辐照交联超高分子量聚乙烯的生物摩擦学性能研究

采用γ-射线对医用超高分子量聚乙烯(UHMWPE)进行辐照交联处理,研究了辐照交联对医用UHMWPE力学性能和生物摩擦学性能的影响。结果表明:辐照交联使UHMWPE的结晶度、硬度、弹性性能、抗划痕能力和摩擦磨损性能提高,但降低了UHMWPE的塑性性能。     

过氧化物交联UHMWPE的动力学与结晶行为的研究

采用过氧化二异丙苯(DCP)交联改性超高相对分子质量聚乙烯(UHMWPE),通过差示扫描量热和广角X射线衍射测试,研究了DCP交联UHMWPE的反应动力学以及DCP含量对交联UHMWPE片材的热性能、结晶性能和晶粒尺寸的影响。结果表明:DCP与UHMWPE交联反应为放热反应,其非等温交联反应符合一级反应,反应活化能随着DCP含量的增加而降低;随着DCP含量的增加,交联UHMWPE片材的结晶度、重结晶度、熔点和结晶温度均降低,结晶峰强度和晶粒尺寸减小,当DCP质量分数为2. 5%时,交联UHMWPE片材(110)晶面和(200)晶面所对应的晶粒尺寸分别降低至18. 6 nm和12. 1 nm。     

超高分子量聚乙烯及其交联材料的消声机理研究

采用热压法制备了纯超高分子量聚乙烯(UHMWPE)板以及交联UHMWPE板,研究了二者在0～4 000 Hz内的消声性能,提出了纯UHMWPE和交联UHMWPE的分子链缠结模型,并利用该模型探讨了二者在0～4 000Hz内的消声机理。结果表明:纯UHMWPE与交联UHMWPE在40～1 250 Hz频段内耗掉的能量最多,在3 150～3 800 Hz频段内消耗的能量适中,在1 250～3 150 Hz频段内消耗掉的能量最少;对比纯UHMWPE板,交联UHMWPE板在40～940 Hz、1 080～1 550 Hz以及2 240～3 800 Hz频段内的耗能增加,消声性能更好;在940～1 080 Hz、1 550～2 240 Hz频段耗能降低,消声性能下降。     

硅烷交联UHMWPE非等温结晶动力学

利用差示扫描量热分析(DSC)方法研究了超高分子量聚乙烯(UHMWPE),硅烷交联UHMWPE的非等温结晶动力学。通过Jeziorny法和Mo法分别对非等温结晶过程进行处理,结果表明:硅烷交联UHMWPE分子链之间形成的三维网状结构抑制了分子链及链段之间的相对运动,阻碍了分子链的规则排列,影响了链段在晶区扩散迁移规整排列的速度,使结晶速率变慢,对晶体生长产生抑制作用。但在所有的结晶速率下,试样的Avrami指数n的值均在1.6～2.0之间,说明交联对UHMWPE的结晶成核机理和生长方式没有改变。     

超高摩尔质量聚乙烯氧化行为对生物摩擦学性能的影响

采用热压成型工艺制备了超高摩尔质量聚乙烯(UHMWPE),测试了加速老化前后辐照交联UHMWPE的力学和生物摩擦学性能的变化.DSC测试结果显示,加速老化后辐照交联UHMWPE的结晶度有所提高;红外光谱分析表明,加速老化后辐照交联UHMWPE的氧化指数大幅度提高;冲压剪切强度测试结果显示,加速老化导致辐照交联UHMWPE的弹性和塑性性能显著降低;摩擦磨损测试结果表明,加速老化后辐照交联UHMWPE的耐磨性能显著降低,并出现大量的压片状破裂.     

