热喷涂（焊）金属WC涂层组织、性能及抗磨粒磨损行为研究
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摘要
传统镀硬铬涂层具有良好的防腐蚀和抗磨损性能,但是,镀硬铬会带来严重的环境污染,随着社会发展对环保要求越来越高,急需寻找一种新的替代镀硬铬的表面工程技术。热喷涂(焊)金属WC涂层具有优异的抗磨损和良好的抗腐蚀性能,在工业生产中被广泛地应用到各种需要防腐和抗磨粒磨损的场合。
我国是钨资源丰富的国家,一方面大量低价出口WC原材料,但是,另一方面,又从国外进口大量价格昂贵的金属WC喷涂(焊)粉末。为此,本文开展新型金属WC粉末设计和相应的涂层工艺优化,以期得到性能优异的金属WC喷涂(焊)粉末和与之相匹配的喷涂工艺,以替代价格昂贵的进口粉末。对新设计的粉末制备的涂层开展组织、抗磨粒磨损和抗腐蚀性能以及相应的机理研究,为更好地替代镀硬铬涂层提供理论和实践依据。
本文从改变WC粒度及粒度分布的角度,设计了超细、亚微米、微米和双峰等四种WC-12Co、微米和双峰两种WC-10Co-4Cr超音速火焰喷涂粉末和14种WC粒度和添加比例不同的Ni基喷焊粉末。在JP-8000型超音速火焰喷涂系统上,采用正交实验方法对设计的喷涂粉末开展工艺参数优化,每种粉末按L9(34)正交表设定的参数各制备9组涂层；采用成熟的“一步法”氧乙炔火焰喷焊工艺将设计的14种喷焊粉末制成相应的喷焊涂层。采用X衍射仪测试了各粉末和相应涂层的相结构,用扫描电镜观察了各粉末的形貌,用金相显微镜、扫描电镜和透射电镜研究了各涂层的截面和表面组织、结构和形貌,分别测试了这些涂层的抗磨损和腐蚀性能,并与进口粉末制备的涂层和镀硬铬涂层进行了对比。得出以下结论：
1.在采用JP-8000型超音速火焰(HVOF)喷涂工艺制备金属基陶瓷涂层时,参数变化对涂层的相结构影响不大,但对涂层的其它性能却有不同程度的影响。增大煤油和氧气的流量、减小喷涂距离以及减小送粉量一般会使涂层的硬度提高、气孔率降低,但同时也会降低喷涂粉末的沉积效率和涂层的开裂韧性。其中煤油流量对涂层的硬度、孔隙率和开裂韧性影响最大；送粉率对单道次沉积厚度影响最大。根据涂层的制备成本和应用场合对涂层的性能要求,可以分别选择经济型(煤油流量22.7L/h,氧气流量：55.2m3/h,送粉率：75g/min,喷涂距离：380mm)、中档型(煤油流量24.6L/h,氧气流量：55.2mmg/h,送粉率：75g/min,喷涂距离：326mm)和高档型(煤油流量26.5L/h,氧气流量：59.5L/h,送粉率：75g/min,喷涂距离：326mm)喷涂参数制备相应WC/Co(Cr)涂层。
2.采用HVOF工艺制备WC/Co(Cr)涂层的开裂韧性与硬度成反比,抗磨粒磨损性能与其硬度成正比,因此,当涂层零件所受冲击力不大时,可以采用提高涂层硬度的方法来提高其抗磨粒磨损性能。
3.采用HVOF工艺制备WC/Co(Cr)涂层时,喷涂粒子中的WC在焰流中氧化分解有直接脱碳和间接脱碳两种形式,WC的分解程度主要取决于焰流的温度和性质(氧化焰、中性焰和还原焰)、粒子在焰流中的停留时间、WC粒子的粒度大小和粉末的致密度等因素。焰流温度越高、粒子在焰流中停留时间越长、WC的粒度越小、WC/Co粉末的粒子越疏松、粘结相的分布越不均匀、并且熔融半熔融的高温粒子沉积到基体上的冷却速度越慢,WC的分解脱碳就越严重。其中,粘结相分布不均匀既促进了WC的直接氧化分解,又加强了WC的间接氧化分解。WC发生轻微的脱碳将生成W2C相,脱碳较严重时,在涂层中不仅生成WzC相,还会生成W相,其中粘结相Co在涂层中主要以非晶的形式存在。
4. WC/Co(Cr)涂层磨粒磨损失效机理随磨粒的硬度不同而有所不同,当磨粒是比涂层硬度高的SiC时,涂层的磨损率很大,涂层中的粘结相和硬质颗粒同时被磨粒犁沟和切削,涂层快速微切削磨损。当磨粒是比涂层硬度稍低的Si02时,属于过渡区域磨损,涂层的磨损率较低,但涂层磨损率随着磨损载荷和磨粒的尺寸增加而增加。其磨损机理是粘结相优先被切除,逐渐失去固结作用的WC粒子在磨粒的作用下发生破碎、松动、直至脱落。
5.WC的粒度及粒度分布对WC/Co(Cr)涂层的性能影响较大。在同种喷涂工艺条件下,当涂层中的WC粒子呈双峰分布时,相对于其它涂层,该双峰涂层中的粘结相分布更均匀且其名义自由路径更小,使得这种双峰WC/Co(Cr)涂层中WC分解较少、涂层结构更致密、开裂韧性和硬度更高,从而表现出更优异的抗磨粒磨损性能。
6.采用超音速火焰喷涂的WC/Co(Cr)涂层,在WC分解不是十分严重时,在WC边缘分布的W2C薄层对涂层的抗磨粒磨损性能并没有损害。在这种情况下,由于粉末在焰流中熔融相对较充分,涂层结构更致密,反而还会使得这种涂层具有更好的抗磨粒磨损和抗腐蚀性能。可见,在WC只发生轻微脱碳的情况下,涂层中的金属粘结相分布情况和涂层组织致密度对涂层硬度和抗磨粒磨损的影响更为显著。
