The effect of particle size of alumina dispersions on the oxidation resistance of Ni-Cr alloys

The oxidation behavior of Ni-Cr alloys with various chromium concentrations and particle sizes of a dispersion of 10 vol.% Al₂O₃ was observed in 1 atm of oxygen at 1000°C. This study was intended to determine the critical chromium concentration to form a protective Cr₂O₃ oxide layer for different Al₂O₃ particle sizes. The oxidation rate of Ni-Cr alloys containing 10 vol.% Al₂O₃ followed a parabolic rate law and a Cr₂O₃ protective layer continuously formed when the oxidation rate decreased rapidly. Times to form a continuous and protective Cr₂O₃ layer during the initial oxidation shortened as the size of the dispersion decreased. The critical chromium concentration to form a protective Cr₂O₃ layer in the oxide scale was 69 wt.% and was related strongly to the particle size of the Al₂O₃ dispersion.     

The high-temperature oxidation behavior of vanadium-aluminum alloys

The oxidation behavior in air of pure vanadium, V-30Al, V-30Al-10Cr, and V-30Al-10Ti (weight percent) was investigated over the temperature range of 700–1000° C. The oxidation of pure vanadium was characterized by linear kinetics due to the formation of liquid V₂O₅ which dripped from the sample. The oxidation behavior of the alloys was characterized by linear and parabolic kinetics which combined to give an overall time dependence of 0.6–0.8. An empirical relationship of the form: W/A=Bt + Ct^1/2 + D was found to fit the data well, with the linear contribution suspected to be from V₂O₅ formation for V-30Al and V-30Al-10Cr, and a semi-liquid mixture of V₂O₅ and Al₂O₃ for V-30Al-10Ti. The parabolic term is presumed related to the formation of a solid mixture of V₂O₅ and Al₂O₃ for V-30Al and V-30Al-10Cr, and TiO₂ for V-30Al-10TiThe addition of aluminum was found to reduce the oxidation rate of vanadium, but not to the extent predicted by the theory of competing oxide phases proposed by Wang, Gleeson, and Douglass. This was attributed to the formation of a liquid-oxide phase in the initial stages of exposure from which the alloys could not recover. Ternary additions of chromium and titanium were found to decrease the oxidation rate further, with chromium being the most effective. The oxide scales of the alloys were found to be highly porous at 900° C and 1000° C, due to the high vapor pressure of V₂O₅ above 800° C.     

Influence of a mixed Al2O3+Cr2O3 superficial coating on the non-isothermal oxidation behavior of Fe and Fe-Cr alloys

The non-isothermal oxidation behavior of electrolytic-grade iron and Fe-Cr alloys in dry air has been studied using linear heating rates of 6 K/min, 10 K/ min, and 15 K/min up to a final temperature of 1273–1473 K. Some of the iron and iron-chromium alloy samples were given a surface treatment by dipping them in an aqueous solution containing both Cr and Al ions before their oxidation studies. This pretreatment has resulted in improved oxidation resistance and scale adherence as depicted by no scale rupture even after a second thermal cycle. Mass changes were recorded gravimetrically, and scales have been characterized by SEM, EPMA, and x-ray diffraction analyses.     

The effect of fe on high temperature oxidation of NiAl

A study was conducted to observe the oxidation of NiAl+3.5at.%Fe alloy inβ-NiAl phase field at air temperatures of 1000, 1200 and 1400°C, and these results were compared with those of pure NiAl alloys. The primary effects of the Fe-addition in NiAl were found to be: 1) decrease in oxidation resistance and adherence of scales during both isothermal and cyclic oxidation tests, 2) enhancement of phase transformation rate from θ toα-AL₂O₃, 3) more rapid formation of characteristically ridgedα-A1₂O₃ scales during initial oxidation stages, and 4) partial sealing of voids formed at the scale-substrate interface and dissolution of Fe inside the alumina scale by the outward diffusion of Fe from the substrate alloy.     

