The corrosion behavior of Fe-Nb-Al alloys in H2/H2O/H2S atmospheres

The corrosion behavior of eight Fe-Nb-Al ternary alloys was studied over the temperature range 700–980°C in H₂/H₂O/H₂S atmospheres. The corrosion kinetics followed the parabolic rate law for all alloys at all temperatures. The corrosion rates were reduced with increasing Nb content for Fe-x Nb -3Al alloys, the most pronounced reduction occurred as the Nb content increased from 30 to 40 wt.%. The corrosion rate of Fe-30Nb decreased by six orders of magnitude at 700°C and by five orders of magnitude at 800°C or above by the addition of 10 wt.% aluminum. The scales formed on low-Al alloys (3 wt.% Al) were duplex, consisting of an outer layer of iron sulfide (with Al dissolved near the outer-/inner-layer interface) and an inner complex layer of Fe_xNb₂S₄(FeNb₂S₄ or FeNb₃S₆), FeS, Nb₃S₄ (only detected for Nb contents of 30 wt.% or higher) and uncorroded Fe₂Nb. No oxides were detected on the low-Al alloys after corrosion at any temperature. Platinum markers were found to be located at the interface between the inner and outer scales for the low-Al alloys, suggesting that the outer scale grew by the outward transport of cations (Fe and Al) and the inner scale grew by the inward transport of sulfur. The scales formed on high-Al alloys (5 wt.% Al) were complex, consisting primarily of Nb₃S₄, Al₂O₃ and (Fe, Al)_xNb₂S₄, and minor amounts of (Fe, Al)S and uncorroded intermetallics (FeAl and Fe₂Nb). The formation of Nb₃S₄ and Al₂O₃ blocked the transport of iron through the inner scale, resulting in the significant reduction of the corrosion rates.     

On the reaction mechanism of nickel with SO2+O2/SO3

High-purity nickel has been reacted with 96% O₂+4% SO₂ at 700–900°C. The reaction has been studied at 700°C as a function of the total gas pressure (0.06–1 atm) and at 1 atm as a function of temperature (700–900°C). The reaction mechanism changes with the effective pressure of p(SO₃) in the gas. When NiSO₄ (NiO + SO₃ = NiSO₄) is formed on the scale surface, the scale consists of a two-phase mixture of NiO + Ni₃S₂; in addition, sulfur is enriched at the metal/scale interface. A main process in the reaction is rapid outward diffusion of nickel through the Ni₃S₂ phase in the scale; the nickel reacts with NiSO₄ to yield NiO, Ni₃S₂, and possibly NiS as an intermediate product. When NiSO₄ cannot be formed, the scale consists of NiO, and small amounts of sulfur accumulate at the metal/scale interface. It is proposed that the reaction under these conditions is primarily governed by outward grain boundary diffusion of nickel through the NiO scale, and in addition, small amounts of SO₂ migrate inward through the scale—probably along microchannels.     

Variation of microstructure and composition of the Cr2AlC coating prepared by sputtering at 370 and 500 °C

Cr₂AlC coating was deposited at 370 and 500 °C by D.C. magnetron sputtering from an as-synthesized bulk Cr₂AlC target. The phase composition and preferential orientation of the coating were investigated using XRD, and the microstructure of the coating was characterized by TEM. Results indicated that Cr₂AlC coating with a strong (110) preferential orientation could be obtained. The coating microstructure was clearly affected by the deposition temperature. At 370 °C, the deposited coating possessed a triple-layered structure with an α-(Cr, Al)₂O₃ inner layer, an amorphous intermediate layer and a crystalline Cr₂AlC outer layer. However, the coating deposited at 500 °C had a single-layered structure consisting of crystalline Cr₂AlC layer. The growth mechanism of the Cr₂AlC coating at different deposition temperatures is discussed.     

The effect of preoxidation on the sulfidation of Ni-20Cr (2–5)Al Alloys

Ni-20Cr alloys with 2, 3.5, and 5 wt.% Al have been preoxidized up to 100 hr at 1000°C in dry H₂, in H₂/23% H₂O and in air and subsequently exposed to an H₂/5% H₂S atmosphere at 750° C. During the preoxidation treatment different types of oxide scales were formed which affect the sulfidation protection in different ways. Optimum results were obtained for alloys with 3.5 and 5 wt.% Al after 20 hr exposure to dry H₂ at 1000°C. A thin Al₂O₃ scale is formed which decreases the sulfur attack by more than one order of magnitude. Preoxidation conditions for Ni-20Cr-2Al alloys in H₂ and for Ni-20Cr-2Al and Ni-20Cr-3.5Al in H₂/H₂O were observed to be less effective. No improvement was found for preoxidation in air or for Ni-20Cr-5Al alloys preoxidized in H₂/H₂O.     

The high-temperature corrosion behavior of Fe-Mo-Al alloys in H2/H2O/H2S mixed-gas environments

The corrosion behavior of 11 Fe-Mo-Al ternary alloys was studied over the temperature range 700–980°C in H₂/H₂O/H₂S mixed-gas environments. With the exception of Fe-10Mo-7Al, for which breakaway kinetics were observed at higher temperatures, all alloys followed the parabolic rate law, despite two-stage kinetics which were observed in some cases. A kinetics inversion was observed for alloys containing 7 wt.% Al between 700–800°C. The corrosion rates of Fe-20Mo and Fe-30Mo were found to be reduced by five orders of magnitude at all temperatures by the addition of 9.1 or higher wt.% aluminum. The scales formed on low-Al alloys (5 wt.% Al) were duplex, consisting of an outer layer of iron sulfide (with some dissolved Al) and a complex inner of Al_0.55Mo₂S₄, FeMo₂S₄, Fe_1.25Mo₆S_7.7, FeS, and uncorroded FeAl and Fe₃Mo₂. Platinum markers were always located at the interface between the inner and outer scales for the low-Al alloys, indicating that outer-scale growth was due mainly to outward diffusion of cations (Fe and Al), while the inner scale was formed primarily by the inward flux of sulfur anions. Alloys having intermediate Al contents (7 wt.%) formed scales that consisted of FeS and Al₂O₃. The amount of Al₂O₃ increased with increasing reaction temperature. The high-Al-content alloys (9.1 and 10 wt.%) formed only Al₂O₃ which was responsible for the reduction of the corrosion rates.     

Preventing the accelerated low-temperature oxidation of MoSi2 (pesting) by the application of superficial alkali-salt layers

Previous work showed that MoSi₂ diffusion coatings formed by a NaF-activated pack cementation process did not pest. A Na–Al-oxide by-product layer resulting from the NaF activator formed a Na-silicate layer to passivate MoSi₂. Superficial NaF layers were then used to prevent the pesting of MoSi₂ diffusion coating that were otherwise susceptible to pest disintegration. In this study, the use of superficial alkali-salt layers to prevent the accelerated oxidation of bulk MoSi₂ at 500°C is investigated more broadly. The application of Na-halide, KF, LiF, Na₂B₄O₇, or Na-silicate layers prior to oxidation prevented accelerated oxidation and pesting for at least 2000 hr at 500°C in air. The formation of a fast-growing, Na-silicate layer passivates MoSi₂. The MoO₃ that forms during oxidation absorbs sodium by intercolation to form stable Na-molybdate precipitates. Na₂B₄O₇, Na-silicate, LiF, and KF prevented accelerated oxidation at 500°C by a similar mechanism. The application of alkali-halide salts is a simple, effective solution to prevent the accelerated oxidation and pesting of MoSi₂.     

Effects of K2O-Li2O doping on surface and catalytic properties of Fe2O3/Cr2O3 system

The effects of K₂O and Li₂O-doping (0.5, 0.75 and 1.5 mol%) of Fe₂O₃/Cr₂O₃ system on its surface and the catalytic properties were investigated. Pure and differently doped solids were calcined in air at 400-600 °C. The formula of the un-doped calcined solid was 0.85Fe₂O₃:0.15Cr₂O₃. The techniques employed were TGA, DTA, XRD, N₂ adsorption at −196 °C and catalytic oxidation of CO oxidation by O₂ at 200-300 °C. The results revealed that DTA curves of pure mixed solids consisted of one endothermic peak and two exothermic peaks. Pure and doped mixed solids calcined at 400 °C are amorphous in nature and turned to α-Fe₂O₃ upon heating at 500 and 600 °C. K₂O and Li₂O doping conducted at 500 or 600 °C modified the degree of crystallinity and crystallite size of all phases present which consisted of a mixture of nanocrystalline α- and γ-Fe₂O₃ together with K₂FeO₄ and LiFe₅O₈ phases. However, the heavily Li₂O-doped sample consisted only of LiFe₅O₈ phase. The specific surface area of the system investigated decreased to an extent proportional to the amount of K₂O and Li₂O added. On the other hand, the catalytic activity was found to increase by increasing the amount of K₂O and Li₂O added. The maximum increase in the catalytic activity, expressed as the reaction rate constant (k) measured at 200 °C, attained 30.8% and 26.5% for K₂O and Li₂O doping, respectively. The doping process did not modify the activation energy of the catalyzed reaction but rather increased the concentration of the active sites without changing their energetic nature.     

