相对分子质量分布对双峰聚乙烯薄膜树脂等温结晶动力学的影响

研究了2种双峰聚乙烯薄膜树脂（9455F1 W和9455F1 100）的等温结晶动力学行为,并讨论了相对分子质量分布的双峰相对含量对结晶过程的影响。结果表明,2种样品都呈现双峰分布的特征,且其相对分子质量相差不大,但高/低相对分子质量级分含量不同;其中,9455F1 W样品的高相对分子质量级分的相对含量大,9455F1 100样品的低相对分子质量级分的相对含量大;随低相对分子质量级分含量的增加,样品的结晶速率常数增大,半结晶时间减小,结晶速率增大。     

PBS-PTMO嵌段共聚物的合成及其结晶动力学北大核心

以丁二酸、丁二醇以及聚四氢呋喃醚(PTMO)为原料制备了w(PTMO)为50%的可生物降解聚丁二酸丁二酯(PBS)-PTMO嵌段共聚物(记作PBSPTMO50)。采用核磁共振氢谱仪,凝胶渗透色谱仪对共聚物进行了表征,利用差示扫描量热仪研究了PBS硬段和软段的非等温结晶动力学。结果表明:PBSPTMO50的数均分子量和重均分子量分别为53 083,152 407,相对分子质量分布指数为2.87;PBSPTMO50有两个结晶峰;Ozawa方程能拟合PBS硬段的非等温结晶过程,但不适合PTMO软段;而莫志深方程能拟合PBS硬段和PTMO软段的非等温结晶过程。     

PBS-PTMO嵌段共聚物的合成及其结晶动力学

以丁二酸、丁二醇以及聚四氢呋喃醚(PTMO)为原料制备了w(PTMO)为50%的可生物降解聚丁二酸丁二酯(PBS)-PTMO嵌段共聚物(记作PBSPTMO50)。采用核磁共振氢谱仪,凝胶渗透色谱仪对共聚物进行了表征,利用差示扫描量热仪研究了PBS硬段和软段的非等温结晶动力学。结果表明:PBSPTMO50的数均分子量和重均分子量分别为53 083,152 407,相对分子质量分布指数为2.87;PBSPTMO50有两个结晶峰;Ozawa方程能拟合PBS硬段的非等温结晶过程,但不适合PTMO软段;而莫志深方程能拟合PBS硬段和PTMO软段的非等温结晶过程。     

聚丁二酸丁二醇酯的等温结晶动力学研究

采用差示扫描量热仪(DSC)对聚丁二酸丁二醇酯(PBS)的等温结晶动力学进行了研究,并用Avrami方程对实验数据进行了量化分析。研究结果表明:在等温结晶时,PBS倾向于以均相成核的三维生长方式结晶,并通过偏光显微镜进行了验证;同时,随着结晶温度的升高,PBS的结晶速率常数K值下降,半结晶时间t1/2延长。     

等规聚丙烯在静态条件下的结晶行为北大核心

采用热台偏光显微镜研究了等规聚丙烯(i PP)结晶形态随时间的变化。通过控制目标结晶温度,比较了不同结晶温度条件下,成核速率、球晶生长速率随时间的变化以及温度对结晶完成时间的影响,并讨论了相对分子质量对结晶速率的影响。结果表明:等温结晶时,晶核数目和球晶直径都与时间呈良好的线性关系;成核速率与球晶生长速率均随温度的升高而逐渐降低;结晶完成时间实际上是球晶生长速率的反映,随温度的升高而增加;相对分子质量对i PP结晶速率的影响程度具有明显的温度依赖性,温度较低时,影响不明显,随着温度的升高,影响逐渐增大,并且成核时间和结晶完成时间均随着相对分子质量的增加而增加。     

等规聚丙烯在静态条件下的结晶行为

采用热台偏光显微镜研究了等规聚丙烯(i PP)结晶形态随时间的变化。通过控制目标结晶温度,比较了不同结晶温度条件下,成核速率、球晶生长速率随时间的变化以及温度对结晶完成时间的影响,并讨论了相对分子质量对结晶速率的影响。结果表明:等温结晶时,晶核数目和球晶直径都与时间呈良好的线性关系;成核速率与球晶生长速率均随温度的升高而逐渐降低;结晶完成时间实际上是球晶生长速率的反映,随温度的升高而增加;相对分子质量对i PP结晶速率的影响程度具有明显的温度依赖性,温度较低时,影响不明显,随着温度的升高,影响逐渐增大,并且成核时间和结晶完成时间均随着相对分子质量的增加而增加。     

