硬弹性聚丙烯的排状堆积片晶

用广角X射线衍射、小角X光散射等手段对硬弹性聚丙烯中排状堆积片晶的形成及结构进行了研究。结果表明,应力场下聚丙烯熔体结晶,得到的硬弹性聚丙烯具有垂直于挤出方向而又平行堆积的片晶结构(即排状堆积片晶)。熔融温度越高,排状堆积片晶所需的熔体拉伸比越高。而随着熔体所受拉伸比的增加,片晶厚度有所增加。随着熔融温度升高,片晶厚度下降。热处理温度在110-120℃之间,片晶厚度随热处理温度升高明显增加。     

应力场下聚丙烯熔体的结晶与硬弹性的形成

应力场下聚丙烯熔体的结晶与硬弹性的形成胡继文＊孙友德许耀光岑美柱（中国科学院广州化学研究所广州５１０６５０）关键词聚丙烯，硬弹性，应力导致结晶１９９６－１２－２０收稿，１９９７－０５－２０修回研究表明，具有硬弹性的聚合物形态的获得最关键的因素是熔纺时...     

聚合物环带球晶的结晶机理

聚合物环带球晶作为一类特殊的球晶结构,其结晶机理一直倍受关注.经过几十年的研究,对于环带球晶形成机理的认识在不断深入,但是仍有许多问题尚未解决.本文总结了常见聚合物环带球晶的分类,综述了国内外在聚合物环带球晶片晶组织形式和片晶扭转机理研究上的主要进展,力图展示聚合物环带球晶研究的整体概况.根据前期研究结果,总结了手性聚...     

硬弹性聚丙烯的表观密度特征

研究了硬弹性聚丙烯形成过程中表观密度的变化特征。结果表明,熔体温度下降、所受拉伸比增加或冷却风速度升高均可使表观密度增加。硬弹性聚丙烯经热处理后,表观密度有所增加。硬弹性聚丙烯在拉伸过程中,表观密度先下降而后增加,呈现出最低值,这一变化规律与硬弹性聚丙烯中片晶分离形成微孔的特性有关。     

结晶聚合物的单轴拉伸和取向态结构 Ⅰ 拉伸结晶聚合物的形变机理

本文综述了关于拉伸结晶聚合物形变机理的研究工作,重点介绍了拉伸聚合物在形成细颈过程中,从原来的球晶(或堆积片晶)结构向纤维结构的转化过程,以及有关这一形变过程。目前存在的不同观点及各方面的实验证据。指出拉伸结晶聚合物的形变机理可能依赖于拉伸条件。     

聚合物流动诱导结晶研究进展

在外力作用下,半结晶聚合物的结晶形态、结晶动力学等与静态条件下相比,均发生了较大的变化,并继而影响到成型制品的性能.自上世纪六十年代人们从溶液中发现外力诱导结晶现象以来,相继开展了大量相关的理论和实验研究,提出了一些模型,随着测试手段的改进,流动诱导结晶研究取得了较大的进展,但仍存在许多争议.本文回顾了围绕聚合物流动诱导结晶所开展的工作,重点综述了流动诱导结晶形态变化、分子量及其分布、剪切速率、温度等因素对聚合物结晶动力学的影响,并指出了今后的研究方向.     

硬弹性聚丙烯纤维分子链的取向特征

硬弹性聚丙烯是在应变结晶和热结晶两个复合过程中形成的。利用双折射并结合广角X射线衍射（WAXD）等方法，研究了硬弹性聚丙烯在制备过程中晶相及非晶相分子链取向的变化，讨论了分了链的取向与硬弹性的关系。结果发现：降低熔体温度或提高熔体拉伸比可以提高晶相及非晶相分子链的取向，热处理时，晶相分子链的取向程度有所提高，而非晶相分子链的取向程度有所下降。在所研究的热处理温度的范围内，硬弹性聚丙烯的弹性回复率越高，晶相分子链的取向程度越高。     

硬弹性聚丙烯晶相和非晶相分子链取向的研究

本文用力学-振动光谱研究了硬弹性聚丙烯(HEPP)晶区和非晶区分子链在拉伸时取向的变化.我们发现在红外光谱中,1130—1190cm~(-1)波数范围内存在着三个峰,其中1167cm~(-1)处的峰是与结晶相长螺旋分子链相关的构象谱带,其谱带的强弱变化是与998cm~(-1)结晶谱带在拉伸时的变化趋势一致的.1159cm~(-1)谱带能够被归属于无定形谱带.而1152cm~(-1)处的峰也许是与短螺旋分子链构象谱带相关的.我们用计算机的二次微分、解卷积以及分峰程序测定了拉伸时HEPP晶区和非晶区分子链的取向函数,结果发现HEPP无定形分子链取向随拉伸比增加而增加,而晶区分子链的取向随拉伸比的增加先下降,直至拉伸比为1.5(第二次屈服点)后才逐渐增加.     

