Surface modification of ultra-high molecular weight polyethylene (UHMWPE) by argon plasma

In this work, argon (Ar) plasma generated by microwave electron cyclotron resonance (MWECR) has been used to modify the UHMWPE in order to increase the wear resistance. The results showed that the wettability, anti-scratch and wear resistance of UHMWPE treated by the Ar plasma had been improved, comparing with native UHMWPE. The FTIR and XPS spectra indicated the improvement of wettability should come from the oxygen based functional groups generated on the surface of UHMWPE. The improvement of anti-scratch and wear resistance may come from the enhancement of crosslinking of UHMWPE by Ar plasma treatment.     

Tribological characterisation of Zr-based bulk metallic glass in simulated physiological media

Due to their excellent wear resistant properties and high strength, as well as a low Young's modulus, Zr-based bulk metallic glasses (BMGs) are potentially suitable biomaterials for low-friction arthroplasty. The wear characteristics of the Zr_60.14Cu_22.31Fe_4.85Al_9.7Ag₃ bulk amorphous alloy against ultra-high-molecular-weight polyethylene (UHMWPE) compared to a CoCrMo/UHMWPE combination were investigated in two different wear screening test devices, reciprocating and unidirectional. Hank's solution and sterile calf bovine serum were selected as the lubricant fluid media. It was found that different fluid media had insignificant effect on polyethylene wear against BMG counterfaces. The wear behaviour obtained on both test devices demonstrated that Zr-based BMG achieved UHMWPE counterface wear rates superior to conventional cast CoCrMo alloy, where the wear rate of UHMWPE is decreased by over 20 times. The tribological performance of these joints is superior to that of conventional metal-on-polymer designs. Contact angle measurements suggested that the advantage of BMG over a CoCrMo alloy counterface is attributed to its highly hydrophilic surfaces.     

The friction and wear properties of divinylbenzene-grafted UHMWPE fiber-filled serpentine/PTFE composite

Divinylbenzene-grafted Ultra-high-molecular-weight polyethylene (UHMWPE) fibers were used to reinforce the Polytetrafluoroethylene (PTFE) composite and the friction and wear behaviors of UHMWPE/PTFE composite were studied on the ring-block machine under vacuum condition. The worn surfaces of specimens were investigated using scanning electron microscopy and energy dispersive spectroscopy (EDS). The results showed that the friction coefficient and temperature of UHMWPE/PTFE composites with surface-treated UHMWPE fiber were apparently lower than that with untreated one. In conclusion, the surface treatment favored the improvement of the higher interface strength and so had good effect on improving the tribological properties of the composites. The dominant wear mechanisms were adhesion wear, plastic deformation, brittle facture, and spalling. The EDS analysis of the worn surface indicated the trend of the tribochemical reaction of the Fe related to the transfer of the PTFE.     

Ion Implantation on Ultra High Molecular Weight Polyethylene (Uhmwpe) for Medical Prosthesis

In order to improve the wear resistance of ultra high molecular weight polyethylene (UHMWPE), a surface modification is induced by ion implantation of different ions at 300 keV energy with doses ranging between 10¹⁴ -10¹⁷ ions/cm². Wear measurements, in terms of weight loss, are performed with a “pin on disc” friction machine; these tests measure the wear properly of the UHMWPE against a metallic probe before and after the ion implantation treatment. Results demonstrate that in the implanted samples the wear resistance increases by about 76% with respect to the non-irradiated samples. The irradiated polymeric layer was characterized with the mass quadrupole spectrometry, Raman spectroscopy, infrared absorption analysis, scanning electron microscopy, atomic force microscopy and calorimetric analysis. The results suggest that wear decrease effect can be attributed to the ion bombardment inducing a high carbon surface concentration and cross-linking effects in the irradiated polymeric layer. The irradiated UHMWPE surfaces find special applications in the field of the mobile prosthesis such as hip joints.     

