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。     

常用碳基固体润滑薄膜的研究现状与展望

首先从碳基固体润滑薄膜的应用需求与成本效益出发,探讨了研究碳基固体润滑薄膜的迫切要求和重要意义,然后对类金刚石(DLC)薄膜、类富勒烯(FLC)薄膜及石墨烯薄膜三类最常用的碳基固体润滑薄膜的研究现状进行了较详细的介绍。其中,重点介绍了DLC薄膜的三种减摩抗磨机理,探讨了掺杂元素改性对DLC薄膜硬度、摩擦系数和磨损率等多个方面的影响,并指出外部因素(基体材料、过渡层和应用环境等)对DLC薄膜性能的重要作用。探讨了掺氢、掺氟和掺氮对FLC薄膜构性转变和摩擦学性能的影响。总体来说,氟掺杂导致FLC结构变化,并显著改变薄膜硬度;掺氮会诱导类富勒烯微结构的增加;掺氢FLC薄膜热处理后可达到超润滑状态。总结了石墨烯薄膜制备工艺的发展、石墨烯基复合薄膜的摩擦学性能和石墨烯薄膜在不同基体材料的应用。最后,指出了碳基润滑薄膜领域亟待解决的关键难题,并对未来的研究方向做出了预测。     

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。     

不同过渡层对DLC薄膜力学性能和摩擦学性能的影响

薄膜与基体间的界面结合性能是决定薄膜性能发挥的关键要素。针对类金刚石薄膜(DLC)在硬质合金上结合力差的问题,采用线性阳极离子束复合磁控溅射技术在硬质合金YG8基体上设计制备了单层W过渡层、WC过渡层、双层W过渡层和三层W过渡层4种不同W过渡层的DLC薄膜,探讨了不同过渡层对DLC薄膜力学和摩擦学性能的影响。结果表明:不同过渡层结构的DLC薄膜结构致密,界面柱状生长随着层数增加及过渡层厚度的降低而打断,有利于改善薄膜的韧性。当为三层W过渡层时,DLC薄膜的断裂韧性达到最大值6.44 MPa·m1/2;与单层W过渡层相比,薄膜硬度有小幅下降,但薄膜内应力降低了55%,且膜/基匹配性更佳,结合强度高达85N,此时薄膜具有较低的摩擦因数和磨损率,表现出比较优异的抗磨减摩性能。     

Influence of substrate surface topography in the deposition of nanostructured diamond-like carbon films by high density plasma chemical vapor deposition

In this work, we have studied the influence of the substrate surface condition on the roughness and the structure of the nanostructured DLC films deposited by High Density Plasma Chemical Vapor Deposition. Four methods were used to modify the silicon wafers surface before starting the deposition processes of the nanostructured DLC films: micro-diamond powder dispersion, micro-graphite powder dispersion, and roughness generation by wet chemical etching and roughness generation by plasma etching. The reference wafer was only submitted to a chemical cleaning. It was possible to see that the final roughness and the sp³ hybridization degree strongly depend on the substrate surface conditions. The surface roughness was observed by AFM and SEM and the hybridization degree of the DLC films was analyzed by Raman Spectroscopy. In these samples, the final roughness and the sp³ hybridization quantity depend strongly on the substrate surface condition. Thus, the effects of the substrate surface on the DLC film structure were confirmed. These phenomena can be explained by the fact that the locally higher surface energy and the sharp edges may induce local defects promoting the nanostructured characteristics in the DLC films.     

