Evolution of crystallinity and of crystallographic orientation in isotactic polypropylene during rolling and heat treatment

The development of the crystallinity and of the crystallographic orientation of isotactic polypropylene during rolling deformation and subsequent heat treatment is studied. The experiments are conducted by using X-ray diffraction with an area detector. The evolution of crystallographic orientation is tracked by calculating the pole figures and by applying a quantitative 3D texture component fit method. The rolling orientation after a true strain of −1.5 mainly consists of the (0 1 0)[0 0 1], (1 3 0)[0 0 1], and [0 0 1]//RD fiber components (RD: rolling direction). The results reveal that the crystallinity drastically decreases during rolling. We suggest that decrystallization (disaggregation) is a deformation mechanism which takes place as a microscopic alternative to crystallographic intralamellar shear depending on the orientation of the lamellae relative to the imposed deformation tensor. Heat treatment after rolling leads to the recrystallization of amorphous material and to a strong enhancement of the fiber orientation component. The recrystallization orientation is explained in terms of an oriented nucleation mechanism where amorphous material aligns along existing crystalline lamellae blocks which prevailed during the preceding deformation.     

在低频振动场中注塑成型iPP试样的结构与性能研究

利用自行研制的低频振动注塑成型装置进行等规聚丙烯(iPP)试样的结构与性能研究.实验中对常规注射和振动注射成型的试样力学性能和微观形态进行了对比实验.采用低频振动注塑成型工艺实现了IPP试样的自增强,在190℃下进行注射,强度由常规试样的41.3 MPa最大提高到振动试样的48.4 MPa(振幅PA=59.4 MPa,振频FR=0.7 Hz),强度提高了17.2%;SEM显示常规试样芯层结构主要由球晶构成,振动注射使球晶在流动方向上变形、取向,晶粒尺寸得到细化;DSC表明振动注射促进熔融峰向高温漂移,晶体结晶更加完善,结晶度最大提高了12.1%;WAXD显示低频大振幅振动注塑有利于γ晶型的生成,γ晶型有利于试样实现自增强.     

Simultaneous Enhancement of Toughness and Strength of Stretched iPP Film via Tiny Amount of β-Nucleating Agent under "Shear-free"Melt-extrusion

Herein,isotactic polypropylene films with small β-nucleating agent content were fabricated via a melt-extrusion-stretched technology with intended "shear-free" in barrel and die.Compared with neat films,the tensile strength,elongation at break and strain energy density at break of iPP film with 0.05 wt％ β-nucleating agent are significantly improved by 13.8％,39.6％ and 90.6％,respectively,indicating the simultaneously enhanced toughness and strength.Additionally,the β-crystal content gradually increases with increasing β-NA content,while the relative total daughter content of α-and β-crystal exhibits opposite tendency.Moreover,nucleation and crystal growth induced by various β-NA contents are different.This work proves an efficient strategy to enhance mechanical properties of isotactic polypropylene film via controlling elongation flow and addition of appropriate β-NA content.     

Effects of stereo-defect distribution on the crystalline morphology and tensile behavior of isotactic polypropylene prepared by compression molding process

In this study, the aggregation morphology, tensile behavior, and morphology evolution during the tensile test of two isotactic polypropylene (iPP) samples with similar molecular weight and average isotacticity but different uniformities of stereo-defect distribution are investigated by differential scanning calorimetry (DSC), two-dimensional wide angle X-ray diffraction (2D-WAXD), and scanning electronic microscopy (SEM). The results revealed that the uniformity of stereo-defect distribution of iPP determines the crystalline structure and aggregation morphology, and further influences the tensile behavior and morphology evolution during the tensile test. For PP-A with less uniform stereo-defect distribution, its ability of crystallization is stronger compared with PP-B, resulting in smaller spherulite sizes, higher melting point and degree of crystallinity, and narrower distribution of lamellar thickness of the compression molding specimens. During the tensile test, mainly the inter-spherulite deformation takes place at the early stage for deformation, which further results in drastic deformation of lamellar and high degree of reorientation at the strain increases, exhibiting higher yield strength and elastic modulus, and lower elongation at break compared with PP-B; for PP-B with more uniform stereo-defect distribution, larger spherulite sizes, lower melting point and degree of crystallinity in its compression molding sample are observed. During the tensile test, intra-spherulite deformation mainly takes place, which can disperse the tensile stress more uniformly. As the strain increases, lower degree of crystalline destruction and reorientation of the crystallites take place. The yield strength and elastic modulus of PP-B is lower than PP-A, and its elongation at break is higher.     

Is osmium diboride an ultra-hard material?

We report first-principles calculations of ideal tensile and shear strength for the recently synthesized orthorhombic OsB2 that is a primary example of a new class of ultra-hard materials synthesized by combining small, light, and covalent elements with large, electron-rich transition metals. Our calculations show that the shear strength on the (001) plane is highly anisotropic with a low peak stress of 9.1 GPa in the (001)[010] shear direction but a much higher peak stress of 26.9 GPa in the (001)[100] direction. The strong resistance against (001)[100] shear deformation prevents the indenter from making a deep imprint, giving rise to a high Vickers hardness on the (001) plane, despite the weak shear strength in the (001)[010] shear direction. The calculated peak stress of 26.9 GPa in the (001)[100] shear direction agrees well with the 30 GPa Vickers hardness observed experimentally on the (001) plane in OsB2. However, the weak shear strength (9.1 GPa) in the (001)[010] shear direction severely limits its application as abrasives and cutting tools for ferrous metals as well as scratch-resistance coatings. Our results highlight the importance of understanding atomistic deformation modes under various loading conditions in designing new ultra-hard materials.     

iPS－b－iPP共聚物对iPS／iPP共混物的性能和形态影响的研究

报道了苯乙烯－丙烯等规嵌段共聚物（ｉＰＳ－ｂ－ｉＰＰ）增溶作用及ｉＰＳ－ｂ－ｉＰＰ／ｉＰＳ／ｉＰＰ三组分共混体系微观形态和力学性能的研究结果。ｉＰＳ－ｂ－ｉＰＰ的加入明显地改善了ｉＰＳ／ｉＰＰ二组分共混物的力学性能;共聚物含量超过１５％时,三组分共混物的抗冲击强度超过ＮＩＰＳ的抗冲击强度,并具有较高的耐热性。ＳＥＭ结果表明,ｉＰＳ－ｂ－ｉＰＰ在ｉＰＳ／ｉＰＰ共混中起到了相分散和相间“偶联”作用,并降低了共混体系的微相尺寸和增加相间相互作用或粘附性。ｉＰＳ－ｂ－ｉＰＰ／ｉＰＳ／ｉＰＰ共混合金具有高的软化温度和刚性。     

A STUDY ON THE MORPHOLOGY AND PROPERTIES OF IPP/IIR BLENDS

The effect of isobutylene-isoprene rubber (IIR) on the crystallizing behavior of isotactic polypropylene (IPP) as well as the morphology of the blends in relation with its properties have been studied by DSC, WAXD, polarized light microscope, SEM and mechanical properties test. The experimental results show that IIR has slight influence on melting point, crystallinity, crystallization rate of IPP. It seems certain that IIR has not entered into IPP phase in melt state. IIR has retarding action on the growth of IPP crystal and is an effective nucleating agent of IPP spherulites. The impact strength of the blend increases rapidly with IIR content more than 30 parts; the tensile strength of the blend, however, decreases as IIR content increases. The temperature and time of alter heat-treatment also have great influence on the impact strength of the blend. The impact strength of IPP/IIR (100/20) heat-treated at about 130℃for 2h is 5 times as high as that of the untreated blend.     

In situ synchrotron SAXS/WAXD studies during melt spinning of modified carbon nanofiber and isotactic polypropylene nanocomposite

The structural development of a nanocomposite, containing 95 wt% isotactic polypropylene (iPP) and 5 wt% modified carbon nanofiber (MCNF), during fiber spinning was investigated by in situ synchrotron small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) techniques. The modification of carbon nanofibers (CNFs) was accomplished by a chemical surface treatment using in situ polymerization of olefin segments to enhance its compatibility with iPP, where the iPP/MCNF nanocomposite was prepared by twostep blending to ensure the dispersion of MCNF. X-ray results showed that at low spin-draw ratios, the iPP/MCNF nanocomposite fiber exhibited much higher iPP crystalline orientation than the control iPP fiber. At higher spin-draw ratios, the crystalline orientation of the nanocomposite fiber and that of the pure iPP fiber was about the same. The crystallinity of the composite fiber was higher than that of the control iPP fiber, indicating the nucleating effect of the modified carbon nanofibers. The nanocomposite fiber also showed larger long periods at low spin-draw ratios. Measurements of mechanical properties indicated that the nanocomposite fiber with 5 wt% MCNF had much higher tensile strength, modulus and longer elongation to break. The mechanical enhancement can be attributed to the dispersion of MCNF in the matrix, which was confirmed by SEM results.Dedicated to Prof. E D. Fischer on his 75th birthday.     

Plastic deformation behavior of β phase isotactic polypropylene in plane‐strain compression at elevated temperatures

Isotactic polypropylene (iPP) rich in β crystal modification was deformed by plane‐strain compression at T = 55–100 °C. The evolution of phase structure, morphology, and orientation were studied by DSC, X‐Ray, and SEM. The most important deformation mechanisms found were interlamellar slip operating in the amorphous layers, resulting in numerous fine deformation bands and the crystallographic slip systems, including the (110)[001]_β chain slip and (110)[ ]_β transverse slip. Shear within deformation bands leads to β→α solid state phase transformation in contrast to β→smectic transformation observed at room temperature. Newly formed α crystallites deform with an advancing strain by crystallographic slip mechanism, primarily the (010)[001]_α chain slip. As a result of deformation and phase transformation within deformation bands β lamellae are locally destroyed and fragmented into smaller crystals. Deformation to high strains, above e = 1, brings further heavy fragmentation of lamellae, followed by fast rotation of crystallites with chain axis towards the direction of flow FD. This process, together with still active crystallographic slip, leads to the final texture with molecular axis of both crystalline β and α phase oriented along FD. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 92–108, 2008     

Structure and properties of sequentially polymerized propylene-b-[ethylene-co-propylene]-b-propylene copolymers

The structure and properties of presumed block copolymers of polypropylene (PP) with ethylene-propylene random copolymers (EPR), i.e., PP-EPR and PP-EPR-PP, have been investigated by viscometry, transmission electron microscopy, dynamic mechanical analysis, differential scanning calorimetry, gel permeation chromatography, wide-angle x-ray diffraction, and other techniques testing various mechanical properties. PP-EPR and PP-EPR-PP were synthesized using δ-TiCl₃-Et₂-AlCl as a catalyst system. The results indicate that the intrinisic viscosity of these polymers increases with each block-building step, whereas the intrinsic viscosity of those prepared by chain transfer reaction (strong chain-transfer reagent hydrogen was introduced between block-building steps during polymerization) hardly changes with the reaction time. Compared with PP/EPR blends, PP-EPR-PP block copolymers have lower PP and polyethylene crystallinity, and lower melting and crystallization temperatures of crystalline EPR. Two relaxation peaks of PP and EPR appear in the dynamic spectra of blends. They merge into a very broad relaxation peak with block sequence products of the same composition, indicating good compatibility between PP and EPR in the presence of block copolymers. Varying the PP and EPR content affects the crystallinity, density, and morphological structure of the products, which in turn affects the tensile strength and elongation at break. Because of their superior mechanical properties, sequential polymerization products containing PP-EPR and PP-EPR-PP block copolymers may have potential as compatibilizing agents for isotactic polypropylene and polyethylene blends or as potential heat-resistant thermoplastic elastomers.     

Evolution of crystalline orientation and texture during solid phase die‐drawing of PP‐Talc composites

The objective of the present work was to examine the development of crystalline orientation and texture in the polypropylene matrix of talc‐filled i‐PP and in unfilled i‐PP with increasing draw ratio during solid‐phase die‐drawing at high strain rates (～1 s^?1) and a die temperature of 145 °C. After drawing, the entire billet was cooled rapidly “under tension” to room temperature before releasing the billet and cutting specimens from different axial locations for analysis. Orientation distributions of the three crystal axes for increasing axial strains have been presented as pole figures in the MD‐TD plane with the direction of draw (MD) as the reference direction. While disruption of spherulites was noticed within the die for neat PP at a draw ratio of 1.5, transcrystalline domains within the composite persisted even at a draw ratio of 3.5 in the free draw region outside the die. The transformation to fibrillar crystal morphology was complete in both materials at a draw ratio of 4.5 but the texture continued to develop beyond this stage. While the (110)[001] texture component was found to be dominant at all draw ratios for neat PP, the (010)[001] texture component was dominant at the higher draw ratios in the drawn composite. This may be attributed to the (010)[001] slip system being more active as the transverse spacing between elongated voids encasing the particles was decreased. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1528–1538     

Morphology and mechanical behavior of isotactic polypropylene with different stereo‐defect distribution in injection molding

Large amount of work has been published on the isotacticity–properties relationship of isotactic polypropylene (iPP). However, the stereo‐defect distribution dependence of morphology and mechanical properties of iPP injection molding samples is still not clear. In this study, two different isotactic polypropylene (iPP) resins (PP‐A and PP‐B) with similar average isotacticity but different stereo‐defect distribution were selected to investigate the morphology evolution and mechanical properties (tensile and notching) of their injection molding samples using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), 2D wide angle X‐ray diffraction (2D‐WAXD), and scanning electron microscope (SEM). The results of DMA showed that the molecular movement ability of PP‐A (with less uniform distribution of stereo‐defect) was stronger than that of PP‐B, meanwhile the analysis of DSC and SEM suggested that after injection molding, smaller spherullites, and crystals with higher perfection had formed in the specimens of PP‐A. The resulting of tensile properties of PP‐A were found to be better than that of PP‐B. The results of morphology evolution by SEM observation and 2D‐WAXD showed that PP‐A is more likely to occur interspherulite deformation and can disperse the tensile stress more efficiently, and therefore, its crystal structure can withstand a greater force when tensile stress is applied. On the other hand, PP‐B has larger spherulites and boundaries, and low perfection of lamellaes, and the intraspherulte deformation tend to take place. It is easier for the crystal of PP‐B to be broken up and reoriented along the tensile direction. Copyright © 2014 John Wiley & Sons, Ltd.     

β型聚丙烯注塑件的分层结构与力学性能

用X-射线衍射仪研究了不加和加成核剂形成不同晶型的三种聚丙烯注塑件的分层结晶结构,获得各层结晶度和β晶型含量(k_β)随皮芯距离的分布规律,测定了试件弯曲、拉伸和冲击性能。发现,纯等规聚丙烯试件主要含α晶型,皮层的结晶度和k_β低于芯层。加有α成核剂的试件仅含有α晶型,皮层的结晶度也低于芯层。加有β成核剂的试件主要含β晶型,皮层的结晶度和k_β值高于芯层。纯聚丙烯试件和β型为主的试件的分层结构中存在α晶和β晶间的转变。与α型聚丙烯相比,β型聚丙烯有较低的屈服强度,却有较高的抗张强度,显示很高的拉伸韧性和延展性,可明显提高室温以及玻璃化温度以下的低温抗冲击性能。     

铈对2090铝锂合金织构和力学性能的影响

为了解Ｃｅ对铝锂合金力学性能各向异性的影响,对不同Ｃｅ含量２０９０铝锂合金织构进行了ＯＤＦ（取向分布函数）测算,对合金不同方向性能进行了测量,分析了Ｃｅ对合金 构和力学性能的影响。２０９０铝锂合金主织构类型为（２２５〈５５４〉,Ｃｅ不改变合金主织构类型,但造成主织构类型分布漫散;由于Ｃｅ降低了蛔屈服强度各向异性织构成分的含量,故Ｃｅ可改变２０００铝锂合金理想织构成分的体积分数,减小屈服强度各向异性     

The compatibilizing effect of epoxy resin (EP) on polypropylene (PP)/recycled acrylonitrile butadiene rubber (NBRr) blends

A new method was used to prepare thermoplastic elastomers based on polypropylene (PP)/recycled acrylonitrile butadiene rubber (NBRr) with improved mechanical properties. An epoxy resin (EP) was used as a compatibilizing agent. The effect of EP on mechanical properties, swelling percentage and morphological characteristics of the blends was investigated with different blend compositions. The results showed that the incorporation of EP has improved the tensile strength, Young's modulus and elongation at break of PP/NBRr-EP blends compared with PP/NBRr blends. The enhancement of tensile properties of PP/NBRr-EP blends is due to the better adhesion between the two phases with the incorporation of EP. This is quite evident by scanning electron microscopy of tensile fractured surfaces. PP/NBRr-EP blend exhibits lower stabilization torque and swelling percentage than PP/NBRr blends. The lower stabilization torque is an indication of better processing characteristics.     

Thermoplastic starch films: DOE and O2PLS methodology for optimization and increased understanding of polymer processing

The combined effect of a plasticiser (glycerol) and a cross-linking agent (borax) on the mechanical properties of commercially extruded thermoplastic hydroxypropylated starch films was examined. The use of Design of Experiment (DOE) was demonstrated and used to predict and optimise formulations for a given set of material properties. As an extension to DOE, Orthogonal 2 Partial Least Squares (O2PLS) provided insight into joint correlations between the machine and transverse direction mechanical properties. Specific information regarding individual measurements or samples was also obtained with this analysis. O2PLS identified unique variables in individual compositions that were potentially incorrect measurements, or processing defects, which in turn can be used to aid quality control or processing optimisation with regards to DOE. Overall, DOE and O2PLS showed that within a starch borax-glycerol blend, borax increased mechanical strength and enhanced creep and recovery, whilst glycerol increased elongation and decreased modulus. There were competing interactions between the two dependent on concentration, and variation between machine and transverse properties was due to the extrusion induced molecular orientation of amylose. The optimum concentrations of borax and glycerol needed to achieve higher elongation, tensile strength, modulus and creep recovery than a control was found to be approximately 0.5% and 10%, respectively.     

低乙烯含量共聚聚丙烯链结构和相结构与应力应变行为的关系

研究了两种典型的低温抗冲共聚聚丙烯(ICPP)的应力应变行为及温度依赖性,其低温应力应变行为揭示ICPP具有优异的低温抗冲性能和综合力学性能的结构本质.从初始弹性模量、屈服应力及断裂伸长随温度变化所显示的变化规律进一步确认了两种ICPP的序列结构特征和相结构特征.断裂伸长变化显示了乙丙橡胶相的增韧作用,屈服应力变化显示了分散相对基质结合紧密程度的影响,弹性模量则与基质的结晶状况和结晶形态有着比较密切的关系,同时也与乙丙橡胶相和聚丙烯基质的玻璃化转变温度密切相关.     

脂肪族水性聚氨酯的力学性能研究

考察了软段的种类、分子量大小、混合软段的组成对产物力学性能的影响作用。同时还研究了二羟甲基丙酸(DMPA)用量以及中和剂的影响作用．实验结果表明。软段结构对脂肪族水性聚氨酯成膜的力学性能影响很大，聚酯型产物具有较高的模量和拉伸强度。聚醚型产物则具有较高的伸长率．混合软段对产物力学性能的影响较为复杂，随着软段中聚醚含量的升高，产物的硬度和模量均大幅度下降，但拉伸强度和伸长率的变化并不是一个线性关系．产物的模量随软段分子量的提高而降低，但伸长率和拉伸强度却有所提高．当DMPA用量较高时。产物的模量和拉伸强度均较高：当DMPA用量较低时，产物则具有较高的伸长率．中和剂的种类对产物力学性能的影响明显，当以NaOH为中和剂时，产物具有较高的硬度、模量、拉伸强度：以三乙胺为中和剂时，产物具有较高的伸长率．     

High-velocity stretching of polyolefin tapes

Stretched polyolefin films and tapes are used in many packaging applications, such as BigBags. Stretching is elongation of polymer tapes in one direction, resulting in improved mechanical properties. Both, amorphous and crystalline polymers are in principle stretchable but linear, unbranched macromolecules are highly stretchable. Hence, the stretchability of e.g. branched low density polyethylene (PE-LD) is lower than of high-density polyethylene (PE-HD). Basic requirements for stretching of thermoplastics are known, but correlations between material parameters and stretching behaviour are scarce. Moreover, stretching of polymers is usually studied with tensile tests at stretching velocities much lower (1–500 mm/min) than in industrial processes (400–1000 mm/s), while results from high-velocity stretching tests or on production machines have not been published as of yet. We investigated high-velocity (800 mm/s) stretching of PE-LD, PE-HD and isotactic polypropylene films and tapes and which stretching parameters resulted in maximum mechanical properties. It was found that sample geometry, temperature, and the degree of stretching have a significant influence on the properties of stretched tapes, e.g. higher stretching temperature resulted in higher mechanical properties and orientation of crystallites. Furthermore, about 80% of the maximum stretching degree resulted in maximum mechanical properties.     

在低频振动场中注射成型HDPE试样的力学性能及其形态控制

利用自行研制的低频振动注射实验装置探讨HDPE振动注射试样力学性能和微观形态之间的关系 .实验中对常规注射和振动注射成型的试样力学性能和微观形态进行了对比实验 .SEM实验结果显示 ,振动注射制件芯层的形态由常规注射的球晶转变为垂直于振动波传递方向排列的片晶结构 ,在剪切层中同时存在串晶或柱状堆砌的片晶结构 .频率的改变 (0 相似文献