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ISSN 1005-4537
CN 21-1474/TG
创刊于 1981 年 (双月刊)
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  2009年, 第29卷, 第4期 刊出日期:2009-08-20 上一期    下一期
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Effect of Alloyingm Additions on the Oxidation of High Speed Steels under Dry and Wet Conditions
中国腐蚀与防护学报. 2009, 29 (4): 241-247.  
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An investigation has been carried out into the effects of chromium and vanadium content on the oxidation rate and on the adhesion of oxide scales grown on three different chemical compositions of high speed steels under dry and wet conditions. The oxidation tests were carried out in a thermobalance at 650 ℃ for up to 14.4 ks.  The mass gain of the specimens increased with increasing contents of water vapour. Alloy composition had no effect on the oxidation rate in dry conditions. The “adhesion” of the oxide scale was determined using indentation with a Rockwell C diamond and the pull adhesion test to determine the interfacial toughness and the tensile strength of the oxide metal bond, respectively. Generally, the results of the investigation indicated that oxide adhesion was lowest for the specimens exposed to dry conditions, and that with increasing water vapour content, the scale was more adherent. Indentation test results showed that an increase in the V concentration was deleterious to oxide adhesion in both the dry and wet environments, whereas an increase in the Cr-content had little effect on adhesion.

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High Temperature Oxidation as a Production Route for Electronic Materials
中国腐蚀与防护学报. 2009, 29 (4): 248-252.  
摘要   PDF (1494KB)

Oxidation of metallic components often results in degradation and structural failure, prevention is therefore an important topic. On the other hand, oxidation process creates new products such as metal oxides, can be used as a production route. A well-known process in semiconductor industry is that oxidation in dry or wet atmosphere is a popular way for growth of multi-functional SiO2 films on Si wafers. Recently, oxidation processes under controlled conditions (atmosphere, temperature, and time) are used to prepare various oxides, carbides, or nitrides with micro-/nano-structures, well-defined composition, dimension, shape and properties. The use of oxidation now includes thin film and nano-/micro-sized devices, and porous oxides for sensing and catalysis purposes. This paper introduces the research activities in the authors' group on applications of oxidation as a tool for synthesis of functional materials.

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Complete Maps for the Internal Oxidation of Ideal Ternary Alloys Forming Insoluble Oxides under High Oxidant Pressures
中国腐蚀与防护学报. 2009, 29 (4): 253-261.  
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This paper presents an analysis of the conditions of stability of the different forms of internal oxidation of ideal ternary A-B-C alloys, where A is the most noble and C the most reactive component, forming insoluble oxide and exposed to high pressures of a single oxidant. The treatment, based on an extension to ternary alloys of Wagner’s criterion for the transition from internal to external oxidation in binary alloys, allows to predict the existence of three different forms of internal oxidation. In fact, in addition to the most common kinds of internal attack, involving the coupled internal oxidation of B+C beneath external AO scales and the internal oxidation of C beneath external BO scales, a third mode, involving the internal oxidation of C beneath external scales composed of mixtures of AO+BO, becomes also possible under special conditions. A combination of the boundary conditions for the existence of these different types of internal oxidation allows to predict three different kinds of complete maps for the internal oxidation in these systems, one of which involves only two modes, while the other two involve all the three possible modes of internal oxidation.

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Metal Dusting-Mechanisms and Preventions
中国腐蚀与防护学报. 2009, 29 (4): 262-276.  
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Metaldusting attacks iron, low and high alloy steels and nickel-or cobalt-base alloys by disintegrating bulk metals and alloys into metal particles in a coke deposit. It occurs in strongly carburising gas atmospheres (carbon activity aC>1) at elevated temperatures (400 ℃~1000 ℃). This phenomenon has been studied for decades, but the detailed mechanism is still not well understood. Current methods of protection against metal dusting are either directed to the process conditions-temperature and gas composition-or to the development of a dense adherent oxide layer on the surface of the alloy by selective oxidation. However, metal dusting still occurs by carbon dissolving in the base metal via defects in the oxide scale. The research work at UNSW is aimed at determining the detailed mechanism of metal dusting of both ferritic and austenitic alloys, in particular the microprocesses of graphite deposition, nanoparticle formation and underlying metal destruction. This work was carried out using surface observation, cross-section analysis by focused ion beam and electron microscopic examination of coke deposits at different stages of the reaction. It was found that surface orientation affected carbon deposition and metal dusting at the initial stage of the reaction. Metal dusting occurred only when graphite grew into the metal interior where the volume expansion is responsible for metal disintegration and dusting. It was also found that the metal dusting process could be significantly changed by alterations in alloy chemistry. Germanium was found to affect the iron dusting process by destabilising Fe3C but increasing the rate of carbon deposition and dusting, which questions the role of cementite in ferritic alloy dusting. Whilst adding copper to iron did not change the carburisation kinetics, cementite formation and coke morphology, copper alloying reduced nickel and nickel-base alloy dusting rates significantly. Application of these fundamental results to the dusting behaviour of engineering alloys is discussed.

