光学窗口用低应力类金刚石薄膜

类金刚石(DLC)薄膜自身具备较好的光学性能,从而在红外光学窗口具有极大的应用前景,但其残余应力决定了薄膜的稳定性。基于射频磁控溅射技术,在双面抛光Si (100)基底上,采用射频功率350 W、本底真空2.0×10^-7Pa、溅射气压7.1×10^-3Pa、氩气流量50 mL/min等工艺,沉积厚度为2.5785μm、残余应力为0.9 GPa的DLC薄膜,膜基结合力良好。Raman光谱测试显示薄膜具备DLC薄膜特性。轮廓仪测试的S_q为0.957 nm,样品表层较为平滑。利用剥离法,用3M胶带检测薄膜附着力等级达到3B,未出现薄膜脱离现象。     

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.     

微波ECR等离子体源增强非平衡磁控溅射DLC膜的制备与表征

介绍了微波ECR等离子体源增强非平衡磁控溅射设备的结构和工作原理,详细叙述了利用该设备制备类金刚石膜的过程。Raman光谱证实了薄膜的类金刚石特性;采用原子力显微镜(AFM)观察薄膜的微观表面形貌,均方根粗糙度大约为1．9nm,结果表明薄膜表面非常光滑;利用CERT微摩擦计进行摩擦、磨损和划痕实验,薄膜的平均摩擦系数较小,大约为0．175;DLC膜和Si衬底磨损情况的扫描电镜图片相对比,可以看到DLC膜的磨痕小的多,说明薄膜有较好的耐磨性能;划痕测试结果表明制备薄膜临界载荷大约为40mN。     

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.     

Preparation of diamond-like carbon films by cathodic micro-arc discharge in aqueous solutions

Diamond-like carbon films (DLC) and silicon doped diamond-like carbon films were deposited on Ni substrate by cathodic micro-arc discharge at room temperature in aqueous solutions. The deposit potential was 130 V. The structure of the films was characterized by a scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Raman spectra and XPS analysis demonstrated that the films were diamond-like carbon clearly. SEM observation showed that the DLC films were uniform and the thickness was about 200 nm. Potentiodynamic polarization curve indicated the corrosion resistance of the Ni substrate was markedly improved by DLC films.     

An examination of trace surface on diamond-like carbon film after ball-on disk measurement

Hydrogenated diamond-like carbon (DLC) films were prepared by the radio frequency plasma-enhanced chemical vapor deposition method on silicon substrates using methane (CH₄) and hydrogen (H₂) gas. The wear track on DLC films was examined after the ball-on disk (BOD) measurement with a Raman mapping method. The BOD measurement of DLC films was performed for 1 to 3 h with a 1-hour step time. The sliding traces on the hydrogenated DLC film after the BOD measurement were also observed using an optical microscope. The films synthesized in this work had a very low friction coefficient (about 0.06) and were adhered very well without peeling off during the BOD measurement even with very thin thickness. Energy dispersive X-ray spectra show the decrease of C atomic % and the increase of O atomic % according to the sliding time. The novel Raman mapping method effectively showed the graphitization of DLC films according to the sliding time.     

Formation mechanisms of zinc,molybdenum, sulfur and phosphorus containing reaction layers on a diamond-like carbon (DLC) coating

