Preparation of nanostructured high-temperature TZM alloy by mechanical alloying and sintering

Mechanical milling proceeded by sintering was used to synthesize nanostructured temperature-resistant TZM alloy. Milling under Ar for different times (1, 2, 3, 5, 10, 15, 20, 25, and 30 h) and sintering at 1500, 1600 and 1700 °C for 30, 45, 60 and 90 min resulted in increasing of low-energy grain boundaries (LEGBs) and dispersion of TiC and ZrC with a size of ~ 65 nm in the matrix near LEGBs. Morphology and grain size of the products were determined from scanning electron microscope (SEM) images and X-ray diffraction (XRD) patterns, almost precisely. Optimum density of nanostructured TZM alloy ~ 9.95 ± 0.01 g/cm³ was achieved by sintering at 1700 °C for 90 min.     

An investigation on the microstructure and oxidation behavior of laser remelted air plasma sprayed thermal barrier coatings

NiCrAlY bond-coat was coated on Inconel 718 substrate by air plasma spraying (APS) followed by APS ZrO₂-8 wt.%Y₂O₃ as top-coat. Using CO₂ laser of different energy densities, ceramic top-coat surface was remelted. Laser remelting with high energy density (4 J/mm²) produced a dense microstructure over the whole thickness of top-coat, while low energy density (0.67 J/mm²) laser remelting produced a ~ 50 μm thick dense layer on the top-coat surface. It was found that the volume fraction of monoclinic phase decreased from 9% in as-sprayed coating to 4% and 3% after laser remelting with high and low energy density respectively. After isothermal oxidation at 1200 °C for 200 h, the thickness of oxide layer (TGO) in the sample produced by low energy density laser remelting was ~ 5.6 μm, which was thinner than that of oxide layer in as-sprayed (~ 7.6 μm) and high energy density laser remelted (~ 7.5 μm) samples. A uniform and continuous oxide layer was found to develop on the bond-coat surface after low energy density laser remelting. Thicker oxide layer containing Cr₂O₃, NiO and spinel oxides was observed in both as-sprayed and high energy density laser remelted coatings. After cyclic oxidation at 1200 °C for 240 h, the weight gain per unit area of as-sprayed coating was similar to that of high energy density laser remelted coating while a significantly smaller weight gain was found in low energy density laser remelted coating.     

SiC nanowire-toughened MoSi2-SiC coating to protect carbon/carbon composites against oxidation

To protect carbon/carbon (C/C) composites against oxidation, a SiC nanowire-toughened MoSi₂-SiC coating was prepared on them using a two-step technique of chemical vapor deposition and pack cementation. SiC nanowires obtained by chemical vapor deposition were distributed random-orientedly on C/C substrates and MoSi₂-SiC was filled in the holes of SiC nanowire layer to form a dense coating. After introduction of SiC nanowires, the size of the cracks in MoSi₂-SiC coating decreased from 18 ± 2.3 to 6 ± 1.7 μm, and the weight loss of the coated C/C samples decreased from 4.53% to 1.78% after oxidation in air at 1500 °C for 110 h.     

Oxidation protection of gamma-titanium aluminide using glass-ceramic coatings

γ-TiAl intermetallic alloys are presently considered an efficient structural material for advanced turbine blades and aero-engine components due to their various advantages compared to the traditionally used superalloys. However, their poor oxidation resistance at temperatures > 750 °C severely limits their wider application. The present study dealt with the improvement of oxidation resistance of this alloy by applying impervious glass-ceramic coatings by vitreous enameling technique. Results showed that MgO-SiO₂-TiO₂ glass-ceramic coating could offer excellent oxidation resistance to γ-TiAl at 800 °C even up to 100 h with negligible weight gain (~ 0.10 mg/cm²) compared to that of the bare alloy (~ 1.3 mg/cm²). The coatings those were belonging from BaO-MgO-SiO₂, ZnO-Al₂O₃-SiO₂ and BaO-SiO₂ systems also extend appreciable improvement in the oxidation resistance of the alloy at 800 °C up to 100 h. At further higher temperature such as at 1000 °C, the ABK-13 and ABK-103 glass-ceramic coatings offered significant protection to the alloy up to 25 h of exposure in air with minimum weight gain (~ 0.34 mg/cm²). However, after that the coated layers started to peel off from the alloy surface.     

