不同掺杂对类金刚石薄膜的影响

目的研究单掺Si和共掺Ag、Si对类金刚石薄膜的结构、摩擦学性能和耐腐蚀性能的影响。方法以高纯石墨靶、石墨与金属复合靶、Si靶作为靶材,采用射频增强磁控溅射技术制备不同掺杂种类的薄膜。通过XPS、拉曼光谱仪对薄膜的化学组成和结构进行分析,通过纳米压痕仪、摩擦磨损试验机、电化学工作站等,对薄膜的力学性能、摩擦学性能及耐腐蚀性能进行了系统研究。结果 Si元素单掺DLC会引起薄膜中sp~3C含量增加。Ag、Si共掺DLC后,由于Ag以金属相分布在薄膜中,并促进sp~2相的形成,导致sp~3C含量降低。掺杂元素后的DLC薄膜,硬度下降,但韧性提高,其中Ag、Si共掺的DLC薄膜的弹性恢复系数达到79%。此外,Ag、Si共掺DLC薄膜在多种气氛(Ar、O_2、N_2)中都具有优异的摩擦学性能,磨损寿命均超过30 min,其中在N_2气中的摩擦系数最低(0.1),并在NaCl溶液中的腐蚀电流密度比304不锈钢基体降低了近2个数量级,具有良好的耐腐蚀性。结论 Si与Ag共掺DLC薄膜较Si单掺薄膜具有更好的摩擦环境适应性和耐腐蚀性能。     

钽掺杂对多层Ta-DLC薄膜摩擦及腐蚀行为的影响

目的 解决316L不锈钢在苛刻海洋环境中易磨损、易腐蚀的问题。方法 采用中频磁控溅射技术在316L不锈钢上沉积了Ta/TaN/TaCN/Ta-DLC薄膜。通过扫描电子显微镜、拉曼光谱、X射线光电子能谱、X射线衍射、纳米压痕、往复摩擦磨损试验和电化学测试等手段,重点研究了DLC膜层中Ta元素掺杂含量对薄膜结构、组成成分、力学性能、摩擦学性能和耐腐蚀性能的影响规律。结果 随着Ta元素含量(原子数分数)从2.04%增到4.16%,薄膜中的sp³键含量呈现先升高后降低的趋势,当Ta原子数分数为3.60%时,薄膜中sp³键含量最高,且薄膜的硬度及弹性模量达到最大,分别为7.01 GPa和157.87 GPa。随着Ta元素含量的增加,薄膜的平均摩擦因数逐渐减小,在4.16%(原子数分数)时达到最小0.21。Ta元素含量对薄膜的结合力影响较小,且所有薄膜结合力总体在10 N左右。当Ta原子数分数为3.60%时,薄膜的腐蚀电流密度及钝化电流密度最小,分别为0.006 μA/cm²和0.63 μA/cm²,比其他薄膜的低1~2个数量级,并且薄膜电阻及电荷转移电阻最大,展现出最为优异的耐腐蚀性能。结论 Ta元素的掺杂提高了薄膜的耐摩擦性能,且适当的Ta元素掺杂能够提高Ta/TaN/TaCN/Ta-DLC薄膜的耐磨耐蚀性能。     

镍基涂层/碳基薄膜复合体系磨蚀行为

利用非平衡磁控溅射技术在316L不锈钢基底和316L不锈钢基底喷焊Ni60C涂层表面分别制备a-C、a-C:H、a-C:Cr3种类金刚石碳基(DLC)薄膜,对比分析了不同防护体系在5%H_2SO_4(质量分数)溶液中的耐磨蚀性能。结果表明:较单层DLC薄膜,Ni60C/DLC复合体系膜-基结合强度大幅提高,腐蚀磨损性能显著改善,其摩擦系数在0.05～0.14之间,腐蚀磨损率在0.66×10~(-8)～5.7×10~(-8) mm~3/N·m之间。Ni60C涂层作为硬质支撑层提高了薄膜的承载能力,且有效抑制了腐蚀摩擦过程中碳基(DLC)薄膜的石墨化进程,提高了Ni60C/DLC复合体系耐磨蚀性能。     

