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 cryst...

Structure and Properties of Self-reinforced Material Made from Ultra-high Molecular Weight Polyethylene-montmorillonite Nanocomposite

High-strength and high-modulus ultra-high molecular weight polyethylene(UHMWPE), named self-reinforced material, was obtained by the elongation of UHMWPE-montmorillonite nanocomposite at melting temperature. According to the scanning electron microscope(SEM) analysis, a great deal of fibrillar texture formed in the direction of elongation, and the tensile fractured surface was similar to that of highly oriented fiber. The transmission electron microscope(TEM) and selective area electron diffraction(SAED) analyses reveal that the reinforced phase of the self-reinforced material is an extended chain crystal and its size is about 50_200 nm wide and several microns long, and the montmorillonite layers are broken up to pieces in the size from 100 to 10 nm. The broken layers which have a huge surface area interacting strongly with macromolecules reduces the entanglement density of UHMWPE and induces the chain orientation in flow field. It is supposed that the astriction of montmorillonite layers to polyethylene chains is not only end-tethered but also side-tethered. The differential scan calorimetry(DSC) analysis shows that there are two endothermal peaks for the self-reinforced material, of which the peak at a higher temperature(136.4 ℃) is ascribed to the melting of the reinforced phase.

Determination and Temperature Dependence of Plateau Modulus for Polymerization of Propylene to Isotactic Polypropylene with Ultra-high Molecular Weight under Catalysis of Ziegler-Natta Catalyst

The viscoelastic behavior of isotactic polypropylene with ultra-high molecular weight(UHPPH) and broad molecular weight distribution(MWD), produced in the presence of Ziegler-Natta catalyst, was investigated by means of oscillatory rheometry at 180 and 200 ℃, whose loss modulus(G″) plots at 180 and 200 ℃ versus the natural logarithm of angular frequency(ω) present a pronounced maximum at 34.35 and 69.21 rad/s, respectively, and do not show a maximum peak at 0.01-100 rad/s for Ziegler-Natta catalyzing ethylene-propylene random copolymerization(PPR) with a conventional molecular weight and broad MWD. The fact indicates that the high molecular weight is responsible for a maximum peak of G″(ω) vs. lnω curves for UHPPH. This makes it possible to determine the plateau modulus(G 0_N) of UHPPH from a certain experimental temperature G″(ω) curve directly. For UHPPH, the G 0_N determined to be 4.28×10 5 and 3.62×10 5 Pa at 180 and 200 ℃, respectively, decreases with the increase of temperature and is independent of the molecular weight, which directly confirms reputation theoretical prediction that the G 0_N has no relation to the molecular weight.

Ultra-High Molecular Weight Polyethylene Tape Applied for Distal Humeral Condyle Fracture around Total Elbow Arthroplasty in Patients with Rheumatoid Arthritis: Report of Two Cases

Managing fractures of distal humerus in patients with rheumatoid arthritis (RA) is technically challenging. Total elbow arthroplasty (TEA) is one of the treatment options for these fractures. While elbow motion is largely regained by TEA, comminuted condyle fragments are often ignored. Although numerous approaches for repair of condylar fragments around TEA are described, any universal fixation strategy for these fractures has not been established. This report describes, for the first time, application of an ultra-high molecular weight polyethylene (UHMWPE) tape for the treatment of distal humerus fracture in 2 patients with rheumatic elbow arthropathy. The post-operative clinical courses were good. Radiographs showed bony union of the condylar fragments without loosening in two cases. Because of its flat configuration, softness, and flexibility, UHMWPE tape is a promising material for stabilizing fracture of the distal humerus associated with TEA.

Manufacturing of Ultra-high Molecular Weight Polyethylene Fiber Reinforced Tape and the Loss of Strength

Due to the low density and excellent mechanical proper-ties,high performance fiber reinforced materials have aconsiderable application in the area of high technologyand dally usage.In this paper,the Ultra-high Molecu-lar Weight Polyethylene(UHMWPE)fiber reinforcedPE tape prepared with the method of powder impregnat-ion was studied.The effect of impregnate length and thetensile force of the yarn on the fiber content as well as on the strength and modulus of the tape were discussed.Calculation shows that the strength and the modulus ofthe ULMWPE fiber can keep about 85％ after it undergothe process.