Multi-layered silicides coating for vanadium alloys for generation IV reactors

The halide-activated pack-cementation technique was employed to fabricate a diffusion coating that is resistant both to isothermal and to cyclic oxidation in air at 650 °C on the surface of the V–4Cr–4Ti vanadium alloy that is a potential core component of future nuclear systems. A thermodynamic assessment determined the deposit conditions in terms of master alloy, activator, filler and temperature. The partial pressures of the main gaseous species (SiCl₄, SiCl₂ and VCl₂) in the pack were calculated with the master alloy Si and the mixture VSi₂ + Si. The VSi₂ + Si master alloy was used to limit vanadium loss from the surface. The obtained coating consisted of multi-layered V_xSi_y silicides with an outer layer of VSi₂. This silicide developed a protective layer of silica at 650 °C in air and was not susceptible to the pest phenomenon, unlike other refractory silicides (MoSi₂, NbSi₂). We suggest that VSi₂ exhibits no risk of rapid degradation in the gas fast reactor (GFR) conditions.     

Formation of MoSi2 and Al doped MoSi2 coatings on molybdenum base TZM (Mo–0.5Ti–0.1Zr–0.02C) alloy

Formation of aluminium (Al) doped molybdenum di-silicide (MoSi₂) coatings was studied to improve the high temperature oxidation behavior of TZM (Mo–0.5Ti–0.1Zr–0.02C) alloy. The pack composition of the halide activated pack cementation process was successfully optimized to form silicide and Al doped silicide coatings on the TZM alloy substrates. Mo(Si, Al)₂ phase was found to form at the outer layer of the coating prepared by doping Al in MoSi₂. A change in composition of the phases with increase in coating temperature was detected with Al doping, whereas un-doped silicide coating process was dominated by the formation and growth of MoSi₂ phase. Oxidation test and the characterization studies using SEM, EDS, XRD, and micro-hardness measurements indicated the improved performance of Al doped silicide coating during high temperature oxidation in dry air due to the formation of the protective alumina scale.     

Oxidation resistance of TiAl3-Al composite coating on orthorhombic Ti2AlNb based alloy

The TiAl₃-Al composite coating on orthorhombic Ti₂AlNb based alloy was prepared by cold spray. Oxidation in air at 950 °C indicated that the bare alloy exhibited poor oxidation resistance due to the formation of TiO₂/AlNbO₄ mixture and intended to scale off at the TiO₂ rich zone. A nitride layer about 2 µm was formed under the oxide layer. The oxygen invaded deeply into the alloy and caused severe microhardness enhancement in the near surface region. The TiAl₃-Al composite coating exhibited parabolic oxidation kinetics and showed no sign of degradation after oxidized up to 1098 h at 950 °C in air under quasi-isothermal condition. No scaling of the coating was observed after oxidized at 950 °C up to the tested 150 cycles. The major oxide in the oxidized coating was Al₂O₃. The AlTi₂N, TiAl and small amount of TiO₂ were also observed in the oxidized coating. The EPMA and microhardness tests showed that inward oxygen diffusion was prevented by the interlayer, which was formed between the composite coating and the substrate during heat-treatment. Microstructure analyses demonstrated that the interlayer play a major role in protecting the substrate alloy from high temperature oxidation and interstitial embrittlement.     

