钨极氩弧原位合成TiC增强铁基熔敷层的研究
摘要
在矿山开采、重型冶金、油气钻探等重工业领域，能够承受剧烈冲击及抗腐蚀、抗磨损成为机械零部件的基本要求，在耐磨部件表面熔敷具有高硬度、高耐磨损性能的涂层成为这些领域修复部件、强化零件使用寿命的重要途径。本文利用钨极氩弧热源，熔敷预涂在普通碳钢表面上的合金粉末，制备出原位合成TiC增强的铁基熔敷层，并对熔敷层的微观组织、TiC增强相的生长机制、熔敷层磨损性能等进行了系统分析，研究了影响熔敷层组织及性能的因素及规律。
预涂合金粉末组分是钨极氩弧原位合成TiC铁基熔敷层的关键。试验表明，纯钛粉+石墨组分在熔敷过程中容易氧化生成TiO_2，致使熔渣的熔点升高，钨极氩弧熔敷时工艺性较差；加入铁基自熔性合金粉末的组分(G314+Ti+C)能够获得较多的原位合成TiC增强相，熔敷工艺性能优良，具有TiC+M_(23)C_6碳化物复合增强的熔敷层，但其抗裂性能下降；钛铁+石墨组分由于铁．钛低熔点共晶的存在，有利于TiC增强相的原位合成，提高了熔敷层中TiC的合成数量，获得了以聚集树枝状分布伴以较少数量弥散分布的TiC分布特征，增强效果明显。且该粉末组分工艺性好，价格低廉，能够获得与母材结合良好、抗磨损性能和抗裂性能俱佳的铁基熔敷层，是钨极氩弧原位合成TiC增强铁基熔敷层的理想组分。
钨极氩弧熔敷是在非平衡热力学条件下进行的，由于熔池中热传导及结晶潜热的综合作用，使熔池中不同区域形成温度梯度和成分过冷，初生TiC沿树枝状方向断续形核，熔池中Ti、C原子因浓度梯度而扩散至最近的TiC晶核，使得初生TiC以侧面生长方式长大，形成了呈树枝状排列的“长砖块”状TiC颗粒微观形貌。距离较近的TiC晶核在长大过程中粘连生长，形成了尺寸较大TiC颗粒。而在熔池凝固过程的共晶转变中，TiC的形核生长是扩散机制，先凝固Fe基体的包覆使TiC生长的各向异性被抑制，形成了不同形状的共晶TiC颗粒。原位合成的TiC颗粒呈典型的小面生长形态，其显露面为生长速度较慢的密排[111]晶面。TiC颗粒与基体金属的结合界面洁净，无反应物、附着物生成，与基体金属的结合强度高。
预涂层厚度、焊接电流、熔敷速度、熔敷层数等不同的熔敷参数影响着熔敷层的成形和耐磨性能。研究表明，当预涂层厚度为1.2mm，焊接电流150A，熔敷速度为55-60mm／min，熔敷层数为三层时，能够获得成形好、与基体结合强度高组织与性能优异的TiC增强铁基熔敷层。不同熔敷层数的对比试验表明，三层熔敷能有效降低组分中Ti、C元素的稀释率，提高了熔敷层中增强颗粒的数量及尺寸，初生TiC颗粒树枝状分布和共晶TiC颗粒弥散分布相结合，基体为低碳马氏体组织，有利于熔敷层硬度及抗磨损性能的提高，又能有效避免裂纹形成。
预涂粉末的组分及含量影响着熔敷层中原位合成TiC的数量、尺寸、分布特征和基体组织构成。当组分中Ti∶C摩尔数比为1∶1.2时，熔敷层中Fe_2Ti有害相消失，原位合成TiC颗粒的数量增多，尺寸增大，基体为低碳马氏体组织，能够获得硬度较高，抗磨损性能较好的铁基熔敷层；粉末组分中加入稀土La_2O_3，增加了原位合成TiC的异质形核核心，使得熔敷层中TiC颗粒由发达的树枝状分布变为细小的树枝状或者颗粒状弥散分布。另一方面稀土La_2O_3改变了TiC形核与长大方式，降低了TiC中的碳饱和度，对TiC晶体的力学性能带来不利影响，使TiC的强度和硬度降低，影响了其增强效果，使得熔敷层的硬度降低，也使得加入稀土后熔敷层的抗磨损性能有所下降；粉末组分中加入钒铁后，熔敷层中TiC-VC增强相数量增多，呈聚集树枝状和弥散颗粒状分布，形成了TiC-VC复合增强效果。TiC-VC晶粒的元素分布特征表明，TiC-VC晶粒中TiC、VC独立存在并生长，形成了TiC-VC的共生晶粒。另外V元素的加入细化了基体组织晶粒，提高了基体金属和熔敷层的硬度。
通过对母材、熔敷层的对比磨损试验表明，在相同磨损条件下，钨极氩弧原位合成TiC增强铁基熔敷层的磨损体积为母材金属的1／20～1／23，具有优异的抗磨损性能。熔敷层磨损过程中，参与摩擦更多的是暴露于摩擦面的TiC颗粒，由于其阻碍和钉扎作用，摩擦过程需要消耗更多的摩擦功，磨损量降低。熔敷层基体金属的磨损主要是显微切削与粘着损失，TiC增强相则是经摩擦副较长距离、多次重复摩擦后磨损变小，直至最终剥离脱落。磨痕内有浅而小的凹坑及短而浅的犁沟，犁沟始于磨损变小的TiC颗粒脱落位置而止于下一个耐磨TiC前。不同层数熔敷层对比试验表明，尺寸较大的呈聚集树枝状分布的TiC颗粒与基体金属相互绞接在一起，结合更紧密，阻磨作用更强，三层熔敷层能够获得最优的抗磨损性能。
