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.     

Role of Al2O3 layer in oxidation resistance of Cu-Al dilute alloys pre-annealed in H2 atmospheres

Copper was alloyed with small amounts of Al (0.2, 0.5, 1.0 and 2.0 mass%) to improve the oxidation resistance. Copper (6 N) and the Cu-Al alloys were oxidized at 773-1173 K in 0.1 MPa oxygen atmosphere after hydrogen annealing at 873 K. Continuous very thin Al₂O₃ layers were formed on the surface of all Cu-Al dilute alloys during the hydrogen annealing. Oxidation resistance of Cu-Al alloys was improved especially for Cu-2.0Al at 773-973 K, while it decreases on increasing the oxidation temperature. Cu-Al alloys followed the parabolic rate law at 1173 K, but most of other cases do not at and below 1073 K. Oxidation resistance for Cu-Al alloys was found relevant to the maintenance of the thin Al₂O₃ layer at the Cu₂O/Cu-Al alloy interface.     

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.     

Effect of lamellar microstructure on oxidation kinetics of Fe3Al sintered by hot isostatic pressing

The present paper focuses on the investigation of the relationship between microstructure of Fe₃Al prepared by hot isostatic pressing (HIP) and kinetics of alumina layer formation during oxidation at 900 °C, 1000 °C and 1100 °C. As prepared HIPed Fe₃Al sample reveals lamellar microstructure with inhomogeneous Al distribution which originates from the preliminary mechanical activation of Fe-Al mixture. At 900 °C, Fe₃Al oxidation is characterized by selective growth of very rough alumina layer containing only transient aluminium oxides. In addition to these transient oxides, α-Al₂O₃ stable phase is formed at 1000 °C. At the highest temperature (1100 °C), continuous and relatively smooth alumina layer mainly contains fine crystallites of α-Al₂O₃. The initial lamellar structure and phase inhomogeneity in as-HIPed Fe₃Al samples are supposed to be the main factors that determine observed peculiarities after Fe₃Al oxidation at 900 °C and 1000 °C.     

Enhanced performance of α-Al2O3 coatings by control of crystal orientation

α-Al₂O₃ coatings with (101?2), (101?4), (0001) and (101?0) textures were obtained using chemical vapour deposition. The textured coatings were compared with α-Al₂O₃ obtained through the κ→α phase transformation. The coating microstructures were studied by scanning electron microscopy and transmission electron microscopy and residual stress and texture were determined by X-ray diffraction using Cr K_α and Cu K_α radiation, respectively. Microtexture was investigated using electron back-scatter diffraction. Wear properties of the α-Al₂O₃ coatings were evaluated in turning of cast iron and steel. All the studied coatings were under a tensile stress of the order of 0.2-0.7 GPa. The cutting tests confirmed substantial texture effects especially in cutting of steel. The best performance was exhibited by the (0001) textured coatings i.e. when the basal planes of α-Al₂O₃ grains were nearly parallel to the coating surface. As compared with the other textured coatings, the (0001) textured coating showed a clearly enhanced ability to undergo uniform plastic deformation. The present work also established that the texture of α-Al₂O₃ coatings could be controlled by process data during deposition.     

Preparation, microstructure and properties of molybdenum alloys reinforced by in-situ Al2O3 particles

The conventional molybdenum alloys, lacking of hard particles enhancing wear property, have relative poor wear resistance though they are widely used in wear parts. To resolve the above question, Mo alloys reinforced by in-situ Al₂O₃ particles are developed using powder metallurgy method. The in-situ α-Al₂O₃ particles in molybdenum matrix are obtained by the decomposition of aluminum nitrate after liquid-solid incorporation of MoO₂ and Al(NO₃)₃ aqueous solution. The α-Al₂O₃ particles well bonded with molybdenum distribute evenly in matrix of Mo alloys, which refine grains of alloys and increase hardness of alloys. The absolute density of alloy increases firstly and then decreases with the increase of Al₂O₃ content, while the relative density rises continuously. The friction coefficient of alloy, fluctuating around 0.5, is slightly influenced by Al₂O₃. However, the wear resistance of alloy obviously affected by the Al₂O₃ particles rises remarkably with the increasing of Al₂O₃ content. The Al₂O₃ particles can efficiently resist micro-cutting to protect molybdenum matrix, and therefore enhances the wear resistance of Mo alloy.     

