聚合物流动诱导结晶数值模拟

通过模型定性分析剪切对熔体结晶动力学、晶体取向和流变学的影响.根据Avrami方程和晶体成核速率与第一法向应力差的关系模型模拟剪切对聚合物结晶动力学的加速作用,随着剪切速率和剪切时间的增加,整个结晶过程发展更快,活化晶核数目显著增多,剪切停止,活化晶核数目不再变化.但剪切对结晶的加速作用不是无限的,随着剪切速率和剪切时...     

力场下聚合物的结晶行为研究进展

介绍了聚合物在力场作用下结晶行为的研究进展;概述了不同力场(剪切、拉伸、振动)对聚合物结晶形态和结晶动力学的影响;重点论述了剪切力场下,剪切速率、剪切方式、分子量和分子量分布等对聚合物成核和生长的影响,简述了拉伸、振动对结晶的影响。认为力场的加入对聚合物的成核和晶体生长都有促进作用。     

注塑成型制品结晶取向数值模拟

注塑成型时非等温、非稳态的流动过程,使聚合物各部分经历不同的热历史和力历史,产生多样的晶体和取向结构。通过黏性流体力学基本方程,计算注塑流体的温度场和速度场,根据Avrami方程和晶体成核速率与第一法向应力差的关系模型模拟剪切流场对聚合物结晶动力学的加速作用,结合熔体结晶度的发展模拟制品不同位置沿厚度方向的取向。指出剪切速率较大的近模壁处呈现高度取向层,在中心层剪切速率低、取向因子小,呈现自由取向。     

限域空间内的结晶研究进展

在经典成核理论基础之上,综述了无机、有机化合物和大分子聚合物等几类物质在不同的限域空间内的结晶行为,并与普通溶液结晶行为进行了比较。分析了不同限域空间对晶体的成核、生长以及相转化产生的影响,如成核速率、生长取向、晶型种类等。研究表明,在高度分散的纳米孔基质中,孔径尺寸、形貌对晶体成核与生长的控制机理不同,从而影响了最终的晶体结构。     

溶剂超声波协同法用于有机物系结晶快速成核

<正> 引言 有机物系结晶大多属于溶液群体结晶范畴,是工业结晶的重要组成部分.晶核是过饱和溶液中新生成的微小晶体粒子,是晶体生长过程必不可少的核心. A.VanHook在论述晶核的生成时指出,声波辐照由于具有强烈的定向效应,有补充和加强形成临界晶核所需的波动作用,故能加速起晶过程.高大维提出了蔗糖溶液的溶剂超声波协同成核法,该法已被利用来进行味精、含水α-葡萄糖、木糖醇等的成核研究并获得成功,所需的成核溶剂、超声波强度及刺激时间因不同物质而异.与传统的晶种制备方法(如粉碎机破碎法、球磨法、晶浆中留一部分晶体作为晶种等)相比,该法具有简单、快速、晶核数目容易控制的优点.同时还具有晶核形状好、投种量小并减少结晶生长过程中用于整晶的能耗、成品质量高等优点.溶剂超声波协同成核法的原理是溶析效应与超声波的机械(分散)效应、空化效应的结合.从溶液成核速率公式可看出表面张力σ、粘度η和过饱和度S对成核速率J的关系     

剪切流场中聚乙烯结晶过程的建模与模拟

基于Eder模型推导了剪切流场中球晶、串晶形态演化的数学模型,将第一法向应力差作为串晶成核的驱动,并引入两相悬浮模型描述体系,认为其由无定形相和半结晶相组成,分别用FENE-P模型和刚性哑铃模型描述。基于上述数学模型,分别构造了捕捉球晶、串晶生长的Monte Carlo法与体系控制方程求解的有限差分法,成功模拟了二维剪切流场中聚乙烯的结晶过程,给出了球晶、串晶的形态演化,分析了剪切时间、剪切速率对串晶成核密度、结晶速率、流体黏度等的影响。数值结果表明:所构造的Monte Carlo法合理有效,不仅成功捕捉了晶体的生长与碰撞,而且较为准确地预测了结晶速率。此外,提高剪切时间或剪切速率,将增加串晶成核密度、提高结晶速率、使流体黏度突增的时间点提前。     

