Comparing internal stress in diamond-like carbon films with different structure

Diamond-like carbon (DLC) films with different structures were deposited on Si (100) and stainless steel substrates in a hybrid deposition system with Ar and CH₄ as the feedstocks. The effects of the bias voltage, Ti-interlayer, Ti functional gradient layer and Ti-doping on the internal stress in DLC films were investigated. The results show that the internal stress in DLC films arises from both the intrinsic stress generated during the film growth and the thermal stress generated due to the mismatching of the thermal expansion coefficient between the DLC films and the substrate materials. The intrinsic stress can be released through doping titanium element at the expense of reducing the sp³/sp² ratio. The thermal stress in DLC films can be decreased through introducing Ti-interlayer or Ti functional gradient layer. Noticeably, DLC films with very low internal stress deposited on stainless steel can be obtained through the combination of Ti-doping and Ti functional gradient layer.     

基于RFPECVD方法不锈钢上沉积类金刚石薄膜的机械与摩擦特性

讨论用射频等离子体增强化学气相沉积(RFPECVD)工艺,在室温下实现在1Cr18Ni9Ti不锈钢基底上镀类金刚石(DLC)膜.为提高DLC膜的结合力,首先在不锈钢基底上沉积Ti/TiN/TiC功能梯度膜.借助所设计的界面过渡层,成功地在不锈钢基底上沉积了一定厚度的DLC膜.通过优化沉积参数,所沉积的DLC膜在与100Cr6钢球对磨时摩擦系数低于0.020.在摩擦过程中DLC膜的磨损机制借助SEM、Raman分析进行了研究.     

Microstructure, mechanical and tribological properties of Ti(C, N)/a-C gradient composite films

Ti(C, N)/a-C composite films with compositional gradient from Ti-TiN-Ti(C, N) to Ti-containing a-C layers have been prepared by closed-field unbalanced magnetron sputtering. Within the composite films, the carbon contents gradually increase and achieve maximum in the a-C layer by increasing the power applied to the graphite targets, the nitrogen contents gradually decrease to zero from Ti(C, N) layer of the interface to a-C layer of the films. In order to achieve a good combination of the mechanical and tribological properties in the composite films, a designed experimental parameter basing on various substrate rotation speeds is also selected. Results show that the compositional gradient result in the microstructure change of composite films where the Ti(C, N) layers consist of fine nanocolumnar Ti(C, N) grains and the a-C layers consist of 2-7 nm TiC nanocrystallites embedded in an amorphous C matrix. The Ti(C, N) layers also exhibit clear multilayer structure where the period thickness gradually decreases as substrate rotation speed increases. Under higher rotation speed, disappearance of the multilayer structure is accompanied with simultaneous increase in the crystallinity of Ti(C, N) layer and also the Ti(C, N) grain size. In the a-C layer, the TiC nanocrystallites embedded in the a-C matrix is produced by the high rotation speeds. The Ti(C, N)/a-C gradient composite films exhibit high microhardness values (~5000 H_V) and low friction coefficient (~ 0.15), which is related to the hard Ti(C, N) layer and self-lubricate a-C layer, respectively. The combination of the Ti(C, N) layer with a-C layer increases the load and the wear resistance capacity of the composite films, which gives satisfactory friction performance in the pin-on-disk tests with a wear rate of 3.7 × 10^− 17 m³/mN.     

Internal stresses and interdiffusion of Ti-Pd-Au films studied by X-ray diffraction techniques

The electrical and structural properties of three layer Ti-Pd-Au films which are widely used for interconnections and terminations in thin film circuits change upon heat treatment at elevated temperatures. The annealing can cause stress relaxation, interdiffusion between the different layers and diffusion-induced structural changes. The objective of this investigation was to study the effect of aging at temperatures between 284° and 425°C on the mechanical and structural properties of these conductor films. It was found that the stresses in the Au film on Pd-Ti were independent of the substrate material and were lower than those of the Au films deposited directly on the Ti bonding layer. During aging, substantial interdiffusion between Au and Pd took place and it was found that the diffusion rate of Pd was higher than that of Au.     