High temperature oxidation of chromium nitrides

Chromium nitride powders oxidized to Cr₂O₃ noticeably above 400°C. Bulk chromium nitrides that were manufactured by sintering were oxidized between 900 and 1100°C in atmospheric air. The Cr₂O₃ layer that formed on bulk chromium nitrides having pores was relatively dense, and grew primarily via the inward transport of oxygen. The Cr₂O₃ layer to some degree deterred the nitrogen evolution from bulk chromium nitrides.     

The influence of reactive-element coatings on the high-temperature oxidation of pure-Cr and high-Cr-content alloys

The influence of various reactive-element (RE) oxide coatings (Y₂O₃, CeO₂, La₂O₃, CaO, HfO₂, and Sc₂O₃) on the oxidation behavior of pure Cr, Fe–26Cr, Fe–16Cr and Ni–25Cr at 900°C in O₂ at 5×10^–3 torr has been investigated using the¹⁸O/SIMS technique. Polished samples were reactively sputtercoated with 4 nm of the RE oxide and oxidized sequentially first in¹⁶O₂ and then in¹⁸O₂. The effectiveness of each RE on the extent of oxidation-rate reduction varied with the element used. Y₂O₃ and CeO₂ coatings were found to be the most beneficial, whereas Sc₂O₃ proved to be ineffective, for example, for the oxidation of Cr. SIMS sputter profiles showed that the maximum in the RE profile moved away from the substrate-oxide interface during the early stages of oxidation. After a certain time the RE maximum remained fixed in position with respect to this interface, its final relative position being dependent on the particular RE. The position of the RE maximum within the oxide layer also varied with the substrate composition. For all coatings¹⁸O was found to have diffused through the oxide to the substrate-oxide interface during oxidation, the amount of oxide at this interface increasing with increasing time. The SIMS data confirm that for coated substrates there has been a change in oxidegrowth mechanism to predominantly anion diffusion. The RE most probably concentrates at the oxide grain boundaries, generally as the binary oxide (RE) CrO₃. Cr³⁺ diffusion is impeded, while oxygen diffusion remains unaffected.     

The effect of aluminum as an alloying addition or as an implant on the high-temperature oxidation of Ni-25Cr

The oxidation behavior of aluminum-implanted Ni-25Cr and Ni-25Cr containing 1 wt.% Al has been studied at 1000°C and 1100°C in oxygen. As did Y alloying addition or Y-implantation, 1 wt.% Al added to Ni-25Cr prevented nodular formation of Ni-containing oxides, improved spalling resistance of the scale upon cooling to a similar degree, and eliminated the formation of large voids between the alloy and the scale at the oxidation temperature. However, the Al addition did not alter the rate of growth of the Cr₂O₃ scale, nor did it change the growth direction. Al-implantation produced no effect even when the maximum concentration and depth of penetration were adjusted to be identical with those of the yttrium in the Y-implanted alloy. The implications of these results concerning the reactive element effect are discussed.     

The oxidation of cobalt based alloys containing partially dissolved particles of Si3N4 at 1000°C

The isothermal oxidation behavior of Co-Cr and Co-Cr-Si alloys with and without 5, 10, and 15 vol.% dispersions of unstable Si₃N₄ particles was studied in 1 atm of oxygen at 1000°C. The dispersion of Si₃N₄ which dissolved partially in the matrix, greatly reduced the oxidation rate of Co-Cr alloys. Silicon nitride was found to promote the formation of continuous Cr₂O₃ layers at low chromium concentrations. Furthermore, the unstable Si₃N₄ was more effective in reducing the oxidation rate than an alloy containing an equivalent amount of silicon. Additions of 15vol.% Si₃N₄ tended to increase the oxidation rate by forming nonprotective SiO₂ particles which disrupted the protective Cr₂O₃ scale. The mechanism of oxidation was altered due to the Si₃N₄ additions. Marker experiments indicated oxygen diffusion inward via the CoO lattice, rather than a combination of both oxygen and metal ion motion which is encountered in Co-Cr alloys.     