Diamond-like carbon (DLC) coatings are nowadays successfully applied on industrial components like pistons, piston rings and bearings in lubricated tribological contacts due to friction and wear reducing effects. In contradiction thereto, todays lubricants and additives are designed for tribological steel/steel contacts, whereby the knowledge on tribochemical layer formation on steel surfaces is comprehensive in contrast to the physical-chemical interactions between diamond-like carbon coatings, lubricants and additives. Therefore the formation mechanisms of zinc, molybdenum, sulfur and phosphorus containing reaction layers on a zirconium modified diamond-like carbon coating a-C : H : Zr (ZrC_g) in lubricated tribological contacts were analyzed by means of pin-on-disc (PoD) tribometer by varying the distances from s = 200 m–3,000 m under boundary and mixed friction conditions at T = 90 °C and a contact pressure p = 1,300 MPa regarding the application of diamond-like carbon coatings on gears. The base lubricant poly-alpha-olefin (PAO) was formulated using the anti-wear (AW) and extreme pressure (EP) additive zinc dialkyldithiophosphate (ZnDTP) and the friction modifier (FM) additive molybdenum dialkyldithiophosphate (MoDTP). The chemical composition of the tribochemical reaction layers by means of and Raman spectroscopy and x-ray photoelectron spectroscopy (XPS) as well as for the thickness differ significantly by varying the additivation.     

Structure and Mechanical Performance of Nitrogen Doped Diamond-like Carbon Films

Nitrogen doped diamond-like carbon （DLC：N） films were prepared by electron cyclotron resonance chemical vapor deposition （ECR-CVD） on polycrystalline Si chips. Film thickness is about 50 nm. Auger electron spectroscopy （AES） was used to evaluate nitrogen content, and increasing N2 flow improved N content from 0 to 7.6%. Raman and X-ray photoelectron spectroscopy （XPS） analysis results reveal CN-sp^3C and N-sp^2C structure. With increasing the N2 flow, sp^3C decreases from 73.74% down to 42.66%, and so does N-sp^3C from 68.04% down to 20.23%. The hardness decreases from 29.18 GPa down to 19.74 GPa, and the Young＇s modulus from 193.03 GPa down to 144.52 GPa.     

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.     

Optical study of ion-deposited diamond-like carbon films using spectroscopic ellipsometry

Spectroscopic ellipsometry was used for the characterization of ion-deposited diamond-like carbon (DLC) films, including the determination of film thickness and optical properties of DLC. The measured spectra in the wavelength range from 300 to 850 nm were analyzed with an appropriate fitting model, which was constructed according to the nominal sample structure in which the optical properties of DLC were described by a Cauchy dispersion model. Reasonably good agreement was found between the measured and calculated spectra for all samples studied, indicating that the models used were appropriate and that the calculated results were reliable. The results of our analysis suggest that, under the same deposition conditions (i.e., same substrate temperature and same chamber pressure), the optical properties of ion-deposited DLC film did not change much even if the film was prepared with quite different gas flow ratios.     

Hybrid plasma CVD of diamond-like carbon (DLC) at low temperatures

Diamond-like carbon coatings have been deposited onto various substrates at 100–150°C using a hybrid plasma assisted chemical vapour deposition technique activated by radio frequency at 13.56 MHz. The coatings have been characterized using a number of techniques including scanning electron microscopy, Raman spectroscopy, thermoanalysis and pin-on-disc wear testing. Results show the films to be diamond like, with the addition of nitrogen (prior to deposition) promoting the formation of crystallites. In addition the condition and type of substrate have been found to have a strong influence on the structural characteristics of the deposited diamond-like films. SEM analysis of diamond-like carbon coatings deposited onto metal matrix composite materials such as Si-Al MMC is reported. The hybrid CVD technology enabled films to be deposited evenly onto the porous MMC structure. Commercially manufactured drills, coated with DLC and titanium nitride (TiN), have been compared to examine their cutting wear resistance characteristics. This revised version was published online in November 2006 with corrections to the Cover Date.     

Minderung von Reibung und Verschleiß von Bauteilen aus Aluminium mit diamantähnlichen Kohlenstoffschichten (DLC)

Reduction of friction and wear for parts made of aluminium by diamond-like carbon coatings Reduction of friction and wear of machine parts and tools is usually achieved by separating the participating surfaces. This is predominantly done by liquid lubricants. Solid lubricant coatings replace them where hydrodynamic lubrication is not possible or not active. Among the hard and friction reducing layers diamond-like carbon films (DLC) have distinguished themselves as the most interesting representatives. They are deposited on metallic and ceramic parts in a glow discharge of a hydrocarbon gas at temperatures between 150 and 200 °C. Those low deposition temperatures, their very low dry sliding friction coefficient of 0.05 to 0.1, and an elastic recovery of 90 % differentiate them from PVD coatings to a high degree. DLC can also be deposited on light metals with thicknesses of more than 30 μm. For closed films an outstanding protection against corrosion is established. Machining and forming of light metals can be done without cooling lubricants.     

