Glass–ceramic coatings on titanium alloys for high temperature oxidation protection: Oxidation kinetics and microstructure

A glass–ceramic coating is applied on Ti–6Al–4V alloy for oxidation protection at 800 °C. Its dynamic oxidation and microstructure evolution are investigated. The titanium alloy substrate is effectively protected by the glass–ceramic coating, of which the oxidation develops at constant rate. The linear relationship of oxidation is deduced dm/dt = Dρ(C₁ − C₂)/(bC′), and the diffusion coefficient of oxygen at 800 °C in glass is obtained. Oxygen diffusion through glass coating is the controlling step. After the initial firing, silicide interlayer forms between the glass coating and titanium alloy substrate, where the ratio of Ti/Si decreases after oxidation due to Si diffusion and Ti consumption.     

Effect of hot-dip aluminizing on the oxidation resistance of Ti–6Al–4V alloy at high temperatures

Hot-dip aluminizing and interdiffusion treatment were used to develop a TiAl₃-rich coating on Ti–6Al–4V alloy. Interrupted oxidation at temperatures from 600 to 900 °C and isothermal oxidation at 700 and 800 °C of the coating were conducted. The coating markedly decreases the oxidation rate in comparison with the alloy at temperatures below 800 °C during the interrupted oxidation. The oxidation kinetics follows parabolic relations at 700 and 800 °C during the isothermal oxidation. A layered structure of Al₂O₃/TiAl₃/TiAl₂/TiAl/alloy from the outside to the inside forms after oxidation at 700 °C without changing the main body of the coating.     

Microstructure and oxidation resistance of Mo–Si–B coating on Nb based in situ composites

The development of robust high temperature oxidation resistant coatings for Nb–Si based alloy was evaluated for a Mo–Si–B coating system that was applied by a two step process. It is observed that the coating is composed of an outer layer of MoSi₂ containing boride dispersoids and an inner layer of unreacted Mo. The mass gain of substrate and Mo–Si–B coating is 190.08 and 1.28 mg cm⁻² after oxidation at 1250 °C in dry air for 100 h, respectively. The good oxidation resistance of the coating is attributed to the formation of a continuous borosilicate glass coverage.     

Magnetron-sputtered oxidation protection coatings for Mo–Si–B alloys

Oxidation protective Mo–70Al, Mo–37Si–15B and Mo–46Si–24B (at.%) coatings with 5–10 μm thickness were deposited on Mo–9Si–8B alloys by magnetron sputtering; and their oxidation behavior was studied at 800, 1000 and 1300 °C in air. On the Mo–70Al layer a dense aluminum borate scale grew at 800 °C; however, this coating rapidly degraded at 1000 °C linked to substrate oxidation at uncoated areas. The Mo–37Si–15B and Mo–46Si–24B layers provided oxidation protection to the Mo–Si–B alloy at 800 and 1000 °C for up to 100 h due to formation of a borosilicate scale. The latter coating was protective for short times even at 1300 °C.     

Formation and oxidation resistance of Hf and Al modified silicide coating on Nb–Si based alloy

Codeposition of Si, Al and Hf were prepared by pack cementation at 1300 °C for 10 h. The results show that the coating is composed of a thick (Nb, X)Si₂ outer layer, a (Ti, Nb)₅Si₄ middle layer and a thin discontinuous (Cr, Al)₂(Nb, Ti) inner layer. The mass gain of the coating is only 4.12 mg/cm² after isothermal oxidation at 1250 °C for 100 h. Some “oxide pegs” form at the interface of the oxide scale and coating. The coating exhibits good cyclic oxidation resistance due to the improved adhesion between the oxide scale and coating.     

SiO2–Al2O3–glass composite coating on Ti–6Al–4V alloy: Oxidation and interfacial reaction behavior

A SiO₂–Al₂O₃–glass composite coating was prepared on Ti–6Al–4V alloy by air spraying and subsequent firing. The oxidation behavior of the specimens at 800 °C and 900 °C for 100 h was studied. The thermal shock resistance of the coating was tested by heating up to 900 °C and then quenching in water. The composite coating acted as an oxygen migration barrier and exhibited good resistance against high temperature oxidation, thermal shock, and oxygen permeation on the Ti–6Al–4V alloy. Coating/alloy interfacial reaction occurred, forming a Ti₅Si₃/Ti₃Al bilayer structure. A thin Al₂O₃ rich layer formed beneath the composite coating during oxidation at 900 °C.     

