含钛镍基合金及电弧离子镀涂层的高温氧化和热腐蚀行为
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摘要
为满足制备适用于海洋气候条件下使用的舰船燃气轮机中热端部件的工作需要,研制一种含钛镍基合金。由于热端部件镍基合金在工作时受高温氧化和热腐蚀双重侵害,故本文采用电弧离子镀技术在镍基合金表面制备了Ni28Cr11A10.5Y和Ni19Co27Cr11A10.5Y两种涂层,以提高镍基合金的抗氧化和抗热腐蚀性能。据此,本文通过对镍基合金及NiCrAlY涂层合金进行不同条件的高温氧化和热腐蚀试验,研究了合金及涂层合金的高温氧化和热腐蚀行为,并进行了高温氧化和热腐蚀机理分析。
结果表明,镍基合金在850℃、900℃、950℃和1000℃初期氧化动力学曲线增重较快合金呈现氧化,随氧化时间延长氧化增重趋于平缓的特征；在高温氧化期间,合金发生外氧化和内氧化,且合金表面的氧化物膜明显分为外层氧化物和内层氧化物,外层氧化物主要由CrO3、A12O3、TiO2和NiCr2O4复合尖晶石相组成,内层氧化物仅为A12O3;内氧化物层的深度仅与温度有关,随温度升高内氧化层的深度增加；镍基合金在高温氧化期间,合金中的Ti元素加速了合金的外氧化和内氧化。
采用涂盐在多晶合金表面涂覆3-4mg/cm275%Na2SO4+25%K2SO4混合硫酸盐盐膜后,分别在850℃和950℃进行恒温热腐蚀试验。结果表明：盐膜加剧镍基合金的腐蚀,热腐蚀期间,合金发生了氧化、硫化现象,且在合金内部形成了内氧化物区域和内硫化物区域,腐蚀层的厚度随温度提高而增厚,内硫化层随温度提高而加深；腐蚀后表面形成三层腐蚀产物,外层氧化物由Al2O3(?)NiCr2O4组成,中间层为A12O3内氧化物,内层为CrS和Ti2S硫化物层。
采用涂盐在多晶合金表面涂覆3-4mg/cm250%Na2SO4+50%NaCl混合硫酸盐盐膜后,分别在700℃和800℃进行恒温热腐蚀试验。热腐蚀期间,合金发生了氧化、硫化现象,且在合金内部形成了内氧化物区域和内硫化物区域,腐蚀层的厚度随温度提高而增厚,内硫化层随温度提高而加深；腐蚀期间形成的腐蚀产物层可分为三层,外氧化层以A12O3、Cr2O3和NiCr2O4(?)为主,中间层为A12O3相,内层为CrS和Ti2S硫化物层;由于NaCl的存在加速了合金的腐蚀过程；随腐蚀温度提高,合金表面的腐蚀层厚度,形成的A1203内氧化层厚度,及内硫化层的深度增加。
对电弧离子镀Ni28Cr11A10.5Y涂层表面涂覆3-4mg/cm275%Na2SO4+25%K2SO4混合硫酸盐盐膜后,在950℃进行恒温热腐蚀试验。结果表明,腐蚀120h后,涂层发生了腐蚀现象,合金基体无明显的腐蚀和氧化现象发生,离子镀涂层中活性元素Y和A1203氧化膜的共同作用,可阻碍合金的内氧化和内硫化,是使涂层具有良好抗熔融硫酸盐热腐蚀的主要原因。腐蚀期间涂层发生热腐蚀和高温氧化行为,腐蚀初期涂层表面生成了A1203；腐蚀期间涂层表面A12O3发生碱性溶解反应,导致A1203溶解区域生成Cr2O3；腐蚀120h后,涂层表面生成的硫化物Y20S2,延缓了S对涂层的腐蚀。
对电弧离子镀Ni28Cr11A10.5Y涂层和Ni19Co27Cr11A10.5Y涂层,在900℃和1000℃高温氧化行为的研究表明,氧化初期,涂层试样的氧化动力学曲线增重幅度较小,而后趋于平缓,在900℃和1000℃氧化期间,两种涂层氧化动力学曲线近似服从抛物线规律；高温氧化期间,涂层合金外表面仅发生元素A1的氧化,且在氧化过程中发生0-A1203向a-A1203的相转变；在900℃和1000℃氧化300h内Ni28Cr11A10.5Y涂层的抗氧化性能优于Ni19Co27Cr11lA10.5Y涂层。
A kind of Ni-base superalloy has been studied to meet the requirement of jet-engine turbine vane served in the sea climate. Due to high-temperature oxidation and hot corrosion of turbine vane, both Ni28Crl1A10.5Y coating and Ni19Co27Cr11A10.5Y were prepared respectively by arc ion plating technique to improve the oxidation and corrosion resistance of Ni-base superalloy. Therefore, the high-temperature oxidation and hot corrosion behavior and mechamism of Ni-base superalloy, NiCrAlY coated Ni-base superalloy, were studied with a series of high-temperature and corrosion experiments under different conditions.