Effect of alloying with Al on oxidation behavior of MoSi2 coatings at 1100 °C

MoSi₂ - 0, 15.3, 22, and 29.3 at.% Al coatings were prepared on the nickel-based super-alloy substrates by electro-thermal explosion ultrahigh speed spraying technology. The analysis showed that the coatings had fine microstructure with grain sizes ranging from 0.5 to 2 μm. The bonding between coating and substrate was typically metallurgical cohesion. The oxidation resistance of the coating was further studied at 1100 °C in air. Al alloyed in MoSi₂ coatings increased the oxidation resistance of the coatings, and the oxidation resistance of MoSi₂-15.3 at.% Al coating was higher than the other two MoSi₂–Al coatings. This suggested the oxidation resistance might have close relations to the obtained grain size.     

Oxidation resistance of boronized CoCrMo alloy

Boronizing of CoCrMo alloy has been performed by means of a powder-pack method using commercial LSB powders at 850, 900 and 950 °C for 8 h, respectively. In this study, the boronized CoCrMo alloy before and after oxidation tests were characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The distribution of alloy elements of boronized samples from surface to interior was determined using energy-dispersive X-ray spectroscopy (EDS). XRD study showed the boride layer formed at 950 °C/8 h consisted of the phases Co₂B and CrB. Depending on boronizing temperature, the thickness of boride layer ranged from 2 to 11 μm. Cyclic oxidation behavior of the boride layer has been investigated at an oxidation temperature of 950 °C with a total exposure time up to 50 h in air. The test results indicated that the boronized CoCrMo alloy had superior oxidation resistance compared to unboronized sample.     

Ceria/stannate multilayer coatings on AZ91D Mg alloy

In this work, CeO₂/stannate multilayer coatings on AZ91D magnesium alloy were successfully obtained by chemical conversion and sol–gel dip coating. The stannate conversion coatings were prepared from a stannate aqueous bath containing Na₂SnO₃, CH₃COONa, Na₃PO₄ and NaOH at different temperatures and immersion times. Ceria films were produced on stannate/AZ91D starting from Ce(III) nitrate solutions in H₂O. In some cases, the PVA was added as chelating agent. Ceria top coatings were fired at 200 °C for 1 h. Coating microstructure was examined by FE-SEM. Finally, the corrosion resistance features of the coatings were tested by the electrochemical impedance spectroscopy (EIS) in 3 wt.% NaCl solution. The effect of PVA addition was evaluated in terms of microstructure and corrosion resistance features. CeO₂/stannate multilayer films, 3 μm thick, uniform, well adherent and nearly crack free were obtained. The formation of CeO₂ phase was confirmed by XRD and XPS analyses. The XPS depth profiles showed a limited diffusion of Mg towards the ceramic film. The EIS tests showed a significant improvement of corrosion resistance of the multilayer coatings (~ 16.6 kΩ after 48 h in NaCl solution) with respect to the blank alloy (~ 2.4 kΩ after 48 h in NaCl solution).     

The corrosion of Fe3Al alloy in liquid zinc

A systematic study of the isothermal corrosion testing and microscopic examination of Fe₃Al alloy in liquid zinc containing small amounts of aluminum (less than 0.2 wt.%) at 450 °C was carried out in this work. The results showed the corrosion of Fe₃Al alloy in molten zinc was controlled by the dissolution mechanism. The alloy exhibited a regular corrosion layer, constituted of small metallic particles (diameter: 2-5 μm) separated by channels filled with liquid zinc, which represented a porosity of about 29%. The XRD result of the corrosion layer formed at the interface confirmed the presence of Zn and FeZn_6.67. The corrosion rate of Fe₃Al alloy in molten zinc was calculated to be approximately 1.5 × 10⁻⁷ g cm⁻² s⁻¹. Three steps could occur in the whole process: the superficial dissolution of metallic Cr in the corrosion layer, the new phase formation of FeZn_6.67 and the diffusion of the dissolved species in the channels of the corrosion layer.     

