order equation.     

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。     

Nonisothermal crystallization behavior and mechanical properties of poly(butylene succinate)/silica nanocomposites

Silica nanoparticles and poly(butylene succinate) (PBS) nanocomposites were prepared by a melt‐blending process. The influence of silica nanoparticles on the nonisothermal crystallization behavior, crystal structure, and mechanical properties of the PBS/silica nanocomposites was investigated. The crystallization peak temperature of the PBS/silica nanocomposites was higher than that of neat PBS at various cooling rates. The half‐time of crystallization decreased with increasing silica loading; this indicated the nucleating role of silica nanoparticles. The nonisothermal crystallization data were analyzed by the Ozawa, Avrami, and Mo methods. The validity of kinetics models on the nonisothermal crystallization process of the PBS/silica nanocomposites is discussed. The approach developed by Mo successfully described the nonisothermal crystallization process of the PBS and its nanocomposites. A study of the nucleation activity revealed that the silica nanoparticles had a good nucleation effect on PBS. The crystallization activation energy calculated by Kissinger's method increased with increasing silica content. The modulus and yield strength were enhanced with the addition of silica nanoparticles into the PBS matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Unique nucleation of multi-walled carbon nanotube and poly(ethylene 2,6-naphthalate) nanocomposites during non-isothermal crystallization

Multi-walled carbon nanotube (MWCNT) and poly(ethylene 2,6-naphthalate) (PEN) nanocomposites are prepared by a melt blending process. There are significant dependence of non-isothermal crystallization behavior and kinetics of PEN/MWCNT nanocomposites on the MWCNT content and cooling rate. The incorporation of MWCNT accelerates the mechanism of nucleation and crystal growth of PEN, and this effect is more pronounced at lower MWCNT content. Combined Avrami and Ozawa analysis is found to be effective in describing the non-isothermal crystallization of the PEN/MWCNT nanocomposites. The MWCNT in the PEN/MWCNT nanocomposites exhibits much higher nucleation activity than any nano-scaled reinforcement. When a vary small quantity of MWCNT was added, the activation energy for crystallization is lower, then gradually increased, and becomes higher than that of pure PEN above 1.0 wt% MWCNT content. The incorporation of MWCNT improves the storage modulus and loss modulus of PEN/MWCNT nanocomposites.     

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。     

Effects of fumed silica on the crystallization behavior and thermal properties of poly(hydroxybutyrate‐co‐hydroxyvalerate)

The effects of fumed silica on the crystallization behavior and thermal properties of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) were investigated. The PHBV/silica composites were prepared by a melt‐blending method. The nonisothermal crystallization, melting process, and isothermal crystallization kinetics of PHBV and PHBV/silica composites were characterized with differential scanning calorimetry. The spherulite development and morphology were observed by polarized optical microscopy. In addition, the thermal degradation properties were determined via thermogravimetric analysis. The results indicated that the melting and crystallization kinetics of PHBV were greatly affected by fumed silica, and this was due to the effective nucleation function of silica, which enhanced the crystallization process. The thermal onset degradation temperature of PHBV increased with the addition of fumed silica. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

笼状硅氧烷/硅橡胶复合材料的非等温结晶性能

采用溶液共混法制备了笼状硅氧烷低聚物(POSS)/硅橡胶复合材料,用差示扫描量热仪在不同降温速率下研究了POSS/硅橡胶复合材料的非等温结晶性能,考察了POSS质量分数分别为5%(试样P5)、10%(试样P10)和30%(试样P30)时对复合材料非等温结晶参数和活化能的影响,并选用Ozawa及Ozawa-Avrami联合法对POSS/硅橡胶的非等温结晶性能进行了分析。结果表明,Ozawa-Avrami联合方法适合描述POSS/硅橡胶的非等温结晶现象;POSS/硅橡胶复合材料成核速率的大小依次为P5、P15和P30,生长速率则相反,而结晶速率大小依次为P30、P5和P15。     

成核剂对PET/PEN共混物性能影响及其机理研究

利用差示扫描量热法、X射线衍射和转矩流变测试等手段,研究了成核剂碳酸氢钠、苯甲酸钠和乙烯-甲基丙烯酸离子键聚合物(Surlyn)对聚对苯二甲酸乙二醇酯/聚萘二甲酸乙二醇酯（PET/PEN）共混物结晶性能和力学性能的影响。结果表明,3种成核剂均能显著提高共混物的成核作用,其中,Surlyn和苯甲酸钠能明显提高共混物结晶性能,结晶峰温度提高约20 ℃,结晶速度提升近1倍;3种成核剂中,只有Surlyn在提高结晶性能的同时,还能提高共混物的力学性能;Surlyn是PET/PEN共混物理想的成核剂。     

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。     

Synthesis and crystallization behavior of segmented copolyesters/silica composites

Silica were introduced to segmented copolyester system (poly(butylene terephthalate)‐poly(ethylene terephthalate‐co‐isophthalate‐co‐sebacate) (PBT‐PETIS)) by in situ polymerization. Investigations on melting behavior and crystalline structure were undertaken, and the dispersion situation of silica in segmented copolyester composites was detected. A diverse crystallization characteristic has been found when the modified Avrami analytical method was applied to investigate nonisothermal crystallization behavior of the composites. Crystallization rate was restricted rather than be promoted by increasing loading of silica. The values of Avrami exponent ranged from 2.25 to 2.45, presenting a mechanism of three‐dimensional spherulitic growth with heterogeneous nucleation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1052–1058, 2006     

