成型方式对聚乳酸结晶行为的影响

通过差示扫描量热仪(DSC)对不同成型方式得到的聚乳酸的结晶行为进行了研究。在相同成型方式下,光学纯度越低的聚乳酸,其结晶行为受到剪切作用的影响越小。聚乳酸的结晶行为与成型方式的剪切作用强弱有关,模压成型的影响比流延、注射成型的影响小。拉伸过程对聚乳酸制品的结晶形态产生影响,对聚乳酸制品的缠结状态影响不大。     

熔体状态对等规聚丙烯结晶行为的影响

通过Linkam CSS450剪切热台控制等规聚丙烯(iPP)的熔融温度,研究了不同熔融温度下熔体有序程度对iPP静态结晶和剪切诱导结晶行为的影响。结果表明:降低熔融温度能有效提高iPP静态结晶动力学;对于剪切诱导结晶过程,随着熔融温度的降低,iPP分子链取向程度得到提高,相同剪切速率下,低温熔融样品的分子链取向程度较高;熔体中有序结构含量随熔融温度升高而降低,这些有序结构能沿流动方向进行取向排列。     

长支链聚乳酸的结晶性能

通过均苯四甲酸酐(PMDA)和异氰尿酸三缩水甘油酯(TGIC)与聚乳酸的连续官能团反应,制备出了长支链聚乳酸,小振幅振荡剪切(SAOS)测试结果显示产物中存在长支链组分。通过差示扫描量热(DSC)实验对长支链聚乳酸的结晶行为进行了研究,结果表明:长支链聚乳酸比线形聚乳酸具有更高的成核密度,从而能够提高聚乳酸的结晶速率。在长支链和增塑剂的协同作用下,聚乳酸的结晶性能得到更大程度的改善。     

不同流场对聚乙烯蜡/UHMWPE体系结构与性能的影响

选取低分子量聚乙烯蜡(PE-wax)作为解缠结助剂,研究不同流场对超高分子量聚乙烯(UHMWPE)缠结程度的影响规律,分别利用推拉混炼仪与转矩流变仪对PE-wax/UHMWPE进行熔融共混,研究不同加工时间下拉伸流场与剪切流场对复合体系的微观结构与宏观性能的影响。结果表明,在剪切流场作用下,随着塑化混炼时间的增加,体系缠结度逐渐增加,复合体系的拉伸性能呈现先上升后下降的趋势。在拉伸流场的作用前期,UHMWPE初生态粒子规整的分子链结构被破坏,缠结程度升高,其塑化混炼效率高于剪切流场;而在拉伸流场的作用后期,UHMWPE分子链解缠结速率高于缠结速率,缠结程度下降,结晶度与熔点升高,样品的可拉伸性提高。     

分子链有序化混合对PLLA/PDLA共混物熔融稳定性的影响

左旋聚乳酸(PLLA)和右旋聚乳酸(PDLA)可通过共结晶形成兼具高强、耐热、耐水解等优异特性的立构复合聚乳酸(SC-PLA),在工程塑料领域展现出广阔的应用前景。然而,由于PLLA/PDLA共混物的熔融稳定性很差(即PLLA/PDLA分子链对或链簇在熔融时易解离、甚至发生微相分离),导致在熔融结晶过程中会同时形成大量的SC和均质(HC)晶体,制品性能远不及预期。针对这一问题,尝试采用溶液混合-沉淀、熔融混合和静电纺丝等方法来调控共混物中分子链的有序化混合程度(即有序配对的PLLA/PDLA链簇的数量),并研究了链混合对熔融稳定性的影响规律,发现链有序混合是提高熔融稳定性的关键。随着分子链有序混合程度的提高,共混物的熔融稳定性得到明显改善,因此在熔融结晶时形成的SC晶体的含量显著增加,这可为高性能SC-PLA制品的开发提供新思路。     

结晶行为改善聚乳酸韧性的研究进展

聚乳酸作为环境友好型材料具有诸多优良性能,如良好的生物降解性、生物相容性、高模量、易于成型加工、透明性优等性能。但因其本身存在性脆、结晶性能差等缺点而限制了它的应用,所以通过对聚乳酸进行改性可有效提高其韧性。从聚乳酸结晶的角度出发,通过改变聚乳酸的结晶性能可提高聚乳酸的韧性。主要探讨了有机高分子和无机粒子在聚乳酸结晶过程中的不同作用方式对聚乳酸力学性能的影响,通过调控聚乳酸的结晶行为可达到增韧聚乳酸的目的。其中,有机合成高分子主要通过减弱分子间力来抑制结晶,通过减少缠结点使分子链段发生滑移以达到增韧目的;无机粒子通过提供成核位点促进结晶使晶粒减小来传递应力,吸收变形功,阻止裂纹扩展从而增韧聚乳酸。     

