IMR OpenIR
Fe-Cr-Al/Cu-Zn-Al合金高温氧化中的第三元素效应(TEE)研究
其他题名Study of the Third-Element Effect in the High-Temperature Oxidation of Fe-Cr-Al and Cu-Zn-Al alloys
高锋
学位类型硕士
导师牛焱
2007-06-09
学位授予单位中国科学院金属研究所
学位授予地点金属研究所
学位专业材料学
关键词Fe-cr-al Cu-zn-al 三元合金 临界铝浓度 第三元素效应 氧化
摘要本文选择了Fe-Cr-Al和Cu-Zn-Al两种合金体系,分别研究了它们的高温氧化行为,目的在于探究其中的第三元素Cr/Zn的作用机理。由于第三元素的添加对氧化性能的改善是通过促进最活泼元素的外氧化膜来实现的,所以作为与三元合金氧化行为的对比,需要了解相应的二元Fe-Al、Fe-Cr、Cu-Zn、Cu-Al合金各氧化模式之间相互转变所需要的活泼元素的临界含量,其中关于Cu-Zn和Cu-Al合金的研究还很少见,因此在本工作中对这两种合金的氧化模式随成分的转变进行了专门的研究。 在1000oC的氧气中氧化24小时的实验结果显示,Fe-3Al合金中随着Cr的添加量的逐渐增加,合金的抗氧化性能不断改善,添加3 at.% 铬之后,氧化模式由Cr+Al的同时内氧化转变到三种合金元素的混合外氧化,当铬的添加量得到10 at.%或更高时,氧化模式进一步转变成形成单一的Al2O3外层保护膜。 800oC的氧气中氧化24小时的实验结果显示,二元Cu-Al和Cu-Zn合金中随着活泼元素Al/Zn浓度的提高,氧化模式也依次从内氧化转变到两种合金元素的混合外氧化,再到活泼元素的选择性外氧化。Cu-Al合金中发生两种氧化模式的转变的临界Al含量分别为2.5at.%和4at.%左右;Cu-Zn合金中发生两种氧化模式的转变的临界Zn含量分别为12at.%和14at.%左右。分别运用Wagner关于二元合金中发生内氧化向外氧化转变的临界判据和发生活泼组元的选择性外氧化的临界判据对上述两种二元合金的临界转变浓度进行理论计算,并将计算值与实验值进行了对比,并分析了导致两者之间差别的可能原因。 Cu-Zn-Al合金中铝含量一定时,氧化速率随着锌含量的增加而不断降低。向Cu-2Al合金中添加5at. %锌能够抑制内氧化,但即使添加10 at.%锌仍不足以促成保护性Al2O3膜的生成,直到添加15at.%锌才能达到这样的效果。由于Cu-4Al合金已经能够发生铝的选择性外氧化,所以锌元素的加入只是缩短保护性Al2O3膜的形成时间,减少氧化初期铜的氧化物的生成。 结合三元合金氧化热力学-动力学氧化相图,并通过理论计算和实验结果研究分别绘制了四元Fe-Cr-Al-O和Cu-Zn-Al-O体系在高氧压下的氧化图,分析了Cr在Fe-Cr-Al合金以及Zn在Cu-Zn-Al合金中的第三元素效应,提出了一种新的具有一定普适性的第三元素效应作用机制。
其他摘要Several Fe-Cr-Al and Cu-Zn-Al alloys with different compositions have been oxidized in 1 atm O2 at high temperature to investigate the third-element effect due to Cr and Zn. Cr/Zn act as third elements in these two systems and improve the high temperature oxidation resistance of the ternary alloys by promoting the transition to the formation of external scales of the most reactive alloy component. In order to compare the oxidation behavior of these ternary alloys with that of the corresponding binary alloys, it was necessary to know the critical contents of active components required for the transitions between different oxidation modes in binary Fe-Cr, Fe-Al, Cu-Zn and Cu-Al alloys. Since there are few investigations concerning these transitions for Cu-Zn and Cu-Al alloys, five binary Cu-Al alloys with Al contents ranging approximately from 1 to 7 at.% and five Cu-Zn alloys with Zn contents ranging approximately from 5 to 20 at.% have been prepared and oxidized at high temperature in 1 atm O2. The progressive addition of Cr improved gradually the oxidation resistance of a Fe-3Al alloy at 1000oC in 1 atm O2 for 24 h, promoting first a transition from internal oxidation of Al to the mixed external oxidation of all the three alloy components, with an addition of 3 at.% Cr, and then allowing to establish an exclusive external Al2O3 scale for Cr additions above 10 at.%. The increase of the concentration of Zn and Al in binary Cu-Zn and Cu-Al alloys transformed their oxidation mode at 800oC in 1 atm O2 for 24 h first from internal oxidation of the active elements to a mixed external oxidation of both alloy components and later to the selective external oxidation of Zn and Al. The critical Al contents of Cu-Al alloys for the two transitions are about 2.5 at.% and 4at.%, while the corresponding Zn contents of Cu-Zn alloys are about 12 at.% and 14 at.%, respectively. These critical concentrations have also been calculated by Wagner’s criterion for the transition between internal and external oxidation of the active component in binary alloys and the criterion for the selective external oxidation of the active component. All the calculated values have been compared with the experimental results, and possible reasons for the discrepancies observed between them have been analyzed. The oxidation rates at high temperature of ternary Cu-Zn-Al alloys with a constant Al content reduced gradually with a progressive increase of their Zn content. The addition of 5 at.% Zn to a Cu-2Al alloy can inhibit the internal oxidation completely, but even the addition of 10 at.% Zn is still not sufficient to induce the formation of a protective Al2O3 scale, which requires the addition of at least 15 at.% Zn. The effect of the Zn additions to a Cu-4Al alloy is only to shorten the time required for the establishment of the protective Al2O3 scale and to inhibit the formation of external CuxO scales during the initial oxidation stage. The oxidation maps of the quaternary Fe-Cr-Al-O and Cu-Zn-Al-O systems have been drawn by combining the results from both theoretical calculations and experimental measurements. The possible mechanisms of the third-element effect due to Cr in Fe-Cr-Al and to Zn in Cu-Zn-Al alloys have been interpreted with the help of these oxidation maps.
页数92
语种中文
文献类型学位论文
条目标识符http://ir.imr.ac.cn/handle/321006/17072
专题中国科学院金属研究所
推荐引用方式
GB/T 7714
高锋. Fe-Cr-Al/Cu-Zn-Al合金高温氧化中的第三元素效应(TEE)研究[D]. 金属研究所. 中国科学院金属研究所,2007.
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