热处理和合金元素对MCrAlY（Re）粘结层材料高温氧化行为的影响
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摘要
本论文以γ/β复相MCrAlY(Re)合金为研究对象，以提高合金的抗氧化性能为主要研究内容，系统研究了该系合金的组织特征、高温氧化行为及氧化机理并实现了对服役寿命的预测。
为了阐述热处理和合金元素对MCrAlY(Re)系列γ/β复相合金高温氧化行为的影响，本文主要借助背散射电子显微术及能谱分析技术进行研究。研究结果表明，热处理促进了富铝相的均匀化分布，均匀分布的富铝相有利于合金表面迅速形成致密化的α-Al_2O_3氧化膜，降低了氧化速率，提高了合金的抗氧化性能。
为了阐明合金元素在高温氧化时的作用机理，本文系统研究了合金元素在合金中的分配及析出、氧化动力学、氧化产物的组成、物相转变和氧化膜/合金界面的元素分布。与单一地添加Al、Re相比，Al和Re的联合添加能够增加β相含量，在氧化过程中强化了α-(Cr,Re)相的界面析出行为，降低了氧化速率。添加3~5%wt.%Pt能够形成富Pt的β相。同原始合金相比，Pt改性的合金在高温氧化时具有较快的θ-→α-Al_2O_3相转变、较低的氧化速率和β相消耗速率，能够抑制内氧化及尖晶石氧化物的生成。微量的Dy对合金的组织无明显的影响。在氧化过程中，Dy对合金的作用效果与温度及Re的存在与否有关。对于MCrAlY合金，添加Dy能够细化氧化产物的晶粒、促进过渡相转变、显著降低了氧化速率。1100℃循环氧化时，Dy的添加有助于合金形成单一且致密的α-Al_2O_3氧化膜，抑制了MCrAlY合金表面氧化膜的开裂、剥落及内氮化。Dy对含Re合金的氧化产物的晶粒细化的作用不明显，且阻碍了过渡相的转变。在800℃氧化时，Dy对含Re合金的氧化性能无明显作用。但在较高温度下，Dy能够显著降低该合金的氧化速率，抑制尖晶石氧化物的生成，改善了合金的抗氧化性能。
基于氧化过程中富铝β相的消耗机制建立模型并预测了合金的服役寿命。预测结果表明，添加微量Dy改进的合金的服役寿命两倍于原始合金。
The paper works at γ/β duplex-phase MCrAlY(Re) alloys, and its main part isthe improvement of the high-temperature anti-oxidation properties of these alloys.The present work studies the microstructural features, the oxidation behaviors andmechanisms of the tested alloys, and subsequently predicted the in-service lifetime ofthose alloys.
With the help of back-scattered electron microscopy and energy-dispersiveanalysis, the present work is to study the influences of heat-treatment and alloyingelements on the high-temperature oxidation behaviors of γ/β duplex-phaseMCrAlY(Re) alloys. Heat-treatment homogenizes the distribution of Al-rich phase,which is beneficial to prompt the formation of the α-Al_2O_3protective layer, lower theoxidation rate and improve the anti-oxidation properties of alloys.
In order to clarify the influence mechanisms of alloying elements on the testedalloys during the oxidation process, the paper conducted systematic studies on thepartition and precipition of alloying elements, the oxidation kinetics, the compostionand the phase transformation of oxides, and the element-distribution characteristics atthe scale/alloy interface. Compared with the individual addition of Al or Re, thecombined addition of Al and Re could increase the amount of β-phase; strengthen theprecipitation behaviors of α-(Cr,Re) underneath the scale/alloy interface and loweroxidation rate. Additon of3~5wt.%Pt could form a Pt-rich β-phase. By contrast withthe original alloys, the Pt-modified alloys showed the accelerated phasetransformation, lowered oxidation rate and consumption rate of β-phase. Pt couldsuppress the formation of the internal oxidation and spinels. Alloys with or withoutadding small amount of Dy showed the parellel microstructural features. The effectsof Dy on the tested alloys were sensitive to the temperature and the existence of Re.For MCrAlY alloy, addition of Dy could bring the accelerated phase transformation,the refined oxide grains and the significantly lowered oxidation rate. Under cyclicoxidation at1100℃, Dy addition formed a sole and protective α-Al_2O_3scale, which elminated the cracks and spallations of the oxide scale and internal nitrides. ForRe-containing alloy, Dy had not obvious effects on the refinement of the oxides andinhibited the phase transformation. At800℃, Dy had no influence on theanti-oxidation properties. However, Dy could greatly lower the oxidation rate;suppress the formation of spinels and improve the anti-oxidation resistance at highertemperature.