7.对WC-12Co涂层分别在550℃、750℃、950℃和1150℃下进行1h的保护气氛热处理,涂层中的W2C和W相逐渐减少直至消失,涂层中逐渐生成Co3W3C、Co6W6C和Co2W4C等η相。这些η相的形核位置一般在W2C与粘结相的交界部位,在这些部位发生固态相变所需的元素成分容易通过短程扩散而达到。涂层的硬度和脆性都随着热处理温度的升高呈现出先升高后逐渐降低的趋势。经过950℃下进行保护气氛热处理的WC-12Co涂层具有较高的韧性、硬度和最好的抗磨粒磨损性能。另外,涂层与基体界面元素的扩散速度随着热处理温度的升高而增加,特别在1150℃下进行保护气氛热处理后,在涂层与基体的界面发生大量的元素扩散,在界面靠涂层一侧形成接近10μm宽的扩散带,在基体侧形成了尺寸为1～10μm的Kirkendall扩散孔洞。
8.采用氧乙炔火焰喷焊Ni基WC涂层的硬度随WC添加比例的增加,呈现先增加后降低的变化趋势,其中采用熔铸方式添加的细颗粒WC的最佳添加比例为25wt.%,采用机械混合方式添加粗颗粒WC的最佳比例为35wt.%。当喷焊涂层中WC含量相同时,采用机械混合方式添加粗颗粒WC制备的涂层硬度和耐磨粒磨损性能均高于采用熔铸方式添加的细颗粒WC制备的涂层。在所有Ni基WC喷焊涂层中,WC粒子呈双峰分布(细颗粒WC与粗颗粒的总量为35wt.%,比例为3：7)的Ni基WC复合喷焊涂层抗磨粒磨损性能最好,均匀分布的金属粘结相是这种Ni基WC喷焊涂层具有优异抗磨粒磨损性能的主要原因。
9.采用HVOF制备的双峰WC-12Co、WC-10Co-4Cr和氧乙炔火焰工艺制备的双峰Ni-35WC喷焊涂层的抗磨粒磨损性能和抗腐蚀性能与国外同类涂层抗磨损性能相当甚至更好；与较厚的镀硬铬涂层相比,其抗磨粒磨损性能分别提高10.6、9.2和2倍,相应的抗腐蚀性能也更好。因此,采用优化后的工艺制备的这些WC粒子呈双峰分布的WC/Co(Cr)喷涂层和Ni基WC喷焊涂层完全可以取代价格昂贵的进口粉末制备的相应涂层,另外,还可以在既受到磨损又受到腐蚀的场合应用该涂层代替电镀硬铬涂层,减小电镀硬铬涂层给环境带来巨大污染。
Electrolytic hard chrome (EHC) plating is an industrially widespread technology for their high wear and corrosion resistance, restrictive environmental norms which will increasingly limit the applicability of EHC plating because of its giving of a lot of Cr6+and SO42-ions which can cause great damage to human health. Therefore, the need to find technically and economically feasible alternatives arises.
Metals and cermets deposited by HVOF-spraying and oxy-acetylene flame spraying and fusing is one of the most promising coatings for the replacement of EHC plating in those field which need high wear and corrosion resistance coatings.
China is a country rich in tungsten, on the one hand, a lot of low-cost WC raw materials were exported, on the other hand a lot of spraying or spraying and fusing WC based powder with promising quality were imported with high price.
In order to obtain high quality spraying and fusing WC based powder and high quality coatings which can replace of the importing materials, some new metals and WC were designed and corresponding process optimization were also carried.
Microstructure, abrasive wear and corrosion resistance of these coatings deposited by new designing powders have been tested in order to obtain theoretical and practical basis for an alternative method for EHC process.
