Early stages of the oxidation of a FeCrAlRE alloy (Kanthal AF) at 900 °C: A detailed microstructural investigation

Early stages of the evolution of Al₂O₃ scales formed on a FeCrAlRE alloy (Kanthal AF) have been investigated by analytical TEM. The samples were oxidized isothermally at 900 °C in dry O₂ or O₂ + 40% H₂O for 1 h or 24 h. All oxide scales exhibited a two-layered structure, with a continuous inward growing α-Al₂O₃ inner layer and an outward growing outer layer. After 1 h, the outer oxide layer consisted of γ-Al₂O₃ in both environments. After 24 h exposure in dry O₂, the γ-Al₂O₃ in the outer oxide layer was partly transformed to α-Al₂O₃ and spinel oxide (Mg_1−xFe_xAl₂O₄). In contrast, the γ-Al₂O₃ in the outer layer was not transformed after 24 h in O₂ + 40% H₂O, showing that water vapour stabilizes γ-Al₂O₃. All oxide scales contained a Cr-rich band, a product of the initial oxidation. The inner α-Al₂O₃ layer is suggested to nucleate on Cr₂O₃ or Cr_2−xFe_xO₃ in the initial oxide.     

Plasma electrolytic oxidation of pre-anodized aluminium

The influence of an anodizing pre-treatment in sulphuric acid is investigated on plasma electrolytic oxidation (PEO) of aluminium in silicate electrolyte under constant rms current. The presence of the anodic film is shown to promote the establishment of a micro-arc regime that is favourable for growth of the PEO coating. The incorporation of the pre-formed film into the coating appears to proceed by thermal transformation of the anodic alumina, accompanied by formation of oxide beneath the pre-formed layer. The final coatings contain α- and γ-Al₂O₃, with increased concentrations of silicon, sodium and potassium in an outer region of the coating.     

Anodic oxidation and dielectric behaviour of aluminium-niobium alloys

The anodizing behaviour of sputtering-deposited Al-Nb alloys, containing 21, 31 and 44 at.% niobium, has been examined in 0.1 M ammonium pentaborate electrolyte with interest in the composition and the dielectric properties of the anodic oxides. RBS and TEM revealed amorphous oxides, containing units of Nb₂O₅ and Al₂O₃ in proportion to the alloy composition. Xenon marker experiments indicated their growth through migration of the Nb⁵⁺, Al³⁺ and O²⁻ species, with cation transport numbers, in the range 0.31-0.35, and formation ratios, in the range 1.35-1.64 nm V⁻¹, intermediate between those of anodic alumina and anodic niobia. Al³⁺ ions migrate slightly faster than Nb⁵⁺ ions, promoting a thin alumina layer at the film surface, although this layer is penetrated by fingers of the underlying niobium-containing oxide of relatively reduced ionic resistivity. The incorporation of units of Nb₂O₅ into anodic alumina increases the dielectric constant from about 9 to the range 11-22 for the investigated alloys.     

Cyclic oxidation behavior and thermal barrier effect of YSZ-(Al2O3/YAG) double-layer TBCs prepared by the composite sol-gel method

Novel YSZ (6 wt.% yttria partially stabilized zirconia)-(Al₂O₃/YAG) (alumina-yttrium aluminum garnet, Y₃Al₅O₁₂) double-layer ceramic coatings were fabricated using the composite sol-gel and pressure filtration microwave sintering (PFMS) technologies. The thin Al₂O₃/YAG layer had good adherence with substrate and thick YSZ top layer, which presented the structure of micro-sized YAG particles embedded in nano-sized α-Al₂O₃ film. Cyclic oxidation tests at 1000 °C indicated that they possessed superior properties to resist oxidation of alloy and improve the spallation resistance. The thermal insulation capability tests at 1000 °C and 1100 °C indicate that the 250 μm coating had better thermal barrier effect than that of the 150 μm coating at different cooling gas rates. These beneficial effects should be mainly attributed to that, the oxidation rate of thermal grown oxides (TGO) scale is decreased by the “sealing effect” of α-Al₂O₃, the “reactive element effect”, and the reduced thermal stresses by means of nano/micro composite structure. This double-layer coating can be considered as a promising TBC.     