硼掺杂DLC薄膜在海水环境中的腐蚀磨损性能

目的 研究硼（B）掺杂对类金刚石（DLC）薄膜在人工海水介质中耐腐蚀性能和摩擦磨损性能的影响。方法 利用非平衡磁控溅射的方法,通过控制碳化硼靶材和石墨靶材电流,在304不锈钢基底表面沉积了一种无掺杂DLC薄膜和两种不同B含量的DLC薄膜（B的原子数分数分别为7.23%、13.27%）。采用扫描电子显微镜、拉曼光谱仪、纳米压痕仪、划痕仪、摩擦实验机对薄膜的化学成分、显微结构、纳米硬度、结合力及摩擦性能进行研究。通过测试薄膜在人工海水介质中的静态极化曲线和交流阻抗谱以及监测薄膜在摩擦前后和摩擦过程中的开路电位变化,来研究薄膜在人工海水中的摩擦学和耐腐蚀性能。结果 与未掺杂的DLC薄膜相比,掺杂B原子数分数为7.23%的DLC薄膜的硬度和弹性模量变化不明显,但ID/IG增大,与基底的结合力增大到36 N（无掺杂DLC薄膜为20 N）,自腐蚀电位升高,自腐蚀电流密度减小,极化电阻增大,并且在人工海水介质中的摩擦系数降低了10.7%,磨损量降低了37.0%,开路电位大幅升高。掺杂B原子数分数为13.27%的DLC薄膜的摩擦学及耐蚀性能则大幅度下降。结论 在DLC薄膜中掺杂适量的B有助于提高DLC薄膜在人工海水介质中的耐腐蚀性能和磨蚀性能。     

Structure, scratch resistance and corrosion performance of nickel doped diamond-like carbon thin films

Nickel doped diamond-like carbon (DLC:Ni) thin films were fabricated on conductive p-Si (100) substrates with DC magnetron sputtering deposition by varying DC power applied to a Ni target. The bonding structure, surface morphology, scratch resistance and corrosion resistance of the DLC:Ni films were studied using X-ray photoelectron spectroscopy (XPS), micro-Raman spectroscopy, atomic force microscopy (AFM), micro-scratch test, potentiodynamic polarization test and open circuit potential measurement. The results indicated that the corrosion resistance of the DLC:Ni films in a 0.6 M NaCl solution decreased with increased Ni content in the films though the films showed good passivation behavior in the NaCl solution.     

Zr掺杂类金刚石薄膜摩擦性能及耐腐蚀性能的影响

目的改善不锈钢摩擦性能及耐腐蚀性能。方法通过线性阳极层离子源辅助非平衡磁控溅射法,制备了不同Zr含量的类金刚石(DLC)薄膜,采用扫描电子显微镜、拉曼光谱仪、纳米硬度仪、高温销盘磨损仪、电化学工作站,对薄膜的化学成分、显微结构、纳米硬度、薄膜摩擦性能及耐腐蚀性能进行测试研究。结果随着Zr靶功率的增大,Zr含量线性增加。Zr含量从4.9%增加至16.3%时,I_D/I_G增大,薄膜硬度从12.1 GPa逐渐下降至8.4 GPa;Zr含量增大至21.2%时,I_D/I_G减小,薄膜硬度增大至11.4 GPa。涂镀类金刚石薄膜的不锈钢基体比无涂层的不锈钢基体有更低的摩擦系数,更好的耐磨损性能。Zr掺杂DLC薄膜的最小摩擦系数为0.07。Zr含量从4.9%增加至16.3%,DLC薄膜的耐腐蚀性能减弱;Zr含量继续增加,DLC薄膜的耐腐蚀性能增强。当Zr含量不大于11.9%时,沉积Zr掺杂DLC膜的不锈钢基体的耐腐蚀性能比不锈钢基体的更强。结论 Zr含量不大于11.9%时,Zr掺杂类金刚石薄膜既可以有效地改善不锈钢基体的摩擦磨损性能,又可以大幅提高耐腐蚀性能。     

射频辉光放电等离子体辅助化学气相沉积法制备类金刚石碳膜工艺与性能表征

使用射频辉光放电等离子体辅助化学气相沉积技术（简称RFGDPECVD）在玻璃载玻片表面沉积类金刚石薄膜。用原子力显微镜（AFM）、摩擦试验仪、划痕试验机测定了其表面形貌、耐磨性及附着性。采用X射线光电子能谱（XPS）、分光光度计对两种气源（C4H10、C2H2）制备的DLC薄膜微观组成和透光率进行了检测和对比。结果表明：DLC薄膜的表面光滑、平整,表面粗糙度随沉积时间的增加单调递增;耐磨性及附着性优良;与C4H10相比使用C2H2作为碳源气体可以得到较高Sp^3含量和较低Sp^1含量的DLC膜;C2H2制备DLC薄膜的透光率低于C4H10;同一种碳源气体,反应流量比例越小,则DLC薄膜的透光性越好。     