In this paper, ultra-fine, submicron, micron and bimodal WC-12Co as well as micron and bimodal WC-10Co-4Cr HVOF spray powder were designed by means of changing the grain of WC,14kinds of spraying and fusing powders were also designed by means of changing the grain or proportion WC with NiCrBSi alloy.
WC/Co(Cr) coatings were deposited by JP-8000HVOF spraying system using L9(34) orthogonal experiment, NiCrBSi/WC coatings were produced by promising oxy-acetylene flame spraying and fusing process.
The abrasive wear resistances of all the coatings have been studied by wet sand rubber wheel abrasion tester. The phase compositions of the feedstock powders and coatings were analyzed by XRD. The characterizations of spraying feedstock powders, microstructure and surface micrographs of the prophase and anaphase attrition surfaces of these coatings were analyzed by SEM, the hardness, porosity and fracture toughness of these coatings have also been examined. The results indicated that:
The spraying parameters had little effects on the phase composition but can brought great influence on the performance of sprayed coatings by using of JP-8000HVOF spraying system.
The porosity, fracture toughness and the depositing efficient decreased while the hardness of all the coatings increase with the kerosene and oxygen flux, while all the coatings show reverse tendency when increase the feed rate and the spraying distance. The kerosene flux affects hardness mostly, and the feed rate is the most important parameters which affect the per pass thick of coating.
According to the costing and the required performance of the coating, three group parameters could be obtained by optimizing spraying permanents. The economical spraying parameter is22.7L/h kerosene flux,55.2m3/h oxygen flux,75g/min powder feed rate and380mm spray distance, The moderate parameter is24.6L/h kerosene flux,55.2m3/h oxygen flux,75g/min powder feed rate and326mm spray distance, The highest spraying parameter is26.5L/h kerosene flux,59.5m3/h oxygen flux,75g/min powder feed rate and326mm spray distance,
The hardness is inversely proportional to fracture toughness and proportional to the abrasive wear resistance, the abrasive wear resistance of coating can be increased in great degree by mean of increasing its hardness, when the coating service in the low attacking field.