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Impurity Segregation at TGO/Bondcoat Interfaces and Its Effect on TGO Adherence
中国腐蚀与防护学报. 2009, 29 (4): 277-285.  
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Impurity segregation at the interfaces between thermally grown aluminum oxide and a few coatings deposited on single crystal Ni-based superalloys are reviewed. Results are compared with studies made at oxide/metal interfaces formed on model Al2O3-forming alloys. The coatings were NiPtAl on CMSX4 or AM1 with two different bulk sulfur contents, and NiCoCrAlY on PWA1484. Auger electron microscopy was used to study the chemistry at the TGO/coating interface after portions of the oxide scale were removed in ultra high vacuum by scratching the oxidized sample. The extent of oxide spallation in relation to the scratch width was utilized to evaluate the interfacial strength, which was then related to the interface chemistry, particular its sulfur level. Results show strong relationship between sulfur segregation and the alloy substrate composition. This relationship is discussed in terms of the effects of Pt, Hf, Y and Cr and the alloy sulfur content.

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Effect of Zr on the Oxidation Properties of Fe3Al Intermetallic Compound
K. Przybylski S. Chevalier P. Juzoń
中国腐蚀与防护学报. 2009, 29 (4): 286-292.  
摘要   PDF (3454KB)

This review is concerned with the effect of the addition of zirconium as a third element on the heat-resisting properties of Fe3Al intermetallic compounds and explains their high-temperature oxidation mechanism. The Fe3Al and Fe3Al-0.05Zr specimens were isothermally oxidized in the temperature range of 1173~1473 K in synthetic air for 100 h. The formation of the alumina layer approximately obeyed the parabolic rate law, with the exception of short initial stage. The parabolic rate constant values for the Zr-doped Fe3Al decreased at all tested temperatures. Fe3Al revealed massive spallation, whereas Fe3Al-Zr produced a flat, adherent oxide layer. The microstructure investigations of the alumina scales grown thermally on the Fe3Al-Zr alloy by means of SEM-EDS showed that they were 1.5~2 μm thick and consisted of a small inner columnar layer and an equiaxed outer grain layer. Additionally, very fine (50~150 nm) oxide particles rich in Zr were found across the alumina scales. The addition of Zr significantly affected the oxidation behavior of Fe3Al by improving the adherence of the α-Al2O3 scale. TEM-SAD investigations of the alumina scales on samples prepared using the FIB (Focused Ion Beam) method confirmed the presence of small tetragonal zirconia grains near the scale/gas and alloy/scale interfaces, most of which were formed along alumina grain boundaries(gbs). Zr gb-segregation was found using HRTEM. The role of preferential formation of zirconium oxide along the alumina scale grain boundaries and the effect of Zr gb-segregation on oxidation and scale growth mechanisms were analyzed by means of two-stage oxidation experiments using 16O2/18O2. The SIMS oxygen isotope profiles for the Fe3Al-Zr alloy oxidized at 1373 K,\linebreak after two-stage oxidation experiments, revealed that oxygen anion diffusion is predominant compared to that of aluminum cation diffusion.

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Evidence for Vacancy Injection during the Oxidation of Iron
D.G.Lees R.Francis
中国腐蚀与防护学报. 2009, 29 (4): 293-295.  
摘要   PDF (528KB)

Iron discs have been oxidised at 890 ℃ on one side only, with the other side protected by an inert gas. The scale-metal adhesion was very good. Initially, scale-metal adhesion was maintained by the scale relaxing towards the metal but after a time which depended upon the initial metal thickness, oxide relaxation ceased and the inert face moved towards the scale-metal interface. When the face which was normally inert was covered with a non-growing oxide layer, the scale-metal adhesion deteriorated. The results show that vacancies which were produced by oxidation were annihilated within the metal, that the inert face played a part and that the scale-metal interface is not a good sink for vacancies.

