Wear resistance of nano- and micro-crystalline diamond coatings onto WC-Co with Cr/CrN interlayers

Cr/CrN bi-layers have been used recently to promote the growth of high quality Hot Filament Chemical Vapour Deposition (HFCVD) diamond coatings onto Co-cemented tungsten carbide (WC-6 wt.%Co) substrates. In the present investigation, the influence of the crystalline size of the diamond coatings on their wear endurance is looked into.Nano- (NDC) and micro-crystalline Diamond Coatings (MDC) were deposited by HFCVD onto untreated and Fluidized Bed (FB) treated Cr/CrN interlayers. NDCs, characterized by a cauliflower-like morphology, showed improved wear resistance. However, the superimposition of NDCs onto Cr/CrN interlayers micro-corrugated by FB treatment was found to be the most promising choice, leading to the formation of highly adherent and wear resistant coatings.     

Fluidized bed micro-machining and HFCVD of diamond films onto Co-cemented tungsten carbide (WC-Co) hardmetal slabs

The effect of fluidized bed (FB) treatment upon hot filament chemical vapor deposition (HFCVD) of polycrystalline diamond films onto WC-Co hardmetal substrates was investigated. Several scenarios to make the substrates ready for HFCVD were, comparatively, evaluated and the resulting diamond films were examined in terms of their morphology and adhesion. The diamond grain density was measured by scanning electron microscopy. The adhesion of continuous diamond film to substrate was evaluated by the reciprocal of the slope of crack radius-indentation load functions. Surface binder dissolution followed by FB treatment (PF pretreatment) allowed very high diamond nucleation density and smaller grain size. The adhesion of films grown on PF pretreated substrates was found to be very close to that of films deposited on hardmetal slabs pretreated by Murakami's reagent followed by Co etching with Caro's acid and seeded with diamond suspension in an ultrasonic vessel (MPS pretreatment). However, diamond coatings on MPS pretreated samples exhibited a rougher surface morphology as a result of both lower diamond nucleation density and larger substrate surface roughening by Murakami's etching. Based upon experimental findings, our newly developed PF pretreatment was found to be a very promising technique in substrates conditioning as well as in promoting adherent, uniform and smooth diamond coatings onto hardmetal tools and wear parts.     

低压气相金刚石薄膜镀膜刀具膜/基附着性能压痕测试分析

低压气相金刚石薄膜硬质合金刀具在直流弧光放电等离子体CVD镀膜设备上制备.基底为YG6(WC-6%Co,质量分数)硬质合金刀具.采用洛氏(HRA)、表面洛氏(HRM)、维氏(HV)硬度试验机对所制备的金刚石薄膜刀具进行压痕测试;采用扫描电镜(SEM)观察压痕形貌并定性评价膜/基附着性能.结果表明:所制备的金刚石薄膜镀膜刀具的优选膜/基附着性能压痕测试方法是表面洛氏压痕法;优选测试条件为采用120°金刚石圆锥压头,测试加载载荷441N.     

Physical vapor deposition of copper over Lexan

Lexan is a polymer which is light-weight and extremely smooth, and is a candidate material for radio-frequency reflecting mirrors provided that they are coated with strongly adherent copper coatings. In the present investigation copper was sputtered from a dc magnetron source and deposited on Lexan surfaces. Various pretreatments were given to the Lexan surface, e.g., being exposed to pulsed dc or rf argon plasma. During deposition the Lexan surface was biased to various pulsed voltages ranging upto − 5 kV with various repetition rates and on times. All these parameters decide whether the copper coatings are strongly adherent to the Lexan surface. The results indicate that the coatings deposited over pretreated (etched) substrates showed better adhesion to the Lexan surface and the deposited coatings in general exhibit compressive stress. XRD studies revealed polycrystalline coatings with nano-sized grains and having a preferred (111) orientation.     

电镀铬-金刚石复合过渡层提高金刚石膜/基结合力

在铜基体上沉积铬-金刚石复合过渡层, 用热丝CVD系统在复合过渡层上沉积连续的金刚石涂层. 用扫描电镜(SEM)、X射线(XRD)、拉曼光谱及压痕试验对所沉积的镶嵌结构界面金刚石膜的相结构及膜/基结合性能进行了研究. 结果表明, 非晶态的电镀Cr在CVD过程中转变成Cr₃C₂, 由于金刚石颗粒与Cr₃C₂的相互咬合作用, 金刚石膜/基结合力高; 在294 N载荷压痕试验时, 压痕外围不产生大块涂层崩落和径向裂纹, 只形成环状裂纹.     

