Ultrahigh-molecular-weight polyethylene: Raman spectroscopic study of melt anisotropy

The Raman spectrum of ultrahigh-molecular-weight polyethylene (UHMWPE) has been obtained in the temperature interval 135–208°C, a region where optical anisotropy was observed to exist. On the basis of our spectroscopic evidence, we believe that ordered regions persist in the melt above the calorimetrically determined melting point, and that part of the polyethylene chain is in an enviroment which is similar to that of the orthorhombic crystal. These ordered domains disappear with increasing temperature, but no calorimetric phase transition is associated with this change. We postulate that the very long relaxation times associated with the highly viscous melt keep the polyethylene chains in ordered environments which persist until decreased viscosity at increased temperature allows long-range segmental motion. Our evidence supports the view that the melt anisotropy of UHMWPE arises from oriented slowly melting superheated crystals and not from a smectic liquid-crystalline phase.     

超高分子量聚乙烯温等静压成型工艺及性能

利用全软模温等静压成型方法成功制备出直径达120mm,高105mm的超高分子量聚乙烯柱状制件,研究了成型压力对成型性能的影响。利用扫描电镜、X射线衍射及示差扫描量热法研究了不同成型压力下结晶度的差异。结果表明:提高压力更有利于结晶,160 MPa下成型样品的熔点为143.0℃,片晶厚度为123nm,结晶度达到69.39%,抗拉强度达到36.8 MPa,缺口冲击强度达到152.3kJ/m~2,断裂伸长率达到634%。     

Hybrid materials based on polymethylsilsesquioxanes containing Fe,Pt, and Fe–Pt metallic nanoparticles

New hybrid materials based on Pt, Fe, and Pt–Fe nanoparticles stabilized in a matrix of polymethylsilsesquioxane nanogel and ultrahigh molecular weight polyethylene (UHMWPE) were prepared. Metal vapor synthesis was used to produce mono- and bimetallic nanoparticles. It was shown that organosilicon nanogel effectively stabilizes Pt nanoparticles with an average size of 0.9 nm. Using the nanogel results in the formation of superparamagnetic Fe particles 3–5 nm in size that consist of ferromagnetic Fe⁰ core and antiferromagnetic shells of Fe oxides. It is established that using an organosilicon matrix in the formation of Pt-Fe/UHMWPE systems helps reduce the average particle size of Fe in the material from 6.5 to 4.5 nm and narrow their particle size distribution. The composition, magnetic and electronic characteristics of the nanocomposites are studied via transmission electron microscopy, X-ray photoelectron spectroscopy, Mössbauer spectroscopy, XANES, and EXAFS.     

PREPARATION OF MICROPOROUS ULTRA HIGH MOLECULAR WEIGHT POLYETHYLENE (UHMWPE) BY THERMALLY INDUCED PHASE SEPARATION OF A UHMWPE/LIQUID PARAFFIN MIXTURE

Ultra-high molecular weight polyethylene (UHMWPE) with a microporous structure was prepared via thermally induced phase separation (TIPS).Liquid paraffin (LP) was used as a diluent in the preparation of microporous UHMWPE. Small angle laser light scattering (SALLS) and differential scanning calorimetry (DSC) were used to determine the phase separation temperatures,i.e.the cloud points and the dynamic crystallization temperatures,respectively.It was found that the cloudI points were coincident with the cr...     

稀土聚乙烯的形态结构及性能

本文研究了用稀土催化剂聚合得到的聚乙烯(稀土聚乙烯)的结构及性能。发现初生聚乙烯粉末具有条状形态结构,其支化度、结晶度及晶粒尺寸均与低压聚乙烯相似,但其熔点和特性粘数较高。用各种物理方法初步证明,稀土聚乙烯熔点较高的原因可能与其具有伸展链结晶结构有关。     

Polypeptide‐based nanocomposite: Structure and properties of poly(L‐lysine)/Na+‐montmorillonite

The feasibility of constructing polymer/clay nanocomposites with polypeptides as the matrix material is shown. Cationic poly‐L‐lysine · HBr (PLL) was reinforced by sodium montmorillonite clay. The PLL/clay nanocomposites were made via the solution‐intercalation film‐casting technique. X‐ray diffraction and transmission electron microscopy data indicated that montmorillonite layers intercalated with PLL chains coexist with exfoliated layers over a wide range of relative PLL/clay compositions. Differential scanning calorimetry suggests that the presence of clay suppresses crystal formation in PLL relative to the neat polypeptide and slightly decreases the PLL melting temperature. Despite lower crystallinity, dynamic mechanical analysis revealed a significant increase in the storage modulus of PLL with an increase in clay loading producing storage modulus magnitudes on par with traditional engineering thermoplastics. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2579–2586, 2002     

