中温作用下的涂层界面组织结构
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摘要
热喷涂技术的优点是生产效率高,选材广,可在大工件上得到厚涂层,这是其它表面技术所不及的。热喷涂技术在工业中有着广泛的应用,但由于现有技术的热喷涂涂层与基体的结合主要依靠机械物理结合,涂层结合强度不高,严重影响了它在苛刻工况下的应用,涂层最易出现失效的环节也在界面上。在热喷涂涂层的形成过程中,涂层材料与基体间的结合强弱是影响涂层性能的关键。
采用传统氧—乙炔火焰粉末喷涂设备在不引起Ni/Al放热反应的情况下,将Ni-Al粉末喷涂于Q235基体上,在氢气保护气氛炉内经中温处理,利用OM,SEM,EDX等对涂层界面进行了观察、研究、分析,对涂层界面结合强度提高因素作了综合研究;为了阐明中温作用增强涂层结合性能的机制,利用纯铁表面氧化和中温还原处理,直接观察到了微裂纹的愈合及还原生成的Fe原子在Fe表面的结晶形态,揭示了中温处理增强涂层结合性的机制,本研究的主要结果有:
<1> Ni-Al涂层中温处理后界面结合强度明显高于常规涂层;界面出现约10μm的Fe-Ni固溶区,界面呈现分区冶金结合;界面显微硬度高出涂层及基体约20HV,EDX分析表明界面主要是Ni-Fe固溶体相,并在4～5μm宽的范围内可能存在Ni_3Fe有序固溶体。
<2> 纯铁表面微裂纹可通过氧化—还原处理在993K条件下实现自愈合,还原反应生成的铁原子在表面凝聚结晶时呈现出明显的准有序层状结构,层片厚度在100nm左右。
<3> Ni基、Cu基、Co包WC涂层中温处理后界面结合强度明显高于常规涂层,界面组织在未腐蚀条件下与基体连成一片,没有常规涂层所有的明显分界;腐蚀后的可见明显“锯齿”状新相,表明界面有新相生成。
<4> 中温处理增强涂层结合力的过程可近似概化分为为三个阶段:①应力驰豫;②金属氧化膜在Al、H_2的还原作用下形成层状准有序结构体;③中温作用下互相紧密接触且表面具有这种层状结构的金属颗粒之间的结合过程。
The advantage of hot spraying technology is high efficiency and wide selecting suitable materials, it can get form coating on big work piece, which are other surface technology can't be obtained. It has extensive application in industry in hot spraying technology. But particle hot spraying coating of technology rely on mechanically physics combined mainly. Layer structure of hot spraying coating and not-too-high bonding strength unit its application under harsh circumstance. Also the interface is the first abate position. During the form of hot spraying coating bonding strength between the material and coating is the key problem.When Ni and A1 powder is mixed without reaction, by means of the traditional oxygen - the acetylene flame powder spraying equipment Ni-A1 powder on Q235 and heat treatment with H2 as protection atmosphere, Utilize OM, SEM, EDX, etc. have observed to the coating interface, research , analysing, combine to coating interface intensity raise factor act as comprehensive research; In order to expounded the mechanism which coating combine is strengthened under middle temperature treatment, utilize pure iron surface after oxidizing and reduce reaction under middle temperature.Have observed the self-healing of the microcrack and reduced the crystallization shape on Fe surface of Fe atom produced directly. The mechanism is opened which strengthens coating associatively under middle temperature treatment. The main result of this research is as follows,<1> Ni-Al coating middle temperature treated interface combine intensity obviously higher than the routine coating; It is about 10μm that there are the interfaces Ni-Fe solution area, and appear divide metallurgy combine on interface: It is shown that HV on the interface is obviously higher than that of the substrate and the coating by 20HV. The results
采用传统氧—乙炔火焰粉末喷涂设备在不引起Ni/Al放热反应的情况下,将Ni-Al粉末喷涂于Q235基体上,在氢气保护气氛炉内经中温处理,利用OM,SEM,EDX等对涂层界面进行了观察、研究、分析,对涂层界面结合强度提高因素作了综合研究;为了阐明中温作用增强涂层结合性能的机制,利用纯铁表面氧化和中温还原处理,直接观察到了微裂纹的愈合及还原生成的Fe原子在Fe表面的结晶形态,揭示了中温处理增强涂层结合性的机制,本研究的主要结果有:
<1> Ni-Al涂层中温处理后界面结合强度明显高于常规涂层;界面出现约10μm的Fe-Ni固溶区,界面呈现分区冶金结合;界面显微硬度高出涂层及基体约20HV,EDX分析表明界面主要是Ni-Fe固溶体相,并在4～5μm宽的范围内可能存在Ni_3Fe有序固溶体。
<2> 纯铁表面微裂纹可通过氧化—还原处理在993K条件下实现自愈合,还原反应生成的铁原子在表面凝聚结晶时呈现出明显的准有序层状结构,层片厚度在100nm左右。
<3> Ni基、Cu基、Co包WC涂层中温处理后界面结合强度明显高于常规涂层,界面组织在未腐蚀条件下与基体连成一片,没有常规涂层所有的明显分界;腐蚀后的可见明显“锯齿”状新相,表明界面有新相生成。
<4> 中温处理增强涂层结合力的过程可近似概化分为为三个阶段:①应力驰豫;②金属氧化膜在Al、H_2的还原作用下形成层状准有序结构体;③中温作用下互相紧密接触且表面具有这种层状结构的金属颗粒之间的结合过程。
The advantage of hot spraying technology is high efficiency and wide selecting suitable materials, it can get form coating on big work piece, which are other surface technology can't be obtained. It has extensive application in industry in hot spraying technology. But particle hot spraying coating of technology rely on mechanically physics combined mainly. Layer structure of hot spraying coating and not-too-high bonding strength unit its application under harsh circumstance. Also the interface is the first abate position. During the form of hot spraying coating bonding strength between the material and coating is the key problem.When Ni and A1 powder is mixed without reaction, by means of the traditional oxygen - the acetylene flame powder spraying equipment Ni-A1 powder on Q235 and heat treatment with H2 as protection atmosphere, Utilize OM, SEM, EDX, etc. have observed to the coating interface, research , analysing, combine to coating interface intensity raise factor act as comprehensive research; In order to expounded the mechanism which coating combine is strengthened under middle temperature treatment, utilize pure iron surface after oxidizing and reduce reaction under middle temperature.Have observed the self-healing of the microcrack and reduced the crystallization shape on Fe surface of Fe atom produced directly. The mechanism is opened which strengthens coating associatively under middle temperature treatment. The main result of this research is as follows,<1> Ni-Al coating middle temperature treated interface combine intensity obviously higher than the routine coating; It is about 10μm that there are the interfaces Ni-Fe solution area, and appear divide metallurgy combine on interface: It is shown that HV on the interface is obviously higher than that of the substrate and the coating by 20HV. The results
引文
[1] 邱长军(1)·Ni-Al喷涂层中温处理时界面的则优演变[J].《材料导报》.2001,14(4):65～66
[2] 樊湘芳,邱长军.Ni-Al喷涂层中温处理的组织演变与结合机制[J].《材料科学与工艺》.2002,10(2):183～185
[3] 徐滨士.材料界面结构与性能[M].科学出版社,北京,1999
[4] J. Duszcayk. J. Zhow. In-situ reactive Synthesis of Ni_3Al intermetallicompoudn and subsequest diffusion bonding with different steels for surface coating[J]. Mater. Sci. 1999, 34: 3937～3950(?)
[5] 王华彬等.Ni-Al粉连续加热过程中的反应机理[J].金属学报.1998,34(9):992～998(?)
[6] 王华彬等.原位合成Ni/Ni-Al金属间化合物层板复合材料的组织与性能[J].金属学报.1998,34(4)431～436
[7] V. I. DYBKOV. Interaction of iron-nickel alloys with liquid aluminium[J]. Mater. Sci 35(2000)1729～1736
[8] 果世驹.粉末烧结理论[M].冶金工业出版社,北京,1998
[9] 何声太等.表面包敷 1-壬基硫醇的银纳米粒子形成过程及其自组织阵列[J].中国科学.2001,31(6):534～538(?)
[10] 戴达煌,周克松,袁镇海.现代材料表面技术科学[M].冶金工业出版社,北京,2004
[11] 曾晓雁,吴懿平.表面工程学[M].机械工业出版社,北京,2001
[12] 中国腐蚀与防护学会主编,高荣发编著.热喷涂[M].化学工业出版社,北京,1992
[13] 韦福水,蒋伯平,汪行恺,李俊岳.热喷涂技术[M].机械工业出版社,北京,1986
[14] 李明伟等.陶瓷/金属高温热障涂层研究进展[J].材料导报.2000,14(8):19～21
[15] 马岳,段祝平,吴承康.激光熔覆对改善等离子涂层界面结合性能的研究[J].金属学报.1999,35(9):985～988
[16] 梅志,顾明远,吴人洁.金属基复合材料界面表征及其进展[J].材料科学与工程.1996,14(3):1～5
[17] 鲍明远,孟凡吉.氧乙炔粉末喷涂和喷焊技术[M].机械工业出版社,北京,1993
[18] 樊湘芳,邱长军,刘瑞林.Ni-Al喷涂层中温处理的组织演变与结合机理[J].材料科学与工艺,2002,10(2):183～185
[19] 崔国文.缺陷扩散与烧结[M].北京:清华大学出版社,1990
[20] 宋玉强,李世春.影响铜粉和镍粉界面过程的因素[J].金属热处理2003.28(4):17～21
[21] 王化宇,韩志海.几种Ni-Cr系热喷涂涂层的抗热腐蚀性能和结合强度[J].材料保护2004.12(2):12～15
[22] 曾杰,刘军和.超音速火焰喷涂涂层评析[J].新工艺·新技术·新设备2004(3):72-78
[23] Yihui QI,Jianting Guo and Chanyong CUI.Microstructures and Creep Behavior of a Directionally Solidified NiAI—Fe(Nb)Multiphase Intermetallic.Alloy.[J] Master.Sci.Tschnol,Vol.2003.19(1):59～62
[24] 刘震云,林栋梁,黄伯云,曲选辉.NiAl金属间化合物研究现状[J],机械工程材料,1998.22(2):1～5
[25] 杨松岚,王福会.NiAl金属间化合物高温氧化的研究现状[J],腐蚀科学与技术,2002.14(2):109～112
[26] 顾宜.材料科学与工程基础[M].化学工业出版社,北京,2002
[27] 徐滨士,朱绍华,刘世参,马世宁.表面工程与维修[M].机械工程出版社,北京,2000
[28] 王兴庆,吕海波.粉末冶金法制取Fe-Al金属间化合物的研究[J].上海大学学报,2000,6(6):511～515
[29] 范润华,孙康宁,尹衍升.Fe_3Al金属间化合物的机械合金化[J].机械工程学报,2000,36(8):55～58
[30] 孙康宁,尹衍升,李爱民.金属间化合物/陶瓷基复合材料[M].机械工业出版社,北京,2003
[31] 张彩碚,崔建忠.不锈钢/Al固液轧制复合板材界面剪切强度与界面结构[J].金属学报 1999.35(2):113～116
[32] 宋玉强,李世春.元素粉末法制备Fe-Ni合金的工艺研究[J].新技术新工艺,2004,4
[33] [日]长崎城三,平林真编著.刘安生译.二元合金状态图集[M].北京,冶金工业出版社.2004
[34] 崔燕岭,曹伟涛,张培峰.Ni—3Fe合金反相畴界结构和能量研究[J].焦作工学院学报,2004,23(1):77～79
[35] 王松,万晓景,姚美意.有序和无序态Ni_3Fe的环境氢脆研究[J].金属学报,1999.35(12)1262～1265
[36] 陈爱萍,陈业新,万晓景,王建国,程晓英.有序度对Ni—3Fe合金环境氢脆的影响[J].材料研究学报,2003.17(1):74～78
[37] 林杨,朱逢吾.Ni_3Fe的有序化和反相畴界的FIM—AP研究[J].中国科学:A辑,1994,24(10):1084～1091
[38] 何正明,许士跃,张正明,董传华,施耀铭,钟敏建.Fe_(100-X)Ni_x系合金超细粉末的结构和磁性研究[J].上海大学学报(自然科学版),1999,5(3)
[39] H. S. Green and C. A. Hurst, Order-disorder Phenomena[M]. Interscience, London, 1964.
[40] A. G. Khachaturyan[J], Progress in materials Science, Vol. 22, p. 1, 1979.
[41] D. de Fontaine[J], Solid State Physics, Vol, 34, p. 73, 1979.
