阳极氧化Ti-6Al-4V合金表面TiO_2多孔膜的制备及研究

在一定浓度的H_2SO_4溶液中对Ti-6Al-4V合金表面进行阳极氧化处理,通过改变阳极氧化处理的电压、氧化时间和电解液浓度,研究了预处理工艺参数对钛合金表面形貌、物相、润湿性及粗糙度的影响.试验结果表明:钛合金经过阳极氧化处理后,表面出现了二氧化钛(TiO_2)纳米多孔结构,多孔氧化膜由锐钛矿型和金红石型TiO_2组成;在0.5mol·L~(-1)H_2SO_4溶液中,随着阳极氧化电压的增加,多孔膜的孔径逐渐增大,基体表面与模拟体液(SBF)的接触角明显降低,经120V氧化处理的试样表面接触角由预处理前的52.8°降至16.9°左右,具有良好的润湿性;并且试样表面的粗糙度明显增加,在电压为120V时粗糙度达到0.56μm.在电压120 V时,随着阳极氧化时间或电解液浓度的增加,TiO_2多孔膜的含量和孔径尺寸逐渐增大,试样表面的润湿性和粗糙度也不断增加,在氧化时间10 min或电解液浓度0.5 mol·L~(-1)时达到最大,氧化时间大于10 min或电解液浓度高于0.5 mol·L~(-1)时,试样表面出现裂纹,多孔结构被破坏.     

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。     

TiAl合金表面阴极微弧制备的Al_2O_3膜结构与性能

以Al(NO3)3乙醇溶液为电解液,采用阴极微弧放电沉积方法,在TiAl合金表面制备连续的Al2O3薄膜,并对膜的结构与性能进行研究.利朋扫描电镜(SEM)观察到样品表面分布着熔融状颗粒,颗粒的平均直径约20μm,颗粒中间有小孔存在.X射线衍射(XRD)分析表明氧化膜的相成分主要为α-Al2O3和γ-Al2O3相,还有少量的ε-Al2O3相;氧化膜中α-Al2O3和γ-Al2O3的相对含量随着制备电压改变而变化.显微划痕实验测得膜与TiAl基体之间结合力大于20 N,表明制得的氧化膜与基体有良好的结合力.900℃的高温氧化实验表明氧化膜能够有效地提高基体的抗氧化性能.     

Ni-Cr-Al合金在1000℃空气中的氧化

研究了两种不同Cr含量的常规熔炼Ni-Cr-Al合金在1000℃空气中的氧化行为.合金氧化动力学遵循抛物线规律,Ni-20Cr-2.5Al合金在1000℃的氧化增重略小于Ni-15Cr-2.5Al合金,二者的氧化增重都明显小于Ni-20Cr合金.Ni-20Cr-2.5Al合金1000℃氧化后形成了外层的Cr2O3及内层极薄的Al2O3型氧化膜,在Ni-Cr合金中加入Al,由于Cr、Al的相互作用,降低了形成Cr2O3和Al2O3外氧化膜所需的Cr或Al的临界含量,促进了保护性Al2O3或Cr2O3膜的生成.     

电解液内含物与钛表面阳极氧化膜早期结晶的关系

钛是一种兼具高强度和低密度的材料,已被应用于航空航天、石油化工和医疗等诸多领域。钛在大多数水溶液环境中具有优异的耐腐蚀性,这是由于有氧存在时其表面会自然形成几个纳米厚的钝化薄膜。类似其他所有阀金属,这层自然氧化膜可以通过阳极氧化长厚,形成薄（干涉色的）膜或厚的多孔膜层。根据所施加的氧化条件（例如电解液的类型、浓度和电解电压等）可以生成致密的或多孔的,无定形或结晶态的,或呈纳米管排列的薄膜。钛阳极氧化过程中,由于热能和电场的作用,离子在膜层中迁移和扩散使氧化物生长。膜层在金属／氧化物和氧化物／电解液2种界面问生长。     

