铜材表面激光合金化和激光熔覆制备Ni/Cu-Cr_3C_2/Co梯度涂层
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摘要
目的提高铜合金的表面硬度,改善其耐磨性能。方法利用激光表面合金化和激光熔覆工艺在铜合金表面制备出Ni/Cu-Cr_3C_2/Co梯度涂层。采用X射线衍射仪、扫描电镜及能谱仪,系统分析了合金化过渡层与熔覆层的物相构成及显微组织,通过硬度测试、摩擦磨损实验,对梯度涂层的显微硬度和耐磨性进行评估。结果合金化过渡层组织致密且具有单一柱状晶结构,主要由α-(Cu,Ni)固溶体、Ni_3Al和Ni Al构成。Cr_3C_2/Co复合熔覆层中分布着未熔Cr_3C_2颗粒,且以未熔Cr_3C_2颗粒为中心,四周有大量呈杆状(或针状)的M_(23)C_6和M_7C_3型碳化物,这种碳化物可以有效提高熔覆层的硬度。梯度涂层的显微硬度从基体的80HV逐渐增加到熔覆层的640HV,梯度涂层的摩擦磨损失重仅为铜合金基体的1/8。铜基体的磨损表面发生大规模破坏并形成大量磨屑,其磨损机制主要是粘着磨损;Cr_3C_2/Co喷涂层由于内部结合力较弱,出现了大量的疲劳磨损面,其磨损机制为表面疲劳磨损;而Ni/Cu-Cr_3C_2/Co梯度涂层的磨损表面比较平整,只存在轻微的"犁沟",其磨损机制为典型的磨粒磨损。结论梯度涂层由于Cr_3C_2、M_(23)C_6及M_7C_3相的存在,显微硬度和耐磨性能显著提高。同时,涂层的成分与性能均呈一定的梯度变化,改善了铜基体与涂层的相容性。
The work aims to improve surface hardness and wear resistance of copper alloys. A Ni/Cu-Cr_3C_2/Co gradient coating was prepared successfully on the surface of copper alloy by combining laser alloying and laser cladding technologies. Phase composition and microstructure of the gradient coating were analyzed by X-ray diffractometer, scanning electron micro-scope, energy dispersive spectrometer, etc. Microhardness and wear resistance of the gradient coating were evaluated by hardness test and friction-wear test. The alloying transition layer was dense and had a single columnar crystal structure, and phases were mainly composed of α-(Cu,Ni), Ni_3Al and Ni Al. Undissolved Cr_3C_2 particles were distributed in the Cr_3C_2/Co composite cladding layers. A large number of rod-like(or needle-like) M_(23)C_6 and M_7C_3 carbides centered around the undissolved Cr_3C_2 particles, which could effectively improve hardness of the cladding layer. Microhardness of the gradient coating gradually increased from the 80 HV(substrate) to 640 HV(cladding layer), and friction-wear loss of the gradient coating was only 1/8 of copper substrate. There was much debris on the worn surface of copper substrate due to massive destruction, and its wear mechanism was mainly adhesive wear. Due to weak internal bonding force, a large number of fatigue wear surfaces appeared on the Cr_3C_2/Co sprayed coating, and the wear mechanism was surface fatigue wear. However, worn surface of the Ni/Cu-Cr_3C_2/Co gradient coating was relatively smooth, there were some slight "furrows", and its wear mechanism was typical abrasive wear. Because of the existence of Cr_3C_2, M_(23)C_6 and M_7C_3 phases, microhardness and wear resistance of the gradient coating are significantly improved. Meanwhile, composition and properties of the coating show a certain gradient change, which improves the compatibility between copper substrate and coating.
The work aims to improve surface hardness and wear resistance of copper alloys. A Ni/Cu-Cr_3C_2/Co gradient coating was prepared successfully on the surface of copper alloy by combining laser alloying and laser cladding technologies. Phase composition and microstructure of the gradient coating were analyzed by X-ray diffractometer, scanning electron micro-scope, energy dispersive spectrometer, etc. Microhardness and wear resistance of the gradient coating were evaluated by hardness test and friction-wear test. The alloying transition layer was dense and had a single columnar crystal structure, and phases were mainly composed of α-(Cu,Ni), Ni_3Al and Ni Al. Undissolved Cr_3C_2 particles were distributed in the Cr_3C_2/Co composite cladding layers. A large number of rod-like(or needle-like) M_(23)C_6 and M_7C_3 carbides centered around the undissolved Cr_3C_2 particles, which could effectively improve hardness of the cladding layer. Microhardness of the gradient coating gradually increased from the 80 HV(substrate) to 640 HV(cladding layer), and friction-wear loss of the gradient coating was only 1/8 of copper substrate. There was much debris on the worn surface of copper substrate due to massive destruction, and its wear mechanism was mainly adhesive wear. Due to weak internal bonding force, a large number of fatigue wear surfaces appeared on the Cr_3C_2/Co sprayed coating, and the wear mechanism was surface fatigue wear. However, worn surface of the Ni/Cu-Cr_3C_2/Co gradient coating was relatively smooth, there were some slight "furrows", and its wear mechanism was typical abrasive wear. Because of the existence of Cr_3C_2, M_(23)C_6 and M_7C_3 phases, microhardness and wear resistance of the gradient coating are significantly improved. Meanwhile, composition and properties of the coating show a certain gradient change, which improves the compatibility between copper substrate and coating.