Surface modification of ultra‐high molecular weight polyethylene fibers by chromic acid

Ultra‐high molecular weight polyethylene (UHMWPE) fibers were modified by chromic acid. The effects of surface modification were evaluated with Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), contact angle measurement, and scanning electron microscope (SEM). The results showed that both the content of O‐containing functional groups and surface roughness of modified fibers increased. The polar groups on the modified fiber surface decreased the contact angles with water and ethylene glycol, as evidenced by contact angle measurement. The tensile test results showed the strength and the elongation at break of UHMWPE fibers decreased but the modulus increased after chromic acid modification. Copyright © 2016 John Wiley & Sons, Ltd.     

A calorimetric study of normal high density and ultra-high molecular weight polyethylene blends

The melting and the crystallization of blends of ultra-high molecular weight polyethylene (UHMWPE) and polyethylene high density with normal molecular weight (NMWPE) are investigated by means of differential scanning calorimetry (DSC). Mixing the components at a temperature below the flow temperature of UHMWPE (215 °C) results in segregated melting and crystallization. The segregated melting and crystallization temperatures of both components do not depend on composition of the blend. The extreme enthalpy dependence on blend composition is explained in terms of mutual influence exhibited by the components with respect to each other. It is due to the inner stresses in nonflowing UHMWPE characterized with a lot of entangled tie molecules. Mixing the components above the flow temperature of UHMWPE results in only one peak of melting and crystallization respectively. Complete mixing and probably co-crystallization between the components takes place on mixing NMWPE with flowing UHMWPE.     

Mechanical properties of fiber reinforced styrene-butadiene rubbers using surface-modified UHMWPE fibers under EB irradiation

Aiming to develop a high performance fiber reinforced rubber of SBR, a special technique using electron beam (EB) irradiation-induced graft-polymerization was applied to ultra-high molecular-weight polyethylene (UHMWPE) fibers. Although UHMWPE is chemically inert, N-vinyl formamide (NVF) could be graft-polymerized onto the UHMWPE fiber surface with this special technique. A maximum grafting percentage of 23.6% was achieved. The composite of SBR and grafted UHMWPE fibers with maximum grafting indicated a linear increase in the initial modulus and strength with the fiber content. At the fiber content of 10%, the initial modulus was improved about five times with respect to that of the pure SBR, while the strength was done about twice. At this moment, only a small reduction could be observed in the strain compared with that of pure SBR. The fiber reinforced rubber with a good performance was obtained in the system of SBR and grafted UHMWPE fibers.     

超高分子量聚乙烯烧结制品的链缠结调控及其对性能影响

利用新的单中心Ziegler-Natta(Z-N)催化剂,通过干预分子链的生长与聚集行为,可获得低缠结的超高分子量聚乙烯(UHMWPE)初生树脂.本研究利用这类低缠结UHMWPE,通过设置不同的烧结温度(Ts)来改变熔体缠结状态,并探讨了链缠结程度对烧结制品结构与性能的影响.实验结果表明TS=220℃下,UHMWPE样品发生显著的复缠,造成高缠结度;而Ts=170℃下,初始低缠结状态能够得以充分保留,从而获得了缠结度具有明显差别的不同样品.示差扫描量热法(DSC)测试表明,在Ts=170℃下,低缠结度有利于在随后等温及冷却结晶过程中生成高熔点(最高达141℃)晶体与高的结晶度(最高达65%).力学测试表明低缠结度制品的综合力学性能显著提升,其中屈服强度提高72%,拉伸断裂强度提升139%,弹性模量提升162%以及断裂伸长率提升36%,实现了同时增强增韧.这就提供了一种从调节链缠结温度实现UHMWPE烧结制品高性能化的新思路.     

The melt anisotropy of ultrahigh-molecular-weight polyethylene

In the course of melt-flow crystallization studies with ultrahigh-molecular-weight polyethylene (UHMWPE), we observed that the melt of UHMWPE is highly anisotropic above its equilibrium melting point and has a tendency to fibrillate. An examination of the melt anisotropy of UHMWPE by optical, Thermal, and x-ray analysis indicates that the melt anisotropy persists at 345°C, i.e., the temperature at which the polymer degrades under nitrogen, and appears similar to a smectic liquid-crystalline phase.     