Criteria for the formation of protective Al2O3 scales on Fe-Al and Fe-Cr-Al alloys

The conditions for the formation of external alumina scales on binary Fe-Al alloys and the nature of the third-element effect due to chromium additions have been investigated by studying the oxidation at 1000 °C in 1 atm O₂ of a binary Fe-10 at.% Al alloy (Fe-10Al) and of two ternary Fe-Cr-10 at.% Al alloys containing 5 and 10 at.% chromium (Fe-5Cr-10Al and Fe-10Cr-10Al, respectively). An Al-rich scale developed initially on Fe-10Al was subsequently replaced by a multi-layered scale containing mixtures of Fe and Al oxides plus a large number of Fe-rich oxide nodules: internal aluminum oxidation was essentially absent from this alloy. Addition of 5 at.% chromium to Fe-10Al did not suppress the formation of nodules, but they were eventually healed by the growth of an alumina layer at their base, resulting in a significant reduction of the oxidation rate. Finally, the alloy with 10 at.% Cr formed continuous external alumina scales without any Fe-rich nodule. Thus, the addition of sufficient amounts of chromium to Fe-10Al produces a third-element effect as expected. However, the process found in this alloy system does not involve a prevention of the internal oxidation of Al. Instead, it shows a transition from the growth of mixed Fe- and Al-rich external scales directly to an external Al₂O₃ scale formation. An interpretation of this kind of mechanism involving a third-element is presented along with a prediction of the critical Al contents required to produce the various possible scaling modes on binary Fe-Al alloys.     

Effect of α-Al2O3 on in situ synthesis low density O′-sialon multiphase ceramics

In this paper, the effect of α-Al₂O₃ on in situ synthesis low density O′-sialon multiphase ceramics was investigated. Thermodynamics analysis was used to illustrate the feasibility of synthesizing O′-sialon at a low temperature of 1420 °C. The crystalline phase and microstructure were investigated by X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. The actual substitution parameter x value of O′-sialon was estimated via lattice correction. The results showed that, O′-sialon multiphase ceramics with different x values could be synthesized successfully through varying α-Al₂O₃ content. Bulk densities of samples ranging from 1.64 to 2.11 g cm⁻³ were adjusted with the percentage of α-Al₂O₃ increasing from 5.21 wt.% to 15.62 wt.%. Formation of nearly single-phase O′-sialon was obtained in the sample containing 10.42 wt.% α-Al₂O₃. The actual substitution parameter x increased with the increase of α-Al₂O₃, whereas it was lower than the original designation, and the O′-sialon with a low x value was achieved.     

Control of polymorphism in Al2O3 scale formed by oxidation of alumina-forming alloys

The selective oxidation of specific components in alumina-forming alloy such as CoNiCrAlY under precisely regulated oxygen partial pressures (P_O2) can be used to control polymorphism in Al₂O₃ scale formed on the alloy. Dense, smooth α-Al₂O₃ scale was formed rapidly by treatment at 1323 K under a thermodynamically determined P_O2, where both aluminum and chromium in the alloy were oxidized and elements such as cobalt and nickel were not oxidized. By contrast, under a higher P_O2 all the components in the alloy were oxidized, the transformation was obviously retarded, and (Co,Ni)(Al,Cr)₂O₄ was produced.     