WC decarburizes in the model of direct and indirect during spraying HVOF process, the decarburizing degree of WC/Co(Cr) coating increases with the residual time in the flame, the temperature of the flame, distribution of bonding metal phase and decrease with the size of the WC grain and the density of sprayed powder. The inhomogeneity distribution of bonding metal phase increases the decomposition of WC both on the direct and indirect way. HVOF-sprayed WC-Co coatings still suffer from decomposition and decarburization during spraying process leading to generating of detrimental phases such as W2C, W and amorphous Co-W-C phase.
The wear rate was primary affected by the relative hardness of abrasive compared with coating, when the hardness of abrasive is higher than WC/Co(Cr) coating such as SiC, the coating was severely cut by the SiC with high hardness and the wear rate of coating was high. When the hardness of abrasive is lower than WC/Co(Cr) coating such as SiO2, the wear rate of coating was low but increase with size of abrasive and the applied load. The mechanism of wear for WC-Co coatings was by selective removal of the binder caused probably by plastic deformation and fatigue due to the repeated action of the abrasive particles followed by the undermining of the carbide particles resulting in their eventual pull out.
The grain size and distribution of WC affected the performance of HVOF WC/Co(Cr) coatings in great degree, the bimodal coating showed the highest hardness, fracture toughness and abrasive wear resistance in all the coatings, the smallest the mean free path of Co phase was responsible for the highest abrasive wear resistance.
The small content of W2C phase in the WC/Co(Cr) coating showed no harmfulness on the abrasive resistance. In this case, the microstructure of coating was much more compact and the hardness of coating was higher which can lead to the increase of the abrasive and corrosion resistance of coating. As a result, the primary factors that affected the performance of coating are the distribution of Co bonding phase and the microstructure of the WC/Co(Cr) coating.
The bimodal and conventional micron WC-12Co coating were heat treated at the temperature of550℃,750℃,950℃and1150℃in the protection of argon. The W2C and W phase disappear and the η phase such as Co3W3C, Co6W6C and Co2W4C gradually appear in the WC-12Co coating with the increase of heat treatment temperature. These η phase usually nucleate at the interface between W2C phase and bonding metal phase, because content of Co, C and W can easily attained by short distance diffusion of these elements. Both the hardness and fracture toughness of coating increased with heat treatment temperature first and then decrease after the950℃.The best abrasive wear resistance of the coating appeared at the temperature of950℃. The diffusion speed of element such as W, Fe and Co at the interface of coating and substrate also increase with the heat treatment temperature, an obvious diffusion bond at the width of10μm at the coating side and some Kirkendall voids with the size of1-10μm at the side of substrate appeared at the temperature of1150℃.
The hardness of spray and fused Ni base WC composite coatings firstly increased and then decreased with content of an added WC, the WC content for the highest hardness of coating with the WC added in the way of mechanical blended is35wt.%, while the WC content for the highest hardness of coating with the WC added in the way of melt and casting was25wt.%.
When the WC content were similar, the hardness of the coatings that the WC added in the way of mechanically blended were higher than those coatings that the WC added in the way of melt and casting. The highest abrasive wear resistance of coating in all the spray and fused Ni base WC composite coatings was the bimodal coating with the WC content of35wt.%, and the ratio of fine and coarse WC in the coating were3:7.The excellent abrasive wear resistance of bimodal Ni based WC spray and fused coating can be attributed to the homogeneous distribution of bonding metal phase and dense coating microstructure.
The HVOF WC/Co(Cr) coatings and the Ni based with WC composite coatings deposited by these bimodal powders designed in this paper showed similar or even higher abrasive wear and corrosion resistance compared with those coatings produced by imported powder and showed similar corrosion resistance and10.6,9.2and2times abrasive wear resistance in comparison to the EHC coating with high thickness respectively. As a result, the new bimodal HVOF WC/Co(Cr) coatings and spraying and fused Ni based WC composited coatings deposited by optimal process and parameter can replace the corresponding coatings deposited by expensive imported powders and EHC that can bring great damage to human health.