The results showed the mass gain per unit surface area was faster in the early stage, and then tended to be slower and steady based on oxidation dynamics curves of Ni-base superalloy at850℃,900℃,950℃and1000℃. The internal and external oxidation of Ni-base superalloy took place during high-temperature oxidation and obviously the oxide layers were composed of outside layer, which consisted of Cr2O3, A12O3, TiO2and NiCr2O4, and inside layer, which consisted only of Al2O3. The depth of inside oxide layer related only to temperature, deepening with the increase of temperature. The Ti element of Ni-base superalloy accelerated the internal and external oxidation during high-temperature oxidation.
The Ni-base polycrystal superalloy was coated with3-4mg (Na2SO4+K2SO425wt.%salt mixture)/cm2and oxidized at850℃and950℃respectively. The results showed the salt mixture accelerated the corrosion due to oxidation and sulfuration during hot corrosion and the internal oxidation and sulfuration zones were formed and the corrosion and internal sulfuration layers deepened with the increase of temperature. The three layers of corrosion were formed and the outer was Al2O3and NiCr2O4, the intermediate was Al2O3, the inside was CrS and Ti2S.
The Ni-base polycrystal superalloy was coated with3-4mg (Na2SO4+NaCl50wt.%salt mixture)/cm2and oxidized at700℃and800℃respectively. The oxidation and sulfuration took place during hot corrosion and the internal oxidmation and sulfuration zones were formed and the corrosion and internal sulfuration layers deepened with the increase of temperature. The corrosion products can be divided into three layers and the outer was AI2O3, Cr2O3and NiCr2O4the intermediate was Al2O3, the inside was CrS and Ti2S. The NaCl accelerated the corrosion process and the corrosion, internal oxidation and internal sulfuration layers deepened as the increase of temperature.
The arc ion plated Ni28Crl1A10.5Y coating was coated with3-4mg (Na2SO4+K2SO425wt.%salt mixture)/cm2and oxidized at950℃. The results showed the corroded coating prevents the Ni-base superalloy substrate from obvious corroding and oxidating after120h mainly due to active element Y and Al2O3synergy effect which hindered the internal oxidation and sulfuration of superalloy. An Al2O3scale was formed on the coating surface in the early stage, and then the alkaline dissolution reaction of Al2O3took place during hot corrosion to form Cr2O3. The Y2OS2formed on the coating surface to delay the corrosion of S element.
The results showed that the mass gain per unit surface area of both arc ion plated Ni28Crl1A10.5Y coating and Nil9Co27Crl1A10.5Y coating was faster in the early stage, and then tended to be much slower and steady based on oxidation dynamics curves, which approximately obeyed parabola law, at900℃and1000℃. The only Al element oxidation took place on the coating surface and the0-Al2O3to a-Al2O3transformation occurred during high-temperature oxidation. The oxidation resistance of Ni28Cr11A10.5Y coating was superior to that of Ni19Co27Crl1A10.5Y coating at900℃and1000℃.
结果表明,镍基合金在850℃、900℃、950℃和1000℃初期氧化动力学曲线增重较快合金呈现氧化,随氧化时间延长氧化增重趋于平缓的特征；在高温氧化期间,合金发生外氧化和内氧化,且合金表面的氧化物膜明显分为外层氧化物和内层氧化物,外层氧化物主要由CrO3、A12O3、TiO2和NiCr2O4复合尖晶石相组成,内层氧化物仅为A12O3;内氧化物层的深度仅与温度有关,随温度升高内氧化层的深度增加；镍基合金在高温氧化期间,合金中的Ti元素加速了合金的外氧化和内氧化。
采用涂盐在多晶合金表面涂覆3-4mg/cm275%Na2SO4+25%K2SO4混合硫酸盐盐膜后,分别在850℃和950℃进行恒温热腐蚀试验。结果表明：盐膜加剧镍基合金的腐蚀,热腐蚀期间,合金发生了氧化、硫化现象,且在合金内部形成了内氧化物区域和内硫化物区域,腐蚀层的厚度随温度提高而增厚,内硫化层随温度提高而加深；腐蚀后表面形成三层腐蚀产物,外层氧化物由Al2O3(?)NiCr2O4组成,中间层为A12O3内氧化物,内层为CrS和Ti2S硫化物层。
采用涂盐在多晶合金表面涂覆3-4mg/cm250%Na2SO4+50%NaCl混合硫酸盐盐膜后,分别在700℃和800℃进行恒温热腐蚀试验。热腐蚀期间,合金发生了氧化、硫化现象,且在合金内部形成了内氧化物区域和内硫化物区域,腐蚀层的厚度随温度提高而增厚,内硫化层随温度提高而加深；腐蚀期间形成的腐蚀产物层可分为三层,外氧化层以A12O3、Cr2O3和NiCr2O4(?)为主,中间层为A12O3相,内层为CrS和Ti2S硫化物层;由于NaCl的存在加速了合金的腐蚀过程；随腐蚀温度提高,合金表面的腐蚀层厚度,形成的A1203内氧化层厚度,及内硫化层的深度增加。
对电弧离子镀Ni28Cr11A10.5Y涂层表面涂覆3-4mg/cm275%Na2SO4+25%K2SO4混合硫酸盐盐膜后,在950℃进行恒温热腐蚀试验。结果表明,腐蚀120h后,涂层发生了腐蚀现象,合金基体无明显的腐蚀和氧化现象发生,离子镀涂层中活性元素Y和A1203氧化膜的共同作用,可阻碍合金的内氧化和内硫化,是使涂层具有良好抗熔融硫酸盐热腐蚀的主要原因。腐蚀期间涂层发生热腐蚀和高温氧化行为,腐蚀初期涂层表面生成了A1203；腐蚀期间涂层表面A12O3发生碱性溶解反应,导致A1203溶解区域生成Cr2O3；腐蚀120h后,涂层表面生成的硫化物Y20S2,延缓了S对涂层的腐蚀。
