前驱体对激光熔覆复合溶胶凝胶制备陶瓷涂层的影响
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摘要
目的研究不同前驱体配比下,激光熔覆复合溶胶凝胶在3Cr13不锈钢表面制备的陶瓷涂层的性能,并对强化机理进行分析。方法通过溶胶凝胶法制备均匀的前驱体,即Ti O2和C(微米石墨和碳纳米管),利用激光熔覆技术,在3Cr13不锈钢基体表面制备出高性能的涂层。采用光学显微镜、X射线衍射仪、扫描电镜和能谱仪对涂层组织和相成分进行分析,采用维氏硬度计对涂层的硬度进行测试,采用HT-600型高温摩擦磨损试验机测试基体和熔覆层在常温下的磨损性能。结果通过溶胶凝胶法,制备出均匀的Ti O2和C混合粉末。激光熔覆后,在覆层中均匀分布着Ti C和Cr7C3强化相。改变前驱体配比,当C和Ti O2的摩尔比增大时,涂层组织明显细化,且涂层中无气孔,显微硬度也有较大提高。当n(TiO2)∶n(C)=1∶8时,次表面显微硬度达到810HV0.2,涂层硬度从上到下呈现递减的趋势,且涂层的耐磨性最好,为基体的4.5倍。结论增大C和Ti O2两者摩尔比,可以提高熔覆层的显微硬度和耐磨性。在熔池中,Ti C密度较小,涂层中硬质颗粒从上到下依次减少,与之对应,硬度也依次递减。同时,碳纳米管的加入将对涂层起到细晶强化的效果。Ti与碳纳米管和微米石墨结合生成微米级和亚微米级Ti C,提高了形核率,Cr7C3以亚微米级Ti C为非均质核心,形核长大,生成均匀分布的Cr7C3强化相。
The work aims to study the properties of the ceramic coating of 3 Cr13 stainless steel prepared by laser claddingcomposite sol gel under the different ratios of precursor, and analyze the strengthening mechanism. A homogeneous precursor ofTiO2 and C(micro-graphite and carbon nanotubes(CNTs)) was prepared by sol-gel method, and a high-performance coatingwas prepared on the surface of the 3 Cr13 stainless steel substrate by laser cladding. The microstructure and phase compositionof the coating were analyzed by optical microscopy(OM), X-ray diffractometry(XRD), scanning electron microscopy(SEM)and energy dispersive spectroscopy(EDS). The hardness of the coating was tested by Vickers hardness tester and the wear re-sistance of substrate and cladding layer was tested by HT-600 high temperature friction machine. A homogeneous mixed powderof TiO2 and C could be prepared by the sol-gel method. The TiC and Cr_7C_3 strengthening phases were uniformly distributed inthe cladding layer. If the precursor ratio was changed, when the moral ratio of C and TiO2 increased, the coating structure wasremarkably refined, there was no pore in the coating, and the microhardness was also greatly improved. When n(TiO2)∶n(C)was 1∶8, the microhardness of subsurface reached 810 HV0.2 and the coating tended to decrease and had the best wear resis-tance which was 4.5 times that of the substrate. When the mole ratio of C and TiO2 is increased, the microhardness and wearresistance of cladding layer can be improved. The hard particles in the coating gradually decreases from top to bottom when theTiC density is lower in the molten pool. Correspondingly, the hardness of the coating has a tendency of decrease. At the sametime, the addition of CNTs has a fine grain strengthening effect on the coating. The Ti element combines with CNTs and microngraphite to form micro-scale TiC, and then Cr_7C_3 will use micro-scale TiC as a nucleus to grow and form a wrap-like Cr_7C_3 strengthening phase.
The work aims to study the properties of the ceramic coating of 3 Cr13 stainless steel prepared by laser claddingcomposite sol gel under the different ratios of precursor, and analyze the strengthening mechanism. A homogeneous precursor ofTiO2 and C(micro-graphite and carbon nanotubes(CNTs)) was prepared by sol-gel method, and a high-performance coatingwas prepared on the surface of the 3 Cr13 stainless steel substrate by laser cladding. The microstructure and phase compositionof the coating were analyzed by optical microscopy(OM), X-ray diffractometry(XRD), scanning electron microscopy(SEM)and energy dispersive spectroscopy(EDS). The hardness of the coating was tested by Vickers hardness tester and the wear re-sistance of substrate and cladding layer was tested by HT-600 high temperature friction machine. A homogeneous mixed powderof TiO2 and C could be prepared by the sol-gel method. The TiC and Cr_7C_3 strengthening phases were uniformly distributed inthe cladding layer. If the precursor ratio was changed, when the moral ratio of C and TiO2 increased, the coating structure wasremarkably refined, there was no pore in the coating, and the microhardness was also greatly improved. When n(TiO2)∶n(C)was 1∶8, the microhardness of subsurface reached 810 HV0.2 and the coating tended to decrease and had the best wear resis-tance which was 4.5 times that of the substrate. When the mole ratio of C and TiO2 is increased, the microhardness and wearresistance of cladding layer can be improved. The hard particles in the coating gradually decreases from top to bottom when theTiC density is lower in the molten pool. Correspondingly, the hardness of the coating has a tendency of decrease. At the sametime, the addition of CNTs has a fine grain strengthening effect on the coating. The Ti element combines with CNTs and microngraphite to form micro-scale TiC, and then Cr_7C_3 will use micro-scale TiC as a nucleus to grow and form a wrap-like Cr_7C_3 strengthening phase.
引文
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[21]BRAMFITT B L.Planar lattice disregistry theory and its application on heterogistry nuclei of metal[J].Metallurgical and materials transactions,1970(1):1987-1990.
[2]成瑜,丁浩,朱世根.3Cr13不锈钢刃口的强化方法研究[J].热加工工艺,2018,47(4):80-82.CHENG Yu,DING Hao,ZHU Shi-gen.Study on strengthening methods for cutting edge of 3Cr13 stainless steel[J].Hot working technology,2018,47(4):80-82.
[3]张洁,蒋力,谢德明,等.3Cr13钢表面氟盐浴TD法VC涂层的制备及表征[J].稀有金属材料与工程,2017,46(7):2028-2034.ZHANG Jie,JIANG Li,XIE De-ming,et al.Preparation and characterization of vanadium carbide coating on3Cr13 steel by thermal diffusion process with fluoride salt bath[J].Rare metal materials and engineering,2017,46(7):2028-2034.
[4]张玲玲,侯惠君,詹肇麟,等.活性屏等离子氮碳共渗温度对3Cr13不锈钢组织和性能的影响[J].热加工工艺,2016,45(4):113-116.ZHANG Ling-ling,HOU Hui-jun,ZHAN Zhao-lin,et al.Effect of nitrocarburizing temperature on microstructure and properties of active screen plasma nitrocarburizing layer of 3Cr13 stainless steel[J].Hot working technology,2016,45(4):113-116.
[5]CHEN J L,LI J,SONG R,et al.Effect of the scanning speed on microstructural evolution and wear behaviors of laser cladding NiCrBSi composite coatings[J].Optics&laser technology,2015,72:86-99.
[6]刘恋,石倩,代明江,等.脉冲偏压对电弧离子镀TiCN薄膜组织结构的影响[J].表面技术,2018,47(9):199-205.LIU Lian,SHI Qian,DAI Ming-jiang,et al.Effects of pulsed bias on microstructure of TiCN films by arc ion plating[J].Surface technology,2018,47(9):199-205.
[7]HE W,MAUER G,GINDRAT M,et al.Investigations on the nature of ceramic deposits in plasma spray-physical vapor deposition[J].Journal of thermal spray technology,2017,26(1-2):1-10.
[8]LI M,HAN B,WANG Y,et al.Investigation on laser cladding high-hardness nano-ceramic coating assisted by ultrasonic vibration processing[J].Optik-international journal for light and electron optics,2016,127(11):4596-4600.
[9]MA Q,LI Y,WANG J,et al.Microstructure evolution and growth control of ceramic particles in wide-band laser clad Ni60/WC composite coatings[J].Materials&design,2016,92:897-905.
[10]DE B A,SANTAGATA A,GALASSO A,et al.Formation of titanium carbide(TiC)and TiC@core-shell nanostructures by ultra-short laser ablation of titanium carbide and metallic titanium in liquid[J].Journal of colloid and interface science,2017,489:76-84.
[11]LI Y,GAO Y,XIAO B,et al.The electronic,mechanical properties and theoretical hardness of chromium carbides by first-principles calculations[J].Journal of alloys&compounds,2011,509(17):5242-5249.
[12]LIU X B,WANG H M.Microstructure and tribological properties of laser cladγ/Cr7C3/TiC composite coatings onγ-TiAl intermetallic alloy[J].Wear,2007,262(5):514-521.
[13]李浩,吴钱林,吴刚,等.激光熔覆TiC-Cr7C3-CNTs增强涂层制备及其显微组织[J].材料热处理学报,2015,36(s1):166-170.LI Hao,WU Qian-lin,WU Gang,et al.Microstructure and preparation of laser cladding TiC-Cr7C3-CNTs reinforced coating[J].Transactions of materials and heat treatment,2015,36(s1):166-170.
[14]ZHANG C H,HAO Y X,QI L,et al.Preparation of Ni-base alloy coatings on monel alloy by laser cladding[J].Advanced materials research,2012,472-475:313-316.
[15]曾启,张群莉,徐柠,等.激光复合溶胶凝胶法制备TiC强化涂层的工艺研究[J].激光与光电子学进展,2012,49(7):136-141.ZENG Qi,ZHANG Qun-li,XU Ning,et al.Research on technics of TiC hardened coating prepared by hybrid process of laser and sol-gel[J].Laser and optoelectronics progress,2012,49(7):136-141.
[16]张群莉,曾启,姚建华,等.激光复合溶胶-凝胶法制备TiN-TiB2强化涂层的组织与性能[J].应用激光,2012,32(6):469-473.ZHANG Qun-li,ZENG Qi,YAO Jian-hua,et al.Microstructure and property of TiN-TiB2 hardened coating prepared by hybrid method combined sol-gel with laser hardening[J].Applied laser,2012,32(6):469-473.
[17]唐强强,张群莉,王梁,等.半导体激光复合溶胶-凝胶工艺对原位合成TiC强化涂层组织形态的影响[J].中国激光,2015,42(9):190-196.TANG Qiang-qiang,ZHANG Qun-li,WANG Liang,et al.Influence of diode laser cladding and sol-gel compound technique on microstructure of in-situ synthesis TiC enhanced coating[J].Chinese journal of lasers,2015,42(9):190-196.
[18]倪自飞,孙扬善,薛烽.原位VC颗粒弥散强化304不锈钢的组织与性能[J].东南大学学报(自然科学版),2010,40(6):1308-1312.NI Zi-fei,SUN Yang-shan,XUE Feng.Microstructure and properties of in-situ VC dispersion-reinforced 304stainless steel[J].Journal of Southeast University(natural science edition),2010,40(6):1308-1312.
[19]舒玲玲,李文静,吴钱林,等.原位合成VC-Cr7C3复相陶瓷增强铁基激光涂层研究[J].热加工工艺,2011,40(22):126-129.SHU Ling-ling,LI Wen-jing,WU Qian-lin,et al.Study on in-situ synthesized VC-Cr7C3 complex phase ceramics reinforced Fe-based composite coating by laser cladding[J].Hot working technology,2011,40(22):126-129.
[20]周野飞.Fe-Cr-C-X堆焊合金显微组织演变及其耐磨性[D].秦皇岛:燕山大学,2013.ZHOU Ye-fei.Microstructural evolution and wear resistance of Fe-Cr-C-X hard facing alloy[D].Qinhuangdao:Yanshan University,2013.
[21]BRAMFITT B L.Planar lattice disregistry theory and its application on heterogistry nuclei of metal[J].Metallurgical and materials transactions,1970(1):1987-1990.