Based on the mechanisms of the consumption of β-phase, a model was proposedto predict the in-service lifetime of the tested alloys. The prediction results revealedthe doubled lifetime of the Dy-modified alloys compared with the original alloys.
为了阐述热处理和合金元素对MCrAlY(Re)系列γ/β复相合金高温氧化行为的影响，本文主要借助背散射电子显微术及能谱分析技术进行研究。研究结果表明，热处理促进了富铝相的均匀化分布，均匀分布的富铝相有利于合金表面迅速形成致密化的α-Al_2O_3氧化膜，降低了氧化速率，提高了合金的抗氧化性能。
为了阐明合金元素在高温氧化时的作用机理，本文系统研究了合金元素在合金中的分配及析出、氧化动力学、氧化产物的组成、物相转变和氧化膜/合金界面的元素分布。与单一地添加Al、Re相比，Al和Re的联合添加能够增加β相含量，在氧化过程中强化了α-(Cr,Re)相的界面析出行为，降低了氧化速率。添加3~5%wt.%Pt能够形成富Pt的β相。同原始合金相比，Pt改性的合金在高温氧化时具有较快的θ-→α-Al_2O_3相转变、较低的氧化速率和β相消耗速率，能够抑制内氧化及尖晶石氧化物的生成。微量的Dy对合金的组织无明显的影响。在氧化过程中，Dy对合金的作用效果与温度及Re的存在与否有关。对于MCrAlY合金，添加Dy能够细化氧化产物的晶粒、促进过渡相转变、显著降低了氧化速率。1100℃循环氧化时，Dy的添加有助于合金形成单一且致密的α-Al_2O_3氧化膜，抑制了MCrAlY合金表面氧化膜的开裂、剥落及内氮化。Dy对含Re合金的氧化产物的晶粒细化的作用不明显，且阻碍了过渡相的转变。在800℃氧化时，Dy对含Re合金的氧化性能无明显作用。但在较高温度下，Dy能够显著降低该合金的氧化速率，抑制尖晶石氧化物的生成，改善了合金的抗氧化性能。
基于氧化过程中富铝β相的消耗机制建立模型并预测了合金的服役寿命。预测结果表明，添加微量Dy改进的合金的服役寿命两倍于原始合金。
The paper works at γ/β duplex-phase MCrAlY(Re) alloys, and its main part isthe improvement of the high-temperature anti-oxidation properties of these alloys.The present work studies the microstructural features, the oxidation behaviors andmechanisms of the tested alloys, and subsequently predicted the in-service lifetime ofthose alloys.
With the help of back-scattered electron microscopy and energy-dispersiveanalysis, the present work is to study the influences of heat-treatment and alloyingelements on the high-temperature oxidation behaviors of γ/β duplex-phaseMCrAlY(Re) alloys. Heat-treatment homogenizes the distribution of Al-rich phase,which is beneficial to prompt the formation of the α-Al_2O_3protective layer, lower theoxidation rate and improve the anti-oxidation properties of alloys.
In order to clarify the influence mechanisms of alloying elements on the testedalloys during the oxidation process, the paper conducted systematic studies on thepartition and precipition of alloying elements, the oxidation kinetics, the compostionand the phase transformation of oxides, and the element-distribution characteristics atthe scale/alloy interface. Compared with the individual addition of Al or Re, thecombined addition of Al and Re could increase the amount of β-phase; strengthen theprecipitation behaviors of α-(Cr,Re) underneath the scale/alloy interface and loweroxidation rate. Additon of3~5wt.%Pt could form a Pt-rich β-phase. By contrast withthe original alloys, the Pt-modified alloys showed the accelerated phasetransformation, lowered oxidation rate and consumption rate of β-phase. Pt couldsuppress the formation of the internal oxidation and spinels. Alloys with or withoutadding small amount of Dy showed the parellel microstructural features. The effectsof Dy on the tested alloys were sensitive to the temperature and the existence of Re.For MCrAlY alloy, addition of Dy could bring the accelerated phase transformation,the refined oxide grains and the significantly lowered oxidation rate. Under cyclicoxidation at1100℃, Dy addition formed a sole and protective α-Al_2O_3scale, which elminated the cracks and spallations of the oxide scale and internal nitrides. ForRe-containing alloy, Dy had not obvious effects on the refinement of the oxides andinhibited the phase transformation. At800℃, Dy had no influence on theanti-oxidation properties. However, Dy could greatly lower the oxidation rate;suppress the formation of spinels and improve the anti-oxidation resistance at highertemperature.
Based on the mechanisms of the consumption of β-phase, a model was proposedto predict the in-service lifetime of the tested alloys. The prediction results revealedthe doubled lifetime of the Dy-modified alloys compared with the original alloys.
引文
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