Ni-P/Ti/DLC多层膜的摩擦磨损性能

目的研究摩擦速度、载荷及加热温度对Ni-P/Ti/DLC多层膜摩擦磨损性能的影响。方法用化学镀镍磷工艺在模具钢基体表面镀上Ni-P层作切削层,采用过滤阴极真空电弧(FCVA)技术分别沉积Ti过渡层和DLC保护层。通过摩擦磨损实验,评价该多层膜的摩擦磨损性能。利用纳米压痕测试和拉曼光谱检测,研究该多层膜在不同加热温度下的硬度、弹性模量和结构成分。利用扫描电镜及表面轮廓仪分别对该多层膜的磨痕形貌和横截面轮廓进行分析。结果随着摩擦速度的增大,Ni-P/Ti/DLC多层膜的摩擦系数呈下降趋势,磨损率和磨损体积呈先减后增的趋势。不同载荷下的摩擦系数变化幅度较小,磨损率和磨损体积随着载荷的增大呈增加的趋势。随着加热温度的升高,摩擦系数呈下降趋势,磨损率和磨损体积呈先增后减的趋势。此外,随着加热温度的升高,多层膜表层DLC膜中石墨相逐渐增多,硬度和弹性模量随之呈先增后减的趋势。结论较高摩擦速度下,多层膜表层DLC膜石墨化趋势增强,摩擦系数变化幅度较大,且表面磨痕宽度和深度显著增加,磨损加剧。多层膜中软质的Ti金属层和硬质的DLC层,能有效提高多层膜在高载荷下的摩擦磨损性能。随着加热温度的升高,多层膜表层DLC膜中石墨相逐渐增多,摩擦过程更易生成转移膜。     

Deposition and properties of Al-containing diamond-like carbon films by a hybrid ion beam sources

Metal incorporation is one of the most effective methods for relaxing internal stress in diamond-like carbon (DLC) films. It was reported that the chemical state of the incorporated metal atoms has a significant influence on the film internal stress. The doped atoms embedding in the DLC matrix without bonding with C atoms can reduce the structure disorder of the DLC films through bond angle distortion and thus relax the internal stress of the films. In present paper, Al atoms, which are inert to carbon, were incorporated into the DLC films deposited by a hybrid ion beams system comprising an anode-layer ion source and a magnetron sputtering unit. The film composition, microstructure and atomic bond structure were characterized using X-ray photoelectron spectroscopy, transmission electron microscopy and Raman spectroscopy. The internal stress, mechanical properties and tribogoical behavior were studied as a function of Al concentration using a stress-tester, nanoindentation and ball-on-disc tribo-tester, respectively. The results indicated that the incorporated Al atoms were dissolved in the DLC matrix without bonding with C atoms and the films exhibited the feature of amorphous carbon. The structure disorder of the films tended to decrease with Al atoms incorporation. This resulted in the distinct reduction of the internal stress in the films. All Al-DLC films exhibited a lower friction coefficient compared with pure DLC film. The formation of the transfer layer and the graphitization induced by friction were expected to contribute to the excellent friction performance.     

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。     

类金刚石薄膜的摩擦性能及其应用

首先从成键结构的角度分析了DLC薄膜摩擦性能的由来,然后分别从DLC薄膜的沉积工艺(包括制备方法、气源种类和掺杂元素)、摩擦环境条件和基底材料选择等三方面入手,讨论了影响DLC薄膜摩擦性能的主要因素及其影响规律。经过总结发现,通过调节DLC薄膜的沉积工艺可以改变DLC薄膜中sp~2杂化碳的含量以及氢的含量,进而影响DLC薄膜的摩擦性能;真空、惰性气体和低湿环境有利于获得更好的摩擦效果;过渡层和偏压有利于提高DLC薄膜与基底之间的附着力,其摩擦性能也会得到提升。最后对DLC薄膜在机械加工及耐磨器件、光学和电子保护以及生物医学领域的应用进行了综述,并对应用过程中存在的两大问题——DLC薄膜的内应力和热稳定性进行了分析,归纳了一些具体的解决方案,并对DLC薄膜的发展趋势进行了展望。     

Ti/Al过渡层对共掺杂类金刚石薄膜性能的影响

目的研究Ti/Al过渡层对不同溅射电流下的Ti/Al共掺杂DLC薄膜的成分、结构、机械性能和结合力的影响。方法采用线性离子束复合磁控溅射技术在316L基底上沉积含有Ti/Al过渡层的Ti/Al共掺杂DLC薄膜,利用场发射扫描电子显微镜(SEM)、X射线光电子能谱仪(XPS)、高分辨透射电镜(HRTEM)及共聚焦激光拉曼光谱仪分析了薄膜的界面形貌及键态结构。采用辉光放电光谱仪对样品成分进行深度分析,纳米压痕仪测量薄膜硬度及弹性模量,划痕测试系统测量膜基结合力,残余应力仪测量薄膜内应力。结果与未添加过渡层相比,添加Ti/Al过渡层对薄膜的结构和机械性能影响较小,且均在溅射电流为2.5 A时有最优的机械性能;然而,溅射电流为2.5 A时,添加过渡层使结合力从54.5 N提高到了67.2 N,提高了19%,残余应力从1.28 GPa降低到了0.25 GPa,降低了80%。结论 Ti/Al过渡层可缓解因DLC薄膜和基体的晶格匹配差异和膨胀系数不同而导致的高界面应力。在薄膜与基底界面,过渡层呈现典型柱状晶结构,可促进膜基界面间的机械互锁,显著改善薄膜与基体之间的结合力而不损伤其机械性能。     