添加Fe-Al金属间化合物对12Cr-ODS铁素体合金氧化性能的影响

为了提升12Cr-ODS铁素体合金的抗氧化性能,本文通过同时添加Fe-Al合金粉末颗粒和Y2O3粉末颗粒,制备出一种新型的12Cr-ODS铁素体合金,并对其进行了氧化实验。通过X射线衍射(XRD)对氧化产物进行了分析;通过增重法对合金的氧化速率进行了计算;通过扫描电镜(SEM)对合金基体和氧化层进行了形貌和元素面分布分析。与只添加Y2O3粉末的合金相比,同时添加两种第二相颗粒的合金呈现出了协同效应,基体表面生成了Cr-O和Al2O3两种氧化膜,表现出了更好的抗氧化性能。     

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。     

Ni-Cu-Fe-Al合金在850℃空气中的氧化行为

为研发铝电解惰性阳极连接导杆新材料,采用粉末冶金法制备Ni-Cu-Fe-Al四元合金,在850℃的空气气氛中进行氧化实验,并用XRD、SEM、EDS等测试设备对其表面氧化膜的成分、形貌和组成进行分析.结果表明,在该合金表面形成的氧化膜连续、致密,分为内、中、外三层,外层以铜镍复合氧化膜为主,中间层分布着岛状的铁氧化物,其中含有一定数量的NiFe2O4尖晶石相,内层为连续致密的Al3O3膜,能阻碍元素扩散,从而有效提高合金的高温抗氧化性能.     

硫酸浓度对多孔氧化铝膜的影响

在H2SO4电解液中对高纯铝箔进行阳极氧化,考察分析了电解液浓度对多孔阳极氧化铝膜的影响,结果表明:随硫酸电解液浓度的增加,纳米孔孔径逐渐增大,孔密度降低,孔的有序性先提高后降低;采用23 V直流电压进行阳极氧化,电解液浓度为0.6~1.0 mol/L时制得的氧化铝膜孔径均匀性及有序度均较好,尤其以0.8 mol/L H2SO4最佳;阳极氧化铝膜的厚度随电解液浓度的提高而增大;电解液浓度过高易于将铝箔快速击穿。     

NiCrAlY涂层对镍基单晶高温合金氧化性能的影响

采用磁控溅射方法在镍基单晶高温合金基体上沉积NiCrAlY微晶涂层.用热重分析(TGA)、X射线衍射(XRD)、扫描电镜(SEM)等手段研究了镍基单晶高温合金及其NiCrAlY微晶涂层在900～1100℃静止空气中的氧化行为.结果表明,镍基单晶合金及其微晶涂层在900℃表现出相同的增重规律,即经初期快速增重后,两者的氧化增重都变得非常平缓;在1000℃,单晶合金的氧化膜不断剥落,使动力学曲线上下起伏,而微晶涂层经初期快速增重后,动力学曲线趋于平缓;在1100℃,单晶合金由于氧化增重远大于氧化膜剥落所造成的失重,使氧化动力学曲线在整个氧化过程中都呈迅速增长趋势,而微晶涂层的氧化动力学基本符合抛物线规律.单晶合金表面形成含Al2O3、Cr2O3、NiO、CrTaO4和Ni(Al,Cr)2O4尖晶石等的复合氧化膜.施加NiCrAlY微晶涂层后,镍基单晶合金表面形成连续、致密且结合良好的单一氧化物Al2O3,使合金的抗氧化性能明显提高.     

烧结镍基高温合金丝网多孔材料的抗氧化性能研究

采用静态增重法,测试了两种不同尺寸的烧结镍基高温合金丝网多孔材料样品及致密单丝样品在900℃下的氧化动力学曲线与氧化速率;采用9410型全自动压汞仪测试多孔小样品的表面积,同时通过透气系数计算其表面积,并据此对多孔小样品的氧化速率进行修正;用SEM、EDS及XRD等手段观察分析多孔样品氧化100 h后的显微形貌与氧化物的组成情况。结果表明:经过100 h氧化实验,大、小多孔样品的氧化速率为单丝样品的7倍左右;多孔小样品修正后的氧化速率远远小于修正前的氧化速率,也小于单丝样品的氧化速率;多孔样品的表面氧化物呈球形,分布较为均匀,其组成主要为Ni Cr_2O_4。     

