镍基高温合金表面铬铝涂层的制备与抗高温腐蚀性能研究
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摘要
随着高温结构材料服役环境越来越苛刻,高温防护涂层正向高性能、复杂环境、多功能化方向发展。通过对在高温结构材料表面进行渗合金化处理,获得防护涂层是提高其抗高温腐蚀性能的有效方法。本文采用渗铬和渗铝相结合的工艺在镍基高温合金基体表面制备了铬铝合金涂层,并研究了其对基体的防护效果。
两步法制备的铬铝涂层的微观结构、厚度、抗剥蚀性与制备工艺参数相关。当渗铬温度为1080℃,保温时间9h,渗铬剂配比为：氯化铵质量百分含量为1%、铬粉质量百分含量为30%、氧化铝质量百分含量为69%；渗铝温度为750℃,保温时间15h,渗铝剂配比为：氯化铵质量百分含量为1.5%、铝粉质量百分含量为10%、氧化铝质量百分含量为88.5%；热处理温度为800℃保温15h时可以得到期望的内扩散型β-NiAl与y'-NiAl相,涂层组织均匀致密。
单一渗铝涂层、内扩散型铬铝涂层和单一渗铬涂层都可以提高K38G合金在800℃、950℃、1100℃下的抗氧化性能。由于铝化物涂层表面产物是生长速度较慢的氧化铝膜,所以单一渗铝涂层与内扩散铬铝涂层的抗氧化性能优于单一渗铬涂层。又由于单一渗铝涂层在氧化过程中发生了严重的元素互扩散现象导致表面生成了生长较快的氧化物相,所以单一渗铝涂层氧化性能不如内扩散型铬铝涂层。
单一渗铬涂层、内扩散型铬铝涂层都可以提高K38G合金在950℃下的抗热腐蚀性能。在以热腐蚀为主要破坏形式的环境中,铬元素可以迅速生成稳定的铬化物涂层,所以单一渗铬涂层、内扩散型铬铝涂层和K38G合金拥有比单一渗铝涂层更好的抗热腐蚀性能。由于在热腐蚀过程中内扩散型铬铝涂层外层富Al的氧化膜在熔盐中发生溶解而失去保护性,但因为涂层内层富Cr能迅速发生反应形成抗热腐蚀的Cr203膜同时抑制Al进一步发生碱性溶解,从而使内扩散型铬铝涂层拥有比K38G合金更优的抗热腐蚀性能。
考虑高温抗氧化性能和抗热腐蚀性能,内扩散型铬铝涂层具有最佳的综合抗高温腐蚀性能。
One of the most effective ways to improve the high temperature corrosion resistance of the high temperature structural materials is the application of surface coatings. The protective coatings are being improved towards high performance, complicated structure and multi-functions in order to meet requirements for materials used in aggressive environments. The Cr-Al coating is fabricated by two-step packing diffusion method on the surface of K38G alloy. The protective effects of coatings were studied.
The microstructure, thickness and anti-spalling property of the two-step fabricated Cr-Al coating are related to the fabrication parameters such as diffusion temperature, diffusion time and the content of the diffusion reagent.In the present study,the optimized fabrication steps are diffusion Cr at 1080℃for 9h using the diffusion reagent content:NH4Cl:1wt.%,Al2O3: 59wt.%,Cr:40wt.%;and then diffusion Al at 750℃for 9h using the diffusion reagent content: NH4Cl:1.5wt%, Al2O3:88.5wt%, Cr:10wt%.After heat treatment at 800℃for 15h,dense and homogenous inner diffusion Cr-Al coating consisted ofβ-NiAl and y'-NiAl can be fabricated.During the oxidation process, Al2O3 layer was formed on the surface of the Al coating and the inner diffusion Cr-Al coatings, which grows more slowly than that of Cr2O3 layer formed on the surface of the Cr coating.Therefore, the oxidation resistances of the Al coating and the inner diffusion Cr-Al coating are better than that of the Cr coating.Compared to the inner diffusion Cr-Al coating, the worse oxidation resistance of the Al coating can be attributed to the heavy interdiffusion between the Al coating and K38G alloy.
Cr coating,inner diffusion Cr-Al coating can be the hot corrosion resistance coatings of K38G alloy at 950℃.Because of the producing of Cr2O3 which is stable in the hot corrosion environment, the hot corrosion resistance of Cr coatings,inner diffusion Cr-Al coatings and K38G alloy are better than that of Al coatings.And the hot corrosion resistance of Cr coating is better than that of the inner diffusion Cr-Al whose hot corrosion resistance is better than that of K38G alloy.In the hot corrosion environment,the Cr element in the coating would form protective Cr2O3 scales even if the Al2O3 layer initially formed lost its protection.
