电镀铬-金刚石复合过渡层提高金刚石膜/基结合力

doi:10.3724/SP.J.1077.2012.00205

摘要/Abstract

摘要：

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.

关键词: 金刚石膜, 镶嵌, 复合镀, 压痕, 结合力

Abstract:

The diamond films were fabricated by using a two-step process on copper substrates. Firstly, chromium (Cr)-diamond composite interlayer was electroplated on copper substrates, then continuous diamond films were deposited by using hot-filament chemical vapor deposition (HFCVD) method. The interfacial characteristics were investigated by indentation test. The film surface morphology, phase structure and inner stress were analyzed by scanning electron microscope (SEM), X-ray diffraction (XRD) and Raman spectrum. The results show that the diamond particles are deeply imbedded in chromium layer and the amorphous Cr in the composite interlayer is carborized to Cr₃C₂in the CVD process. Low inner stress is detected in the diamond films and good adhesive strength between film and substrate is obtained due to the deep anchoring of the diamond particles in the Cr₃C₂ matrix. Concentric cracks but no delaminate area and radial cracks are observed on the periphery of the indentation in 294 N load indentation test.

Key words: diamond films, inlay structure, composite plating, indentation, adhesive strength

中图分类号:

TB43

邱万奇, 潘建伟, 刘仲武, 余红雅, 钟喜春, 曾德长. 电镀铬-金刚石复合过渡层提高金刚石膜/基结合力[J]. 无机材料学报, 2012, 27(2): 205-208.

QIU Wan-Qi, PAN Jian-Wei, LIU Zhong-Wu, YU Hong-Ya, ZHONG Xi-Chun, ZENG De-Chang. Improvement of Adhesive Strength of Diamond Films by Plating Cr-diamond Composite Interlayer[J]. Journal of Inorganic Materials, 2012, 27(2): 205-208.

图/表 5

图1 经底镀+上砂+加固镀样品表面SEM照片

Fig. 1 SEM surface morphologies of samples after Cr-diamond composite plating (a) Distribution and density of diamond particles; (b) A deeply imbedded diamond particle

图2 是经第一步和第二步沉积工艺制备样品的XRD图谱. 经第一步沉积的样品(图2(a)), XRD谱线中出现了尖锐的Cu基体峰和微弱的金刚石峰, 但没有Cr峰, 这是因为三价铬镀液电沉积出来的Cr多为非晶态[9], X射线衍射峰很弱, 加上强尖锐的基体Cu峰的共同作用, 使很弱的Cr峰和非晶铬包络峰难以探测到. 沉积CVD金刚石膜后的样品(图2(b)), 金刚石峰显著增强, 基体Cu峰减弱, 并出现系列的Cr3C2峰. 非晶Cr在CVD过程中因基体温度升高而转变成Cr晶体, 同时含有甲烷的氢气流在经高温热丝分解成活性氢原子和各种碳氢基团, 到达样品表面时首先使Cr碳化, 形成碳化铬, 镶嵌在Cr中的颗粒金刚石, 在界面也部分转化为碳化铬, 碳化铬含量随沉积时间的延长而增多, 当金刚石长大成连续膜后, 碳氢气流对Cr的碳化停止, 界面金刚石因碳向镶嵌过渡层内部扩散, 碳化铬继续形成. Cr有多种稳定的碳化物, 经长时间高温CVD过程处理, Cr被充分碳化成含碳量最高的Cr3C2.

图2 经第一步(a)和第二步(b)沉积工艺制备样品的XRD图谱

Fig. 2 XRD patterns of the sample prepared after first (a) and second (b) step fabrication

图3 经16 h CVD沉积后金刚石膜的表面SEM形貌(a)和Raman光谱(b)

Fig. 3 Surface morphology (a) and Raman spectrum (b) of the diamond films after 16 h CVD process

图4 镶嵌结构金刚石薄膜压痕的SEM形貌(a)和压痕边缘的环状裂纹(b)

Fig. 4 SEM micrographs of the indentation crater on inlay structure diamond films (a) and the concentric cracks on periphery of the crater (b)

参考文献 13

[1]	Coe S E, Sussmann R S. Optical, thermal and mechanical properties of CVD diamond. Diamond Relat. Mater., 2000, 9(9/10): 1726-1729.
[2]	Polini R, Barletta M, Cirstofanilli G. Wear resistance of nano- and micro-crystalline diamond coatings onto WC-Co with Cr/CrN interlayers. Thin Solid Films, 2010, 519(5): 1629-1635.
[3]	Tang Y, Li Y S, Yang Q, Hirose A. Deposition and characterization of diamond coatings on WC-Co cutting tools with W/Al interlayer. Diamond Relat. Mater.. 2010, 19(5/6): 496-499.
[4]	Sikder A K, Sharada T, Misra D S, et al. Chemical vapor deposition of diamond on stainless steel: the effect of Ni-diamond composite coated buffer layer. Diamond Relat. Mater., 1998, 7(7): 1010-1013.
[5]	Lin C R, Kuo C T. Improvement of mechanical properties of electroplated diamond tools by microwave plasma CVD diamond process. Surf. Coat. Technol., 1998, 110(1/2): 19-23.
[6]	de Resende L W, Corat E J, Trava-Airoldi V J, et al. Multi-layer structure for chemical vapor deposition diamond on electroplated diamond tools. Diamond Relat. Mater., 2001, 10(3-7): 332-336.
[7]	Silva F J G, Fernandes A J S, Costa F M, et al. Unstressed PACVD diamond film on steel pre-coated with a composited multilayer. Surf. Coat. Technol., 2005, 191(1): 102-107.
[8]	Huang Yuan Sheng, Qiu Wan Qi, Luo Cheng Ping. Effect of molybdenum on diamond deposition and adhesion. Thin Solid Films, 2005, 472(1/2): 20-25.
[9]	邱万奇. 一种铬/金刚石复合镀层及其制备方法, 中国, ZL200710032268.3, 2007.
[10]	Zeng Z, Wang L, Liang A, et al. Tribological and electrochemical behavior of thick Cr-C alloy coatings electrodeposited in trivalent chromium bath as an alternative to conventional Cr coatings. Electrochimica Acta, 2006, 52(3): 1366-1373.
[11]	Fortunato W, Chiquito A J, Galzerani J C, et al. Crystalline quality and phase purity of CVD diamond films studied by Raman spectroscopy. J. Mater. Sci., 2007, 42(17): 7331-7336.
[12]	Vlassak J J, Ciavarella M, Barber J R, et al. The indentation modulus of elastically anisotropic materials for indenter of arbitrary shape. J. Mech. Phys. Solids, 2003, 51(9): 1701-1721.
[13]	BareiβJ C, Hackl G, Popovska N, et al. CVD diamond coating of steel on a CVD-TiBN interlayer. Surf. Coat. Technol., 2006, 201(3/4): 718-723.

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