硬质合金气态渗硼预处理及其对金刚石薄膜附着性能的影响
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摘要
目的保持硬质合金预处理后基体的强度和表面光洁度,并且提升沉积的金刚石薄膜的膜基结合力。方法使用真空管式炉设备对硬质合金进行真空热处理气态渗硼,然后使用热丝化学气相沉积系统(HFCVD)沉积金刚石薄膜。之后采用X射线衍射仪、扫描电子显微镜(SEM)、能谱分析仪(EDS)、拉曼光谱仪、表面轮廓仪和洛氏压痕测试仪等对样品的结构、形貌和膜基结合性能进行了分析。结果使用真空热处理气态渗硼法可以在较短时间内完成硬质合金的硼化处理,得到以Co WB相为主的渗硼层,并且具有高温稳定性,表面硬度较未硼化处理的样品提高了15%～20%,最高硬度达到2445HV。相较于酸碱刻蚀二步法预处理,渗硼处理更加有效地改善了膜基结合力,当渗硼温度在1000℃时,可以更加有效抑制基体中的Co颗粒向外扩散,制备的金刚石薄膜质量最优,薄膜和基体的结合性能也更加优异。结论采用真空管式炉进行的热处理气态渗硼预处理法可以简单高效地实现对硬质合金的硼化处理,重复性好,并且可大批量处理,处理后沉积的金刚石薄膜有良好的膜基结合力。
The work aims to maintain the strength and surface finish of the cemented carbide after pretreatment and enhance the adhesion of the deposited diamond film. Vacuum heat treatment gaseous boronizing was proposed to the WC-Co by vacuum tube furnace. Then, the diamond films were deposited by hot filament chemical vapor deposition(HFCVD). The structure,morphology and film-substrate adhesion strength of the samples were measured by X-ray diffraction(XRD), scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), Raman spectroscopy, surface profiler and Rockwell indentation test.The boronization treatment of cemented carbide could be completed in a short time by vacuum heat treatment gaseous boronizing method to obtain a boride layer mainly composed of CoWB phase and with high temperature stability. The surface hardness was increased by 15%～20% compared with the samples without boronization treatment, and the maximum hardness was2445 HV. Compared with the two-step pretreatment of acid and alkali etching, the boronizing treatment was better to improve the film-substrate adhesion. When the boronizing temperature was 1000 ℃, the outward diffusion of Co particles from the internal substrate could be more effectively inhibited, the quality of the deposited diamond films was the best, and the film-substrate adhesion property was also more outstanding. The heat treatment gaseous boronizing provides a simple and efficient mean to pretreat the WC-Co, which has good repeatability and can be used for mass processing. The deposited diamond films after pretreatment have good film substrate adhesion.
The work aims to maintain the strength and surface finish of the cemented carbide after pretreatment and enhance the adhesion of the deposited diamond film. Vacuum heat treatment gaseous boronizing was proposed to the WC-Co by vacuum tube furnace. Then, the diamond films were deposited by hot filament chemical vapor deposition(HFCVD). The structure,morphology and film-substrate adhesion strength of the samples were measured by X-ray diffraction(XRD), scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), Raman spectroscopy, surface profiler and Rockwell indentation test.The boronization treatment of cemented carbide could be completed in a short time by vacuum heat treatment gaseous boronizing method to obtain a boride layer mainly composed of CoWB phase and with high temperature stability. The surface hardness was increased by 15%～20% compared with the samples without boronization treatment, and the maximum hardness was2445 HV. Compared with the two-step pretreatment of acid and alkali etching, the boronizing treatment was better to improve the film-substrate adhesion. When the boronizing temperature was 1000 ℃, the outward diffusion of Co particles from the internal substrate could be more effectively inhibited, the quality of the deposited diamond films was the best, and the film-substrate adhesion property was also more outstanding. The heat treatment gaseous boronizing provides a simple and efficient mean to pretreat the WC-Co, which has good repeatability and can be used for mass processing. The deposited diamond films after pretreatment have good film substrate adhesion.
引文
[1]魏秋平,刘培植,余志明,等.稀土-硼共渗预处理对YG6表面金刚石薄膜质量的影响[J].粉末冶金材料科学与工程,2010,15(4):331-337.WEI Qiu-ping,LIU Pei-zhi,YU Zhi-ming,et al.Effects of CeO2 and B co-infiltration pretreatment on the quality of diamond films deposited on cemented carbide[J].Materials science and engineering of powder metallurgy,2010,15(4):331-337.
[2]付德君,杨慧娟,吴大维,等.刀具涂层技术的新进展[J].航空制造技术,2009(13):80-83.FU De-jun,YANG Hui-juan,WU Da-wei,et al.Latest development of coating technology for cutting tool[J].Aeronautical manufacturing technology,2009(13):80-83.
