Fe-Cr-Al合金氧化膜形成机理电子理论研究

通过自编软件建立了Fe-Cr-Al合金表面、氧化膜/基体界面模型,采用递归法计算了合金元素在Fe-Cr-Al合金表面、氧化膜/基体界面的环境敏感镶嵌能、亲和能、结合能、态密度等电子结构参数.从电子层次系统研究了Fe-Cr-Al合金氧化膜的形成机理、稀土元素和杂质硫对氧化膜形成过程及黏附性的影响机理.研究表明Fe-Cr-Al合金中Al的偏聚驱动力远大于Y,Cr.氧化初期氧从合金表面向合金内部扩散,合金内部Al向合金表面扩散,使合金形成富铝、氧表面层;氧与Al间的亲和力较大（亲和能低）,氧原子容易与Al结合生成Al₂O₃保护膜;合金中加入Y后,Y在合金表面偏聚,抑制Al向合金表面扩散,氧化膜的横向生长得到有效控制,从而避免氧化膜皱褶形貌的发生,提高氧化膜的黏附性;合金内部的S通过扩散汇集在基体/氧化膜界面,S使界面区原子的总能增高,总态密度降低,减小了界面的稳定性,进而削弱氧化膜与合金基体的结合力. 关键词： 电子结构 高温氧化 Fe-Cr-Al合金     

Nb-Ti-Al合金高温氧化机理电子理论研究

采用递归法计算了Nb合金的电子态密度、原子镶嵌能、亲和能和团簇能等电子结构参数,研究Nb合金高温氧化机理.研究表明,氧在Nb合金表面的吸附能较低,易在合金表面吸附,并逐渐扩散到Nb合金的基体中.氧在合金基体中镶嵌能为负值,氧的态密度和Nb相似,在Nb中具有很高的溶解度.Ti,Al在合金晶内的镶嵌能均高于各自在合金表面的镶嵌能,Ti,Al从合金内部向合金表面扩散,最终在Nb合金表面偏聚,形成富Ti,Al的表层.团簇能计算结果表明Nb合金表面的Ti,Al原子各自均有聚集倾向,分别形成Ti和Al原子团.氧与合金     

铌合金电子结构及其高温氧化行为

为了从电子层面揭示Nb合金高温氧化的物理本质,采用递归法计算了Nb合金的电子态密度、原子镶嵌能、亲和能等电子结构参数,探索Nb合金高温氧化机理.研究表明:氧在Nb中具备较高的扩散速率和溶解度,且氧与Nb较易发生反应,生成氧化物,这使Nb的抗高温氧化性较差.原子镶嵌能的计算结果表明,合金元素Ti,Si,Cr在基体中稳定性较低,易向Nb合金表面扩散,形成富Ti,Si,Cr的表层.合金表层中氧与Nb,Ti,Si,Cr间具有较大亲和性,可以生成相应的氧化物,形成对合金具有保护作用的氧化膜. 关键词： 递归法 高温氧化 Nb合金     

Fe-Cr-Al合金高温氧化行为电子理论研究

从电子层面系统研究Fe-Cr-Al合金氧化膜的形成机理,杂质硫对氧化膜黏附性的影响,稀土元素在改善氧化膜黏附性方面的作用,揭示合金氧化的物理本质.研究表明氧使Al在合金表层的环境敏感镶嵌能最低,促使Al原子从合金内部向合金表面扩散,最终在合金表面偏聚.由于氧与Al间的亲和力较大,氧原子易与Al结合生成Al2O3保护膜.杂质S在基体/氧化膜界面的环境敏感镶嵌能较低,可通过扩散偏聚在基体/氧化膜界面,削弱氧化膜与合金基体的结合力.当合金中加入Y后,Y易与S结合形成稳定的硫化物,阻碍S向基体/氧化膜界面的偏聚,显著提高氧化膜的黏附性,提高合金抗高温氧化能力.     