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。     

初始过饱和度对谷氨酸结晶的影响研究

以谷氨酸一钠(MSG)水溶液模拟发酵液,采用pH-shift模式研究溶液初始过饱和度对谷氨酸结晶的影响。结果表明:过饱和度同时影响谷氨酸结晶的晶习和粒度分布。当过饱和度S≤7.15时,谷氨酸主要以α型晶习析出,粒径呈对数对称分布。随着过饱和度增大,β型结晶比例增大,中位径趋小且粒度分布范围变宽。当S≥14.17以后,晶体全部是β型晶习,晶体粒度分布分散且无规律。根据经典成核理论计算了不同过饱和度/MSG浓度时两种谷氨酸晶习的成核速率,证明两种晶习的成核速率均随过饱和度增加而加快,相同过饱和度时α型晶习成核速率大于β型,而相同MSG浓度时β型成核速率大于α型。研究认为,结晶成核速率随过饱和度增大而加快是影响谷氨酸结晶粒度分布的主要原因,而晶体晶习主要取决于α、β型两种晶核的竞争性成核速率的差值。基于已有研究报道及实验结果,提出了α和β型谷氨酸晶体的C-pH相图模型,解释了过饱和度影响谷氨酸结晶晶习的规律。     

SAPO-34分子筛晶化机理及晶化动力学研究

对SAPO-34分子筛晶化过程中预相形成、诱导期内晶核生成、晶体生长和晶化过程的研究进行综述。SAPO-34分子筛晶化过程首先形成不稳定的层状预相结构,进而发展为具有有序排列晶格骨架的晶核。结晶热力学控制晶相结构,晶化动力学控制晶体成核和生长速率。影响晶化动力学的关键因素是温度和浓度,成核速率和晶体生长速率互相竞争控制晶粒大小。晶化过程的Si取代机理和Si分布影响分子筛酸性。晶化动力学研究结果表明,温度升高,结晶速率增加,成核时间缩短。     

长链支化聚丙烯结晶行为的流变学研究

以长链支化聚丙烯(LCBPP)为对象,用流变学方法研究了LCBPP的等温结晶行为和剪切流动诱导结晶行为。结果表明:在LCBPP的等温结晶过程中,长链支化结构起到了成核作用,从而加速了结晶过程,且支化度越高,加速效应越明显;对LCBPP施加预剪切流场,其结晶速度明显加快,且支化度越高,LCBPP结晶行为对流场的响应越敏感,即使在很低的剪切速率下,结晶诱导时间也会明显缩短。     

Shear induced crystallization of poly(m-xylylene adipamide) with and without nucleating additives

The shear induced crystallization of the poly(m-xylylene adipamide) (MXD6) which is a semi-aromatic polyamide, was studied for a virgin (PA1) and a nucleated (PA2) grades using a shearing hot stage coupled with a microscope. Half crystallization times were measured according to the crystallization conditions (crystallization temperature, shear rate and shearing time). The effect of shear on the crystallization kinetics was shown by a strong decrease of the crystallization times for both materials. PA2 sensitivity to shear was much lower than that of PA1. This was attributed to the presence of nucleating agents which increased the primary nucleation density in the unsheared quiescent melt, leading to a higher necessary shear rate to overcome the quiescent nucleation. Kinetic models were proposed to predict the crystallization process as a function of the crystallization conditions. They were based on both Avrami and Hoffman-Lauritzen theories and modified to take into account the effect of shear. In the model the nucleation rate of the crystalline entities was related to the shear rate by a power function. Besides, crystalline morphology and orientation were studied by wide and small angle X-ray scattering to confirm the orientation effect of the shear in the crystalline part of the material.     

Flow‐induced crystallization of polylactide stereocomplex under pressure

Although shear and pressure fields always coexist in practical polymer processing, their combined influence on the crystallization behavior of polylactide stereocomplex (SC) is ambiguous due to the limit of experiment device. In that case, a homemade device was employed to prepare samples under the coexistence of shear and pressure and explore the crystallization behavior of SC. Differential scanning calorimetry and synchrotron radiation were used to investigate the combined effect of shear flow and pressure on SC crystallization. The results show that shear flow was helpful for SC formation. Shear flow promoted the phase mixing of the polymer blends and improved the nucleation efficiency of SC. Pressure had a negative effect on SC formation because of the decrease in free volume. Regard to polylactide homogeneous (HC), pressure played a positive role on HC formation. Pressure suppressed the formation of SC network which could impede HC generation. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46378.     

