不锈钢316L氮化/(Cr,Ti)N涂层原位复合制备
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摘要
目的研究不同复合涂层的结构及其对力学性能的影响。方法采用等离子体增强磁控溅射系统在奥氏体不锈钢表面分别进行等离子体氮化、(Cr,Ti)N涂层、氮化+(Cr,Ti)N涂层、氮化+Cr+(Cr,Ti)N涂层四种复合表面强化处理。采用XRD、SEM、纳米压痕仪、摩擦磨损仪和划痕仪等分别研究了不同改性层对微观结构以及力学性能的影响。结果氮化后,形成了较高含氮量的过饱和固溶体相(γN),并伴有少量Cr_2N和Fe_2N析出,硬度及杨氏模量分别为18.3 GPa、264.7 GPa。氮化后原位沉积涂层有效避免了氮化物相的析出,过饱和氮原子向基体进一步扩散,增加了氮化层的深度。两种氮化后复合(Cr,Ti)N涂层的硬度和模量均高于单一的(Cr,Ti)N涂层(分别为20.2GPa和271.8GPa),其中氮化+(Cr,Ti)N涂层的硬度和模量均最高(分别为25.4 GPa和345.6 GPa),氮化+Cr+(Cr,Ti)N涂层次之(22.4 GPa和326.3 GPa)。由于氮化层起到了良好的梯度过渡作用,氮化+(Cr,Ti)N涂层的膜基结合力最高,从单一涂层的9.5 N提高到50.9 N,其摩擦系数降低到0.43,磨损量最低,仅为基体的0.66%。结论氮化+(Cr,Ti)N复合涂层的力学性能最佳。
The work aims to study the micro-structure of different composite coatings and the effects on mechanical properties. Plasma nitriding,(Cr,Ti)N coating, nitriding+(Cr,Ti)N coating and nitriding+Cr+(Cr,Ti)N coating were strengthened on the surface of austenitic stainless steel by plasma enhanced magnetron sputtering system. The effects of different modified layers on micro-structure and mechanical properties were studied respectively by XRD, SEM, nano-indentation tester, pin-on-disk tribometer and scratch tester. After nitriding, supersaturated solid solution phase with high nitrogen content(γN) was formed with a few precipitations of Cr_2N and Fe_2N. The hardness and modulus were respectively 18.3 GPa and 264.7 GPa. The in-situ deposition of the coating after nitriding effectively prevented the precipitation of the nitride phase, and promoted the diffusion of supersaturated nitrogen into the substrate, thus increasing the depth of nitrided layer. The nano-hardness and modulus of(Cr,Ti)N coatings combined with nitriding were higher than those of single(Cr,Ti)N coating(20.2 GPa and 271.8 GPa), and those of nitriding+(Cr,Ti)N were the highest(25.4 GPa and 345.6 GPa), followed by those of nitriding+Cr+(Cr,Ti)N(22.4 GPa and 326.3 GPa). The adhesion strength of(Cr,Ti)N coating combined with nitriding was the highest due to the gradient transition of nitrided layer, which improved from that of the single coating of 9.5 N to 53 N. The friction coefficient decreased to 0.43, and the wear-rate was the minimum, namely 0.66% of that of the substrate. The(Cr,Ti)N composite coating combined with nitriding has the best mechanical properties.
The work aims to study the micro-structure of different composite coatings and the effects on mechanical properties. Plasma nitriding,(Cr,Ti)N coating, nitriding+(Cr,Ti)N coating and nitriding+Cr+(Cr,Ti)N coating were strengthened on the surface of austenitic stainless steel by plasma enhanced magnetron sputtering system. The effects of different modified layers on micro-structure and mechanical properties were studied respectively by XRD, SEM, nano-indentation tester, pin-on-disk tribometer and scratch tester. After nitriding, supersaturated solid solution phase with high nitrogen content(γN) was formed with a few precipitations of Cr_2N and Fe_2N. The hardness and modulus were respectively 18.3 GPa and 264.7 GPa. The in-situ deposition of the coating after nitriding effectively prevented the precipitation of the nitride phase, and promoted the diffusion of supersaturated nitrogen into the substrate, thus increasing the depth of nitrided layer. The nano-hardness and modulus of(Cr,Ti)N coatings combined with nitriding were higher than those of single(Cr,Ti)N coating(20.2 GPa and 271.8 GPa), and those of nitriding+(Cr,Ti)N were the highest(25.4 GPa and 345.6 GPa), followed by those of nitriding+Cr+(Cr,Ti)N(22.4 GPa and 326.3 GPa). The adhesion strength of(Cr,Ti)N coating combined with nitriding was the highest due to the gradient transition of nitrided layer, which improved from that of the single coating of 9.5 N to 53 N. The friction coefficient decreased to 0.43, and the wear-rate was the minimum, namely 0.66% of that of the substrate. The(Cr,Ti)N composite coating combined with nitriding has the best mechanical properties.
引文
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[13]袁志钟,陈康敏,戴起勋,等.高氮奥氏体钢的Cr2N晶间析出研究[J].金属热处理, 2004, 29(3):37-40.YUAN Zhi-zhong, CHEN Kang-min, DAI Qi-xun, et al.StudyonCr2N-phaseprecipitationalongintercrystalline of high nitrogen austenitic steels[J]. Metal heat treatment,2004, 29(3):37-40.
[14]SUN P L, SU C Y, LIOU T P, et al. Mechanical behavior ofTiN/CrNnano-multilayerthinfilmdepositedbyunbalanced magnetron sputter process[J]. Journal of alloys&compounds, 2011, 509(6):3197-3201.
