三元合金高温理论氧化图 Ⅱ.低氧压下的近似分析

在假设三元Ａ－Ｂ－Ｃ固溶合金中三组无氧化物不互溶且不形成复合氧化物,并忽略合金内氧化的条件下,计算并建立了合金在单一氧化剂、低氧压下形成各氧化物的动力学氧化图并考虑组元的扩散作用,描述了变氧压条件下该四元系合金与各氧化物之间的平衡关系以及合金的成膜规律．     

三元合金高温理论氧化图Ⅱ.低氧压下的近似分析

在假设三元A-B-C固溶合金中三组元氧化物不互溶且不形成复合氧化物，并忽略合金内氧化的条件下，计算并建立了合金在单一氧化剂、低氧压下形成各氧化物的动力学氧化图，并考虑组元的扩散作用，描述了变氧压条件下该四元系合金与各氧化物之间的平衡关系以及合金的成膜规律。     

在600～800℃低氧压下Fe—Nb合金的氧化

研究了Ｆｅ－１５Ｎｂ和Ｆｅ－３０Ｎｂ（ｗｔ％）合金在６００～８００℃低氧压气氛的化行为，实验所用的氧压处于煤的所气化气氛下的氧分压范围，氧化后合金仅发生了Ｎｂ的氧化，生成ＮｂＯ２与Ｎｂ２Ｏ５，有些情况下还生成ＦｅＮｂ２Ｏ６。在６００℃时氧化速度很低，但在７００～８００℃时则颇高。这些合金内氧化的重要特征之一，是其内氧化物的分布向乎完全与合金的高含Ｎｂ相一致。此外，合金氧化后均不出现外氧化层，这些坷     

三元合金的高温理论氧化图Ⅰ.高氧压下的近似分析

通过对三元合金系高温氧化行为的分析,把Ｗａｇｎｅｒ关于形成不互溶氧化物的二元合金经典理论扩展到三元合金体系,忽略活泼组元内氧化,以热力学稳定相图为参考,建立了相应的动力学氧化图并分析了影响动力学氧化图的因素,为进上步研究三元合金高温氧化行为提供了重要的理论依据。     

纯Ce及Fe—Ce合金在低氧压下的氧化

研究了纯Ｃｅ和含１５％Ｃｅ（质量分数,下同）的Ｆｅ－Ｃｅ合金在６００￣８００℃低氧分压下的氧化。纯Ｃｅ氧化后形成ＣｅＯ２的外氧化。而Ｆｅ－１５Ｃｅ则产生快速Ｃｅ的内氧化,且内氧化区的显微组织保持了原始合金的显微组织,在内氧化区的前沿没有观察到Ｃｅ的贫化。     

在600～800℃低氧压下Fe－Nb合金的氧化

研究了Ｆｅ－１５Ｎｂ和Ｆｅ－３０Ｎｂ（Ｗｔ％）合金在６００～８００℃低氧压气氛中的氧化行为，实验所用的氧压处于煤的气化气氛下的氧分压范围。氧化后合金仅发生了Ｎｂ的内氧化，生成Ｎｂ２与Ｎｂ２Ｏ５，有些情况下还生成ＦｅＮｂ２Ｏ６。在６００℃时氧化速度很低，但在７００～８００℃时则颇高。这些合金内氧化的重要特征之一，是其内氧化物的分布几乎完全与合金中的高含Ｎｂ相一致。此外，合金氧化后均不出现外氧化层。这些可能都是由于Ｎｂ在Ｆｅ中溶解度很低且合金呈两相组织所致。     

在600-800℃低氧压下Co-Nb合金的氧化

研究了含15与30wt%Nb的两种Co-Nb合金在600-800℃低氧压F的氧化性能选择的氧压低于相应温度的氧化钴分解压,由H2-CO2混合气获得,在600℃为10-24atm,而700与800℃为10-20atm.两种合金在600与700℃氧化结果仅产生由α-CO与氧化铌(NbO2与Nb2O5)混合物组成的内氧化带在700℃尚可能生成双元氧化物CONb2O6在内氧化带界而无贫Nb层可见.两会金,尤其是Co-30Nb在800℃时发生了由内氧化向外氧化的转变,伴随有贫Nb的单相区出现于合金的表层.从Co中N     