The spalling modes and degradation mechanism of ZrO2-8 wt.% Y2O3/CVD-Al2O3/Ni-22Cr-10Al-1Y thermal-barrier coatings

State-of-the-art conventional thermal-barrier coatings consist of a thermalinsulating, partially-stabilized ZrO₂ top coat and a bond coat. In this study, a continuous alumina-diffusion-barrier layer was deposited and interposed between the top coat and bond coat by chemical-vapor deposition (CVD). Both the conventional and the experimental TBC systems were cyclically tested at 1000°C, 1050°C, 1100°C, and 1150°C to evaluate and compare oxidation, performance, and fracture behavior. Introduction of the intermediate CVD-Al₂O₃ layer effectively suppressed the oxidation rate of the bond coat and sufficiently altered its oxidation behavior. The thermal-cyclic life of TBCs was improved by the new system. The failure of the ZrO₂-8 wt.% Y₂O₃/CVD-Al₂O₃/Ni-22Cr-10Al-1Y TBC specimens was observed to propagate mainly along the lamellar splats of the top coat, and secondarily along the top coat/CVD-Al₂O₃ interface.     

Morphological Development of Subscale Formation in Fe–Cr–(Ni) Alloys with Chloride and Sulfates Coating

Three types of stainless steel (430, 304, and 310) with a coating of NaCl, NaCl/AlCl₃, or NaCl/Al₂(SO₄)₃ are exposed at 750 and 850°C. Results show that NaCl has a major effect on corrosion and sulfur plays an important role in intergranular corrosion. After high-temperature exposure with a 100% NaCl coating, the morphologies of alloys 304 and 310 show typical uniform subscale attack the depths of attack increasing with temperature, while alloy 430 showed a planar attack. Alloy 310 has the highest chromium content and has the least metal loss. After high-temperature exposure with a NaCl/AlCl₃ coating, the corrosion morphologies and depths of attack are similar to those associated with an NaCl coating, but only voids are larger in the subscale. When coated with NaCl/Al₂(SO₄)₃, the alloys are attacked simultaneously by sulfur and chlorine at 750°C, resulting in a typical sulfur-attack intergranular corrosion. However, as the temperature increases to 850°C, the corrosion morphology changes to a uniform subscale attack.     

Diffusion of18O in massive Cr2O3 and in Cr2O3 scales at 900°C and its relation to the oxidation kinetics of chromia forming alloys

The lattice and grain-boundary diffusion coefficients of¹⁸O atP _{O 2}=0.1 atm and at 900°C were determined in massive Cr₂O₃ and in Cr₂O₃ scales which were grown on a Ni–30Cr alloy. The diffusion profiles were established by SIMS and analyzed considering two domains in the case of polycrystalline Cr₂O₃ (massive or scales), the first one relative to apparent diffusion and the second to grain-boundary diffusion. A ridge model is proposed for Cr₂O₃ scales to modify thef value, fraction of sites associated with the grain boundary. With such a model,f is equal to 0.0006 and 0.0005 for the scales formed during 15 hr and 165 hr, respectively. The oxygen-lattice diffusion coefficients determined in Cr₂O₃ scales are in very good agreement with those in massive Cr₂O₃. With some assumptions, our diffusion data lead to a calculated parabolic oxidation constant equal to the experimental one. Scale growth occurs by countercurrent diffusion of oxygen and chromium, mainly by grain-boundary diffusion.     

The Hot Corrosion of Fe-Mn-Al–C Alloy with NaCl/Na2SO4 Coating Mixtures at 750°C

The high-temperature corrosion behavior of Fe-30.1Mn-9.7Al-0.77C alloy initially coated with 2 mg/cm² NaCl/Na₂SO₄ (100/0, 75/25, 50/50, 25/75 and 0/100 wt.%) deposits has been studied at 750°C in air. The result shows that weight-gain kinetics in simple oxidation reveals a steady-state parabolic rate law after 3 hr, while the kinetics with salt deposits all display multi-stage growth rates. The corrosion morphology of the alloy with 100% Na₂SO₄ coating is similar to that of simple oxidation. NaCl acts as the predominant corrosion species for Fe-Mn-Al-C alloy, inhibiting the formation of a protective oxide scale. For the alloy coated with over 50% NaCl in salts, NaCl induces selective oxidation of manganese and results in the formation of secondary ferrite in the alloy substrate as well as void-layers with different densities of voids layer by layer in the secondary-ferrite zone.     