Oxidation resistance and corrosion behavior of hot-dip aluminized coatings on commercial-purity titanium

Aluminizing is an effective method to protect alloys from oxidation and corrosion. In this article, the microstructure, morphology, phase composition of the aluminized layers and the oxide films were investigated by SEM, EDS and X-ray diffraction. The high temperature oxidation resistance and electrochemical behavior of hot dip aluminizing coatings on commercial-purity titanium had been studied by cyclic oxidation test and potentiodynamic polarization technique. The results show that the reaction between the titanium and the molten aluminum leads to form an aluminum coating which almost has the composition of the aluminum bath. After diffusion annealing at 950 °C for 6 h, the aluminum coating transformed into a composite layer, which was composed of an inner layer and an outer layer. The inner layer was identified as Ti₃Al or Ti₂Al phase, and the outer layer was TiAl₃ and Al₂O₃ phase. The cyclic oxidation treatment at 1000 °C for 51 h shows that the oxidation resistance of the diffused titanium is 13 times more than the bare titanium. And the formation of TiAl₃, θ-Al₂O₃ and compact α-Al₂O₃ at the outer layer was thought to account for the improvement of the oxidation resistance at high temperature. However, the corrosion resistance of the aluminized titanium and the diffused titanium were reduced in 3.5 wt.% NaCl solution. The corrosion resistance of the aluminized titanium was only one third of bare titanium. Moreover, the corrosion resistance of the diffused titanium was far less than bare titanium.     

Preparation and oxidation resistance of a crack-free Al diffusion coating on Ti22Al26Nb

A crack-free Al diffusion coating has been developed to improve the oxidation resistance of Ti22Al26Nb. It was produced by a two-step method; an Al film was deposited on the substrate alloy by arc ion plating followed by a diffusion process conducted at 873 K in pure Ar to form the Al diffusion coating. The two-step method lowers the temperature required to form the diffusion coating, which dramatically decreases the thermal stress developed in the coating and results in it being crack-free. The oxidation resistance of the non-coated Ti22Al26Nb alloy in isothermal and cyclic tests in air at 1073 K was poor, but the coated specimens possessed excellent oxidation resistance because a protective α-Al₂O₃ scale formed. The life of the Al diffusion coating greatly depends upon the rapid initial formation of a protective Al₂O₃ scale and interdiffusion between coating and substrate. Once the stable Al₂O₃ scale has formed and the composition changes from (Ti, Nb)Al₃ into (Ti, Nb)Al₂, the coating has a long life.     

Anodic oxidation of InAlAs

The anodic oxidation of InAlAs is investigated by transmission electron microscopy, Rutherford backscattering spectroscopy and medium energy ion scattering in order to elucidate the mechanism of oxide growth. For this purpose, anodizing was carried out at 5 mA cm⁻² in 0.1 M sodium tungstate and 0.1 M ammonium pentaborate electrolytes at 293 K, which results in relatively efficient film growth over an initial voltage increment of about 70 V. In this period, an amorphous oxide develops with a formation ratio of 2.0 ± 0.2 nm V⁻¹. The film consists mainly of an outer layer of In₂O₃ and an inner layer of units of In₂O₃, Al₂O₃ and As₂O₃, the former representing about 14% of the film. There is suggestion of a fine, intermediate layer containing units of In₂O₃ and Al₂O₃ only. The layering correlates with the bond energies of the cation and oxygen species in the oxide and hence their relative migration rates. Further, for films formed in tungstate electrolyte, tungsten species are incorporated into the outer 40% of the film. Bubbles of oxygen gas are present in the film, probably developed within the In₂O₃ layer. At higher voltages, the film undergoes breakdown, with resulting major changes in the film morphology.     

