稀土6063变形铝合金阳极氧化与电解着色的研究

本文系在硫酸、硫酸亚锡溶液中对添加有稀土的6063变形铝合金进行了阳极氧化和电解着色。比较系统地研究了氧化电解液的浓度、温度、时间、电流密度对膜层厚度的影响;以及着色电流密度、电压、时间对膜层色度的影响。结果证实,稀土可以明显地提高6063变形铝合金氧化膜厚度和电解着色的色度,稀土含量以0.30％为好。     

粉末冶金Ti-Al合金表面多孔氧化膜的制备

以含CrO3的氢氟酸水溶液为电解液,采用阳极氧化法于粉末冶金Ti-Al合金表面制备多孔氧化膜。采用场发射扫描电镜(SEM)、X射线衍射仪(XRD)和X射线光电子能谱仪(XPS)对多孔氧化膜的形貌和结构进行分析,研究电解液各组份及浓度、阳极氧化电压对多孔氧化膜的影响规律,并利用电化学测试技术探讨多孔氧化膜的成膜机理。结果表明:合金在不含CrO3的HF电解液中阳极氧化不能获得多孔氧化膜,而是发生严重的腐蚀溶解。电解液中HF浓度和电压均影响氧化膜的形貌,在HF含量为0.2%时可获得规则的多孔氧化膜,孔径在50nm左右;当氧化电压为10V时形成的多孔氧化膜规则性较好,电压增大时多孔氧化膜结构遭到破坏。氧化膜中主要含有无定型的TiO2、Al2O3以及少量晶态的Ti2O、单质Al。多孔氧化膜的生长过程包括阻挡层的形成、多孔氧化膜的初始形成和多孔氧化膜的稳定生长3个阶段。     

LY12铝合金微弧氧化陶瓷膜的性能研究

以铝合金LY12为试验材料,采用MA0240/750微弧氧化设备、TT260测厚仪和AMARY-1000B扫描电子显微镜,研究了起弧电压、电流密度和氧化时间等参数对陶瓷层性能的影响.结果表明:起孤电压随着Na2SiO3浓度的增加而降低;在相同氧化时间内,随着电流密度的增加,陶瓷膜的厚度也显著地增加,陶瓷膜的致密层显微硬度也在逐渐地增加,但不是线性地增加;在相同电流密度条件下,随着时间的增加,膜层厚度和致密层硬度非线性增加,但致密层所占比例却减小.     

干氧氧化单晶硅氧化膜形态研究

用扫描电子显微镜和超高压电子显微镜观察和分析了(111)单晶硅1100℃干氧氧化的不同厚度氧化膜的形态和结构。结合单晶硅氧化动力学三段理论,提出了氧化膜生长机制。电子和 X-射线衍射分析,确定氧化膜是由具有不同晶体结构的二氧化硅构成。文中还讨论了氧化膜生长时,在 Si-SiO_2界面处的层错及位错的成因。     

硅酸盐体系负向电压对氢化锆表面微弧氧化膜的影响

采用WHD-30型双向交流脉冲电源对氢化锆表面进行微弧氧化处理,研究了负向电压对氢化锆表面微弧氧化膜的厚度、表面形貌、截面形貌、相结构及阻氢性能的影响。实验选取电解液体系为Na2SiO3-NaOH-Na2EDTA体系,正向电压为350V,电源频率为200Hz,氧化时间为20min;氢化锆表面微弧氧化膜的阻氢性能采用真空脱氢实验进行测试。研究结果表明:负向电压在120~160V范围内变化时,氢化锆表面微弧氧化膜的厚度在30~90μm范围内,氧化膜的厚度随着负向电压的升高而增大。氧化膜外部为疏松层,存在孔洞和裂纹缺陷,氧化膜内部为致密层,与基体结合紧密,无孔洞和裂纹缺陷。氧化膜相结构由单斜相氧化锆(M-ZrO2)和四方相氧化锆(T-ZrO1.88)构成,并以单斜相氧化锆(M-ZrO2)为主。负向电压升高有利于增大氧化膜致密层的厚度,进而提高氧化膜的阻氢能力。当负向电压为160V时,氧化膜的阻氢能力最高,氢渗透降低因子(PRF,permeationreductionfactor)值达到10.4。     