Deposition of a-C:H films on UHMWPE substrate and its wear-resistance

In prosthetic hip replacements, ultrahigh molecular weight polyethylene (UHMWPE) wear debris is identified as the main factor limiting the lifetime of the artificial joints. Especially UHMWPE debris from the joint can induce tissue reactions and bone resorption that may lead to the joint loosening. The diamond like carbon (DLC) film has attracted a great deal of interest in recent years mainly because of its excellent tribological property, biocompatibility and chemically inert property. In order to improve the wear-resistance of UHMWPE, a-C:H films were deposited on UHMWPE substrate by electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-PECVD) technology. During deposition, the working gases were argon and acetylene, the microwave power was set to 800 W, the biased pulsed voltage was set to −200 V (frequency 15 kHz, duty ratio 20%), the pressure in vacuum chamber was set to 0.5 Pa, and the process time was 60 min. The films were analysed by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, nano-indentation, anti-scratch and wear test. The results showed that a typical amorphous hydrogenated carbon (a-C:H) film was successfully deposited on UHMWPE with thickness up to 2 μm. The nano-hardness of the UHMWPE coated with a-C:H films, measured at an applied load of 200 μN, was increased from 10 MPa (untreated UHMWPE) to 139 MPa. The wear test was carried out using a ball (Ø 6 mm, SiC) on disk tribometer with an applied load of 1 N for 10000 cycles, and the results showed a reduction of worn cross-sectional area from 193 μm² of untreated UHMWPE to 26 μm² of DLC coated sample. In addition the influence of argon/acetylene gas flow ratio on the growth of a-C:H films was studied.     

Tribological characteristics of UHMWPE composite and relationship with its compressive behavior

The triboogical characteristics and the mechanics compress behaviors of pure and composite ultra high molecular weight polyethylene (UHMWPE) were investigated using tribological apparatus and universal materials testing apparatus respectively.Results show that there are direct relationships between the sliding friction, wear characteristics, and compression behaviors of UHMWPE composite. The composite of UHMWPE with added copper particles had great improvement in tribological characteristics and mechanics behaviors. Based on the experimental results, a microstructure model of UHMWPE-copper composite is preliminarily proposed.     

Tribological characteristics of UHMWPE composite and relationship with its compressive behavior

The triboogical characteristics and the mechanics compress behaviors of pure and composite ultra high molecular weight polyethylene (UHMWPE) were investigated using tribological apparatus and universal materials testing apparatus respectively. Results show that there are direct relationships between the sliding friction, wear characteristics, and compression behaviors of UHMWPE composite. The composite of UHMWPE with added copper particles had great improvement in tribological characteristics and mechanics behaviors. Based on the experimental results, a microstructure model of UHMWPE-copper composite is preliminarily proposed.

     

Association of polyethylene friction and thermal unfolding of interfacial albumin molecules

Under the articulation of artificial joints, ultra-high molecular weight polyethylene (UHMWPE) acts as a bearing surface under the lubrication of synovial fluid containing various proteins. Albumin is the most abundant composition and acts as the interfacial molecule in the boundary lubrication regime. The dissipated energy including thermal energy from the tribological process may lead to the conformational change of albumin molecules.In this study, a series of experiments were designed and carried out to investigate the association of thermal unfolding albumin and the frictional characteristics of highly-crosslinked UHMWPE (x-UHMWPE). An accelerated oxidation experiment was used to prepare x-UHMWPE with an oxidized surface. Analysis of the albumin protein by circular dichroism (CD) spectroscopy was performed to detect the conformational changes during a thermal process. In addition, a molecular simulation was performed to understand the structural change of albumin at various temperatures and the exposed hydrophobic contact areas. Linear reciprocating frictional tests were carried out to obtain the start-up friction coefficients. The results indicate that a decrease of α-helix content and an unfolding of the secondary structure of albumin were observed with increasing temperatures which may come from the frictional heat of joint articulation process. The conformational change of albumin differentiates the frictional characteristics for x-UHMWPE with different oxidation levels. A model, describing that the properties of the lubricating molecules and articulating surfaces may affect the adsorption of the boundary lubrication thin film which is critical to the tribological behavior, is proposed.     

Self-Lubricating Ultrahigh Molecular Weight Polyethylene Thin Films with Excellent Wear Resistance at Light Friction Loads on Glass and Silicon

Thin films of ultrahigh molecular weight polyethylene (UHMWPE) were prepared on glass and silicon using a dip-coating technique, followed by removal of the decahydronaphthalene solvent at 140?°C for 20?hours and cooling in the oven in air. The wetting ability of the films was investigated by a contact angle method. The tribological behavior of the films was investigated using a ball-on-disk configuration in reciprocating mode. The reciprocating frequency of 4?Hz and single sliding distance of 5?mm used corresponded to a sliding speed of 40?mm/s. The counterface was a GCr15 steel ball with diameter of 3?mm and the normal frictional loads were 10–300?g. The worn surfaces on the films and wear scars on the steel ball were observed and analyzed by scanning electron microscopy (SEM). It was found that the surface morphologies of the films on glass and silicon were different, which is ascribed to the difference in thermal conductivity of the glass and silicon. Evaporation of the solution caused micro-orifices in the films on glass. The water contacting angle of about 87° on the films on the two substrates was similar to that of bulk UHMWPE. Their friction coefficient of about 0.1–0.2 indicated the films were self-lubricating. The wear life of the films decreased quickly with the increase of friction load. At light friction loads, the films showed excellent wear resistance. Extrusion was believed to be the main wear mechanism of the films.     

Three-dimensional human femoral strain analysis using ESPI

With age, disease or injury the joints in the human body can wear out or bones may even fail catastrophically. In many cases it is possible to replace joints and bones with artificial components (prostheses). However, prosthetic joints can have a very limited life (often less than 10 years) and require replacement or ‘revision’. In order to optimise prosthetic life, it is necessary to improve the design of components and implantation techniques, which is clearly also beneficial to both patients and hospitals.     

Impact of Dose-Rate on Rheology,Structure and Wear of Irradiated UHMWPE

Ultrahigh molecular weight polyethylene (UHMWPE) is used as a bearing material in total joint replacements (TJR). UHMWPE for TJR is usually modified by irradiation and thermal treatment to increase wear resistance. We modified UHMWPE in three ways, differing in radiation dose-rate and/or atmosphere during irradiation. Rheological properties before and after irradiation were determined by means of oscillatory shear measurements. Structural changes were followed by X-ray diffraction, infrared spectroscopy, electron spin resonance, and solubility measurements. Wear resistance of selected samples was obtained by the pin-on-disk method. Rheological properties changed sensitively with modification conditions including radiation dose rate. Moreover, rheological results correlated well with both crosslinking extent and wear resistance. Finally, it was demonstrated that the optimal radiation dose, i.e. the dose leading to maximum crosslinking density and wear resistance, was different for each of the three modification procedures.     

Statistical analysis of the strength of ultra-oriented ultra-high-molecular-weight polyethylene film filaments in the framework of the Weibull model

A statistical analysis of the distribution of the tensile strength σ of ultra-oriented ultra-high-molecular-weight polyethylene (UHMWPE) film filaments has been performed in the framework of the Weibull model using the results obtained from a large number (50) of measurements. The UHMWPE film filaments have been produced by means of high-temperature multistage zone drawing of xerogels prepared from 1.5% UHMWPE solutions in decalin. The Weibull modulus has been determined for this type of materials. It has been shown that, for the ultimate draw ratio λ = 120, the average tensile strength is equal to 4.7 GPa, which is significantly higher than the tensile strength σ = 3.5 GPa for commercial gel-spun UHMWPE fibers manufactured by the DSM Company (The Netherlands) and the Honeywell International Incorporation (United States). It has been demonstrated that, for 20% of the specimens thus prepared, the tensile strength reaches record-high values σ = 5.2–5.9 GPa.     

Raman characterisation of conventional and cross‐linked polyethylene in acetabular cups run on a hip joint simulator

Five sets of differently sterilised conventional ultra‐high molecular weight polyethylene (UHMWPE) and cross‐linked polyethylene (XLPE) acetabular cups were run for 5 million cycles on a hip joint simulator in order to evaluate their wear behaviour in relation to material properties (PE grade, conventional or cross‐linked) and sterilisation method (ethylene oxide (EtO) treatment or γ‐irradiation). Gravimetric measurements revealed that conventional UHMWPE wore significantly more than XLPE. The differences in wear behaviour could be partly related to the orthorhombic contents obtained by Raman spectroscopy in the unworn areas of the cups: XLPE cups showed a significantly higher crystallinity degree than the UHMWPE specimens. Raman analysis showed that wear testing did not significantly modify the orthorhombic content of any of the tested acetabular cups. However, the set of cups that showed the highest weight loss, i.e. γ‐sterilised PE GUR1020, appeared the most homogeneously polished upon wear testing; from a molecular point of view, only this set of cups showed a significant increase of the I₁₁₃₀/I₁₀₆₀ intensity ratio, suggesting the occurrence of chain orientation. On the other hand, XLPE cups, despite the lowest weight loss undergone, showed a decrease in the amorphous content upon wear testing as well as a limited orthorhombic → monoclinic transformation, which did not appear detrimental. Copyright © 2011 John Wiley & Sons, Ltd.     

氧等离子体处理对纳米二氧化硅溶胶涂覆高强、高模聚乙烯纤维拉伸性能的影响

基于艾琳方程,提出用于定量分析纤维表面和纳米涂覆层间的纳米界面结构的理论模型.实验结果表明,纤维高分子链段受力塑性变形时,纳米界面结构内纳米微粒阻碍其形貌变化产生热激活体积,该热激活体积是纳米界面结构性能的重要表征;氧等离子体处理对纳米二氧化硅溶胶涂覆高强、高模聚乙烯纤维有增韧作用.由不同处理样品的扫描电子显微镜图片和傅里叶变换红外光谱曲线对比分析可知,经氧等离子体处理纳米二氧化硅溶胶涂覆高强、高模聚乙烯纤维的纳米涂覆层纳米颗粒分布均匀,纳米颗粒还填补纤维表面微观缺陷,活性官能团被引入到纤维表面. 关键词： 激活体积 氧等离子体 高强、高模聚乙烯纤维 纳米界面结构     

Effects of Addition of Ultra-High Molecular Weight Polyethylene on Tie-Molecule and Crystallization Behavior of Unimodal PE-100 Pipe Materials

With the fast-growing global market demand for high-grade plastic pipe materials, high-density polyethylene (HDPE) products, such as PE-100, are playing a more and more important role. On the other hand, lack of basic understanding about these materials hinders the further development of this field. To investigate the effects of addition of an ultra-high molecular weight polyethylene (UHMWPE) on tie-molecules, crystallization kinetics and long-term properties of a unimodal HDPE pipe material (UMPE-100) made from a Cr-based catalyst, the blends of UMPE-100/UHMWPE were prepared through a twin-screw extruder. The probability of tie-molecules was calculated by a statistical approach, which has been proposed by Huang and Brown (Huang, Y.L.; Brown, N.J. Polym. Sci. B. 1991, 29, 129–137). It showed that as UHMWPE was added, the probability of tie-molecules increased due to increased molecular weight. The crystallization kinetics of the blends was investigated by an isothermal crystallization method using differential scanning calorimetry. Addition of small amount of UHMWPE improved the crystallization rate greatly. The natural draw ratio of blends decreased with improvement of tie-molecule probability and crystallization rate, indicating improvement in long-term properties.     

过渡金属Cu、Cr掺杂TiO2表面氧化性气体NO2光学气敏传感特性

采用密度泛函理论（DFT）体系广义梯度近似（GGA）第一性原理平面波超软赝势方法,分析锐钛矿型TiO₂（101）表面吸附NO₂分子光学气敏传感的微观机理.结果表明：Cu和Cr原子易于掺入TiO₂（101）表面,掺杂表面能稳定地吸附NO₂分子且吸附后光学性质发生显著变化.表面吸附NO₂分子后,Cu掺杂TiO₂（101）表面对分子的吸附能最大,吸附后结构更稳定,分子与表面的距离最短.通过分析差分电荷密度和电荷布居数发现,NO₂分子与基底表面间发生电荷转移,转移电子数目：Cu掺杂表面 > Cr掺杂表面 > 无掺杂表面.对比吸收光谱和反射光谱发现,在Cu掺杂表面吸附分子后,光学性质变化最明显,说明表面与吸附分子间氧化还原能力是决定光学气敏传感性能的核心因素.在过渡金属中,Cu与Cr都有4s价电子结构,其4s电子降低了材料表面氧空位的氧化性,增加了其还原性.对于氧化性气体,可以提升表面与分子的氧化还原作用,而Cu的4s电子更加活泼,从而光学气敏传感特性更加明显.因此,Cu掺杂的TiO₂对氧化性气体是一种较好的光学气敏传感材料.     

