Characterization of thermally cycled alumina scales

Abstract

Cross-sectional transmission electron microscopy was used to characterize the alumina scales formed on several Ni-base alumina-formers. The alumina scale microstructure of Ni–20at%Cr–19Al–0.05Y after 100, 1 h cycles at 1,100°C was compared to an isothermally-grown scale. Despite being near the onset of mass loss in cyclic testing, very few defects were noted in either scale microstructure. The more adherent scales that form on Hf-doped NiAl and Ni–49at%Al–2Cr were also characterized. With the addition of Cr, the formation of α-Cr precipitates at the metal–oxide interface coincided with increased long-term scale spallation. No similar precipitation mechanism was observed to be associated with scale spallation on NiCrAlY.     

环氧富锌底漆不挥发分中金属锌含量测定及探讨

介绍了测定环氧富锌底漆不挥发分中金属锌含量的方法,探讨了影响实验结果的主要因素,并对现行富锌底漆标准规定的测定方法条件进行了一些调整,以便得到满意的实验结果。     

Study of optical losses of Nd doped silicon rich silicon oxide for laser cavity

Planar and strip-loaded waveguides made of Nd³⁺-doped silicon rich silicon oxide (SRSO) have been fabricated by reactive magnetron sputtering and characterized, with special emphasis on the optical losses. The refractive index of Nd³⁺-doped SRSO layers was measured by both m-line method and reflectance spectroscopy. From these measurements, the Si volume fraction and also the Nd³⁺-doped SRSO index dispersion were deduced by using the Bruggeman model. At 1.06 μm, Nd³⁺-doped SRSO refractive index was equal to 1.543 corresponding to a Si volume fraction of 6.5%. The opto-geometrical parameters of waveguides have been studied in order to obtain single mode waveguides at 1.06 μm. The optical losses are measured as a function of wavelength and are found to be about 0.8 and 0.4 dB/cm at 1.06 and 1.55 μm, respectively. Measurements are confirmed by theoretical models showing that the losses are essentially attributed to surface scattering. From these optical loss values, a percentage value of the Nd active concentration superior of 14.5% was deduced to have a positive modal gain of waveguide.     

High temperature carbon corrosion in solid oxide fuel cells

Abstract

Operating conditions in a current design for a planar geometry oxide fuel cell plant are briefly reviewed and the danger of encountering “metal dusting” conditions identified. Laboratory tests were designed to produce accelerated metal dusting by exposing heat resisting alloys to a CO–26 H₂–6 H₂O (vol. pct) gas mixture at 680°C under thermal cycling conditions. The hot gas composition corresponded to a_c = 2.9 and an oxygen potential high enough to oxidise chromium and aluminium, but not iron or nickel. The alloys tested included ferritic and austenitic chromia formers and two ferritic alumina formers, all with electropolished surfaces. Thermal cycling of the chromia formers led to oxide scale damage followed by internal carburisation, metal dusting and coking. This failure occurred very rapidly on most austenitic materials (Alloy 800, Inconel 601, 690, 693, Alloy 602CA), but did not commence until after approximately 50 one-hour cycles for the ferritic steel Fe–27Cr–0.001Y (wt %). The alloy with the best performance was Inconel 625, which was still protected by its Cr₂O₃ scale after 500 cycles. The alumina forming alloys showed superior performance, with no damage apparent after 1200 cycles. Additional tests using ground metal surfaces showed that they were more resistant to dusting in the case of chromia formers, but more susceptible in the case of alumina formers, metal dusting.     

Finite element analysis of the effects of comers on residual stresses in protective oxide scales

Finite element simulations are used to examine residual thermal stresses and strains in corner regions of protective Al₂O₃ scales on Fe₃Al specimens, both during cooling from oxide formation temperatures and during subsequent thermal cycling. The effects of a corner's radius of curvature and oxide thickness, as well as the impact of aluminide plasticity, are considered. Localized plasticity is found to have a major influence on net deformation and on the magnitude and location of maximum stress. As the ratio of corner curvature to oxide thickness (r_s/t) is reduced, stresses within the oxide corner shift from highly compressive to tensile and the location of the maximum principal stress moves from the substrate to the oxide scale. Based on these stress distributions prior to the development of any flaws, key implications about the tendencies for damage are addressed. The stress evolution during cooling and thermal cycling is presented; these results demonstrate the effects of temperature-dependent material properties. For the material behavior assumed in this study, thermal cycling does not cause significant stress relaxation.     