Comparison between oxidation kinetics of HVOF sprayed WC–12Co and WC–10Co–4Cr coatings

In this study, the high temperature oxidation behavior of HVOF-sprayed WC–12Co and WC–10Co–4Cr coatings were investigated. To explore the oxidation mechanism, thermo-gravimetric analysis (TGA) was applied for isothermal treatments in the range of 500–800 °C for 3 h. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to evaluate the structural changes and microstructural evolutions during oxidation tests. The TGA experiments showed negligible oxidation mass gains at 500 °C for both coatings. At higher temperatures, i.e. 700 and 800 °C, the oxidation mass gains of WC–12Co were found to be much higher than those for WC–10Co–4Cr coating, respectively. The higher oxidation resistance of WC–10Co–4Cr coating probably results from the formation of compact chromium oxide layers and higher MWO₄ type tungstate (M: Co and/or Cr) to tungsten trioxide (WO₃) ratios which provide lower porosity and consequently more efficient passivation effect against oxidation. The time dependent mass gain of WC–12Co coating obeys the linear law within temperature range of 600–800 °C with apparent oxidation activation energy of ~ 104 kJ/mol. As for the oxidation of WC–10Co–4Cr coating, a negligible deviation from linear law was observed possibly due to the presence of chromium oxide and higher tungstate to tungsten trioxide ratio which hinders the diffusion process through the scales compared with WC–12Co coating. The apparent activation energy for oxidation of the WC–10Co–4Cr coating was found to be ~ 121 kJ/mol.     

Novel thermal protection coating based on Zr0.75Ce0.25O2/phosphate duplex system for polyimide matrix composites fabricated via a combined sol–gel/sealing treatment process

Thermal protection coating based on Zr_0.75Ce_0.25O₂/phosphate system was fabricated on polymer–matrix composites via a combined sol–gel/sealing treatment process. Phosphates sealed the cracks and enhanced the adhesion property via chemical bonding and binding. The Zr_0.75Ce_0.25O₂/phosphate duplex coating exhibited good thermal shock resistance and improved thermal oxidation resistance of the substrate. Due to the protection of the duplex coating, the weight loss of the specimen reduced from (4.83 ± 0.12)% to (0.98 ± 0.08)% and the mass ablation rate decreased from 0.088 ± 0.002 mg cm⁻² s⁻¹ to 0.018 ± 0.002 mg cm⁻² s⁻¹ when testing at 810 °C. Coating failure was attributed to the formation of cracks and delamination.     

High temperature oxidation of AlCrFe complex metallic alloys

Isothermal oxidation of Al₆₅Cr₂₇Fe₈ and Al₈₀Cr₁₅Fe₅ was studied in the 600–1080 °C range. Formation of transient alumina layers is obtained up to 900 °C. On Al₆₅Cr₂₇Fe₈ transient to α-phase transformations occur when performing oxidation at 1000 °C, together with the possible appearance of (Al_0.9Cr_0.1)₂O₃. At 1080 °C, direct formation of α-alumina is obtained. On Al₈₀Cr₁₅Fe₅, spallation of the oxide layer during the cooling stage is observed following oxidation at 800 and 900 °C, revealing thermal etching of the underneath alloy surface. At 1050 °C the α-Al₂O₃ scale is directly formed but plastic deformation and recrystallization of the underneath alloy into several intermetallic phases is observed.     

The high-temperature oxidation of bulk nanocrystalline 304 stainless steel in air

The high-temperature oxidation of bulk nanocrystalline 304 stainless steel (BN-SS304) and its conventional polycrystalline counterpart (CP-SS304) in air at 900 °C for 24 h were studied by thermogravimetric analysis, X-ray photoelectron spectroscopy and scanning electron microscope. We studied the valence electron configurations of BN-SS304, CP-SS304 and their oxide scales by ultra-violet photoelectron spectroscopy. The high-temperature oxidation resistance of BN-SS304 was enhanced in both initial and isothermal oxidation, which was attributed to its larger work function and more chemical stability, its more chemically stable and compact oxide scale, its weaker O₂ adsorption and diffusion, its weaker Cr and Mn atoms diffusions.     