XTEM STUDY ON ION PLATED STAINLESS STEEL MULTI LAYER FILMS

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Characteristics of phosphorus-doped diamond-like carbon films synthesized by plasma immersion ion implantation and deposition (PIII and D)

Plasma immersion ion implantation and deposition (PIII and D) is an effective approach to synthesize high quality thin films for different industrial applications. This dual implantation and deposition process can produce a graded layer that mitigates delamination and poor adhesion. In this work, phosphorus-doped diamond-like carbon (DLC) films were synthesized by PIII and D. Thin DLC films with various phosphorus concentrations were produced by using different experimental parameters. The chemical composition was determined by X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS). Micrographs obtained by cross-sectional transmission electron microscopy (X-TEM) reveal good adhesion between the films and substrates. The biocompatibility was evaluated using platelet adhesive tests. The results show that the sample doped with an optimal amount of phosphorus exhibits less platelet adhesive and activation, and the overall results are better than that observed on low-temperature isotropic pyrolytic carbon (LTIC). Phosphorus-doped DLC films thus have potential applications in blood contacting medical devices.     

铝合金表面沉积类金刚石薄膜的研究进展

类金刚石(Diamond-like Carbon,DLC)薄膜因其高硬度、良好的化学惰性以及优异的摩擦性能等优势,有望成为一种理想的铝合金表面防护涂层。对比了物理气相沉积(Physical vapor deposition,PVD)技术制备DLC改性材料与传统铝合金表面改性技术的优劣,概述了DLC薄膜在提升铝合金表面力学性能、减摩抗磨方面取得的最新成果,以及在复杂服役工况下面临的抗塑性变形差、易发生结合失效等瓶颈性问题。通过分析铝合金基体上生长高性能DLC薄膜的不利因素,指出界面化学结合强度低、薄膜残余应力大以及软基体/硬质薄膜的结构体系限制是导致上述问题产生的主要原因。在此基础上,重点综述了国内外研究学者为提高铝合金表面沉积DLC薄膜的膜基结合力所采取的有效措施及结果,包括:通过基体前处理增强基体力学性能与改善宏观表面缺陷;采用PVD或其他表面处理方法制备一层或多层的中间过渡层,缓解DLC薄膜与铝合金基体结构、性能之间的差异;调控DLC薄膜组分与结构以降低残余应力。最后展望了在铝合金基体表面制备DLC防护薄膜的发展趋势。     

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。     

Plasma immersion ion implantation induced improvements of mechanical properties, wear resistance, and adhesion of diamond-like carbon films deposited on tool steel

Nitrogen-rich layers are formed on the surface of JIS-SKH51 tool steel substrates using the plasma immersion ion implantation (PIII) technique. An unbalanced magnetron sputtering (UBMS) system is then used to coat the steel substrates with diamond-like carbon (DLC) films of various thicknesses. The adhesive strength and wear resistance of the DLC films are then examined by performing nanoscratch and nanowear tests. Finally, the microstructures of the DLC films are analyzed using TEM and Raman spectroscopy. The nanoindentation test results show that the PIII treatment yields an effective improvement in both the hardness and the Young's modulus of the SKH51 substrates. Moreover, cross-sectional observations show that the implantation depth and microstructure of the nitrogen-rich surface layer are dependent on the nitrogen/hydrogen flow ratio used in the PIII process. The nanoscratch test results show that the PIII treatment improves the adhesion of the DLC film to the steel substrate. Furthermore, the Raman spectroscopy results indicate that the use of hydrogen in the PIII process limits the increase in the I(D)/I(G) ratio by increasing the DLC film thickness. Finally, the nanowear test results show that the deposition of a DLC coating with a sufficient thickness yields a significant improvement in the wear resistance of the steel substrate.     