8407钢渗铝氧化处理形成的氧化膜组织与结构

对渗铝后的8407钢试样进行常温硬质阳极氧化处理,使其表面形成氧化膜。通过金相显微镜观察氧化膜横截面组织,并探讨了氧化膜的形成机制;采用扫描电镜观察氧化膜表面形貌,并检测氧化膜沿厚度方向的化学成分及其分布;利用X射线衍射仪对氧化膜相组成进行分析。结果表明,渗铝8407钢经过常温硬质阳极氧化后,试样表面分为3层,从基体向外侧依次为基体、渗层、氧化膜。氧化膜连续致密,厚度均匀,与基体结合紧密,其主要成分为O、Al和Fe,且各元素分布均匀,主要相组成为Fe3O4和Al2O3。     

Al-Zn-Mn-Si-Mg系压铸铝合金阳极氧化工艺

在传统铝合金阳极氧化电解工艺基础上,添加草酸、酒石酸和柠檬酸等形成硫酸-有机酸混合体系氧化处理液,对Al-Zn-Mn-Si-Mg系压铸铝合金进行阳极氧化处理,探索阳极氧化工艺参数和有机酸种类对氧化膜微观形貌、耐腐蚀和耐磨性能的影响.研究结果表明：在硫酸质量分数为10%、氧化电压为18V、氧化时间为60 min、氧化温度为20℃的条件下,与纯硫酸体系相比,混合酸体系能显著增加Al-Zn-Mn-Si-Mg系压铸铝合金阳极氧化膜厚度,提高氧化膜的耐腐蚀性能和耐磨性能;其中10%硫酸-15%柠檬酸混合体系(百分数均为质量分数,下同)下的氧化膜耐腐蚀性能较强,10%硫酸-10%酒石酸体系下的氧化膜耐磨性能较优.     

正脉冲电压对Mg-4Gd-3Y-0.5Zr合金微弧氧化膜组织形貌与耐蚀性能的影响

采用SEM、覆层测厚仪、电化学工作站等研究了正脉冲电压对Mg-4Gd-3Y-0.5Zr稀土镁合金双脉冲微弧氧化膜的组织形貌及耐蚀性能的影响。结果表明：随正脉冲电压的升高,膜层厚度增加,膜层表面微孔数量减少、孔径增大,烧结强度增加,裂纹增大;耐蚀性能先增强后降低,均显著优于合金基体;最佳正脉冲电压为450 V,腐蚀电位与腐蚀电流分别为-1.495 V、10-8.62 A/cm2。     

钛合金表面微弧氧化制备二氧化钛陶瓷膜的研究

采用微弧氧化法在钛合金表面制备二氧化钛膜层(即生物医学用陶瓷膜),利用SEM、XRD和EDX对膜层的物相结构、形貌和元素组成进行了分析。研究了电解液pH值和微弧氧化电压对微弧氧化过程的影响。结果表明:随着电解液pH值和微弧氧化电压的升高,膜层表面孔洞数量增加,孔径增大,膜层更加均匀;膜层主要由锐钛矿型和金红石型二氧化钛组成,且金红石相含量随微弧氧化电压的升高而增加;微弧氧化电流密度随氧化时间的延长先增大后减小,随电解液pH值的增大而增大。当电解液pH值为11、微弧氧化电压为500V时,可制得多孔状陶瓷膜,且其孔洞分布均匀。     

节镍奥氏体耐热不锈钢的高温性能研究

通过Thermo-Calc热力学相图计算软件设计了一种节镍含氮奥氏体耐热不锈钢,采用氧化增重法、光学显微镜、等温线外推法对节镍奥氏体耐热不锈钢的高温氧化动力学、氧化膜截面形貌及高温持久强度进行分析。结果表明：节镍奥氏体不锈钢在1150℃时的氧化速度随氧化时间的延长呈现下降趋势,高温氧化120h后节镍奥氏体不锈钢的氧化速度趋于稳定;节镍奥氏体不锈钢在1150℃循环氧化144h后,氧化膜厚度不均匀,氧化膜平均厚度约20μm,基体与氧化膜交界处出现晶界氧化现象;节镍奥氏体不锈钢在900℃和1000℃的持久强度外推值分别为23MPa和13MPa,高于310S的15MPa和9MPa,说明在900℃和1000℃时节镍奥氏体不锈钢的持久强度优于310S。     