我国是钨资源丰富的国家,一方面大量低价出口WC原材料,但是,另一方面,又从国外进口大量价格昂贵的金属WC喷涂(焊)粉末。为此,本文开展新型金属WC粉末设计和相应的涂层工艺优化,以期得到性能优异的金属WC喷涂(焊)粉末和与之相匹配的喷涂工艺,以替代价格昂贵的进口粉末。对新设计的粉末制备的涂层开展组织、抗磨粒磨损和抗腐蚀性能以及相应的机理研究,为更好地替代镀硬铬涂层提供理论和实践依据。
本文从改变WC粒度及粒度分布的角度,设计了超细、亚微米、微米和双峰等四种WC-12Co、微米和双峰两种WC-10Co-4Cr超音速火焰喷涂粉末和14种WC粒度和添加比例不同的Ni基喷焊粉末。在JP-8000型超音速火焰喷涂系统上,采用正交实验方法对设计的喷涂粉末开展工艺参数优化,每种粉末按L9(34)正交表设定的参数各制备9组涂层；采用成熟的“一步法”氧乙炔火焰喷焊工艺将设计的14种喷焊粉末制成相应的喷焊涂层。采用X衍射仪测试了各粉末和相应涂层的相结构,用扫描电镜观察了各粉末的形貌,用金相显微镜、扫描电镜和透射电镜研究了各涂层的截面和表面组织、结构和形貌,分别测试了这些涂层的抗磨损和腐蚀性能,并与进口粉末制备的涂层和镀硬铬涂层进行了对比。得出以下结论：
1.在采用JP-8000型超音速火焰(HVOF)喷涂工艺制备金属基陶瓷涂层时,参数变化对涂层的相结构影响不大,但对涂层的其它性能却有不同程度的影响。增大煤油和氧气的流量、减小喷涂距离以及减小送粉量一般会使涂层的硬度提高、气孔率降低,但同时也会降低喷涂粉末的沉积效率和涂层的开裂韧性。其中煤油流量对涂层的硬度、孔隙率和开裂韧性影响最大；送粉率对单道次沉积厚度影响最大。根据涂层的制备成本和应用场合对涂层的性能要求,可以分别选择经济型(煤油流量22.7L/h,氧气流量：55.2m3/h,送粉率：75g/min,喷涂距离：380mm)、中档型(煤油流量24.6L/h,氧气流量：55.2mmg/h,送粉率：75g/min,喷涂距离：326mm)和高档型(煤油流量26.5L/h,氧气流量：59.5L/h,送粉率：75g/min,喷涂距离：326mm)喷涂参数制备相应WC/Co(Cr)涂层。
2.采用HVOF工艺制备WC/Co(Cr)涂层的开裂韧性与硬度成反比,抗磨粒磨损性能与其硬度成正比,因此,当涂层零件所受冲击力不大时,可以采用提高涂层硬度的方法来提高其抗磨粒磨损性能。
3.采用HVOF工艺制备WC/Co(Cr)涂层时,喷涂粒子中的WC在焰流中氧化分解有直接脱碳和间接脱碳两种形式,WC的分解程度主要取决于焰流的温度和性质(氧化焰、中性焰和还原焰)、粒子在焰流中的停留时间、WC粒子的粒度大小和粉末的致密度等因素。焰流温度越高、粒子在焰流中停留时间越长、WC的粒度越小、WC/Co粉末的粒子越疏松、粘结相的分布越不均匀、并且熔融半熔融的高温粒子沉积到基体上的冷却速度越慢,WC的分解脱碳就越严重。其中,粘结相分布不均匀既促进了WC的直接氧化分解,又加强了WC的间接氧化分解。WC发生轻微的脱碳将生成W2C相,脱碳较严重时,在涂层中不仅生成WzC相,还会生成W相,其中粘结相Co在涂层中主要以非晶的形式存在。
4. WC/Co(Cr)涂层磨粒磨损失效机理随磨粒的硬度不同而有所不同,当磨粒是比涂层硬度高的SiC时,涂层的磨损率很大,涂层中的粘结相和硬质颗粒同时被磨粒犁沟和切削,涂层快速微切削磨损。当磨粒是比涂层硬度稍低的Si02时,属于过渡区域磨损,涂层的磨损率较低,但涂层磨损率随着磨损载荷和磨粒的尺寸增加而增加。其磨损机理是粘结相优先被切除,逐渐失去固结作用的WC粒子在磨粒的作用下发生破碎、松动、直至脱落。