Slurry based multilayer environmental barrier coatings for silicon carbide and silicon nitride ceramics — II. Oxidation resistance

In part I of this study, the dip-coat processing of mullite/gadolinium silicate (Gd₂SiO₅) environmental barrier coatings (EBCs) applied on α-SiC and SN282™ Si₃N₄ through alcohol based and sol based slurries was presented. Here, the performance of selected EBCs by evaluating their oxidation resistances during thermal cycling in simulated combustion (90% H₂O-balance O₂) environment between 1350 °C and RT for up to 400 cycles is being reported. Oxidation of un-coated α-SiC was severe, leading to aligned and layered porous silica scale formation (~ 17 μm thick) on its surface with frequent scale spallation when exposed to 100 cycles. Mullite/Gd₂SiO₅/B₂O₃ (83.5/11.5/5 wt.%) EBCs remained adherent to α-SiC substrate with an underlying porous silica layer formed at substrate/coating interface, which was ~ 12 μm after 100 cycles, ~ 16 μm after 200 cycles, and ~ 25 μm after 400 cycles. In contrast, α-SiC substrate coated with mullite/Gd₂SiO₅ (88/12 wt.%) EBC had only limited oxidation of ~ 10 μm even after 1350 °C/400 cycles. The sol based mullite/Gd₂SiO₅ (88/12 wt.%) EBC on α-SiC substrate after 400 cycles was adherent, but showed more interfacial damages (~ 20 μm after 400 cycles) though it had increased coating density. However, the mullite/Gd₂SiO₅ (88/12 wt.%) EBC (alcohol based) delaminated from the SN282™ Si₃N₄ substrate after 1350 °C/100 cycles, because of the formation of interconnected interfacial voids and hairline cracks. Parabolic growth kinetics for the underlying silica was observed for both the alcohol and sol based coated samples.     

Development of hard intermetallic coatings on austenitic stainless steel by hot dipping in an Al-Si alloy

The austenitic stainless steel was coated by dipping it into a molten Al-12.4%Si alloy at 765 °C. The effect of immersion times in the range of 60 to 900 s was investigated with respect to the crystalline structure, thickness, and microhardness of the coating. A uniform layer (~ 12 µm) of intermetallic Al₁₂(Fe,Cr)₃Si₂ with hexagonal crystalline structure is formed, irrespective of the immersion time. Incorporation of Si to the coating changes the growth mode of the coating from inwards to outwards, which favours the development of a flat substrate/coating interface. Microhardness of the coating decreases with increasing dipping time, ranging between 850 and 600 HV for the shortest and longest immersion time, respectively. These hardness values are higher than that for the substrate of about 200 HV, irrespective of the immersion time.     

Structure and oxidation behavior of Si-Y co-deposition coatings on an Nb silicide based ultrahigh temperature alloy prepared by pack cementation technique

In order to improve the oxidation resistance of silicide coatings on Nb silicide based alloys, Y-modified silicide coatings were prepared by co-depositing Si and Y at 1050, 1150 and 1250 °C for 5-20 h, respectively. It has been found that the coatings prepared by co-depositing Si and Y at 1050 and 1150 °C for 5-20 h as well as at 1250 °C for 5 h were composed of a thick (Nb,X)Si₂ (X represents Ti, Cr and Hf elements) outer layer and a thin (Nb,X)₅Si₃ inner layer, while the coatings prepared by co-depositing Si and Y at 1250 °C for 10-20 h possessed a thin outer layer composed of (Ti,Nb)₅Si₃ and Ti-based solid solution, a thick (Nb,X)Si₂ intermediate layer and a thin (Nb,X)₅Si₃ inner layer. EDS analyses revealed that the content of Y in the (Nb,X)Si₂ layers of all the coatings was about 0.34-0.58 at.% while that in the outer layers of the coatings prepared by co-depositing Si and Y at 1250 °C for 10-20 h was about 1.39-1.88 at.%. The specimens treated by co-depositing Si and Y at 1250 °C for 10 h were selected for oxidation test. The oxidation behavior of the coating specimens at 1250 °C indicated that the Si-Y co-deposition coating had better oxidation resistance than the simple siliconized coating because the oxidation rate constant of the Si-Y co-deposition coating was lower than that of the simple siliconized coating by about 31%. The scale developing on the Si-Y co-deposition coating consisted of a thicker outer layer composed of SiO₂ and TiO₂ and a thinner SiO₂ inner layer.     