聚合物受限结晶的研究进展

随着纳米材料研究的迅速发展,聚合物由于其分子固有的纳米尺度结构,无论作为纳米器件或在模板应用方面都受到广泛瞩目.在微纳领域的应用中,特定受限环境下,结晶聚合物的结晶行为也因此受到广泛关注.本文从均聚物(及无规共聚物)和半晶型嵌段聚合物两方面总结了近年来聚合物受限结晶领域的研究进展.对于均聚物和无规共聚物,人们主要关注其在薄膜、超薄膜条件下的受限结晶性能,关注点为随着膜厚减小而引入的空间效应和界面效应对聚合物结晶性能的影响.而对于半晶型嵌段共聚物受限结晶的研究则多从本体出发,来研究纳米相分离与结晶的竞争过程、纳米相分离区域对于可结晶嵌段结晶生长的几何限制(空间效应)以及嵌段连接点(结晶嵌段的末端)对于结晶嵌段结晶行为的影响.     

Crystal Adaptronics: Mechanically Reconfigurable Elastic and Superelastic Molecular Crystals

Mechanically reconfigurable molecular crystals—ordered materials that can adapt to variable operating and environmental conditions by deformation, whereby they attain motility or perform work—are quickly shaping a new research direction in materials science, crystal adaptronics. Properties such as elasticity, superelasticity, and ferroelasticity, which are normally related to inorganic materials, and phenomena such as shape‐memory and self‐healing effects, which are well‐established for soft materials, are increasingly being reported for molecular crystals, yet their mechanism, quantification, and relation to the crystal structure of organic crystals are not immediately apparent. This Minireview provides a condensed topical overview of elastic, superelastic, and ferroelastic molecular crystals, new classes of materials that bridge the gap between soft matter and inorganic materials. The occurrence and detection of these unconventional properties, and the underlying structural features of the related molecular materials are discussed and highlighted with selected prominent recent examples.     

Designing Elastic Organic Crystals: Highly Flexible Polyhalogenated N‐Benzylideneanilines

The intermolecular interactions and structural features in crystals of seven halogenated N‐benzylideneanilines (Schiff bases), all of which exhibit remarkable flexibility, were examined to identify the common packing features that are the raison d’être for the observed elasticity. The following two features, in part related, were identified as essential to obtain elastic organic crystals: 1) A multitude of weak and dispersive interactions, including halogen bonds, which may act as structural buffers for deformation through easy rupture and reformation during bending; and 2) corrugated packing patterns that would get interlocked and, in the process, prevent long‐range sliding of molecular planes.     

Modification of Recycled Polymer Blends with Activated Natural Zeolite

The growing interest in the natural zeolite is based on some specific peculiarities of its structure, which after dehydration enables adsorption processes of some polymer molecules and/or segments to take place on the zeolite surface. The main goal of the study is to investigate the effect of dehydrated zeolite on the flow behavior, mechanical properties and morphology of immiscible blends from unsorted polymer wastes. A tetra-component blend consisting of 40 wt.% polypropylene (PP), 40 wt.% high-density polyethylene (HDPE), 15 wt.% low-density polyethylene (LDPE) and 5 wt.% polystyrene (PS), was studied as a model system of commingled plastic wastes. Compositions from recycled blend and dehydrated zeolite in a wide concentration range (from 0 to 20 wt.%) were prepared using a twin-screw extruder Brabender DSE 35/17D in the temperature range from 140 to 190 °C. The compositions were characterized by capillary rheometry, differential scanning calorimetry (DSC), site-resolved wide-angle X-ray scattering (WAXS) and mechanical tests. The results show a compatibilizing effect of dehydrated zeolite at low concentration levels (1-2 wt.%) and open wide possibilities for utilization of dehydrated zeolite in the recycling of unsorted polymer wastes.     