Properties of endurance impact, corrosion resistance and wear resistance are the basic requirements for components which are employed in commercial application such as mine exploration, heavy metallurgy and gasoline drilling. The method of development high-hardness and anti-resistant coating on the surface of components is a valuable way to repair it and prolong their service life. In this research, the Fe-based coating reinforced by in-situ TiC was fabricated by tungsten-inert gas (TIG) melting process employing a proper amount of alloy powder prepared on the surface of ordinary carbon steel substrate, and the microstructure, wear properties of the coatings and the growth mechanism of TiC carbides were analyzed systematically. At same time, the factors and rules influencing microstructure and properties were investigated.
It is found that the powders constituents are the key factor to synthesize in-situ TiC reinforced coatings by using TIG welding process. Because of the lower energy-flux density of TIG compared to laser and plasma, it is necessary to select powder elements with lower melting point which can quickly form molten pool. And then, metallurgical reaction occurs between titanium and carbon and synthesizes well-shaped overlap with high effective mass of TiC. The reaction equation is as followed: Ti + C→TiC. According to this principle, the powders composed of ferrotitanium and graphite (FeTi+C ) has excellent processing properties, which can produce a good bonding, excellent mechanical and wear resistant properties of the coating. The in-situ TiC in the coating distribute in dendritic mode majority, with small TiC grains in diffusion minority. Although iron-based self-fluxing alloy powder (G314) has a lower melting point and well manufacturability, complex carbide M_(23)C_6 emerges besides the in-situ TiC reinforced phase in the coating, which increases the crack sensitivity of the coatings. In addition, TiC carbides can also be formed via pure Ti element and graphite, however, the active chemical property of pure titanium, it can react with oxygen easily and form TiO_2, which result in the increasing of the components melting point and poor shaping.