Comparative study of the nucleation activity of third‐generation sorbitol‐based nucleating agents for isotactic polypropylene

The nucleation activity of the sorbitol derivatives 1,2,3,4‐bis(3,4‐dimethylbenzylidene sorbitol) and methyldibenzylidene sorbitol are compared with that of talc, a conventional nucleating agent for the monoclinic crystalline phase of isotactic polypropylene. The thermal parameters associated with the dynamic crystallization process are studied as a function of the cooling rate by differential scanning calorimetry, and the nucleating efficiency is assessed by comparison with self‐nucleation, the highest values being observed for 1,2,3,4‐bis(3,4‐dimethylbenzylidene sorbitol) over the whole concentration range. The nature of the polymer crystals formed in the nucleated polymer was studied by X‐ray diffraction, and the data show an increase in a preferred orientation of the polymer crystallites with increasing concentration of nucleating agent. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2440–2450, 2002     

振动共混对PC/PP多重结晶行为的影响

在传统转矩流变仪上叠加机械振动帛成了振动共混流变仪，叠加机械振动的流动影响共混物的相形态，因此影响了PC／PP的多重结晶行为。DSC和偏光显微联用分析发现，所有峰对应的结晶都是异相成核，共混频率或振幅增高，减小分散相相畴尺寸，PP粒子的异相核会向PC迁移，所以制备的共混物的低温结晶峰越强，而高温结晶峰减弱，共混振幅很大时，中等尺寸粒子界面附生非均相成核等效增加了较高温度成核率，结晶温度较高。     

Effect of shearing on crystallization behavior of poly(ethylene terephthalate)

The shear‐induced crystallization behavior of PET was investigated by measuring the time‐dependent storage modulus (G′) and dynamic viscosity (η′) with a parallel‐plate rheometer at different temperatures and shear rate. The morphology of shear‐induced crystallized PET was measured by DSC, X‐ray, and polarizing optical microscopy. When a constant shear rate was added to the molten polymer, the shear stress increased with the time as a result of the orientation of molecular chains. The induction time of crystallization is decreased with frequency. Moreover, the rate of isothermal crystallization of PET was notably decreased with increasing temperature. The shape of spherulites is changed to ellipsoid in the direction of shear. In addition, aggregation of spherulites is increased with increasing frequency. Particularly, the row nucleation morphology could be observed under polarized light for ω = 1. From the results of DSC, the melting point and enthalpy have a tendency to decrease slightly with increasing frequency. The crystallite size and perfectness decreased with frequency, which was confirmed with X‐ray data. The unit length of the crystallographic unit cell of the PET increased and the (1 0 3) plane peak increased with increasing frequency. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2640–2646, 2001     

Modeling of flow‐induced crystallization in blends of isotactic polypropylene and poly(ethylene‐co‐octene)

Poly(ethylene‐co‐octene) (PEOc) has been shown to provide a high toughening contribution to isotactic polypropylene (iPP). The theoretical modeling of flow‐induced crystallization (FIC) of blends of iPP and PEOc is not much reported in the literature. The aim of the present work is to clarify the FIC of iPP upon addition of PEOc in terms of theoretical modeling. The crystallization of iPP and PEOc blends in flow is simulated by a modified FIC model based on the conformation tensor theory. Two kinds of flow fields, shear flow and elongational flow, are considered in the prediction to analyze the influence of flow field on the crystallization kinetics of the polymer. The simulation results show that the elongation flow is much more effective than shear flow in reducing the dimensionless induction time of polymer crystallization. In addition, the induction time of crystallization in the blends is sensitive to the change of shear rate. In comparison with experimental data, the modified model shows its validity for the prediction of the induction time of crystallization of iPP in the blends. Moreover, the simulated relaxation time for the blends becomes longer with increasing percentage of PEOc in the blends. Copyright © 2012 Society of Chemical Industry     

Nonisothermal crystallization behaviors of silk‐fibroin‐fiber‐reinforced poly(ϵ‐caprolactone) biocomposites

With differential scanning calorimetry measurements, the nonisothermal crystallization of biocomposites of poly(?‐caprolactone) (PCL) reinforced with silk fibroin fiber (SF) was investigated. With the gradual addition of SF, the strengthening of the heterogeneous nucleation reagent effect of SF led to the acceleration of PCL crystallization, and secondary crystallization occurred and became more remarkable with increases in the cooling rate and SF content. Moreover, with the introduction of SF and an increase in the cooling rate, the nucleation and growth mode of the PCL crystalline phase was slightly changed. Because of the confinement of the fiber network structure, the crystallite size of PCL was reduced, the crystallization exothermicity of PCL decreased, and the crystallization activation energy of PCL increased. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009