金刚石双金属层的镀覆工艺

陈蕾莹; 陈雷明; 刘雪婷; 王旭磊; 程绍坤; 朱子怡; 陈博宇; 鞠恒冬; 潘晓宇; 姚梦媛

doi:10.13394/j.cnki.jgszz.2024.0098

金刚石双金属层的镀覆工艺

doi: 10.13394/j.cnki.jgszz.2024.0098

1.
郑州航空工业管理学院材料学院, 郑州 450046
2.
河南省航空材料与应用技术重点实验室, 郑州 450046

基金项目: 河南省科技攻关项目（202102210216，232102231005）。

详细信息

通讯作者:
陈雷明，男，1979年生，博士、教授。主要研究方向：超硬材料制品设计及性能优化。E-mail：lmchen@zua.edu.cn

中图分类号: TQ164; TB39
计量
- 文章访问数: 1016
- HTML全文浏览量: 454
- PDF下载量: 13
- 被引次数: 0
出版历程
- 收稿日期: 2024-06-15
- 修回日期: 2024-07-31
- 录用日期: 2025-04-29
- 网络出版日期: 2024-10-11
- 刊出日期: 2025-08-20

Plating process of diamond bimetallic layer

1.
School of Materials Science and Engineering, Zhengzhou University of Aeronautics, Zhengzhou 450046, China
2.
Henan Key Laboratory of Aeronautical Material and Application Technology, Zhengzhou, 450046, China

