无金属粘结相TiCN基金属陶瓷在NaOH溶液中的电化学腐蚀行为
|
摘要
采用放电等离子烧结技术制备TiC_(0.4)N_(0.6),TiC_(0.7)N_(0.3),TiC_(0.7)N_(0.3)-29WC-12TaC和TiC_(0.7)N_(0.3)-29WC-12TaC-2Mo_2C等4种无金属粘结相金属陶瓷,材料的相对密度≥98.5%;扫描电镜观察结果表明,TiC_(0.4)N_(0.6)金属陶瓷的晶粒较其它3种的晶粒明显粗大。采用动电位极化曲线和电化学阻抗谱,研究4种材料在浓度为0.1 mol/L的NaOH溶液(pH=13)中的电化学腐蚀行为。结果表明,4种材料在NaOH腐蚀介质中的耐腐蚀性排序为TiC_(0.7)N_(0.3)>TiC_(0.7)N_(0.3)-29WC-12TaC>TiC_(0.7)N_(0.3)-29WC-12Ta C-2Mo2C>TiC_(0.4)N_(0.6);原料中氮含量增加和金属碳化物的添加均会导致金属陶瓷耐腐蚀性能降低;在一定条件下,无金属粘结相的TiCN金属陶瓷材料在碱性介质中可形成含氧化合物的表面钝化膜,导致腐蚀过程中出现伪钝化现象。4种无金属粘结相TiCN金属陶瓷材料中,TiC_(0.7)N_(0.3)的耐腐蚀性能最优,相对密度最高,达到99.5%。
Four binderless TiCN-based cermets TiC_(0.4) N_(0.6), TiC_(0.7) N_(0.3), TiC_(0.7) N_(0.3)-29 WC-12 TaC and TiC_(0.7) N_(0.3)-29 WC-12 TaC-2 Mo_2 C with a relative density greater than 98.5% were prepared by spark plasma sintering(SPS). Scanning electron microscopy SEM observation shows that the average grain size of binderless TiC_(0.4) N_(0.6) is substantially larger than that of other three groups. Electrochemical corrosion behaviors of binderless TiCN-based cermets in 0.1 mol/L NaOH solution were investigated by potentiodynamic polarization curve and electrochemical impedance spectroscopy.The results show that the corrosion resistance of the cermets in NaOH solution follows the following order, i.e., TiC_(0.7) N_(0.3)>TiC_(0.7) N_(0.3)-29 WC-12 TaC>TiC_(0.7) N_(0.3)-29 WC-12 TaC-2 Mo_2 C>TiC_(0.4) N_(0.6). The increase of nitrogen and the addition of metal carbides are detrimental to the corrosion resistance of cermets. The oxidation product formed during the corrosion process can act as a passivation film, which results in a pseudo-passivation phenomenon. Binderless TiC_(0.7) N_(0.3) cermet has the highest relative densification(99.5%) and the best corrosion resistance.
Four binderless TiCN-based cermets TiC_(0.4) N_(0.6), TiC_(0.7) N_(0.3), TiC_(0.7) N_(0.3)-29 WC-12 TaC and TiC_(0.7) N_(0.3)-29 WC-12 TaC-2 Mo_2 C with a relative density greater than 98.5% were prepared by spark plasma sintering(SPS). Scanning electron microscopy SEM observation shows that the average grain size of binderless TiC_(0.4) N_(0.6) is substantially larger than that of other three groups. Electrochemical corrosion behaviors of binderless TiCN-based cermets in 0.1 mol/L NaOH solution were investigated by potentiodynamic polarization curve and electrochemical impedance spectroscopy.The results show that the corrosion resistance of the cermets in NaOH solution follows the following order, i.e., TiC_(0.7) N_(0.3)>TiC_(0.7) N_(0.3)-29 WC-12 TaC>TiC_(0.7) N_(0.3)-29 WC-12 TaC-2 Mo_2 C>TiC_(0.4) N_(0.6). The increase of nitrogen and the addition of metal carbides are detrimental to the corrosion resistance of cermets. The oxidation product formed during the corrosion process can act as a passivation film, which results in a pseudo-passivation phenomenon. Binderless TiC_(0.7) N_(0.3) cermet has the highest relative densification(99.5%) and the best corrosion resistance.