RF-PECVD制备类金刚石膜的研究

采用RF-PECVD法在锗(Ge)基片上沉积类金刚石(DLC)薄膜,研究了气体流量和气压对沉积区域均匀性的影响,以及基片厚度与沉积时间的关系。用拉曼光谱(Raman)分析DLC膜的结构组成,用傅立叶红外光谱仪(IR)对DLC膜的透过率进行了测量。结果表明,在气体流量为50 sccm,气压为10 Pa,功率800 W条件下薄膜厚度均匀性可达2.1%,极值透过率达62%。     

电化学沉积DLC膜及其表征

采用电化学沉积方法，甲醇有机溶剂作碳源，在直流电源作用下在单晶硅表面沉积得到碳薄膜。薄膜不溶于苯、丙酮等有机溶剂，具有较高的硬度(16GPa左右)，用AFM、Raman和FTIR分析手段对该薄膜表面形貌和结构进行表征，Raman和FTIR结果表明电化学沉积得到的是含氢的类金刚石碳薄膜。通过研究样品薄膜的XPS和XAES谱图特征，进一步证实薄膜是DLC薄膜，并用线性插入法估算出样品薄膜中SP^3的相对含量为60％，同时推测了电化学沉积DLC薄膜的生长机理。     

Investigation of the properties of diamond-like carbon thin films deposited by single and dual-mode plasma enhanced chemical vapor deposition

In this study diamond-like carbon (DLC) films were deposited by a dual-mode (radio frequency/microwave) reactor. A mixture of hydrogen and methane was used for deposition of DLC films. The film structure, thickness, roughness, refractive index of the films and plasma elements were investigated as a function of the radio frequency (RF) and microwave (MW) power, gas ratio and substrate substance. It was shown that by increasing the H₂ content, the refractive index grows to 2.63, the growth rate decreases to 10 (nm/min) and the surface roughness drops to 0.824 nm. Taking into consideration the RF power it was found that, as the power increases, the growth rate increases to 11.6 (nm/min), the variations of the refractive index and the roughness were continuously increasing, up to a certain limit of RF power. The Raman G-band peak position was less dependent on RF power for the glass substrate than that of the Si substrate and a converse tendency exists with increasing the hydrogen content. Adding MW plasma to the RF discharge (dual-mode) leads to an increase of the thickness and roughness of the films, which is attributed to the density enhancement of ions and radicals. Also, optical emission spectroscopy is used to study the plasma elements.     

轮胎模具无氢DLC涂层的制备及表征

为探究轮胎模具类金刚石(DLC)涂层的应用前景,提高模具表面的硬度和疏水性,按照模具加工工艺制备35钢基体试样,利用电弧离子镀在基体上沉积无氢DLC涂层,对涂层粗糙度、三维表面形貌、断面结构、元素组成及含量、Raman光谱、纳米硬度和疏水性进行了分析.结果表明:通过改变粗糙度可以改善涂层的疏水性,涂层疏水性随粗糙度增大而显著增加,水接触角最高可达96°,且涂层硬度可达30.3 GPa.无氢DLC涂层可满足轮胎模具耐磨性和易清洁的使用要求,为制造高性能轮胎模具提供了一种可行的工艺选择.     

