Microstructure,adhesion and growth kinetics of protective scales on metals and alloys

Currentunderstanding of the complex interrelationships among growth kinetics, microstructure, and adhesion of protective Cr₂O₃ and Al₂O₃ scales is critically reviewed. Similarities and differences in the behavior of these two systems are highlighted. The morphology of the alloy-scale interface appears to be a critical factor. Recent ideas are advanced to interpret the effect of oxygen-active elements on the development of a tortuous interface conducive to improved scale tenacity.This work was supported by the Director, Office of Energy Research, Office of Basic Energy Sciences, Materials Sciences Division of the U.S. Department of Energy under Contract No. DE-AC03-76SF00098.Deceased.on leave to Industrial Materials Research Institute, NRC, Montreal, Quebec, H4C 2K3 Canada.     

Protective effect in sulfuric acid media of alumina and ceria oxide layers electrodeposited on stainless steel

The influence of thin layers of Al₂O₃ and Ce₂O₃-CeO₂, electrodeposited on stainless steel OC4004, on the corrosion behaviour of the systems Al₂O₃/SS, Ce₂O₃-CeO₂/SS and Al₂O₃-Ce₂O₃-CeO₂/SS has been studied in sulfuric acid medium. A pronounced stabilizing effect on the passive state of steel and enhancement of its corrosion resistance has been established both for the samples as deposited and for the thermally treated Ce₂O₃-CeO₂/SS systems. In comparison to them the layers of Al₂O₃ have a substantial impact on the corrosion resistance of the Al₂O₃/SS system only in the cases when the system is not subjected to thermal treatment. The consecutive deposition of Al₂O₃ and Ce₂O₃-CeO₂ films on SS gives as a result an outstanding corrosion-protective effect, whereupon the corrosion potential of the system Al₂O₃/Ce₂O₃-CeO₂/SS is shifted in positive direction with ∼ 0.3 V for the samples as deposited and with ∼ 1 V—for the thermally treated samples. The so established favourable effect has been explained by the increased concentration of chromium oxides in the surface passive film, caused by the presence of cerium oxides, as well as by their action as cathode, effective with respect to the reduction corrosion reaction, shifting strongly the potential (at which this reaction is occurring) in positive direction.     

Carbon transport through oxide scales on Fe-Cr alloys

The penetration of carbon through Cr₂O₃ layers was studied for a series of different Fe-Cr alloys using a radioactive tracer method. Preoxidized samples were exposed at 900°C for 700 hr in a H₂ -H₂O -CO-CO₂ atmosphere tagged with¹⁴C; carbon penetration profiles were then determined, and the lateral distribution of carbon was observed by autoradiography. Even minute amounts of carbon (0.05 ppm) within the scale and in the alloy could be detected. The carbon uptake into different Fe-Cr alloys decreased with increasing Cr content to a minimum for the alloys with 12.5–20% Cr, indicating low porosity and good adherence of the Cr₂O₃ layers. Poor scale adherence was observed for Fe-10% Cr but could be improved by Ce additions. Porosity increased with contents >20% Cr of the alloys. Pore formation could be induced by impurities, e.g., SiC particles distributed on the surface.     

Nano-grain Al2O3 crystals grown by sputtering of aluminium on CoCrPt thin films for potential application in ultra-high-density recording media

Designing supraceramic assemblies based on Al₂O₃ has remained a challenge due to the problems associated with the suitable dispersion in neat compounds and ability to control the preferred orientation in a unique fashion. Herein, granular HCP-(CoCrPt)_100−X(Al₂O₃)_X (X represents the percent weight) thin films with Si(1 0 0) substrates have been fabricated using sputtering technique followed by annealing treatment. Structural and magnetic properties of thin film have been investigated for potential application in magnetic recording media. It was shown that coercivity increased from 0.5 to 2.5 kOe by increasing the nano-grain Al₂O₃ content in the CoCrPt magnetic layers. In CoCrPt-Al₂O₃ thin films coercivity of 2.5 kOe has been obtained with increasing the Al₂O₃ content from 3 to 13 wt.% in the annealed thin films. The structural properties of the samples were studied using X-ray diffraction (XRD) and transmission electron microscope (TEM) equipped with selected area electron diffraction (SAED). The magnetic properties of the samples were measured with a vibrating sample magnetometer (VSM). The VSM results showed that the HCP-CoCrPt-Al₂O₃ granular films are a promising candidate for ultra-high-density recording media because of its low Al₂O₃ content and simple manufacturing process.     