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.     

The high-temperature corrosion behavior of Nb-Al alloys in a H2/H2S/H2O gas mixture

The corrosion behavior of pure Nb and three Nb Al alloys containing 12.5, 25, and 75 at.% Al was studied over the temperature range of 800–1000°C in a H₂/H₂S/H₂O gas mixture. Except for the Nb-12.5Al alloy consisting of a two phase structure of -Nb and Nb₃Al, other alloys studied were single phase. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants increased with increasing temperature, but fluctuated with increasing Al content. The Nb-75Al alloy exhibited the best corrosion resistance among all alloys studied, whose corrosion rates are 1.6–2.2 orders of magnitude lower than those of pure-Nb (depending on temperature). An exclusive NbO₂ layer was formed on pure Nb, while heterophasic scales were observed on Nb-Al alloys whose compositions and amounts strongly depended on Al content and temperature. The scales formed on Nb-12.5Al consisted of mostly NbO₂ and minor amounts of Nb₂O₅, NbS2, and -Al₂O₃, while the scales formed on Nb-25Al consisted of mostly Nb₂O₅ and some -Al₂O₃. The scales formed on Nb-75Al consisted of mostly -Al₂O₃ and Nb₃S₄ atT 900°C, and mostly -Al₂O₃ , Nb₃S₄ and some AlNbO₄ at 1000°C. The formation of -Al₂O₃ and Nb₃S₄ resulted in a significant reduction of the corrosion rates.     

Al2O3-nanodiamond composite coatings with high durability and hydrophobicity prepared by aerosol deposition

We attempted the room-temperature fabrication of Al₂O₃-based nanodiamond (ND) composite coating films on glass substrates by an aerosol deposition (AD) process to improve the anti-scratch and anti-smudge properties of the films. Submicron Al₂O₃ powder capable of fabricating transparent hard coating films was used as a base material for the starting powders, and ND treated by 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) was added to the Al₂O₃ to increase the hydrophobicity and anti-wear properties. The ND powder treated by PFOTES was mixed with the Al₂O₃ powder by ball milling to ratios of 0.01 wt.%, 0.03 wt.%, and 0.05 wt.% ND. The water contact angle (CA) of the Al₂O₃-ND composite coating films was increased as the ND ratio increased, and the maximum water CA among all the films was 110°. In contrast to the water CA, the Al₂O₃-ND composite coating films showed low transmittance values of below 50% at a wavelength of 550 nm due to the strong agglomeration of ND. To prevent the agglomeration of ND, the starting powders were mixed by attrition milling. As a result, Al₂O₃-ND composite coating films were produced that showed high transmittance values of close to 80%, even though the starting powder included 1.0 wt.% ND. In addition, the Al₂O₃-ND composite coating films had a high water CA of 109° and superior anti-wear properties compared to those of glass substrates.     

The corrosion behavior of Ni-Al alloys and Ni-Nb-Al alloys in a H2/H2O/H2S gas mixture

The corrosion behavior of two Ni-Al alloys and four Ni-Nb-Al alloys was studied over the temperature range of 600° C to 1000° C in a mixed-gas of H₂/H₂O/H₂S. The parabolic law was generally followed, although linear kinetics were also observed. Multiple-stage kinetics were observed for the Ni-Al alloys. Generally, the scales formed on Ni-13.5Al and Ni-Nb-Al alloys were multilayered, with an outer layer of nickel sulfide with or without pure Ni particles and a complex inner scale. The outer scale became porous and discontinuous with increasing temperature. Very thin scales formed on Ni-31Al. The reduction in corrosion rate with increasing Al content is ascribed to the formation of Al₂O₃ and Al₂S₃ in the scale. Platinum markers were found at the interface between the outer and inner scales.     

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.     