摘要

摘要: 采用盐浴镀覆法对金刚石表面进行双金属层改性处理，以实现金刚石/金属界面结合力的提升。通过对Ti-Ni、Ti-Mo、Ti-W、Ti-Co 4种双金属层改性金刚石的物相组成、微观形貌、镀层厚度、表面粗糙度等进行测试及分析，探究金属组合差异对金刚石镀层性能的影响。结果表明：金属化合物的热力学稳定性、界面相容性以及金属间晶格失配度影响镀层质量；Ti-W改性的金刚石表面因Ti_xW_1−x化合物的高稳定性、W的低扩散速率及Ti-W的高效还原性，其镀层厚度最大为3.4 μm，较界面亲和度较弱且晶格失配度较大的Ti-Co样品的镀层厚度提高了161.54%；Ti-Mo与Ti-W改性的金刚石表面因晶格失配度低，在金刚石(111)晶面表现出优异的表面平整性，其表面粗糙度R_a较Ti-Ni样品的分别降低了12.41%、21.05%，较Ti-Co样品的分别降低了57.16%、61.39%。
- 盐浴镀 /
- 金刚石 /
- 碳化物 /
- 双金属镀层
Abstract: Objectives With the increasing demand for superhard tool performance in precision machining, the problems of weak bonding between diamond and metal interface, and high cost of controlling coating thickness urgently need to be solved. In this study, the molten salt plating process is adopted. The diamond surface is subjected to bimetallic synergistic modification treatment through the combination of four different metals, namely Ti-Ni, Ti-Mo, Ti-W and Ti-Co, in order to enhance the bonding force at the diamond/metal interface. Meanwhile, the influences of the differences in metal combinations on the coating are explored. Methods Four kinds of bimetallic modified diamond samples are prepared by the same molten salt plating process. The phase composition, the microscopic morphology, coating thickness and roughness of the samples are tested and analyzed to explore the influences of metal composition differences on the performance of diamond coatings. Taking the Ti-Ni plated sample as an example, its preparation process is as follows: (1) Under the conditions of NaCl mass fraction of 20.31%, KCl mass fraction of 25.84%, diamond mass fraction of 23.08%, titanium mass fraction of 7.69%, and nickel mass fraction of 23.08%, the masses of each raw material are weighed, and the mixture with a total mass of 3 g is placed in a burning boat. (2) The mixture is subjected to metallization plating treatment in a tubular furnace fully protected by argon gas. The plating temperature is 1 000 ℃, the holding time is 60 min, and the argon gas flow rate is 0.2 L/min. (3) After plating, the product is ultrasonically cleaned at 40 kHz for 30 minutes to remove the residual salt and the metal particles on its surface. Then, it is dried under vacuum at 60 ℃, ground and sieved to obtain the coated sample. Results (1) The thermodynamic stability and the interfacial compatibility of metal compounds affect the coating thickness. For the Ti-W modified diamond sample, due to the high stability of the Ti_xW_1−x compound, the low diffusion rate of W and the efficient reducing property of Ti-W, the maximum coating thickness is 3.4 μm. Due to the weak affinity of Ti-Co, the thinnest coating of the Ti-Co modified sample is 1.3 μm. Therefore, the coating thickness of the Ti-W sample is increased by 161.54% compared with that of the Ti-Co sample. Moreover, in the same sample, the thickness of the Ti-C layer formed by chemical bonding and the intermetallic compound layer varies greatly. The thickness difference between the Ti-C layer formed by chemical bonding and the intermetallic compound layer in the same sample is significant, with the former accounting for more than 79% of the thickness, while the physically deposited elemental metal layer is thinner. Therefore, the synergistic effect of the Ti-C covalent bond dominated by chemical bonding and the intermetallic compound interface structure with the metal layer assisted by physical deposition can effectively coordinate the interfacial stress and improve the bonding stability of the coating. (2) The lattice mismatch between metals affects the surface roughness R_a of bimetallic modified diamond. Low mismatch Ti-Mo (with mismatch degree of 0.064 6) and Ti-W (with mismatch degree of 0.070 7) bimetallic modified diamonds exhibit better surface quality on the (111) crystal plane, with R_a values of 17.021 and 15.341 nm, respectively, which are 12.41% and 21.05% lower than those of Ti-Ni (with mismatch degree of 0.193 8) bimetallic modified diamond, and 57.16% and 61.39% lower than those of Ti-Co (with mismatch degree of 0.151 8) bimetallic modified diamond, respectively. This is due to the regulatory effect of lattice compatibility on the interfacial bonding strength, which in turn affects the surface morphology of the coating. The mismatch degree between Ti-Co is lower than that between Ti-Ni, but its roughness is actually higher, which is related to the surface protrusions on the coating surface caused by the accumulation of cobalt elements during the deposition process. Conclusions The use of the molten salt method for bimetallic modification of diamond successfully triggers the interfacial chemical reaction between diamond and metal, transforming the bonding mode from single physical coating to a comprehensive combination of chemical bonding and physical coating. This significantly enhances the interfacial bonding strength of diamond/metal, providing a reference for the experimental optimization of high-performance diamond tools.
- salt bath plating /
- diamond /
- carbide /
- bimetallic coating