钙盐浓度对复合氧化法制备多孔二氧化钛涂层表面结构的影响

为了分析微弧氧化电解液中钙盐浓度对复合氧化法(即预氧化和微弧氧化复合处理)制备多孔二氧化钛涂层表面结构的影响，利用X射线衍射、扫描电镜及附带的能谱对涂层的表面相结构、形貌及元素组成进行了观测与分析，利用图像分析软件对涂层表面孔隙率进行测试。结果表明：复合氧化法制备的多孔二氧化钛涂层表面均含有单质钛、锐钛矿型二氧化钛和金红石型二氧化钛：钙盐浓度的变化对涂层表面结构有一定影响，随着钙盐浓度的增加，涂层中锐钛矿型二氧化钛相对含量减少，金红石型二氧化钛相对含量增加；涂层表面的钙、磷元素含量降低，钙磷原子比增加：在所选钙盐浓度下，表面孔隙率的变化不十分显著。     

Thermal oxidation behavior of an Al-Li-Cu-Mg-Zr alloy

The chemical composition of oxide films formed during thermal treatments of an Al-Li-Cu-Mg-Zr alloy has been studied by means of Auger electron spectroscopy and X-ray photoelectron spectroscopy. The oxide layers formed after oxidation of 2.5 minutes to 30 minutes at 530 °C in lab air have been characterized. In the early stages of oxidation the surface is composed of both the lithium rich oxides and magnesium rich oxides. However, after longer oxidation times the oxidation of lithium becomes predominant and the air/oxide interface is completely covered by lithium compounds. Oxidation products formed on the alloy surface have been studied by X-ray diffraction analysis. The following three phases, namely, Li₂CO₃, α-Li₅AlO₄, and γ-LiAlO₂, were identified. During heat treatment in lab air at 530 °C and at atmospheric pressure the dominating reaction product is Li₂CO₃. Due to the selective oxidation of lithium a soft surface layer is developed. The width of the soft layer formed during solution heat treatments carried out in lab air and in salt bath environments has been determined by microhardness measurements. The lithium concentration profiles were calculated from a diffusion equation. The depletion of alloying elements from the near surface region during heat treatments has been investigated using energy dispersive X-ray analysis. The oxide morphology was examined using scanning electron microscopy and optical microscopy.     

X-Ray Photoelectron Spectroscopy Depth Profiling of Electrochemically Prepared Thin Oxide Layers on Duplex Stainless Steel

The surface oxidation of duplex stainless steel (DSS 2205) was studied by X-ray photoelectron spectroscopy (XPS). The experiments were performed on the alloy after controlled oxidation in a chloride-enriched solution at controlled potentials. The evolution of the passive film formed on the DSS in a chloride solution was studied using cyclic voltammetry with XPS surface characterization at selected potentials. The evolution of the oxide films and its specific compositions formed on the DSS was studied as a function of depth. Fe/Cr oxidized layers and oxide thicknesses were observed and correlated with the various potentiostatic potentials. The importance of Mo and Cr inside the oxide films in this article is studied and described, whereas their role in the protective layer, as oxides, is significant.     

Wear resistance of the oxide layers formed on AK9pch silumin by microarc oxidation in an electrolyte modified by silicon dioxide nanoparticles

The structure, the phase composition, the surface morphology, the microhardness, and the tribological characteristics of the oxide layers of various thicknesses formed on AK9pch alloy during microarc oxidation are studied. A positive influence of a small addition (5 g/L) of nanosized silicon dioxide to an electrolyte on these characteristics of the oxide layers is revealed.     

Fundamental studies of copper anode passivation during electrorefining: Part II. Surface morphology

Passivation of commercial copper anodes and pure copper has been previously analyzed by performing electrochemical measurements. Chronopotentiometry results revealed four characteristic regions involving I—active dissolution, II—prepassivation, III—passivation onset, and IV—passivation, for commercial copper anodes, while only active dissolution was observed for pure copper under the conditions employed. In order to establish the relationship between surface morphology and passivation response, scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM), and energy dispersive X-ray spectroscopy (EDS) were applied to characterize morphology of the product layers formed on a commercial copper anode surface for the distinctive electrochemical regions. The morphology studies suggested that the formation and stability of copper oxide surface films are critical to the onset and development of passivation. The structure and porosity of the slimes layer present in the outer layer of the anode influence the stability of copper oxide surface films which dominantly control the passivation response.     