不同粒径的PP粉的相对分子质量及其分布、结晶性能和力学性能

采用差示扫描量热仪和凝胶渗透色谱仪研究了PP粉粒径大小对其相对分子质量及分布、结晶行为和力学性能的影响。结果表明,粒径大小对PP粉的相对分子质量及分布、结晶温度、结晶速率、成核能力、力学性能等均有明显的影响。随着粒径的减小,PP粉的数均相对分子质量下降,相对分子质量分布变宽,熔体流动速率逐渐增大;结晶温度和结晶起始温度升高,成核能力增加,起始结晶速率增大,晶粒更加细化均匀;但其拉伸强度和缺口冲击强度有不同程度的下降。     

聚丁二酸丁二醇酯/聚乙二醇硬脂酸酯共混物非等温结晶行为

以聚丁二酸丁二醇酯（PBS）和聚乙二醇硬脂酸酯（PEOST）为原料,采用溶液共混法制备了PEOST质量分数分别为10%（POS-10）和30%（POS-30）的两种合金材料。通过差示扫描量热法（DSC）研究了合金材料的非等温结晶行为,用莫志深（Mo）法分析了PBS的非等温结晶动力学,采用Kissinger法和Friedman法计算PBS的结晶活化能,并用红外（FTIR）和偏光显微镜（POM）进行表征。研究结果表明：PBS先结晶形成结晶微区不利于PEOST结晶,而较高含量的PEOST有利于PBS的结晶。受PBS先结晶的影响,POS-10降温DSC曲线没有出现PEOST的结晶峰,而POS-30在低的降温速率情况下出现了PEOST双结晶峰;升温DSC曲线中两试样均出现了PEOST的熔融峰。在相同的冷却速率下,POS-30的PEOST熔融温度（T_m）和熔融焓（△H_m）大于POS-10;POS-30的PBS结晶峰温度（T_p）、结晶焓（△H_c）大于POS-10,而结晶半峰宽（D）值更小;但两者的T_m和△H_m相当。随冷却速率的增加,PBS的D值增大,而PEOST的D值却降低;冷却速率的增加对PBS的T_m值影响不大,但使PEOST的T_m略有减小。Mo法适合用于共混物中PBS的非等温结晶动力学分析。POS-30的PBS绝对值结晶活化能要大于POS-10。POS-30在红外光谱谱图中出现了PEOST结晶的红外响应峰（1109cm^-1和841cm^-1）而POS-10没有。     

生物降解PBS/MMT共混体系结晶行为研究

通过差示扫描量热仪及Avrami方程对聚丁二酸丁二醇酯/蒙脱土(PBS/MMT)共混体系的结晶熔融行为和非等温结晶动力学进行了表征和分析。结果表明:PBS在86.9℃处出现结晶峰;随着无机成核剂MMT的添加(添加量1%~5%),PBS/MMT共混体系在120℃以上出现高温区结晶峰。PBS/MMT共混体系的低温区结晶温度、绝对结晶度和结晶活化能均高于纯PBS。随着MMT加入量的增加,共混体系的低温区结晶温度和绝对结晶度逐渐降低,结晶活化能呈现先升高后下降的趋势;高温区的结晶温度和结晶活化能逐渐升高,绝对结晶度则迅速下降,且当MMT加入量达到7%时,高温区结晶峰消失。MMT具有明显的异相成核作用,可以改变PBS结晶过程中的成核和增长方式,而对其结晶速率影响不显著,其结晶速率受降温速率的影响较大。     

硫酸钙晶须/PBS共混物等温结晶动力学研究

用差示扫描量热仪(DSC)测试了硫酸钙晶须/聚丁二酸丁二醇酯(PBS)共混物的等温结晶过程。采用Hoffm-weeks方程拟合的方法得到了4种配比的硫酸钙晶须/PBS共混物的平衡熔点,并根据实验数据拟合出描述硫酸钙晶须/PBS共混物等温结晶过程的Avrami方程。结果表明:共混物的平衡熔点随着硫酸钙晶须含量的提高而降低;硫酸钙晶须的加入,对PBS的成核机理和生长方式没有明显的影响;等温结晶温度不影响共混物的结晶机理,但会影响结晶速率,等温结晶温度越高,结晶速率越慢。     