HTML全文

图 1 镀覆效果对比

Figure 1. Comparison of coating effect

下载: 全尺寸图片幻灯片

图 2 金刚石及金属原粉的XRD图谱

Figure 2. XRD patterns of diamond and metal powders

下载: 全尺寸图片幻灯片

图 3 金刚石双金属镀层的XRD图谱

Figure 3. XRD patterns of bimetallic coatings on diamond

下载: 全尺寸图片幻灯片

图 4 金刚石双金属镀层的EDS图谱

Figure 4. EDS spectrums of bimetallic coatings on diamond

下载: 全尺寸图片幻灯片

图 5 金刚石双金属镀层的XPS总谱图

Figure 5. XPS total spectrum of bimetallic coatings on diamond

下载: 全尺寸图片幻灯片

图 7 金刚石Ti-Mo双金属镀层的XPS分谱图

Figure 7. XPS spectra of titanium molybdenum bimetal coating on diamond

下载: 全尺寸图片幻灯片

图 8 金刚石Ti-W双金属镀层的XPS分谱图

Figure 8. XPS spectra of titanium tungsten bimetal coating on diamond

下载: 全尺寸图片幻灯片

图 6 金刚石Ti-Ni双金属镀层的XPS分谱图

Figure 6. XPS spectra of titanium nickel bimetal coating on diamond

下载: 全尺寸图片幻灯片

图 9 金刚石Ti-Co双金属镀层的XPS分谱图

Figure 9. XPS spectra of titanium cobalt bimetal coating on diamond

下载: 全尺寸图片幻灯片

图 10 金刚石双金属镀层的SEM形貌

Figure 10. SEM morphology of bimetallic coating on diamond

下载: 全尺寸图片幻灯片

图 11 金刚石双金属镀层厚度上的EDS图谱

Figure 11. EDS spectra of diamond bimetallic coating thickness

下载: 全尺寸图片幻灯片

图 12 金刚石双金属镀层表面粗糙度的AFM测试图

Figure 12. AFM test diagram of surface roughness of bimetallic coating on diamond

下载: 全尺寸图片幻灯片

图 13 金刚石Ti-Ni镀层结构图

Figure 13. Diamond titanium nickel coating structure diagram

下载: 全尺寸图片幻灯片

表 1 实验原料

Table 1. Experimental raw materials

原料	纯度 φ / %
NaCl	> 99.50
KCl	> 99.50
Ti	99.50
Ni	99.99
Mo	99.90
W	99.90
Co	99.50

下载: 导出CSV

表 2 样品配方

Table 2. Sample formula

样品名称	NaCl质量分数 ω₁ / %	KCl质量分数 ω₂ / %	金刚石质量分数 ω₃ / %	Ti粉质量分数 ω₄ / %	第二相金属质量分数 ω₄ / %
DTNi	20.31	25.84	23.08	7.69	23.08
DTMo	20.31	25.84	23.08	7.69	23.08
DTW	20.31	25.84	23.08	7.69	23.08
DTCo	20.31	25.84	23.08	7.69	23.08

下载: 导出CSV

表 3 主要实验仪器

Table 3. Main experimental apparatus

仪器名称	型号	生产厂家
管式炉	XD-1200NT	郑州兄弟窑炉有限公司
X射线衍射仪	SmartLab3	日本理学株式会社
X射线光电子能谱	Thermo Scientific K-Alpha	美国赛默飞世尔科技公司
扫描电子显微镜	JSM-7001F	日本电子株式会社
X射线能谱仪	EDS INCA X-act	牛津仪器科技有限公司
金相镶嵌机	XQ-2B	莱州市蔚仪试验器械制造有限公司
原子力显微镜	Solver Next	NT-MDT

下载: 导出CSV

表 4 金属晶格参数统计表

Table 4. Statistical table of metal lattice parameters

金属	晶格常数 d / m	晶型	与金刚石的失配度 L_m	与Ti的失配度 L_Ti
α-Ti	2.956 × 10⁻¹⁰	HCP	0.169 7
β-Ti	3.307 × 10⁻¹⁰	BCC	0.169 7
Ni	3.529 × 10⁻¹⁰	FCC	0.008 7	0.193 8
Mo	3.147 × 10⁻¹⁰	BCC	0.116 0	0.064 6
W	3.165 × 10⁻¹⁰	BCC	0.111 0	0.070 7
Co	2.507 × 10⁻¹⁰	HCP	0.295 8	0.151 8

下载: 导出CSV

表 5 金刚石双金属镀层厚度统计表

Table 5. Diamond bimetal coating thickness statistics table

厚度	DTNi				DTMo				DTW				DTCo
厚度	Ti-C	Ti	Ti-Ni	Ni	Ti-C	Ti	Ti-Mo	Mo	Ti-C	Ti	Ti-W	W	Ti-C	Ti	Ti-Co	Co
分厚度 h₁ / μm	1.1	0.2	0.8	0.3	1.7	0.1	1.0	0.2	2.0	0.1	1.1	0.1	0.8	0.1	0.3	0.1
总厚度 h₂ / μm	2.4				3.0				3.4				1.3