The formation of aluminum oxide scales on high-temperature alloys

This paper is a brief review of the extensive literature relating to the formation of protective —Al₂O₃ scales on alloys at high temperature. Emphasis is placed on the proposed mechanisms of scale growth based on observations of scale morphologies and microstructures, inert-marker experiments and the distribution of oxygen isotope tracers within thermally-grown oxides. Attention is also given to the determination of ionic-transport mechanisms by electrochemical methods and to the effects of reactive elements such as yttrium in modifying ionic-diffusion processes.     

包覆量对铝酸锶复合包覆效果的影响

目的对铝酸锶进行复合包覆处理,以提高荧光粉的抗水解性能。方法采用液相水解法在铝酸锶表面包覆SiO2/Al2O3膜,并对膜层进行耐水性、发光性能测试及形貌分析,研究包覆量对包覆效果的影响。结果包覆量对包膜效果有着重要的影响。包覆量太低,荧光粉的耐水性能受到限制,很容易发生水解;包覆量太高,会影响荧光粉的发光性能,发光亮度降低。结论要想得到包膜效果较好的产品,SiO2和Al2O3占铝酸锶的质量百分比最好控制在5%左右。     

Reactive-element effect of electrodeposited Y2O3 oxide films on the oxidation of Fe−25Cr and Fe−25Cr−10Al alloys

Thin Y₂O₃ films were deposited by the electrochemical deposition-pyrolysis process on Fe–25Cr and Fe–25Cr–10Al alloys. The influence of the films on the oxidation behavior of the alloys was studied at 850°C and 1000°C. The results showed that Y₂O₃ films remarkably decreased the oxidation rate of Cr₂O₃-forming alloys and spallation of the scales, but they did not decrease the oxidation rate of the Al₂O₃-forming alloys, although they do reduce the spallation of Al₂O₃ scales. Y₂O₃ films remarkably change the morphology of the scales on both alloys, depending on the oxidation temperatures. These results show that the reactive-element effects of Y₂O₃ films on the Cr₂O₃ formers and Al₂O₃ formers are different.     

Investigation of residual stress effects in an alloy reinforced ceramic/metal composite

This study aims at investigating the thermal expansion behavior and internal residual strains in metal reinforced ceramic matrix composites (CMCs). A variety of Al₂O₃/A356 CMCs composites with an interpenetrating network structure and varying metal content, ranging from 10 to 40 vol.%, were produced using the pressure infiltration technique of Squeeze casting. Values of coefficients of thermal expansion (CTEs) were found to vary significantly with temperature, indicating an influence of the flow characteristics of the metal. Comparisons are made with well known methods for predicting CTEs values of metal/ceramic composites. The overall strain was found to increase with temperature and scaled proportionally with the metal content of the composite. Comparisons were also made with non-infiltrated porous ceramic preforms and a pure metallic sample. The uniform heating and cooling curves for the composite samples were found to exhibit hysterisis. Residual stress analysis and failure simulation were performed based on thermomechanics and the finite element method (FEM). This analysis is often utilized for the analysis of stress distribution or deformation of a structure. High angle X-ray and CTEs mismatch equation analysis were utilized to analyze the residual stresses at the ceramic/metal interface of the Al₂O₃/A356 composites. The relationship of residual stresses and the contact area of the ceramic/metal interface are also discussed.     

