Oxidation resistance of diffusion coatings formed by pack-codeposition of Al and Si on γ-TiAl

Oxidation resistance of the aluminide and silicide diffusion coatings pack-deposited on -TiAl were studied in air over the temperature range of 800 and 850°C for up to 4596 h. The oxidation kinetics of the coatings was monitored by intermittent weight gain measurement at room temperature. The XRD and SEM/EDS techniques were used to identify the oxide scales formed during the oxidation process and to assess the thermal stability of the coatings at the oxidising temperatures. It was revealed that the TiAl₃ coating underwent preferential Al oxidation to form the Al₂O₃ scale in the early oxidation stage, which resulted in Al depletion and formation of TiAl₂ in the subsurface of the coating. The Al depletion could not be sufficiently compensated by Al diffusion from the inner layer of the coating and eventually, in the late oxidation stage, led to the Ti oxidation and formation of the TiO₂ phase in the scale. The preferential Si oxidation was the main oxidation mechanism for the coatings with an outer silicide layer and an inner TiAl₃ layer with the formation of SiO₂ as the stable oxide scale. The thermal stability of the coatings over the temperature range up to 850°C was discussed in relation to the high-temperature stability of diffusion couples of different coating layers.     

Wetting behaviour of SiC ceramics: Part II—Y2O3/Al2O3 and Sm2O3/Al2O3

Wettability is the most significant phenomenon in SiC liquid phase sintering. The wetting of Y₂O₃/Al₂O₃ and Sm₂O₃/Al₂O₃ on SiC was analysed by the “Sessil drop” method. The wetting of liquid on solid during liquid phase sintering is very important. The behaviour of the additive on the SiC plate was observed using an imaging system with a CCD camera, and the contact angle measurements were analysed by Qwin Leica software. The samples were cut transversally and characterized by scanning electron microscopy and X-ray spectrometry (SEM/EDS). The wetting was found to be strongly influenced by the temperature; the SiC/additive contact angle decreased with increasing temperature. The YA and SA additives presented low contact angle values, indicating their good wetting on SiC in the argon atmosphere. The contact angle could not be measured when the test was performed in the nitrogen atmosphere because bubbles formed in the liquid during the test. The best atmosphere for this sintering was found to be argon, which allows uniform spreading.     

Co-deposition of aluminide and silicide coatings on γ-TiAl by pack cementation process

Thermochemical analyses were carried out for a series of pack powder mixtures for deposition of aluminide and for co-deposition of aluminide and silicide coatings on -TiAl by the pack cementation process. Based on the results obtained, experimental studies were undertaken to identify optimum pack powder mixtures for depositing adherent and coherent aluminide and silicide coatings. Pack powder mixtures activated by 2 wt% AlCl₃ was used to aluminise -TiAl at 1000°C. With proper control of pack compositions and coating conditions, an aluminide coating of TiAl₃ with a coherent structure free from microcracking was deposited on the substrate surface via inward diffusion of aluminium. The results of thermochemical calculations indicated that co-deposition of Al and Si is possible with CrCl₃ · 6H₂O and AlCl₃ activated pack powders containing elemental Al and Si as depositing sources. Experimental results obtained at 1100°C revealed that CrCl₃ · 6H₂O is not suitable for use as an activator for co-depositing aluminide and silicide coatings on -TiAl. It caused a significant degree of degradation instead of coating deposition to the substrate. However, adherent coatings with excellent structural integrity consisting of an outer TiSi₄ layer and an inner TiAl₃ layer were successfully co-deposited at 1100°C and 1000°C using pack powder mixtures activated by AlCl₃. IT is suggested that such coatings were formed via a sequential deposition mechanism through inward diffusion of aluminium and silicon. Discussion is presented on the issues that need to be considered to ensure the deposition of aluminide and silicide coatings with coherent structure free from microcracking on -TiAl by the pack cementation process.     

Investigation of the microstructure and oxidation behavior of Cr-modified aluminide coatings on γ-TiAL alloys

The microstructure and oxidation behavior of aluminide coatings are investigated. The layers are examined by the optical microscopy, scanning electron microscopy (SEM) equipped with EDS, and the X-ray diffraction method. The isothermal oxidation behaviors of samples are investigated at 950°C for 200 h. The results show that TiAl₃ is formed on the substrate. In addition, the aluminide coating improves the oxidation resistance of γ-TiAl alloys by forming a protective alumina scale. Moreover, during oxidation treatment, the interdiffusion of the TiAl₃ layer with γ-TiAl substrate results in the depletion of aluminum in the TiAl₃ layer and the growth of the TiAl₂ layer. After the oxidation treatment, the coating layer preserves a microstructure with phases including TiAl₃, TiAl₂, and Al₂O₃.     

