Si含量对VAlSiN涂层微结构、力学性能和摩擦磨损性能的影响

采用反应磁控溅射技术,在300℃下制备不同Si含量的VAlSiN涂层。研究Si含量的变化对VAlSiN涂层相结构、生长形貌、化学状态、力学性能和摩擦磨损性能的影响。结果表明:不含Si的VAlN涂层呈现(111)择优取向生长。随着Si含量的增加,VAlSiN涂层的(111)择优取向逐渐消失,最终转变为非晶结构。Si含量大于1.8%(原子分数,下同)的VAlSiN涂层是由nc-VAlN和a-Si_3N_4组成的多相复合涂层。与VAlN涂层相比,添加少量Si(0.8%)的VAlSiN涂层晶粒尺寸减小,致密度得到提高,对应的涂层硬度也得到显著增大,达到30.1GPa。继续增加Si的含量,VAlSiN涂层的柱状生长结构被打断,硬度逐渐下降,最后稳定在22GPa左右。VAlSiN涂层的摩擦因数随着Si含量的增加先降低后升高。当Si含量为0.8%时涂层的磨损率最低,达1.2×10~(-16)m~3·N~(-1)·m~(-1)。     

陶瓷颗粒填充PTFE复合材料的摩擦磨损性能研究

利用MHK－500型坏－块磨损试验机,对陶瓷颗粒SiC,Si3N4,BN和B2O3填充的聚四氟乙烯（PTFE）复合材料在干摩擦条件下与GCr15轴承钢对摩时的摩擦磨损性能进行了较为系统的研究,并利用扫描电子显微镜（SEM）和光学显微镜对PTEF复合材料的摩察表现进行了观察,结果表明,添加B2O3降低了PTEF的摩擦系数,而添加SiC,Si3N4及BN则增大了PTFE的摩擦系数,但是,SiC,Si3N4,BN和B2O3均可将PTFE的磨损量降低1－2个数量级,其中以Si3N4的减磨效果最好,B2O3的减磨效果最差。     

Improving Bearing Surfaces of Artificial Joints

The requirements for materials to be used for bearing surfaces in joint replacement are corrosion resistance in the body environment, reliability, hardness, and stiffness. Most important is coverage of the bearing surface with a stable oxide layer, so that the articulating surfaces can be lubricated by the synovial fluid. The synovial fluid, being a protein, can degenerate during frictional heating. This can be avoided if the materials used for wear couples have very good thermal conductivity. Bioceramics for joint replacement have been used since the 1970s. Alumina ceramics reduce the wear rate and solve the problem of implant loosening (osteolysis). Although the in vivo fracture rate for alumina parts is very small, further improved reliability is demanded. Alternative materials may be non‐oxide ceramics, zirconia ceramics, or hard coatings on metals. Advanced non‐oxide ceramics, such as SiC and Si₃N₄, are not suitable for bearing surfaces in knee‐ and hip‐joint replacement because the surface oxide formed is SiO₂, which chips off. Y‐TZP zirconia does not have adequate phase stability. All hard coatings tried hitherto (TiN, DLC) have not been good enough. Alumina matrix composite (AMC) is a new type of bioceramics. AMC offers excellent tribological properties, no frictional heating, improved mechanical strength and fracture toughness, thus more in vivo reliability. So far test results have been very promising.     

Microstructure and wear behaviour of silicon doped Cr–N nanocomposite coatings

Hard Cr–N and silicon doped Cr–Si–N nanocomposite coatings were deposited using closed unbalanced magnetron sputtering ion plating system. Coatings doped with various Si contents were synthesized by changing the power applied on Si targets. Composition of the films was analyzed using glow discharge optical emission spectrometry (GDOES). Microstructure and properties of the coatings were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), and nano-indentation. The harnesses and the elastic modulus of Cr–Si–N coatings gradually increased with rising of silicon content and exhibited a maximum at silicon content of 4.1 at.% and 5.5 at.%. The maximum hardness and elastic modulus of the Cr–Si–N nanocomposite coatings were approximately 30 GPa and 352 GPa, respectively. Further increase in the silicon content resulted in a decrease in the hardness and the elastic modulus of the coatings. Results from XRD analyses of CrN coatings indicated that strongly preferred orientations of (111) were detected. The diffraction patterns of Cr–Si–N coatings showed a clear (220) with weak (200) and (311) preferred orientations, but the peak of CrN (111) was decreased with the increase of Si concentration. The XRD data of single-phase Si₃N₄ was free of peak. The peaks of CrN (111) and (220) were shifted slightly and broadened with the increase of silicon content. SEM observations of the sections of Cr–Si–N coatings with different silicon concentrations showed a typical columnar structure. It was evident from TEM observation that nanocomposite Cr–Si–N coatings exhibited nano-scale grain size. Friction coefficient and specific wear rate (SWR) of silicon doped Cr–N coatings from pin-on-disk test were significantly lower in comparison to that of CrN coatings.     