Surface-engineered metal-on-metal bearings improve the friction and wear properties of local area contact in total joint arthroplasty

Metal-on-metal articulating total joint arthroplasty has the potential to eliminate polyethylene-wear-induced osteolysis and aseptic loosening around the prosthesis. Metal surface coatings, however, are subject to delamination in areas of local contact. Various studies have been conducted to reduce metal wear debris and corrosion by introducing surface treatments.In this study we applied carbon ion implantation (CII) and diamond-like carbon (DLC) films to a cobalt-chrome alloy substrate by plasma source ion implantation. Once the films were prepared, we put them through simple geometry wear tests under high contact pressure (an average load of 1030 MPa) to establish the tribological properties during the phase of local contact that leads to severely increased wear in total joint arthroplasty. The CII-coated bearings showed less wear, lower friction coefficients, and higher resistance to catastrophic damage compared to uncoated Co-Cr alloy and DLC couples, even under high contact pressure. The CII-coated surface offers potential advantages as a hard coating for articulating joints.     

Cr基过渡层对钛合金表面类金刚石薄膜摩擦学性能的影响

采用磁控溅射技术在钛合金(Ti6Al4V)表面制备Cr、Cr/Cr N和Cr/Cr N/Cr NC过渡层结构的类金刚石(DLC)薄膜。采用扫描电子显微镜、拉曼光谱仪与原子力显微镜分析薄膜的结构和表面形貌,利用纳米压痕仪、薄膜内应力测试仪、划痕测试仪、摩擦试验机和二维轮廓仪研究薄膜的硬度、内应力、结合力和摩擦磨损性能。结果表明:随着Cr基梯度过渡层的引入,DLC薄膜的内应力逐渐下降,结合力逐渐上升。Cr/Cr N/Cr NC/DLC薄膜具有优异减摩抗磨性能,摩擦因数和磨损率低至0.09±0.02和(1.89±0.15)×10-7 mm3/N·m。试验结果对钛合金表面高性能DLC薄膜制备及应用具有一定的参考价值和指导意义。     

Tribological behavior under aggressive environment of diamond-like carbon films with incorporated nanocrystalline diamond particles

Nanocrystalline diamond (NCD) particles are incorporated into diamond-like carbon (DLC) films in order to prevent NCD-DLC electrochemical corrosion. In the current paper, tribological behavior of NCD-DLC films under aggressive solutions is discussed. DLC and NCD-DLC coated steel disks and coated and uncoated steel ball were used under rotational sliding conditions. Raman scattering spectroscopy analyzed the film's atomic arrangements and graphitization level before and after tribocorrosion tests. The NCD-DLC films confirmed to be effective in the corrosion wear resistance under corrosive environments. The results pointed that NCD-DLC films are promising corrosion protective coating in aggressive solutions for many applications.     

Properties of Zr-ZrC-ZrC/DLC gradient films on TiNi alloy by the PIIID technique combined with PECVD

The Zr-ZrC-ZrC/DLC gradient composite films were prepared on TiNi alloy by the techniques combined plasma immersion ion implantation and deposition (PIIID) and plasma enhanced chemical vapor deposition (PECVD). With this method, the Zr-ZrC intermixed layers can be obtained by the ion implantation and deposition before the deposition of the ZrC/DLC composite film. In our study, an optimal gradient composite film has been deposited on the NiTi alloys by optimizing the process parameters for implantation and deposition. The surface topography was observed through AFM and the influence of the deposition voltage on the surface topography of the film was investigated. XPS results indicate that on the outmost layer, the Zr ions are mixed with the DLC film and form ZrC phase, the binding energy of C 1s and the composition concentration of ZrC depend heavily on the bias voltage. With the increase of bias voltage, the content of ZrC and the ratio of sp³/sp² firstly increases, reaching a maximum value at 200 V, and then decreases. The nano-indentation and friction experiments indicate that the gradient composite film at 200 V has a higher hardness and lower friction coefficient compared with that of the bare NiTi alloy. The microscratch curve tests indicate that gradient composite films have an excellent bonding property comparing to undoped DLC film. Based on the electrochemical measurement and ion releasing tests, we have found that the gradient composite films exhibit better corrosion resistance property and higher depression ability for the Ni ion releasing from the NiTi substrate in the Hank's solution at 37°C.     