Effects of temperature and the incorporation of W on the oxidation of ZrB2 ceramics

The effects of tungsten additions and temperature on the oxidation behavior of nominally pure ZrB₂ and ZrB₂ containing 4, 6 or 8 mol% of W after oxidation at temperatures ranging from 800 to 1600 °C were investigated. For pure ZrB₂, the protective liquid/glassy layer covering the surface as a result of oxidation was evaporated above 1500 °C. For (Zr,W)B₂ specimens, the liquid/glassy layer was present after exposure up to 1600 °C. The higher stability of the liquid/glassy phase in the W-containing compositions was attributed to the presence of tungsten in the liquid/glassy phase, resulting in improved oxidation resistance for ZrB₂ samples containing W.     

Oxidation behavior of micro-sized Al2O3–TiC–Co composites prepared from cobalt-coated powders

The oxidation behavior of hot-pressed Al₂O₃–TiC–Co composites prepared from cobalt-coated powders has been studied in air in the temperature range from 200 °C to 1000 °C for 25 h. The oxidation resistance of Al₂O₃–TiC–Co composites increases with the increase of sintering temperature at 800 °C and 1000 °C. The oxidation surfaces were studied by XRD and SEM. The oxidation kinetics of Al₂O₃–TiC–Co composites follows a rate that is faster than the parabolic-rate law at 800 °C and 1000 °C. The mechanism of oxidation has been analyzed using thermodynamic and kinetic considerations.     

Long term oxidation resistance and thermal stability of Ni-aluminide/Fe-aluminide duplex diffusion coatings formed on ferritic steels at low temperatures

A coating with a duplex structure consisting of an outer Ni₂Al₃ layer and an inner Fe₂Al₅ layer was formed on a commercial type of ferritic steel P92 using a two step process of electroless Ni/B plating followed by pack aluminising at 650 °C. Nearly 11,000 h oxidation test in air and more than 13,000 h isothermal annealing test in argon atmosphere were carried out to assess the long term oxidation resistance and thermal stability at 650 °C. The amount of oxidation was only about 0.66 mg/cm² for the coating as compared to 10.3 mg/cm² for the uncoated steel after nearly 11,000 h oxidation test. Inward Al diffusion took place during oxidation test, which led to the transformation of the outer Ni₂Al₃ layer to NiAl and increase in the Al diffusion depth. However, once the outer Ni₂Al₃ layer was completely transformed to NiAl, it stayed stable during the remaining period of oxidation test, providing long term oxidation resistance. Kirkendall voids formed and grew and then finally disappeared in the coating layers due to interdiffusion processes taking place at the oxidizing temperature at the interfaces between different layers of the duplex coating. No spallation was observed in the coating during the entire period of the oxidation or isothermal annealing tests.     

The isothermal and cyclic oxidation behaviour of two Co modified aluminide coatings at high temperature

The isothermal and cyclic oxidation behaviour of two Co modified aluminide coatings together with the simple aluminide coating were performed at 1000 °C and 1100 °C. All the three coatings show a much lower oxidation rate compared with the bare alloy. Results also indicate the addition of Co to the aluminide coating decreases the oxidation resistance slightly. It can be ascribed to that Co is easier to be oxidized than Ni at high temperature, and the Cr(W) rich phases which could act as a diffusion barrier are less in the coating with higher Co content.     

Evolution of surface chemistry and morphology of oxide scale formed during initial stage oxidation of modified 9Cr–1Mo steel

Initial stage oxidation characteristics of the modified 9Cr–1Mo steel in ambient air at 650 °C have been investigated, for exposure times ranging from 5 to 500 h. Oxygen flux from the gas phase causes high initial oxidation rate, but the growth kinetics do not follow parabolic law. In “as-received” condition, binary oxides of Fe and Cr were found as native oxides. Upon oxidation, segregation of Mn resulted in the formation of MnCr₂O₄ along with FeCr₂O₄ and binary oxides of Fe, Cr and Mn. Thus, the initial oxide scale constitutes multiple oxides with delineated interface, unlikely to have a layered structure.     

Oxidation induced phase transformation of duplex stainless steel 25Cr–10Mn–2Ni–3Mo–0.8W–0.8Cu–0.5N

Isothermal oxidation behaviour of duplex stainless steel 25Cr–10Mn–2Ni–3Mo–0.8W–0.8Cu–0.5N was investigated at 1050 °C in air through scanning electronic microscopy and Raman spectroscopy. The weight gain per unit area was in parabolic relation to oxidation time with a parabolic rate constant (k_p) 1.39 × 10^?12 g² mm^?4 min^?1. An oxidation induced transformed ferrite diffusion layer was observed due to the preferential oxidation of manganese.     