Intermediate temperature tribological behavior of carbon nanotube reinforced plasma sprayed aluminum oxide coating

Tribological behavior of plasma sprayed carbon nanotube (CNT) reinforced aluminum oxide (Al₂O₃) composite coatings was examined at room temperature, 573 K and 873 K using tungsten carbide (WC) ball-on-disk tribometer. The weight loss due to wear of Al₂O₃ coating was found to be increasing with the temperature while Al₂O₃-CNT coating showed a decreasing trend in the weight loss with the temperature. Relative improvement in the wear resistance of Al₂O₃-CNT coating compared to Al₂O₃ coating was found to be 12% at room temperature which gradually increased to ∼ 56% at 573 K and ∼ 82% at 873 K. Protective layer as a result of tribo-chemical reaction was observed on the wear track of both of the coatings. The improvement in the wear resistance of Al₂O₃-CNT coating was attributed to three phenomena viz. (i) higher hardness at the elevated temperature as compared to Al₂O₃ coating, (ii) larger area coverage by protective film on the wear surface at the elevated temperature and (iii) CNT bridging between splats. The coefficient of friction (COF) of Al₂O₃ coating was nearly constant at room and elevated temperature whereas COF for Al₂O₃-CNT coating decreased at the elevated temperature (873 K).     

Spark anodizing of β-Ti alloy for wear-resistant coating

Spark anodizing of a bcc solid solution Ti-15% V-3% Al-3% Cr-3% Sn alloy has been performed in an alkaline electrolyte containing aluminate and phosphate using dc-biased ac anodizing to form a wear-resistant coating on the alloy. The coating consists mainly of Al₂TiO₅, with rutile and γ-Al₂O₃ being present as minor oxide phases. Depth profiles of the coating, examined by glow discharge optical emission spectroscopy, have revealed that aluminium species, highly enriched in the coating, distribute uniformly in the coating, while phosphorus species, incorporated from the electrolyte, are located mainly in the inner part of the coating near the coating/alloy interface. The location of the phosphorus species should be associated with the porous nature of the coating, allowing access of the electrolyte directly to the inner parts of the coating. The porosity of the coating is reduced by anodizing to high voltages. The marked improvement of the wear resistance by the coating has been demonstrated from a pin-on-disc wear test.     

Corrosion behaviour of AIP NiCoCrAlYSiB coating in salt spray tests

NiCoCrAlYSiB coatings were deposited by arc ion plating (AIP) and annealed/pre-oxidised under various conditions. The corrosion behaviour of as-deposited and annealed/pre-oxidised coatings was studied by salt spray testing in a neutral mist of 5 wt% NaCl at 35 °C for 200 h. The results showed that the as-deposited NiCoCrAlYSiB coating behaved poorly while the annealed and pre-oxidised ones performed much better in salt spray tests. The dense microstructure in annealed coatings and formation of α-Al₂O₃ scales on the surface during pre-oxidation improved the corrosion resistance in salt spray test. The corrosion process was investigated from the aspects of corrosion products, and its electrochemical mechanism was proposed as well.     

Microstructure and oxidation behaviour of an AlSiY/NiCrAlYSi composite coating at 1150 °C

A composite coating consisting of an outer AlSiY layer and an inner NiCrAlYSi layer has been prepared by a two-step arc ion plating method. The isothermal and cyclic oxidation behaviour of the composite coating at 1150 °C, including the growth of oxide scale and the microstructure transformation of the coatings, have been investigated comparing with the reference coating, NiCrAlYSi. The results show enhanced oxidation performance of the composite coating, which is concerned with its abundant possession of β-NiAl phase reservoirs, providing it the long term healing capacity of re-growing the α-Al₂O₃ scale.     

Cyclic oxidation behaviour of electrodeposited Ni3Al-CeO2 base coatings at 1050 °C

This paper presents the cyclic oxidation behaviour of electrodeposited pure, nano CeO₂ (9-15 nm)- and micron CeO₂ (5 μm)-modified Ni₃Al coatings on Fe-Ni-Cr substrate at 1050 °C for periods up to 500 h. The pure Ni₃Al coating had a marginal resistance to cyclic oxidation at 1050 °C, while the CeO₂-dispersed Ni₃Al coatings showed much better cyclic oxidation resistance. This difference was attributed to many beneficial effects of CeO₂ including changing the growth mechanism of α-Al₂O₃ scale, reducing the growth rate of the scale, improving mechanical properties of the scale, and reducing void formation at the scale/coating interface and at the scale-grain boundaries.     