注射成型中聚合物剪切诱导结晶行为的三维模拟

在考虑剪切导致分子链取向并升高其平衡熔点的基础上,建立了基于Nakamura方程的剪切诱导结晶动力学模型。在WLF-Cross黏度模型中引入结晶对黏度系数的影响,构建了考虑结晶的注射成型过程模型。采用改进的有限体积法对聚合物剪切诱导结晶行为进行了三维数值模拟,模拟中耦合了流动场、熔体压力、温度、诱导时间与结晶度。结果表明,本方法可清晰模拟出注射成型过程中聚合物的三维"喷泉"流动行为以及3层"皮-芯"结晶结构,同时,诱导结晶时间指数与相对结晶度的模拟结果与理论及实验结果吻合。     

超声辅助双螺杆机制备高密度聚乙烯/超高分子量聚乙烯复合材料及性能研究

利用超声辅助双螺杆挤出机制备高密度聚乙烯（PE-HD）/超高分子量聚乙烯（PE-UHMW）复合材料，并考察PE-UHMW含量对复合材料流变性能、结晶行为及力学性能的影响。结果表明，当PE-UHMW的含量不超过2.0 %（质量分数，下同）时，PE-UHMW在PE-HD基体内均匀分散，不存在相分离；由于PE-UHMW的相对分子质量非常大，分子链非常长，缠结程度大，其分子链松驰时间较长，有利于形成结晶前驱体，直至成核，随着PE-UHMW含量的增加，有利于成核，晶核数目明显增加，同时，PE-UHMW与PE-HD的缠结程度变大，约束了PE-HD分子链的运动，使其吸附于晶核心表面，分子链折叠排列形成结晶，最终复合材料体系的结晶度逐渐增大，片晶增厚；加入PE-UHMW后，复合材料的屈服强度、拉伸强度和断裂伸长率均明显提高。     

聚乳酸/环氧化聚丁二烯抗冲树脂结晶性能的研究

采用差示扫描量热仪(DSC)对聚乳酸/环氧化聚丁二烯抗冲聚乳酸树脂(PLA/PB(EPB))的结晶性能进行了考察,并与纯聚乳酸(PLA)的结晶行为进行了对比,研究了环氧化聚丁二烯(EPB)对PLA等温/非等温条件下结晶行为的影响规律。结果表明:聚丁二烯橡胶(PB)对PLA的结晶行为影响较小,而EPB对PLA的晶体完善程度影响较为明显。PLA和PLA/PB更倾向于在低温条件下结晶,而PLA/EPB20.9%和PLA/EPB46.5%更倾向于在高温条件下结晶。抗冲聚乳酸树脂的结晶速率高于纯PLA,并且随着EPB环氧化度的增大,抗冲聚乳酸树脂的结晶速率呈逐渐增大的趋势。     

拉伸条件下聚乳酸的结晶行为

通过红外拉伸技术研究了聚乳酸(PLA)非晶样品的结晶行为。结果发现:样品在接近玻璃化转变温度(T_g)拉伸时加快了分子链运动,其构象不断调整,直接发生了由无序相到有序相的转变;基于热力学和形变对结晶的贡献,在稍高于T_g时,拉伸能促使分子链发生取向,导致分子链间的堆砌越来越紧密,晶体结构不断完善,以至晶体相出现,从而诱导PLA结晶。此外,拉伸过程中所对应的真应变受到温度影响,温度越高,开始结晶时对应的真应变就越小。PLA样品在开始结晶后均出现了明显的应变硬化现象,这说明应变诱导结晶对材料的力学行为也有一定的影响。     

Synergistic effects of shear flow and nucleating agents on the crystallization mechanisms of Poly (Lactic Acid)

This paper presents a study of the effects of microscopic particles of talc on the crystallization kinetics of PLA. Our study covers the quiescent conditions and the case where a shear flow is applied “short term shearing”. The incorporation of talc increases the crystallization rate; it enhances the nucleation mechanism through additional heterogeneous nuclei. The microstructure is highly affected by the addition of talc due to the increase of the number of nuclei (i.e. reduced crystalline size). The application of a shear flow increases the ability of PLA to crystallize even in the presence of talc particles. The impact of shear rate becomes dramatically important just after a critical shear rate of 0.1 s^?1. It turns out that the shear rate enhances more the crystallization of PLA with talc than the pure PLA under quiescent conditions. Consequently, a supplementary contribution “synergistic effects” is responsible of the relative enhancement of the crystallization of PLA in the presence of shear flow and talc. With combining different experimental analysis techniques and modeling of the crystallization kinetics, the synergistically effects were quantified in terms of the nucleation density induced by the mutual interaction between shear flow and particles.     