下载: 导出CSV

表 6 金刚石双金属镀层的表面粗糙度统计表

Table 6. Diamond bimetallic coating surface roughness statistics table

双镀层	(111)面 R_a / nm	(111)面 R_q / nm	(100)面 R_a / nm	(100)面 R_q / nm
DTNi	19.432	25.424	23.801	28.025
DTMo	17.021	20.998	24.396	29.947
DTW	15.341	17.794	18.625	22.068
DTCo	39.731	48.084	48.700	56.200

下载: 导出CSV

参考文献(28)

[1]	窦志强, 肖长江, 栗正新. 金刚石微粉表面镀覆技术研究进展 [J]. 电镀与精饰, 2017, 39(10): 23-27. doi: 10.3969/j.issn.1001-3849.2017.10.005 DOU Zhiqiang, XIAO Changjiang, LI Zhengxin. Research progress of plating technology on ultrafine diamond surface [J]. Plating and Finishing, 2017, 39(10): 23-27. doi: 10.3969/j.issn.1001-3849.2017.10.005
[2]	杨彪, 杨军, 袁光生. 金刚石表面镀覆前处理工艺研究 [J]. 航天标准化, 2020(1): 34-35. doi: 10.3969/j.issn.1009-234X.2020.01.011 YANG Biao, YANG Jun, YUAN Guangsheng. Study on pretreatment technology of diamond surface plating [J]. Aerospace Standardization, 2020(1): 34-35. doi: 10.3969/j.issn.1009-234X.2020.01.011
[3]	方莉俐, 刘韩, 姜羽飞, 等. 线锯用金刚石微粉表面化学镀镍工艺及性能研究 [J]. 工具技术, 2024, 58(4): 54-58. doi: 10.3969/j.issn.1000-7008.2024.04.009 FANG Lili, LIU Han, JIANG Yufei, et al. Research on electroless nickel plating process and performance of diamond powder surface for wire saws [J]. Journal of Tool Technology, 2024, 58(4): 54-58. doi: 10.3969/j.issn.1000-7008.2024.04.009
[4]	马芝存. 辐照损伤合金化制备Mo/Ag系列层状金属基复合材料的研究 [D]. 天津: 天津大学, 2014. MA Zhicun. Research on preparation of Mo/Ag series laminar metal matrix composites using irradiation damage alloying method [D]. Tianjin: Tianjin University, 2014.
[5]	KANG Q, HE X, REN S, et al. Preparation of copper–diamond composites with chromium carbide coatings on diamond particles for heat sink applications [J]. Applied Thermal Engineering, 2013, 60(1/2): 423-429. doi: 10.1016/j.applthermaleng.2013.05.038
[6]	项东, 李木森, 刘科高, 等. 金刚石表面盐浴镀Ti层研究 [J]. 热加工工艺, 2009, 38(4): 74-77. doi: 10.3969/j.issn.1001-3814.2009.04.023 XIANG Dong, LI Musen, LIU Kegao, et al. Study on salt-bath plating Ti layers on diamond surface [J]. Hot Working Technology, 2009, 38(4): 74-77. doi: 10.3969/j.issn.1001-3814.2009.04.023
[7]	杜全斌, 张志康, 崔冰, 等. 金刚石表面改性技术研究进展与应用 [J]. 金属加工(热加工), 2023(12): 5-7. doi: 10.3969/j.issn.1674-165X.2023.12.001 DU Quanbin, ZHANG Zhikang CUI Bing, et al. Research progress and application of diamond surface modification technology [J]. MW Metal Forming, 2023(12): 5-7. doi: 10.3969/j.issn.1674-165X.2023.12.001
[8]	崔露露, 张磊. Ⅳ族及Ⅵ族过渡金属改性金刚石表面的热力学分析及应用 [J]. 有色金属(中英文), 2025, 15(2): 209-216. doi: 10.20242/j.issn.2097-5384.2025.02.004 CUI Lulu, ZHANG Lei. Thermodynamic analysis and application of Ⅳ and Ⅵ transition metals modify diamond surface [J]. Nonferrous Metals, 2025, 15(2): 209-216. doi: 10.20242/j.issn.2097-5384.2025.02.004