引文
[1]LENGAUER W,SCAGNETTO F.Ti(C,N)-based cermets:critical review of achievements and recent developments[J].Solid State Phenomena,2018,274:53-100.
[2]SHANKAR E,PRABU S B.Microstructure and mechanical properties of Ti(C,N)based cermets reinforced with different ceramic particles processed by spark plasma sintering[J].Ceramics International,2017,43(14):10817-10823.
[3]陈敏,肖玄,张雪峰.TaC含量对TiCN基金属陶瓷组织与性能的影响[J].粉末冶金材料科学与工程,2016,21(2):270-275.CHEN Min,XIAO Xuan,ZHANG Xuefeng.Effect of Ta Ccontent on microstructure and properties of TiCN-based cermets[J].Powder Metallurgy Materials Science and Engineering,2016,21(2):270-275.
[4]余金川,罗兵辉,柏振海,等.铁镍替代钴硬质合金的微观结构与性能[J].粉末冶金材料科学与工程,2015,20(6):844-851.YU Jinchuan,LUO Binghui,BAI Zhenhai,et al.Microstructure and properties of cemented carbides prepared with iron and nickel for substituting cobalt[J].Powder Metallurgy Materials Science and Engineering,2015,20(6):844-851.
[5]钱中良,熊惟皓.Ti(C,N)基金属陶瓷的耐腐蚀性[J].硬质合金,1998,15(1):16-20.QIAN Zhongliang,XIONG Weihao.Corrosion resistance of Ti(C,N)-based cermets[J].Cemented Carbide,1998,15(1):16-20.
[6]WAN W,XIONG J,GUO Z,et al.Research on the contributions of corrosion,erosion and synergy to the erosion-corrosion degradation of Ti(C,N)-based cermets[J].Wear,2015,326/327(5):36-43.
[7]ZHANG L,FENG Y P,NAN Q,et al.Zhe Wang.Effects of titanium-based raw materials on electrochemical behavior of Ti(C,N)-based cermets[J].International Journal of Refractory Metals and Hard Materials,2015,48:11-18.
[8]左晓婷,姚萍屏,贡太敏,等.WC粒度对超音速火焰喷涂WC-10Co-4Cr涂层耐腐蚀性能的影响[J].粉末冶金材料科学与工程,2015(1):106-111.ZUO Xiaoting,YAO Pingping,GONG Taimin,et al.Effect of WC size on corrosion resistance of WC-10Co-4Cr coatings by high velocity oxygen fuel[J].Powder Metallurgy Materials Science and Engineering,2015(1):106-111.
[9]GUO Z,XIONG J,WAN W,et al.Effect of binder content on the erosive wear of Ti(C,N)-based cermet in SiO2 particlecontaining simulated seawater[J].International Journal of Applied Ceramic Technology,2015,11(6):1045-1053.
[10]TANG W,ZHANG L,CHEN Y,et al.Corrosion and strength degradation behaviors of binderless WC material and WC-Co hardmetal in alkaline solution:a comparative investigation[J].International Journal of Refractory Metals and Hard Materials,2017,68:1-8.
[11]李重典,时凯华,王海霞,等.烧结工艺对低粘结相硬质合金性能及微观结构的影响[J].粉末冶金材料科学与工程,2014,19(5):695-700.LI Zhongdian,SHI Kaihua,WANG Haixia,et al.Effect of sintering process on properties and microstructure of low binder cemented carbides with low cobalt content[J].Powder Metallurgy Materials Science and Engineering,2014,19(5):695-700.
[12]TANG W,ZHANG L,ZHU J F,et al.Effect of direct current patterns on densification and mechanical properties of binderless tungsten carbides fabricated by the spark plasma sintering system[J].International Journal of Refractory Metals and Hard Materials,2017,64:90-97.
[13]朱骥飞,张立,徐涛,等.基于ImageJ软件的硬质合金显微组织参数化定量分析[J].粉末冶金材料科学与工程,2015,20(1):26-31.ZHU Jifei,ZHANG Li,XU Tao,et al.Quantificational characterization of microstructural parameters of cemented carbides based on ImageJ software[J].Powder Metallurgy Materials Science and Engineering,2015,20(1):26-31.
[14]LIU C,MA Y Z,LIU W S,et al.Influence of various concentrations(TiC and TiN)on the microstructure and properties of Ti(CN)-based cermets prepared by spark plasma sintering[J].Transactions of the Indian Ceramic Society,2016,75(3):166-169.