Degradation behaviour of sputtered Co–Al coatings on superalloy

Degradation behaviour of sputtered Co–Al coatings on Superni-718 substrate has been investigated. Cyclic high temperature oxidation tests were conducted on uncoated and coated samples at peak temperatures of 900 °C for up to 100 thermal cycles between the peak and room temperatures. The results showed that a dense scale formed on the coated samples during thermal cycling at the peak temperature of 900 °C. The external scale exhibited good spallation resistance during cyclic oxidation testing at both temperatures. The improvement in oxide scale spallation resistance is believed to be related to the fine-grained structure of the coating. Nanostructured Co–Al coatings on Superni-718 substrate were deposited by DC/RF magnetron sputtering. FE-SEM/EDS, AFM, and XRD were used to characterize the morphology and formation of different phases in the coatings, respectively. The Co–Al coating on superalloy substrate showed better performance of cyclic high temperature oxidation resistance due to its possession of β-CoAl phase as Al reservoir and the formation of Al₂O₃ and spinel phases such as CoCr₂O₄ and CoAl₂O₄ in scale. The oxidation results confirmed an improved oxidation resistance of the Co–Al coating on superalloy as compare to bare substrate in air at 900 °C temperature up to 100 cycles.     

Oxidation behaviour of nanocrystalline Fe–Ni–Cr–Al alloy coatings

Abstract

Nanocrystalline Fe–Ni–Cr–Al alloy coatings with ～4 wt-%Al were produced using the unbalanced magnetron sputter deposition technique with a composite 310S stainless steel target embedded with aluminium plugs. The oxidation behaviour of the coatings was studied, during which complete external α-Al₂O₃ scales were formed. During isothermal oxidation tests at 950, 1000, and 1050°C, the oxidation kinetics followed an essentially parabolic rate law, and the oxidation constants were measured to be 2·06 × 10^-3, 4·23 × 10^-3, and 1·14 × 10^-2 mg² cm^-4 h^-1 respectively. During a cyclic oxidation test at 1000°C the α-Al₂O₃ scale showed good scale spallation resistance. The surface hardness of the coatings was measured with a Knoop indentor before and after oxidation. After oxidation, the coating surface hardness was still significantly higher than that of the uncoated specimen, demonstrating the potential this coating has in the improvement of high temperature erosion resistance.     

Effects of Al2O3 Particulates on the Thickness of Reaction Layer of Al2O3 Joints Brazed with Al2O3-Particulate-Contained Composite Filler Materials

In order to understand the rate-controlling process for the interracial layer growth of brazing joints brazed with active composite filler materials, the thickness of brazing joints brazed with conventional active filler metal and active composite filler materials with different volume fraction of AI203 particulate was studied. The experimental results indicate although there are Al2O3 particulates added into active filler metals, the time dependence of interracial layer growth is t^2 as described by Fickian law for the joints brazed with conventional active filler metal. It also shows that the key factor affecting the interracial layer growth is the volume fraction of alumina in the composite filler material compared with the titanium weight fraction in the filler material.     

Electro-codeposition of Al2O3-Y2O3 composite thin film coatings and their high-temperature oxidation resistance on γ-TiAl alloy

In this paper, electro-codeposition based on electrophoretic deposition and electrolytic deposition was developed to prepare Al₂O₃-Y₂O₃ composite thin film coatings on a γ-TiAl based alloy. Scanning electron microscope observations showed that the Al₂O₃-Y₂O₃ composite coatings were very compact and consisted of uniform nano-particles after microwave sintering. Cyclic oxidation at 900 °C indicated that the Al₂O₃-Y₂O₃ composite thin film coatings improved the oxidation and scale spallation resistance of the γ-TiAl alloy significantly. The superior oxidation and spallation resistance of the coatings were attributed to the suppression of outward diffusion of Ti and Al and inward diffusion of O, the promoted selective oxidation of Al in the γ-TiAl alloy, and the improved adhesion of oxide scale induced by the Al₂O₃-Y₂O₃ composite thin film coatings.     

Electro co-deposition of Ni–Al2O3 composite coatings

Nickel–Al₂O₃ composite coatings have been successfully deposited galvanostatically on to stainless steel substrates by electro co-deposition from a Watts bath containing between 50 and 150?g/l of sub-micron or nano- sized alumina particles applying current density of ?10, ?20 and ?32?mA?cm^?2. The alumina distribution in the composite films on the two sides of the substrate was remarkably different due to solution hydrodynamics and electric field effects. The effect of current density, particle concentration in the bath and particle size are studied systematically producing a comprehensive set of data for better understanding the effects of these variables on the amount of particles co-deposited. The amount of Al₂O₃ co-deposited in the films increases with the particle concentration in the bath and strongly depends on the current density and on particle size. The effect of the current density and of the alumina inclusions on the crystallinity of the Ni matrix and on the Ni crystallites grain size has also been studied. The inclusions of nano or sub-micron-Al₂O₃ particles are found to strongly influence the metallic nickel microstructure.     