Phase transformations in face centered cubic (Al0.32Cr0.68)2O3 thin films

Face centered cubic (Al_0.32Cr_0.68)₂O₃ thin films have been annealed in the temperature range of 500–1000 °C during 2–8 h. The fcc structure of the film remains intact when annealed at temperatures up to 700 °C for 8 h. X-ray diffraction and transmission electron microscopy show the onset of phase transformation to corundum phase alloys in the sample annealed at 900 °C for 2 h, where annealing at 1000 °C for 2 h results in complete phase transformation to α-(Al_0.32Cr_0.68)₂O₃. In-plane and out-of-plane line scans performed in EDX TEM and θ/2θ XRD patterns did not show any phase separation into α-Cr₂O₃ and Al₂O₃ prior and after the annealing. The apparent activation energy of this process is 380–480 kJ/mol as determined by the Johnson–Mehl–Avrami model.     

Studies on the AlCl3/dimethylsulfone (DMSO2) electrolytes for the aluminum deposition processes

This paper presents a study of the aluminum deposition processes in dimethylsulfone (DMSO₂)-based electrolytes. The electrical conductivities of the AlCl₃/DMSO₂ electrolytes were investigated as a function of temperature (70-180 °C) and molar ratio of AlCl₃ to DMSO₂ (from 0.1:1 to 0.8:1). The results show that the temperature-dependent conductivities of the electrolytes fit well with the Vogel-Tamman-Fulcher (VTF) equation. The optimum operating conditions for the electrodeposition of aluminum from AlCl₃/DMSO₂ electrolytes were determined based on the studies of the effects of current density, electrolyte temperature and the molar ratio of AlCl₃ to DMSO₂ on the quality of the deposited coatings. Dense, bright and adherent aluminum coatings were obtained in AlCl₃/DMSO₂ electrolytes over a wide range of temperatures (110-150 °C) and current densities (5 to 20 A dm^− 2). The preliminary results from Al refining experiments showed that Al alloy can be purified via electrolysis in 0.2:1 AlCl₃/DMSO₂ at 130 °C with a current density of 10 A dm^− 2.     

Microstructure and electrical properties of Y(NO3)3·6H2O-doped ZnO-Bi2O3-based varistor ceramics

Y(NO₃)₃·6H₂O-doped ZnO-Bi₂O₃-based varistor ceramics were prepared using a solid reaction route. The microstructure, electrical properties, degradation coefficient (D_V), and dielectric characteristics of varistor ceramics were studied in this paper. With increasing amounts of Y(NO₃)₃·6H₂O in the starting composition, Y-containing Bi-rich, Y₂O₃, and Sb₂O₄ phases were formed, and the average grain size decreased. Results also showed that with the addition of 0.16 mol% Y(NO₃)₃·6H₂O, Y(NO₃)₃·6H₂O -doped ZnO-based varistor ceramics exhibit comparatively better comprehensive electrical properties, such as a threshold voltage of 425 V/mm, a nonlinear coefficient of 73.9, a leakage current of 1.78 μA, and a degradation coefficient of 1.7. The dielectric characteristics and lightning surge test also received the same additional content of Y(NO₃)₃·6H₂O. The results confirmed that doping with rare earth nitrates instead of rare earth oxides is very promising route in preparing high-performance ZnO-Bi₂O₃-based varistor ceramics.     