5.WC的粒度及粒度分布对WC/Co(Cr)涂层的性能影响较大。在同种喷涂工艺条件下,当涂层中的WC粒子呈双峰分布时,相对于其它涂层,该双峰涂层中的粘结相分布更均匀且其名义自由路径更小,使得这种双峰WC/Co(Cr)涂层中WC分解较少、涂层结构更致密、开裂韧性和硬度更高,从而表现出更优异的抗磨粒磨损性能。
6.采用超音速火焰喷涂的WC/Co(Cr)涂层,在WC分解不是十分严重时,在WC边缘分布的W2C薄层对涂层的抗磨粒磨损性能并没有损害。在这种情况下,由于粉末在焰流中熔融相对较充分,涂层结构更致密,反而还会使得这种涂层具有更好的抗磨粒磨损和抗腐蚀性能。可见,在WC只发生轻微脱碳的情况下,涂层中的金属粘结相分布情况和涂层组织致密度对涂层硬度和抗磨粒磨损的影响更为显著。
7.对WC-12Co涂层分别在550℃、750℃、950℃和1150℃下进行1h的保护气氛热处理,涂层中的W2C和W相逐渐减少直至消失,涂层中逐渐生成Co3W3C、Co6W6C和Co2W4C等η相。这些η相的形核位置一般在W2C与粘结相的交界部位,在这些部位发生固态相变所需的元素成分容易通过短程扩散而达到。涂层的硬度和脆性都随着热处理温度的升高呈现出先升高后逐渐降低的趋势。经过950℃下进行保护气氛热处理的WC-12Co涂层具有较高的韧性、硬度和最好的抗磨粒磨损性能。另外,涂层与基体界面元素的扩散速度随着热处理温度的升高而增加,特别在1150℃下进行保护气氛热处理后,在涂层与基体的界面发生大量的元素扩散,在界面靠涂层一侧形成接近10μm宽的扩散带,在基体侧形成了尺寸为1～10μm的Kirkendall扩散孔洞。
8.采用氧乙炔火焰喷焊Ni基WC涂层的硬度随WC添加比例的增加,呈现先增加后降低的变化趋势,其中采用熔铸方式添加的细颗粒WC的最佳添加比例为25wt.%,采用机械混合方式添加粗颗粒WC的最佳比例为35wt.%。当喷焊涂层中WC含量相同时,采用机械混合方式添加粗颗粒WC制备的涂层硬度和耐磨粒磨损性能均高于采用熔铸方式添加的细颗粒WC制备的涂层。在所有Ni基WC喷焊涂层中,WC粒子呈双峰分布(细颗粒WC与粗颗粒的总量为35wt.%,比例为3：7)的Ni基WC复合喷焊涂层抗磨粒磨损性能最好,均匀分布的金属粘结相是这种Ni基WC喷焊涂层具有优异抗磨粒磨损性能的主要原因。
9.采用HVOF制备的双峰WC-12Co、WC-10Co-4Cr和氧乙炔火焰工艺制备的双峰Ni-35WC喷焊涂层的抗磨粒磨损性能和抗腐蚀性能与国外同类涂层抗磨损性能相当甚至更好；与较厚的镀硬铬涂层相比,其抗磨粒磨损性能分别提高10.6、9.2和2倍,相应的抗腐蚀性能也更好。因此,采用优化后的工艺制备的这些WC粒子呈双峰分布的WC/Co(Cr)喷涂层和Ni基WC喷焊涂层完全可以取代价格昂贵的进口粉末制备的相应涂层,另外,还可以在既受到磨损又受到腐蚀的场合应用该涂层代替电镀硬铬涂层,减小电镀硬铬涂层给环境带来巨大污染。
Electrolytic hard chrome (EHC) plating is an industrially widespread technology for their high wear and corrosion resistance, restrictive environmental norms which will increasingly limit the applicability of EHC plating because of its giving of a lot of Cr6+and SO42-ions which can cause great damage to human health. Therefore, the need to find technically and economically feasible alternatives arises.