Understanding the effect of silica nanoparticles and exfoliated graphite nanoplatelets on the crystallization behavior of isotactic polypropylene

This study explores how the presence of nanofillers with different structural and chemical characteristics, specifically silica nanoparticles and exfoliated graphite nanoplatelets (GNP), alters the crystallization behavior and polymorphism of a semicrystalline polymer, such as polypropylene (PP). The main focus of this research is to investigate how silica and GNP affect the nucleation and growth of PP crystals during isothermal crystallization. The nonisothermal crystallization behavior, including crystal structures, crystallization temperature, and rate, is also determined. PP composites with nanomaterial content up to 7 wt% were produced by melt mixing and injection molding. Both silica and graphite were found to be effective nucleating agents, significantly increasing the crystallization rate during isothermal crystallization, with greater changes observed in case of GNP composites. The effect of filler type and amount on the PP polymorphism and lamella thickness was studied by X‐ray diffraction and modulated differential scanning calorimetry. Both silica and graphite were found to be effective nucleating agents for the less common β‐phase of PP crystals even at low nanomaterial concentration. α‐?crystal perfection and the recrystallization of the β‐form in the α‐form and/or at the transcrystalline regime were found to be responsible for the recrystallization occurring upon melting in nanocomposites at high silica or medium GNP content. POLYM. ENG. SCI., 55:672–680, 2015. © 2014 Society of Plastics Engineers     

聚乳酸/可反应性纳米SiO2复合材料的等温结晶动力学

采用熔融共混法制备了聚乳酸/可反应性纳米二氧化硅(PLLA/RNS)复合材料。利用差示扫描量热仪研究了RNS对PLLA等温结晶行为的影响;用Avrami 方程研究了PLLA及其复合材料的等温结晶动力学。结果表明,加入RNS对PLLA结晶起到了异相成核作用,随着RNS含量的增加,PLLA的结晶速率(K)提高,半结晶时间(t1/2)减小,而Avrami指数(n)变化不大,说明RNS没有改变PLLA结晶的成核机理;利用Arrhenius方程和Lauritzen-Hoffman理论分别对PLLA及其复合材料的结晶活化能(ΔE)、成核参数(Kg)和折叠链端表面自由能(σe)进行计算后发现,复合材料的ΔE比纯聚乳酸的小,Kg 、σe略有增加。这表明加入RNS降低了复合材料的ΔE,从而有效地促进了PLLA基体的结晶。     

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。     

PEN短纤维增强PET复合材料的结构与性能研究

通过在PET树脂中混入聚对苯二甲酸乙二脂（PEN）短纤维，制备了聚萘二甲酸乙二酯（PEN）增强PET复合材料，并以X射线衍射，DSC，扫描电镜，力学测试等手段分析了样品的结构，热学及力学性能，结果表明：复合材料中的PET树脂呈无定型状态，PEN纤维的加入使PET的冷结晶温度移向高温；此方法能够在一定程度上提高复合材料的断裂强度与初始模量，但可能由于复合材料中纤维含量较低。且与基体的粘结性能尚不理想，造成样品的力学性能随纤维含量和长度的变化规律并不明显。     

Crystallization and melting behavior of nano‐CaCO3/polypropylene composites modified by acrylic acid

Nano‐CaCO₃/polypropylene (PP) composites modified with polypropylene grafted with acrylic acid (PP‐g‐AA) or acrylic acid with and without dicumyl peroxide (DCP) were prepared by a twin‐screw extruder. The crystallization and melting behavior of PP in the composites were investigated by DSC. The experimental results showed that the crystallization temperature of PP in the composites increased with increasing nano‐CaCO₃ content. Addition of PP‐g‐AA further increased the crystallization temperatures of PP in the composites. It is suggested that PP‐g‐AA could improve the nucleation effect of nano‐CaCO₃. However, the improvement in the nucleation effect of nano‐CaCO₃ would be saturated when the PP‐g‐AA content of 5 phf (parts per hundred based on weight of filler) was used. The increase in the crystallization temperature of PP was observed by adding AA into the composites and the crystallization temperature of the composites increased with increasing AA content. It is suggested that the AA reacted with nano‐CaCO₃ and the formation of Ca(AA)₂ promoted the nucleation of PP. In the presence of DCP, the increment of the AA content had no significant influence on the crystallization temperature of PP in the composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2443–2453, 2004     

Non‐isothermal crystallization behavior of PLA/acetylated cellulose nanocrystal/silica nanocomposites

Poly(lactide) (PLA)/acetylated cellulose nanocrystals (ACN)/silica nanocomposites were prepared by solution casting. Surface modification of cellulose nanocrystal (CNC) was performed to prepare the ACN. The ACN and silica were expected to act as a mechanical reinforcement of PLA and a nucleation agent, respectively, to increase the crystallization rate. Introduction of acetyl groups on the surface of the cellulose nanocrystals was confirmed by Fourier transform infrared spectroscopy. A combined Avrami ? Ozawa analysis described the non‐isothermal crystallization effectively. The activation energy for the crystallization was calculated from the Kissinger and the Takhor equations. Spherulite growth behavior was observed by polarizing optical microscope and spherulite growth rate, the number of spherulite versus crystallization time have investigated. The development of PLA crystals and the thermal stability had a tendency to improve with increasing silica content. Increased tensile strength was observed due to the reinforcement effect of ACN and the morphology of the nanocomposites was investigated. © 2015 Society of Chemical Industry