Cyclic voltammetry response of an undoped CVD diamond electrodes

The polycrystalline undoped diamond layers were deposited on tungsten wire substrates by using hot filament chemical vapor deposition (HFCVD) technique. As a working gas the mixture of methanol in excess of hydrogen was used. The morphologies and quality of as-deposited films were monitored by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy respectively. The electrochemical activity of the obtained diamond layers was monitored by using cyclic voltammetry measurements. Analysis of the ferrocyanide–ferricyanide couple at undoped diamond electrode suggests that electrochemical reaction at diamond electrode has a quasireversibile character. The ratio of the anodic and cathodic peak currents was always close to unity. In this work we showed that the amorphous carbon admixture in the CVD diamond layer has a crucial influence on its electrochemical performance.     

Synthesis and characterization of TiBCN coatings deposited by ion beam assisted, co-evaporation electron beam-physical vapor deposition (EB-PVD)

TiC, TiB₂, and super hard TiBCN coatings were successfully deposited by ion beam assisted, electron beam-physical vapor deposition. Titanium, titanium diboride, and carbon (through tungsten) were co-evaporated by energetic electron beams while simultaneously bombarding the substrates with varying ionized gas ratios of nitrogen and argon to obtain super hard TiBCN coatings. The hardness of the TiBCN coating was reported to be equivalent to a soft diamond like carbon film. The adhesion was determined to be greater than 50 N. The hardness, grain size, structure, morphology, crystallographic texture and degree of stress within the coatings were determined using a variety of characterization methods including Vicker's hardness measurements, electron probe microanalysis (EPMA), optical microscopy (OM), scanning electron microscopy (SEM), and X-ray diffraction. The author is not aware of previous TiBCN coatings being deposited by this method.     

MPCVD法在氧化铝陶瓷上的金刚石膜沉积及其成核分析

用微波等离子体化学气相沉积（ＭＰＣＶＤ）法在氧化铝陶瓷基片上沉积了金刚石薄膜。实验表明，对基片进行适当的预处理，包括用金刚石研磨膏仔细研磨和沉积前原位沉积一层无定形碳层，可显著提高成核密度；对硅衬底和氧化铝基片上金刚石膜的成核过程进行了对比分析，并提出了提高氧化铝基片上沉积金刚石的成核的措施。     

Composition profiles and adhesion evaluation of conductive diamond coatings on dielectric ceramics

Sintered silicon nitride (Si₃N₄) ceramic substrates were investigated as dielectric substrates for the growth of metal-like boron-doped nanocrystalline diamond (NCD) and microcrystalline diamond coatings via the Hot Filament Chemical Vapor Deposition (HFCVD) technique. The structural, electrical and chemical properties of both the ceramic substrates and the diamond coatings may potentiate their applicability in particular in harsh environments and highly demanding situations. Boron doping was achieved via a boron oxide solution in ethanol dragged into the reaction chamber with argon. The coatings were characterized by scanning electron microscopy, UV μ-Raman scattering, X-ray diffraction, time-of-flight secondary ion mass spectroscopy, Brale indentation for adhesion evaluation and two-point contact probe for resistivity measurements. The HFCVD technique led to a maximal growth rate of about 1 μm/h. Several metal-like boron doped diamond coatings were obtained. It was found that at lower substrate temperature, lower system pressure and higher methane concentration, the resistivity of the conducting NCD coatings is about 3 orders of magnitude higher when compared with samples obtained with higher substrate temperature, higher system pressure and lower methane concentration. Nevertheless, for every metal-like boron-doped coating the use of the Si₃N₄ ceramic substrate guaranteed a superior adhesion level.     

Diamond chemical vapour deposition on seeded cemented tungsten carbide substrates

Diamond particles were deposited onto seeded cemented tungsten carbide (WC-Co) substrates using conventional hot-filament chemical vapour deposition (HFCVD) and time-modulated CVD (TMCVD) processes. The substrates were pre-seeded ultrasonically with diamond particles of different grit sizes. In this investigation, we employ timed methane (CH₄) gas modulations, which are an integral part of our TMCVD process in order to enhance diamond nucleation density. During diamond deposition using the conventional HFCVD process, methane gas flow was maintained constant. The total hydrogen flow into the reactor during TMCVD process was higher than in the HFCVD process. Hydrogen etching can be expectedly more prominent in the TMCVD process than in HFCVD of diamond particles. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) results showed that a proper selection of the diamond grit size for seeding using ultrasounds can lead to enhancement in the nucleation density values of about two orders of magnitude (10⁷ to 10⁹ cm^− 2). The TMCVD process using the different seeded substrates can result in high nucleation density values of up to 10¹⁰ cm^− 2.     

