碳氮合金化耐磨合金电弧喷涂的熔滴过渡行为及涂层性能研究
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摘要
在设备零件表面制备高性能的耐磨涂层是提高其使用寿命的有效途径。相对于其它热喷涂方法，电弧喷涂由于具有设备简单、操作方便、效率高、成本低的特点而得到广泛应用。目前制备电弧喷涂耐磨涂层主要采用碳强化的合金丝材，但是此种喷涂丝材中的碳化物容易长大、脱落，从而使涂层难以获得高耐磨性能和结合强度。本文通过使用氮替代部分碳进行碳氮合金化，并添加适量的钒、铌等强碳氮化合物形成元素，在涂层中形成了碳氮化物等硬质相颗粒，显著地提高了涂层的耐磨性能和结合强度，开辟了具有较高综合性能电弧喷涂耐磨涂层材料的新途径。
以自主研发的4Cr13马氏体涂层为基础合金涂层，通过添加适量的氮化物以及钒铁、铌铁，设计了新型碳氮合金化耐磨合金材料，并研制出工艺性良好的碳氮合金化耐磨合金电弧喷涂药芯丝材；研究了合金涂层金属基体中氮的析出行为，并确定了合金涂层的合理氮含量，结果表明：4Cr13马氏体不锈钢涂层中最大氮含量约为0.10％，而加入微量的固氮元素钒和铌能使合金涂层的氮含量达到0.20％以上。铌和钒提高氮在马氏体不锈钢涂层溶解度的主要原因为：这两种元素降低氮在熔滴金属中的活性系数，从而增大了氮的固溶度；作为碳氮化物形成元素与氮作用，形成复杂的碳氮化物粒子，增大涂层的含氮量。
应用高速摄影技术研究了电弧喷涂雾化熔滴过渡行为，并分析其对耐磨合金涂层质量的影响，结果发现：制备碳氮合金涂层时雾化熔滴的尺寸差别较大，最大熔滴体积约为最小熔滴的几十倍。电弧喷涂电流和雾化空气压力越大，雾化熔滴的尺寸就越小，雾化效果就越好，熔滴速度也就越快。熔滴最高速度达78m/s，而最低速度只有21m/s。电弧喷涂雾化熔滴过渡行为研究为电弧喷涂工艺和涂层质量的分析与评定提供了有效手段和依据。
系统研究喷涂电流、喷涂电压、喷涂距离、雾化空气压力等主要电弧喷涂工艺参数对碳氮合金化耐磨合金涂层组织和性能的影响，并优化了喷涂工艺参数；分析了基材表面粗化处理、涂层厚度及喷涂后热处理对涂层组织性能的影响，结果表明：制备碳氮合金化涂层的最优电弧喷涂工艺参数是：喷涂电压为30V，喷涂电流为240A，雾化空气压力为0.5MPa，喷涂距离为200mm；采用Ni95Al5喷涂丝材制备碳氮合金化涂层的打底层（即过渡涂层），其最佳厚度值约为0.1mm，而工作涂层的最佳厚度值约为0.6mm；550℃～650℃的回火热处理细化了涂层的基体组织，提高了涂层的综合性能。
深入分析了碳氮合金化耐磨合金涂层的组织结构与性能，结果表明：碳氮合金化涂层组织为板条马氏体、少量残余奥氏体以及弥散分布在涂层基体中的碳化物硬质相颗粒。涂层致密，成形良好，呈典型层状结构。钒和铌元素能改善碳氮合金化涂层的组织和性能，当添加4%的钒铁和6%的铌铁时，涂层获得最佳综合性能，此时涂层的氧化物含量和孔隙率较低。与4Cr13涂层相比，碳氮合金化涂层具有更高的显微硬度和结合强度，其显微硬度平均值约为556HV0.1，结合强度达38.9MPa，耐磨粒磨损性能约为4Cr13涂层的1.78倍。涂层经550℃回火热处理后，其微观组织形貌无明显变化，而涂层硬度、耐磨粒磨损性能以及结合强度有一定提高。
全面探析了耐磨合金中碳氮化物硬质相及耐磨粒磨损机理，结果表明：碳氮析出相为MX复合物（M为Nb、V和Ti；X为C、N），弥散分布在涂层金属中的晶界和晶内，尺寸均不大于3.5μm。碳氮化物在涂层中起到了细化一次结晶组织、钉扎位错阻碍晶粒长大的细化作用；碳氮化物分布均匀而且在高温下不易产生分解，对涂层金属起到了沉淀强化作用，上述作用显著提高了涂层的强度和韧性。大量的碳氮化物质点沉淀析出，提高了涂层硬度，抵御了磨粒对涂层金属基体的有效切削，从而使涂层获得较高的耐磨粒磨损性能。
研究了碳氮合金耐磨合金涂层残余应力的形成机理及影响因素，用射线衍射法检测了涂层的残余应力，并与采用有限元方法模拟的结果进行比较，结果表明：碳氮合金化涂层与基材结合面处的残余应力值最大且为压应力。用数值分析方法成功模拟了涂层应力分布和形成情况，其分析结果与XRD检测的涂层残余应力为同一量级。数值模拟为预防和控制涂层残余应力提供了可靠依据，并由此将涂层残余应力控制在较低水平。
在搅拌车的搅拌筒叶片及泵轴等零件表面制备碳氮合金化耐磨合金并进行了生产应用研究，采用外观分析法和划痕试验法检测了涂层性能，结果表明：碳氮合金化涂层有较高的结合强度、耐磨损性能以及良好的加工性能，适合有耐磨损要求零件的生产与修复，因而碳氮合金化涂层具有较高的推广和应用价值。
Coatings with good wear-resistant prepared on the surface of the machine partshave emerged as an effective way to improve its service life. Compared with otherthermal spraying, arc spraying begin to be widely used for its advantages, such assimple device, convenient operation, higher efficiency and lower cost. The carbonalloying flux-cored wire is mainly used in the alloying arc sprayed coatings at present,but the adhesion strength and wear resistanc of this kind of coatings is lower for thecarbides is easy to grow and pee. In this article, element N was added into the wirebeing replaced parts of element C to be carbonitride alloying, and element V and Nbwere also added into the coatings to form carbonitride hard phase particles, which cangreatly improve properties of the coatings, especially the adhesion strength and wearresistanc. The research opened up a new path for arc sprayed resistant coatingsmaterials with good comprehensive properties.
