Microscale wear behavior and crosslinking of PEG-like coatings for total hip replacements

The predominant cause of late-state failure of total hip replacements is wear-mediated osteolysis caused by wear particles that originate from the ultrahigh molecular weight polyethylene (UHMWPE) acetabular cup surface. One strategy for reducing wear particle formation from UHMWPE is to modify the surface with a hydrophilic coating to increase lubrication from synovial fluid. This study focuses on the wear behavior of hydrophilic coatings similar to poly(ethylene glycol) (PEG). The coatings were produced by plasma-polymerizing tetraglyme on UHMWPE in a chamber heated to 40°C or 50°C. Both temperatures yielded coatings with PEG-like chemistry and increased hydrophilicity relative to uncoated UHMWPE; however, the 40°C coatings were significantly more resistant to damage induced by atomic force microscopy nanoscratching. The 40°C coatings exhibited only one damage mode (delamination) and often showed no signs of damage after repeated scratching. In contrast, the 50°C coatings exhibited three damage modes (roughening, thinning, and delamination), and always showed visible signs of damage after no more than two scratches. The greater wear resistance of the 40°C coatings could not be explained by coating chemistry or hydrophilicity, but it corresponded to an approximately 26–32% greater degree of crosslinking relative to the 50°C surfaces, suggesting that crosslinking should be a significant design consideration for hydrophilic coatings used for total hip replacements and other wear-dependent applications.     

Metal-doped (Ti, WC) diamond-like-carbon coatings: Reactions with extreme-pressure oil additives under tribological and static conditions

In contrast to non-doped diamond-like-carbon (DLC) coatings, reliable chemical evidence of the reactions between metal-doped DLC coatings and oil additives under tribological conditions using state-of-the-art surface-sensitive chemical analyses is still scarce. In this study we have investigated the reactivity of metal-doped (Ti, WC) DLC coatings with the extreme-pressure (EP) dialkyl dithiophosphate additive — without the presence of a steel counter body in the contact that befogs the actual coating reactions. Static “reactivity” experiments without any tribological or mechanical effects were also performed to provide a further insight into the lubrication mechanisms. The results confirmed the chemical reactions between the EP additive and all the DLC coatings, as well as their oxidation during the tribological contacts. We measured an about 10-times higher chemical activity (a 25-fold P/S ratio increase) for the Ti-doped DLC compared to the WC-doped or non-doped DLC, which also agrees with it having the lowest amount of wear in this study. We suggest that the Ti-DLC boundary lubrication is achieved via binding sites at the O vacancies present in the Ti-doped DLC coating. The data also clearly show, in contrast to most of literature reports, that even though small, some direct chemical activity between the W-DLC and the dialkyl dithiophosphate EP additive is also possible without any iron catalytic effect. However, the chemical changes were significantly smaller, also allowing coating graphitization, which might be one of the reasons for the 50% higher wear of the WC-doped compared to the Ti-doped DLC.     

Wear of ultra-high molecular weight polyethylene against damaged and undamaged stainless steel and diamond-like carbon-coated counterfaces

The wear of ultra-high molecular weight polyethylene (UHMWPE) in artificial joints and the resulting wear debris-induced osteolysis remains a major clinical concern in the orthopaedic sector. Third-body damage of metallic femoral heads is often cited as a cause of accelerated polyethylene wear, and the use of ceramic femoral heads in the hip is gaining increasing favour. In the knee prostheses and for smaller diameter femoral heads, the application of hard surface coatings, such as diamond-like carbon, is receiving considerable attention. However, to date, there has been little or no investigation of the tribology of these coatings in simulated biological environments. In this study, diamond-like carbon (DLC) has been compared to stainless steel in its undamaged form and following simulated third-body damage. The wear of UHMWPE was found to be similar when sliding against undamaged DLC and stainless steel counterfaces. DLC was found to be much more damage resistant than DLC. Under test conditions that simulate third-body damage to the femoral head, the wear of UHMWPE was seven times lower against DLC than against stainless steel (P < 0.05). The study shows DLC has considerable potential as a femoral bearing surface in artificial joints.     

甘油环境下不同涂层配副摩擦力矩的对比研究

利用磁控溅射技术在单晶硅P(111)、不锈钢表面分别制备了类金刚石(DLC)、CrN、TiN涂层。采用CSM球-盘摩擦磨损试验机,对比研究高接触应力下在甘油环境中三种涂层摩擦学性能,采用Falex-6多样品试验机对比分析了不同涂层配副在不同的载荷下摩擦力矩的变化规律。结果表明,在甘油环境下三种涂层摩擦系数均低于0.1,DLC和CrN涂层磨损较小;DLC-CrN涂层配副在不同接触应力下的整个测试过程中最大摩擦力矩均比较小,且样块表面均无明显的磨损及划痕,为甘油环境中的最优配副。     