Metals and cermets deposited by HVOF-spraying and oxy-acetylene flame spraying and fusing is one of the most promising coatings for the replacement of EHC plating in those field which need high wear and corrosion resistance coatings.
China is a country rich in tungsten, on the one hand, a lot of low-cost WC raw materials were exported, on the other hand a lot of spraying or spraying and fusing WC based powder with promising quality were imported with high price.
In order to obtain high quality spraying and fusing WC based powder and high quality coatings which can replace of the importing materials, some new metals and WC were designed and corresponding process optimization were also carried.
Microstructure, abrasive wear and corrosion resistance of these coatings deposited by new designing powders have been tested in order to obtain theoretical and practical basis for an alternative method for EHC process.
In this paper, ultra-fine, submicron, micron and bimodal WC-12Co as well as micron and bimodal WC-10Co-4Cr HVOF spray powder were designed by means of changing the grain of WC,14kinds of spraying and fusing powders were also designed by means of changing the grain or proportion WC with NiCrBSi alloy.
WC/Co(Cr) coatings were deposited by JP-8000HVOF spraying system using L9(34) orthogonal experiment, NiCrBSi/WC coatings were produced by promising oxy-acetylene flame spraying and fusing process.
The abrasive wear resistances of all the coatings have been studied by wet sand rubber wheel abrasion tester. The phase compositions of the feedstock powders and coatings were analyzed by XRD. The characterizations of spraying feedstock powders, microstructure and surface micrographs of the prophase and anaphase attrition surfaces of these coatings were analyzed by SEM, the hardness, porosity and fracture toughness of these coatings have also been examined. The results indicated that:
The spraying parameters had little effects on the phase composition but can brought great influence on the performance of sprayed coatings by using of JP-8000HVOF spraying system.
The porosity, fracture toughness and the depositing efficient decreased while the hardness of all the coatings increase with the kerosene and oxygen flux, while all the coatings show reverse tendency when increase the feed rate and the spraying distance. The kerosene flux affects hardness mostly, and the feed rate is the most important parameters which affect the per pass thick of coating.
According to the costing and the required performance of the coating, three group parameters could be obtained by optimizing spraying permanents. The economical spraying parameter is22.7L/h kerosene flux,55.2m3/h oxygen flux,75g/min powder feed rate and380mm spray distance, The moderate parameter is24.6L/h kerosene flux,55.2m3/h oxygen flux,75g/min powder feed rate and326mm spray distance, The highest spraying parameter is26.5L/h kerosene flux,59.5m3/h oxygen flux,75g/min powder feed rate and326mm spray distance,
The hardness is inversely proportional to fracture toughness and proportional to the abrasive wear resistance, the abrasive wear resistance of coating can be increased in great degree by mean of increasing its hardness, when the coating service in the low attacking field.