A new kind of carbonitride wear-resistant coating based on the basis alloyingcoating of the4Cr13martensitic stainless steel coating had been designed by addingCrN, ferrovanadium and ferrocolumbium. And arc sprayed flux-cored wires withgood performance had also been developed successfully. The precipitation behaviorof nitrogen in the coating had been studied, and the reasonable nitrogen content in thealloy was obtained. The results indicated that maximal nitrogen content in4Cr13steelis approximately0.10%, which can be up to0.20%after adding extremely a littlequantitiy of element V and Nb. The main reason that additions of Nb, V and Ti canincrease nitrogen solubility in the coatings are: first, they can reduce activitycoefficient of nitrogen in molten drop and increase its solid solubility; Second, as themost effective carbonitride forming elements added in the coating, these alloyingelements can enlarge nitrogen content.
The transitional behavior of arc sprayed droplet was studied using high-speedvideo techniques, and effects on the coatings were also analyzed, the results showedthat the sizes of atomized droplets were different obviously when being sprayed, thebig droplet was about dozens of times than that of small one. The higher the value ofsprayed current and air pressure, the smaller the atomized droplets, the better theeffect of atomizing, and the higher the speed of atomized droplets. The highest speedof droplet was about78m/s, and the lowest speed of droplet was about21m/s. Theresearch on the droplet provided an effective way to analyzing and evaluating on thearc spraying process and coatings quality.
The effects of mainly arc spraying process parameters of the spraying current,voltage, pressure and distance of the air atomizing on the microstructure andproperties of the carbonitride alloying coatings had been studied systematically. Theprocess parameters of arc spraying had been optimized. The effects of surfaceroughtening treatment of the workpiece, thicness of coatings and heat treatment onthe properties and microstructure of the coatings had also been studied. The resultsindicted that the optimal process parameters preparing carbonitride alloying coatingswere as follow:240A of current,30V of voltage,200mm of spraying distance and0.5MPa of the air atomizing pressure. The arc sprayed wire Ni95Al5was used toprepare the trasitional coatings, the thickness is about0.1mm, and the workingcoatings is about0.6mm. And550℃～650℃of tempering heat treatment canenharnce the comprehensive properties.