SiO_2-CaO-MgO-Al_2O_3熔渣中铁氧化物的分解电压

电解含有铁氧化物的熔融电解质提铁是一种钢铁冶炼短流程新工艺,该工艺可以减少甚至消除CO2排放。为测定熔渣中铁氧化物的分解电压,采用一端封闭的氧离子传导的氧化锆基固体电解质管内装熔渣,并以烧结在固体电解质管封闭端外侧表面的多孔铂金作为阳极,构建一种阴、阳极相互隔离的新型管状电解池。将该电解池的多孔铂金阳极置于恒定氧分压的气氛下,在熔渣中分别插入铱丝、铁棒作为阴极,利用线性扫描伏安法测定了1 723K下SiO2-CaO-MgO-Al2O3熔渣中FeO的分解电压,研究了熔渣碱度、阴极材料以及阳极气氛氧分压等因素对FeO分解电压的影响。结果表明,增大熔渣碱度、阴极还原合金化以及降低电解产物气体O2的分压,均可降低FeO的分解电压,有利于FeO的电解。测定结果与采用FactSage 6.1热力学软件理论计算的结果一致。证实采用氧离子传导的固体电解质管构建新型管状电解池,测定固体电解质管内熔渣中氧化物的分解电压是可行的。     

On the nature of the Fe-bearing particles influencing hard anodizing behavior of AA 7075 extrusion products

The deleterious effects of Fe-bearing constituent particles on the fracture toughness of wrought Al alloys have been known. Recent studies have shown that the presence of Fe-bearing constituent particles is also detrimental to the nature and growth of the hard anodic oxide coating formed on such materials. The present study, using a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron probe microanalysis (EPMA), was made to examine the influence of the nature of the Fe-bearing particles on the hard anodizing behavior of AA 7075 extrusion products containing varying amounts of Si, Mn, and Fe impurities. It was found that, in the alloy containing 0.25 wt pct Si, 0.27 wt pct Mn, and 0.25 wt pct Fe, the Fe-bearing constituent particles are based on the Al₁₂(FeMn)₃Si phase (bcc with a=1.260 nm). These particles survive the hard anodizing treatment, add resistance to the electrical path, causing a rapid rise in the bath voltage with time, and cause a nonuniform growth of the anodic oxide film. In the materials containing 0.05 wt pct Si, 0.04 wt pct Mn, and 0.18 wt pct Fe, on the other hand, the formation of the Al₁₂(FeMn)₃Si-based phase is suppressed, and two different Fe-bearing phases, based on Al-Fe-Cu-Mn (simple cubic with a=1.265 nm) and Al₇Cu₂Fe, respectively, form. Neither the Al-Fe-Cu-Mn-based phase nor the Al₇Cu₂Fe-based phase survive the hard anodizing treatment, and this results in a steady rise in the bath voltage with time and a relatively uniform growth of the anodic oxide film. Consideration of the size of the Fe-bearing particles reveals that the smaller the particle, the more uniform the growth of the anodic oxide film.     

阳极氧化法制备TiO2多孔膜

通过对TiO2多孔膜阳极氧化制备工艺的研究，提出了其成膜机理。实验以硫酸为电解液，以纯钛(TAl)为阳极，铜片为阴极，采用了恒压和恒流2种阳极氧化方式，在纯钛的表面获得TiO2多孔膜。用FESEM观察其孔径分布在100nm～200nm之间，并且随着阳极氧化电压和电流密度的增加，多孔膜的孔径有增大的趋势。最后，讨论了在硫酸电解液中TiO2多孔膜的形成机制。     

On the nature of the Fe-bearing particles influencing hard anodizing behavior of AA 7075 extrusion products