TEM analysis of the microstructure of thermal barrier coatings after isothermal oxidation

Thermal barrier coatings (TBCs) are extensively used to protect metallic components in applications where the operating conditions include an aggressive environment at high temperatures. The most important factor controlling TBC durability is the nucleation, and subsequent thickening, of a thermally grown oxide (TGO) layer which is formed during high-temperature oxidation. For this reason, the aim of this work is to analyse the TGO microstructure evolution during isothermal oxidation to explain the macroscopic oxidation behaviour. To this end, transmission electron microscopy (TEM) was used to evaluate the TGO fine microstructure. ZrO₂(Y₂O₃) top coat and NiCrAlY bond coating were air plasma sprayed onto an Inconel 600 Ni base alloy. The TBCs were isothermally oxidized in air at 950 and 1050 °C for 24, 48, 72, 144 and 336 h and the principal differences in TGO composition were analysed. α-Al₂O₃ was the main TGO constituent in the TBC treated at 950 °C. On the other hand, Al was rapidly consumed in the TBC oxidized at 1050 °C leading to the formation of NiAl₂O₄ spinels, after 72 h exposure, and NiO, after 336 h. The TGO growth kinetics followed a power law, controlled by Al³⁺ diffusion, in the samples treated at 950 °C. However, two different power laws fitted the TGO growth kinetics in the coatings treated at 1050 °C as the diffusion of Ni²⁺ is relevant after 72 h exposure.     

Effects of surface temperature,flow velocity and ambient pressure on the oxidation of graphite at 1400–2000 °C in O2

The effects of surface temperature (1400–2000 °C), flow velocity gradient (130–600 s⁻¹) and ambient pressure (5–101 kPa) on the oxidation behavior of graphite were studied in O₂. The weight loss rate between 1400 and 1800 °C is independent of the surface temperature but slightly decreases at 2000 °C. Besides, it displays quasi-parabolic increases with increasing the flow velocity gradient and the ambient pressure but levels off above the ambient pressure of 20 kPa. According to the theoretical analysis, the enhancement of the gas-phase CO–O₂ reaction has a joint reduction effect on the weight loss rate.     

NiCoCrAlY coatings with and without an Al2O3/Al interlayer on an orthorhombic Ti2AlNb-based alloy: Oxidation and interdiffusion behaviors

The mechanism of oxidation protection of NiCoCrAlY overlay coatings on the orthorhombic Ti₂AlNb-based alloy (O alloy) Ti–22Al–26Nb (at.%) is described. While the bare alloy exhibited poor oxidation resistance at 800 °C, adding NiCoCrAlY coatings significantly improved the oxidation resistance. However, serious interdiffusion between the coatings and the substrate resulted in rapid degradation of the coating system. Several reaction layers were formed at the coating/substrate interface by interdiffusion, and non-protective scales mainly of Cr₂O₃ and TiO₂ were formed due to the degradation of the coating. In order to solve this problem, an Al₂O₃/Al interlayer was sandwiched into the coating system as a diffusion barrier. The isothermal and cyclic oxidation protection of the multilayer coating system on the Ti–22Al–26Nb substrate was evaluated at 800 and 900 °C. The results indicated that the interdiffusion was much suppressed, and the duplex coating system demonstrated improved oxidation resistance on the Ti–22Al–26Nb substrate, with a thin and adherent protective α-Al₂O₃ scale forming on the surface.     

The enhanced passivation of 316L stainless steel in a simulated fuel cell environment by surface plating with palladium

A thin layer of Pd deposition on the surface significantly improves the corrosion resistance of 316L stainless steel in 0.5 mol L⁻¹ H₂SO₄ + 2 ppm F⁻ solution at 80 °C. Compared with the air-formed passive film, the passive film formed in the stainless steel/Pd couple contains more Cr, Cr(OH)₃ and Fe₃O₄ and less point defects, which provides better protection to the stainless steel substrate. The interfacial contact resistance of the stainless steel surface is also decreased. The Pd plated stainless steel is a potential material for bipolar plates in proton exchange membrane (PEM) fuel cells.