Formation of an aluminum-alloyed coating on AZ91D magnesium alloy in molten salts at lower temperature

An aluminum-alloyed coating was formed on an AZ91D magnesium alloy in molten salts containing AlCl₃ at a lower temperature of 380 °C. The microstructure and phase constitution of the alloyed layer were investigated by optical microscopy, scanning electron microscopy, energy dispersive spectrum and X-ray diffraction. The nano-hardness of the coating was studied by nanoindentation associated with scanning probe microscopy. The corrosion resistance of the coated specimen was evaluated in a 3.5 wt.% NaCl solution by electrochemical impedance spectroscopy and cyclic potentiodynamic polarization. The results show that the aluminum-alloyed coating consists of Mg₂Al₃ and Mg₁₇Al₁₂ intermetallic layers. The formation of the coating is dictated by the negative standard free energy of the reaction: 2AlCl₃ + 3 Mg = 3MgCl₂ + 2Al. This process is associated with a displacement reaction mechanism and diffusion process that takes place during the molten salt treatment. High activity of Al elements in molten salts contributes to the lower temperature formation of the Al-alloyed coating. The alloyed coating markedly improves the hardness as well as the corrosion resistance of the alloy in comparison with the untreated AZ91D magnesium alloy, which is attributed to the formation of the intermetallic compounds.     

Control of lubricant transport by a CrN diffusion barrier layer during high-temperature sliding of a CrN-Ag composite coating

CrN-Ag composite coatings, 2 and 5 μm thick and containing 22 at.% Ag solid lubricant, were grown on Si(001) and 440C stainless steel substrates by reactive co-sputtering at T_s = 500 °C, and were covered with 200 nm thick pure CrN diffusion barrier cap layers. Annealing experiments at T_a = 625 °C, followed by quantitative scanning electron microscopy, energy dispersive x-ray spectroscopy, and Auger depth profile analyses indicate considerable Ag transport to the top surface for a barrier layer deposited at a substrate floating potential of −30 V, but negligible Ag diffusion when deposited with a substrate bias potential of −150 V. This is attributed to ion-irradiation induced densification which makes the cap layer an effective diffusion barrier. High temperature tribological sliding tests of this coating system against alumina balls at T_t = 550 °C indicate an initial friction coefficient μ = 0.43 ± 0.04 which decreases monotonically to 0.23 ± 0.03. This is attributed to the development of wear mediated openings in the barrier layer which allow Ag lubricant to diffuse to the sliding top surface. In contrast, pure CrN exhibits a constant μ = 0.41 ± 0.02 while CrN-Ag composite coatings without cap layer show a low transient μ = 0.16 ± 0.03, attributed to Ag transport to the surface, that however increases to μ = 0.39 ± 0.04 after ~ 6000 cycles as the Ag reservoir in the coating is depleted. That is, the dense CrN cap layer reduces the Ag lubricant flow rate and therefore prolongs the time when the coating provides effective lubrication. This results in a cumulative wear rate over 10,000 cycles of 3.1 × 10⁻⁶ mm³/Nm, which is 3.3 × lower than without diffusion barrier layer.     