Ultra-High Molecular Weight Polyethylene with Reduced Fusion Defects and Improved Mechanical Properties by Liquid Paraffin

Products made of ultra-high molecular weight polyethylene (UHMWPE) have a tendency to contain fusion defects, arising during the processing of the reactor powder. These defects have been implicated previously in failures of UHMWPE load-bearing surfaces in knee and hip prostheses. To minimize the fusion defects of UHMWPE products, the low molecular weight substance liquid paraffin (LP) was blended with UHMWPE. Our hypothesis was that the addition of LP could minimize structural defects and thus improve the properties of consolidated UHMWPE. The morphology and property of UHMWPE blends with LP were investigated by SEM, DMA, and stress relaxation. The addition of small amounts of LP improved tensile strength, the elongation at break, and friction and wear properties of UHMWPE, presumably due to structural defect elimination through reducing entanglements and enhancing the chain mobility of UHMWPE.     

由乙烯高效催化聚合而得的超高分子量聚乙烯的研究

本工作系研究以高效催化聚合获得的超高分子量聚乙烯的结构和性能。用扫描电子显微镜观察了高效催化剂及初生聚乙烯的形态。透射电子显微镜观察了初生聚乙烯粉未,发现毛遂边缘的超分子原纤维状织态结构。用偏光显微镜观察了不同分子量聚乙烯粉末的熔融和冷却结晶过程,生成的球晶随分子量增大而增大。用X-射线衍射、差热分析、倒换气相色谱测定了初生聚乙烯的结晶度随分子量而增大;用X-射线衍射、差热分析及密度梯度法测定经退火或热压制的聚乙烯样品的结晶度均随分子量增大而下降。X-射线衍射测定其晶粒尺寸亦随分子量增大而减小。差热分析和倒换气相色谱测定超高分子量聚乙烯粉末的结晶熔点温度(T_m)要比普通分子量聚乙烯高8-12℃。不同分子量聚乙烯的热形变曲线表明,超高分子量聚乙烯在熔融温度后出现明显的橡胶态。此外,还用差热与热重分析研究了超高分子量聚乙烯的热老化行为。测定了超高分子量聚乙烯的优异抗冲强度和沙浆磨耗量。并用扫描电镜对比观察了常规分子量和超高分子量聚乙烯试样的冲击断面的织态结构。     

Crsslinking effect of ultrahigh molecular weight polyethylene-low molecular weight polyethylene blend films produced by gelation/crystallization from solutions

Polyethylene-polyethylene blend films were prepared by gelation/crystallization from semidilute solution by using ultrahigh molecular-weight (mw) polyethylene (UHMWPE) (mw=6×10⁶) and low molecular weight polyethylene (LMWPE) (mw=4×10⁴). The UHMWPE/LMWPE compositions chosen were 50/50, 67/33, and 91/9. Elongation was carried out in a hot oven at 115–130°C. The drawn films were exposed to an electron beam under nitrogen flow. Radiation doses chosen were 10, 20, 40, and 100 Mrad. crosslinking caused a significant effect in improving high temperature resistance for the blend film with draw ratio of 20 in the case of irradiation doses less than 20 Mrad. The elongation beyond 20 times and high doses beyond 20 Mrad hampered the crosslinking effect and the specimens were easily torn manually. This is thought to be due to the fact that the excess irradiation dose causes main chain scission apart from crosslinking.     

Reversible melting of polyethylene extended‐chain crystals detected by temperature‐modulated calorimetry

The melting and crystallization of extended‐chain crystals of polyethylene are analyzed with standard differential scanning calorimetry and temperature‐modulated differential scanning calorimetry. For short‐chain, flexible paraffins and polyethylene fractions up to 10 nm length, fully reversible melting was possible for extended‐chain crystals, as is expected for small molecules in the presence of crystal nuclei. Up to 100 nm length, full eutectic separation occurs with decreasingly reversible melting. The higher‐molar‐mass polymers form solid solution crystals and retain a rapidly decreasing reversible component during their melting that decreases to zero about 1.5 K before the end of melting. An attempt is made to link this reversible melting to the known, detailed morphology and phase diagram of the analyzed sample that was pressure‐crystallized to reach chain extension and practically complete crystallization. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2219–2227, 2002     

Phase transitions in ultraoriented polyethylene fibers under moderate pressures: A synchrotron X-ray study

The effect of pressure on phase transformations of ultradrawn ultra-high-molecular-weight polyethylene (UHMWPE) fibers was examined by in situ X-ray diffraction measurements with synchrotron radiation. The mesomorphic hexagonal phase was metastable even at a relatively low pressure of about 100 bar. The effect of pressure on the melting transitions was larger than in chain-folded structures. The existence and metastability of the hexagonal phase is the basis of compaction technology of UHMWPE fibers in composite materials. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 53–59, 2004     