[15]周伟.高氮含量Ti(C,N)基金属陶瓷的制备及其磨粒磨损特性研究[D].南京:南京航空航天大学,2013.ZHOU Wei.Research on the preparation and abrasive wear properties of Ti(C,N)-based cermets with high nitrogen content[D].Nanjing:Nanjing University of Aeronautics and Astronautics the Graduate School,2013.
[16]SHI Z M,ZHANG D Y,CHEN S,et al.Effect of nitrogen content on microstructures and mechanical properties of Ti(C,N)-based cermets[J].Journal of Alloys and Compounds,2013,568(7):68-72.
[17]SHANKAR E,PRABU S B.Influence of WC and cobalt additions on the microstructural and mechanical properties of TiCN-Cr3C2-nano-TiB2,cermets fabricated by spark plasma sintering[J].International Journal of Refractory Metals and Hard Materials,2017,69:110-118.
[18]VERMA V,KUMAR B V M.Sliding wear behavior of SPSprocessed TaC-containing Ti(CN)-WC-Ni/Co cermets against silicon carbide[J].Wear,2017,376:1570-1579.
[19]叶登峰,陈康华,方华婵.复合添加Zr、Cr、Pr对超高强铝合金腐蚀和断裂行为的影响[J].粉末冶金材料科学与工程,2011,16(3):379-385.YE Dengfeng,CHEN Kanghua,FANG Huachan.Effect of composite additions of Zr,Cr,Pr on corrosion and fracture behavior of super-high strength aluminum alloys[J].Materials Science and Engineering of Powder Metallurgy,2011,16(3):379-385.
[20]HAMADOU L,A?NOUCHE L,Kadri A,et al.Electrochemical impedance spectroscopy study of thermally grown oxides exhibiting constant phase element behavior[J].Electrochimica Acta,2013,113(4):99-108.
[21]CAO Z,KONG G,CHE C,et al.Influence of Nd addition on the corrosion behavior of Zn-5%Al alloy in 3.5wt.%NaCl solution[J].Applied Surface Science,2017,426:67-76.
[22]ZHANG L,CHEN Y,WAN Q L,et al.Electrochemical corrosion behaviors of straight WC-Co alloys:Exclusive variation in grain sizes and aggressive media[J].International Journal of Refractory Metals and Hard Materials,2016,57:70-77.
[23]罗检,张勇,钟庆东,等.晶粒度对一些常用金属耐腐蚀性能的影响[J].腐蚀与防护,2012,33(4):349-352.LUO Jian,ZHANG Yong,ZHONG Qingdong,et al.Influence of grain size on corrosion resistant of commonly used metals[J].Corrosion and Protection,2012,33(4):349-352.
[24]QIU Weibin,LIU Ying,YE Jinwen,et al.Effects of(Ti,Ta,Nb,W)(C,N)on the microstructure,mechanical properties and corrosion behaviors of WC-Co cemented carbides[J].Ceramics International,2017,43(3):2918-2926.
[25]董广彪,熊计,郭智兴,等.Mo2C对Ti(C,N)基金属陶瓷腐蚀性能的影响[J].硬质合金,2012,29(3):160-166.DONG Guangbiao,XIONG Ji,GUO Zhixing,et al.Effect of Mo2C on corrosion behavior of Ti(C,N)-based cermets[J].Cemented Carbide,2012,29(3):160-166.
[26]NEUSA A F,STEPHAN W.Correlation between corrosion potential and pitting potential for AISI 304L austenitic stainless steel in 3.5%NaCl aqueous solution[J].Materials Research,2002,5(1):1236-1245.
[27]马鋆,张立,南晴,等.Cr、V、Ta添加剂对超粗晶和特粗晶硬质合金电化学腐蚀行为的影响[J].粉末冶金材料科学与工程,2012,17(6):825-832.MA Yun,ZHANG Li,NAN Qing,et al.Effects of Cr,V,Ta additives on electrochemical corrosion behaviors of extra coarse and super extra coarse cemented carbides[J].Materials Science and Engineering of Powder Metallurgy,2012,17(6):825-832.
[28]MEMARRASHIDI Z,PLUCKNETT K P.The effects of C:Nratio on the aqueous corrosion response of TiC and Ti(C,N)cermets with a Ni3Al-based binder[J].International Journal of Refractory Metals and Hard Materials,2016,61:162-172.