Correlation between current frequency and electrochemical properties of Mg alloy coated by micro arc oxidation

The present work investigated the electrochemical behavior of Mg alloy subjected to micro arc oxidation coating for 120 s with respect to current frequencies from 60 Hz to 2000 Hz. The microstructure and chemical compound of thin coating layers with a thickness of ~ 3 μm were analyzed using scanning electron microscopy and X-ray photoelectron spectroscopy. The microstructural observations on the surface and cross sections revealed that both the size of pores and the number of discharge channels decreased significantly as the current frequency increased, resulting in a compact coating layer. This was primarily attributed to the transition time of the alternating electrical wave, which was determined by the current frequencies tested. Based on potentiodynamic polarization tests, the sample coated at a frequency of 2000 Hz demonstrated the highest polarization resistance of 6.37 × 10⁵ Ω cm², implying that the corrosion resistance was superior to that obtained under other conditions due to its condensed structure. This electrochemical response was also interpreted in relation to the equivalent circuit model.     

Interactions between Nb-silicide based alloy and yttria mould during directional solidification

Pure yttria moulds have been prepared for directional solidifications of Nb-22Ti-16Si-6Hf-2Al-2Cr (at. %) alloy with a withdrawal rate of 1 × 10^-4 m s^-1 at 1850 °C and 1900 °C. This study demonstrates that a mild interface reaction occurred between the yttria mould and hafnium, the most reactive element in the alloy. A sequential reaction layer of HfO₂ and Y₂O₃ was formed at metal-mould interface, and its thickness depended on both heating temperature and holding time. HfO₂-Y₂O₃ inclusions were dispersed in the metal matrix, and the majority of them concentrated around the solid-liquid interface rather than in steady state growth region. Some inclusions were merged with each other. The reaction mechanism between Nb-silicide based alloy and yttria mould also has been described.     

Oxidation and electrical behavior of AISI 430 coated with cobalt spinels for SOFC interconnect applications

Stainless steel can be used as interconnect plates in solid oxide fuel cells (SOFCs) below operating temperature of 800 °C. Unwanted reactions between the alloy and other SOFC components decrease the efficiency of these energy convertors. One approach to improving interconnect properties is to apply a surface coating to them. In this study, AISI 430 ferritic stainless steel interconnect is coated in a cobalt-base pack mixture using the pack cementation method. Isothermal oxidation, cyclic oxidation and oxidation at different temperatures (400-900 °C) are applied to evaluate the role of the coating layer during oxidation. Area-specific resistance (ASR) of the coated substrates has also been tested as a function of temperature and time. The surface morphology was examined by SEM, the chemical composition and structure of oxide formed were analysed by EDS and XRD. Results showed that the coating layer transforms into MnCo₂O₄, CoCr₂O₄ and CoFe₂O₄ spinels during isothermal oxidation. This scale is protective and acts as an effective barrier against chromium migration into the outer oxide layer and prevents weight gain. The mass gain and spallation indicated that the formation of spinel significantly improved the high temperature oxidation. These spinels also cause a reduction in ASR for coated substrates (9.7 mΩcm²) as compared to uncoated substrates (36.1 mΩcm²) after 200 h of isothermal oxidation at 800 °C.     

Influence of the thermo-chemical conditions on the carbo-chromization process of α-Fe matrices obtained by powder sintering technique

We report on the superficial layer formation resulting from the carburization followed by chromization of α-Fe samples obtained by powder sintering technique. The carburization and chromization were carried out by thermal diffusion between 880-980 °C and 950-1050 °C in a solid powder mixture of charcoal/BaCO₃ and ferrochromium/alumina/NH₄Cl, respectively. The obtained layers were investigated using X-ray diffraction, optical microscopy, Vickers micro-hardness technique and scanning electron microscopy. The results show that the layers are of micrometric size and consist mostly of chromium carbides of different phases. These phases as well as the thickness of the layers are closely related to the treatment temperature used for carburization and to the temperature and Cr initial concentration in the mixture used for chromization. For highly reactive carbo-chromization conditions (high concentration of Cr, and high carburization and chromization temperatures) the superficial layer is constituted of two chromium carbide sub-layers (Cr₃C₂/Cr₇C₃) separated by a sharp interface. The thickness and hardness of the coating layer reached 45 μm and 2300 HV, respectively. Such coating could be used for tools that have to be abrasion and oxygen resistant at high temperatures.