[42] 邓永瑞,许洋,赵青.固态相变[M].冶金工业出版社,北京,1996
[43] I.普利高津,G尼科里斯.非平衡系统的自组织[M].科学出版社,北京,1986
[44] 王笛兴.关于自组织[J],Entropy Information Complexity. 2002
[45] H. L. zhang. Morphological healing evolution of Penny-shaped fatigue microcracks in pure iron at elevated temperaturea[J]. Appl, phys. Lett, 2004. 85(7): 1143
[46] Masuda, Appl[J]. phys. Lett, 2001, 78(6): 826
[47] 周亦胄,脉动电流作用下碳钢淬火裂纹的愈合[J],金属学报.2000,36(1):43～45
[48] Z. J. Zhang. Self-assembled patterns of iron oxide nannoparticles by hydrothermal chemical vapor deposition[J], Aapplied physics Letters2001, 79: 4207～4209
[49] Thomas E. L. Science[J], 1999, 286(5443): 1307(?)
[50] S. Aggarwal. Spontaneous ordering of oxide Nanostructures[J]. Science. 2000, (5461): 2235
[51] Crouse D, Lo Yu-nwa, Miller AE, Crouse M[J]. Applied physics Letters2000, 76(1): 49(?)
[52] L. Yescan. SiGe nanostructures by Selective epitaxy and self-assembling[J]. Materials Sci and Engineering 2001, (6)-13(?)
[53] 李如生.非平衡态热力学和耗散结构[J].清华大学出版社,北京,1986
[54] 孙颖,胆结石组成和形成机理的研究进展[J],中国科学(B).2001,31(5):385～389
[2] 樊湘芳,邱长军.Ni-Al喷涂层中温处理的组织演变与结合机制[J].《材料科学与工艺》.2002,10(2):183～185
[3] 徐滨士.材料界面结构与性能[M].科学出版社,北京,1999
[4] J. Duszcayk. J. Zhow. In-situ reactive Synthesis of Ni_3Al intermetallicompoudn and subsequest diffusion bonding with different steels for surface coating[J]. Mater. Sci. 1999, 34: 3937～3950(?)
[5] 王华彬等.Ni-Al粉连续加热过程中的反应机理[J].金属学报.1998,34(9):992～998(?)
[6] 王华彬等.原位合成Ni/Ni-Al金属间化合物层板复合材料的组织与性能[J].金属学报.1998,34(4)431～436
[7] V. I. DYBKOV. Interaction of iron-nickel alloys with liquid aluminium[J]. Mater. Sci 35(2000)1729～1736
[8] 果世驹.粉末烧结理论[M].冶金工业出版社,北京,1998
[9] 何声太等.表面包敷 1-壬基硫醇的银纳米粒子形成过程及其自组织阵列[J].中国科学.2001,31(6):534～538(?)
[10] 戴达煌,周克松,袁镇海.现代材料表面技术科学[M].冶金工业出版社,北京,2004
[11] 曾晓雁,吴懿平.表面工程学[M].机械工业出版社,北京,2001
[12] 中国腐蚀与防护学会主编,高荣发编著.热喷涂[M].化学工业出版社,北京,1992
[13] 韦福水,蒋伯平,汪行恺,李俊岳.热喷涂技术[M].机械工业出版社,北京,1986
[14] 李明伟等.陶瓷/金属高温热障涂层研究进展[J].材料导报.2000,14(8):19～21
[15] 马岳,段祝平,吴承康.激光熔覆对改善等离子涂层界面结合性能的研究[J].金属学报.1999,35(9):985～988
[16] 梅志,顾明远,吴人洁.金属基复合材料界面表征及其进展[J].材料科学与工程.1996,14(3):1～5
[17] 鲍明远,孟凡吉.氧乙炔粉末喷涂和喷焊技术[M].机械工业出版社,北京,1993
[18] 樊湘芳,邱长军,刘瑞林.Ni-Al喷涂层中温处理的组织演变与结合机理[J].材料科学与工艺,2002,10(2):183～185
[19] 崔国文.缺陷扩散与烧结[M].北京:清华大学出版社,1990
[20] 宋玉强,李世春.影响铜粉和镍粉界面过程的因素[J].金属热处理2003.28(4):17～21
[21] 王化宇,韩志海.几种Ni-Cr系热喷涂涂层的抗热腐蚀性能和结合强度[J].材料保护2004.12(2):12～15
[22] 曾杰,刘军和.超音速火焰喷涂涂层评析[J].新工艺·新技术·新设备2004(3):72-78