PREPARATION AND CHARACTERIZATION OF ULTRA-HIGH MOLECULAR WEIGHT POLY(ETHYLENE TEREPHTHALATE)(PET)FIBER

This paper reports the spinning and drawing behavior of Ultra-high Molecular Weight polyethylene Terephthalate) (UHMW-PET) fibers. The as-spun fibers were produced by dry-jet wet spinning of a 15%-17% solution in 50:50(v:v) trifluroroacetic acid and dichloromethane. Both molecular weight and polymer solution concentration have marked effect on the drawability of the as-spun-fibers. The maximum extension drawing ratio (EDRmax) of as-spun fiber increases with increasing molecular weight, whereas optimal concentration to achieve the EDRmax of as-spun fibers decreases with increasing molecular weight. Drawing speed and temperature during the first step have remarkable effect on the drawability of these fiber during the second step. Relatively lower drawing temperature and drawing speed (19 ℃ , 60 mm/min) during the first drawing step was beneficial to mechanical properties of ultimate fibers. At the range of 210 ℃ to 230 ℃, the draw ratio (DR) during the second step increases with increasing temperature.

Influence of Molecular Weight of Ultra-high Molecular Weight Polyacrylonitrile on Its Rheological Behavior in Dimethylsulfoxide

Ultra-high molecular weight polyacrylonitrile (UHMW PAN ) was prepared by aqueous suspension polymerization, and the effect of molecular weight on its rheological behaviors in dimethylsulfoxide (DMSO) and the spinning stability were investigated. It shows that,compared with common polyacrylonitrile (C-PAN),UHMW- PAN/DMS0 solution has smaller non- Newtonian index, larger structural viscosity index, much longer maximum relaxation time, and no first- Newtonian region appears in the flow curves under the same experimental conditions. The explanations for these phenomena are given in the view of chain- entanglements. The optimal technology of preparing UHMW-PAN fibers and hollow fiber membranes could be obtained based on the theological study.

超高分子质量PVC树脂合成及性能研究

介绍了超高分子质量PVC树脂的合成工艺。以合成的平均聚合度为5000的超高分子质量PVC树脂为研究对象,对其常规质量性能、粒度、颗粒形貌、加工性能等进行表征和分析研究。结果表明:超高分子质量PVC树脂具有较好的孔隙结构和塑化性能,具有较好的柔韧性、耐磨性等力学性能,适用于弹性体制品生产。

NBR/PVC共混胶动态力学及温敏特性研究

研究了中高丙烯腈含量的NBR与低聚合度PVC的加工工艺及动态力学等性能,并利用带温调控装置和万能拉力机测定了NBR/PVC在不同温度(-10~50℃)条件下的应力应变曲线并与NBR、IIR进行对比。结果表明,NBR/PVC共混胶的模量及力学性能具有较强的温度敏感性,在温度10~20℃区间内,NBR/PVC共混胶逐渐从玻璃态向高弹态转移,外力作用下形变量迅速增加,表现为弹性模量、拉伸强度、断裂伸长率的急剧变化。这一结果与DMA测试的玻璃化转变温度结果相吻合。

Structural, Pasting, and Thermal Properties of Ultra-high Pressure-treated Lotus Seed Starch

Lotus seed starch （15%, w/w） was subjected to ultra-high pressure （UHP） at 500 MPa for 10～60 min. The effects of UHP on the structural, pasting, and thermal properties of starch were investigated using solid-state 13C CP/MAS NMR, differential scanning calorimetry （DSC）, HPSEC-MALLS-RI, and a rapid visco analyzer. The 13C CP/MAS NMR results revealed a reduction in the relative crystallinity and peak intensity of the crystalline state with increasing the UHP time. The molecular weight of native starch was 1.433 × 107 Da, which was higher than that of the UHP-treated starch. Viscograms of UHP-treated starch revealed an increase in paste viscosity, peak time, and pasting temperature and a reduction in breakdown and setback viscosity compared to the native starch. Furthermore, the DSC results showed a reduction in gelatinization temperature and gelatinization enthalpy with increasing the UHP time.

Investigation of the Low Molecular Weight Thiol Composition in a Metastatic Prostate Cancer Cell Line (LNCaP) by LC-UV-MS and NMR after Labelling with the Ellman Reagent

The low molecular weight thiols present in the deproteinized extract of a prostate cancer cell line (LNCaP-FGC) were analysed after derivatization with the Ellman reagent (ESSE). The mixed disulphides formed (RSSE) were fractionated, characterized and quantified by liquid chromatography on a C-18 column using UV detection. This revealed the presence, in femtomoles per cell, of glutathione (8.30 ± 0.73), cysteine (2.71 ± 0.04) and cysteinylglycine (0.83 ± 0.10), accounting for the bulk of the thiol present. Further analysis of the cell extracts using a novel and sensitive mass spectrometry technique allowed the detection of low level of an additional derivative which was identified as cysteinylglycerate using NMRspectroscopy.