Morphological characteristics of oxide scales grown on H11 steel oxidised in dry or wet air

Abstract

The oxidation behaviour in dry and wet air of H11 steel was studied at 600 and 700°C by Thermo Gravimetric Analysis (TGA) and in situ oxidation in the specimen chamber of an Environmental Scanning Electron Microscope (ESEM) equipped with a hot stage specimen holder. The oxidation kinetics of H11 steels are quite sensitive to the presence of water vapour and, although the final mass gains show a good overall reproducibility, they are locally rather irregular. The morphology and microstructure of oxide scale are complex and often heterogeneous, particularly at 700°C. In situ oxidation tests permit to follow the evolution of oxide scales and to observe several growth modes of oxide scales. The diversity of the observed scale growth modes can explain the complexity and irregularity of scale growth mechanisms. Some additional in situ oxidation tests were performed in wet nitrogen. Morphology and growth modes of oxide scale grown in wet air and wet nitrogen differ strongly.     

聚合物-过渡金属氧化物纳米复合阴极材料的研究进展

聚合物－过渡金属氧化物纳米复合阴极材料在锂二次电池中是一类具有广阔应用前景的新型材料，本文综述了这类材料的制备方法和性能特征，分析了其导电机理，探讨了该研究领域的前沿问题。     

原子层淀积制备金属氧化物薄膜研究进展

原子层淀积(ALD)技术作为一种先进的薄膜制备方法近年来越来越得到重视,它能精确地控制薄膜的厚度和组分,实现原子层级的生长,生长的薄膜具有很好的均匀性和保形性,因而在微电子和光电子等领域有广泛的应用前景。本文综述了ALD技术的基本原理,及其在金属氧化物薄膜制备上的研究进展。     

Green synthesis of metal/C and metal oxide/C films by using natural membrane as support

A protocol aiming at making use of the huge amount of naturally existing wastes such as defoliation, pericarp and egg shell for nanostructured composite materials was proposed. In this study, a green synthetic route using naturally existing membrane as support was developed for the synthesis of nanostructured and porous metalor metal oxide-carbon composite films. Different metallic ions （Co2＋, Ni2＋, Fe3＋, Mn2＋ or Cu2＋） can be easily adsorbed onto egg membranes and the followed calcination process results in the formation of Co/C, Ni/C, Fe304/C, MnO/C or CulCu2OICuOIC composite films. The electrochemical studies demonstrate that such composite films would have potential applications in energy fields. This method would provide a general green concept for chemical synthesis and be beneficial to the global sustainable future.     

钛基贱金属氧化物涂层阳极的研究进展

介绍了钛基贱金属氧化物涂层阳极的发展概状。论述了贱金属氧化物涂层阳极技术发展的必然和要解决的关键问题。重点阐述了几种有代表性、具有广阔应用前景的贱金属氧化物涂层阳极，并对其未来的发展及应用前景进行了展望．     

TEM analysis of the growth of oxide scales at different temperatures in FeAl grade 3 intermetallic alloy

Abstract

Upon the isothermal oxidation of an ODS FeAl Grade 3 intermetallic alloy, a structured oxide scale is developed between 800 and 950°C. TEM studies have revealed a three-layered structure with a top nanoequiaxed alumina, a central alumina and a bottom Fe-Al spinel. At these temperatures, aluminium outward diffusion does not seem to be suppressed neither by the spinel sub-layer nor by the yttria present in the superalloy. However, the formation of metastable θ-Al₂O₃ seems to be significantly hindered. On the contrary, at 1000°C, the spinel phase no longer forms but a columnar alumina layer topped up with a nanoequiaxed structure. Yttria seems then to segregate at the scale/alloy interface and to randomly coarsen to produce an Y-Al oxide phase.     