[3]ZHANG L,ZHOU K,WEI Q,et al.Thermal conductivity enhancement of phase change materials with 3D porous diamond foam for thermal energy storage[J].Applied energy,2019,233-234:208-219.
[4]熊超,李烈军,苏东艺,等.预处理对金刚石薄膜质量及结合力的影响[J].表面技术,2018(1):203-210.XIONG Chao,LI Lie-jun,SU Dong-yi,et al.Effects of pretreatment on quality and adhesion of diamond films on cemented carbides[J].Surface technology,2018(1):203-210.
[5]CUI Y X,SHEN B,SUN F H.Influence of amorphous ceramic interlayers on tribological properties of CVDdiamond films[J].Applied surface science,2014,313(9):918-925.
[6]HEI H,JING M,LI X,et al.Preparation and performance of chemical vapor deposition diamond coatings synthesized onto the cemented carbide micro-end mills with a SiC interlayer[J].Surface&coatings technology,2015,261:272-277.
[7]POLINI R.Chemically vapour deposited diamond coatings on cemented tungsten carbides:Substrate pretreatments,adhesion and cutting performance[J].Thin solid films,2006,515(1):4-13.
[8]LIU M N,BIAN Y B,ZHENG S J,et al.Growth and mechanical properties of diamond films on cemented carbide with buffer layers[J].Thin solid films,2015,584:165-169.
[9]DUMPALA R,CHANDRAN M,RAO M S R.Engineered CVD diamond coatings for machining and tribological applications[J].JOM,2015,67(7):1565-1577.
[10]WEI Q P,YU Z M,ASHFOLD M N R,et al.Synthesis of micro-or nano-crystalline diamond films on WC-Co substrates with various pretreatments by hot filament chemical vapor deposition[J].Applied surface science,2010,256(13):4357-4364.
[11]XU Z Q,LEV L,LUKITSCH M,et al.Effects of surface pretreatments on the deposition of adherent diamond coatings on cemented tungsten carbide substrates[J].Diamond&related materials,2007,16(3):461-466.
[12]CHANDRAN M,HOFFMAN A.Diamond film deposition on WC-Co and steel substrates with a CrN interlayer for tribological applications[J].Journal of physics D applied physics,2016,49(21):213002.
[13]CHANDRAN M,SAMMLER F,UHLMANN E,et al.Wear performance of diamond coated WC-Co tools with a Cr N interlayer[J].Diamond&related materials,2017,73:47-55.
[14]PING L,GOMEZ H,XIAO X,et al.Coating thickness and interlayer effects on CVD-diamond film adhesion to cobalt-cemented tungsten carbides[J].Surface&coatings technology,2013,215(2):272-279.
[15]YANG T,WEI Q,QI Y,et al.The diffusion behavior of carbon in sputtered tungsten film and sintered tungsten block and its effect on diamond nucleation and growth[J].Diamond&related materials,2015,52:49-58.
[16]JOHNSTON J M,JUBINSKY M,CATLEDGE S A.Plasma boriding of a cobalt-chromium alloy as an interlayer for nanostructured diamond growth[J].Applied surface science,2015,328:133-139.
[17]YU L D,SHUY G W,VILAITHONG T.Friction modification of WC-Co by ion implantation[J].Surface&coatings technology,2000,128(1):404-409.
[18]ULUTAN M,YILDIRIM M M,?ELIK O N,et al.Tribological properties of borided AISI 4140 steel with the powder pack-boriding method[J].Tribology letters,2010,38(3):231-239.
[19]MERCURIO L D,PETROV K,PESHEV P,et al.The elemental and phase composition of boride coatings deposited by diffusion on a WC-Co alloy[J].Journal of the less common metals,1979,67(1):59-63.
[20]ZAKHARIEV Z,ZLATEVA R,PETROV K.Microhardness and high-temperature oxidation stability of Co WB[J].Journal of the less common metals,1986,117(1):129-133.
[21]CREMER R,MERTENS R,NEUSCHüTZ D,et al.Formation of intermetallic cobalt phases in the near surface region of cemented carbides for improved diamond layer deposition[J].Thin solid films,1999,s355-356:127-133.
[22]TANG W,WANG S,LU F.Preparation and performance of diamond coatings on cemented carbide inserts with cobalt boride interlayers[J].Diamond&related materials,2000,9:1744-1748.
[23]TANG W,WANG Q,WANG S,et al.A comparison in performance of diamond coated cemented carbide cutting tools with and without a boride interlayer[J].Surface&coatings technology,2002,153(2):298-303.