DLC基纳米多层膜摩擦学性能的研究进展与展望

类金刚石(DLC)薄膜是一种良好的固体润滑剂,能够有效延长机械零件、工具的使用寿命。DLC基纳米多层薄膜的设计是耐磨薄膜领域的一项研究热点,薄膜中不同组分层具备不同的物理化学性能组合,能从多个角度(如高温、硬度、润滑)进行设计来提升薄膜力学性能、摩擦学性能以及耐腐蚀性能等。综述了DLC多层薄膜的设计目的与研究进展,以金属/DLC基纳米多层膜、金属氮化物/DLC基纳米多层膜、金属硫化物/DLC基纳米多层膜以及其他DLC基纳米多层膜为主,对早期研究成果及现在的研究方向进行了概述。介绍了以上几种DLC基纳米多层膜的现有设计思路(形成纳米晶/非晶复合结构、软/硬交替沉积,诱导转移膜形成,实现非公度接触)。随后对摩擦机理进行了分析总结:1)层与层间形成特殊过渡层,提高了结合力;2)软/硬的多层交替设计,可以抵抗应力松弛和裂纹偏转;3)高接触应力和催化作用下诱导DLC中的sp³向sp²转化,形成高度有序的转移膜,从而实现非公度接触。最后对DLC基纳米多层膜的未来发展进行了展望。     

A critical review of diamond like carbon coating for wear resistance applications

In recent years innovation in carbon based materials have encouraged both researchers as well as industrialists to develop materials/composites with improved tribological properties. Researchers have been fascinated to develop diamond like carbon (DLC) or carbon nanotubes (CNTs) reinforced coatings to their good corrosion resistance, excellent wear resistance, good adhesion strength, and self -lubricious nature. The present review article is mainly focused on various techniques employed in order to process DLC/CNTs coatings as well as provide a summary of DLC/CNTs deposition on different substrates. The present study includes major types, properties and tribological behavior of carbon based materials and mechanisms involved in coating deposition. The study also discusses that deposition of DLC/CNTs coatings on the substrate materials enhances the wear, corrosion and mechanical properties of the substrate.     

Influence of carbon sputtering power on structure, corrosion resistance, adhesion strength and wear resistance of platinum/ruthenium/nitrogen doped diamond-like carbon thin films

Platinum/ruthenium/nitrogen doped diamond-like carbon (PtRuN-DLC) thin films were deposited on conductive p-Si substrates using a DC magnetron sputtering deposition system by varying carbon sputtering power. The chemical composition, bonding structure, surface morphology and adhesion strength of the PtRuN-DLC films were investigated using X-ray photoelectron spectroscopy (XPS), micro-Raman spectroscopy, atomic force microscopy (AFM), and micro-scratch test, respectively. The corrosion behavior of the PtRuN-DLC films in a 0.1 M NaCl solution was investigated using potentiodynamic polarization test. The corrosion results indicated that the corrosion resistance of the PtRuN-DLC films increased with increased carbon sputtering power probably due to decreased porosity level in the films with increased growth rate and film thickness. The wear performance of the PtRuN-DLC films was investigated with a ball-on-disc micro-tribometer. It was found that the increased carbon sputtering power significantly improved the wear performance of the films by enhancing the adhesion strength of the films.     

Duplex diamond-like carbon film fabricated on 2Cr13 martensite stainless steel using inner surface ion implantation and deposition

A duplex plasma immersion ion implantation and deposition (PIIID) process, involving carbon ion implantation and diamond-like carbon (DLC) film deposition, is proposed to treat the inner surface of a tube. Samples of 2Cr13 martensite stainless steel were placed inside the tube to investigate the performance of the films. Carbon ion implantation was finished by biasing the tube with a high voltage, and the DLC film deposition was obtained by biasing the tube with a medium voltage. Raman spectrum, ball-on-disc, indentation and scratch tests were used to investigate the structure, tribological property and adhesion strength of the as-deposited films. The Raman spectrum shows that the sp³ bonding is formed in the as-synthesized film. Tribological and scratch test results reveal that the duplex DLC coating with the implantation time of 1 h has the largest adhesion strength and the best wear resistance.     