Carbon–carbon composite bearing materials in hip arthroplasty: analysis of wear and biological response to wear debris

Ultra-high molecular weight polyethylene wear particles have been implicated as the major cause of osteolysis, implant loosening and late aseptic failure in total hip arthroplasties in vivo. This study initially screened 22 carbon-carbon composite materials as alternatives for UHMWPE in joint bearings. New bearing materials should satisfy certain criteria--they should have good wear properties that at least match UHMWPE, and produce wear particles with low levels of cytotoxic and osteolytic activity. Initial screening was based on wear resistance determined in short-term tribological pin-on-plate tests. Three materials (HMU-PP(s), HMU-RC-P(s), and SMS-RC-P(s)) which had superior wear resistance were selected for long-term testing. All materials had very low wear factors and SMS-RC-P(s), which had a wear factor of 0.08 +/- 0.56 x 10(-7) mm3/Nm, was selected for the subsequent biological testing and particle size analysis. SMS-RC-P(s) showed good biocompatibility in bulk material form and also the wear particles had low cytotoxicity for L929 fibroblasts in culture compared to metal wear particles. Wear debris size analysis by transmission electron microscopy showed that the particles were very small, with the vast majority being under 100 nm in size, similar to metal wear particles. The potential osteolytic effect of SMS-RC-P(s) wear particles was investigated by culturing particles with human peripheral blood mononuclear cells and measuring TNFalpha production. SMS-RC-P(s) did not significantly stimulate TNFalpha production at a particle volume to cell number ratio of 80:1, indicating that the debris had a low osteolytic potential. The results of this study suggest that carbon-carbon composites, particularly those composed of PAN-based fibers may be important biomaterials in the development of next generation bearing surfaces for use in total joint replacements that have very low wear rates and reduced osteolytic and cytotoxic potential.     

SURFACE MODIFICATION ISSUES FOR ORTHOPAEDIC IMPLANT BEARING SURFACES

In total joint replacement, generally a polished metal surface articulates against an ultra high molecular weight polyethylene (UHMWPE) counter bearing surface. Metals used include 316L stainless steel, Co-Cr-Mo alloy, and Ti-6AI-4V alloy (particularly with a hardened N⁺ ion implanted surface). Minimizing friction and UHMWPE wear is of prime concern for long-term performance. Additionally, it is desirable to minimize metal ion release which results from constant removal and reformation of passive surface oxides and oxyhydroxides during articulation. Long term effects from the presence of potentially toxic or carcinogenic ions of Cr, Co, Mo, Ni, V, and Al are not well known. Inert ceramic bearing surfaces eliminate this issue and are also resistant to potential three-body wear from bone cement debris or potential stray porous metal coating material. However ceramic (Al₂O₃ and ZrO₂) materials are only available for total hip replacement. For total knee replacement, ft is too difficult and expensive to manufacture a monolithic ceramic knee surface, thus various surface coating methods are being investigated. These methods include plasma sprayed Al₂O₃ and ZrO₂, TiN and amorphous diamond like coatings via PVD/CVD methods, and in-sKu oxidation. In other cases, the existing metal surfaces are simply hardened using methods such as N⁺ ion implantation and oxygen or nitrogen diffusion hardening. This paper reviews the limitations of existing total joint systems and the effectiveness of various surface modification methods of orthopaedic implant bearing surfaces on friction, abrasion, UHMWPE wear, and metal ion release.     