Under the nonequilibrium condition of TIG fabrication, primary TiC grains in the Fe-based coating reveal dendrite crystal in majority and eutectic form in minority. Because of the directionality of thermal conduction and heat emission in the course of the fabrication of the TiC, component overcooling emerges in the growth front of TiC grains. This results in definite orientation of primary TiC. The primary TiC grows and turns to dendrite distribution. Nevertheless, in the course of eutectic transformation during the solidification of molten pool, the mechanism of TiC nucleation and growth is diffusion. The anisotropic growth of TiC is prohibited by the cladding of iron matrix and the TiC grains become graininess eutectic TiC, the structure and pattern of eutectic TiC_is more close to ideal octahedral shape of face-centered cubic TiC. The growth of in-situ TiC is specific small-plain growth. The exposure plain of TiC grains is the close packing [111] plain which grows slowly. The interface between in-situ TiC carbides and the matrix remains clean and free from deleterious phase. Thus, the carbide-matrix has a strong interface bond.
Cladding parameters affected the microstructure and properties of the coatings obviously. By selecting proper cladding parameters, such as thickness of the pre-coated coating with 1.2mm, welding current with 150A, cladding speed with 55-60/min, and tri-layers cladding, TiC reinforced coatings, which possess well appearance, high interface strength with the substrate and superior microstructure and property can be obtained. Multilayer cladding method was employed to reduce the dilution effect of substrate metal on the Ti and C elements, thus increasing the amount of the reinforcements in the cladding. For multilayer cladding, it is also found that the particle distribution can be characterized as combination of primary TiC dendrites and eutectic particles. In addition, as FeTi alloy could combine with carbon to form lots of TiC carbides and decrease the carbon content in matrix, which leads to change the microstructure to low carbon martensite. It is favourable for improving resistance for crack and wear resistance of the coatings. Experimental results showed that cladded coating with high hardness and good wear resistance was obtained. At same time, the problems of poor appearance and cracking were also avoided.
The present study shows that the ratio of FeTi and graphite influences directly not only on the formation of carbides but also matrix microstructure and hardness. Optimization of the composition and content of the raw alloy powder can influence the microstructure of the coating matrix and the amount, size and distribution of the TiC reinforcements. While the ratio of Ti:C is 1:1.2, the detrimental phase of Fe_2Ti can be effectively decreased, and the microstructure of the matrix is composed of low carbon martensite and residual austenite. Moreover, with increasing of graphite, the amount of in-situ TiC increased, and the primary dendrites of TiC tended to transform from fine dendrites to coarse dendrites, which improve the wear resistance of the coating.
With proper addition of La_2O_3, the nucleus of in-situ TiC was increased and the reinforcement phase of TiC transformed from coarse dendrites to more fine dendrites or diffusive particles. Nevertheless, since the La_2O_3 acted as the heterogeneous nucleus of TiC, the nuclearation and growing mechanism of TiC were changed and the saturation of carbon in TiC was decreased. These brought detrimental effect to the mechanic properties of the TiC crystal, which includes decrease of the hardness of TiC. Consequently, the reinforcing effect was depressed, and the wear resistance of the cladded coating with addition of rear-earth was decreased. When ferrovanadium was added, the TiC/VC grain was formed to produce synergetic reinforcing effect. On the other hand, the grains the coating were thinning and the strength of the substrate were increased.
Wear test of the substrate and cladded coating showed that under the same load and wear sliding" distance, the wear volume loss of the in-situ TiC reinforced coating produced using TIG was only one twentieth of the substrate, or even less. Compared with the substrate, the average value of the wear coefficient of the clad coating was lowered 0.05-0.1. TiC grains exposed in the surface coating contact with the grinding wheel dominantly in wearing. As a result, higher drag force is needed to overcome encumbrance and embedment resulting from the reinforced TiC particles and wear loss can be reduced enormously with the same load.
According to the results of dry wear test, main abrasive mechanism of the coating is pull-out of the diminished reinforcements and micro-plough of the substrate. In grinding crack, there are a lot of depressions owing to pull-out of the diminished TiC, and short and shallow grooves developed in the substrate. The grinding cracks begin at the pull-out point of diminished TiC and stop at next resistant TiC grain. According to the examination with different layers, three-layer coatings have the best wear resistant properties. The volume fraction of the reinforcements in the coating is enhanced by multi-layer cladding, which result in large TiC grains and embedded on the substrate in the form of accumulated petaliform. It combines with the substrate and bonds tightly. Therefore, the TiC grains can not be pull out easily in wearing and reveals good wear resistant properties.