自组织梯度分层结构金属掺杂类金刚石薄膜的制备及其性能研究

金属掺杂是降低类金刚石薄膜(DLC)内应力、提高其机械性能的一种有效方法。通常,金属掺杂类金刚石薄膜(Me-DLC)为均匀的纳米复合结构,但在一定条件下,会形成特殊的自组织分层结构。为了研究不同金属掺杂种类对自组织分层结构和薄膜性能的影响,本文筛选了两种典型的掺杂金属元素Cu和Cr,采用磁控溅射与阳极层离子源复合系统制备了Cu-DLC和Cr-DLC薄膜,同时使用等离子体发射光谱仪检测了沉积过程中金属粒子密度变化;通过能谱仪、辉光放电光谱仪、透射电镜、拉曼光谱仪、X射线光电子能谱仪等表征了薄膜成分和微结构;采用纳米压痕仪与摩擦磨损试验机考察了薄膜的力学和摩擦学性能。结果表明,在靶中毒模式下,溅射出的金属粒子密度逐渐降低,导致薄膜形成了自组织梯度分层结构,即膜基界面处为富金属层,表面为富碳层,沿膜基界面到表面金属含量从13%(原子比)以上逐渐降低至1%以下。Cu-DLC和CrDLC薄膜相似的表面碳键结构和力学性能,并且在干摩擦以及油润滑条件下分别表现出相似的摩擦学行为。以上研究表明自组织梯度分层结构的形成降低了金属种类对Me-DLC薄膜结构和性能的影响。     

Effects of molybdenum dithiocarbamate and zinc dialkyl dithiophosphate additives on tribological behaviors of hydrogenated diamond-like carbon coatings

The tribological behaviors of hydrogenated diamond-like carbon (DLC) coatings under varied load conditions lubricated with polyalpha olefin (PAO), molybdenum dithiocarbamate (MoDTC) and zinc dialkyl dithiophosphate (ZDDP) additives were investigated in this paper. Hydrogenated DLC coatings were synthesized through the decomposition of acetylene by the ion source. The tribological performances were measured on a SRV tribometer. The morphologies and chemical structures of the DLC coatings were investigated by the scanning electron microscope (SEM), Raman spectrometer (Raman) and X-ray photoelectron spectroscope (XPS). It was shown that the low friction and high wear were achieved on the hydrogenated DLC coating under MoDTC lubrication, while low wear was found on the hydrogenated DLC coating lubricated by ZDDP. The primary reason was attributed to different tribofilms formed on the contact area and the formation of graphitic layer. Both factors working together leaded to quite different tribological behaviors.     

超声处理对建筑用EVM表面离子镀DLC涂层组织和摩擦性的影响

通过超声方法处理聚氨基甲酸酯表面,选择脉冲碳离子源,结合阴极放电等离子方法在EVM表面完成DLC涂层的沉积过程,对超声处理过程中温度与时间参数引起的DLC涂层摩擦特性改变进行分析。实验测试研究结果表明:当超声处理的时间延长或者温度升高后,在试样表面形成了更深的条纹,能够显著增强EVM表面发生溶解的能力。DLC涂层在拉曼光谱测试过程中都形成低波数区间中的肩部结构,可以推断其光谱曲线都包含了D峰与G峰,在DLC膜内形成了跟高比例的石墨相。DLC涂层后的表面相对于EVM发生了摩擦系数稳定性下降,该结果表明DLC涂层可以使EVM获得更优耐磨性。当超声温度升高以及时间延长后,试样先发生摩擦系数的略微减小,之后发生逐渐升高。进行超声超声后,试样发生了磨损量的大幅降低,可以获得更致密的DLC涂层。     

Modeling effects of gas adsorption and removal on friction during sliding along diamond-like carbon films

In this paper, the physical and tribochemical processes that occur in a sliding contact between two diamond-like-carbon (DLC)-coated counterparts are discussed. The applicability of some of the most cited of the adsorption kinetics equations for modeling the gas adsorption process when environment molecules form bonds to the surface are examined. The process modeling is also discussed when part of the adsorbate is removed due to rubbing the surface by a slider. A direct connection between a kind of molecular friction and gradual wear is established. The models are compared with some recent experimental results. The present computer simulations of the adsorption and mechanical desorption of oxygen help to explain how microscopic processes, such as the breaking and forming of interatomic bonds, may affect macroscopic phenomena such as friction. In particular, it is shown that the initial roughness of the DLC surface may have a considerable influence on the probability of breaking bonds during mechanical removal of adsorbate and on the process of the gradual tribochemical wear of DLC films.     