Reagent control over the composition of mixed metal oxide nanoparticles

Binary (M¹ ? M² ? O) and ternary (M¹ ? M² ? M³ ? O) metal-oxide nanoparticles (NPs) have been prepared by thermal decomposition in benzyl ether of the appropriate M(acac)_n (M = Fe, Mn, Pd, Cu, Al, Gd) compounds in the presence of a mixture of oleic acid and oleylamine templating (surface capping) ligands, and 1,2-hexadecanediol as an accelerating agent. The metal percentage and the particle size were investigated as a function of the starting composition. The NP composition is controlled by the relative reaction rates of the particular precursors, such that prediction of NP composition from reagent ratios is not straightforward. However, understanding reaction rate limitations allows for alternative synthesis to be developed. In some cases, ligand exchange reaction and subsequent decomposition are possibly more important than thermal decomposition.     

High spatial resolution imaging of the segregation of reactive elements to oxide grain boundaries in alumina scales

Abstract

Although it is well established that reactive elements such as yttrium and hafnium can segregate to oxide/metal interfaces and oxide grain boundaries in thermally grown oxides, their distribution and role at these sites are less certain. For example, their effect on oxide growth, scale plasticity and spallation is still debated. It has also been reported that hafnium and yttrium rich oxide particles can be present within growing alumina scales and that the growth or shrinkage of these particles can affect the Y and Hf distributions in the aluminium oxide grain boundaries in their vicinity. Hence, we now report the use of very high spatial resolution imaging in the SuperSTEM electron microscope to investigate the distribution of Y and Hf in aluminium oxide grain boundaries at the atomic level.

The oxide scales studied were detached from Fe – 20Cr – 5Al alloy substrates doped with Y and Hf, which had been oxidised for up to 100 h at 1250°C in laboratory air. The scales were ion beam thinned prior to examination in the STEM, and a series of tilting experiments and through focal series were used to map out the distributions of the reactive elements. The influence of electron beam/sample interactions was also studied and some evidence for the movement of Hf and Y atoms along the grain boundaries to the surfaces of the thin oxide foils is also reported.     

Characterisation of oxide scales developed on high temperature resistant alloys in pure steam environments

Abstract

Steam oxidation of heat exchanger tubes and pipe work is of growing interest as research into the improvement of power plant efficiencies shows the need for much higher steam temperatures and pressures. This paper reports on the characterisation of the oxide scales grown during the steam oxidation of four alloys (T23, T92, TP347HFG and Inconel 740) in atmospheric pressure steam at four temperatures (600, 650, 700 and 750°C) for periods of 250, 500 and 1000 h. Three methods have been employed in analysing these scales: reflected light optical microscopy, scanning electron microscopy with energy dispersive X-ray analysis and X-ray diffraction.

The thickness, composition, morphology and spalling behaviour of the oxides differed with alloy composition, exposure times/temperatures and sample shapes. The ferritic steels exhibited the most severe oxidation, with the scales formed on these typically being triple-layered: an inner layer of Fe – Cr spinel, central layer of magnetite and outermost layer of haematite. However, the amount of haematite formed changed with the exposure time/temperature, alloy and sample orientation. In comparison TP347HFG and Inconel 740 showed significantly slower oxidation, with generally thin oxide scales (<5 µm) developing even at the highest exposure temperatures, though TP347HFG started to form some nodular growths after 1000 h exposure at the two higher temperatures.     

Organic solar cells with p-type amorphous chromium oxide thin film as hole-transporting layer

Efficient organic solar cells based on the blends of poly (3-hexylthiophene) (P3HT):fullerene derivative [6,6]-phenyl-C₆₁ butyric acid methyl ester (PCBM) composites have been fabricated by using the sputtered amorphous chromium oxide (ACO) film on fluorine-doped tin oxide (FTO) coated glass substrates as a hole-transporting layer (HTL). Through ACO layer sputtering temperature, film thickness and oxygen flow ratio optimization, the highest power conversion efficiency of 3.28% of FTO/ACO/P3HT:PCBM/Al solar cells on glass has been achieved under AM1.5G 100 mW/cm² illumination. It is found that the device with 10 nm thick ACO sputtered at 473 K and oxygen flow ratio f(O₂) (O₂/O₂ + Ar) = 40% shows the best photovoltaic properties. The photovoltaic properties in these devices are discussed in terms of the band diagrams and series resistance of the devices, and characteristics of ACO HTL. It is concluded that ACO is a suitable alternative to poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) as a HTL.     