预涂合金粉末组分是钨极氩弧原位合成TiC铁基熔敷层的关键。试验表明，纯钛粉+石墨组分在熔敷过程中容易氧化生成TiO_2，致使熔渣的熔点升高，钨极氩弧熔敷时工艺性较差；加入铁基自熔性合金粉末的组分(G314+Ti+C)能够获得较多的原位合成TiC增强相，熔敷工艺性能优良，具有TiC+M_(23)C_6碳化物复合增强的熔敷层，但其抗裂性能下降；钛铁+石墨组分由于铁．钛低熔点共晶的存在，有利于TiC增强相的原位合成，提高了熔敷层中TiC的合成数量，获得了以聚集树枝状分布伴以较少数量弥散分布的TiC分布特征，增强效果明显。且该粉末组分工艺性好，价格低廉，能够获得与母材结合良好、抗磨损性能和抗裂性能俱佳的铁基熔敷层，是钨极氩弧原位合成TiC增强铁基熔敷层的理想组分。
钨极氩弧熔敷是在非平衡热力学条件下进行的，由于熔池中热传导及结晶潜热的综合作用，使熔池中不同区域形成温度梯度和成分过冷，初生TiC沿树枝状方向断续形核，熔池中Ti、C原子因浓度梯度而扩散至最近的TiC晶核，使得初生TiC以侧面生长方式长大，形成了呈树枝状排列的“长砖块”状TiC颗粒微观形貌。距离较近的TiC晶核在长大过程中粘连生长，形成了尺寸较大TiC颗粒。而在熔池凝固过程的共晶转变中，TiC的形核生长是扩散机制，先凝固Fe基体的包覆使TiC生长的各向异性被抑制，形成了不同形状的共晶TiC颗粒。原位合成的TiC颗粒呈典型的小面生长形态，其显露面为生长速度较慢的密排[111]晶面。TiC颗粒与基体金属的结合界面洁净，无反应物、附着物生成，与基体金属的结合强度高。
预涂层厚度、焊接电流、熔敷速度、熔敷层数等不同的熔敷参数影响着熔敷层的成形和耐磨性能。研究表明，当预涂层厚度为1.2mm，焊接电流150A，熔敷速度为55-60mm／min，熔敷层数为三层时，能够获得成形好、与基体结合强度高组织与性能优异的TiC增强铁基熔敷层。不同熔敷层数的对比试验表明，三层熔敷能有效降低组分中Ti、C元素的稀释率，提高了熔敷层中增强颗粒的数量及尺寸，初生TiC颗粒树枝状分布和共晶TiC颗粒弥散分布相结合，基体为低碳马氏体组织，有利于熔敷层硬度及抗磨损性能的提高，又能有效避免裂纹形成。
预涂粉末的组分及含量影响着熔敷层中原位合成TiC的数量、尺寸、分布特征和基体组织构成。当组分中Ti∶C摩尔数比为1∶1.2时，熔敷层中Fe_2Ti有害相消失，原位合成TiC颗粒的数量增多，尺寸增大，基体为低碳马氏体组织，能够获得硬度较高，抗磨损性能较好的铁基熔敷层；粉末组分中加入稀土La_2O_3，增加了原位合成TiC的异质形核核心，使得熔敷层中TiC颗粒由发达的树枝状分布变为细小的树枝状或者颗粒状弥散分布。另一方面稀土La_2O_3改变了TiC形核与长大方式，降低了TiC中的碳饱和度，对TiC晶体的力学性能带来不利影响，使TiC的强度和硬度降低，影响了其增强效果，使得熔敷层的硬度降低，也使得加入稀土后熔敷层的抗磨损性能有所下降；粉末组分中加入钒铁后，熔敷层中TiC-VC增强相数量增多，呈聚集树枝状和弥散颗粒状分布，形成了TiC-VC复合增强效果。TiC-VC晶粒的元素分布特征表明，TiC-VC晶粒中TiC、VC独立存在并生长，形成了TiC-VC的共生晶粒。另外V元素的加入细化了基体组织晶粒，提高了基体金属和熔敷层的硬度。
通过对母材、熔敷层的对比磨损试验表明，在相同磨损条件下，钨极氩弧原位合成TiC增强铁基熔敷层的磨损体积为母材金属的1／20～1／23，具有优异的抗磨损性能。熔敷层磨损过程中，参与摩擦更多的是暴露于摩擦面的TiC颗粒，由于其阻碍和钉扎作用，摩擦过程需要消耗更多的摩擦功，磨损量降低。熔敷层基体金属的磨损主要是显微切削与粘着损失，TiC增强相则是经摩擦副较长距离、多次重复摩擦后磨损变小，直至最终剥离脱落。磨痕内有浅而小的凹坑及短而浅的犁沟，犁沟始于磨损变小的TiC颗粒脱落位置而止于下一个耐磨TiC前。不同层数熔敷层对比试验表明，尺寸较大的呈聚集树枝状分布的TiC颗粒与基体金属相互绞接在一起，结合更紧密，阻磨作用更强，三层熔敷层能够获得最优的抗磨损性能。
Properties of endurance impact, corrosion resistance and wear resistance are the basic requirements for components which are employed in commercial application such as mine exploration, heavy metallurgy and gasoline drilling. The method of development high-hardness and anti-resistant coating on the surface of components is a valuable way to repair it and prolong their service life. In this research, the Fe-based coating reinforced by in-situ TiC was fabricated by tungsten-inert gas (TIG) melting process employing a proper amount of alloy powder prepared on the surface of ordinary carbon steel substrate, and the microstructure, wear properties of the coatings and the growth mechanism of TiC carbides were analyzed systematically. At same time, the factors and rules influencing microstructure and properties were investigated.