The microstructure and properties of the carbonitride alloying coatings weredeeply investigated. The results showed that there are three main phases of the lathmartensite, the residual austenite and the hard phase particles distributedhomogeneously in metal matrix of the coatings. Coatings have compact structure andgood forming. Elements V and Nb can improve the microstructure and properties ofthe coatings. Coatings with4%ferrovanadium and6%ferrocolumbium had the bestcomprehensive properties, in which there were less porosity and oxides. The carbonitride alloying coatings had higher value of microhardness and adhesionstrength than that of4Cr13coatings, the average microhardness value is about556HV0.1, and the adhesion strength value reaches38.9Mpa. The value of abrasive wearperformance is about1.78times higher than that of the4Cr13coatings. After thetemper temperature of550℃, the hardness, the wear resistance and the adhesionstrength of the coatings had been improved, but the microstructure had not beenobviously changed.
The carbonitride hard-phases in the coatings and the abrasive wear mechanism ofthe coatings were investigated and analyzed. The results indicated that carbonitrideparticles in the matrix of the coatings are complex MX distributing on the grainboundary or matrix, which sizes are smaller than3.5μm. M is the element of Nb, V orTi, and X is the element of C or N. The carbonitride can effectively refine themicrostructure, and hinder the crystal growing by fixing the crystal boundary. Thehomogeneous distribution of very fine carbonitride can not been easily disintegrated,which has precipitation strengthening effect on the matrix of the coatings. Thuscarbonitride could improve the strength and toughness of the coatings. The coatingswould have good abrasive wear behavior for the large quantities of carbonitrideparticles that precipitated out improving the microhardness of the coatings andhindering effective cutting of particles on the coatings.
Formation mechanism of the carbonitride alloying coatings and influencingfactors on the coatings had been studied. Residual stress of the coatings was tested byXRD, which result was compared with that of the numerical simulation of the finiteelement method. The results indicated that there was the maximum value of residualstress on the interface between coatings and steel plate, which was compressive stress.Distribution and formation of the coatings had been successfully simulated by thenumerical analysis. And the result was the same as the order of XRD, which canprovide evidence to prevent and control the stress of the coatings, the value of theresidual stress was relative low which waw about1000MPa.
Carbonitride alloying coatings were successfully prepared on the surface of theblade of the mixing drum for concrete mixer vehicle and the shaft of pump, the performance of the coatings had been tested by appearance analysis and scratch test,the results indicated that the coatings had high the wear resistance and adhesionstrength after long-time operation, which can meet the need of production. Therefore,the carbonitride alloying coatings have higher value of application and dissemination.
以自主研发的4Cr13马氏体涂层为基础合金涂层，通过添加适量的氮化物以及钒铁、铌铁，设计了新型碳氮合金化耐磨合金材料，并研制出工艺性良好的碳氮合金化耐磨合金电弧喷涂药芯丝材；研究了合金涂层金属基体中氮的析出行为，并确定了合金涂层的合理氮含量，结果表明：4Cr13马氏体不锈钢涂层中最大氮含量约为0.10％，而加入微量的固氮元素钒和铌能使合金涂层的氮含量达到0.20％以上。铌和钒提高氮在马氏体不锈钢涂层溶解度的主要原因为：这两种元素降低氮在熔滴金属中的活性系数，从而增大了氮的固溶度；作为碳氮化物形成元素与氮作用，形成复杂的碳氮化物粒子，增大涂层的含氮量。