Studies concerning the effect of nitrogen on the oxidation behavior of TiAl-based intermetallics at 900°C

The oxidation behavior of the titanium aluminides Ti-50Al and Ti-48Al-5Nb has been investigated in Ar+20%O₂ and in air at 900°C. Thermogravimetric studies in combination with structural analyses using optical metallography, SEM/EDX and X-ray diffraction show a marked influence of nitrogen on the composition and growth rate of the oxide scales. For a more detailed study concerning the effect of nitrogen on the scale-growth kinetics, thermogravimetrical analyses were carried out during which the gas atmosphere was changed from air to Ar–O₂, and vice versa, without intermediate cooling of the specimen. The results show, that nitrogen adversely affects the formation of the initially formed alumina scale and that it enhances the growth rate of the rapidly growing Ti-rich oxide. This effect was observed in both alloys investigated, although the thermogravimetric results at first sight indicated an opposite effect for the Nb-containing alloy. This apparent contradiction is caused by internal oxidation which occurs in this alloy during exposure in Ar–O₂.     

Some observations on the effects of sulfur and active elements on the oxidation of Fe−Cr−Al alloys

A very-low-sulfur-content industrial Fe–Cr–Al alloy has been used both as a baseline and as a charge material for laboratory metlts with variable sulfur and rare-earth additions. No significant differences in behavior were observed in cyclic oxidation tests on 1-mm-thick coupons at 1100°C, except for an excessive rare-earth content, which led to accelerated scale growth. At 1300°C, alloys without rare-earth additions developed high growth stresses in the oxide, leading to large tensile strains in the substrate. The oxide-metal interface in the low-sulfur (<2ppm) material resisted these stresses and the oxide remained adherent. However, as little as 4ppm S was sufficient to cause considerable spalling. Rare-earth additions markedly reduced growth stresses and eliminated both dimensional instability and spalling.     

Electrodeposition and tribological behavior of amorphous chromium-alumina composite coatings

The amorphous chromium-alumina (a-Cr-Al₂O₃) composite coatings with thickness of 50 μm were electrodeposited from Cr(III) electrolytes containing Al₂O₃ particles and Al³⁺. The effects of Al³⁺ on the dispersibility and Zeta potential of Al₂O₃ particles in electrotyles were investigated. It was found that the Al³⁺ promotes the Al₂O₃ particles to uniformly disperse in the Cr coatings. Tribological behavior of a-Cr-Al₂O₃ composite coatings was studied as compared with amorphous chromium (a-Cr) coatings electrodeposited from single Cr(III) electrolytes. The results demonstrate that the introduction of Al₂O₃ particles significantly improves the tribological performance of a-Cr coatings.     

Biomimetic deposition of apatite coatings on micro-arc oxidation treated biomedical NiTi alloy

The biomedical NiTi alloy was treated by micro-arc oxidation in an electrolytes containing sodium aluminate and sodium hypophosphite at 400 V constant voltages for 30 min. The MAO-treated NiTi has a porous microstructure on its surface and coatings consisting only of the γ-Al₂O₃ phase. The ceramic coating prepared by micro-arc oxidation is composed of Al, Ti, Ni, O, and P with the atomic concentration of 26.98%, 3.67%, 3.33%, 65.30% and 0.72%, respectively. The MAO-treated NiTi was soaked in a simulated body fluid (1.0SBF) to investigate the biomimetic deposition of apatite on the surface of Al₂O₃ coated NiTi alloy. It was found that Al₂O₃ coated NiTi alloy shows an excellent apatite-forming ability after soaking in a simulated body fluid (1.0SBF) for 14 days, while no apatite-forming ability was observed on bared NiTi alloy even though soaking time is up to 28 days.     