Synergistic corrosion behavior of coated Ti60 alloys with NaCl deposit in moist air at elevated temperature

In the present paper, the corrosion behavior of Ti60 alloys with an aluminide, TiAlCr, and enamel coatings in moist air containing NaCl vapor at 700-800 °C were studied. The results showed that the TiAlCr and aluminide coatings failed to protect the substrate from corrosion due to the cyclic formation of volatile products during corrosion at 800 °C. However, an uneven continuous protective Al₂O₃ scale could form on the aluminide coating during corrosion at 700 °C. And the enamel coating could protect Ti60 from corrosion due to its high thermochemical stability and matched thermal expansion coefficient with substrates of Ti-base alloys during corrosion.     

Amorphous-like nanocrystalline γ-Al2O3 films prepared by MOCVD

Alumina (Al₂O₃) films were prepared by metalorganic chemical vapor deposition using aluminum tri-acetylacetonate as a precursor. The effects of deposition conditions on film phase, microstructure, and deposition rate were investigated. γ-Al₂O₃ films were obtained at substrate temperatures ranging between 1173 and 1373 K and total chamber pressures ranging between 400 and 1000 Pa, whereas α-Al₂O₃ films incorporating a small amount of the γ phase were obtained at 1373 K and 800 Pa. Al₂O₃ films prepared at 1173 K showed a halo in X-ray diffraction patterns, consistent with amorphous structures. However, TEM observations suggested that these films consisted of a nanocrystalline γ-Al₂O₃ phase containing trace amounts of carbon.     

Coke formation and metal dusting of electroplated Ni3Al-CeO2-based coatings in CO-H2-H2O

Coke formation and metal dusting of electrodeposited pure, 5 μm CeO₂-dispersed, and 9-15 nm CeCO₂-dispersed Ni₃Al coatings were investigated in CO-H₂-H₂O at 650 °C for a period of 500 h. All Ni₃Al coatings showed the inferior long-term resistance to coke formation and metal dusting to the Fe-Ni-Cr alloy due to failure to form a continuous Al₂O₃ scale. CeO₂-dispersed Ni₃Al coatings, especially 9-15 nm CeCO₂-dispersed coatings, exhibited more severe coke formation and metal dusting than the pure Ni₃Al coating. The detrimental effect of CeO₂ is believed to be caused by the enhanced formation of NiO/Ni crystals on the coating surfaces or at the grain boundaries, which catalysed the carbon deposition and promoted the carbon attack on Ni₃Al coatings.     

Spark anodizing behaviour of titanium and its alloys in alkaline aluminate electrolyte

Spark anodizing of titanium, Ti-6Al-4V and Ti-15V-3Al-3Cr-3Sn in alkaline aluminate electrolyte produces highly crystalline anodic films consisting mainly of Al₂TiO₅ with α- and γ-Al₂O₃ as minor oxide phases, irrespective of substrate composition. However, the apparent efficiency for film formation decreases in the following order: Ti-6Al-4V, titanium and Ti-15V-3Al-3Cr-3Sn. A large amount of aluminium species are incorporated from the electrolyte, probably by plasma-chemical reaction, and become distributed throughout the film thickness. This distribution indicates that the electrolyte penetrates near to the film/substrate interface through the discharge channels. Thus, the outwardly migrating aluminium ions under a high electric field can be present even in the inner part of the anodic films. Voids are developed at the film/substrate interface, particularly on the vanadium-containing alloys, reducing the adhesion of the anodic film to the substrate.     