Preparation and analysis of chemically gradient functional bioceramic coating formed by pulsed laser deposition

Bioactive ceramic coatings based on calcium phosphates yield better functionality in the human body for a variety of metallic implant devices including orthopaedic and dental prostheses. In the present study chemically and hence functionally gradient bioceramic coating was obtained by pulsed laser deposition method. Calcium phosphate bioactive ceramic coatings based on hydroxyapatite (HA) and tricalcium phosphate (TCP) were deposited over titanium substrate to produce gradation in physico-chemical characteristics and in vitro dissolution behaviour. Sintered targets of HA and α-TCP were deposited in a multi target laser deposition system. The obtained deposits were characterized by X-ray diffraction, fourier transform infrared spectroscopy, scanning electron microscopy and energy dispersive X-ray analysis. Inductively coupled plasma spectroscopy was used to estimate the in vitro dissolution behaviour of coatings. The variation in mechanical property of the gradient layer was evaluated through scratch test and micro-indentation hardness. The bioactivity was examined in vitro with respect to the ability of HA layer to form on the surface as a result of contact with simulated body fluid. It could be inferred that chemically gradient functional bioceramic coating can be produced by laser deposition of multiple sintered targets with variable chemical composition.     

Plasma-assisted deposition of metal and metal oxide coatings

A combination of physical vapour deposition and plasma-assisted chemical vapour deposition techniques were used to deposit Cu-, Ni- and Sn-rich SnO/SnO2 coatings on metal and ceramic substrates. Cu and Ni were deposited on Al alloy 6061 substrates and Ni deposition was also performed on glass microscope slides and commercially pure alumina substrates. Sn-rich SnO/SnO2, on the other hand, was coated on stainless steel and pure Cu substrates. A direct-current plasma system was used to deposit the pure metals in vacuum with a resistively heated tungsten boat that was coated with alumina. All samples were sputtered for 20 min in an argon:hydrogen (1:1) atmosphere at a pressure of 300 mTorr. To reduce contamination and oxidation of both substrates and deposited layers, Cu and Ni coatings were made with argon:hydrogen (2:1) carrier gas. Sn-rich tin oxide coatings were deposited in a pure argon atmosphere (no hydrogen) to allow for the oxidation of Sn deposits on the stainless steel and copper substrates. Investigations of coated surfaces by scanning electron microscopy and X-ray diffraction showed coatings to be smooth, continuous and pure. Deposition rates showed this application to provide a very high rate when compared with chemical vapour deposition and metal–organic chemical vapour deposition techniques. Scratch tests results prove good attachment of the coatings to their respective substrates. © 1998 Chapman & Hall     

Influence of WC-Co substrate pretreatment on diamond film deposition by laser-assisted combustion synthesis

The quality of diamond films deposited on cemented tungsten carbide substrates (WC-Co) is limited by the presence of the cobalt binder. The cobalt in the WC-Co substrates enhances the formation of nondiamond carbon on the substrate surface, resulting in a poor film adhesion and a low diamond quality. In this study, we investigated pretreatments of WC-Co substrates in three different approaches, namely, chemical etching, laser etching, and laser etching followed by acid treatment. The laser produces a periodic surface pattern, thus increasing the roughness and releasing the stress at the interfaces between the substrate and the grown diamond film. Effects of these pretreatments have been analyzed in terms of microstructure and cobalt content. Raman spectroscopy was conducted to characterize both the diamond quality and compressive residual stress in the films.     

Implementation of the time-modulated process to produce diamond films using microwave-plasma and hot-filament CVD systems

A newly developed process called time-modulated chemical vapour deposition (TMCVD) was employed to deposit smooth polycrystalline diamond films onto silicon substrates using both microwave plasma CVD (MPCVD) and hot-filament CVD (HFCVD) systems. The distinctive feature of the TMCVD process, which separates it from the conventional diamond CVD process, is that it pulses methane (CH₄) at different flow rates for different time durations into the vacuum reactor during the entire diamond CVD process. Generally, both MPCVD and HFCVD systems produced results that displayed similar trends, except that the growth rate results obtained using the two CVD systems were conflicting. In comparison to the conventional CVD diamond films, the time-modulated films, deposited using both MPCVD and HFCVD techniques, were generally found to be (i) smoother, (ii) consisted of smaller diamond crystallites and (iii) displayed approx. similar film quality. The diamond-carbon phase purity of the as-grown films was assessed using Raman spectroscopy. In addition, the surface roughness, Ra, values of the deposited films were obtained using surface profilometry.     