辐照交联GO/UHMWPE复合材料在人工海水润滑介质下的摩擦学性能研究

为改善超高分子量聚乙烯(UHMWPE)在海水润滑介质下的耐磨损性能,采用氧化石墨烯(GO)填充与辐照交联对UHMWPE进行改性处理。利用摩擦磨损试验机研究了辐照前后UHMWPE与GO/UHMWPE复合材料在人工海水润滑介质下的摩擦学性能,利用扫描电子显微镜(SEM)与三维表面轮廓仪扫描试样磨痕表面形貌,计算其磨损率,并分析了其摩擦磨损机理。结果表明,在人工海水润滑介质下,GO填充与辐照交联改性处理均略微增加了UHMWPE的摩擦因数,降低了磨损率;二者共同使用可以协同增强UHMWPE的耐磨性能,降低复合材料的摩擦因数与磨损率; GO填充显著提高了UHMWPE的抗磨粒磨损与抗疲劳磨损性能;辐照交联改性处理进一步提高了GO/UHMWPE复合材料的抗磨粒磨损性能。     

不同成型方式下UHMWPE耐热改性进展

介绍了近年来超高分子量聚乙烯(UHMWPE)在模压成型、挤出成型、注塑成型方面的耐热改性研究进展,分析了采用不同成型方法对UHMWPE耐热改性的方法及改性效果。关于UHMWPE模压与挤出成型的耐热改性方法主要包括物理改性(填充改性、共混改性、共混填充改性)、化学改性(过氧化物交联、偶联剂交联、辐射交联)、聚合填充复合改性,而UHMWPE的注塑成型耐热改性研究较少。对UHMWPE进行耐热改性,加入的改性材料后,能显著提高复合材料耐热性,但是,部分材料的加入却降低了UHMWPE耐磨性、抗冲击性等性能,需要对UHMWPE注塑成型的耐热改性及改性材料的选用进一步研究。最后,对UHMWPE的耐热改性的发展趋势进行了展望。     

交联体系对超高摩尔质量聚乙烯性能的影响

采用两种适用于不同温度的交联体系对超高摩尔质量聚乙烯(UHMWPE)材料进行改性,并对其性能进行研究。结果表明,交联体系的引入可在基体材料中形成交联网络,从而显著提高UHMWPE的承载能力、抗蠕变性及耐热性,同时保持良好的结晶性、韧性和热稳定性;交联温度接近成型温度的交联体系B改性UHMWPE材料的综合性能较优,尤其是机械性能;交联体系引发剂最佳用量均为0.2~0.3份,而后力学性能急剧下降,与引发剂的适用温度无关。     

DTBP交联UHMWPE磨粒磨损性能研究

本文采用二叔丁基过氧化物(DTBP)作为交联剂,对UHMWPE进行化学改性,通过改变DTBP的含量、交联反应时间、交联反应温度来制备试样,并通过性能测试、分析获得最佳的成型工艺条件。实验结果表明:在DTBP交联改性成型工艺中,DTBP与UHMWPE质量比为0.4%、交联反应时间为10分钟、交联反应温度为150℃时,制品的磨粒磨损率最低,磨粒磨损性能最好。与未交联试样相比,磨粒磨损性能提高了2.86倍,并且硬度、拉伸性能有小幅度上升。     

以DCP和DTBP引发制备交联UHMWPE

分别以DcP和DTBP对UHMWPE进行交联改性,通过改变DcP或DTBP的用量、交联温度、交联时间等成型条件制备了模压烧结试样。结果表明：在DcP交联工艺中,DcP与U删1vPE质量比为0．15％、交联温度为155℃、时间为30min时,制品耐磨粒磨损性能最好;在DTBP交联工艺中,DTBP与UHMWPE质量比为O．50％、交联温度为140℃、时间为20min时,制品耐磨粒磨损性能最好。从改进耐磨粒磨损性能角度来说,采用DTBP交联工艺更好。     

UHMWPE摩擦磨损性能及其机理的研究进展

介绍了超高相对分子质量聚乙烯(UHMWPE)的摩擦磨损特性及其机理的研究进展，重点介绍了改进摩擦磨损性能方法的研究进展，包括交联改性、填料填充改性、增强改性、共混和加工方法的研究等，并针对这些方法的不足之处和可能的新方法提出了今后的研究方向。     

A crosslinking method of UHMWPE irradiated by electron beam using TMPTMA as radiosensitizer