TEM and DFT investigation of CVD TiN/κ-Al2O3 multilayer coatings

This paper investigates the interfacial structure in hot-wall CVD TiN/κ-Al₂O₃ multilayer coatings using both HREM and DFT modeling. Two multilayers with different thicknesses of the TiN layers (50 and 600 nm) separating the κ-Al₂O₃ layers are analyzed. The general microstructure of the two multilayers is relatively similar. The TiN layer in the thicker TiN/κ-Al₂O₃ coating is thick enough to be several TiN grains high. This means that epitaxial columns, which are often found in the thinner TiN/κ-Al₂O₃ coatings, are not present. However, the orientation relationships at the TiN/κ-Al₂O₃ interfaces are the same in both multilayers. The HREM investigations show that κ-Al₂O₃ (001) planes can grow directly on flat (111) TiN faces, without any other phases or detectable amounts of impurities, such as sulphur, present. Where the TiN layers are more curved, γ-Al₂O₃ can be grown, at least partly stabilized by the cube-on-cube orientation relationship between γ-Al₂O₃ and the underlying TiN. The DFT calculations show very similar adsorption strengths for an O monolayer positioned on Ti-terminated TiC(111) and TiN(111) surfaces, with preferred adsorption in the fcc site. O adsorption on N-terminated TiN(111) is much weaker, with preferred adsorption in the top site. Calculated elastic-energy contributions yield a higher stability for κ-Al₂O₃ on TiN(111) than on TiC(111) and a higher stability for κ-Al₂O₃ than for α-Al₂O₃ on both TiC and TiN. This indicates that the observed higher stability of κ-Al₂O₃ on TiC(111) than on TiN(111) is not due to the lattice mismatch, while the preferred epitaxial growth of κ-Al₂O₃ over α-Al₂O₃ can be partly attributed to the mismatch.     

Y2O3-BaO-SiO2-B2O3-Al2O3 glass sealant for solid oxide fuel cells

A glass based on Y₂O₃-BaO-SiO₂-B₂O₃-Al₂O₃ (named YBA) has been investigated as sealant for planar solid oxide fuel cells (SOFCs). The YBA glass has been systematically characterized by differential thermal analysis, dilatometer, scanning electron microscopy, impedance analysis, and open circuit voltage to examine their suitability as sealant. The coefficient of thermal expansion of YBA is 11.64 × 10⁻⁶ K⁻¹ between 323 and 873 K. The resistivity is 9.1 × 10⁴ Ω cm at 800 °C. The glass sealant is found to be well adhered with other cell components, such as electrolytes and stainless steels, at an optimum sealing temperature of 800 °C. All measured results showed that the YBA glass appears to be a promising sealant for SOFCs.     

Epitaxial stress and texture in thin oxide layers grown on Fe-Al alloys

The development of internal stress and texture in the oxide scales grown on Fe-15 at.% Al (1 0 0) and (1 1 1) single crystals at 700 °C was determined in situ using synchrotron X-ray diffraction. At this low oxidation temperature oxide scale thickness as revealed by X-ray photoelectron spectroscopy and transmission electron microscopy was situated between 100 and 150 nm after 650 min oxidation. Trigonal α-Fe₂O₃ was found to act as a crystallographic template for the nucleation of isostructural α-Al₂O₃. Strain behavior during oxidation was found to be influenced by the epitaxial relationship between α-Al₂O₃ and α-Fe₂O₃.     

Characteristic of AlON-Al2O3 coatings on Al6061 alloy by electrolytic plasma processing in aluminate and nitride electrolytes

In this work, 6061 series aluminum alloy is used as the matrix material for its wide application in engineering to make AlON coating layers by the electrolytic plasma processing (EPP) method. The experimental electrolytes include: 10 g/L NaAlO₂ as alumina formative agent, 2 g/L NaOH as the electrolytic conductive agent, 0.4 g/L NaNO₃ as a nitride supply agent. A combined composition and structure analysis of the coating layer was carried out by X-ray diffractometer (XRD) and scanning electron microscopy (SEM) for the specimens EPP-treated at 25 °C in 5 to 30 min under a hybrid voltage of 260 V DC plus AC 50 Hz power supplies (200 V). In addition, microhardness values were measured to correlate the evolution of microstructure and resulting mechanical properties. A composite of AlON-Al₂O₃ coating was formed as a result of a reactive process between Al in the alloy itself and O-N supplied by the electrolyte, which presents high hardness and anti-abrasion behaviors.     