Cu-Ni-Fe双相合金在800～900℃的低氧压氧化

研究了经自发分解产生的Cu 30Ni 2 5Fe(摩尔分数 ,% )双相合金在 80 0～ 90 0℃于低氧分压 (只有Fe可被氧化 )条件下的氧化行为。该合金的氧化动力学遵循抛物线规律 ,相同氧化条件下 ,其氧化速率低于纯Fe和二元Cu 2 5Fe合金。氧化膜包括Fe3O4外层和FeO的内氧化物颗粒 ,并且FeO均匀分布在Cu Ni固溶体上 ,与合金两相的初始分布没有联系 ,而内氧化带前沿合金中出现贫Fe的Cu Ni固溶体单相层。讨论了二元 /三元双相合金与单相合金由互固溶度引起的氧化行为差异 ,认为双相合金中难以发生最活泼组元的单一外氧化是由于组元在基体中的扩散受到双相强烈限制的结果。     

低氧分压系统及其在二元合金选择性氧化中的应用

根据氧化锆陶瓷管材在高温（〉８７３Ｋ）时，因管壁内外的氧分压下同形成氧浓差电池（Ｐｔ，Ｏ２（Ｐ＾ＩＯ２）│ＺｒＯ２│空气（Ｐ＾ＩＯ２），Ｐｔ的原理，研制了可控氧分子（Ｏ２）发射量的低氧分压发生系统。用该系统对Ｎｉ２０Ｃｒ合金进行低氧分压预氧处理后，促进了Ｃｒ在１２７３Ｋ时的选择性氧化，提高了合金的抗氧化性能，在低氧分压下，Ｃｕ１．５Ａｌ合金发生了Ａｌ的选择性内氧化。     

Ag—Y两相合金在高—低氧压下的高温氧化

研究了含8mass%Y的Ag-Y合金在10^5Pa和10^-15Pa两个氧压于700℃的氧化。结果表明,在10^5Pa的氧化很快,并遵循近似的抛物线规律;10^15Pa的氧化则很慢且偏离抛物线规律。在高氧压仅发生Y的原位内氧化,这主要是氧快速向内渗通而没有Y明显地外扩散所致,在低氧压则生成含Ag颗粒的Y2O3外氧化层,而其Y的内氧化层则远较高氧压者薄。。内氧化Y2O3颗粒沿深度而变化,近表面处小并呈圆球状,随深度增加逐渐变大并拉长;在深处呈针状且垂直合金表面。此外,在两种氧压下合金最表面有Ag层或分散的Ag颗粒生成。     

The Internal Oxidation of Ternary Alloys. VII: The Transition from the Internal to the External Oxidation of the Two Most-Reactive Components Under Intermediate Oxidant Pressures

The conditions for the transition between the coupled internal oxidation of two most-reactive components and the formation of external scales in the scaling of ternary alloys under oxidant pressures below the stability of the oxide of the most-noble component, denoted as a situation of intermediate oxidant pressures, are examined under a number of simplifying conditions which allow to develop an approximate analytical treatment. If the precipitation of the two oxides occurs at the same front of internal oxidation, the kinetics of internal oxidation as well as the critical B and C contents needed for the transition have a single solution under fixed conditions of all the parameters involved. On the contrary, in the presence of two different fronts, when the most-stable oxide forms at the innermost front, a whole range of possible solutions is predicted. In both cases, the critical-C content needed to avoid the simultaneous internal oxidation of B plus C is progressively reduced by the addition of B. This behavior provides the basis for a possible interpretation of the “third-element effect”. However, the existence and the magnitude of this effect are complicated by the occurrence of other modes of oxidation for these systems. Thus, a general treatment of the third-element effect under intermediate oxidant pressures requires an exhaustive analysis of all the oxidation modes permitted for ternary alloys under these conditions.     

The Internal Oxidation of Ternary Alloys. V: The Transition from Internal to External Oxidation of the Most-Reactive Component under Low Oxidant Pressures

This paper examines the conditions for the transition from internal to external oxidation of the most-reactive component C of ternary A–B–C alloys by a single oxidant under gas-phase oxidant activities below the stability of the oxide of the two most-reactive components using Wagners criterion. For this, approximate relations between the solubility and diffusivity of oxygen and the composition of the binary A–B alloy matrix in the zone of internal oxidation, already developed previously, are used. The critical C content needed for the transition in ternary alloys is calculated as a function of the many parameters involved. At variance with the behavior of binary alloys, for ternary alloys this critical C content depends also on the ratio between the concentrations of A and B in the bulk alloy. The results calculated for ternary alloys are compared with those obtained for binary A–C and B–C alloys under the same values of all the relevant parameters. Finally, complete oxidation maps for ternary alloys under low oxidant pressures,including the condition for the stability of external scales of the C oxide, are also presented.     