It is found that the powders constituents are the key factor to synthesize in-situ TiC reinforced coatings by using TIG welding process. Because of the lower energy-flux density of TIG compared to laser and plasma, it is necessary to select powder elements with lower melting point which can quickly form molten pool. And then, metallurgical reaction occurs between titanium and carbon and synthesizes well-shaped overlap with high effective mass of TiC. The reaction equation is as followed: Ti + C→TiC. According to this principle, the powders composed of ferrotitanium and graphite (FeTi+C ) has excellent processing properties, which can produce a good bonding, excellent mechanical and wear resistant properties of the coating. The in-situ TiC in the coating distribute in dendritic mode majority, with small TiC grains in diffusion minority. Although iron-based self-fluxing alloy powder (G314) has a lower melting point and well manufacturability, complex carbide M_(23)C_6 emerges besides the in-situ TiC reinforced phase in the coating, which increases the crack sensitivity of the coatings. In addition, TiC carbides can also be formed via pure Ti element and graphite, however, the active chemical property of pure titanium, it can react with oxygen easily and form TiO_2, which result in the increasing of the components melting point and poor shaping.
Under the nonequilibrium condition of TIG fabrication, primary TiC grains in the Fe-based coating reveal dendrite crystal in majority and eutectic form in minority. Because of the directionality of thermal conduction and heat emission in the course of the fabrication of the TiC, component overcooling emerges in the growth front of TiC grains. This results in definite orientation of primary TiC. The primary TiC grows and turns to dendrite distribution. Nevertheless, in the course of eutectic transformation during the solidification of molten pool, the mechanism of TiC nucleation and growth is diffusion. The anisotropic growth of TiC is prohibited by the cladding of iron matrix and the TiC grains become graininess eutectic TiC, the structure and pattern of eutectic TiC_is more close to ideal octahedral shape of face-centered cubic TiC. The growth of in-situ TiC is specific small-plain growth. The exposure plain of TiC grains is the close packing [111] plain which grows slowly. The interface between in-situ TiC carbides and the matrix remains clean and free from deleterious phase. Thus, the carbide-matrix has a strong interface bond.