In the present study, the inner diffusion Cr-Al coating performed the best high temperarure corrosion resistance.
两步法制备的铬铝涂层的微观结构、厚度、抗剥蚀性与制备工艺参数相关。当渗铬温度为1080℃,保温时间9h,渗铬剂配比为：氯化铵质量百分含量为1%、铬粉质量百分含量为30%、氧化铝质量百分含量为69%；渗铝温度为750℃,保温时间15h,渗铝剂配比为：氯化铵质量百分含量为1.5%、铝粉质量百分含量为10%、氧化铝质量百分含量为88.5%；热处理温度为800℃保温15h时可以得到期望的内扩散型β-NiAl与y'-NiAl相,涂层组织均匀致密。
单一渗铝涂层、内扩散型铬铝涂层和单一渗铬涂层都可以提高K38G合金在800℃、950℃、1100℃下的抗氧化性能。由于铝化物涂层表面产物是生长速度较慢的氧化铝膜,所以单一渗铝涂层与内扩散铬铝涂层的抗氧化性能优于单一渗铬涂层。又由于单一渗铝涂层在氧化过程中发生了严重的元素互扩散现象导致表面生成了生长较快的氧化物相,所以单一渗铝涂层氧化性能不如内扩散型铬铝涂层。
单一渗铬涂层、内扩散型铬铝涂层都可以提高K38G合金在950℃下的抗热腐蚀性能。在以热腐蚀为主要破坏形式的环境中,铬元素可以迅速生成稳定的铬化物涂层,所以单一渗铬涂层、内扩散型铬铝涂层和K38G合金拥有比单一渗铝涂层更好的抗热腐蚀性能。由于在热腐蚀过程中内扩散型铬铝涂层外层富Al的氧化膜在熔盐中发生溶解而失去保护性,但因为涂层内层富Cr能迅速发生反应形成抗热腐蚀的Cr203膜同时抑制Al进一步发生碱性溶解,从而使内扩散型铬铝涂层拥有比K38G合金更优的抗热腐蚀性能。
考虑高温抗氧化性能和抗热腐蚀性能,内扩散型铬铝涂层具有最佳的综合抗高温腐蚀性能。
One of the most effective ways to improve the high temperature corrosion resistance of the high temperature structural materials is the application of surface coatings. The protective coatings are being improved towards high performance, complicated structure and multi-functions in order to meet requirements for materials used in aggressive environments. The Cr-Al coating is fabricated by two-step packing diffusion method on the surface of K38G alloy. The protective effects of coatings were studied.
The microstructure, thickness and anti-spalling property of the two-step fabricated Cr-Al coating are related to the fabrication parameters such as diffusion temperature, diffusion time and the content of the diffusion reagent.In the present study,the optimized fabrication steps are diffusion Cr at 1080℃for 9h using the diffusion reagent content:NH4Cl:1wt.%,Al2O3: 59wt.%,Cr:40wt.%;and then diffusion Al at 750℃for 9h using the diffusion reagent content: NH4Cl:1.5wt%, Al2O3:88.5wt%, Cr:10wt%.After heat treatment at 800℃for 15h,dense and homogenous inner diffusion Cr-Al coating consisted ofβ-NiAl and y'-NiAl can be fabricated.During the oxidation process, Al2O3 layer was formed on the surface of the Al coating and the inner diffusion Cr-Al coatings, which grows more slowly than that of Cr2O3 layer formed on the surface of the Cr coating.Therefore, the oxidation resistances of the Al coating and the inner diffusion Cr-Al coating are better than that of the Cr coating.Compared to the inner diffusion Cr-Al coating, the worse oxidation resistance of the Al coating can be attributed to the heavy interdiffusion between the Al coating and K38G alloy.
Cr coating,inner diffusion Cr-Al coating can be the hot corrosion resistance coatings of K38G alloy at 950℃.Because of the producing of Cr2O3 which is stable in the hot corrosion environment, the hot corrosion resistance of Cr coatings,inner diffusion Cr-Al coatings and K38G alloy are better than that of Al coatings.And the hot corrosion resistance of Cr coating is better than that of the inner diffusion Cr-Al whose hot corrosion resistance is better than that of K38G alloy.In the hot corrosion environment,the Cr element in the coating would form protective Cr2O3 scales even if the Al2O3 layer initially formed lost its protection.
In the present study, the inner diffusion Cr-Al coating performed the best high temperarure corrosion resistance.
引文
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