硅酮粉改性超高分子量聚乙烯及其熔体纺丝加工性能

针对超高分子量聚乙烯(PE-UHMW)熔体加工性能差的问题,应用硅酮粉,采用熔融共混方法对PE-UHMW进行改性,以提高其熔体加工时的流动性。通过扫描电子显微镜与能量色散谱(EDS)表征了硅酮粉在PE-UHMW中的分布,并采用熔体速率测试、旋转流变测试,分析了硅酮粉含量对PE-UHMW熔体流动速率与流变性能的影响。对改性后的PE-UHMW采用熔体纺丝法制备了PE-UHMW单丝,并进行了拉伸强度测试。实验结果表明,随着硅酮粉的增加,其分散性逐渐变差,PE-UHMW熔体流动速率随硅酮粉含量先增加后降低,当硅酮粉质量分数达到4%,其熔体流动速率最高,复数黏度与储能模量最低,5%质量分数的硅酮粉在PE-UHMW基体中团聚较明显,改性后的PE-UHMW熔体流动性降低。熔体纺丝实验结果表明改性后的PE-UHMW可以通过普通单螺杆挤出机熔融挤出初生丝,经超倍热拉伸可以制备高强度单丝。当拉伸倍率为36时,质量分数3%的硅酮粉改性PE-UHMW单丝拉伸强度最高,可达1565MPa。因此综合考虑加工性能与单丝强度,采用质量分数3%的硅酮粉改性PE-UHMW较合适。

我国超高分子量聚乙烯纤维的发展现状与建议

超高分子量聚乙烯纤维因优异性能在航空航天、军事防护、海洋工程及纺织等领域具有广泛的应用前景,是世界各国竞相发展的战略性新材料。本文梳理了我国超高分子量聚乙烯纤维发展历程,总结了当前产业发展现状,分析了存在的问题,并对未来发展提出建议。

初生态低缠结超高分子量聚乙烯催化剂研究进展

超高分子量聚乙烯(UHMWPE)具有高耐磨性、高强度和刚度、轻质、耐腐蚀、低摩擦系数、生物相容性等特点,作为一种优异的工程塑料广泛应用于高端新材料等各领域,而调控高分子链的缠结程度对于更好地应用UHMWPE至关重要。从均相催化和非均相催化两方面综述了制备初生态低缠结UHMWPE的催化剂技术的研究进展,其中,单中心催化体系和修饰型Ziegler-Natta催化剂在制备初生态低缠结UHMWPE的工业应用中前景广阔。

软质UHMWPVC／LMWPVC共混体系的力学性能和流变性能研究

采用增塑ＵＨＭＷＰＶＣ与ＬＭＷＰＶＣ共混的新方法，在ＵＨＭＷＰＶＣ树脂力学性能下降较少的前提下，大大改善其加工流动性能．同时，在ＵＨＭＷＰＶＣ中加入ＬＭＷＰＶＣ，又可减少增塑剂用量，降低制品成本．系统地研究了ＬＭＷＰＶＣ及增塑剂用量对ＵＨＭＷＰＶＣ／ＬＭＷＰＶＣ共混体系力学性能的影响规律，研究了剪切速率、温度、ＬＭＷＰＶＣ及增塑剂用量对体系流变性能的影响规律．发现了不少新现象，得出的一些结论具有一定理论和实用价值．

双等离子体改性超高分子量聚乙烯复合材料的弹道响应

为揭示双等离子体改性对超高分子量聚乙烯(UHMWPE)复合材料冲击性能的影响,采用真空辅助树脂灌注成型技术(VARI)制成UHMWPE复合材料,借助原子力显微镜等手段对改性前后的纤维表面进行观测,探究复合材料在低速及高速冲击时的抗冲击性能以及防弹机制。低速冲击载荷作为响应值构筑响应曲面模型,高速摄影机捕捉子弹侵彻改性前后复合材料的过程,分析板材的吸能情况并对侵彻后的试样进行表面观测。结果表明:未改性板材通过各层振荡式波动以形成严重分层来耗散能量;改性后的材料能有效地包覆住子弹,背弹面表层纤维呈现原纤化,断口处出现树脂大量富集,阻抗作用增强,吸能值较未改性材料提高45.59%。