Microstructure and high-temperature friction and wear behavior of WC-(W,Cr)2C-Ni coating prepared by high velocity oxy-fuel spraying

WC-(W,Cr)₂C-Ni coating was prepared by high velocity oxy-fuel spraying (HVOF). The microstructure and phase composition of the as-sprayed coating and that after oxidation at high temperature were analyzed by means of scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The oxidation behavior of as-sprayed coating and starting powders was evaluated by thermogravimetry. Dry sliding friction and wear behavior of the WC-(W,Cr)₂C-Ni coating sliding against Si₃N₄ ball at different temperatures (room temperature 20 °C and elevated temperature of 700 °C and 800 °C) was evaluated using an oscillating friction and wear tester. Besides, the microhardness and fracture toughness of the coating was also measured. Results show that sintering agglomerated WC-20 wt.%Cr-7 wt.%Ni powder is an effective method to prepare agglomerated and sintered WC-(W,Cr)₂C-Ni composite powder. The excellent oxidation resistance of WC-(W,Cr)₂C-Ni coating is mainly resulted from a double-decker shell-core microstructure formed in the coating. The composition of the outer shell is (W,Cr)₂C phase and that of the inner shell is Cr₃C₂. During high-temperature friction and wear test, well remained hard WC phase in the WC-(W,Cr)₂C-Ni coating can guarantee its good mechanical properties and wear resistance, and newly generated nano NiWO₄, CrWO₄ and Cr₂WO₆ particles can further improve these properties significantly.     

Oxidation behavior of Ti3AlC2 at 1000-1400 °C in air

The isothermal oxidation behavior of bulk Ti₃AlC₂ has been investigated at 1000-1400 °C in air for exposure times up to 20 h by means of TGA, XRD, SEM and EDS. It has been demonstrated that Ti₃AlC₂ has excellent oxidation resistance. The oxidation of Ti₃AlC₂ generally followed a parabolic rate law with parabolic rate constants, k_p that increased from 4.1×10⁻¹¹ to 1.7×10⁻⁸ kg² m⁻⁴ s⁻¹ as the temperature increased from 1000 to 1400 °C. The scales formed at temperatures below 1300 °C were dense, adherent, resistant to cyclic oxidation and layered. The inner layer of these scales formed at temperatures below 1300 °C was continuous α-Al₂O₃. The outer layer changed from rutile TiO₂ at temperatures below 1200 °C to a mixture of Al₂TiO₅ and TiO₂ at 1300 °C. In the samples oxidized at 1400 °C, the scale consisted of a mixture of Al₂TiO₅ and, predominantly, α-Al₂O₃, while the adhesion of the scales to the substrates was less than that at the lower temperatures. Effect of carbon monoxide at scale/substrate was involved in the formation of the continuous Al₂O₃ layers.     

Effect of the θ–α-Al2O3 Transformation in Scales on the Oxidation Behavior of a Nickel-Base Superalloy with an Aluminide Diffusion Coating

The high-temperature oxidation behavior of a nickel-base superalloy andaluminide-diffusion coating has been investigated over the temperaturerange from 800–1100°C and analyzed by TGA, XRD, EDAX, andSEM. The -NiAl coating was formed by low-pressure gas-phasecementation at 950°C for 3 hr. It was found that the formation of-Al₂O₃ from -Al₂O₃ on the -NiAl coating resulted in asharp decrease in the parabolic rate constant kp by one order ofmagnitude at 1050°C during transient oxidation. The transformationcaused the anomalous behavior of the oxidation kinetics curves of thisdiffusion coating in the temperature range 800–1100°C withinthe first 100 hr. A change in the morphology of scales also occurredwith the transformation. A growth stress was characterized by theformation of convoluted scales, which were observed on the surfaceafter oxidation. The oxidation mechanism of this -NiAl diffusioncoating is described.     

Phase equilibria in the subsolidus region of the NiO-α-Al2O3 system between 1000 and 1920°C

Nickel spinel, Ni_1–xAl_2(1+x/3)O₄, is the only intermediate compound in the quasibinary NiO--Al₂O₃ system at temperatures between 1000 and 1920°C. The spinel equilibrated with NiO occurs at its stoichiometric composition, NiAl₂O₄, independent of temperature. An alumina rich spinel, 0.17 x 0.62, equilibrated with -Al₂O₃ increases in alumina content with increasing temperature. Aluminum oxide solubility in NiO increases from 1 mole % at 1000°Cto 3 mol % at 1800°C. Nickel oxide solubility in -Al₂O₃ was found to increase from 2 mole % at 1000°C to 3 mole % at 1920°C.