衬底表面预处理对金刚石薄膜形核及长大的影响

用燃烧火焰法在 TC4 Ti 合金和单晶 Si(001)面上沉积了金刚石薄膜。对合成的膜进行了扫描电镜、激光喇曼光谱分析。结果表明,金刚石薄膜的结构和形貌强烈取决于沉积温度、O_2/C_2H_2流量比等工艺参数。研究了衬底表面预处理对金刚石薄膜形核及长大的影响,并对表面预处理影响形核的原因进行了初步探讨。     

氧化铝基体表面预处理对金刚石薄膜生长的影响

采用微波等离子体化学气相沉积方法,在经不同预处理的氧化铝衬底上沉积金刚石薄膜.用X射线衍射仪、激光拉曼光谱仪、扫描电镜(SEM)对所得薄膜的成分、物相纯度和表面形貌进行表征,比较不同的预处理方式对金刚石薄膜生长的影响.结果表明,基体表面经过熔融碱腐蚀后形成薄膜的膜基结合良好且膜材质量最佳,但表面平整度较低;而基体只经金刚石微粉乙醇悬浊液超声处理则在沉积时金刚石容易成膜,且结构要更为致密;在经过酸腐蚀的基体上沉积金刚石薄膜时,容易在薄膜与基体之间先形成过渡层,而后才进行金刚石薄膜的沉积.所得结果表明熔融碱腐蚀处理是获得电学应用氧化铝基金刚石薄膜复合材料的最适宜的基体表面预处理.     

Diamond deposition onto WC-6%Co cutting tool material: coating structure and interfacial bond strength

Diamond coatings were grown on WC-6%Co cutting tool material. Measurements were carried out to investigate the effects of diamond seeding of the substrate before deposition, removal of cobalt from the substrate before deposition, and boron incorporation into the coating during growth on the growth rate, morphology and structure of the coating, and coating-substrate edhesion. Diamond seeding of the substrate resulted in a higher growth rate and diamond fraction of the coating relative to a polished and unseeded surface. Etching of cobalt from the substrate resulted in a higher growth rate, diamond fraction and adhesion strength relative to the unetched surface. Introduction of methanol into the gas phase led to a lower growth rate, diamond fraction and adhesion strength relative to the case when no methanol was injected. Introduction of boron oxide (B₂O₃) along with methanol into the gas phase did not affect the growth rate but increased both the diamond fraction and adhesion strength relative to the case when only methanol was added. It is believed that adhesion failure occurs at the diamond-substrate interface, possibly within a soft nanocrystalline graphite transition layer.     

Tribological Performance of Titanium Alloy Ti–6Al–4V via CVD–diamond Coatings

In the present study, HFCVD nanocrystalline, microcrystalline and boron-doped nanocrystalline diamond coatings have been deposited on titanium alloy. The effect of boron doping on coefficient of friction and residual stresses of diamond coatings have been studied. The tribological characteristics of the aforementioned three coatings on Ti–6Al–4V substrates were studied using ball on disc micro-tribometer, the thickness of the coatings being 3 μm. The coated Ti–6Al–4V discs were slid against alumina (Al₂O₃) balls with normal load ranging from 1 to 10 N. The boron-doped NCD coated sample disc was found to possess the lowest average coefficient of friction ~ 0.0804 while the undoped NCD and MCD coated sample discs were found to possess the average coefficients of friction of ~ 0.143 and ~ 0.283, respectively. Raman spectroscopy studies revealed that the residual stresses in boron-doped nanocrystalline coatings were tensile in nature, while the residual stresses in undoped NCD and MCD were found to be of compressive nature.     

Diamond layers grown by chemical vapor deposition on NbN systems and NbN/SiO2-based devices

Deposits of individual diamond grains and continuous polycrystalline diamond layers have been generated by means of a HFCVD technique onto different types of untreated or seeded NbN surfaces. To test the feasibility of using diamond layers as protective coatings for aerospace applications, we carried out diamond deposition onto the lithographically defined NbN microelectrodes of a NbN/SiO2 multifinger device. The morphological and structural features of the diamond deposits and of the substrates were characterized by FE-SEM, XRD and Raman spectroscopy. The preferential growth of diamond on the superconductive NbN enables the selective coating of the NbN microstripes sputtered on the insulating SiO2. Moreover the diamond coating procedure is able to preserve the structural integrity of the substrate material and to retain the shaped architecture of the device. For the polycrystalline diamond layers grown on NbN a residual stress of -9.8 GPa, largely due to thermal stress, has been estimated by Raman analysis. The diamond coatings of the NbN-based architectures result to be mechanically stable.     

Mo2C过渡层对金刚石-碳膜场发射均匀性的影响

在经过不同特殊预处理的金属钼衬底上沉积了金刚石 -碳膜 ,分别用X射线衍射谱 (XRD)、拉曼光谱 (Raman)和扫描电子显微镜 (SEM)对样品进行了分析和测试 ,并研究了样品器件的场发射特性。结果发现在金属钼衬底和金刚石 -碳膜之间形成的Mo2 C过渡层与金刚石 -碳膜场发射均匀性有着密切的联系