Effect of surface treatment with potassium permanganate on ultra-high molecular weight polyethylene fiber reinforced natural rubber composites

The effects of surface treatment using potassium permanganate on ultra-high molecular weight polyethylene (UHMWPE) fibers reinforced natural rubber (NR) composites were investigated. The results showed the surface roughness and the oxygen-containing groups on the surface of the modified fibers were effectively increased. The NR matrix composites were prepared with as-received and modified UHMWPE fibers added 0–6 wt%. The treated fibers increased the modulus and tensile stress at a given elongation. The tear strength increased with increasing fiber mass fraction, attained maximum values at 4 wt%. The hardness of composites exhibited continuous increase with increasing the fiber content. The dynamic mechanical tests showed that the storage modulus and the tangent of the loss angle were decreased in the modified UHMWPE fibers/NR composites. Several micro-fibrillations between the treated fiber and NR matrix were observed, which meant the interfacial adhesion strength was improved.     

The influence of chitin nanocrystals on structural evolution of ultra-high molecular weight polyethylene/chitin nanocrystal fibers in hot-drawing process

Ultra-high molecular weight polyethylene (UHMWPE)/chitin nanocrystal (CNC) fibers were prepared. Compared with the pure UHMWPE fibers, the ultimate tensile strength and Young’s modulus of UHMWPE/CNC fibers are improved by 15.7% and 49.6%, respectively, with the addition of chitin nanocrystals (CNCs) of 1 wt%. The melting temperature (T _m) of UHMWPE/CNC fibers was higher than that of pure UHMWPE fibers. Pure UHMWPE fibers and UHMWPE/CNC fibers were characterized with respect to crystallinity, orientation and kebab structure by wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS) and scanning electron microscopy (SEM). It is found that the CNCs act as the shish structure in UHMWPE/CNC fibers and the kebab crystals are grown around the CNCs. There was almost no difference between pure UHMWPE fibers and UHMWPE/CNC fibers in orientation. But the degree of crystallinity of various stages of UHMWPE/CNC fibers was respectively higher than the corresponding stage of pure UHMWPE fibers. Moreover, the addition of 1 wt% CNCs improved the thickness of kebab crystals and accelerated the transformation of kebab to shish.     

Morphology and mechanical properties of ultra-high molecular weight polyethylene-poly(tetrafluoroethylene) blend films

This paper deals with the morphology and mechanical properties of blend films for polytetrafluoroethylene (PTFE) and ultra-high molecular weight polyethylene (UHMWPE) prepared by kneading techniques. This experiment was carried out for blend films, prepared with different compositions of PTFE and UHMWPE to improve thermal properties of PE. In spite of the incompatibility of the two polymers, the blend film with the PTFE/UHMWPE composition =75/25 was maintained under the measurement of complex modulus at temperature higher than 300°C. This indicates that the UHMWPE chains dispersed in PTFE fibrous texture were not separated by the melting flow of UHMWPE at 300°C. To check the origin of this interesting phenomenon, the morphology of the blend films was investigated by using scanning electron microscopy, X-ray diffraction, and¹³C nuclear magnetic resonance.     

Kinetics of nonisothermal crystallization and melting of normal high density and ultra-high molecular weight polyethylene blends

The kinetics of nonisothermal crystallization and melting of blends of ultra-high molecular weight polyethylene (UHMWPE) and polyethylene high density with normal molecular weight (NMWPE) are investigated by means of differential scanning calorimetry (DSC). Mixing the components at a temperature below the flow temperature of UHMWPE (215 °C) results in increased crystallization/melting rates of the individual components in the blends above the corresponding additive values. The morphological observations of the blends, carried out by means of polarization microscopy, show that a strong boundary of both types of structures (UHMWPE non-flowing aggregates and NMWPE spherulite structures) does not exist. The NMWPE spherulites' dimensions decrease on increasing the UHMWPE concentration in the blends, but their number increases. The facilitation of the crystallization/melting of the components in the blends is explained in terms of mutual influence exhibited by the components with respect to each other. It is due to the inner stresses in nonflowing UHMWPE characterized with a lot of entangled tie molecules and to the partial co-crystallization of NMWPE molecules with the flowing part of UHMWPE. At mixing temperatures above 215 °C the melting/crystallization integral kinetic curves have only one linear part in contrast to these of the same blend (11 ratio of components), prepared at 190 °C. The rates of melting/crystallization remain almost constant with the increase of the mixing temperatures.