Effect of Si3N4 Addition on the Mechanical Properties, Microstructures, and Wear Resistance of Ti-6Al-4V Alloy

In order to improve the wear resistance of Ti-6Al-4V, different amounts of Si3N4 powder were added into the alloy powder and sintered at 1250℃. Porous titanium alloy with higher wear resistance was successfully fabricated. At sintering temperature, reaction took place and a new hard phase of Ti5Si3 formed. The mechanical properties of the fabricated alloys with different amounts of Si3N4 addition were investigated. The hardness of Ti-6Al-4V, which is the index of wear resistance, was increased by the addition of Si3N4. Amounts of Si3N4 addition have very significant influences on hardness and compressive strength. In present study,titanium alloy with 5 wt pct Si3N4 addition has 62% microhardness and 45% overall bulk hardness increase,respectively. In contrast, it has a 16.4% strength reduction. Wear resistance was evaluated by the weight loss during wear test. A new phase of Ti5Si3 was detected by electron probe microanalyzer （EPMA） and X-ray diffraction （XRD） method. The original Si3N4 decomposed during sintering and transformed into titanium silicide. Porous structure was achieved due to the sintering reaction.     

Corrosion behaviour and mechanical properties of functionally gradient materials developed for possible hard-tissue applications

Artificial hip joints have an average lifetime of 10 years due to aseptic loosening of the femoral stem attributed to polymeric wear debris; however, there is a steadily increasing demand from younger osteoarthritis patients aged between 15 and 40 year for a longer lasting joint of 25 years or more. Compliant layers incorporated into the acetabular cup generate elastohydrodynamic lubrication conditions between the bearing surfaces, reduce joint friction coefficients and wear debris production and could increase the average life of total hip replacements, and other human load-bearing joint replacements, i.e. total knee replacements. Poor adhesion between a fully dense substrate and the compliant layer has so far prevented any further exploitation. This work investigated the possibility of producing porous metallic, functionally gradient type acetabular cups using powder metallurgy techniques – where a porous surface was supported by a denser core – into which the compliant layers could be incorporated. The corrosion behaviour and mechanical properties of three biomedically approved alloys containing two levels of total porosity (>30% and <10%) were established, resulting in Ti–6Al–4V being identified as the most promising biocompatible functionally graded material, not only for this application but for other hard-tissue implants.     

Phase composition,structure, and mechanical properties of arc PVD Mo–Si–Al and Mo–Si–Al–N coatings

Using an arc physical vapor deposition process, we have produced nanostructured Mo–Si–Al coatings with a uniform distribution of equiaxed grains 8–12 nm in size and Mo–Si–Al–N coatings with a multilayer structure and a modulation period from 22 to 25 nm. The former coatings consist of MoSi₂ and Mo and the latter consist of Mo2N and amorphous Si₃N₄ and AlN. The hardness of the Mo–Si–Al–N and Mo–Si–Al coatings is 41 and 18 GPa, respectively; they are similar in resistance to elastic deformation; and the Mo–Si–Al–N coating has a considerably higher resistance to plastic deformation. The coatings have roughly identical coefficients of friction (~0.67–0.69 at 20°C and ~0.52–0.56 at 550°C), but the wear resistance of the Mo–Si–Al–N coating is higher by three and two orders of magnitude at 20 and 550°C, respectively. The coatings of the two systems exhibit good adhesion to the substrate and cohesive fracture. Partial wear of the Mo–Si–Al and Mo–Si–Al–N coatings in the course of scratch testing occurs at indentation loads of 80 and 63 N, respectively.     

PIRAC Ti nitride coated Ti–6Al–4V head against UHMWPE acetabular cup–hip wear simulator study

Wear behaviour of TiN(titanium nitride)-coated Ti and Ti-6AI-4V alloy against UHMW polyethylene was studied in hip simulation test. Ti alloys possess an excellent combination of mechanical properties and biocompatibility, however, they suffer from inadequate wear resistance. Thus, their use as articulating components of total joint replacements requires surface hardening, e.g. by TiN. Thirty-two millimetre diameter cp-Ti and Ti-6AI-4V femoral heads were coated with several micrometre thick TiN layers employing an original PIRAC nitriding method based on interaction of Ti alloy substrate with highly reactive monatomic nitrogen. The heads were tested against UHMWPE cups at 37 degrees C in Ringer's solution or in distilled water. Simulator tests were performed at peak pressures of 1.5 and 2.0 MPa in a constant rotation mode at the frequency of 1.5 Hz. The wear of UHMWPE was estimated by weight loss, and the worn metallic and polyethylene surfaces were examined in SEM. The wear rate of UHMWPE cups articulating against PIRAC coated Ti and Ti-6AI-4V after up to 4 x 10(6) cycles was significantly lower than that of UHMWPE articulating against 316L stainless steel. No delamination of TiN coatings was observed after 4 x 10(6) cycles. These results suggest that TiN PIRAC coating on Ti-6AI-4V heads could minimise the wear of total hip replacements without compromising the mechanical properties of the femoral component.     