Trimethylolpropane trimethylacrylate/Ultra high molecular weight polyethylene (TMPTMA/UHMWPE) composite and pure UHMWPE plates were made by compression molding and electron beam (EB) irradiation crosslinking methods. Fourier transform infrared spectroscopy (FTIR), Soxhlet extractor, electromechanical tester, and wear tester were used for the characterization of the structure, mechanical properties, and tribological performance of the crosslinked UHMWPE. FTIR analyses show that trans‐vinylene (965 cm^?1) absorption increases with the increasing dose and the trans‐vinylene intensity of TMPTMA/UHMWPE is higher than that of UHMWPE at the same dose, and Soxhlet experiments reveal that gel fraction increases with the increasing dose, both proving that crosslinking took place in all the irradiated samples. The results of the tensile tests indicate a significant decrease in elongation at break, but the stress of UHMWPE increases to 47 MPa at 10 kGy and then decreases with the increasing dose. The stress of TMPTMA/UHMWPE composites keeps at about 39 MPa before 50 kGy and then decreases with the increasing dose because of plasticization effect. The stress changes indicate that crosslinking and degradation occurred at the same time. Wear rate of 100 kGy 1% TMPTMA/UHMWPE is 1.76 × 10^?7mg/Nm, only 23.5% of wear rate of 0 kGy UHMWPE and 44.2% of wear rate of 100 kGy UHMWPE. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

UHMWPE在人工髋关节中的磨损机制及改性研究

分析了超高分子量聚乙烯(UHMWPE)基人工髋关节假体松动失效的主要因素。介绍了UHMWPE在人工关节中的磨损机制,以及降低UHMWPE磨损最常用的方法,包括辐射交联改性、α-维E抗氧化法、复合增强以及人工关节润滑等。     

Oxidation resistance and abrasive wear resistance of vitamin E stabilized radiation crosslinked ultra‐high molecular weight polyethylene

The effect of gamma radiation on the oxidation and wear resistance of ultra‐high molecular weight polyethylene (UHMWPE) has been extensively studied since these properties are critical for the longevity of UHMWPE components of total joint replacement prostheses. While gamma radiation increases wear resistance of UHMWPE, the free radical generated in the lamellar regions by radiation must be stabilized before oxidative degradation occurs as the polymer ages. Initially, post‐radiation melting conducted to quench free radicals but this treatment also decreases its mechanical properties. Recently, it has been replaced by incorporation of Vitamin E into UHMWPE to combat oxidative degradation. In this study, we assessed wear resistance of Vitamin E stabilized UHMWPE under abrasive wear conditions and oxidation resistance by shelf‐aging irradiated components for 2 years. Equilibrium swelling experiments showed that Vitamin E decreased crosslink density, which affected wear resistance, but oxidation resistance was better preserved with increasing concentration of Vitamin E. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44125.     

More wear‐resistant and ductile UHMWPE composite prepared by the addition of radiation crosslinked UHMWPE powder

Radiation crosslinked ultrahigh molecular weight polyethylene (X‐UHMWPE) powder was prepared by γ‐ray irradiation under nitrogen atmosphere with a dose of 50–200 kGy at a dose rate of 7 kGy/h and further annealing in vacuum at 120 °C for 4 h. The crosslinked powder was characterized by FT‐IR spectroscopy, gel content, and hot‐press molding. Then, X‐UHMWPE was added to pristine UHMWPE to prepare a composite with 0–25 wt % filler. The morphology, wear resistance, and tensile property of the composite were investigated. Using X‐UHMWPE as a filler could sufficiently improve the wear resistance of the composite. Adding 25 wt % X‐UHMWPE (dose: 150 kGy) improved wear resistance by 130% and retained approximately 90% tensile strength and 70% ductility. Wear‐resistant and ductile UHMWPE composite may be potentially used for artificial joint replacement and engineering devices. The proposed route is useful in fabricating UHMWPE material with excellent comprehensive performance or functional polymer composite. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44643.     

Ultrahigh molecular weight polyethylene with improved crosslink density,oxidation stability,and microbial inhibition by chemical crosslinking and tea polyphenols for total joint replacements