对电弧离子镀Ni28Cr11A10.5Y涂层和Ni19Co27Cr11A10.5Y涂层,在900℃和1000℃高温氧化行为的研究表明,氧化初期,涂层试样的氧化动力学曲线增重幅度较小,而后趋于平缓,在900℃和1000℃氧化期间,两种涂层氧化动力学曲线近似服从抛物线规律；高温氧化期间,涂层合金外表面仅发生元素A1的氧化,且在氧化过程中发生0-A1203向a-A1203的相转变；在900℃和1000℃氧化300h内Ni28Cr11A10.5Y涂层的抗氧化性能优于Ni19Co27Cr11lA10.5Y涂层。
A kind of Ni-base superalloy has been studied to meet the requirement of jet-engine turbine vane served in the sea climate. Due to high-temperature oxidation and hot corrosion of turbine vane, both Ni28Crl1A10.5Y coating and Ni19Co27Cr11A10.5Y were prepared respectively by arc ion plating technique to improve the oxidation and corrosion resistance of Ni-base superalloy. Therefore, the high-temperature oxidation and hot corrosion behavior and mechamism of Ni-base superalloy, NiCrAlY coated Ni-base superalloy, were studied with a series of high-temperature and corrosion experiments under different conditions.
The results showed the mass gain per unit surface area was faster in the early stage, and then tended to be slower and steady based on oxidation dynamics curves of Ni-base superalloy at850℃,900℃,950℃and1000℃. The internal and external oxidation of Ni-base superalloy took place during high-temperature oxidation and obviously the oxide layers were composed of outside layer, which consisted of Cr2O3, A12O3, TiO2and NiCr2O4, and inside layer, which consisted only of Al2O3. The depth of inside oxide layer related only to temperature, deepening with the increase of temperature. The Ti element of Ni-base superalloy accelerated the internal and external oxidation during high-temperature oxidation.
The Ni-base polycrystal superalloy was coated with3-4mg (Na2SO4+K2SO425wt.%salt mixture)/cm2and oxidized at850℃and950℃respectively. The results showed the salt mixture accelerated the corrosion due to oxidation and sulfuration during hot corrosion and the internal oxidation and sulfuration zones were formed and the corrosion and internal sulfuration layers deepened with the increase of temperature. The three layers of corrosion were formed and the outer was Al2O3and NiCr2O4, the intermediate was Al2O3, the inside was CrS and Ti2S.
The Ni-base polycrystal superalloy was coated with3-4mg (Na2SO4+NaCl50wt.%salt mixture)/cm2and oxidized at700℃and800℃respectively. The oxidation and sulfuration took place during hot corrosion and the internal oxidmation and sulfuration zones were formed and the corrosion and internal sulfuration layers deepened with the increase of temperature. The corrosion products can be divided into three layers and the outer was AI2O3, Cr2O3and NiCr2O4the intermediate was Al2O3, the inside was CrS and Ti2S. The NaCl accelerated the corrosion process and the corrosion, internal oxidation and internal sulfuration layers deepened as the increase of temperature.
The arc ion plated Ni28Crl1A10.5Y coating was coated with3-4mg (Na2SO4+K2SO425wt.%salt mixture)/cm2and oxidized at950℃. The results showed the corroded coating prevents the Ni-base superalloy substrate from obvious corroding and oxidating after120h mainly due to active element Y and Al2O3synergy effect which hindered the internal oxidation and sulfuration of superalloy. An Al2O3scale was formed on the coating surface in the early stage, and then the alkaline dissolution reaction of Al2O3took place during hot corrosion to form Cr2O3. The Y2OS2formed on the coating surface to delay the corrosion of S element.
The results showed that the mass gain per unit surface area of both arc ion plated Ni28Crl1A10.5Y coating and Nil9Co27Crl1A10.5Y coating was faster in the early stage, and then tended to be much slower and steady based on oxidation dynamics curves, which approximately obeyed parabola law, at900℃and1000℃. The only Al element oxidation took place on the coating surface and the0-Al2O3to a-Al2O3transformation occurred during high-temperature oxidation. The oxidation resistance of Ni28Cr11A10.5Y coating was superior to that of Ni19Co27Crl1A10.5Y coating at900℃and1000℃.
引文
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