[9]	温国栋. 金刚石表面改性单金属镀层的研究进展 [J]. 热加工工艺, 2019, 48(16): 18-21. doi: 10.14158/j.cnki.1001-3814.2019.16.004 WEN Guodong. Research progress of diamond surface modified single metal coating [J]. Hot Working Technology, 2019, 48(16): 18-21. doi: 10.14158/j.cnki.1001-3814.2019.16.004
[10]	CUI L L, ZHANG L, YANG Y F, et al. Enhancing the thermal conductivity of laser powder bed fusion AlSi20 by introducing a novel TiC-Ti coated diamond powder [J]. Metallurgical and Materials Transactions A, 2024, 55(8): 2869-2880. doi: 10.1007/s11661-024-07441-5
[11]	WEI C L, XU X, WEI B Z, et al. Titanium coating on the surface of diamond particles by a novel rapid low-temperature salt bath plating method [J]. Chemical Physics Letters, 2020, 761: 138091. doi: 10.1016/j.cplett.2020.138091
[12]	祝平, 夏一骁, 张强, 等. 金刚石/金属复合材料界面改性研究进展 [J]. 中国材料进展, 2023, 42(12): 974-984. doi: 10.7502/j.issn.1674-3962.202305021 ZHU Ping, XIA Yixiao, ZHANG Qiang, et al. Research progress in interfacial modification of diamond / metal composites [J]. Materials China, 2023, 42(12): 974-984. doi: 10.7502/j.issn.1674-3962.202305021
[13]	王长瑞, 李宏钊, 田威, 等. 金刚石(100)-(111)面微沉积钨/铜复合材料制备与性能 [J]. 复合材料学报, 2022, 39(12): 6004-6016. doi: 10.13801/j.cnki.fhclxb.20211228.002 WANG Changrui, LI Hongzhao, TIAN Wei, et al. Preparation and properties of tungsten micro-deposited on diamond (100)-(111) facets/Cu composites [J]. Acta Materiae Compositae Sinica, 2022, 39(12): 6004-6016. doi: 10.13801/j.cnki.fhclxb.20211228.002
[14]	ANG L, LAN S, WEI Z, et al. A simple way to fabricate Ti6Al4V matrix composites reinforced by graphene with exceptional mechanical properties [J]. Material Letters, 2019, 257: 126750. doi: 10.1016/j.matlet.2019.126750
[15]	张利琪. TiC镀层改性金刚石及其铜基复合材料的热性能研究 [D]. 西安: 长安大学, 2022. ZHANG Liqi. Study of modified diamond by TiC-coated and the thermal properties of its copper matrix composites [D]. Xi′an: Chang′an University, 2022.
[16]	武玺旺, 皇甫战彪, 刘雪坤, 等. 熔盐法合成Ti和TiC镀覆层对金刚石热稳定性的影响 [J]. 金刚石与磨料磨具工程, 2023, 43(2): 196-201. doi: 10.13394/j.cnki.jgszz.2022.0054 WU Xiwang, HUANGFU Zhanbiao, LIU Xuekun, et al. Effect of Ti and TiC coating on the thermal stability of diamond [J]. Diamond & Abrasives Engineering, 2023, 43(2): 196-201. doi: 10.13394/j.cnki.jgszz.2022.0054
[17]	ZHANG H C, YUE W, SHA X H, et al. Vacuum tribological properties and impact toughness of polycrystalline diamond based on titanium-coated diamond particle [J]. Diamont Related Materials, 2020, 103: 107712. doi: 10.1016/j.diamond.2020.107712
[18]	汤英童, 杨长城. 金刚石粉表面化学镀镍工艺改进及镀层显微分析 [J]. 光学与光电技术, 2021, 19(5): 75-81. doi: 10.19519/j.cnki.1672-3392.2021.05.012 TANG Yingtong, YANG Changcheng. Improvement of the electroless nickel plating technology and surface microstructure analyses of the coating on diamond powder [J]. Optics & Optoelectronic Technology, 2021, 19(5): 75-81. doi: 10.19519/j.cnki.1672-3392.2021.05.012
[19]	贾攀, 卢灿华, 郑大方, 等. 金刚石镀钛层的结构讨论 [J]. 超硬材料工程, 2008(5): 5-8. doi: 10.3969/j.issn.1673-1433.2008.05.002 JIA Pan, LU Canhua, ZHENG Dafang, et al. Discussion on the structure of Ti-plated coat of diamond [J]. Superhard Material Engineering, 2008(5): 5-8. doi: 10.3969/j.issn.1673-1433.2008.05.002
[20]	DONG Y H, ZHANG R Q, ZHOU L, et al. Formation mechanism and properties of thickness-controllable tungsten coating on diamond surface by salt bath plating [J]. Materials Science Forum, 2018, 933: 264-273. doi: 10.4028/www.scientific.net/MSF.933.264
[21]	潘彦鹏. 双镀层法制备金刚石/铜复合材料及其性能研究 [D]. 北京: 北京科技大学, 2019. PAN Yanpeng. Preparation and properties of diamond/Cu composites fabricated with double-layer coated diamond particles [D]. Beijing: University of Science and Technology Beijing, 2019.
[22]	谢月扬. 低温熔盐法制备碳化铬镀层改性金刚石及其铜基复合材料的热性能 [D]. 西安: 长安大学, 2023: 32-47. XIE Yueyang. Thermal properties of copper matrix composites reinforced with chromium carbide-coated diamond prepared via low-temperature molten salts [D]. Xi′an: Chang’an University, 2023: 32-47.
[23]	李东鹏, 王卫泽, 黄继波, 等. W, Re过渡层对碳基体表面Al₂O₃涂层高温热匹配性和层间扩散的影响 [J]. 稀有金属, 2022, 46(9): 1181-1189. doi: 10.13373/j.cnki.cjrm.XY21070032 LI Dongpeng, WANG Weize, HUANG Jibo, et al. Alleviating high temperature thermal mismatch and element diffusion of Al₂O₃ coating on carbon substrate by introducing W/Re interlayer [J]. Chinese Journal of Rare Metals, 2022, 46(9): 1181-1189. doi: 10.13373/j.cnki.cjrm.XY21070032
[24]	胡玲. 熔盐电脱氧法制备钛钨合金时物质间的相互影响 [D]. 重庆: 重庆大学, 2016. HU Ling. Research in mutual influences between substances during preparation of Ti-W alloy via molten salt electro-deoxidation [D]. Chongqing: Chongqing University, 2016.
[25]	刘双双. 热扩散过程对Cu/Ni/Ti界面结构及耐蚀性能的影响 [D]. 西安: 长安大学, 2018: 16-55. LIU Shuangshuang. The influence of thermal diffusion on the interface structure and corrosion resistance of Cu/Ni/Ti [D]. Xi′an: Chang′an University, 2018: 16-55.
[26]	WALID M D, HEE S P, SOON H H. Fabrication of TiN/cBN and TiC/diamond coated particles by titanium deposition process [J]. Transactions of Nonferrous Metals Society of China, 2014, 24(11): 3562-3570. doi: 10.1016/S1003-6326(14)63502-0
[27]	徐俊. 金刚石盐浴镀钛对金刚石/铝复合材料组织及性能的影响 [D]. 南京: 东南大学, 2019. XU Jun. Effect of salt bath plating Ti on diamond particles on the microstructure and properties of diamond/Al composites [D]. Nanjing: Southeast University, 2019.
[28]	SHA X H, YUE W, ZHANG H C, et al. Enhanced oxidation and graphitization resistance of polycrystalline diamond sintered with Ti-coated diamond powders [J]. Journal of Materials Science & Technology, 2020, 43(8): 64-73. doi: 10.1016/j.jmst.2020.01.031