Facile conversion of bulk metal surface to metal oxide single-crystalline nanostructures by microwave irradiation: Formation of pure or Cr-doped hematite nanostructure arrays

We report a method for converting the surfaces of bulk metal substrates (pure iron or stainless steel) to metal oxide (hematite or Cr-doped hematite) nanostructures using microwave irradiation. When microwave radiation (2.45 GHz, single-mode) was applied to a metal substrate under the flow of a gas mixture containing O₂ and Ar, metal oxide nanostructures formed and entirely covered the substrate. The nanostructures were single crystalline, and the atomic ratios of the substrate metals were preserved in the nanostructures. When a pure iron sheet was used as a substrate, hematite nanowires (1000 W microwave radiation) or nanosheets (1800 W microwave radiation) formed on the surface of the substrate. When a SUS410 sheet was used as a substrate, slightly curved rod-like nanostructures were synthesized. The oxidation states of Fe and Cr in these nanorods were Fe³⁺ and Cr³⁺. Quantitative analyses revealed an average Fe/Cr atomic ratio of 9.2, nearly identical to the ratio of the metals in the SUS410 substrate.     

Analytical study of the evolution of alumina scales formed on an ODS alloy

Abstract

An original deflection technique, in association with TEM observations, allowed study of the transformation of metastable alumina phases to α phase. This transformation is mainly characterised by a 14% volume decrease. Deflection experiments were performed on PM 2000 after pre-oxidation, in order to create a 3 µm alumina scale, and subsequent mechanical oxide removal of one large sample face. This technique allowed evaluation of the kinetics of transformation. The microstructural and chemical evolutions of the oxide, the interface (morphology, segregation) and the alloy (aluminium depletion, oxide dispersion) were characterised using TEM analyses and thermogravimetric measurements were done in the same conditions as the deflection tests to determine the oxidation rate constants     

氧化锌避雷器测试仪阻容网络校准方法

对氧化锌避雷器测试仪的传统阻容网络校准方法进行分析,指出电阻的时间常数、电容的损耗因数对泄漏电流的校准有一定影响。提出了基于相位差测量的数字化校准方法,采用数字采样方法对关键参数相位差进行测量,通过实验验证,证实了该方法具有较高的准确度,可用于氧化锌避雷器测试仪的校准。     

热处理对磁控溅射制备氧化铬涂层的结构及力学性能的影响

本文采用射频反应磁控溅射技术制备氧化铬涂层并在不同温度及不同的保温时间内进行热处理,通过X射线衍射、纳米压痕、摩擦磨损测试仪等研究温度及保温时间对涂层结构、表面形貌、硬度、弹性模量、耐磨性及涂层与基体间的结合力进行研究.研究表明低于其晶化温度(400℃)进行退火对其结构影响不大,其力学性能没有明显提高,而在高于其晶化温度(500℃)进行退火,其结构变化比较明显,同时其力学性能显著提高,其硬度从初始态的12.3 GPa提高到26GPa,相同试验条件下的磨损量也显著降低,从初始态的1.1×10-3 mm3降低到1×10-5 mm3.涂层与基体之间的结合力随着退火温度的提高、保温时间的延长有明显的改善.保温时间对其结构影响不大,但对其表面形貌有一定的影响,在低于晶化温度延长保温时间表面平均粗糙度降低,而高于晶化温度延长保温时间表面平均粗糙度增加.     

Differential cytotoxicity of metal oxide nanoparticles

Concerns about the potential health hazards of nanomaterials are growing. To determine the potential toxicity of metal oxide nanoparticles, human SH-SY5Y neuroblastoma and H4 neuroglioma cells were exposed to Fe₂O₃, CuO and ZnO nanoparticles and their metal ion counterparts (Fe³⁺, Cu²⁺ and Zn²⁺) at a concentration range of 0.01–100 µM for 48 h, under the cell culture conditions: 95% O₂, 5% CO₂, 85% humidity, 37°C. Their ensemble cell viability was determined by MTS cell proliferation assay. A live/dead cell assay was also performed, and cellular images were acquired by a high-content fluorescence microscope and quantified by a novel computerised image analysis protocol. Our data indicated that exposure of these nanoparticles induced differential toxic effects in both SH-SY5Y and H4 cells, and the cells had dose-dependent toxic responses to the CuO nanoparticle insult. In conclusion, the toxic responses of the nanoparticles are complex, and they warrant further in vivo studies. However, it remains to be determined if these nanopartilces have synergistically enhancing or cancelling toxic effects upon both SH-SY5Y and H4 cells.