The deleterious effects of Fe-bearing constituent particles on the fracture toughness of wrought A1 alloys have been known. Recent studies have shown that the presence of Fe-bearing, constituent particles is also determental to the nature and growth of the hard anodic oxide coating formed on such materials. The present study, using a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron probe microanalysis (EPMA), was made to examine the influence of the nature of the Fe-bearing particles on the hard anodizing behavior of AA 7075 extrusion products containing varying amounts of Si, Mn, and Fe impurities. It was found that, in the alloy containing 0.25 wt pct Si, 0.27 wt pct Mn, and 0.25 wt pct Fe, the Fe-bearing constituent particles are based on the Al₁₂(FeMn)₃Si phase (bcc with α=1.260 nm). These particles survive the hard anodizing treatment, add resistance to the electrical path, causing a rapid rise in the bath voltage with time, and cause a nonuniform growth of the anodic oxide film. In the materials containing 0.05 wt pct Si, 0.04 wt pct Mn, and 0.18 wt pct Fe, on the other hand, the formation of the Al₁₂(FeMn)₃Si-based phase is suppressed, and two different Fe-bearing phases, based on Al−Fe−Cu−Mn-based (simple cubic with a=1.265 nm) and Al₇Cu₂Fe, respectively form. Neither the Al−Fe−Cu−Mn-based phase nor the Al₇Cu₂Fe-based phase survive the hard anodizing treatment, and this results in a steady rise in the bath voltage with time and a relatively uniform growth of the anodic oxide film. Consideration of the size of the Fe-bearing, particles reveals that the smaller the particle, the more uniform the growth of the anodic oxide film.     

钽丝带膜连续退火与平直度的研究

通过对带膜连续退火工艺与原工艺进行比较,并分析带膜连续退火与钽丝平直度的关系以及渗氧参数对钽丝平直度的影响,证明了钽丝连续退火优于原堆积式退火,是钽丝生产工艺的重要突破。     

Microhardness of anodic aluminum oxide formed in an alkaline electrolyte

The microhardness of anodic aluminum oxide formed by anodizing of aluminum sheet in electrolyte on the basis of sodium hydroxide has been determined experimentally. The microhardness of the hard film/soft substrate system has been estimated by three approaches: indentation geometry (length of diagonals) in film surfaces, the sum of the hardnesses of the film and the surface with allowance for the indentation surface area and geometry, and with allowance for the indentation depth. It is demonstrated that the approach accounting for the indentation depth makes it possible to eliminate the influence of the substrate. It is established that the microhardness of the films formed in alkaline electrolytes is comparable with that formed in acid electrolytes.     

The anodic behavior of cerium in AlCl3-1-ethyl-3-methyl-imidazolium chloride ionic liquid

The anodic behavior of cerium (Ce) in AlCl₃-1-ethyl-3-methyl-imidazolium chloride (AlCl₃-EMIC) ionic liquid has been investigated. Linear sweep voltammetry (LSV), electrochemical impedance spectra (EIS), Raman spectra, scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) were carried out to state the process and mechanism during anodic reaction. The results show that Ce can be electrochemically oxidized and dissolved in the ionic liquid. The oxide film of Ce markedly affects its anodic behavior by blocking the dissolution of the underlying metal. Moreover, the dissolution of metal surface brings about the stripping of the oxide film on Ce, thus leading to an oxide free surface. This work demonstrates a theoretical foundation for electrolytic etching of Ce in ionic liquids.     

500kV铝包钢丝绞线良导体地线的研制

针对应用于目前最高电压等级线路500kV线路良导体的铝包钢绞线需要解决的大长度、高耐温、高延伸、高强度、高导电率、高结合力问题及钢芯拉拔、绞线的合理结构和绞制等几个重大的技术难题进行了分析研究。     

转移反应热和去除铝基底实验研究

铝在阳极氧化过程中放出来的热量对阳极氧化铝(AAO)模板的制备易产生不利影响,与铝基底紧连的阻挡层产生的焦耳热是主要热源.通过将铝基底置于草酸电解液外,考察了阳极氧化电压、冷却方式等因素对AAO模板制备的影响.结果表明,阳极氧化电压和冷却方式均影响电解液温度和AAO模板孔道直径尺寸.空气冷却时,30 V电压氧化8 h,制备的模板孔道直径约为40 nm,电解液温度为31℃;水浴冷却时,40 V电压氧化8 h,制备的模板孔道直径约为80 nm,电解液温度为25℃,且制备的AAO模板表面没有纳米氧化铝纤维.采用乙醇/浓盐酸混合溶液溶解铝基底,乙醇/浓盐酸的体积比为2~3时,溶解铝基底的时间约为30 min,AAO模板不受损害.