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。     

X-ray reflectivity studies on DLC films deposited by microwave ECR CVD: Effect of substrate bias

Diamond like carbon (DLC) films were deposited at room temperature on Si (111) substrates by microwave electron cyclotron resonance (ECR) plasma chemical vapor deposition (CVD) process using plasma of methane diluted with argon gas. During deposition, dc self bias (− 25 V to − 200 V) on substrate was varied by application of RF power to the substrate. The influence of substrate bias on density of the deposited films was studied by X-ray reflectivity (XRR). The results from these measurements are further correlated with the results from UV and visible Raman spectroscopy. DLC film is modeled as a structure having three different layers such as low density surface, bulk and interface with the substrate. This three-layer model is used to fit the measured XRR data to evaluate the surface, interface and interlayer roughness, thickness and density of these films. The surface roughness obtained from XRR is correlated with the results from Atomic Force Microscopy (AFM) measurements. The observed results are explained based on the subplantation model for DLC film growth.     

高速钢W18Cr4V离子渗氮层组织对TiN膜与基体结合强度的影响

采用Ｗ１８Ｃｒ４Ｖ高速钢进行离子渗氮－ＰＥＣＶＤ ＴｉＮ复合处理,运用透射电子显微镜、Ｘ射线衍射仪和光学显微镜研究试样的表层组织结构。采用连续压入法研究ＴｉＮ膜与基体的结合强度,结果表明,离子渗氮能够提高膜基结合强度,通过分析渗氮层与膜－基界面的组织特点,认为ＴｉＮ膜在渗氮层上一些与其具有相同或相似晶体结构的氮化物上外延生长,以及强度较高的渗氮层对膜的支撑是基体渗氮提高膜－基结合强度的两大因素。     

High adhesion of diamond-like carbon thin film to an aluminum alloy achieved by substrate sputtering and redeposition method

A novel technique to improve the adhesion of a diamond-like carbon (DLC) film to an Al alloy was demonstrated in this study. DLC films were deposited by diode rf bias sputtering. The Al component in the substrate was initially deposited on a graphite target during the sputter-cleaning of the substrate. Then the graphite target and the deposited Al were simultaneously sputtered to form an interface layer between the DLC film and the substrate in the early stage of deposition. We call this method substrate sputtering and redeposition (SSRD), which enhanced the antiwear lifetime of DLC/Al alloy samples. X-ray photoelectron spectroscopy clarified that a thicker mixed layer of Al and C was formed around the interface in the case of a longer substrate sputtering duration in the SSRD method. This interface structure could account for the strong adhesion of the DLC film to the substrate and the reduced delamination of the film obtained using the SSRD method.     

Microstructural, mechanical and tribological properties of tungsten-gradually doped diamond-like carbon films with functionally graded interlayers

A series of tungsten-gradually doped diamond-like carbon (DLC) films with functionally graded interlayer were prepared using a hybrid technique of vacuum cathodic arc/magnetron sputtering/ion beam deposition. With ‘compositionally graded coating’ concept, the deposition of wear-resistant carbon-based films with excellent adhesion to metallic substrate was realized. In the films, a functionally graded interlayer with layer sequence of Cr/CrN/CrNC/CrC/WC was first deposited onto the substrate, and then, a DLC layer doped with gradually decreasing content of W was coated on. The W concentration gradient along depth of the film was tailored by adjusting the W target current and deposition time. The characterized results indicate that the microstructural, mechanical and tribological properties of these films show a significant dependence on the W concentration gradient. A high fraction of W atom in carbon matrix can promote the formation of sp² sites and WC_1 − x nanoparticles. Applying this coating concept, strongly adherent carbon films with critical load exceeding 100 N in scratch test were obtained, and no fractures or delaminations were observed at the end of the scratched trace. The hardness was found to vary from 13.28 to 32.13 GPa with increasing W concentration. These films also presented excellent tribological properties, especially significantly low wear rate under dry sliding condition against Si₃N₄ ball. The optimum wear performance with friction coefficient of 0.19 and wear rate of 8.36 × 10⁻⁷ mm³/Nm was achieved for the tungsten-gradually doped DLC film with a graded W concentration ranging from 52.5% to 17.8%. This compositionally graded coating system might be a potentially promising candidate for wear-resistant carbon-based films in the demanding tribological applications.