Characterization and analysis of DLC films with different thickness deposited by RF magnetron PECVD

Diamond-like carbon (DLC) films have excellent mechanical and chemical properties similar to those of crystalline diamond giving them wide applications as protective coatings. So far, a variety of methods are employed to deposit DLC films. In this study, DLC films with different thicknesses were deposited on Si and glass substrates using RF magnetron PECVD method with C4H10 as carbon source. The bonding microstructure, surface morphology and tribological properties at different growing stages of the DLC films were tested. Raman spectra were deconvoluted into D peak at about 1370 cm-1 and G peak around 1590 cm-1, indicating typical features of the DLC films. A linear relationship between the film thickness and the deposition time was found, revealing that the required film thickness may be obtained by the appropriate tune of the deposition time. The concentration of sp3 and sp2 carbon atoms in the DLC films was measured by XPS spectra. As the films grew, the sp3 carbon atoms decreased while sp2 atoms increased. Surface morphology of the DLC films clearly showed that the films were composed of spherical carbon clusters, which tended to congregate as the deposition time increased. The friction coefficient of the films was very low and an increase was also found with the increase of film thickness corresponding to the results of XPS spectra. The scratch test proved that there was good bonding between the DLC films and the substrates.     

NiTi合金表面类金刚石膜的表面特征和腐蚀行为

采用等离子浸没离子注入和沉积（PIIID）法以C2H2为等离子源对NiTi合金进行表面改性。利用Raman光谱分析膜层结构。采用原子力显微镜和纳米压痕分析涂层前后NiTi的表面形貌和力学性能。利用电化学测试、扫描电镜和原子吸收光谱测试涂层前后基体的耐腐蚀性和Ni离子析出。结果表明：NiTi合金表面的膜层是类金刚石（DLC）；经过PIIID处理后，基体表面的粗糙度降低；纳米硬度得到提高；耐腐蚀性能获得明显改善；Ni离子析出得到有效的抑制。     

Improving wear resistance and corrosion resistance of AZ31 magnesium alloy by DLC/AlN/Al coating

A novel protective coating, consisting of three layers (top: diamond-like carbon, middle: aluminum nitride, bottom: aluminum), was deposited on the surface of AZ31 magnesium alloy layer by layer. Nano-indenter, electrochemical system and tribological tester were performed to investigate the hardness, wear resistance and corrosion resistance of the coated AZ31 magnesium alloy, respectively. The DLC/AlN/Al coating improved the magnesium alloy's surface hardness and reduced its friction coefficient, which consequently induced a great improvement of the magnesium alloy's wear resistance. Furthermore, the corrosion resistance of the AZ31 magnesium alloy with the DLC/AlN/Al coating was also enhanced with the corrosion current density decreasing from 2.25 × 10⁻⁵ A/cm² to 1.28 × 10⁻⁶ A/cm² in a 3.5 wt.% NaCl solution.     

钛合金表面大气压等离子体枪制备类金刚石薄膜

在大气下,采用大气压介质阻挡放电(DBD)等离子体枪在低温下(350℃),以甲烷为单体,氩气为工作气体,在Ti6Al4V钛合金表面制备一层类金刚石薄膜(DLC),以期改善钛合金表面摩擦学性能。利用激光拉曼(Raman)光谱和X射线光电子能谱(XPS)分析了所制备DLC薄膜的结构;利用扫描电子显微镜(SEM)观察DLC薄膜的表面形貌;利用划痕仪测量了DLC薄膜与基体的结合力;利用球-盘摩擦磨损实验仪对DLC薄膜的耐磨性能进行了研究。结果表明:在本实验工艺条件下沉积的类金刚石薄膜厚度约为1.0μm,薄膜均匀且致密,表面粗糙度Ra为13.23nm。类金刚石薄膜与基体结合力的临界载荷达到31.0N。DLC薄膜具有优良的减摩性,Ti6Al4V表面沉积DLC薄膜后摩擦系数为0.15,较Ti6Al4V基体的摩擦系数0.50明显减小,耐磨性能得到提高。     

钢表面离子束改性类金刚石膜层性能

离子束沉积类金刚石膜是钢表面改性的一项新技术。类金刚石改性膜层显微硬度和表面电阻率在特定轰击能量下出现峰值 ;双离子束轰击混合界面可以提高膜层显微硬度 ,并使峰值向低能量方向偏移 ,而且大大增强膜基结合强度。在大气环境中 ,改性膜层对钢的摩擦系数达到 0 0 80～ 0 1 80 ,在摩擦过程中起减摩作用。另一方面 ,类金刚石膜层显著提高钢的耐磨性 ,试验表明 ,40Cr钢表面镀膜后其磨损量是镀膜前的 1 /2 74。类金刚石膜由于使 2Cr1 3不锈钢在 3 5%NaCl溶液中的自然电位Ecorr和点蚀击穿电位Eb 增大 ,因而明显增强钢的抗点蚀能力。