固溶工艺对6061铝合金硬质阳极氧化膜层质量的影响

采用显微硬度测试、金相和扫描电子显微分析,研究了固溶工艺对6061硬质阳极氧化膜层厚度、硬度、均匀性、致密度的影响。结果表明:阳极氧化膜因内外表面受到电解液的腐蚀程度不同而表现为氧化膜的硬度自膜层表面到基体逐渐升高。固溶工艺的改变对阳极氧化膜的厚度均匀性无显著影响,氧化膜自身的成分结构决定了其膜层厚度的均匀性。试样在530℃×3 h下采用水冷的方式所获得的硬质氧化膜与基体结合平整,不存在针孔、疏松等缺陷,表面无孔残蚀现象。提高固溶温度,虽然能使强化相Mg2Si、第二相质点等全部回溶到基体里,但因形成粗晶组织,使晶粒度极为不均匀。在而后的阳极氧化过程中造成氧化膜的成长速度不一致,生长快的氧化膜和生长慢的氧化膜之间存在一定的内应力,这种内应力在一定条件下转化为微裂纹,因而使得氧化膜层质量下降,硬度降低。     

K2ZrF6含量对ZrH1.8表面微弧氧化阻氢膜层的影响

采用微弧氧化技术在ZrH_1.8表面制备阻氢膜层,研究在Na₅P₃O₁₀-NaOH-Na₂EDTA电解液体系中K₂ZrF₆含量对膜层组织结构和阻氢性能的影响。借助场发射扫描电子显微镜(FESEM)和X射线衍射仪(XRD)分析膜层的微观结构和物相组成。采用涂层测厚仪对膜层的厚度进行测量,通过真空脱氢实验表征膜层的阻氢性能。相比未加入K₂ZrF₆时,电解液中添加适量K₂ZrF₆有助于改善膜层的表面质量,减少膜层中微孔和裂纹等缺陷的出现。XRD分析表明,不同K₂ZrF₆浓度时ZrH_1.8表面微弧氧化制备的膜层均主要由m-ZrO₂,t-ZrO₂和少量c-ZrO₂相组成。膜层厚度和氢渗透降低因子(PRF)随K₂ZrF₆浓度的增加均呈先增大后减小趋势,当K₂ZrF₆为4g·L^-1时,膜层的厚度最大为68.7μm,PRF最大为13.1,且膜层中大尺寸缺陷较少,添加K₂ZrF₆制备的陶瓷膜的阻氢性能均得到提高。K₂ZrF₆添加剂的加入可以使ZrH_1.8表面微弧氧化膜层的厚度增大,致密性增强,进而阻氢性能提高,膜层表面质量也得到改善。     

Influence of Nanometric Ceria Sol-gel Coating on Oxidation Behavior of Chromium at 1000℃

 Isothermal oxidation behavior of chromium with and without nanometric sol-gel CeO2 coating is studied at 1000℃ in air. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) are used to examine the surface morphology and microstructure of their oxide films. It is found that ceria coating greatly improves the anti-oxidation property of chromium. Laser Raman spectrometer and X-ray diffraction spectrometer (XRD) are also used to study the stress level in oxide films formed on ceria-coated and ceria-free Cr. Secondary ion massive spectrum (SIMS) is used to examine Cr, O and Ce element distribution in depth in oxide films. Results show that nano-ceria application greatly reduces the growing speed and grain size of Cr2O3 film, and his fine grain-sized Cr2O3 film probably has better high temperature plasticity, i.e. oxide film relieves part of the compressive stress by means of creeping. Meanwhile, CeO2 changes the oxide film growing mechanism from predominant cation outward diffusion to anion inward diffusion. XRD and Raman testing results both show the stress declination effect due to nano-CeO2 application, and their discrepancy is analyzed concerning to the rare earth effect.