活性炭/超高分子量聚乙烯耐热性研究

为了提高超高分子量聚乙烯(UHMWPE)的耐热性,采用超级电容活性炭(微米级)对UHMWPE进行填充改性,制备活性炭/UHMWPE复合材料。通过热重(TG/DTG)测试和维卡软化点温度测试分析了复合体系的热性能;同时研究了活性炭含量对UHMWPE的电学性能、冲击性能、表面及摩擦系数的影响。结果表明:活性炭填充可使UHMWPE材料失重5%时的分解温度提高17.44℃,维卡软化点提高了约18℃;且活性炭对UHMWPE复合体系的抗静电性、冲击性能、表面均有比较明显的改善。

飞行保护头盔用复合材料结构吸收碰撞能量性能研究

针对碳纤维头盔和超高分子量聚乙烯(PE)头盔,采用坠落式冲击试验台和基于冲击加速度及头部损伤指数(HIC)评价方法,系统研究了材料种类、缓冲垫密度和服役环境温度对头盔吸收碰撞能量的影响。结果表明:随着缓冲垫密度的增加,两种头盔在低温(-20℃)条件下的冲击加速度幅值均表现出增加趋势,在常温(20℃)及高温(50℃)下,碳纤维和PE头盔壳体的冲击加速度幅值均表现出明显的降低趋势。升高温度有利于降低头盔的加速度幅值,对于80g/L和90g/L的缓冲垫,两种头盔的冲击加速度幅值随温度升高都表现出降低趋势。缓冲垫密度和温度显著影响头部损伤指数,随着温度从-20℃升高至50℃,PE头盔的头部损伤指数均表现出增加趋势,然而,碳纤维头盔在50℃表现出与常温和低温相反的趋势,即随着缓冲垫密度增加,其头部损伤指数逐渐降低,但PE头盔的头部损伤指数数值低于碳纤维头盔。两种材料在冲击载荷下的损伤形貌不同:PE头盔有明显的基体凹陷形变特征但均无裂纹形成,而碳纤维头盔均表现出明显的基体开裂及纤维断裂。碳纤维由于其高刚度,在冲击力大于破坏强度后容易产生裂纹,无法通过结构系统塑性形变吸收冲击能量,是导致其在不同缓冲垫密度和不同温度条件下,头部损伤指数以及加速度幅值均高于PE的主要原因。PE具有较高的缓冲作用和吸收冲击能量能力,因此,虽然均表现出较大基体凹陷,但均无裂纹形成,采用PE头盔,头部损伤指数和加速度幅值都低于同等条件下的碳纤维头盔。

AMPS单体和缔合单体的引入对聚合物流变性及驱油性能影响研究

研究了引入AMPS单体形成的超高分多元共聚物(HMWP)和引入缔合单体形成的超高分缔合聚合物(AP-P5)的流变性能与驱油性能。室内实验表明,引入AMPS单体和缔合单体均可以显著提高聚合物的增黏性能与黏弹性能。浓度为2000 mg/L时,相对于常规聚合物,AP-P5与HMWP黏度分别提高250.0%和85.1%,黏弹复合模量分别提高36.7%和34.3%,60 d黏度保留率分别为60.9%和82.6%;静态吸附实验发现,HMWP浓度超过200 mg/L,吸附量趋于平衡,而AP-P5随着浓度的增加吸附量逐渐增加;驱油实验结果表明,AP-P5与HMWP的提高采收率幅度分别为11.0%和15.7%,因此,引入AMPS单体更有利于高温高盐油藏聚合物驱油效果提升。现场实验表明,HMWP降水增油效果显著,可以为胜利油田高温高盐油藏大幅度提高采收率提供技术支持。

电子束辐照超高分子量聚乙烯在加速老化过程中的自由基演变

经过辐照处理的医用超高分子量聚乙烯(UHMWPE)必须通过加速老化试验的验证才能达到植入人体使用的要求,但在加速老化过程中,UHMWPE材料的自由基演化机制尚不明确。本研究从自由基角度出发,对现有加速老化方法的效果进行了系统分析。利用电子顺磁共振波谱研究了电子束辐照交联UHMWPE在加速老化过程中的自由基浓度和组成的变化,分析了自由基在该过程中的演变机理,对比分析了自由基在室温空气和70℃氮气中的演变机理。结果表明:加速老化评估方法有很大的局限性,辐照交联UHMWPE表层和内部的自由基在室温空气环境中的演变与在加速老化环境中的演变有显著区别,氧诱导自由基(OIR)的生成率在室温空气环境中约为2%,在加速老化环境中约为0.3%。OIR自由基在室温空气中会稳定存在,而在加速老化环境中会被快速氧化。