Crystallization of poly(lactic acid) accelerated by cyclodextrin complex as nucleating agent

Poly(lactic acid) (PLA) is a well-known biodegradable and biocompatible polyester with intrinsically slow crystallization rate. To extend its applications to the field where heat resistance is required, increasing the crystallization rate of the material becomes critical. In this note, the nucleation effect of supramolecular inclusion complex (IC), organized by non-covalent interactions through threading α-cyclodextrin molecules onto PLA chains, on the crystallization of PLA was investigated by differential scanning calorimetry (DSC) and polarized optical microscopy. The formation of IC was confirmed by wide-angle X-ray diffraction and DSC measurements. It was found that the presence of PLA-IC significantly promoted the crystallization of PLA from both the non-isothermal and isothermal crystallization experiments. The nucleation mechanism was also discussed to some extent.     

不同构型聚乳酸共混体系的立构复合结晶研究进展

左旋聚乳酸(PLLA)和右旋聚乳酸(PDLA)在共混体系中可形成立构复合(sc)结晶,与聚乳酸(PLA)同质结晶材料相比,sc 结晶材料具有良好的耐热性和耐化学稳定性。因此,sc 结晶是改善PLA 综合性能的一种有效手段。但在PLLA/PDLA 共混体系中,存在各自的同质结晶与两者之间sc 结晶的竞争,所以制备高耐热sc 型PLA 材料的关键之一是理解其sc 结晶的形成条件与机理,进而调控和促进其sc 结晶程度。在PLLA/PDLA 共混物中,sc 结晶受聚合物化学结构、结晶与加工条件等诸多因素影响,其影响规律和机理较复杂。根据PLLA/PDLA共混物sc 结晶行为影响因素的不同,从聚合物分子量、立构规整性、共混比例、分子链拓扑结构、结晶方式与条件、加工助剂和其他组分加入6 个方面出发,详细综述了PLLA/PDLA 共混物sc 结晶及其sc 材料制备的研究进展,以期为高耐热生物基PLA 材料的加工制备提供指导。     

聚乳酸在剪切作用下的结晶行为研究进展

综述了剪切作用对聚乳酸（PLA）结晶动力学、晶体形态和晶型的影响;可以看出剪切对PLA的结晶动力学有显著的促进作用,如缩短结晶诱导时间,提高晶核生长速率并最终提高PLA的结晶度;施加剪切作用时,PLA得到的晶体主要是点晶、柱晶甚至串晶,说明剪切对PLA晶体形态有显著的改善作用;剪切也能促使PLA进行α′-α相转变,即对其晶体结构的完善产生积极影响。     

Compatible and crystallization properties of poly(lactic acid)/poly(butylene adipate‐co‐terephthalate) blends

Differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD) and dynamic mechanical analysis (DMA) properties of poly(lactic acid)/ poly(butylene adipate‐co‐terephthalate) (PLA/PBAT) specimens suggest that only small amounts of poor PLA and/or PBAT crystals are present in their corresponding melt crystallized specimens. In fact, the percentage crystallinity, peak melting temperature and onset re‐crystallization temperature values of PLA/PBAT specimens reduce gradually as their PBAT contents increase. However, the glass transition temperatures of PLA molecules found by DSC and DMA analysis reduce to the minimum value as the PBAT contents of PLA_xPBAT_y specimens reach 2.5 wt %. Further morphological and DMA analysis of PLA/PBAT specimens reveal that PBAT molecules are miscible with PLA molecules at PBAT contents equal to or less than 2.5 wt %, since no distinguished phase‐separated PBAT droplets and tan δ transitions were found on fracture surfaces and tan δ curves of PLA/PBAT specimens, respectively. In contrast to PLA, the PBAT specimen exhibits highly deformable properties. After blending proper amounts of PBAT in PLA, the inherent brittle deformation behavior of PLA was successfully improved. Possible reasons accounting for these interesting crystallization, compatible and tensile properties of PLA/PBAT specimens are proposed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