类金刚石纳米薄膜的表面摩擦规律及磨损模型

为了研究类金刚石（Diamond-like carbon,DLC）薄膜的表面摩擦机制及磨损规律,首先通过对晶体碳高温熔化和快速淬火的方式,使用分子动力学模拟制备出DLC薄膜,然后利用半球形压头对薄膜表面进行摩擦刻划。制备得到的DLC薄膜密度为2.72 g·cm^-3,碳原子sp²、sp³杂化比例分别为37.1%和60.4%。摩擦结果表明,较低压力载荷下磨损率随着载荷力增加而线性增加,与宏观Archard模型一致;摩擦速度的不同会导致材料被加工表面应力分布及切削深度不同,造成磨损率随着摩擦速度的增加而下降,与实验结果相符;当薄膜含有Si原子夹杂且原子含量从0%增加至25%时,磨损率则先上升后下降。最后建立在压头固定载荷为50 nN下描述摩擦速度、材料夹杂含量与磨损率三者关系的磨损模型,建立的磨损模型与仿真模拟相对误差在10%以内;利用模型得到在压头的载荷和摩擦速度不变时,薄膜磨损率最小值对应的Si夹杂含量为7.2%,这一模型为工程在线预测夹杂含量提供了较简单方便的手段。     

Tribological performance of DLC coatings deposited by ion beam deposition under dry friction and oil lubricated conditions

Understanding the reaction between lubricant additives and diamond-like carbon coatings is imperative for the improvement of the friction and wear properties of mechanical parts with diamond-like carbon coatings. Diamond-like carbon coatings were deposited with ion beam deposition and the influence of lubricant additives on the friction coefficients and wear rates of diamond-like carbon coatings under the lubricated conditions was studied. It was revealed that the wear rates of diamond-like carbon coatings under unlubricated conditions are 1.5 × 10⁻¹⁴ m³/(Nm) while they are decreased to 3 × 10⁻¹⁷ m³/(Nm) to 1.7 × 10⁻¹⁶ m³/(Nm) when lubricated by PAO-4 base oil with three additives. The addition of molybdenum dithiocarbamate in PAO-4 base oil decreases the friction coefficients of diamond-like carbon coatings to 0.07, but increases the wear rate of diamond-like carbon coatings. The addition of zinc dialkyl dithiophosphate to PAO-4 can slightly decrease the friction coefficient of diamond-like carbon coatings and improve the wear resistance of diamond-like carbon coatings. The addition of amine sulfuric-phosphate diester in PAO-4 can greatly decrease the wear rate of diamond-like carbon coatings to 3 × 10⁻¹⁷ m³/(Nm) but has a negligible effect on the friction coefficients of diamond-like carbon coatings.     

Micro‐Raman Studies on DLC coatings

Raman scattering is an excellent tool to characterize nanocrystalline clusters and the structural arrangement of carbon atoms in carbon‐based materials. Diamond‐like carbon (DLC) films are used in many industrial applications due to their hardness, wear resistance and biological compatibility. The properties of DLC coatings depend on the carbon coordination and incorporation of other elements, influences onto their Raman spectra will be reviewed.     

非平衡磁控溅射技术制备用于红外减反射的无氢碳膜

红外减反射保护膜具有特定的厚度要求,如能进一步减小无氢类金刚石膜(DLC)的光学吸收,就能使其在较大厚度时不过分损失光通量而得以广泛应用.从这点来讲,无氢类金刚石膜是一种极具开发潜力的材料.本文采用非平衡磁控溅射技术(UBMS)制备了无氢类金刚石膜,并研究了其厚度均匀性.研究结果表明:该非平衡磁控溅射装置有能力获得大于φ150 mm的均匀性范围.对DLC膜红外透射谱的分析表明,分别在Si和Ge基底表面单面制备的DLC薄膜,其峰值透射率在波数2983/cm时分别为68.83%和63.05%,这一结果接近无吸收碳材料理论上所能达到的值.同时,在5000到800/cm范围内,未发现明显的吸收峰.这些优良的光学特性表明,采用非平衡磁控溅射技术制备的无氢DLC膜可以作为窗口的红外增透保护膜使用.