钛铝合金高温氧化机理电子理论研究

为了从电子层面揭示钛铝合金高温氧化的物理本质,采用递归法与Castep相结合的方式, 计算了原子埋置能、亲和能、结合能等电子结构参数,探索合金氧化机理.研究表明: 氧在钛中有较大固溶度,氧原子可以在钛表面的基体内聚集,逐步向深层扩散. 氧与钛具备较强的亲和力,能形成钛的氧化膜.钛基体中铝原子间具有相互吸引力, 能形成铝的原子团簇.铝原子团簇中的钛原子间相互排斥与铝形成化合物. 铝、钛与氧的亲和能相近,不易发生铝的优先氧化,而是同时生成钛的氧化物和铝的氧化物. Al₂O₃比TiO₂的结合能略低,因而更加稳定,铝在TiO₂中有较大的固溶度, 能替换其中的钛形成更稳定的Al₂O₃氧化物.     

氧化处理对非晶态Ni65Nb35合金表面结构和化学组成的影响

用ＳＥＭ及ＸＰＳ方法对非晶态Ｎｉ６５Ｎｂ３５合金氧化处理以后表面的结构及化学组成进行分析。结果表明,弱氧化条件下,Ｎｂ以及Ｎｂ２Ｏ５的形式在表面偏析：强氧化条件下,Ｎｉ妈金属Ｎｉ及ＮｉＯ的形式在表面偏析,金属原子与氧的亲和力可能是上述偏析过程的主要驱动力。     

ICP—AES法测定高温合金中铌,钽,锆,铪

本文研究了高温合金中Ｎｂ，Ｔａ，Ｚｒ和Ｈｆ分析方法，同时探讨了ＩＣＰ－原子发射光谱法中的某些影响因素及其校正，通过精密度与准确度试验，表明该分析方法准确，可靠，并且用于合金样品分析取满意的效果。     

新型高温应变电阻合金

在拉伸时,金属材料的电阻将发生改变.在弹性极限内,电阻相对变化与应变的比值保持常数,该常数称为电阻应变系数.人们利用应变-电阻效应把金属丝材制成电阻应变片,作为传感器元件.它能将构件表面的应变转换成电阻的相对变化.电阻应变系数越大,传感器的灵敏度越高.电阻应变测量技术是实验应力分析的主要方法之一,它在航空、航天、原子能、化工、机械、冶金、交通等部门获得广泛应用. 应变电阻合金是制作电阻应变片的关键材料,它直接决定应变片的各项特性.700-1000℃使用的高温应变电阻合金是国际上近20年共同探索的课题,它要求抗氧化非常好,组…     

Mg合金晶粒细化机理的电子理论研究

采用递归法计算了α-Mg与α-Zr的结构能、原子结合能,Mg/Zr界面能与Mg/液态Mg界面能,Mg中Zr及Zr中Fe,Mn,Si等杂质原子相互作用能.计算发现α-Zr的结构能、原子结合能低于相应的α-Mg,且Mg/Zr界面能低于Mg/液态Mg界面能,从能量角度合理解释了Zr先于Mg从Mg熔体析出,并作为异质核心细化Mg晶粒的实验现象.原子相互作用能的计算结果显示,Zr在Mg中相互吸引形成团簇,并与杂质形成化合物,削弱晶粒细化效果. 关键词： 电子结构 晶粒细化 Mg合金     

钛合金微弧氧化过程中电学参量的特性研究

利用自制的数据采集系统研究了恒定电压下TC4钛合金微弧氧化(MAO)过程中有关电学参量随处理时间的变化规律. 结果表明，通电回路中的阴极和阳极峰值电流随处理时间的变化明显分为4个阶段；膜厚度随处理时间的变化明显分为3个阶段；氧化膜的动态正、反向电阻和动态正、反向电阻率也随处理时间分阶段变化. MAO过程中，各时刻的动态正、反向电阻值不同，一般情况下，动态正向电阻大于反向电阻. 对不同处理时间样品的扫描电子显微镜分析表明，MAO膜呈多孔结构并随处理时间变化.     