Effect of dispersed phase composition on morphological and mechanical properties of PET/EVA/PP ternary blends

Immiscible ternary blends of PET/EVA/PP (PET as the matrix and (PP/EVA) composition ratio = 1/1) were prepared by melt mixing. Scanning electron microscope results showed core‐shell type morphology for this ternary blend. Binary blends of PET/PP and PET/EVA were also prepared as control samples. Two grades of EVA with various viscosities, one higher and the other one lower than that of PP, were used to investigate the effect of components' viscosity on the droplet size of disperse phase. The effect of interfacial tension, elasticity, and viscosity on the disperse phase size of both binary and ternary blends was investigated. Variation of tensile modulus of both binary and ternary blends with dispersed phase content was also studied. Experimental results obtained for modulus of PET/EVA binary blends, showed no significant deviations from Takayanagi model, where considerable deviations were observed for PET/PP binary blends. Here, this model that has been originally proposed for binary blends was improved to become applicable for the prediction of the tensile modulus of ternary blends. The new modified model showed good agreement with the experimental data obtained in this study. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 251–259, 2010     

Physical Properties of the Biodegradable Polymer Compositions Containing Natural Polyesters and their Synthetic Analogues

The thermal, mechanical and thermo-mechanical properties of polymer compositions, containing synthetic biodegradable polymers i.e. polylacide (PLA) and aliphatic-aromatic copolyester (BTA), natural biopolyester n-PHB and its synthetic atactic analog (a-PHB) were investigated. Thermal properties of the polymer compositions were studied by means of DSC . The compositions of various polymer weight ratio were tested. Compositions containing BTA and n-PHB create polyphase systems, what was confirmed by DSC. In this case the two Tg and two Tm values were observed. Polymer compositions containing PLA and BTA showed different behaviours. At the BTA content up to 30 weight % only one Tg and one Tm were indicated. At the increase of the BTA content to 50% weight and above, the two Tg, and two Tm were observed. Mixtures of BTA with n-PHB, PLA and with a-PHB show considerably greater values of the strain (ε) in comparison with initial polymers (n-PHB, PLA). It was found that in contrary to mixtures containing PLA, at the BTA content in the mixture with n-PHB above 50% of weights increases not only the strain, but also the stress at break (σ). Strong increase of the ε value in PLA/a-PHB mixtures with the content of a-PHB above 30% of weights were observed.     

Effect of architecture on the tensile properties of triblock copolymers in a lamellar phase.

We have used self-consistent field theory to calculate the tensile moduli of triblock copolymers in lamellar microstructures prepared from linear and star architectures. The extensional moduli K(33) are the main contributors to the tensile moduli, and the contribution of K(U)33 (the internal energy contribution to K(33)) is the main component of the value of K(33). We find that the tensile moduli of ABC three-miktoarm star terpolymers are smaller than those of ABC linear triblock copolymers having identical components, presumably for two main reasons. First, for the ABC three-miktoarm star terpolymers, the contributions of K(U)33 are larger than those of the linear triblock copolymers; we attribute this phenomenon to the star terpolymers having smaller lamellar domain sizes at equilibrium relative to those of the linear triblock copolymers. Second, conformational entropies play an important role in affecting the tensile moduli, mainly because of the different degrees of freedom of the various chains. In contrast, the shear moduli contribute negligibly to the tensile moduli.     

A study on properties and morphological structure of ferrocene-filled PVC

The crystallization, special interaction, rheological behavior, and mechanical properties of PVC/ferrocene blends were studied through WAXD, FTIR, XPS, capillary rheometry, and mechanical property tests. The experimental results showed that the tensile strength of PVC/ferrocene (100/10) amounts to 82 MPa, 1.3 times as high as that of PVC. In the presence of a small amount of ferrocene, the processability of PVC is also improved. Crystallization of ferrocene in the blend is inhibited. The FTIR characteristic peaks of ferrocene shift or disappear. A new peak appears in the C1s XPS spectra and the Cl (2p) XPS spectra of PVC/ferrocene blends, and most of the ferrocene in the blends cannot be extracted by solvent alcohol, indicating the existence of some intermolecular interactions between PVC and ferrocene which cause the mechanical strength of the blends to increase. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2828–2834, 1999     

Influence of morphology on the fracture toughness of isotactic polypropylene

An adaptation of the fracture toughness test method, the J-integral technique, is described within the general framework of polymer fracture behavior. It is shown that there is a strong interaction between different morphological parameters in the way they affect the fracture behavior of isotactic polypropylene (iPP). The fracture toughness decreases with increasing crystallinity at a fixed spherulite size. The fracture toughness also decreases slightly with increasing spherulite size at a constant crystallinity, but this may not be a pure spherulite size effect. The use of a nucleating agent results in a very fine spherulitic structure but facilitates crack growth and reduces the material toughness beyond the crack initiation stage. This suggests that the material behavior is dictated by the increase in crystallization temperature caused by the presence of the nucleating agent and not by the change in spherulite size. © 1995 John Wiley & Sons, Inc.