Effect of Al and Ce oxide layers electrodeposited on OC4004 stainless steel on its corrosion characteristics in acid media

The changes in the corrosion characteristics of stainless steel OC4004 in 0.1 M HNO₃ after electrodeposition of thin Al and Ce oxide films on it has been investigated. The Ce₂O₃–CeO₂ layers have been found to possess a pronounced stabilizing effect on the steel passive state and on its corrosion resistance, respectively, whereas the Al₂O₃ layers do not improve considerably the corrosion behaviour of the SS/Al₂O₃ system. A twice-lower corrosion current was observed with a ternary SS/Al₂O₃/Ce₂O₃–CeO₂ system in the passive region, while the zones of potentials, where the steel is in a stable passive state, are not changed. The obtained results permit the assumption that the cerium oxides layer acts as an effective cathode playing a determining role with respect to the improvement of the corrosion behavior of the steel. It has been concluded that when the SS/Al₂O₃/Ce₂O₃–CeO₂ system is used in media containing nitric acid, the corrosion will proceed at potentials where the passive state of steel would not be disturbed.     

Effect of the increase in the entrance convergent section length of the gun nozzle on the high-velocity oxygen fuel and cold spray process

Nozzle geometry, which influences combustion gas dynamics and, therefore, sprayed particle behavior, is one of the most important parameters in the high-velocity oxygen-fuel (HVOF) thermal spray process. The nozzle geometry is also important in the cold spray method. The gas flows in the entrance convergent section of the nozzle exhibit a relatively higher temperature and are subsonic; thus, this region is most suitable for heating spray particles. In this study, numerical simulation and experiments investigated the effect of the entrance geometry of the gun nozzle on the HVOF process. The process changes inside the nozzle, as obtained by numerical simulation studies, were related to the coating properties. An Al₂O₃-40 mass% TiO₂ powder was used for the experimental studies. The change in entrance convergent section length (rather than barrel part length or total length) of the gun nozzle had a significant effect on the deposition efficiency, microstructure, and hardness. The deposition efficiency and hardness increased as this geometry increased. On the other hand, the calculated and measured particle velocity showed a slight decrease. This effect on the HVOF process will also be applied to the nozzle design for the cold spray method.     

HOPG上ALD沉积Al2O3介电薄膜的生长行为研究

本文采用原子层沉积(ALD)的方法,选择三甲基铝(TMA)和H₂O₂作为反应前驱体,在高定向热解石墨(HOPG)基体上沉积Al₂O₃。系统研究了反应温度和生长周次对Al₂O₃生长行为的影响。研究表明：受HOPG表面饱和成键的影响,Al₂O₃在衬底表面处形核困难,在生长初期主要表现为台阶处择优生长,其形态为线状结构。当沉积100周次Al₂O₃时,其中在沉积温度为50 °C、150 °C和200 °C时呈现为纳米线状结构,而在100 °C时呈现为非连续薄膜。随着生长周次的增加,不同温度下沉积态Al₂O₃都趋于形成连续薄膜,表明其生长行为发生了由三维岛状生长模式向二维平面生长模式的转变。分析认为,生长模式的转变是由纳米线状结构横向生长造成的;横向生长速率主要受生长温度影响。拉曼结果表明：沉积后的石墨烯层结构未受影响,可保留其原有的优越性能。     

Oxide scale adhesion and impurity segregation at the scale/metal interface

The chemistry at scale/metal interfaces was studied using scanning Auger microscopy after removal of the scale in ultra-high vacuum using an in situ scratching technique. Al₂O₃ and Cr₂O₃ scales formed between 900°C and 1100°C on Fe-18 wt.% Cr-5 wt.% Al and on Ni-25 wt.% Cr alloys, respectively, were investigated. The adhesion of these scales was determined qualitatively by way of micro-indentation and scratching on the surface oxide. All of the alumina scales fractured to the same degree to expose the metal surface, regardless of the oxidation temperature. The chromia-forming alloy on the other hand, developed more adherent scales at lower oxidation temperatures. About 20 at.% sulfur was found at the metal surface in all cases, and its presence was not only detected on interfacial voids, but also on areas where the scale was in contact with the alloy at temperature. Results from this study clearly demonstrated that sulfur as an alloying impurity does segregate to the scale/alloy interface. However, for alumina scales and chromia scales, the effect of this segregation on oxide adhesion is noticeably different.     