[24]LIN G,ZHANG Z,QIU Z,et al.Boronizing mechanism of cemented carbides and their wear resistance[J].International journal of refractory metals&hard materials,2013,41(11):351-355.
[25]HAUBNER R,K?PF A,LUX B.Diamond deposition on hardmetal substrates after pre-treatment with boron or sulfur compounds[J].Diamond&related materials,2002,11(3):555-561.
[26]K?KSAL S.The characterization of WC-Co based materials boronized within molten salt bath[J].Solid state phenomena,2008,144:261-266.
[27]MAN W D,WANG J H,MA Z B,et al.Plasma boronitriding of WC(Co)substrate as an effective pretreatment process for diamond CVD[J].Surface&coatings technology,2003,171(1-3):241-246.
[28]BASTURK S,SENBABAOGLU F,ERTEN M,et al.Titanium machining with new plasma boronized cutting tools[J].CIRP Annals-manufacturing technology,2010,59(1):101-104.
[29]JOHNSTON J M,CATLEDGE S A.Metal-boride phase formation on tungsten carbide(WC-Co)during microwave plasma chemical vapor deposition[J].Applied surface science,2016,364:315-321.
[30]WEI Q P,YU Z M,ASHFOLD M N R,et al.Effects of thickness and cycle parameters on fretting wear behavior of CVD diamond coatings on steel substrates[J].Surface&coatings technology,2010,205(1):158-167.
[31]YANG T,WEI Q,YAO Q,et al.Microstructure evolution of thermal spray WC-Co interlayer during hot filament chemical vapor deposition of diamond thin films[J].Journal of alloys&compounds,2015,639:659-668.
[32]刘兴龙,王兵,熊鹰,等.等离子体硼氮共渗预处理对硬质合金刀具表面金刚石涂层结合强度的影响[J].稀有金属,2016,40(5):460-466.LIU Xing-long,WANG Bing,XIONG Ying,et al.Adhesion between diamond film and cemented carbide affected by plasma boronitriding pretreatment[J].Chinese journal of rare metals,2016,40(5):460-466.
[33]HARRIS S J,WEINER A M,PRAWER S,et al.Diamond film quality:Effects of gas phase concentrations on the Raman spectra[J].Journal of applied physics,1996,80(4):2187-2194.
[2]付德君,杨慧娟,吴大维,等.刀具涂层技术的新进展[J].航空制造技术,2009(13):80-83.FU De-jun,YANG Hui-juan,WU Da-wei,et al.Latest development of coating technology for cutting tool[J].Aeronautical manufacturing technology,2009(13):80-83.
[3]ZHANG L,ZHOU K,WEI Q,et al.Thermal conductivity enhancement of phase change materials with 3D porous diamond foam for thermal energy storage[J].Applied energy,2019,233-234:208-219.
[4]熊超,李烈军,苏东艺,等.预处理对金刚石薄膜质量及结合力的影响[J].表面技术,2018(1):203-210.XIONG Chao,LI Lie-jun,SU Dong-yi,et al.Effects of pretreatment on quality and adhesion of diamond films on cemented carbides[J].Surface technology,2018(1):203-210.
[5]CUI Y X,SHEN B,SUN F H.Influence of amorphous ceramic interlayers on tribological properties of CVDdiamond films[J].Applied surface science,2014,313(9):918-925.
[6]HEI H,JING M,LI X,et al.Preparation and performance of chemical vapor deposition diamond coatings synthesized onto the cemented carbide micro-end mills with a SiC interlayer[J].Surface&coatings technology,2015,261:272-277.
[7]POLINI R.Chemically vapour deposited diamond coatings on cemented tungsten carbides:Substrate pretreatments,adhesion and cutting performance[J].Thin solid films,2006,515(1):4-13.
[8]LIU M N,BIAN Y B,ZHENG S J,et al.Growth and mechanical properties of diamond films on cemented carbide with buffer layers[J].Thin solid films,2015,584:165-169.
[9]DUMPALA R,CHANDRAN M,RAO M S R.Engineered CVD diamond coatings for machining and tribological applications[J].JOM,2015,67(7):1565-1577.
[10]WEI Q P,YU Z M,ASHFOLD M N R,et al.Synthesis of micro-or nano-crystalline diamond films on WC-Co substrates with various pretreatments by hot filament chemical vapor deposition[J].Applied surface science,2010,256(13):4357-4364.
[11]XU Z Q,LEV L,LUKITSCH M,et al.Effects of surface pretreatments on the deposition of adherent diamond coatings on cemented tungsten carbide substrates[J].Diamond&related materials,2007,16(3):461-466.