Al(Ni)含量对钛合金激光熔覆AlNiMoSi复合涂层摩擦学性能的影响

研究含Al、Si元素涂层的摩擦学性能可为其应用提供重要的理论参考。以Al、Ni、Mo、Si粉末为原料,采用激光熔覆技术在Ti6Al4V合金表面制备了Al质量分数分别为20%(Ni的为40%),30%(Ni的为30%),40%(Ni的为20%)的AlNiMoSi复合涂层,分别命名为20Al、30Al、40Al复合涂层。采用XRD、SEM和EDS分析了涂层的物相和显微组织,并测试了复合涂层的干滑动磨损性能。结果表明:20Al、30Al和40Al复合涂层的平均摩擦系数和磨损率分别为0.380,0.258,0.325和9.36×10~(-5),8.43×10~(-5),1.05×10~(-4)mm~3/(N·m),30Al复合涂层的磨损性能最好,主要是因为该涂层中TiC和Ti3Al含量较高;20Al和40Al复合涂层的磨损机理主要为黏着磨损和磨粒磨损,30Al复合涂层的磨损机理主要为轻微的磨粒磨损。     

Hard plasmachemical a-SiCN coatings

The amorphous SiCN coatings have been plasmachemically (PECVD) deposited onto silicon substrates using the heksamethyldisylazan as the basic precursor. The effect of the deposition temperature on the structure, chemical composition, and mechanical properties of the coatings has been studied. It has been found that at temperatures below 400°C the deposition of hydrogenated amorphous SiCN (a-SiCN:H) coatings, whose hardness does not exceed 23 GPa, takes place. At the further increase of the temperature the distribution of the Si–C, Si–N, and C–N strong bonds in coatings does not practically change, while the number of C–H, Si–H and N–H weak hydrogen bonds decreases. As a result of such a redistribution of chemical bonds, at the temperature 600–700°C a-SiCN coatings are deposited with hardness up to 32 GPa. The annealing in vacuum at 1200°C is shown not to noticeably affect the structure, hardness, and elastic modulus of a-SiCN coatings.     

Mechanical characterization of anti-infectious,anti-allergic,and bioactive coatings on orthopedic implant surfaces

In total joint replacement much effort has been made to reduce implant loosening. We investigated different implant coatings (copper integrated titanium dioxide (TiO₂–Cu), titanium nitride (TiN), plasma polymerized allylamine (PPAAm), and calcium phosphate (CaP)) regarding the adhesion strength and wear resistance. Standardized scratch and adhesive tests were applied. Abrasive wear was measured with artificial bone and bone cement using a special testing machine. All tested coatings have higher bonding strengths than the 22 N/mm² required for medical implant surface coatings by ASTM standard 4711-F. Using bone cement, wear testing revealed higher wear rates in most cases. Polished surfaces reduce the amount of wear, whereas rough surfaces highly increase the wear rate due to three-body wear, especially ceramic surfaces. In general, the application of bone cement in conjunction with modified implant surfaces can lead to an increase in wear rate.     

Architectural design of diamond-like carbon coatings for long-lasting joint replacements

Surface engineering through the application of super-hard, low-friction coatings as a potential approach for increasing the durability of metal-on-metal replacements is attracting significant attention. In this study innovative design strategies are proposed for the development of diamond-like-carbon (DLC) coatings against the damage caused by wear particles on the joint replacements. Finite element modeling is used to analyze stress distributions induced by wear particles of different sizes in the newly-designed coating in comparison to its conventional monolithic counterpart. The critical roles of architectural design in regulating stress concentrations and suppressing crack initiation within the coatings is elucidated. Notably, the introduction of multilayer structure with graded modulus is effective in modifying the stress field and reducing the magnitude and size of stress concentrations in the DLC diamond-like-carbon coatings. The new design is expected to greatly improve the load-carrying ability of surface coatings on prosthetic implants, in addition to the provision of damage tolerance through crack arrest.     

Ti6Al4V钛合金表面Ta2O5/Ta2O5-Ti/Ti多涂层的制备与性能研究

采用磁控溅射技术在Ti6Al4V钛合金表面制备了Ta_2O_5/Ta_2O_5-Ti/Ti多层涂层;利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)和X射线光电子能谱仪 (XPS),分析了涂层的微观结构、物性组成和化学价态;通过划痕仪、纳米压痕仪、摩擦磨损试验机和电化学工作站,检测了涂层的结合强度、力学性能、摩擦系数和耐腐蚀性。研究结果表明,Ta_2O_5/Ta_2O_5-Ti/Ti多层涂层表面由峰型颗粒组成,粒径大小均匀,涂层结构致密。与Ti6Al4V相比,Ta_2O_5/Ta_2O_5-Ti/Ti多层涂层试样具有较小的摩擦系数,较高的腐蚀电位和较小的腐蚀电流密度,表现出良好的耐磨和耐腐蚀性能,能对Ti6Al4V合金植入材料起到较好的保护作用。     

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.     

纳米Si3N4及其与石墨、MoS2混合填充PTFE摩擦磨损性能研究

用M-2000型摩擦磨损试验机对纳米Si3N4及其与石墨、MoS2混合填充聚四氟乙烯(PTFE)复合材料在干摩擦条件下与45#钢对磨时摩擦磨损性能进行了研究,用洛氏硬度仪对其进行了测量,用扫描电子显微镜对磨损表面进行了观察.结果表明:纳米Si3N4的加入能提高PTFE复合材料的硬度和耐磨性,纳米Si3N4与MoS2混合填充会使PTFE复合材料的耐磨性能提高更多,特别是在载荷增大时其耐磨效果更好.纳米Si3N4能阻止PTFE复合材料中磨损微裂纹的产生,在纳米Si3N4的富聚区,磨损微裂纹较少,在纳米Si3N4的贫聚区,磨损的微裂纹较多.纳米Si3N4填充PTFE复合材料的摩擦系数比纯PTFE大,且随着载荷增加有所减小,石墨的加入可降低PTFE的摩擦系数.     

TiAlSiN-Ti(Mo)N/MoS2复合涂层微观结构及摩擦学性能的研究

采用磁控溅射技术在AISI-304不锈钢上制备了TiAlSiN-Ti(Mo)N/MoS2复合涂层。采用电子显微镜(SEM)、X射线衍射仪(XRD)、显微硬度计、球盘摩擦磨损试验机、表面形貌仪等对涂层的表面形貌、显微组织、硬度和摩擦学性能进行了系统的研究。结果表明TiAlSiN-Ti(Mo)N/MoS2复合涂层的硬度为27.56 GPa,相比于TiAlSiN涂层的硬度(29.1 GPa)有所下降,但是涂层的耐磨性能得到明显提高。在室温至600℃条件下TiAlSiN-Ti(Mo)N/MoS2复合涂层的主要磨损机理为黏着磨损,200和400℃时的磨损率分别为0.0339×10^-3和0.1122×10^-3mm^3/(Nm),相较于TiAlSiN涂层分别降低了38%和57%,600℃时的磨损率接近TiAlSiN涂层。总体来说TiAlSiN-Ti(Mo)N/MoS2复合涂层的性能高于单一的TiAlSiN涂层。     

QT600材料表面离子镀AlCrN涂层的耐磨性能研究

采用多弧离子镀膜的方法在空压机转子QT600表面制备AlCrN涂层,详细研究干滑动摩擦条件下,不同载荷对涂层和基体的滑动摩擦学特性。研究结果表明:转子基体的磨损形式主要为黏着与磨粒磨损,载荷越高,磨粒磨损越严重;AlCrN涂层在2N载荷下的磨损形式主要为黏着磨损,在8N载荷下主要为黏着与磨粒磨损。     

Abrasive wear behaviour of powder flame sprayed coatings on steel substrates

The main purpose of thermal spraying method is to produce wear resistant surfaces. Easy applicability, very low possibility of metallurgical changes and low distortion of coated parts due to low heat transfer to the substrate and salvation of worn parts are some of the practical advantages of this process. In this study, abrasive wear behaviour of powder flame sprayed coatings on steel substrates has been investigated. Coating was carried out onto both hot and cold substrates by using four types of powders. Prior to the wear tests, the coated specimens were machined on a lathe and surface roughness and hardness measurements were carried out on the machined surfaces. Heating the substrates prior to the coating led to the decrease in the hardness of the coating layers. Abrasive wear resistance of flame sprayed coatings was seen to be dependent on the chemical composition and characteristics of coating materials and coating condition.