新鲜和老化Pd/Al2O3密偶催化剂上催化C3H8转化催化性能

采用等体积浸渍法制备了以改性氧化铝为载体材料的Pd/Al₂O₃ 密偶催化剂, 并采用H₂程序升温还原(H₂-TPR), CO 化学吸附和X射线光电子能谱(XPS)对催化剂进行了表征. 在模拟尾气条件下对催化剂的总包反应及与C₃H₈相关的单反应活性进行了测试. 结果表明, 老化处理后活性PdO_x 数量下降, 并伴随有金属态Pd₀的产生. 老化后, 起燃温度(T₅₀)和完全转化温度(T₉₀) 分别提高了 76 oC和64 oC, 即催化剂低温活性比高温活性下降明显. 对比新鲜和老化催化剂上单反应活性, 结果表明, 老化后无水条件下有NO参与的反应的低温活性下降显著. 老化处理过程突出了NO对低温活性的抑制作用和H₂O对高温活性的促进作用.     

An approach to predict the solid film thickness possibly yielded from an alumina sol-gel liquid film

The Landau-Levich-Derjaguin (LLD) equation is widely used to predict the thickness of wet layer deposited on substrate by dip-coating. But it cannot effectively predict the solid film thickness yielded from the sol-gel liquid layer. Considering the solid content, the amount of solution sticking to the surface of substrate and the density of the sol-gel derived solids materials are the main factors determining the solid film thickness, a new approach capable of directly predicting what an oxide film thickness of a liquid layer on the substrate could yield without really sintering at high temperature was developed. It was found that the predicted and measured thicknesses for both compact and porous Al₂O₃ films were in good accordance. The approach uses very common testing techniques and does not concern the aspects such as solution composition, Newtonian or non-Newtonian fluid, withdrawal speed, viscosity, and liquid-vapor surface tension, etc. So the method is much timesaving and economical, and will be a good supplement for thickness determination techniques, especially under some circumstances where use of SEM, XRR, ellipsometer analyses are limited.     

La2O3含量对Al2O3/Cu基复合材料组织与性能的影响

以La₂O₃粉、Al粉、CuO粉为反应物原料、纯铜为基体,采用原位合成技术和近熔点铸造法制备颗粒增强Cu基复合材料,研究La₂O₃对Al-CuO体系制备的Cu基复合材料组织及性能的影响。结果表明：添加La₂O₃可获得纳米Al₂O₃颗粒,且弥散分布于Cu基体中,制备的材料组织更加细小、均匀,其材料的电导率及摩擦磨损性能明显提高。当添加0.6%wtLa₂O₃,复合材料的电导率达到90.2%IACS,磨损量达到最小,相比未添加La₂O₃,其导电率提高10.1%,磨损量减小36.6%。     

Studies on Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> high K gate dielectrics applied in a fully depleted SOI MOSFET

Al₂O₃/ZrO₂/Al₂O₃ gate stacks were prepared on ultrathin SOI (Silicon on insulator) substrates by ultrahigh vacuum electron beam evaporation and post-annealed in N₂ at 450°C for 30 min. Three clear nanolaminate layered structure of Al₂O₃(2.1 nm)/ZrO₂(3.5 nm)/Al₂O₃(2.3 nm) was observed with a high-resolution cross-sectional transmission electron microscope (HR-XTEM). High frequency capacitance voltage (C-V) characteristics of a fully depleted (FD) SOI MOS capacitor at 1 and 5 MHz were studied. The minority carriers determine the high frequency C-V properties, which is opposite to the case of bulk MOS capacitors. The series resistance of the SOI substrate is found to be the determinant factor of the high frequency characteristics of FD SOI MOS capacitors. This article is based on a presentation in “The 7th Korea-China Workshop on Advanced Materials” organized by the Korea-China Advanced Materials Cooperation Center and the China-Korea Advanced Materials Cooperation Center, held at Ramada Plaza Jeju Hotel, Jeju Island, Korea on August 24≈27, 2003.     