[15]SAIKIA P, JOSEPH A, RANE R, et al. Role of substrate and deposition conditions on the texture evolution of titanium nitride thin film on bare and plasma-nitrided highspeedsteel[J].Journaloftheoretical&appliedphysics,2013, 7(1):1-12.
[16]LEYLANDA,MATTHEWSA.Onthesignificanceof the H/E, ratio in wear control:A nano-composite coating approachtooptimizedtribologicalbehaviour[J].Wear,2000, 246(1):1-11.
[17]MUSILJ.Hardandsuperhardnano-compositecoatings[J].Surface&coatingstechnology,2000,125(1):322-330.
[18]YAN P, DENG J, WU Z, et al. Friction and wear behavior of the PVD(Zr,Ti)N coated cemented carbide against40Cr hardened steel[J]. International journal of refractory metals&hard materials, 2012, 35(9):213-220.
[2]夏铭,王泽华,柏芳,等.反应等离子喷涂Ti N涂层的研究进展[J].表面技术, 2015(8):1-8.XIAMing,WANGZe-hua,BAIFang,etal.Research progress of reactive plasma sprayed TiN coating[J]. Surface technology, 2015(8):1-8.
[3]WIKLUNDU,HEDENQVISTP,HOGMAIKS.Multilayer cracking resistance in bending[J]. Surface&coatings technology, 1997, 97(1):773-778.
[4]金恒毅,于志明.不同底层TiN离子镀复合涂层的研究[J].表面技术, 1995(1):5-9.JINHeng-yi,YUZhi-ming.Studyontechnologyof IP-TiN coating on pretreated surface[J]. Surface technology, 1995(1):5-9.
[5]BIN-SUDIN M, LEYLAND A, JAMES A S, et al. Substrate surface finish effects in duplex coatings of PAPVD TiN and CrN with electroless nickel-phosphorus interlayers[J].Surface&coatingstechnology,1996,81(2-3):215-224.
[6]GILEWICZ A, MURZYNSKI D, DOBRUCHOWSKA E,et al. Wear and corrosion behavior of CrCN/CrN coatings deposited by cathodic arc evaporation on nitrided 42CrMo4steel substrates[J]. Protection of metals&physical chemistry of surfaces, 2017, 53(2):312-321.
[7]BASHIR M I, SHAFIQ M, NAEEM M, et al. Enhanced surfacepropertiesofaluminumbyPVD-Ti Ncoating combined with cathodic cage plasma nitriding[J]. Surface&coatings technology, 2017, 327:59-65.
[8]BATISTAJCA,GODOYC,MATTHEWSA.Microscaleabrasiveweartestingofduplexandnon-duplex(single-layered)PVD(Ti,Al)N, TiN and Cr-N coatings[J].Tribology international, 2002, 35(6):363-372.
[9]LEE S Y. Mechanical properties of TiNx/Cr1?xN thin films on plasma nitriding-assisted AISI H13 steel[J]. Surface&coatings technology, 2005, 193(1-3):55-59.
[10]刘一梅,王亮,黑祖昆.离子渗氮提高硬质膜层与普通结构钢基体结合力的研究[J].大连海事大学学报,1997(4):89-92.LIU Yi-mei, WANG Liang, HEI Zu-kun. To enhance the binding force between hard coating and a common structure steel substrate by ion nitriding[J]. Journal of Dalian Maritime University, 1997(4):89-92.
[11]BASSO R L O, PIMENTEL V L, WEBER S, et al. Magneticandstructuralpropertiesofionnitridedstainless steel[J]. Journal of applied physics, 2009, 105(12):3965.
[12]SIMMONS J W, ATTERIDGE D G, RAWERS J C. Sensitization of high-nitrogen austenitic stainless steels by dichromiumnitrideprecipitation[J].Corrosionscience,1994, 50(7):491-501.
[13]袁志钟,陈康敏,戴起勋,等.高氮奥氏体钢的Cr2N晶间析出研究[J].金属热处理, 2004, 29(3):37-40.YUAN Zhi-zhong, CHEN Kang-min, DAI Qi-xun, et al.StudyonCr2N-phaseprecipitationalongintercrystalline of high nitrogen austenitic steels[J]. Metal heat treatment,2004, 29(3):37-40.
[14]SUN P L, SU C Y, LIOU T P, et al. Mechanical behavior ofTiN/CrNnano-multilayerthinfilmdepositedbyunbalanced magnetron sputter process[J]. Journal of alloys&compounds, 2011, 509(6):3197-3201.
[15]SAIKIA P, JOSEPH A, RANE R, et al. Role of substrate and deposition conditions on the texture evolution of titanium nitride thin film on bare and plasma-nitrided highspeedsteel[J].Journaloftheoretical&appliedphysics,2013, 7(1):1-12.
[16]LEYLANDA,MATTHEWSA.Onthesignificanceof the H/E, ratio in wear control:A nano-composite coating approachtooptimizedtribologicalbehaviour[J].Wear,2000, 246(1):1-11.
[17]MUSILJ.Hardandsuperhardnano-compositecoatings[J].Surface&coatingstechnology,2000,125(1):322-330.
[18]YAN P, DENG J, WU Z, et al. Friction and wear behavior of the PVD(Zr,Ti)N coated cemented carbide against40Cr hardened steel[J]. International journal of refractory metals&hard materials, 2012, 35(9):213-220.