[2]SHANKAR E,PRABU S B.Microstructure and mechanical properties of Ti(C,N)based cermets reinforced with different ceramic particles processed by spark plasma sintering[J].Ceramics International,2017,43(14):10817-10823.
[3]陈敏,肖玄,张雪峰.TaC含量对TiCN基金属陶瓷组织与性能的影响[J].粉末冶金材料科学与工程,2016,21(2):270-275.CHEN Min,XIAO Xuan,ZHANG Xuefeng.Effect of Ta Ccontent on microstructure and properties of TiCN-based cermets[J].Powder Metallurgy Materials Science and Engineering,2016,21(2):270-275.
[4]余金川,罗兵辉,柏振海,等.铁镍替代钴硬质合金的微观结构与性能[J].粉末冶金材料科学与工程,2015,20(6):844-851.YU Jinchuan,LUO Binghui,BAI Zhenhai,et al.Microstructure and properties of cemented carbides prepared with iron and nickel for substituting cobalt[J].Powder Metallurgy Materials Science and Engineering,2015,20(6):844-851.
[5]钱中良,熊惟皓.Ti(C,N)基金属陶瓷的耐腐蚀性[J].硬质合金,1998,15(1):16-20.QIAN Zhongliang,XIONG Weihao.Corrosion resistance of Ti(C,N)-based cermets[J].Cemented Carbide,1998,15(1):16-20.
[6]WAN W,XIONG J,GUO Z,et al.Research on the contributions of corrosion,erosion and synergy to the erosion-corrosion degradation of Ti(C,N)-based cermets[J].Wear,2015,326/327(5):36-43.
[7]ZHANG L,FENG Y P,NAN Q,et al.Zhe Wang.Effects of titanium-based raw materials on electrochemical behavior of Ti(C,N)-based cermets[J].International Journal of Refractory Metals and Hard Materials,2015,48:11-18.
[8]左晓婷,姚萍屏,贡太敏,等.WC粒度对超音速火焰喷涂WC-10Co-4Cr涂层耐腐蚀性能的影响[J].粉末冶金材料科学与工程,2015(1):106-111.ZUO Xiaoting,YAO Pingping,GONG Taimin,et al.Effect of WC size on corrosion resistance of WC-10Co-4Cr coatings by high velocity oxygen fuel[J].Powder Metallurgy Materials Science and Engineering,2015(1):106-111.
[9]GUO Z,XIONG J,WAN W,et al.Effect of binder content on the erosive wear of Ti(C,N)-based cermet in SiO2 particlecontaining simulated seawater[J].International Journal of Applied Ceramic Technology,2015,11(6):1045-1053.
[10]TANG W,ZHANG L,CHEN Y,et al.Corrosion and strength degradation behaviors of binderless WC material and WC-Co hardmetal in alkaline solution:a comparative investigation[J].International Journal of Refractory Metals and Hard Materials,2017,68:1-8.
[11]李重典,时凯华,王海霞,等.烧结工艺对低粘结相硬质合金性能及微观结构的影响[J].粉末冶金材料科学与工程,2014,19(5):695-700.LI Zhongdian,SHI Kaihua,WANG Haixia,et al.Effect of sintering process on properties and microstructure of low binder cemented carbides with low cobalt content[J].Powder Metallurgy Materials Science and Engineering,2014,19(5):695-700.
[12]TANG W,ZHANG L,ZHU J F,et al.Effect of direct current patterns on densification and mechanical properties of binderless tungsten carbides fabricated by the spark plasma sintering system[J].International Journal of Refractory Metals and Hard Materials,2017,64:90-97.
[13]朱骥飞,张立,徐涛,等.基于ImageJ软件的硬质合金显微组织参数化定量分析[J].粉末冶金材料科学与工程,2015,20(1):26-31.ZHU Jifei,ZHANG Li,XU Tao,et al.Quantificational characterization of microstructural parameters of cemented carbides based on ImageJ software[J].Powder Metallurgy Materials Science and Engineering,2015,20(1):26-31.
[14]LIU C,MA Y Z,LIU W S,et al.Influence of various concentrations(TiC and TiN)on the microstructure and properties of Ti(CN)-based cermets prepared by spark plasma sintering[J].Transactions of the Indian Ceramic Society,2016,75(3):166-169.