A spectroscopic study of the effect of humidity on the atmospheric pressure helium plasma jets

Atmospheric-pressure plasma has a great potential in many applications due to its simplicity rather than low pressure plasmas. In material processing, biomedical applications, and many other applications, the input power, gas flow rate, and the geometry of electrode have been mainly considered and studied as important external parameters of atmospheric-pressure plasma control. Besides, since the atmospheric-pressure plasmas are typically generated in an open air, the relative humidity is difficult to control and can change day by day. Therefore, the relative humidity cannot be ignored for plasmas. Thus, in this work, the atmospheric-pressure plasma jet was characterized by changing relative humidity, and it was found that the increase in electron density and OH radicals are due to Penning ionization between helium metastable and water vapors at higher humidity condition.     

New and Simple Staining Method for Visualizing UHMWPE Lamellar Structure in TEM

Ultra-high-molecular-weight polyethylene (UHMWPE) is used in arthroplasty as a key component of total joint replacements. In order to increase its wear resistance, the polymer is often cross-linked in a two-step procedure comprising irradiation and thermal treatment. Both modification steps impact UHMWPE lamellar structure. In this study we introduce a new staining method that makes it possible to visualize the UHMWPE lamellae by transmission electron microscopy (TEM). The method consists of one-step staining with oleum (H ₂ SO ₄ solution of SO ₃ ) for 4 days and ultramicrotomy; this is significantly simpler than previously described techniques and yields micrographs of the same quality. The lamellar thicknesses from TEM correlated well with those from small- and wide-angle X-ray scattering and differential scanning calorimetry. It has also been demonstrated that the exact values of lamellar thicknesses obtained from TEM micrographs strongly depend on the place selected for image analysis.     

基于PIII技术的高真空洁净环境中润滑问题

针对高洁净的真空环境下终端光学组件内运动机构的润滑问题,采用等离子体浸没离子注入（PIII）技术对复杂形状的零件进行表面改性,通过轴承内外圈表面改性前后的对比实验分析,结果表明,通过对注入元素、剂量和能量的选择,可以大幅度提高材料表面的硬度及耐磨性,并且零件的尺寸精度及表面粗糙度保持性好,充分证明了PIII技术可以在满足颗粒洁净度和有机物洁净度的双重要求条件下,提高运动部件抗摩擦磨损性能,延长微驱动机构的运动精度寿命,是解决终端光学组件中润滑问题的有效途径。     

Fretting Wear Behavior of UHMWPE Under Different Temperature Conditions

The fretting wear behavior of ultra-high molecular weight polyethylene (UHMWPE) against a GCr15 steel ball was investigated using an Optimal SRV-IV oscillating reciprocating friction and wear tester (Optimal Corp., Germany). The influence of temperature, stroke size and frequency was studied in detail under a normal load of 10 N. The results showed that the friction coefficients initially decreased and then increased afterward with the increasing of temperature, having the lowest value at 0°C. The wear loss of UHMWPE at a stroke of 100 µm showed a similar tendency as the friction coefficients, but monotonously increased with increasing of temperature for a stroke of 200 µm. According to an analysis of the worn surface, it was concluded that abrasive wear accompanied with local plastic deformation dominated the wear mechanism in the process of the fretting test at ?30°C. The plastic deformation was slightly less at 0°C than that at ?30°C. With the increasing of temperature, the hardness of UHMWPE decreased significantly, plastic deformation and adhesive wear became more severe. In addition, a lubricating transfer film was formed on the steel ball.