Electrochemical Al2O3–ZrO2 composite coatings on non-oxide ceramic substrates

Aqueous solutions of xAl(NO3)3+(1–x)ZrO(NO3)2 were used for electrodeposition of ceramic Al2O3–ZrO2 composite on TiC, TiB2 and SiC sunstrates. The weight of the deposit was studied versus the duration of deposition, the current density and the temperature of the bath for Al-rich (x=0.9), Zr-rich (x=0.4) and eutectic (x=0.75) electrolyte compositions. Optimal current densities and durations of deposition were determined to obtain maxima weights of deposits. Amorphous deposits with thicknesses up to 10 m were formed. The microstructure and microchemical composition of the as-deposited and sintered deposits were characterized. Increase in the temperature of the bath inhibited microcracking due to shrinkage during drying. Coated TiC substrates exhibited enhanced oxidation resistance in air at 1100°C.     

Sintering behaviour of slip-cast Al2O3 – Y-TZP composites

The sintering behaviour of alumina–Y-TZP composites prepared by slip-casting technique were studied. Slip-cast samples containing varying amounts of Y-TZP ranging up to 90 vol% were prepared and evaluated. Sintering studies were carried out at 1450°C to 1600°C. Sintered samples were characterised where appropriate to determine phases present, grain sizes, bulk density and mechanical properties. Good correlation was obtained between the calculated prepared powder density and experimental results. The sintered bulk density of the composites was observed to increase with increasing Y-TZP content and sintering temperature up to 1550°C. Maximum hardness values (>14 GPa) were obtained for all samples containing <60 vol% Y-TZP and when sintered at 1550°C. It has been found that the additions of up to 50 vol% Y-TZP was effective in suppressing Al₂O₃ grain growth.     

Sintering of pseudo-boehmite and γ-Al2O3

Sintering of pseudo-boehmite, acicular-Al₂O₃ produced by dehydration of pseudo-boehmite, and-Al₂O₃ ex alum was investigated. The sintering process was studied by X-ray diffraction, transmission electron microscopy with selected area electron diffraction and BET surface area measurements. The solid state reaction to-Al₂O₃ causes a steep drop of the surface area to less than 10 m²g^–1. The acicular pseudo-boehmite and-Al₂O₃ supports exhibit an intermediate state where the acicular particles assume a rod-like shape and the surface area falls from about 300 to 100 m²g^–1. It was established that reaction to -Al₂O₃ and, hence, sintering proceeds via a nucleation and growth mechanism. The rate-limiting step is nucleation of -Al₂O₃. Consequently, the contacts between the elementary alumina particles dominate the sinter process. The contact between the acicular elementary particles of pseudoboehmite and-Al₂O₃ studied leads to the reaction to -Al₂O₃ to be almost complete after keeping samples for 145 h at 1050 °C. Decomposition of alum produces very small particles showing negligible mutual contacts. Consequently an elevated thermal stability is exhibited. Treatment of the alumina ex alum with water and drying results in a xerogel in which contact between elementary particles is much more intimate. Accordingly, treatment at 1050 °C causes a sharp drop in surface area.     

Pack codeposition of Al and Cr to form diffusion coatings resistant to high temperature oxidation and corrosion for γ-TiAl

Abstract

Thermochemical analyses were carried out for a series of pack powder mixtures formulated for codepositing Al with Cr to form diffusion coatings on γ-TiAl resistant to high temperature oxidation by the pack cementation process. Based on the results obtained, experimental studies were undertaken to identify optimum pack powder mixtures for codepositing Al with Cr to form diffusion coatings with an adherent and coherent coating structure. The results of the thermochemical calculations performed indicated that codeposition of Al and Cr is possible with CrCl₃.6H₂O and AlCl₃ activated pack powders containing elemental Al and Cr as depositing sources. However, experimental results obtained at 1100°C revealed that CrCl₃.6H₂O is not suitable for use as an activator for codepositing Al with Cr on γ-TiAl. It caused a significant degree of degradation indicated by weight losses instead of coating deposition to the substrate. However, adherent coatings with excellent structural integrity consisting of an outer Cr doped TiAl₃ layer containing Al₆₇Cr₈Ti₂₅ phase and an inner layer containing TiAl₃ and TiAl₂ phases were successfully codeposited at 1100°C using pack powder mixtures activated by AlCl₃. It is suggested that such coatings were formed via a sequential deposition mechanism through inward diffusion of aluminium and chromium. Conditions that affect the pack codeposition process, and hence need to be carefully controlled, are discussed in relation to the mechanism of the formation of diffusion coatings with an integral structure free from microcracking on γ-TiAl.     