引文
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[16]何宜柱,斯松华,徐锟,等.Cr3C2对激光熔覆钴基合金涂层组织与性能的影响[J].中国激光,2004,31(9):1143-1148.HE Yi-zhu,SI Song-hua,XU Kun,et al.Effect of Cr3C2particles on microstructure and corrosion-wear resistance of laser cladding Co-based alloy coating[J].Chinese journal of lasers,2004,31(9):1143-1148.
[2]于朝清,秦秀芳,刘安利.无氧铜的制备及电子铜的发展趋势[J].电工材料,2006(1):10-13.YU Chao-qing,QIN Xiu-fang,LIU An-li.Preparation of oxygen-free copper and developing trend of electron copper[J].Electrical engineering materials,2006(1):10-13.
[3]李晓杰,王占磊,李瑞勇,等.爆炸粉末烧结法制取WC/Cu复合材料的研究[J].材料开发与应用,2006,21(3):16-17.LI Xiao-jie,WANG Zhan-lei,LI Rui-yong,et al.Experimental study on WC/Cu composites produced by explosive powder compaction[J].Development and application of materials,2006,21(3):16-17.
[4]YAN H,WANG A,XU K,et al.Microstructure and interfacial evaluation of Co-based alloy coating on copper by pulsed Nd:YAG multilayer laser cladding[J].Journal of alloys&compounds,2010,505(2):645-653.
[5]马文有,陈兴驰,周克崧,等.铜合金表面热喷涂镍基合金层激光重熔后的显微组织及耐磨性能[J].材料保护,2010,43(2):47-49.MA Wen-you,CHEN Xing-chi,ZHOU Ke-song,et al.Microstructure and wear resistance of laser remelted plasma sprayed Ni-based alloy coating on copper alloy[J].Journal of materials protection,2010,43(2):47-49.
[6]高泽平.连铸结晶器铜板及镀层的应用进展[J].特殊钢,2007,28(4):39-41.GAO Ze-ping.Application progress of concasting mould copper plate and coat material[J].Special steel,2007,28(4):39-41.
[7]MAJUMDAR J D.Development of in-situ composite surface on mild steel by laser surface alloying with silicon and its remelting[J].Surface&coatings technology,2010,205(7):1820-1825.
[8]TOMIDA S,NAKATA K,SAJI S,et al.Formation of metal matrix composite layer on aluminum alloy with Ti C-Cu powder by laser surface alloying process[J].Surface&coatings technology,2001,142(1):585-589.
[9]LIU J,ZHANG S,WANG H.Microstructure and wear resistance of C-W elements laser surface alloyed coating of TA15 titanium alloy[J].Heat treatment of metals,2012,37(3):37-41.
[10]陈岁元,董江,陈军,等.结晶器铜合金表面激光原位制备纳米颗粒增强钴基梯度涂层[J].中国激光,2011,38(7):131-137.CHEN Sui-yuan,DONG Jiang,CHEN Jun,et al.Nanoparticles reinforced Co-based gradient coating with high wear-resistance prepared in-situ by laser on surface of crystallizer copper alloy[J].Chinese journal of lasers,2011,38(7):131-137.
[11]赵静梅,高士友,牟明强,等.铜合金表面搅拌摩擦焊和激光熔覆制备镍基合金涂层[J].中国激光,2016,43(1):136-141.ZHAO Jing-mei,GAO Shi-you,MU Ming-qiang,et al.Ni-based alloy surface layer on copper fabricated by combination of laser cladding and friction stir welding[J].Chinese journal of lasers,2016,43(1):136-141.
[12]赵健,刘光,马冰,等.铜表面激光合金化和激光熔覆制备Ni/Ni Cr BSi梯度涂层[J].兵器材料科学与工程,2018,41(2):53-57.ZHAO Jian,LIU Guang,MA Bing,et al.Ni/Ni Cr BSi gradient coating on copper surface fabricated by combination of laser surface alloying and laser cladding[J].Ordnance material science and engineering,2018,41(2):53-57.
[13]程广萍,何宜柱.激光熔覆镍基合金与铝反应合成Ni-Al金属间化合物覆层的研究[J].材料工程,2010(3):29-33.CHENG Guang-ping,HE Yi-zhu.Ni-Al Intermetallic coatings prepared by laser-cladding synthesize with Ni-based alloy and Al[J].Journal of materials engineering,2010(3):29-33.
[14]闫华,张培磊,于治水.铜合金表面激光熔覆Ni基涂层的组织及界面结构[J].特种铸造及有色合金,2013,33(12):1093-1097.YAN Hua,ZHANG Pei-lei,YU Zhi-shui.Microstructure and interfacial characteristics of laser cladding Ni-based coating on copper alloy[J].Special-cast and non-ferrous alloys,2013,33(12):1093-1097.
[15]贺海燕.H13钢表面激光熔覆Ni基、Co基合金粉末的试验研究[D].太原:太原理工大学,2010.HE Hai-yan.Experimental study on laser cladding properties of Ni-based powders and Co-based powders on the surface of H13 steel[D].Taiyuan:Taiyuan University of Technology,2010.
[16]何宜柱,斯松华,徐锟,等.Cr3C2对激光熔覆钴基合金涂层组织与性能的影响[J].中国激光,2004,31(9):1143-1148.HE Yi-zhu,SI Song-hua,XU Kun,et al.Effect of Cr3C2particles on microstructure and corrosion-wear resistance of laser cladding Co-based alloy coating[J].Chinese journal of lasers,2004,31(9):1143-1148.