The Characteristics of Alumina Scales Formed on HVOF-Sprayed MCrAlY Coatings

HVOF MCrAlY (M=Ni, Co) coatings were isothermally oxidized in synthetic airbetween 850 and 1050°C for times up to 167 hr. During thermal spraying,aluminum and yttrium oxidized to form a fine oxide dispersion. The HVOFMCrAlY coatings exhibited a microstructure similar to ODS alloys. The finedispersion consisted of Al₂O₃ and aluminum–yttriumoxides. The oxidation experiments showed that the oxidation rate of HVOFcoatings was two times slower than the oxidation rate of VPS MCrAlYcoatings. The oxidation mechanism changed mainly in the transient-stage(no metastable modification of Al₂O₃ formed) and it wasassumed that the oxide dispersion hindered diffusion of various elementsfrom the bulk material during oxidation. The formation of the fine oxidedispersion also influenced the adherence of the oxide scale. Themicrostructures of the transient oxide scales were examined by X-raydiffraction (XRD) scanning electron microscopy (SEM), and transmissionelectron microscopy (TEM).     

Some observations on the effects of sulfur and active elements on the oxidation of Fe−Cr−Al alloys

A very-low-sulfur-content industrial Fe–Cr–Al alloy has been used both as a baseline and as a charge material for laboratory metlts with variable sulfur and rare-earth additions. No significant differences in behavior were observed in cyclic oxidation tests on 1-mm-thick coupons at 1100°C, except for an excessive rare-earth content, which led to accelerated scale growth. At 1300°C, alloys without rare-earth additions developed high growth stresses in the oxide, leading to large tensile strains in the substrate. The oxide-metal interface in the low-sulfur (<2ppm) material resisted these stresses and the oxide remained adherent. However, as little as 4ppm S was sufficient to cause considerable spalling. Rare-earth additions markedly reduced growth stresses and eliminated both dimensional instability and spalling.     

Effect of Al2O3 reinforcement and precipitates on corrosion behaviour of 2618 and 6061 aluminium MMCs

ABSTRACT

The corrosion resistance features of two different Metal Matrix Composites based on 6061 and 2618 aluminium alloys reinforced by 20% Al₂O₃ particles by stir casting process, were studied in 3.5% NaCl and compared. The composites and their respective base alloys were characterised in terms of microstructure by optical and scanning electron microscopy and in terms of corrosion resistance by polarisation curves and electrochemical impedance. Results show how the presence of Al₂O₃ has different effects depending on matrix composition. In 6061 MMC, Al₂O₃ promotes the formation of Mg₂Si which has a cathodic behaviour altering the pitting susceptibility of the composite. In 2618 MMC, the high content of Cu induces a strong uniform attack. The subsequent increase in the Open Circuit Potential caused a pitting attack.     

Al2O3陶瓷表面化学镀铜工艺及其低温连接

进行了Al2O3陶瓷表面的化学镀铜处理,制定了前处理流程.研究了硫酸铜浓度、甲醛浓度、施镀温度、施镀时间等对镀层沉积速率的影响,对镀层进行了金相分析,在此基础上得到化学镀铜的优化工艺.进行了镀铜后Al2O3陶瓷低温钎焊工艺试验,研究了不同化学镀工艺条件对接头组织及力学的影响.结果表明,在试验条件下,随着焊接温度升高,接头致密度变差;焊接时间增加,焊缝宽度也增加;硫酸铜,甲醛浓度增加,镀层厚度增加,相对影响了钎焊焊缝宽度和质量.