应用高速摄影技术研究了电弧喷涂雾化熔滴过渡行为，并分析其对耐磨合金涂层质量的影响，结果发现：制备碳氮合金涂层时雾化熔滴的尺寸差别较大，最大熔滴体积约为最小熔滴的几十倍。电弧喷涂电流和雾化空气压力越大，雾化熔滴的尺寸就越小，雾化效果就越好，熔滴速度也就越快。熔滴最高速度达78m/s，而最低速度只有21m/s。电弧喷涂雾化熔滴过渡行为研究为电弧喷涂工艺和涂层质量的分析与评定提供了有效手段和依据。
系统研究喷涂电流、喷涂电压、喷涂距离、雾化空气压力等主要电弧喷涂工艺参数对碳氮合金化耐磨合金涂层组织和性能的影响，并优化了喷涂工艺参数；分析了基材表面粗化处理、涂层厚度及喷涂后热处理对涂层组织性能的影响，结果表明：制备碳氮合金化涂层的最优电弧喷涂工艺参数是：喷涂电压为30V，喷涂电流为240A，雾化空气压力为0.5MPa，喷涂距离为200mm；采用Ni95Al5喷涂丝材制备碳氮合金化涂层的打底层（即过渡涂层），其最佳厚度值约为0.1mm，而工作涂层的最佳厚度值约为0.6mm；550℃～650℃的回火热处理细化了涂层的基体组织，提高了涂层的综合性能。
深入分析了碳氮合金化耐磨合金涂层的组织结构与性能，结果表明：碳氮合金化涂层组织为板条马氏体、少量残余奥氏体以及弥散分布在涂层基体中的碳化物硬质相颗粒。涂层致密，成形良好，呈典型层状结构。钒和铌元素能改善碳氮合金化涂层的组织和性能，当添加4%的钒铁和6%的铌铁时，涂层获得最佳综合性能，此时涂层的氧化物含量和孔隙率较低。与4Cr13涂层相比，碳氮合金化涂层具有更高的显微硬度和结合强度，其显微硬度平均值约为556HV0.1，结合强度达38.9MPa，耐磨粒磨损性能约为4Cr13涂层的1.78倍。涂层经550℃回火热处理后，其微观组织形貌无明显变化，而涂层硬度、耐磨粒磨损性能以及结合强度有一定提高。
全面探析了耐磨合金中碳氮化物硬质相及耐磨粒磨损机理，结果表明：碳氮析出相为MX复合物（M为Nb、V和Ti；X为C、N），弥散分布在涂层金属中的晶界和晶内，尺寸均不大于3.5μm。碳氮化物在涂层中起到了细化一次结晶组织、钉扎位错阻碍晶粒长大的细化作用；碳氮化物分布均匀而且在高温下不易产生分解，对涂层金属起到了沉淀强化作用，上述作用显著提高了涂层的强度和韧性。大量的碳氮化物质点沉淀析出，提高了涂层硬度，抵御了磨粒对涂层金属基体的有效切削，从而使涂层获得较高的耐磨粒磨损性能。
研究了碳氮合金耐磨合金涂层残余应力的形成机理及影响因素，用射线衍射法检测了涂层的残余应力，并与采用有限元方法模拟的结果进行比较，结果表明：碳氮合金化涂层与基材结合面处的残余应力值最大且为压应力。用数值分析方法成功模拟了涂层应力分布和形成情况，其分析结果与XRD检测的涂层残余应力为同一量级。数值模拟为预防和控制涂层残余应力提供了可靠依据，并由此将涂层残余应力控制在较低水平。
在搅拌车的搅拌筒叶片及泵轴等零件表面制备碳氮合金化耐磨合金并进行了生产应用研究，采用外观分析法和划痕试验法检测了涂层性能，结果表明：碳氮合金化涂层有较高的结合强度、耐磨损性能以及良好的加工性能，适合有耐磨损要求零件的生产与修复，因而碳氮合金化涂层具有较高的推广和应用价值。
Coatings with good wear-resistant prepared on the surface of the machine partshave emerged as an effective way to improve its service life. Compared with otherthermal spraying, arc spraying begin to be widely used for its advantages, such assimple device, convenient operation, higher efficiency and lower cost. The carbonalloying flux-cored wire is mainly used in the alloying arc sprayed coatings at present,but the adhesion strength and wear resistanc of this kind of coatings is lower for thecarbides is easy to grow and pee. In this article, element N was added into the wirebeing replaced parts of element C to be carbonitride alloying, and element V and Nbwere also added into the coatings to form carbonitride hard phase particles, which cangreatly improve properties of the coatings, especially the adhesion strength and wearresistanc. The research opened up a new path for arc sprayed resistant coatingsmaterials with good comprehensive properties.
A new kind of carbonitride wear-resistant coating based on the basis alloyingcoating of the4Cr13martensitic stainless steel coating had been designed by addingCrN, ferrovanadium and ferrocolumbium. And arc sprayed flux-cored wires withgood performance had also been developed successfully. The precipitation behaviorof nitrogen in the coating had been studied, and the reasonable nitrogen content in thealloy was obtained. The results indicated that maximal nitrogen content in4Cr13steelis approximately0.10%, which can be up to0.20%after adding extremely a littlequantitiy of element V and Nb. The main reason that additions of Nb, V and Ti canincrease nitrogen solubility in the coatings are: first, they can reduce activitycoefficient of nitrogen in molten drop and increase its solid solubility; Second, as themost effective carbonitride forming elements added in the coating, these alloyingelements can enlarge nitrogen content.