Annealing temperature effect on the corrosion parameters of autocatalytically produced Ni-P and Ni-P-Al2O3 coatings in artificial seawater

Ni-P and Ni-P-Al₂O₃ amorphous alloy coatings with 9.3 and 8.3 wt.% P respectively were obtained by autocatalytic deposition at 90 °C on carbon steel substrates. The effect of annealing temperature (100, 200, 300, 400 and 500 °C) upon the corrosion parameters of the coatings in artificial seawater with pH 5.0 and 8.1 at room temperature was evaluated by potentiodynamic polarisation and electrochemical impedance spectroscopy. It was found that deposits annealed at 400 and 500 °C presented an increase of the charge transfer resistance and negligible changes on samples annealed at lower temperature. Polarisation tests showed a charge transfer controlled anodic kinetics on both Ni-P and Ni-P-Al₂O₃ deposits and diffusion controlled cathodic reaction in artificial seawater at pH 5.0 and 8.1. The coatings did not present passive behaviour in the electrolytes and impedance measurements showed a single time constant for all cases with the lowest double layer capacitance (C_dl) for samples annealed at 400 and 500 °C. The best corrosion parameters were observed on Ni-P and Ni-P-Al₂O₃ coatings annealed at temperatures higher than 400 °C, which is the temperature where crystallisation of this kind of coatings takes place.     

The nature of the third-element effect in the oxidation of Fe-xCr-3 at.% Al alloys in 1 atm O2 at 1000 °C

The oxidation of an Fe-Al alloy containing 3 at.% Al and of four ternary Fe-Cr-Al alloys with the same Al content plus 2, 3, 5 or 10 at.% Cr has been studied in 1 atm O₂ at 1000 °C. Both Fe-3Al and Fe-2Cr-3Al formed external iron-rich scales associated with an internal oxidation of Al or of Cr+Al. The addition of 3 at.% Cr to Fe-3Al was able to stop the internal oxidation of Al only on a fraction of the alloy surface covered by scales containing mixtures of the oxides of the three alloy components, but not beneath the iron-rich oxide nodules which covered the remaining alloy surface. Fe-5Cr-3Al formed very irregular external scales where areas covered by a thin protective oxide layer alternated with others covered by thick scales containing mixtures of the oxides of the three alloy components, undergrown by a thin layer rich in Cr and Al, while internal oxidation was completely absent. Conversely, Fe-10Cr-3Al formed very thin, slowly-growing external Al₂O₃scales, providing an example of third-element effect (TEE). However, the TEE due to the Cr addition to Fe-3Al was not directly associated with a prevention of the internal oxidation of Al, but rather with the inhibition of the growth of external scales containing iron oxides. This behavior has been interpreted on the basis of a qualitative oxidation map for ternary Fe-Cr-Al alloys taking into account the existence of a complete solid solubility between Cr₂O₃ and Al₂O₃.     

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.     

Thermal stability of γ-Al2O3 coatings for challenging cutting operations

Crystalline PVD Al₂O₃ coatings offer great potential for their use in cutting operations. They promise high hot hardness and high oxidation resistance at elevated temperatures. Alumina exists in different crystallographic phases. α-Al₂O₃ appears to be the only thermodynamically stable phase at all common temperatures and pressures. Today there are many efforts to generate α-Al₂O₃ by means of physical vapour deposition. In this regard one problem is the high deposition temperature, which does not allow the deposition on temperature-sensitive materials.Another promising candidate is γ-Al₂O₃ which is more fine-grained than α-Al₂O₃ and can be deposited at lower temperatures. At high temperatures γ-Al₂O₃ might be transformed into α-Al₂O₃, which could limit the application temperature. But until now it is not clearly proved, up to which temperatures γ-Al₂O₃ thin films are stable and which mechanisms influence the stability. In the present work different (Ti,Al)N/γ-Al₂O₃ coatings are deposited on cemented carbides by means of Magnetron Sputter Ion Plating (MSIP). The (Ti,Al)N bond coat was employed to improve adhesion of γ-Al₂O₃ on the substrate. It could be shown that the γ-phase is stable in vacuum up to 1200 °C. In the atmosphere the formation of α-Al₂O₃ begins at 900 °C and it is influenced by the choice of transition zone between the (Ti,Al)N interlayer and γ-Al₂O₃. The results show that the thermal stability of the γ-phase and therefore the application temperature of the coating can be enhanced by the choice of interlayer.