An in-depth study on crystallization kinetics of PET/PLA blends

The crystallization behavior and mechanical properties of PET/PLA blends with various amounts of PLA were investigated using a wide angle X-ray diffraction (WAXD), differential scanning calorimeter (DSC) and tensile analyses. The crystallization rate and relative crystallinity of the PET/PLA blends were studied by theoretical models of Kissinger, Avrami, Ziabicki and Ozawa. The WAXD analysis showed that the PLA phase was wholly amorphous in all blends after cooling from the melt to ambient temperature. Crystallization behavior assessments on PET/PLA blends suggest that PLA acts as a nucleating agent for PET phase leading to an increase in the initial and peak crystallization temperatures. Kissinger’s model showed a rise in activation energy up to 72% for the PET/PLA blends containing 30 wt% PLA. Ziabicki’s model gave a minimum value for kinetic parameter in PET/PLA (70/30 w/w) due to the nucleating action of PLA. On the other hand, PLA acted as a retarder for chain segments of PET tending to diffuse through the surface of growing crystals. Therefore, at an optimal composition of PET/PLA, crystallization occurs appropriately. However, an increase in PET content leads to fall in ductility, tensile strength, modulus, elongation-at-break, and fracture toughness of PET/PLA blends.     

苎麻纤维表面改性对聚乳酸结晶及拉伸性能的影响

采用偏光显微镜（PLM）、差示扫描量热仪（DSC）、扫描电子显微镜（SEM）等探究了苎麻纤维（RF）表面处理参数对模压聚乳酸（PLA）/RF复合材料结晶行为和拉伸性能的影响。结果表明,碱处理参数影响RF诱导PLA的结晶行为,碱处理时间为3 h时RF促进PLA结晶,降低冷结晶温度（T_c）,提高相对结晶度,增加横晶致密程度;碱处理时间为6 h时,RF对PLA结晶有阻碍作用。Mo方法量化分析PLA非等温结晶动力学研究结果表明,植物纤维表面形貌的变化不改变PLA的结晶机制。拉伸性能测试结果表明,碱处理时间为6 h时增强和增韧效果最佳,PLA/RF复合材料的拉伸强度和断裂伸长率分别提高了19.6 %和23.9 %。     

Unique isothermal crystallization phenomenon in the ternary blends of biopolymers polylactide and poly[(butylene succinate)-co-adipate] and nano-clay

Melt and cold isothermal crystallization studies were carried out on polylactide (PLA)/poly[butylene succinate)-co-adipate] (PBSA) neat blend and blend-clay composites. The neat blend and blend-clay composites were prepared by melt-blending in a batch mixer. The weight ratio of PLA to PBSA was fixed at 70:30, while the content of the organoclay was varied from 0 to 9 wt%. The spherulitic growth rates and morphologies of PLA and PBSA in the samples were examined through polarized optical microscopy, while the rate of crystallization and the extent of crystallinity were studied through differential scanning calorimetry. The kinetics of melt and cold crystallization of PLA were adequately described by the Avrami model. There was a strong dependence of the rate of crystallization and extent of crystallinity of PLA on the extent of clay loading and flow induced morphology. For composites with 2 and 6 wt% clay loading, uniquely slower crystallization occurred. A qualitative relationship between phase morphology and crystallization, as affected by clay loading, is therefore described.     

Structure variation of tensile-deformed amorphous poly(l-lactic acid): Effects of deformation rate and strain

The present work explored the structure-property correlations for the biopolymer poly(l-lactic acid) (PLA) by studying deformation-mediated molecular orientation and crystallization. The structural and morphological variations of amorphous PLA under different strain rates were investigated. The result showed that strain rate significantly influences its strain-hardening behavior. The crystallinity and orientation as well as cavitation of deformed PLA increase with the increase of strain rates. The structure evolution has been divided into three potential stages: (i) at small strains (<100%), the crystallinity of PLA increases by orientation-induced crystallization; (ii) at intermediate strains (100%–160%), the crystallinity of deformed PLA slightly decreases due to the breakage of existing crystals under stress accompanying with newly formed voids and cavities; (iii) at high strains (>160%), the increasing number of oriented chains in the amorphous regions promotes the crystallization of PLA. Our study suggests that strain rate and stretching strain play important roles on modulating the crystallization and orientation of amorphous PLA.