The transitional behavior of arc sprayed droplet was studied using high-speedvideo techniques, and effects on the coatings were also analyzed, the results showedthat the sizes of atomized droplets were different obviously when being sprayed, thebig droplet was about dozens of times than that of small one. The higher the value ofsprayed current and air pressure, the smaller the atomized droplets, the better theeffect of atomizing, and the higher the speed of atomized droplets. The highest speedof droplet was about78m/s, and the lowest speed of droplet was about21m/s. Theresearch on the droplet provided an effective way to analyzing and evaluating on thearc spraying process and coatings quality.
The effects of mainly arc spraying process parameters of the spraying current,voltage, pressure and distance of the air atomizing on the microstructure andproperties of the carbonitride alloying coatings had been studied systematically. Theprocess parameters of arc spraying had been optimized. The effects of surfaceroughtening treatment of the workpiece, thicness of coatings and heat treatment onthe properties and microstructure of the coatings had also been studied. The resultsindicted that the optimal process parameters preparing carbonitride alloying coatingswere as follow:240A of current,30V of voltage,200mm of spraying distance and0.5MPa of the air atomizing pressure. The arc sprayed wire Ni95Al5was used toprepare the trasitional coatings, the thickness is about0.1mm, and the workingcoatings is about0.6mm. And550℃～650℃of tempering heat treatment canenharnce the comprehensive properties.
The microstructure and properties of the carbonitride alloying coatings weredeeply investigated. The results showed that there are three main phases of the lathmartensite, the residual austenite and the hard phase particles distributedhomogeneously in metal matrix of the coatings. Coatings have compact structure andgood forming. Elements V and Nb can improve the microstructure and properties ofthe coatings. Coatings with4%ferrovanadium and6%ferrocolumbium had the bestcomprehensive properties, in which there were less porosity and oxides. The carbonitride alloying coatings had higher value of microhardness and adhesionstrength than that of4Cr13coatings, the average microhardness value is about556HV0.1, and the adhesion strength value reaches38.9Mpa. The value of abrasive wearperformance is about1.78times higher than that of the4Cr13coatings. After thetemper temperature of550℃, the hardness, the wear resistance and the adhesionstrength of the coatings had been improved, but the microstructure had not beenobviously changed.
The carbonitride hard-phases in the coatings and the abrasive wear mechanism ofthe coatings were investigated and analyzed. The results indicated that carbonitrideparticles in the matrix of the coatings are complex MX distributing on the grainboundary or matrix, which sizes are smaller than3.5μm. M is the element of Nb, V orTi, and X is the element of C or N. The carbonitride can effectively refine themicrostructure, and hinder the crystal growing by fixing the crystal boundary. Thehomogeneous distribution of very fine carbonitride can not been easily disintegrated,which has precipitation strengthening effect on the matrix of the coatings. Thuscarbonitride could improve the strength and toughness of the coatings. The coatingswould have good abrasive wear behavior for the large quantities of carbonitrideparticles that precipitated out improving the microhardness of the coatings andhindering effective cutting of particles on the coatings.
Formation mechanism of the carbonitride alloying coatings and influencingfactors on the coatings had been studied. Residual stress of the coatings was tested byXRD, which result was compared with that of the numerical simulation of the finiteelement method. The results indicated that there was the maximum value of residualstress on the interface between coatings and steel plate, which was compressive stress.Distribution and formation of the coatings had been successfully simulated by thenumerical analysis. And the result was the same as the order of XRD, which canprovide evidence to prevent and control the stress of the coatings, the value of theresidual stress was relative low which waw about1000MPa.
Carbonitride alloying coatings were successfully prepared on the surface of theblade of the mixing drum for concrete mixer vehicle and the shaft of pump, the performance of the coatings had been tested by appearance analysis and scratch test,the results indicated that the coatings had high the wear resistance and adhesionstrength after long-time operation, which can meet the need of production. Therefore,the carbonitride alloying coatings have higher value of application and dissemination.
引文
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