PBS结晶影响因素的研究

采用偏光显微镜对聚丁二酸丁二醇酯(PBS)的结晶影响因素进行了研究。结果表明:在等温结晶时,PBS的最佳结晶温度随着分子量的增大而提高,当分子量增到一定值后,最佳结晶温度受分子量的影响很小。结晶温度一定时,PBS的晶体尺寸随着结晶时间的延长而增大。结晶时间一定时,PBS的晶体尺寸随着结晶温度的提高而先增大后减小。数均分子量为1×103、8×103、6×104、1×105的PBS最佳结晶温度分别为40℃~50℃、80℃、80℃、90℃。低分子量的PBS在较短的结晶时间内晶体尺寸就已较大,而高分子量的PBS在较长的时间内才能形成较大尺寸的晶体,数均分子量为8×103、6×104、1×105的PBS在最佳结晶温度形成较好结晶的时间分别为10min、20min、25min。     

外场作用对PBS及嵌段共聚物PBS-b-PEG结晶形态的影响

采用偏光显微镜对聚丁二酸丁二醇酯(PBS)及聚酯嵌段共聚物聚丁二酸丁二醇酯-b-聚乙二醇(PBS-b-PEG)在不同外场环境下的结晶形态进行研究。结果表明:在等温结晶过程中,PBS及PBS-b-PEG的球晶尺寸及形貌同结晶温度和时间密切相关,PBS在90℃等温结晶2 h后可形成明显的环带球晶形态;PBS及PBS-b-PEG在水环境下等温结晶,水起到成核剂的作用,使球晶尺寸细化,球晶形貌发生改变;超声振动作用具有使PBS球晶尺寸细化作用,而对PBS-b-PEG结晶影响较小。     

Crystallization regimes and reptation in polypropylene molecular weight fractions

Crystal growth rate data based on the kinetic nucleation theory of chain folding and the effect of reptation, have been used to predict the rate of crystal growth at moderate to high supercoolings in iPP molecular weight fractions. Growth rate data obtained for the fractions seem to be in agreement with the theoretical predictions of the regime theory. However, an extension of the gambler ruin treatment to the iPP data has not been successful with regard to the dominant morphology in regime II. The variable cluster model suggested as the morphology for polyethylene in regime II does not appear to be evident from this study. The effect of polydispersity, molecular weight, and tacticity on the crystallization behavior of iPP fractions have also been studied and correlated with the structure of polymer samples investigated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 579–584, 1999     

Multiwalled carbon nanotube nucleated crystallization behavior of biodegradable poly(butylene succinate) nanocomposites

Poly(butylene succinate) (PBS) nanocomposites with multiwalled carbon nanotubes (MWNTs) prepared by melt compounding were studied for the effect of MWNT dispersion on the modulus and crystallization kinetics. The nucleating effect of the addition of 0.1 wt % MWNT to PBS was clearly demonstrated. Differential scanning calorimetry nonisothermal crystallization studies showed a clear decrease in the half‐time of crystallization with increasing MWNT content in PBS/MWNT nanocomposites. It was observed with the Ozawa method that the Ozawa parameter values for the nanocomposites were lower than those for neat PBS, and this indicated that the crystal morphology was different. The storage modulus of the nanocomposites increased about 23% with the addition of only 0.1% MWNT in comparison with neat PBS, whereas the glass‐transition temperature was unaltered. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystallization behavior and morphology of double crystalline poly(butylene succinate)-poly(ethylene glycol) multiblock copolymers

The crystallization kinetics, morphology and crystal structure of biodegradable double crystalline poly(butylene succinate)-poly(ethylene glycol) (PBS-PEG) multiblock copolymers (PBSEGs) were studied with different composition and segment chain length by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide-angle X-ray diffraction (WAXD). The isothermal crystallization kinetics results show that the overall crystallization rate and the equilibrium melting point of PBS increase with the increasing PBS fraction and the segment chain length (L_PBS); on the other hand, the higher content or longer PEG segment within PBSEGs possesses larger crystallization rate of PEG chains. The nucleation mechanisms are demonstrated to be instantaneous 3D and 2D aggregates for PBS and PEG segments within PBSEGs, respectively (except for PBSEG_2K?50, 2D and 3D aggregates for PBS and PEG segments, respectively). POM observations indicate that the PBS within PBSEG multiblock copolymers presents banded spherulites in the investigated temperature range. After quenched to lower temperature, PBS templates the morphology for PEG crystallization, and PEG crystallization just changes the magnitude of birefringence (lighting the spherulites) but not influences the superstructure. Finally, WAXD measurements determine that the crystal structure is not changed with the compositions.     

Molecular weight dependence of melt crystallization behavior and crystal morphology of low molecular weight linear polyethylene fractions

Melt crystallization behavior and corresponding crystal morphology of five low molecular weight (3,900 ≤ MW ≤ 20,800) linear polyethylene (PE) fractions have been investigated. The overall crystallization data indicate that the lower molecular weight (MW) fraction possesses a higher crystallization rate at the same undercooling (ΔT). On the contrary, at the same crystallization temperature (T_c) the rate increases with MW. The Avrami exponent (n) varies from ca. 3 to 4 with decreasing ΔT for the fractions studied, which implies the nucleation process changes from athermal type to thermal type as T_c increases. For the low MW PE’s, the different crystal growth regimes (regime I and II) have been first time identified via linear crystal growth rate (G) measurements. The regime I/II transition temperatures are close to previously reported data, which were obtained through a different method. As reported for intermediate MW PE’s, the transitions occur at an almost constant ΔT of 17.5±1 °C for each fraction studied. Morphological study shows that single crystals could be formed isothermally at low ΔT’s. Typical banded spherulites and axialites, which are MW and ΔT dependent, are also observed. Orthorhombic structure is ascertained to be the dominant crystal structure that exists irrespective of MW and crystal growth regime.     

Effect of copolymerized ethylene unit on the crystallization behavior of poly(propylene-co-ethylene)s

The crystallization behavior of two kinds of commercial poly(propylene-co-ethylene)s (PPE1, PPE2) with similar average molecular weight and molecular weight distribution, isotacticity and copolymerized ethylene unit content and their fractions was investigated by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and polarized optical microscopy (POM) techniques. The results indicate that the PPE1 isothermally crystallized films possess thicker and less cross-hatched lamellar structure than those of the PPE2. As for the fractionated samples, the thin films of low temperature (≤90 °C) fractions (PPE1-80, PPE2-80) of both PPE1 and PPE2 exhibit similar crystallization behavior, while for the high temperature (≥95 °C) fractions (PPE1-108, PPE2-108), the crystalline morphology has marked differences. Compared with PPE2-108, the PPE1-108 isothermally crystallized thin films possess thicker lamellae and less cross-hatched lamellar structure, while for the fibrous crystal number, the former is less than that of the latter. The main reason to create the crystallization behavior differences between the two PPEs and their fractions is due to the effect of molecular chain structure, i.e. the different distribution of copolymerized ethylene unit in polypropylene chains.     

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     

In situ polymerized nanocomposites of poly(butylene succinate)/Tio2 nanofibers: molecular weight,morphology, and thermal properties

In this study, the nanocomposites of poly(butylene succinate) (PBS) and TiO₂ nanofibers were first synthesized via in situ polymerization. Molecular weight, morphology, and thermal properties of the nanocomposites were characterized. As the weight percentage of TiO₂ nanofibers increased from 0 to 2%, the molecular weight of PBS in the nanocomposites decreased gradually compared with that of pure PBS. In morphology, the nanocomposites were constituted by free PBS and PBS‐grafted TiO₂ nanofibers (PBS‐g‐TiO₂), which were proved by the Fourier transform infrared, scanning electron microscopy (SEM), and transmission electron microscopy. In addition, the SEM demonstrated the strong interfacial interaction and homogeneous distribution between TiO₂ nanofibers and PBS matrix. The thermal properties determined by differential scanning calorimetry and thermogravimetric analysis included the increasing of cold crystallization temperatures, the melting temperatures, and the thermal stability. Besides, the crystallinity and the rate of crystallization of the nanocomposites were enhanced, which were also observed by the X‐ray diffraction. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crystallization,morphology, and mechanical properties of poly(butylene succinate)/poly(ethylene oxide)‐polyhedral oligomeric silsesquioxane nanocomposites

The biodegradable poly(butylene succinate) (PBS)/poly(ethylene oxide)‐polyhedral oligomeric silsesquioxane (PEO‐POSS) nanocomposites were prepared by the solution blending and melt‐injection methods. The effect of PEO‐POSS on the non‐isothermal and isothermal crystallization, morphology, as well as mechanical properties of PBS was carefully investigated. The PEO‐POSS nanoparticles dispersed well in the PBS matrix, with the diameters around 30 nm. From isothermal crystallization analysis, the incorporation of PEO‐POSS enhanced the crystallization of PBS due to the heterogeneous nucleation effect while the crystal structure of PBS remained. PBS/PEO‐POSS nanocomposites showed of higher glass transition temperatures than that of neat PBS, attributing to the existence of PEO‐POSS decreasing the flexibility of PBS chains. The elongation at break of the PBS/PEO‐POSS nanocomposites reached the maximum value with PEO‐POSS content of 5 wt%. However, the elastic modulus of PBS decreased after the incorporation of PEO‐POSS. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers