“PP-PE”聚合合金结构与性能的关系及PP/HDPE共混体系增容改性的新途径

试图澄清“PP-PE”结构与性能的关系，并以此为指导寻求增容改性PP/HDPE体系的新途径是本工作的主要内容。在本工作中，考虑到分子量、EPC组分和共混均匀性因素之后发现，“PP-PE”与相同条件下合成的均聚物样品构成的共混物之间在应力-应变行为、抗冲击性能和动态力学行为上并没有明显差别。在结合文献中有关现象详尽讨论了关于活性链寿命报导值和“（PP-PE）_(200)"的C~(13)NMR谱支持嵌段结构观点的可靠性之后，得到的结论是，现有实验现象不中以证明“PP-PE”具有嵌段结构，尽管四十年来这一观点已被普遍接受。通过TEM观察到，“PP-PE”与PP/HMWPE共混物结晶结构相同，“PP-PE”中的PE部分明显具有HMWPE的片晶特征，应力-应变和SEM实验的结果显示，“PP-PE”与HMWPE具有完全相同的增容PP/HDPE的作用。结合有关共混物结构和性能的实验结果，发现“PP-PE”主要是一个共混物，其中的HMWPE和EPC组分是决定其性能行为的主要因素。尽管在理论和实验上都已确认，分子量的增大不利于共混物组分间的相容，但通过应力-应变实验和形态结构的观察发现，虽然均聚物HMWPE的加入使PP/HDPE体系中PE组分平均分子量增大，但是体系中分散相尺寸却随HMWPE含量的增加大幅度减小，力学性能全面提高。HMWPE这种同接枝和嵌段共聚相似的增容作用既不能用“相似相容”，也不能用所谓“特殊相互作用”来阐明。为此，在本工作中提出了一个新的增容机制——“缠结作用”。应力-应变实验表明，PP/HMWPE体系的力学性能明显优于PP/HDPE体系。前者强度和断裂伸长率都高于后者，其差别尤以断裂伸长率为甚，而模量相差不大。SEM形态结构的观察发现，虽然PP/HDPE体系中的分散相尺寸随其量的增加而增大，并且界面清晰，但PP/HMWPE中的缠结作用使得组分间界面模糊，甚至消失。这种较强的组分间相互作用使得材料由脆性断裂转变为韧性断裂。PP/HMWPE的性能特点进一步证实了非理想换气条件下制备的“PP-PE”结构与性能的关系。

Characterization of the Microstructure of Bimodal HDPE Resin

In this work, two industrial bimodal high density polyethylene resins, resin A and resin B having similar molecular weight (M-w), molecular weight distribution (M-wD), and short-chain branching (SCB) content but different mechanical properties, were fractionated through cross-fractionation. The fractions were further, characterized by GPC, C-13 NMR, DSC AND FT IR techniques. These two resins were firstly fractionated into two franctions, i.e. high-temperature and low temperature fractions, via preparative solution crystallization fractionation. Resin A with much better mechanical properties contains more high-temperature fractions with longer crystalizable sequences. The SCB content in the low temperature fraction of resin A is lower than the of resin B. Both low-temperature fractions were then further fractionated using solvent gradient fractionation (SGF). The characterization of SGF fraction indicates that most of the branches fall into the high molecular weight chain in both low-temperature fractions.

Nanostructure and mechanical measurement of highly oriented lamellae of melt-drawn HDPE by scanning probe microscopy

Scanning probe microscopy was used to simultaneously determine the molecular chain structure and intrinsic mechanical properties, including anisotropic elastic modulus and friction, for lamellae of highly oriented high-density polyethylene (HDPE) obtained by the melt-drawn method. The molecular-scale image of the highly oriented lamellae by friction force microscopy (FFM) clearly shows that the molecular chains are aligned parallel to the drawing direction, and the periodicities along and perpendicular to the drawing direction are 0.26 and 0.50 nm, respectively. The results indicate that the exposed planes of the lamellae resulting from the melt-drawn method are (200), which is consistent with results of transmission electron microscopy and electron diffraction. Because of the high degree of anisotropy in the sample, coming from alignment of the molecular chains along the drawing direction, the measured friction force, F, determined by FFM is strongly dependent on the angle, theta, between the scanning direction and the chain axis. The force increases as theta is increased from 0 degrees (i.e., parallel to the chain axis) to 90 degrees (i.e., perpendicular to the chain axis). The structural anisotropy was also found to strongly influence the measurements of the transverse chain modulus of the polymer by the nanoindentation technique. The measured value of 13.8 GPa with transverse modulus was larger than the value 4.3 GPa determined by wide-angle X-ray diffraction, which we attributed to anisotropic deformation of the lamellae during nanoindentation measurements that was not accounted for by the elastic treatment we adopted from Oliver and Pharr. The present approach using scanning probe microscopy has the advantage that direct correlations between the nanostructure, nanotribology, and nanomechanical properties of oriented samples can be determined simultaneously and simply.

Morphology, thermal behavior, and mechanical properties of PA6/UHMWPE blends with HDPE-g-MAH as a compatibilizing agent

A functionalized high-density polyethylene (HDPE) with maleic anhydride (MAH) was prepared using a reactive extruding method. This copolymer was used as a compatibilizer of blends of polyamide 6 (PA6) and ultrahigh molecular weight polyethylene (UHMWPE). Morphologies were examined by a scanning electron microscope. It was found that the dimension of UHMWPE and HDPE domains in the PA6 matrix decreased dramatically, compared with that of the uncompatibilized blending system. The size of the UHMWPE domains was reduced from 35 mu m (PA6/UHMWPE, 80/20) to less than 4 mu m (PA6/UHMWPE/HDPE-g-MAH, 80/20/20). The tensile strength and Izod impact strength of PA6/UHMWPE/HDPE-g-MAH (80/20/20) were 1.5 and 1.6 times as high as those of PA6/UHMWPE: (80/20), respectively. This behavior could be attributed to chemical reactions between the anhydride groups of HDPE-g-MAH and the terminal amino groups of PA6 in PA6/UHMWPE/HDPE-g-MAH blends. Thermal analysis was performed to confirm that the above chemical reactions took place during the blending process. (C) 2000 John Wiley & Sons, Inc.

PA6/UHMWPE/HDPE-g-MAH共混物反应增容作用的研究

通过 DSC、SEM、Molau试验和力学性能测试 ,研究了 PA6/ UHMWPE共混过程中 HDPE- g- MAH对体系的增容作用、力学性能及结晶行为的影响。结果表明 ,共混体系为热力学不相容体系 ;在熔融共混过程中 ,PA6和 HDPE- g- MAH发生化学反应 ,生成的接枝共聚物对 PA6/ UHMWPE体系有增容作用 ,分散性和界面形态以及力学性能明显改善 ;共混体系中两相的结晶行为亦发生变化 ,尼龙组分的熔融热焓明显下降

Epitaxial crystallization of sPP on the (100) lattice plane of HDPE crystals

Crystallization behavior of syndiotactic polypropylene(sPP) on the (100) lattice plane of high-density polyethylene(HDPE) crystals was studied by means of transmission electron microscopy and electron diffraction. The results indicate that sPP crystals can grow epitaxially on the (100) PE lattice plane with their chain directions +/-37 degrees apart from the chain direction of the HDPE substrate. The contact planes are (100) lattice planes for both polymers. This kind of epitaxy is explained in terms of parallel alignment of HDPE chains along the rows formed by the {CH3, CH2,CH3} groups in the (100) lattice plane of the sPP crystals. This implies that in the epitaxial crystallization of sPP with fiber oriented HDPE substrate, not only the (110) but also the (100) HDPE lattice planes can act as the oriented nucleation sites. Furthermore, according to the poor matching between HDPE chains in the (100) lattice plane and the {CH3, CH2, CH3} group rows in the (100) lattice plane of the sPP crystals, it is concluded that the geometric matching is not the only controlling factor for the occurrence of polymer epitaxy.

Deformation process and mechanism of HDPE/LDPE blends

Blends of HDPE in more LDPE, with appropriate heat treatment, produce a dispersion of separate entities of HDPE in a matrix of LDPE. The system offered an especially favourable means of studying the deformation of melt-crystallized lamellae. It has been found that sheaf-like spherulites are transformed under tensile deformation into hourglass shapes i.e. a double cone aligned along the drawing direction with origin in the center of the object. This is a consequence of different modes of deformation according to the relation of an individual lamella to the tensile axis. The work shows that the lamellae have not undergone melting and recrystallization in the deformation process at room temperature.

HDPE、UHMWPE稀溶液成膜的形态结构研究

几十年来，在高分子结晶学领域开展了大量的研究工作，取得了重大进展，但仍存在许多问题有待进一步研究和探讨，特别是有关高分子结晶形成和生长过程，仍是高分子凝聚态的主要研究方向之一。从溶液结晶的ｉＰＰ和ＩＤＰＥ等烯烃类聚合物是高分子物理学中研究最为广泛的课…

HDPE/LDPE共混物形变过程中的结构变化及机理

聚合物熔体结晶由于链缠结等因素的影响，其形态结构非常复杂，这给研究结晶聚合物的微观结构，特别是聚合物在拉伸过程中的形态变化带来很大困难．本文将高密度聚乙烯（ＨＤＰＥ）和低密度聚乙烯（ＬＤＰＥ）两种不相容的组分进行共混，使少量ＨＤＰＥ分散在ＬＤＰＥ中，…

LLDPE及VLDPE对LDPE\HDPE共混物拉伸性能的影响

研究了线性低密度聚乙烯（ＬＬＤＰＥ）和极低密度聚乙烯（ＶＬＤＰＥ）对高密度聚乙烯（ＨＤＰＥ）＼低密度聚乙烯（ＬＤＰＥ）共混物拉伸性能的影响。由于ＬＬＤＰＥ或ＶＬＤＰＥ的加入，改善了ＨＤＰＥ与ＬＤＰＥ间的相互作用，提高了ＨＤＰＥ＼ＬＤＰＥ共混物的拉伸性能。

Epitaxial recrystallization of HDPE-quenched ultrathin films on oriented iPP substrates

The recrystallization behavior of high-density polyethylene (HDPE) on the highly oriented isotactic polypropylene (iPP) substrates at temperatures below the melting temperature of HDPE has been investigated by means of transmission electron microscopy. The results obtained by the bright-field observation and the electron diffraction show that upon annealing the HDPE-quenched films on the oriented iPP substrates at temperatures below 125 degrees C, only a small amount of HDPE recrystallizes on the iPP substrate with [001](HDPE)//[001](iPP), while annealing the HDPE-quenched films at temperatures above 125 degrees C, all of the HDPE crystallites recrystallize epitaxially on the iPP substrate with [001](HDPE)//[101](iPP). (C) 1997 John Wiley & Sons, Inc.

Recrystallization of HDPE in HDPE/iPP quenched films

Epitaxial crystallization behavior of HDPE/iPP double layers under quenching and annealing conditions has been studied by means of transmission electron microscopy (TEM). The results obtained from bright field TEM observations indicate that in the as-quenched state the HDPE that is in direct contact with the surface of the oriented iPP substrate recrystallizes in the form of oriented crystallites dispersed on the iPP substrate. The electron diffraction results show that besides the two normally observed epitaxial orientations between HDPE and iPP, there is also a special orientation with [001](HDPE)parallel to[001](iPP). The HDPE which is in contact with the clean surface of a glass slide crystallizes in small lamellae with random orientation. In the boundary region, the epitaxially crystallized HDPE small lamellae stop right on the boundary of the oriented iPP film. If the quenched samples are annealed at 128 degrees C (below T-m of HDPE) for 2 h, the small HDPE crystals grow to thick lamellae in both areas. But only the epitaxial orientation of HDPE with [001](HDPE)parallel to[101](iPP) has been observed.

EPITAXIAL BEHAVIOR OF HDPE ON THE BOUNDARY OF HIGHLY ORIENTED IPP SUBSTRATES

The epitaxial crystallization behavior of high-density polyethylene on the boundary of highly oriented isotactic polypropylene (iPP) substrates has been investigated by means of atomic force microscopy (AFM) and transmission electron microscopy (TEM). The results obtained from AFM and TEM indicate that the epitaxial nucleation of HDPE on the highly oriented iPP substrates occurs earlier than that in the pure HDPE phase, i.e., homogeneous nucleation. Therefore the epitaxially grown HDPE lamellae can grow across the boundary of the iPP substrate into the HDPE spherulitic phase with the epitaxial orientation relationship remaining.

MODIFICATION OF PP/HDPE BLENDS BY PP-PE SEQUENTIAL POLYMERIZATION PRODUCT

The morphology and mechanical properties of polypropylene/high-density polyethylene (PP/HDPE) blends in a wide range of compositions modified by a sequential Ziegler-Natta polymerization product (PP-PE) have been investigated. PP-PE contains multiple components such as PP, ethylene-propylene copolymer (EPC), and high molecular weight polyethylene (HMWPE). The effects of PP-PE on the mechanical properties and morphology of the PP/HDPE blends are the aggregative results of all its individual components. Addition of PP-PE to the blends not only improved the tensile strength of the blends, but the elongation at break increased linearly while the moduli were nearly unchanged. Morphological studies show that the adhesion between the two phases in all the blends of different compositions is enhanced and the dispersed domain sizes of the blends are reduced monotonously with the increment of the content of PP-PE. PP-PE has been demonstrated to be a more effective compatibilizer than EPC. Based on these results, it can be concluded that the tensile strength of the blends depends most on the adhesion between the two phases and the elongation at break depends most on the domain size of the dispersed component. (C) 1995 John Wiley & Sons, Inc.