[15]周伟.高氮含量Ti(C,N)基金属陶瓷的制备及其磨粒磨损特性研究[D].南京:南京航空航天大学,2013.ZHOU Wei.Research on the preparation and abrasive wear properties of Ti(C,N)-based cermets with high nitrogen content[D].Nanjing:Nanjing University of Aeronautics and Astronautics the Graduate School,2013.
[16]SHI Z M,ZHANG D Y,CHEN S,et al.Effect of nitrogen content on microstructures and mechanical properties of Ti(C,N)-based cermets[J].Journal of Alloys and Compounds,2013,568(7):68-72.
[17]SHANKAR E,PRABU S B.Influence of WC and cobalt additions on the microstructural and mechanical properties of TiCN-Cr3C2-nano-TiB2,cermets fabricated by spark plasma sintering[J].International Journal of Refractory Metals and Hard Materials,2017,69:110-118.
[18]VERMA V,KUMAR B V M.Sliding wear behavior of SPSprocessed TaC-containing Ti(CN)-WC-Ni/Co cermets against silicon carbide[J].Wear,2017,376:1570-1579.
[19]叶登峰,陈康华,方华婵.复合添加Zr、Cr、Pr对超高强铝合金腐蚀和断裂行为的影响[J].粉末冶金材料科学与工程,2011,16(3):379-385.YE Dengfeng,CHEN Kanghua,FANG Huachan.Effect of composite additions of Zr,Cr,Pr on corrosion and fracture behavior of super-high strength aluminum alloys[J].Materials Science and Engineering of Powder Metallurgy,2011,16(3):379-385.
[20]HAMADOU L,A?NOUCHE L,Kadri A,et al.Electrochemical impedance spectroscopy study of thermally grown oxides exhibiting constant phase element behavior[J].Electrochimica Acta,2013,113(4):99-108.
[21]CAO Z,KONG G,CHE C,et al.Influence of Nd addition on the corrosion behavior of Zn-5%Al alloy in 3.5wt.%NaCl solution[J].Applied Surface Science,2017,426:67-76.
[22]ZHANG L,CHEN Y,WAN Q L,et al.Electrochemical corrosion behaviors of straight WC-Co alloys:Exclusive variation in grain sizes and aggressive media[J].International Journal of Refractory Metals and Hard Materials,2016,57:70-77.
[23]罗检,张勇,钟庆东,等.晶粒度对一些常用金属耐腐蚀性能的影响[J].腐蚀与防护,2012,33(4):349-352.LUO Jian,ZHANG Yong,ZHONG Qingdong,et al.Influence of grain size on corrosion resistant of commonly used metals[J].Corrosion and Protection,2012,33(4):349-352.
[24]QIU Weibin,LIU Ying,YE Jinwen,et al.Effects of(Ti,Ta,Nb,W)(C,N)on the microstructure,mechanical properties and corrosion behaviors of WC-Co cemented carbides[J].Ceramics International,2017,43(3):2918-2926.
[25]董广彪,熊计,郭智兴,等.Mo2C对Ti(C,N)基金属陶瓷腐蚀性能的影响[J].硬质合金,2012,29(3):160-166.DONG Guangbiao,XIONG Ji,GUO Zhixing,et al.Effect of Mo2C on corrosion behavior of Ti(C,N)-based cermets[J].Cemented Carbide,2012,29(3):160-166.
[26]NEUSA A F,STEPHAN W.Correlation between corrosion potential and pitting potential for AISI 304L austenitic stainless steel in 3.5%NaCl aqueous solution[J].Materials Research,2002,5(1):1236-1245.
[27]马鋆,张立,南晴,等.Cr、V、Ta添加剂对超粗晶和特粗晶硬质合金电化学腐蚀行为的影响[J].粉末冶金材料科学与工程,2012,17(6):825-832.MA Yun,ZHANG Li,NAN Qing,et al.Effects of Cr,V,Ta additives on electrochemical corrosion behaviors of extra coarse and super extra coarse cemented carbides[J].Materials Science and Engineering of Powder Metallurgy,2012,17(6):825-832.
[28]MEMARRASHIDI Z,PLUCKNETT K P.The effects of C:Nratio on the aqueous corrosion response of TiC and Ti(C,N)cermets with a Ni3Al-based binder[J].International Journal of Refractory Metals and Hard Materials,2016,61:162-172.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |