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超超临界汽轮机叶片用高温合金Nimonic 80A成分优化、微结构及其高温强化机理研究
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摘要
超超临界火力发电技术具有效率高、温室气体排放低和运行可靠性高等优点,目前已成为国际上技术成熟、经济性好且已经实现商业化运行的发电技术。大容量、高参数(高温和高压)、高热效率的超超临界机组代表了未来火力发电技术的发展趋势,同时超超临界机组的发展也迫切需要和必将带动新材料的发展。镍基合金具有较好的组织稳定性,是高温合金中高温强度较高和应用最广的一类合金。Nimonic80A高温合金已经被使用了半个多世纪,是一种时效强化合金,且具有良好的抗蠕变性能和抗氧化性能,过去它主要用作比汽轮机叶片服役时间更短的航空发动机叶片材料。超超临界汽轮机叶片的技术要求非常严格,超超临界汽轮机叶片用Nimonic80A高温合金在750°C/310MPa持久寿命的工厂考核标准必须大于100h。因此,本文对超超临界汽轮机叶片用Nimonic80A高温合金的成分和热处理工艺等因素进行优化,最终形成一个可以用于规模生产的稳定的制造工艺并在超超临界机组批量使用。
     本文应用原子探针层析(APT)、高分辨透射电子显微镜(HRTEM)、扫描电子显微镜(SEM)、X射线衍射(XRD)和相图计算等技术研究了不同合金元素对Nimonic80A高温合金室温力学性能、750oC/310MPa持久性能、600°C/450MPa长时持久性能和750oC/240MPa蠕变性能的影响,优化出最佳合金成分,并在此基础上研究不同热处理制度的影响。主要结论如下:
     1)随着Al+Ti含量从2.8wt.%增加到4.5wt.%,Nimonic80A合金中γ′相体积分数增加,室温强度提高,当Al+Ti=4.05wt.%时持久寿命最长。随着Ti/Al比从0.14增加到4.0,室温强度显著提高,而持久寿命先升高后降低且当Ti/Al=1.22时持久寿命最长。当Ti/Al比较低时,在晶内析出的β-NiAl相容易引起晶内裂纹,从而导致高温下材料的断裂;当Ti/Al比较高时,在晶界析出的η-Ni_3Ti相容易引起沿晶开裂。因此,过低或者过高的Ti/Al比对高温持久寿命都不利,并且高Ti/Al比的合金其高温塑性也较差。随着Al含量从1.4wt.%增加到1.8wt.%,室温抗拉强度和屈服强度有少量增加,相应的延伸率和断面收缩率有少量减少,而持久寿命显著增加,同时改善高温塑性。Ti含量从1.8wt.%增加到2.7wt.%可以显著提高γ′相的体积分数,从而显著提高室温抗拉强度和屈服强度,而持久寿命先升高后降低,当Ti含量为2.25wt.%时持久寿命最长并且具有良好的高温塑性。当Ti含量过高时,析出相由γ′相变为γ′+η相。因此,当Al+Ti含量、Ti/Al比或者Ti含量过高时,块状的脆性Ni_3Ti相在晶界的析出易引起沿晶裂纹,对持久寿命不利,但是Ni_3Ti相的析出对室温力学性能影响不大。
     2)随着C含量从0.01wt.%增加到0.10wt.%,在晶界和晶内析出的Cr_(23)C_6碳化物数量增加,阻碍晶界运动,抑制晶粒长大,提高室温强度和持久寿命。当C含量为0.10wt.%时,在晶界析出的Cr_(23)C_6碳化物与γ基体存在一定的位向关系,有利于提高高温时的晶界强度。此外,C含量的增加可以提高γ′相与γ基体相的共格错配度。当C含量为0.10wt.%时,持久寿命最长并且具有较高的塑性。
     3)在Nimonic80A合金中加入1.5wt.%的Nb元素可以提高γ′相的析出温度和数量,显著改善室温力学性能、750°C/310MPa持久性能和750°C/240MPa蠕变性能。Nb取代γ′相中的Ti以及(Nb,Ti)C碳化物的析出降低γ′相中的Ti含量,同时Nb元素从γ基体相扩散到γ′相使得部分细小的γ′2相在高温时可以和较粗大的γ′1相共存。845°C时效后析出的δ-Ni_3Nb相与块状的(Nb,Ti)C碳化物在{100}晶面存在一定位向关系:(100)δ||(100)MC&[010]δ||[010]MC。(Nb,Ti)C碳化物在晶内或者晶界的析出可以分别抑制γ′相的长大和晶界的滑移。此外,晶界(Nb,Ti)C碳化物的析出可以抑制晶界孔洞的连接。
     4)研究了四种热处理制度T1(1070oC×8h, AC+700oC×16h, AC)、T_2(1070oC×8h,AC+980oC×4h,AC+700oC×16h,AC)、T(31070oC×8h,AC+845oC×24h, AC+700oC×16h, AC)和T4(1070oC×8h, AC+980oC×4h,AC+845oC×24h, AC+700oC×16h, AC)对Nimonic80A力学性能和显微组织的影响。研究表明:与T1热处理制度相比,T_2或者T3热处理制度均可以提高室温强度,并且T3热处理后的室温力学性能最佳,然而T4热处理制度对室温力学性能不利。T_2热处理后的持久寿命有少量降低,T3和T4热处理后,高温持久寿命明显下降。与T1热处理后的持久寿命相比,虽然T_2和T4热处理后持久寿命都降低了,但是这两种热处理制度都可以改善高温塑性。T1~T4热处理后及高温持久试验后,γ′相与γ基体相保持良好的共格位向关系,细小的γ′相呈球状,而当γ′相大于75nm时呈立方状。16~20nm的γ′相数量的增加可以提高持久寿命。晶界析出的棒状碳化物可以阻碍晶界滑移,提高持久寿命。粗大的γ′相有利于位错运动,改善高温塑性。多重体积分数和大小的γ′相析出可以使Nimonic80A合金获得较佳的持久寿命和塑性。
     5)非均匀晶粒结构的Nimonic80A合金600°C/450MPa高温长时持久寿命约4512h,异常晶粒长大结构的合金长时持久寿命增加到约6863h,均匀晶粒结构的合金长时持久寿命最长约10765h。在长时持久测试过程中,γ′相非常稳定并且始终与γ基体保持良好的共格位向关系。Cr_(23)C_6碳化物优先在晶界析出,然后在晶内析出。随着长时持久寿命的增加,在晶界析出的Cr_(23)C_6碳化物由片状向条状和球状转变,并且与γ基体呈现出一定位向关系。在晶界析出的片状Cr_(23)C_6碳化物易引起大小晶粒过渡区的沿晶开裂。同时,在晶界析出的块状TiC碳化物随长时持久寿命的增加有少量的长大,但是在晶内析出的细小TiC碳化物始终非常稳定。具有均匀晶粒结构的组织有利于提高长时持久寿命。
     综合上述大量实验研究结果,超超临界汽轮机叶片用Nimonic80A的成分控制可建议如下:C控制在0.06~0.08wt.%,Al控制在1.7~1.8wt.%,Ti控制在2.0~2.5wt.%,Ti/Al比控制在1.2~1.4,Cr控制在19~20wt.%,微合金元素B控制在80ppm左右,Mg控制在50ppm左右。此外,在较佳Nimonic80A合金成分基础上,加入1.5wt.%的Nb可以提高高温强度。
Due to the high efficiency, reduced environmental pollution and high reliability,ultra-supercritical coal-fired technology becomes the world leading andcommercialized power generation technology. The ultra-supercritical technology withhigh capacity, parameters and efficiency is the development trend of coal-fired powerplants. With the development of ultra-supercritical plants, it requires advanced hightemperature materials which can be used at higer temparture and stress. Nickel-basedsuperalloys show high strength and have wide applications at high temperature due tothe stable microstructure. Nimonic80A has been developed for more than half acentury and is a kind of precipitate strengthening alloy with excellent creep andoxidation resistance properties. Nimonic80A was mainly used as blade material inaero-engine which required shorter service time than that in steam turbine in the past.The technical requirements for ultra-supercritical steam turbine blade are very strictand the stress-rupture life of Nimonic80A at750°C/310MPa must be higher than100h in factory. So the chemical composition and heat treatment have been optimized inorder to form a stable manufacturing process for mass production in ultra-supercriticalsteam turbine.
     Atom probe tomography (APT), high resolution transmission electronmicroscopy (HRTEM), scanning electron microscopy (SEM), X-ray diffraction (XRD)and thermal-calculation were employed to study the effects of alloying elements onroom temperature mechanical properties, stress-rupture properties at750oC/310MPa,long-term stress-rupture properties at600°C/450MPa and creep properties at750oC/240MPa of Nimonic80A. The chemical compositions have been optimizedand the effects of heat treatments on mechanical properties have also beeninvestigated. The conclusions are shown as follows:
     1) The volume fraction of γ′phase increases with the increase of Al+Ti contentfrom2.8to4.5wt.%, which improves room temperature tensile strength. Thestress-rupture life is the longest when Al+Ti content is about4.05wt.%. Room temperature tensile strength increases significantly with the increase of Ti/Al ratiofrom0.14to4.0, but stress-rupture life first increases then decreases and the longeststress-rupture life appears when Ti/Al ratio is about1.22. The β-NiAl phase canprecipitate in the grain interior when Ti/Al ratio is low, which can easily lead to thecracking in the grain interior and finally the fracture of alloys at high temperature. Theη-Ni_3Ti phase can precipitate at grain boundary when Ti/Al ratio is high, which canlead to the grain boundary cracking. Hence, low or high Ti/Al ratio is harmful tostress-rupture life and the ductility at high temperature is also bad for the alloy withhigh Ti/Al ratio. Room temperature tensile strength increases slightly with theincrease of Al contents from1.4to1.8wt.%, while the corresponding elongation andreduction in area decrease slightly. Stress-rupture life increases significantly with theincrease of Al content, and the high temperature ductility is also improved. Theincrease of Ti content from1.8to2.7wt.%can increase the volume fraction of γ′phase, which improves room temperature tensile strength, however, stress-rupture lifefirst increases then decreases. The longest stress-rupture life appears with good hightemperature ductility when Ti content is about2.25wt.%. But the η-Ni_3Ti phase canprecipitate when Ti content is too high. The η-Ni_3Ti phase can precipitate at grainboundary when Al+Ti, Ti/Al ratio or Ti contents are too high, the brittle η-Ni_3Ti phasecan easily lead to grain boundary cracking, which reduces stress-rupture life but doesno harm to room temperature tensile properties.