Highly crosslinked ultrahigh molecular weight polyethylene (UHMWPE) stabilized by vitamin E (VE) is widely applied in artificial joints as the bearings. Despite the approval, there is a discord that VE lowers the crosslinking efficiency, limiting its use at high concentration. In this work, we aim to obtain highly crosslinked and oxidation resistant UHMWPE through the conjunction of tea polyphenol and chemical crosslinking. We hypothesized that highly incorporated tea polyphenol with multiple reactive sites can ameliorate crosslinking efficiency of chemical crosslinked UHMWPE in comparison to VE. Epigallocatechin gallate (EGCG) as representative tea polyphenol was incorporated into UHMWPE at high concentration (2–8 wt%), followed by chemical crosslinking with 2 wt% organic peroxide. Unlike VE/UHMWPE blends as the control, chemical crosslinking achieved an increasing trend in crosslink density of EGCG/UHMWPE blends with increasing antioxidant concentration. High concentration of EGCG also enhanced the oxidation stability of UHMWPE. Intriguingly, EGCG endowed UHMWPE with an excellent antimicrobial property, which was inefficient in VE/UHMWPE. Cell viability was hardly affected by the high loaded antioxidant and peroxide. The chemically crosslinked UHMWPE blended with EGCG is proved to be a reasonable, cost effective and realistic alternative for use in artificial joints.     

Dielectric behavior induced by vitamin E and electron beam irradiation in ultra high molecular weight polyethylene

Radiation cross‐linked ultra high molecular weight polyethylenes (UHMWPEs) have been successfully used as wear resistant bearing surfaces in total joint arthroplasty. A recent development in this field is the incorporation of the antioxidant vitamin E into radiation cross‐linked UHMWPE. This study investigates the effects of radiation cross‐linking and vitamin E incorporation on the dielectric behavior of UHMWPE. The dielectric relaxations of virgin and 0.1 wt % vitamin E‐blended UHMWPE and their irradiated counterparts (up to 300 kGy dose) were investigated. To determine the effect of vitamin E content alone, vitamin E‐loaded UHMWPEs were used. The results showed that radiation cross‐linking and vitamin E content both increased dielectric polarization in UHMWPE and under some conditions induced electrical conductivity. This result is significant because it shows that the conductive response of UHMWPE‐bearing surfaces may depend on manufacturing processes and additives. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40844.     

Preparation and characterization of ultrahigh molecular weight polyethylene and polyisoprene solvent-cast blend films

This study covers the preparation of noncrosslinked and crosslinked solvent-cast blend films of ultrahigh molecular weight polyethylene (UHMWPE) and polyisoprene rubber (PIR) and their mechanical, thermal, IR spectroscopic, and morphological characterizations. Solvent-cast films of polymer blends with 0, 10, 20, 35, 50, and 65% PIR composition were prepared by vigorous stirring from a hot decalin solution. The films were crosslinked chemically by using acetophenone as a crosslinking agent under UV radiation. The mechanical properties, measured as ultimate properties and tensile modulus, were found to decrease with PIR content but crosslinking was found to enhance the ultimate strength and tensile modulus. DSC results revealed that melting point of UHMWPE remains almost constant in blends. However, upon crosslinking, the melting point of UHMWPE is depressed almost 5°C. We observed a similar trend in the enthalpy change of the melting of UHMWPE and the variation of percent crystallinity in UHMWPE. Scanning electron microscopy (SEM) studies on the fractured surfaces of the blends showed that the fibrillar texture is present in both crosslinked and noncrosslinked blends. The crosslinking appeared to be through oxygen linkages, which are preferentially conjugated to double bonds, in addition to the possible carbon–carbon crosslinks. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1619–1630, 1998     

Synthesis and characterization of CNTs/POM nanocomposite acetabular hip cup

Polyoxymethylene (POM) considered as the most appropriate alternative for ultra-high molecular weight polyethylene (UHMWPE) in the hip joint replacement application due to their biocompatibility, high mechanical properties, and cheapness. The wear is the main cause of the failure in the hip joint and the wear resistance of UHMWPE is still better than the wear resistance of POM. This research aims to improve the wear behavior of POM by blending it with 0.02?wt% of functionalized carbon nanotubes (CNTs) and using paraffin oil dispersion technique to obtain a uniform dispersion. The injection molding and machining process were used to produce the new (CNTs/POM) nanocomposite acetabular hip cup which has a high wear performance. The wear rate of the CNTs/POM cups was evaluated using a total leg joint’s simulator at 1,000?N for 3 million cycles under serum-based lubricated conditions. Moreover, the wear mechanism of cups was examined by scanning electron microscopy as well as the dispersion of CNTs inside the cup matrix. The results show that the wear resistance of POM cup has been improved by adding functionalized CNTs ～402% and ～221%, when compared with a virgin POM and UHMWPE, respectively, because of increasing the melting temperature and crystallinity degree.