Cladding parameters affected the microstructure and properties of the coatings obviously. By selecting proper cladding parameters, such as thickness of the pre-coated coating with 1.2mm, welding current with 150A, cladding speed with 55-60/min, and tri-layers cladding, TiC reinforced coatings, which possess well appearance, high interface strength with the substrate and superior microstructure and property can be obtained. Multilayer cladding method was employed to reduce the dilution effect of substrate metal on the Ti and C elements, thus increasing the amount of the reinforcements in the cladding. For multilayer cladding, it is also found that the particle distribution can be characterized as combination of primary TiC dendrites and eutectic particles. In addition, as FeTi alloy could combine with carbon to form lots of TiC carbides and decrease the carbon content in matrix, which leads to change the microstructure to low carbon martensite. It is favourable for improving resistance for crack and wear resistance of the coatings. Experimental results showed that cladded coating with high hardness and good wear resistance was obtained. At same time, the problems of poor appearance and cracking were also avoided.
The present study shows that the ratio of FeTi and graphite influences directly not only on the formation of carbides but also matrix microstructure and hardness. Optimization of the composition and content of the raw alloy powder can influence the microstructure of the coating matrix and the amount, size and distribution of the TiC reinforcements. While the ratio of Ti:C is 1:1.2, the detrimental phase of Fe_2Ti can be effectively decreased, and the microstructure of the matrix is composed of low carbon martensite and residual austenite. Moreover, with increasing of graphite, the amount of in-situ TiC increased, and the primary dendrites of TiC tended to transform from fine dendrites to coarse dendrites, which improve the wear resistance of the coating.
With proper addition of La_2O_3, the nucleus of in-situ TiC was increased and the reinforcement phase of TiC transformed from coarse dendrites to more fine dendrites or diffusive particles. Nevertheless, since the La_2O_3 acted as the heterogeneous nucleus of TiC, the nuclearation and growing mechanism of TiC were changed and the saturation of carbon in TiC was decreased. These brought detrimental effect to the mechanic properties of the TiC crystal, which includes decrease of the hardness of TiC. Consequently, the reinforcing effect was depressed, and the wear resistance of the cladded coating with addition of rear-earth was decreased. When ferrovanadium was added, the TiC/VC grain was formed to produce synergetic reinforcing effect. On the other hand, the grains the coating were thinning and the strength of the substrate were increased.
Wear test of the substrate and cladded coating showed that under the same load and wear sliding" distance, the wear volume loss of the in-situ TiC reinforced coating produced using TIG was only one twentieth of the substrate, or even less. Compared with the substrate, the average value of the wear coefficient of the clad coating was lowered 0.05-0.1. TiC grains exposed in the surface coating contact with the grinding wheel dominantly in wearing. As a result, higher drag force is needed to overcome encumbrance and embedment resulting from the reinforced TiC particles and wear loss can be reduced enormously with the same load.
According to the results of dry wear test, main abrasive mechanism of the coating is pull-out of the diminished reinforcements and micro-plough of the substrate. In grinding crack, there are a lot of depressions owing to pull-out of the diminished TiC, and short and shallow grooves developed in the substrate. The grinding cracks begin at the pull-out point of diminished TiC and stop at next resistant TiC grain. According to the examination with different layers, three-layer coatings have the best wear resistant properties. The volume fraction of the reinforcements in the coating is enhanced by multi-layer cladding, which result in large TiC grains and embedded on the substrate in the form of accumulated petaliform. It combines with the substrate and bonds tightly. Therefore, the TiC grains can not be pull out easily in wearing and reveals good wear resistant properties.
引文
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