外加偏置电场对类金刚石薄膜激光损伤形貌影响研究

研究了使用非平衡测控溅射技术沉积的类金刚石(DLC)薄膜其抗激光损伤能力;通过对比施加偏置电场前后薄膜的损伤情况,发现:DLC薄膜施加偏置电场后,薄膜的激光损伤区域内有大量丝状薄膜,损伤形貌存在明显不同,损伤面积减小;薄膜的激光损伤情况得到改善。实验结果显示,外加偏置电场对DLC薄膜的损伤有影响。认为:激光在DLC薄膜中激励产生的光生电子在电场的作用下产生快速漂移,间接降低了激光辐照区域内的局部能量密度,减缓了薄膜的石墨化,提高了DLC薄膜的抗激光损伤能力。     

Relative performance of hydrogenated, argon-incorporated and nitrogen-incorporated diamond-like carbon coated Ti-6Al-4V samples under fretting wear loading

Hydrogenated diamond-like carbon (DLC) (H-DLC), argon-incorporated DLC (Ar-DLC) and nitrogen-incorporated DLC (N-DLC) coatings were deposited on flat rectangular Ti-6Al-4V samples. The DLC coatings were characterised by Raman spectroscopy and nanoindentation. Fretting wear tests were conducted on uncoated and DLC coated samples with an alumina ball as the counterbody. As the Ar-DLC and N-DLC coatings had relatively more sp² network compared to the H-DLC coating, they exhibited lower values of hardness and elastic modulus. At both loads of 4.9 N and 14.7 N, all DLC coated specimens showed lower values of tangential force coefficient (TFC), wear volume and specific wear rate compared to the uncoated samples. While the Ar-DLC coated sample exhibited the lowest TFC, wear volume and specific wear rate at 4.9 N load, the N-DLC coated specimen exhibited the lowest TFC, wear volume and specific wear rate at 14.7 N load.     

Tribocorrosion behavior of DLC-coated CoCrMo alloy in simulated biological environment

Due to renewed interest in hard-on-hard prosthetic joint replacements, especially metal-on-metal (MOM) and ceramic-on-metal joints (COM), concerns about debris and released metal ions from wear and mechanical-enhanced electrochemical (tribocorrosion) processes have raised. In order to reduce the metal debris quantity and the release of metal ions, a diamond like carbon (DLC) film is deposited on CoCrMo alloy by using a filtered cathodic vacuum arc technique (FCVA). The tribocorrosion behavior of DLC coated CoCrMo alloy is studied in bovine calf serum and 0.9% NaCl solution by using a linear reciprocating pin-on-plate tribometer with an integrated electrochemical cell. The open circuit potential (OCP) and the polarization test are monitored during the reciprocating pin-on-plate test. The results show that the absorbed protein layer on DLC surface play a positive role in reducing wear and metal ion release. The presence of DLC layer improves the tribocorrosion resistance of CoCrMo alloy. And The DLC film has a potential application on hard-on-hard prosthetic joint replacements and it can effectively reduce the metal debris quantity and the release of metal ions.     

Nanoindentation of hard multilayer coatings: Finite element modelling

Stress concentrations undermine the load-bearing ability of superhard TiSiN coatings. Experimental studies have shown that multilayer coatings that contain TiSiN layers alternating with ceramic layers with dissimilar mechanical properties suppress contact damage during nanoindentation. In this work, nanoindentation-induced deformation in TiSiN-based multilayer coatings was simulated by means of finite element modelling (FEM). Stress distributions under moderate indentation loading in the structure were quantified with particular emphasis on the relationship between stress concentrations and crack initiation. The results showed that the structural layering can be used to modify the stress distribution, and lower the overall stress level within the coating. In the case of radial tensile stresses at the coating/substrate interface, a reduction ∼50% has been achieved through layering. The resistance to shear damage can also be improved by optimising the multilayer structure.     

Fabrication and evaluation of SixNy coatings for total joint replacements

Wear particles from the bearing surfaces of joint implants are one of the main limiting factors for total implant longevity. Si(3)N(4) is a potential wear resistant alternative for total joint replacements. In this study, Si(x)N(y)-coatings were deposited on cobalt chromium-discs and Si-wafers by a physical vapour deposition process. The tribological properties, as well as surface appearance, chemical composition, phase composition, structure and hardness of these coatings were analysed. The coatings were found to be amorphous or nanocrystalline, with a hardness and coefficient of friction against Si(3)N(4) similar to that found for bulk Si(3)N(4). The low wear rate of the coatings indicates that they have a potential as bearing surfaces of joint replacements. The adhesion to the substrates remains to be improved.     