Tribological property enhancement of CrN films by metal vapor vacuum arc implantation of Vanadium and Carbon ions

CrN films have been extensively used in precision forming and molding applications because of their excellent tribological properties and oxidation-resisting characteristics. Vanadium and carbon ions are introduced into the near surface layer of deposited CrN films via metal vapor vacuum arc implantation to improve the wear performance of CrN films. Dense and smooth CrN film was deposited using a filtered arc deposition system, which provides fully ionized Cr plasma on the substrate surface. Subsequently, surface bombardment of the deposited CrN film with vanadium and carbon ions densifies the film and forms an alloy near the surface. These CrN-based films were characterized by X-ray photoelectron electron and Auger electron spectroscopies. Examinations of the tribological and mechanical film properties, including wear resistance, corrosion resistance and fracture toughness were performed and correlated with respect to the implantation parameters.     

Structural analysis and corrosion studies on an ISO 5832-9 biomedical alloy with TiO2 sol–gel layers

The aim of this study was to demonstrate the relationship between the structural and corrosion properties of an ISO 5832-9 biomedical alloy modified with titanium dioxide (TiO₂) layers. These layers were obtained via the sol–gel method by acid-catalyzed hydrolysis of titanium isopropoxide in isopropanol solution. To obtain TiO₂ layers with different structural properties, the coated samples were annealed at temperatures of 200, 300, 400, 450, 500, 600 and 800 °C for 2 h. For all the prepared samples, accelerated corrosion measurements were performed in Tyrode’s physiological solution using electrochemical methods. The most important corrosion parameters were determined: corrosion potential, polarization resistance, corrosion rate, breakdown and repassivation potentials. Corrosion damage was analyzed using scanning electron microscopy. Structural analysis was carried out for selected TiO₂ coatings annealed at 200, 400, 600 and 800 °C. In addition, the morphology, chemical composition, crystallinity, thickness and density of the deposited TiO₂ layers were determined using suitable electron and X-ray measurement methods. It was shown that the structure and character of interactions between substrate and deposited TiO₂ layers depended on annealing temperature. All the obtained TiO₂ coatings exhibit anticorrosion properties, but these properties are related to the crystalline structure and character of substrate–layer interaction. From the point of view of corrosion, the best TiO₂ sol–gel coatings for stainless steel intended for biomedical applications seem to be those obtained at 400 °C.     

Corrosion properties of titanium based hard coatings on steel

Titanium nitride TiN, titanium boronitride Ti(B,N) and titanium carbonitride Ti(C,N) coatings were deposited by PA-CVD on tempering and stainless steel substrates. The deposition process can be supervised by OES. The coatings were characterized XRD, SEM and WDS as well as hardness, adhesion and friction tests. Electrochemical impedance measurements and cyclic voltammetry in praxis relevant media were carried out. Mechanical and corrosion properties of the coatings can be controlled by the PA-CVD process parameters. The incorporation of chlorine in the coating can be varied by the process parameters with TiCl₄ or completely avoided using metallo-organic precursors. No influence of the chlorine content on the corrosion behavior was observed. Even coatings with extremely high chlorine content still exhibit an excellent corrosion resistance. Thus, the microstructure of the coating is the key to the corrosion properties of hard coatings on steel. A new micro electrochemical scanning droplet technique with a lateral resolution of 150 μm allows the investigation of TiN-coated substrates of complex geometry. The PA-CVD technique permits the deposition of dense and pinhole free coatings. On structures with simulated aspect ratios less than 3, a dense protective coating is proved. However, if the formation of micro pores is not suppressed by the optimal choice of deposition parameters, low-alloyed steel substrates corrode through pores, causing a detachment of the coating. On layers deposited on stainless steel, no sign of substrate corrosion could be detected. A model for the corrosion mechanism is given in Fig. 17.     