WC decarburizes in the model of direct and indirect during spraying HVOF process, the decarburizing degree of WC/Co(Cr) coating increases with the residual time in the flame, the temperature of the flame, distribution of bonding metal phase and decrease with the size of the WC grain and the density of sprayed powder. The inhomogeneity distribution of bonding metal phase increases the decomposition of WC both on the direct and indirect way. HVOF-sprayed WC-Co coatings still suffer from decomposition and decarburization during spraying process leading to generating of detrimental phases such as W2C, W and amorphous Co-W-C phase.
The wear rate was primary affected by the relative hardness of abrasive compared with coating, when the hardness of abrasive is higher than WC/Co(Cr) coating such as SiC, the coating was severely cut by the SiC with high hardness and the wear rate of coating was high. When the hardness of abrasive is lower than WC/Co(Cr) coating such as SiO2, the wear rate of coating was low but increase with size of abrasive and the applied load. The mechanism of wear for WC-Co coatings was by selective removal of the binder caused probably by plastic deformation and fatigue due to the repeated action of the abrasive particles followed by the undermining of the carbide particles resulting in their eventual pull out.
The grain size and distribution of WC affected the performance of HVOF WC/Co(Cr) coatings in great degree, the bimodal coating showed the highest hardness, fracture toughness and abrasive wear resistance in all the coatings, the smallest the mean free path of Co phase was responsible for the highest abrasive wear resistance.
The small content of W2C phase in the WC/Co(Cr) coating showed no harmfulness on the abrasive resistance. In this case, the microstructure of coating was much more compact and the hardness of coating was higher which can lead to the increase of the abrasive and corrosion resistance of coating. As a result, the primary factors that affected the performance of coating are the distribution of Co bonding phase and the microstructure of the WC/Co(Cr) coating.
The bimodal and conventional micron WC-12Co coating were heat treated at the temperature of550℃,750℃,950℃and1150℃in the protection of argon. The W2C and W phase disappear and the η phase such as Co3W3C, Co6W6C and Co2W4C gradually appear in the WC-12Co coating with the increase of heat treatment temperature. These η phase usually nucleate at the interface between W2C phase and bonding metal phase, because content of Co, C and W can easily attained by short distance diffusion of these elements. Both the hardness and fracture toughness of coating increased with heat treatment temperature first and then decrease after the950℃.The best abrasive wear resistance of the coating appeared at the temperature of950℃. The diffusion speed of element such as W, Fe and Co at the interface of coating and substrate also increase with the heat treatment temperature, an obvious diffusion bond at the width of10μm at the coating side and some Kirkendall voids with the size of1-10μm at the side of substrate appeared at the temperature of1150℃.
The hardness of spray and fused Ni base WC composite coatings firstly increased and then decreased with content of an added WC, the WC content for the highest hardness of coating with the WC added in the way of mechanical blended is35wt.%, while the WC content for the highest hardness of coating with the WC added in the way of melt and casting was25wt.%.
When the WC content were similar, the hardness of the coatings that the WC added in the way of mechanically blended were higher than those coatings that the WC added in the way of melt and casting. The highest abrasive wear resistance of coating in all the spray and fused Ni base WC composite coatings was the bimodal coating with the WC content of35wt.%, and the ratio of fine and coarse WC in the coating were3:7.The excellent abrasive wear resistance of bimodal Ni based WC spray and fused coating can be attributed to the homogeneous distribution of bonding metal phase and dense coating microstructure.
The HVOF WC/Co(Cr) coatings and the Ni based with WC composite coatings deposited by these bimodal powders designed in this paper showed similar or even higher abrasive wear and corrosion resistance compared with those coatings produced by imported powder and showed similar corrosion resistance and10.6,9.2and2times abrasive wear resistance in comparison to the EHC coating with high thickness respectively. As a result, the new bimodal HVOF WC/Co(Cr) coatings and spraying and fused Ni based WC composited coatings deposited by optimal process and parameter can replace the corresponding coatings deposited by expensive imported powders and EHC that can bring great damage to human health.
引文
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