[23] Yihui QI,Jianting Guo and Chanyong CUI.Microstructures and Creep Behavior of a Directionally Solidified NiAI—Fe(Nb)Multiphase Intermetallic.Alloy.[J] Master.Sci.Tschnol,Vol.2003.19(1):59～62
[24] 刘震云,林栋梁,黄伯云,曲选辉.NiAl金属间化合物研究现状[J],机械工程材料,1998.22(2):1～5
[25] 杨松岚,王福会.NiAl金属间化合物高温氧化的研究现状[J],腐蚀科学与技术,2002.14(2):109～112
[26] 顾宜.材料科学与工程基础[M].化学工业出版社,北京,2002
[27] 徐滨士,朱绍华,刘世参,马世宁.表面工程与维修[M].机械工程出版社,北京,2000
[28] 王兴庆,吕海波.粉末冶金法制取Fe-Al金属间化合物的研究[J].上海大学学报,2000,6(6):511～515
[29] 范润华,孙康宁,尹衍升.Fe_3Al金属间化合物的机械合金化[J].机械工程学报,2000,36(8):55～58
[30] 孙康宁,尹衍升,李爱民.金属间化合物/陶瓷基复合材料[M].机械工业出版社,北京,2003
[31] 张彩碚,崔建忠.不锈钢/Al固液轧制复合板材界面剪切强度与界面结构[J].金属学报 1999.35(2):113～116
[32] 宋玉强,李世春.元素粉末法制备Fe-Ni合金的工艺研究[J].新技术新工艺,2004,4
[33] [日]长崎城三,平林真编著.刘安生译.二元合金状态图集[M].北京,冶金工业出版社.2004
[34] 崔燕岭,曹伟涛,张培峰.Ni—3Fe合金反相畴界结构和能量研究[J].焦作工学院学报,2004,23(1):77～79
[35] 王松,万晓景,姚美意.有序和无序态Ni_3Fe的环境氢脆研究[J].金属学报,1999.35(12)1262～1265
[36] 陈爱萍,陈业新,万晓景,王建国,程晓英.有序度对Ni—3Fe合金环境氢脆的影响[J].材料研究学报,2003.17(1):74～78
[37] 林杨,朱逢吾.Ni_3Fe的有序化和反相畴界的FIM—AP研究[J].中国科学:A辑,1994,24(10):1084～1091
[38] 何正明,许士跃,张正明,董传华,施耀铭,钟敏建.Fe_(100-X)Ni_x系合金超细粉末的结构和磁性研究[J].上海大学学报(自然科学版),1999,5(3)
[39] H. S. Green and C. A. Hurst, Order-disorder Phenomena[M]. Interscience, London, 1964.
[40] A. G. Khachaturyan[J], Progress in materials Science, Vol. 22, p. 1, 1979.
[41] D. de Fontaine[J], Solid State Physics, Vol, 34, p. 73, 1979.
[42] 邓永瑞,许洋,赵青.固态相变[M].冶金工业出版社,北京,1996
[43] I.普利高津,G尼科里斯.非平衡系统的自组织[M].科学出版社,北京,1986
[44] 王笛兴.关于自组织[J],Entropy Information Complexity. 2002
[45] H. L. zhang. Morphological healing evolution of Penny-shaped fatigue microcracks in pure iron at elevated temperaturea[J]. Appl, phys. Lett, 2004. 85(7): 1143
[46] Masuda, Appl[J]. phys. Lett, 2001, 78(6): 826
[47] 周亦胄,脉动电流作用下碳钢淬火裂纹的愈合[J],金属学报.2000,36(1):43～45
[48] Z. J. Zhang. Self-assembled patterns of iron oxide nannoparticles by hydrothermal chemical vapor deposition[J], Aapplied physics Letters2001, 79: 4207～4209
[49] Thomas E. L. Science[J], 1999, 286(5443): 1307(?)
[50] S. Aggarwal. Spontaneous ordering of oxide Nanostructures[J]. Science. 2000, (5461): 2235
[51] Crouse D, Lo Yu-nwa, Miller AE, Crouse M[J]. Applied physics Letters2000, 76(1): 49(?)
[52] L. Yescan. SiGe nanostructures by Selective epitaxy and self-assembling[J]. Materials Sci and Engineering 2001, (6)-13(?)
[53] 李如生.非平衡态热力学和耗散结构[J].清华大学出版社,北京,1986
[54] 孙颖,胆结石组成和形成机理的研究进展[J],中国科学(B).2001,31(5):385～389
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