金属过渡层类型对非晶碳膜结构性能的影响

采用直流磁控溅射技术制备不同金属过渡层(Cr, Ti, W)的类石墨非晶碳膜(GLC), 研究过渡层类型对非晶碳膜微结构的影响, 并考察其在人工海水中摩擦性能的变化。研究结果表明: Cr/GLC薄膜sp²杂化键含量最高, 沿GLC表面到铬碳界面方向, sp²杂化键含量逐渐增大, Ti过渡层和W过渡层的sp²杂化键含量变化不明显。Cr/GLC薄膜较高的sp²杂化键含量有助于其在摩擦过程中产生可以充当润滑相的石墨化转化摩擦转移膜。在三种涂层中, Cr/GLC薄膜表现出最高的腐蚀电位-0.16 V和最低的腐蚀电流密度4.42×10^-9 A/cm²。因此相较于Ti, W作过渡层的GLC薄膜, Cr/GLC薄膜在海水环境下表现出优异的摩擦学特性。     

镍基合金基体上离子镀TiN薄膜的制备及性能

在镍基合金Inconel 740H基底上通过多弧离子镀制备Ti N薄膜.控制温度、气体流量、过渡层成分等重要参数,研究其对Ti N薄膜的表面形貌、力学性能以及耐腐蚀性的影响.多弧离子镀沉积过程中,沉积温度分别为200、250、300℃;过渡层成分分别为Al、Cr、Ti;气体流量分别为Ar 5 Sccm∶N240 Sccm,Ar 6 Sccm∶N248 Sccm,Ar 8 Sccm∶N264 Sccm.实验结果表明:在本实验的温度范围内,Ti N薄膜的致密度、结合力以及表面硬度均随着沉积温度的提高而提高;Cr作为过渡层的效果优于Al和Ti,薄膜成分均匀、表面致密,硬度更高,且耐腐蚀性能优异;在Ar、N2流量比一定的情况下,气体流量对Ti N薄膜的表面形貌和力学性能影响不大.本实验的最佳参数是:沉积温度300℃,过渡层成分为Cr,气体流量为Ar 6 Sccm、N248 Sccm.     

GCr15钢等离子体基离子注入Ti和C混合层的XPS研究

用X射线光电子谱研究了GCr15轴承钢不平衡磁控溅射沉积Ti,继之等离子体基离子注入碳的等离子体基离子注入混合层的C ,Ti浓度深度分布及其化学结构。表明混合层的最表层为碳沉积层 ,其C 1s谱峰呈类金刚石特征 ,喇曼光谱肯定了这一特征。碳沉积层下面为C Ti混合区 ,Ti和C各以游离态和化合物态存在。混合层内Ti和C浓度沿层深连续变化 ,无突变区 ,在原Ti沉积层与基材轴承钢发生反冲增强扩散现象     

脉冲真空电弧离子镀在不锈钢上沉积类金刚石薄膜的研究

利用脉冲真空电弧离子镀技术在3Cr13不锈钢上制备了类金刚石(DLC)薄膜,通过Raman光谱分析了膜的结构特征,采用摩擦磨损试验机测试了薄膜在不同载荷下的摩擦系数,运用划痕仪研究了膜基的结合强度.结果表明:所镀制的薄膜具有典型类金刚石结构特征,膜中ID/IG为1.33;摩擦系数随着载荷的增大而减小,载荷为5 N,转速120 r/min时的摩擦系数为0.12;Ti过渡层的引入显著地提高了膜基结合力.     

医用NiTi合金表面溶胶-凝胶法制备TiO2-SiO2薄膜

采用溶胶－凝胶法在ＮｉＴｉ形状记忆合金表面制备了ＴｉＯ_２－ＳｉＯ_２复合薄膜,在提高医用ＮｉＴｉ合金的抗腐蚀性方面,收到了显著的效果．运用电化学方法对不同组成的ＴｉＯ_２－ＳｉＯ_２薄膜在模拟体液中的腐蚀行为进行了研究,结果表明,随薄膜中 Ｔｉ／Ｓｉ比的增加,ＴｉＯ_２－ＳｉＯ_２薄膜的抗腐蚀性增强．划痕试验表明 ＴｉＯ_２－ＳｉＯ_２（Ｔｉ／Ｓｉ＝４：１）膜与ＮｉＴｉ合金基体具有较高的界面结合强度．用原子力显微镜（ＡＦＭ）对ＴｉＯ_２－ＳｉＯ_２薄膜的表面形貌及表面粗糙度进行观察和分析,解释并讨论了ＴｉＯ_２－ＳｉＯ_２薄膜的配方组成与其抗腐蚀性的关系,ＳｉＯ_２含量较少时,薄膜结构致密,膜层均匀平滑,且膜基结合力好,作为医用ＮｉＴｉ合金的表面保护层,可以使其耐腐蚀性有显著提高．     

The influence of DLC coating on the mechanical and frictional properties of unpeened and peened Cu-based bimetal under dry sliding conditions

In this study, the influence of a combination of high-frequency ultrasonic peening (HFUP) technique and diamond-like carbon (DLC) coating on the mechanical and frictional properties of Cu-based alloy sintered on steel by a powder metallurgy (P/M) technique was investigated. The frictional behavior of the Cu-based alloy specimens was assessed using a Schwingung Reibung Verschleiss (SRV) pin-on-disk tribometer sliding against a Cr-plated bearing steel pin under dry sliding conditions. The purpose of this study is to develop a thin wear resistant layer for Cu-based alloy and to extend its application in the automotive industry. Results showed that the over-coated DLC coating deposited onto a peened Cu-based alloy specimen had higher mechanical and lower frictional properties compared to that of the over-coated DLC coating deposited onto an unpeened Cu-based alloy specimen, which may be ascribed to the undulated microstructure caused by HFUP technique resulting in good adhesion. It was revealed that the deposited DLC coating was beneficial for improving the mechanical and frictional properties of Cu-based alloy. Hence, it is expected that the results of this investigation can be applied to improve the frictional behavior of an internal combustion engine (ICE) components which are made of bimetals (sintered Cu-based alloy on a steel back).     

电弧离子镀TiN及其复合膜的腐蚀机理探讨

利用电弧离子镀在高速钢基体上制备了TiN及其复合膜（Ti，Cr）N，通过盐水全浸泡试验测量了薄膜的腐蚀速率。利用SEM观察了薄膜腐蚀后的表面形貌及断口形貌，并用其自带的能谱分析仪测量复合膜中Cr的含量，讨论了带有宏观熔滴颗粒的TiN及其复合膜（Ti，Cr）N的腐蚀机理。结果表明：高速钢表面电弧离子镀TiN和（Ti，Cr）N复合膜均可提高其耐腐蚀性能，薄膜的腐蚀主要有小孔腐蚀、缝隙腐蚀及电偶腐蚀。     

Characterization of Ti-containing amorphous carbon films prepared on titanium substrates

Amorphous carbon (a:C) films prepared on pure titanium (Ti) substrates exhibit relatively high intrinsic compressive stress. In order to obtain low stress films with varied electrical and mechanical properties, metal (Ti) ions are incorporated into the plasma. This is done with the help of metal containing carbon targets. Amorphous carbon films with varied percentage of Ti were deposited on polished pure Ti substrates using Filtered Cathodic Vacuum Arc (FCVA) technique together with substrate pulse biasing. Characterizations of the films were carried out using various equipments including Raman Spectroscopy, X-ray diffractometer, Atomic Force Microscopy (AFM), Pin-on-Disk Tribometer and Micro-Scratch Tester; and properties such as microstructure, crystallography, film stress, morphology, frictional coefficient and critical load were investigated as a function of Ti content in the target. The results suggest that the film prepared with 5 at.% Ti-containing carbon target, under 7 kV substrate pulse bias voltage, displays almost zero stress. However such films are inferior in its Tribological properties compared to that of pure a:C films.     

Brazing of titanium to steel with different filler metals: analysis and comparison

Evaluations of vacuum brazed commercially pure titanium and low-carbon steel joints using one copper-based alloy (Cu–12Mn–2Ni) and two silver-based braze alloys (Ag–34Cu–2Ti, Ag–27.25Cu–12.5In–1.25Ti) have been studied. Both the interfacial microstructures and mechanical properties of brazed joints were investigated to evaluate the joint quality. The optical and scanning electron microscopic results showed that all the filler metals interact metallurgically with steel and titanium, forming different kinds of intermetallic compounds (IMC) such as CuTi, Cu2Ti, Cu4Ti3, and FeTi. The presence of IMC (interfacial reaction layers) at the interfacial regions strongly affects the shear strength of the joints. Furthermore, it was found that the shear strength of brazed joints and the fracture path strongly depend on the thickness of the IMC. The maximum shear strength of the joints was 113 MPa for the specimen brazed at 750 °C using an Ag–27.25Cu–12.5In–1.25Ti filler alloy.     

Ti和TiO2薄膜在血管支架表面附着状况的研究

采用非平衡磁控溅射法在316L不锈钢制成的血管支架表面制备Ti以及TiO2薄膜,初步研究了Ti薄膜厚度、TiO2薄膜沉积速率对薄膜在血管支架表面附着状况的影响.结果表明,支架表面较薄的Ti薄膜附着状况较厚的Ti薄膜好;低沉积速率制备的TiO2薄膜在支架表面附着状况好于高沉积速率制备的TiO2薄膜;对于Ti/TiO2复合薄膜,Ti层厚度过大不利于Ti/TiO2复合薄膜在支架表面附着.     

Improved electrochemical performance of nitrocarburised stainless steel by hydrogenated amorphous carbon thin films for bone tissue engineering

In this study, hydrogenated amorphous carbon thin films, structurally similar to diamond‐like carbon (DLC), were deposited on the surface of untreated and plasma nitrocarburised (Nitrocarburizing‐treated) stainless steel medical implants using a plasma‐enhanced chemical vapour deposition method. The deposited DLC thin films on the nitrocarburising‐treated implants (CN+DLC) exhibited an appropriate adhesion to the substrates. The results clearly indicated that the applied DLC thin films showed excellent pitting and corrosion resistance with no considerable damage on the surface in comparison with the other samples. The CN+DLC thin films could be considered as an efficient approach for improving the biocompatibility and chemical inertness of metallic implants.Inspec keywords: tissue engineering, bone, biomedical materials, electrochemistry, amorphous state, carbon, hydrogen, thin films, plasma CVD, adhesion, corrosion resistance, surface hardeningOther keywords: electrochemical performance, plasma nitrocarburised stainless steel medical implants, hydrogenated amorphous carbon thin films, bone tissue engineering, plasma‐enhanced chemical vapour deposition method, adhesion, corrosion resistance, biocompatibility, chemical inertness, metallic implants, C:H     

NiTi合金上沉积氮化碳薄膜的力学和血液相容性研究

采用磁控溅射法在生物医用NiTi合金基体表面制备了Ti/CN_x（x≈0.26）梯度薄膜,并制备了Ti/类金刚石(DLC)以及Ti/TiN薄膜进行对比研究. 利用显微硬度计、划痕仪比较分析了上述各薄膜的力学性能,通过表面接触角法研究了薄膜的亲水性. 着重测试并分析了溶血率和血小板粘附行为,进而对薄膜的血液相容性进行评估. 结果表明：Ti/CN_x梯度薄膜与NiTi合金基底的结合牢固,结合力达到63.6N. Ti/CN_x薄膜硬度为23.01GPa,和Ti/TiN薄膜硬度相当,略高于Ti/DLC薄膜. 溶血率和血小板粘附试验表明,Ti/CN_x梯度薄膜能有效改善NiTi合金基底的亲水性和血液相容性,与Ti/TiN和Ti/DLC薄膜相比,Ti/CN_x梯度薄膜具有最小的溶血率,仅为1.12％,并且无论在血小板的粘附数量还是在血小板变形程度都最少,因此具有良好的血液相容性.     

金刚石薄膜用钢基表面过渡层研究进展

介绍了影响钢基表面金刚石薄膜沉积的不利因素,分析和综述了近10年来在提高金刚石薄膜质量以及薄膜粘结性等方面所采用的各种中间过渡层及其研究进展.过渡层可采用沉积法制备,也可采用表面改性法制备.过渡层可以制备成单层膜结构,也可制备成多层膜结构.对于不同的基底材料应选择不同的过渡层.