铝合金微弧氧化过程中电学参量的特性研究

利用自制的数据采集系统研究了恒定电压下铝合金微弧氧化过程中有关电学参量随时间的变化规律.结果表明：通电回路中的阴极和阳极峰值电流随处理时间的变化明显分为5个阶段；陶瓷膜的动态正向电阻和电阻率随处理时间分阶段变化，而动态的反向电阻和电阻率随时间的变化不大.在微弧氧化过程中，各时刻的动态正、反向电阻值不同，一般情况下，动态正向电阻远大于反向电阻.对不同处理时间样品的扫描电子显微镜分析表明，陶瓷膜呈多孔结构并随处理时间分阶段变化. 关键词： 铝合金 微弧氧化 电学参量 陶瓷膜     

A finite element analysis of the reactive element effect in oxidation of chromia-forming alloys

In many situations, failures such as spallation or cracking occur when chromia-forming alloys are subjected to high-temperature thermal treatment. On the other hand, a small amount of reactive element addition can remarkably increase the adherence between chromia scales and alloys. A two-dimensional finite element model has been developed to analyze the effects of reactive elements on the selective oxidation of chromia scale-forming binary alloys. The quantitative relation between the diffusivities of chromium ions and the activities of reactive element (yttrium) has been derived for the first time and has been incorporated with a continuum thermodynamic model accounting for stress–diffusion interaction in the oxidation of Cr–Fe alloys. The model predicts that the diffusivities of Cr ions are affected by the activities of reactive element compounds, which eventually leads to a decrease of the interfacial spallation driving force, as well as an increase of the interfacial adherence.     

Microstructure characteristic of ceramic coatings fabricated on magnesium alloys by micro-arc oxidation in alkaline silicate solutions

Micro-arc oxidation (MAO) of AZ31B magnesium alloys was studied in alkaline silicate solutions at constant applied current densities. The microstructure, phase composition and elemental distribution of ceramic coatings were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive spectroscopy (EDX). There are two inflections in the voltage-time response, three regions were identifiable and each of the regions was almost linear. The pores with different shapes distributed all over the coating surface, the number of the pores was decreasing, while the diameter was apparently increasing with prolonged MAO treatment time. There were also cracks on the coating surface, resulting from the rapid solidification of the molten oxide. The ceramic coating was comprised of two layers, an outer loose layer and an inner dense layer. The ceramic coating was mainly composed of forsterite phase Mg₂SiO₄ and MgO; the formation of MgO was similar to conversional anodizing technology, while formation of Mg₂SiO₄ was attributed to a high temperature phase transformation reaction. Presence of Si and O indicated that the electrolyte components had intensively incorporated into coatings.     

Kinetic aspects of aluminium titanate layer formation on titanium alloys by plasma electrolytic oxidation

The paper reports on a systematic investigation into the effects of process parameters on the growth kinetics and associated changes in the structure, phase composition and mechanical properties of surface layers formed on Ti–6Al–4V alloy by plasma electrolytic oxidation (PEO) treatment in 0.05–0.2 mol l⁻¹ solutions of sodium aluminate. Methods of gravimetric, SEM and XRD analysis, as well as microhardness and scratch testing, are employed to investigate mass transfer and phase-structure transformations in the surface layer. The probable mechanisms of layer formation are discussed, which comprise electrochemical oxidation of the Ti-electrode by OH⁻ anions, complimented by chemical precipitation of Al(OH)₃ and plasma-induced transformations in the surface discharges. Running with a total yield efficiency of 20–30%, these processes lead to the formation of predominantly the Al₂TiO₅ phase with heterogeneous precipitation of Al₂TiO₅·TiO₂ and 3Al₂TiO₅·Al₂O₃ eutectics. Al- and Ti-enriched constituents of this structure show hardnesses of 1050–1480 and 300–845 H_K, 0.02, respectively. The layer growth rate increases with increasing electrolyte concentration, providing a maximum thickness of over 60 μm and a surface roughness (R_a) of 3–4 μm. Increasing the electrolyte pH from 12.0 to 12.8 results in smoothing and thickening of the surface layer but a lower sample weight gain, associated with an enhancement of the Ti electro-oxidation process. Morphological changes during PEO formation of the surface layer include gradual transformation of the original fine grained but porous structure into a dense, fused morphology which is adversely affected by discharge-induced thermal stresses, causing a degradation of the layer adhesion strength.