[12]CHANDRAN M,HOFFMAN A.Diamond film deposition on WC-Co and steel substrates with a CrN interlayer for tribological applications[J].Journal of physics D applied physics,2016,49(21):213002.
[13]CHANDRAN M,SAMMLER F,UHLMANN E,et al.Wear performance of diamond coated WC-Co tools with a Cr N interlayer[J].Diamond&related materials,2017,73:47-55.
[14]PING L,GOMEZ H,XIAO X,et al.Coating thickness and interlayer effects on CVD-diamond film adhesion to cobalt-cemented tungsten carbides[J].Surface&coatings technology,2013,215(2):272-279.
[15]YANG T,WEI Q,QI Y,et al.The diffusion behavior of carbon in sputtered tungsten film and sintered tungsten block and its effect on diamond nucleation and growth[J].Diamond&related materials,2015,52:49-58.
[16]JOHNSTON J M,JUBINSKY M,CATLEDGE S A.Plasma boriding of a cobalt-chromium alloy as an interlayer for nanostructured diamond growth[J].Applied surface science,2015,328:133-139.
[17]YU L D,SHUY G W,VILAITHONG T.Friction modification of WC-Co by ion implantation[J].Surface&coatings technology,2000,128(1):404-409.
[18]ULUTAN M,YILDIRIM M M,?ELIK O N,et al.Tribological properties of borided AISI 4140 steel with the powder pack-boriding method[J].Tribology letters,2010,38(3):231-239.
[19]MERCURIO L D,PETROV K,PESHEV P,et al.The elemental and phase composition of boride coatings deposited by diffusion on a WC-Co alloy[J].Journal of the less common metals,1979,67(1):59-63.
[20]ZAKHARIEV Z,ZLATEVA R,PETROV K.Microhardness and high-temperature oxidation stability of Co WB[J].Journal of the less common metals,1986,117(1):129-133.
[21]CREMER R,MERTENS R,NEUSCHüTZ D,et al.Formation of intermetallic cobalt phases in the near surface region of cemented carbides for improved diamond layer deposition[J].Thin solid films,1999,s355-356:127-133.
[22]TANG W,WANG S,LU F.Preparation and performance of diamond coatings on cemented carbide inserts with cobalt boride interlayers[J].Diamond&related materials,2000,9:1744-1748.
[23]TANG W,WANG Q,WANG S,et al.A comparison in performance of diamond coated cemented carbide cutting tools with and without a boride interlayer[J].Surface&coatings technology,2002,153(2):298-303.
[24]LIN G,ZHANG Z,QIU Z,et al.Boronizing mechanism of cemented carbides and their wear resistance[J].International journal of refractory metals&hard materials,2013,41(11):351-355.
[25]HAUBNER R,K?PF A,LUX B.Diamond deposition on hardmetal substrates after pre-treatment with boron or sulfur compounds[J].Diamond&related materials,2002,11(3):555-561.
[26]K?KSAL S.The characterization of WC-Co based materials boronized within molten salt bath[J].Solid state phenomena,2008,144:261-266.
[27]MAN W D,WANG J H,MA Z B,et al.Plasma boronitriding of WC(Co)substrate as an effective pretreatment process for diamond CVD[J].Surface&coatings technology,2003,171(1-3):241-246.
[28]BASTURK S,SENBABAOGLU F,ERTEN M,et al.Titanium machining with new plasma boronized cutting tools[J].CIRP Annals-manufacturing technology,2010,59(1):101-104.
[29]JOHNSTON J M,CATLEDGE S A.Metal-boride phase formation on tungsten carbide(WC-Co)during microwave plasma chemical vapor deposition[J].Applied surface science,2016,364:315-321.
[30]WEI Q P,YU Z M,ASHFOLD M N R,et al.Effects of thickness and cycle parameters on fretting wear behavior of CVD diamond coatings on steel substrates[J].Surface&coatings technology,2010,205(1):158-167.
[31]YANG T,WEI Q,YAO Q,et al.Microstructure evolution of thermal spray WC-Co interlayer during hot filament chemical vapor deposition of diamond thin films[J].Journal of alloys&compounds,2015,639:659-668.
[32]刘兴龙,王兵,熊鹰,等.等离子体硼氮共渗预处理对硬质合金刀具表面金刚石涂层结合强度的影响[J].稀有金属,2016,40(5):460-466.LIU Xing-long,WANG Bing,XIONG Ying,et al.Adhesion between diamond film and cemented carbide affected by plasma boronitriding pretreatment[J].Chinese journal of rare metals,2016,40(5):460-466.
[33]HARRIS S J,WEINER A M,PRAWER S,et al.Diamond film quality:Effects of gas phase concentrations on the Raman spectra[J].Journal of applied physics,1996,80(4):2187-2194.
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