     2) The content of Cr_(23)C_6carbide at grain boundary and in the grain interiorincreases with the increase of C content from0.01to0.10wt.%, which suppressesgrain boundary sliding and growth of grains, so room temperature tensile strength andstress-rupture life can be improved. The grain boundary Cr_(23)C_6carbide exhibits anorientation relationship with γ matrix when C content is about0.10wt.%, which isbeneficial to grain boundary strength at high temperature. What is more, the increaseof C content can also increase the lattice misfit of γ′/γ phases. The longeststress-rupture life appears with high ductility when C content is about0.10wt.%.
     3) Nb can increase the precipitate temperature and volume fraction of γ′phase inNimonic80A, which improves room temperature mechanical properties, stress-rupture properties at750°C/310MPa and creep properties at750°C/240MPa.The replacement of Ti by Nb and the precipitate of (Nb, Ti) C reduce Ti content in γ′phase. The diffusion of Nb element from γ to γ′phase makes the co-existance of fineγ′2phase with coarse γ′1phase at high temperature. The δ-Ni_3Nb phase precipitates inγ matrix with an orientation relationship with (Nb, Ti) C carbide on {100} atomicplanes at845°C:(100)δ||(100)MC&[010]δ||[010]MC. The precipitate of (Nb, Ti) Ccarbide at grain boundary or in the grain interior can respectively suppress grainboundary sliding and growth of γ′phase. At the same time, precipitate of (Nb, Ti) Ccarbide can also suppress the connection of grain boundary cavitation.
     4) Four heat treatments T1(1070oC×8h, AC+700oC×16h, AC), T_2(1070oC×8h, AC+980oC×4h, AC+700oC×16h, AC), T3(1070oC×8h, AC+845oC×24h, AC+700oC×16h, AC) and T4(1070oC×8h, AC+980oC×4h, AC+845oC×24h, AC+700oC×16h, AC) have been designed to study the mechanicalproperties and microstructures of Nimonic80A. The results show that heat treatmentT_2or T3can increase room temperature tensile strength and that room temperaturetensile strength is highest after heat treatment T3compared with that after heattreatment T1. However, room temperature tensile strength decreases after heattreatment T4. Stress-rupture life after heat treatment T_2has slightly decreased, andstress-rupture life decreases significantly after heat treatments T3and T4. Althoughstress-rupture life decreases after heat treatments T_2and T4compared with that afterheat treatment T1, heat treatments T_2and T4can significantly improve hightemperature ductility. The γ′phase exhibits a coherent orientation relationship with γphase after heat treatments and stress-rupture test. The fine γ′phase shows anapproximately spherical shape and the coarse γ′phase (>75nm) shows anapproximately cubic shape. The increased volume fraction of γ′phase with averagesize about16~20nm can increase stress-rupture life. The precipitate of blocky carbideat grain boundary can suppress grain boundary sliding and hence increasestress-rupture life. The coarse γ′phase facilites the movement of dislocations andimproves high temperature ductility. The precipitate of multi-modal size distributionsof γ′phases benefits stress-rupture life and ductility at high temperature.
     5) The long-term stress-rupture life at600°C/450MPa increases from4512h ofsample with non-homogeneous grain structure to6863h of sample with abnormalgrain structure and10765h of sample with homogeneous grain structure. The stable γ′phase exhibits a coherent orientation relationship with γ phase during long-termstress-rupture test. The Cr_(23)C_6carbide firstly precipitates at grain boundary thenprecipitates in the grain interior. With the prolonged stress-rupture life, plate likeCr_(23)C_6carbide transfers into strip like and approximately spherical ones, and Cr_(23)C_6carbide exhibits an orientation relationship with γ matrix. The plate Cr_(23)C_6carbidecan easily induce grain boundary cracking at the transitional area of large and smallgrain regions. The average size of TiC carbide at grain boundary grows up slightlywith the increase of long-term stress-rupture life. However, the TiC carbide in thegrain interior is very stable. The microstructure of homogeneous grain structure isbeneficial to long-term stress-rupture life of Nimonic80A.
     The above results indicate that the suggested optimum chemical compositions ofNimonic80A are: C0.06~0.08wt.%, Al1.7~1.8wt.%, Ti2.0~2.5wt.%, Ti/Al ratio1.2~1.4, Cr19~20wt.%, B80ppm, Mg50ppm. And the further addition of1.5wt.%Nb can also improve the high temperature mechanical properties.
引文
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