Oxidation of an Al2O3-γAlON ceramic composite

The oxidation of dispersed aluminium oxynitride particles in an alumina matrix has been studied. The kinetics law of this reaction is linear and the activation energy is 420±40 kJ mol^–1 (100±10 kcal mo^–1). A-alumina layer is formed and leads to-alumina above 1200° C. The-alumina formation produces surface compressive stresses, and thus the mechanical properties ( _f, HV) are improved. We have proved that the formation of-alumina in the Al₂O₃-AION composite can lead to the best properties for this ceramic. A-alumina layer has a very interesting effect on the wear resistance of this material.     

A study of Mg and Cu additions on the foaming behaviour of Al–Si alloys

Aluminium casting alloys containing Mg and Cu in addition to Si were investigated with respect to their potential to be foamed. The kinetics of foam expansion of different alloys was studied and the resulting structures were characterised. Of the stages of evolution of foams, namely (i) pore nucleation, (ii) foam growth in the semisolid state, (iii) further expansion in the fully liquid state, the latter two were explored. Expansion in the semisolid state could be related to the available liquid fraction. Mg-containing Al–Si alloys yielded a less coarse and more uniform pore structure than the other alloys investigated. However, achieving a high volume expansion required restriction to a narrow process window and led to the suggestion of AlMg4Si8 as a practical alloy.     

Study on the effects of Cr2O3 on the reduction behavior of γ-Fe2O3

XRD and TG reduction analysis show that -Fe₂O₃ Fe-Cr catalysts, which contains 0.0 to 14.0 wt %. Cr₂O₃ and prepared by coprecipitating method, consist of crystalline -Fe₂O₃ and non-crystalline Fe₂O₃. Between 150–450 °C, three reduction stages are observed in the catalyst. The first stage is non-crystalline Fe₂O₃ reduced to non-crystalline Fe₃O₄, the second is crystalline -Fe₂O₃ to crystalline Fe₃O₄ and the third is non-crystalline Fe₂O₃ reduced to non-crystalline FeO. About 5 wt %. Cr₂O₃ can enter the lattices of -Fe₂O₃ to form solid solution. With the increasing of Cr₂O₃ content, the relative abundance of non-crystalline Fe₂O₃ and the amount of soluble Cr₂O₃ in non-crystalline increases, while the crystalline size of -Fe₂O₃ decreases.     

Multi-scale fatigue behaviour modelling of Al–Al2O3 short fibre composites

Using very heterogeneous materials in structural parts submitted to cyclic loadings, this paper presents an elasto-plastic micromechanical model. After recalling the homogenisation principle based on a mean field theory, non-linear kinematic and isotropic strain hardening is introduced into the matrix. Validation is made on an Al–3.5%Cu/SiC particle composite, and an Al–Si7Mg/Al₂O₃ fibre composite is treated as a first application. Damage is introduced into the model using a fibre failure criterion. It is based on the evolution of the volume fraction of broken fibres as a function of the maximum principal stress in the fibre family. The damage law is identified by means of in situ tensile tests performed inside the scanning electronic microscope. The number of broken fibres is determined as a function of the applied load and the number of cycles. The model predicts the fatigue behaviour, the loss of stiffness, the volume fraction of broken fibres for different volume fractions, aspect ratios, distributions of orientation and distributions of strength of the fibres. The effect of the mechanical fatigue properties of the matrix is also studied.     

Effect of Al2O3 and Fe3Al on the phase formation and mechanical properties of β-sialon

The paper evaluated the mechanical properties of β-sialon composites prepared by hot-pressing sintering at 1600 °C in N₂ atmosphere using α-Si₃N₄, Al₂O₃, Y₂O₃ and Fe₃Al as raw materials. The influence of Al₂O₃ and Fe₃Al content on flexure strength, fracture toughness, hardness, and relative density was investigated. And phase formation and morphology of the composites were characterized by X-ray diffraction and electron microscopy. The experimental results indicate that the raw material Fe₃Al reacts with α-Si₃N₄ to form silicides at elevated temperature, and supplies more liquid phase to assist densification. Besides, the variation of flexure strength, fracture toughness and hardness is mainly consistent, and also in good agreement with the relative density measurements. The values all increase firstly, and then decrease when the Al₂O₃ content increases. Scanning electron microscopy illustrates that the metal particles act to inhibit the crack propagation.