Microstructural characterization of plasma sprayed Al2O3-40 wt.% TiO2 coatings on high density graphite with different post-treatments

Graphite is one of the candidate materials proposed for application in pyrochemical reprocessing plants involving aggressive molten chloride environment. Post treatments are promising techniques for the improvement of properties of thermal spray coatings for different industrial applications. In the present work, the effect of post treatments like vacuum annealing (VA) and laser melting (LM) on the microstructure and chemical modification of plasma sprayed Al₂O₃-40 wt.% TiO₂ coatings over high density (HD) graphite substrates has been investigated. When compared with sprayed coatings (SC), VA coatings showed cluster morphology and LM coatings exhibited homogenous microstructure. On laser melted surfaces networks of cracks were observed. XRD studies showed that the metastable γ-Al₂O₃ phase present in the SC is transformed to stable α-Al₂O₃ after post treatments. In LM coatings Al₂TiO₅ phase was more predominant in contrast to SC and VA coatings. The microhardness enhancement was observed in case of LM coating compared to the VA and SC. Due to elimination of coating defects in LM samples, there is a considerable reduction in the surface roughness.     

等离子喷涂制备ZrB2/SiC/Ta2O5涂层抗烧蚀性能研究

为了提高C/C复合材料的抗烧蚀性能,通过等离子喷涂法在C/C表面制备了SiC/Al₂O₃内层和ZrB₂/SiC/Ta₂O₅外层的双层涂层,通过XRD,SEM和EDS分析了涂层烧蚀前后的物相组成、微观结构和成分分布。烧蚀前涂层表面没有裂纹并且内层与基体、内层与外层之间结合良好。元素Zr、Si、Ta在涂层表面的分布相近,涂层表面成分分布均匀性良好。通过氧乙炔火焰在1800 ℃下对涂层的抗烧蚀性能进行考核。烧蚀过程中形成的镶嵌结构有利于阻挡氧气的渗入,Ta-Si-O玻璃层的形成封填了涂层孔隙,对基体有良好的保护效果,涂层表现出了较好的抗烧蚀性能。     

Al2O3-ZrO2 mixed oxide composite incorporated aluminium rich zinc coatings for high wear resistance

Corrosion resistance and wear resistance are the two important parameters for high performance of zinc galvanic coating. In the present work, the improvement of these two characteristics was achieved by the incorporation of Al₂O₃-ZrO₂ mixed oxide composite in the coating. Al₂O₃-ZrO₂ mixed oxide composite was synthesized from ZrOCl₂·8H₂O. Aluminium rich zinc coatings with high sliding wear resistance was developed from a galvanic bath containing the mixed oxide. Based on the performance of the coating during physicochemical and electrochemical characterization, the concentration of mixed oxide composite in the bath was optimized as 0.50 wt% Al₂O₃-0.50 wt% ZrO₂. While rich in Al-metal content in the coating caused high corrosion resistance, the incorporation of the mixed oxide improved structural characteristics of the coating resulting in high wear resistance also. The coating was nonporous in nature and even the interior layers had high stability. The coatings have potential scope for high industrial utility.     

Proposal of self-healing coatings for nuclear fusion applications

Avoiding cracks in ceramic coatings is one of the most important problems to be solved for the thermally sprayed tritium permeation barriers in fusion reactor. In this paper, a self-healing composite coating composed of TiC + mixture (TiC/Al₂O₃) + Al₂O₃ was developed to address this problem. The coating was deposited on certain martensitic steel by plasma spraying. The morphology and phase of the coating were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD) while the porosity was analyzed by using Image Pro software. The thermal shock resistance test and residual stress measurement of the coating were also performed. In the experiment, NiAl + TiC + mixture (TiC/Al₂O₃) + Al₂O₃ and mixture (TiC/Al₂O₃) + Al₂O₃ films were also fabricated and studied respectively. The results showed that the TiC + mixture (TiC/Al₂O₃) + Al₂O₃ coating exhibited the best mechanical integrity and self-healing ability among the three samples with the porosity decreased by 90% after heat-treatment under normal atmosphere. The oxidation/expansion of TiC in the coating played an important role in the sealing of pores. This self-healing coating made by thermal spraying is proposed as a good candidate for tritium permeation barrier in fusion reactors.