Pd—Eu合金内氧化

Pd—Eu合金在氧化性气氛中退火时,活性溶质Eu发生内氧化,形成稳定氧化物Eu_2O_3内氧化是由扩散机制控制的Eu_2O_3形核长大过程:氧通过体扩散和晶界扩散进入合金内,Eu由内层扩散到外层研究了内氧化动力学对于圆截面试样,内氧化层深度(ξ)与氧化时间(t)满足公式ξ=Kt~n当温度800—900℃时,n=0.5,符合抛物线规律;当温度高达1200℃时,n=0.75,偏离抛物线规律PdEu0.56合金在800—1200℃内氧化激活能为150kJ/mol     

AgCu合金的内氧化行为

用ＴＧＡ，ＯＭ、ＳＥＭ和ＨＲＥＭ等方法研究了Ｃｕ含量不同的几种ＡｇＣｕ合金在７５０℃及８５０℃的内氧化行为。发现氧化１２ｈ后，Ａｇ－０．８ａｔ％Ｃｕ合金中的Ｃｕ已完全以ＣｕＯ颗粒析出；     

The Internal Oxidation of Ternary Alloys. III: The Coupled Internal Oxidation of the Two Most-Reactive Components under High Oxidant Pressures

The kinetics of the simultaneous internal oxidation of the two most-reactive components B and C in ternary A–B–C alloys, where A is the most-noble and C the most-reactive component, in the presence of an external layer of the A oxide, AO, (high oxidant pressures) are examined assuming the existence of either a single or a double front of internal oxidation. For a single front a unique solution is obtained for the parabolic rate constant of internal oxidation under assigned values of all the parameters involved. When the front is double, a finite range of solutions is allowed with an upper limit equal to the single-front solution and a lower limit equal to the rate constant for the growth of external AO scales. In the case of a single front of internal oxidation, an increase of the rate constant for the growth of the external scales produces an increase of the rate constant for the internal oxidation but a decrease of the degrees of enrichment of the components being oxidized internally within the region of internal oxidation. The behavior in the case of a double front is more complex because it depends also on the actual value of the ratio between the rate constants of internal oxidation for the two fronts.     

The Internal Oxidation of Ternary Alloys I: The Single Oxidation of the Most-Reactive Component Under Low Oxidant Pressures

The internal oxidation of the most-reactive component C of ternary A–B–C alloys by a single oxidant is examined assuming a gas-phase oxidant pressure below the stability of the oxides of the other two components. The precipitation of the most-stable oxide leaves behind a matrix composed of a binary alloy of the two less-reactive components, whose composition affects the solubility and diffusivity of the oxidant within the region of internal oxidation, with an effect on the reaction kinetics. Approximate relations between these properties are proposed and used to predict the kinetics of internal oxidation of C under the assumption of parabolic rate law. The results obtained for the ternary alloys are compared with the behavior of binary A–C and B–C alloys with the same C content. A new important factor in establishing the difference between the internal oxidation in ternary A–B–C alloys and in binary A–C and B–C alloys under a fixed gas-phase oxygen pressure and C content is the ratio between the concentrations of A and B in the bulk ternary alloy.     

The Internal Oxidation of Ternary Alloys. VI: The Transition from Internal to External Oxidation of the Most-Reactive Component under Intermediate Oxidant Pressures

The conditions for the transition from internal to external oxidation of the most-reactive component C of ternary A–B–C alloys are examined, assuming the presence of external scales of the oxide of the component of intermediate reactivity B. For this, approximate expressions for the diffusion coefficient of oxygen and for the concentration of oxygen dissolved in the binary A–B alloy matrix within the zone of internal oxidation as functions of the composition of the metal matrix within the zone of internal oxidation are used. Numerical calculations of the critical content of C needed for this transition are carried out for different combinations of values of the various parameters involved. The results obtained for the ternary alloys are compared with the corresponding data calculated for the binary A–C and B–C alloys under oxygen pressures insufficient to oxidize the most-noble alloy component. This allows to predict the possibility of existence of a third-element effect under intermediate oxidant pressures.