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多弧离子镀(Ti, Al, Zr, Cr) N多元膜的高温氧化行为
赵时璐 张钧 刘常升
中国腐蚀与防护学报. 2009, 29 (4): 296-300.  
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采用多弧离子镀技术,用Ti-Al-Zr合金靶和Cr靶,在 W18Cr4V高速钢基体上沉积了(Ti, Al, Zr,\linebreak Cr)N多元膜,并进行了600 ℃,700 ℃,800 ℃和900 ℃短时(4 h)高温氧化实验及 700 ℃和800 ℃长期(100 h) 高温循环氧化实验。用扫描电镜 (SEM)、能谱(EDS)和X射线衍射(XRD)观察和分析样品表面氧化膜。结果表明,这种多元膜在短时(4 h)高温氧化条件下,800 ℃时仍具有良好的抗高温氧化性,XRD显示氧化膜主要为TiO2;在长期(100 h)高温氧化条件下,该多元膜的抗高温氧化温度大约为700 ℃左右

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钟洪彬 李美栓 周延春 王俊山 许正辉 张中伟 房学良
中国腐蚀与防护学报. 2009, 29 (4): 301-305.  
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从热力学角度出发,采用工程数学软件Matlab计算出了 在涉及超高温(2073 K以上)范围的宽温域内一些典型过渡金属 碳(硼)化物与氧反应的Δ G0,以及相应的平衡氧分压;在此基础上 绘制了2500 K时ZrC-ZrO2体系和SiC-SiO2体系的氧化物蒸气压图以及界面蒸气压随温度的变化曲线。依据上述热力学数据,可以了解不同碳化物的氧活性和平衡氧分压随温度的变化规律,以及ZrC-ZrO2和SiC-SiO2体系氧化物蒸气压特别是界面蒸气压的大小,对于深入了解改性C/C复合材料和超高温陶瓷的超高温氧化行为,特别是对于改性C/C复合材料中有效的抗氧化添加剂的选择有理论指导意义。

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Ti3Al基合金表面两种Cr1-xAlxN(x=0.18, 0.47)涂层热腐蚀性能
朱明 李美栓 周延春
中国腐蚀与防护学报. 2009, 29 (4): 306-311.  
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利用磁控反应溅射的方法在Ti3Al基合金表面制备了两种不同铝含量的Cr0.82Al0.18N与Cr0.53Al0.47N涂层,测试了这两种涂层在800 ℃(Na2SO4 + 25 mass %K2SO4)熔融盐膜下的热腐蚀动力学,并采用X射线衍射仪和带能谱的扫描电镜分析腐蚀产物相组成以及微观结构。结果表明,两种涂层均可降低Ti3Al基合金的热腐蚀速率;涂层热腐蚀产物主要为具有保护性的Cr2O3θ-Al2O3混合氧化膜,θ-Al2O3的含量随着涂层中Al含量上升递增;和-θ-Al2O3相比,Cr2O3在熔融硫酸盐中的稳定性更好,Cr0.82Al0.18N涂层抗热腐蚀性能优于Cr0.53Al0.47N涂层。

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Diffusion Barrier Coating System and Oxidation Behavior of Coated Alloys
Toshio Narita
中国腐蚀与防护学报. 2009, 29 (4): 312-313.  
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Recent Advances in the Quantitative Characterisation of Mechanical Scale Failure
中国腐蚀与防护学报. 2009, 29 (4): 313-314.  
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Environmental and Compositional Effects on the Hot-Corrosion Behavior of Ni-Based Alloys and Coatings
中国腐蚀与防护学报. 2009, 29 (4): 315-315.  
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Kinetic and Microstructural Analyses of Chromia Forming Alloys during Cyclic Oxidation
中国腐蚀与防护学报. 2009, 29 (4): 315-315.  
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High-temperature Oxidation Resistant Coatings Composed of YSZ Particles Packaged by Nano-Al2O3 Film
中国腐蚀与防护学报. 2009, 29 (4): 316-317.  
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Environmental Protection of Gamma Titanium Aluminides by Coatings
中国腐蚀与防护学报. 2009, 29 (4): 317-318.  
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Effect of Water Vapor on the Oxidation of Pt-modified Ni-22Al Alloys
中国腐蚀与防护学报. 2009, 29 (4): 317-317.  
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Oxidation and Coatings for Power Generation: New Super Ultra Critical Steam Turbines
F.J. Pérez
中国腐蚀与防护学报. 2009, 29 (4): 318-319.  
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Continuous Monitoring of Oxygen Chemical Potential on the Surface of Growing Scales and Its Application to High Temperature Oxidation of Metals
中国腐蚀与防护学报. 2009, 29 (4): 319-320.  
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Thin Oxide Film Growth during Final Annealing of Stainless Steels
中国腐蚀与防护学报. 2009, 29 (4): 320-320.  
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