铪掺杂对类金刚石薄膜的结构和光学带隙的影响

以甲烷为源气体,高纯碳和金属铪为靶材,采用双靶共溅射磁控技术制备了铪掺杂类金刚石(Hf-DLC)薄膜,通过现代分析测试技术手段对薄膜的表面形貌、键合结构、化学组成和光学性能等进行表征、分析。结果表明,随着铪靶溅射功率的增大,薄膜中Hf含量增加,且薄膜中Hf与C形成纳米晶HfC;铪掺杂使得薄膜表面颗粒减小,变得更加细密。Hf-DLC薄膜的光学带隙在1.12~1.85 eV,表现出半导体材料带隙特性;Hf掺杂使得薄膜中sp²C含量降低,碳π~π^*带边态密度增大,导致其光学带隙随着掺杂Hf量的增加而减小。因此,通过合理控制Hf-DLC薄膜中Hf的含量,可实现对薄膜的结构和光学带隙的有效调控。     

Verschleissfeste Antihaftschichten auf Basis modifizierter diamantähnlicher Kohlenstoffschichten

In this article technological developments in the field of modified diamond‐like‐carbon (DLC) coatings are described. The most well‐known properties of such DLC‐coatings are high hardness, high wear resistance, a very low friction coefficient (e.g. vs. Steel) and a very good chemical inertness. By doping the amorphous network with non‐metallic elements it is possible to influence the wettability of the DLC coatings over a wide range. This possibility to prepare a wear resistant sticking or non‐sticking DLC‐film opens a wide field of very different technical applications.     

类金刚石薄膜残余应力的研究进展

类金刚石薄膜由于存在很大的残余应力,在实际应用中薄膜易产生裂纹、破裂甚至脱落。这些问题导致类金刚石薄膜在使用过程中过早失效。因此,缓解残余应力是类金刚石薄膜急需解决的问题和实际应用的需要。介绍了类金刚石薄膜残余应力的产生,对国内外调控残余应力的途径以及研究进展进行综述。使用有限元分析法模拟薄膜的残余应力可为类金刚石薄膜的制备和工艺设计提供参考。     

镁合金表面类金刚石膜的研究进展

类金刚石碳(DLC)膜具有高硬度、低摩擦系数、强化学惰性及生物相容性好等优异性能,镁合金表面制备DLC膜可极大地改善基体的使用性能。综述了采用不同制备技术在镁基体表面获得的多种DLC膜系的抗磨损及耐腐蚀性能,并展望了DLC膜表面改性镁合金的医用前景,指出镁合金表面制备DLC膜是其表面改性技术中具有前景的一个研究方向。     

Corrosion protection of carbon fibre reinforced aluminium composite by diamondlike carbon coatings

Abstract

Carbon fibre reinforced aluminium exhibits poor resistance against electrochemical corrosion in 3·5 wt-%NaCl solution. Diamondlike carbon (DLC) coatings provide properties which make them interesting materials for external corrosion protection on metal matrix composites (MMCs). The electrochemical corrosion behaviour of uncoated and DLC coated carbon fibre reinforced aluminium was tested in 3·5 wt-%NaCl solution. It has been found that the pitting potential is shifted significantly in the anodic direction and the corrosion current density is much lower due to the presence of the sealing DLC coating. Additionally, scratch tests and SEM studies were carried out in order to characterise the adhesion of the DLC films on the heterogeneous MMCs. Reliable corrosion protection is connected with sufficient coating durability under loading. In order to ensure sufficient loading capacity of the DLC coating under tribological conditions, wear tests were undertaken which revealed a considerable improvement in wear resistance due to deposition of the DLC coatings.     

Tribologische Beschichtungen

Tribological Coatings Friction and wear limit the life of tribological systems and lead to damage valued in billion. In many cases tribologically stressed components or tools can only be economically operated with the use of lubricants. Tribologically effective films can replace lubricants or reduce the extent of their use. There are many ways to realise coatings with low friction but only carbon based coatings like DLC (diamond‐like carbon) and polycristalline diamond films combine low friction with a high wear resitant.     

基于微观结构的热喷涂WC/Co涂层裂纹生长模拟

涂层微观结构特征直接影响涂层的寿命,基于涂层微观结构研究涂层裂纹扩展特征成为评价热喷涂层性能的重要问题.本文基于WC/Co涂层微观结构建立了有限元模型,并采用XFEM方法研究了单应力状态预存裂纹行了模拟,获得了涂层微观裂纹扩展的损伤规律.研究表明:在拉应力作用下,沿着WC-Co边界产生的应力集中是涂层裂纹产生的根源;WC/Co涂层浅表面(0.125b,b为涂层厚度)的水平裂纹对垂直拉应力敏感、吸收能量快,0.78b处的裂纹扩展后对应力响应迅速,因此0.125b与0.78b是WC/Co涂层裂纹生长的关键深度;在0.78b处,当初始裂纹角度0°～45°时,扩展位移逐渐减小,扩展偏转角增大,45°时存在能量积累导致角度快速偏转.在周期应力作用时,WC/Co涂层的疲劳周期随应变幅值增加而减小;应变幅值相同时,WC/Co涂层的疲劳周期随频率增加而增加.