Pt改性Ni3Al基合金短时高温氧化行为研究

用冷坩埚悬浮熔炼制备了Ni-xPt-25Al(x=0,10,20,30,at%)系列合金,利用X射线衍射仪、同步热分析仪、扫描电镜和光电子能谱仪(XPS)分析了Pt的添加对晶体结构的影响,研究了Ni-xPt-25Al合金的氧化动力学曲线、氧化物形貌以及抗氧化性能。结果表明:随着Pt含量的升高,Pt改性Ni_3Al基合金仍保持γ′相。升温过程和短时等温阶段合金的氧化动力学特征分别符合线性和抛物线氧化物生长动力学规律。Pt有利于氧化物的快速形成,且随Pt含量的增加,氧化膜的完整性和致密性均有所改善。     

Microstructural analysis of YSZ and YSZ/Al2O3 plasma sprayed thermal barrier coatings after high temperature oxidation

Air plasma sprayed TBCs usually include lamellar structure with high interconnected porosities which transfer oxygen from YSZ layer towards bond coat and cause TGO growth and internal oxidation of bond coat.The growth of thermally grown oxide (TGO) at the interface of bond coat and ceramic layer and internal oxidation of bond coat are considered as the main destructive factors in thermal barrier coatings.Oxidation phenomena of two types of plasma sprayed TBC were evaluated: (a) usual YSZ (yttria stabilized zirconia), (b) layer composite of (YSZ/Al₂O₃) which Al₂O₃ is as a top coat over YSZ coating. Oxidation tests were carried out on these coatings at 1100°C for 22, 42 and 100h. Microstructure studies by SEM demonstrated the growth of TGO underneath usual YSZ coating is higher than for YSZ/Al₂O₃ coating. Also cracking was observed in usual YSZ coating at the YSZ/bond coat interface. In addition severe internal oxidation of the bond coat occurred for usual YSZ coating and micro-XRD analysis revealed the formation of the oxides such as NiCr₂O₄, NiCrO₃ and NiCrO₄ which are accompanied with rapid volume increase, but internal oxidation of the bond coat for YSZ/Al₂O₃ coating was lower and the mentioned oxides were not detected.     

Effect of internal oxidation pretreatments and Si contamination on oxide-scale growth and spalling

Internal oxidation pretreatments carried out in quartz capsule with a Rhines pack were found to have a profound effect on the subsequent oxidation behavior of alloys. Specimens of Co-15 wt.% Cr, Co-25 wt.% Cr, Ni-25 wt.% Cr, and Ni-25 wt.% Cr-1 wt.% Al were tested at 1100°C after pre-oxidation treatments. Even without the development of internal oxide particles, pretreated binary CoCr and NiCr alloys oxidized with significantly lower rates. Selective oxidation of chromium was observed on the non-Cr₂O₃-forming Co-base alloys, whereas on the Cr₂O₃-forming Ni-base alloys, elimination of base-metal oxide, reduction in the Cr₂O₃ growth rate, and better scale adhesion were found. These effects were more apparent with pre-oxidation temperatures greater than 1000°C and with longer pretreatment times. Contaimination of Si from the quartz is believed to be the cause.     

Oxidation resistance of refractory γ-TiAlW coatings

The resistance to oxidation of the W-alloyed magnetron sputtered γ-TiAl fine-crystalline 4 μm thick coatings have were investigated in this work. The oxidation tests were performed in an atmosphere of pure oxygen or in the air at a temperature of 1173 K for 120 h. The resistance to high-temperature oxidation was investigated by means of micro-thermogravimetric analysis with continuous or stepwise control of the substrate weight. Before and after the oxidation the morphology of the coatings as well as their chemical and phase composition were investigated by SEM, EDS and EBSD, respectively. The results have been compared with those obtained for the uncoated γ-TiAl substrate.It was found that: (1) the W-alloyed γ-TiAl coatings have a considerably higher oxidation resistance (about four orders of magnitude) than the uncoated γ-TiAl substrates and that their resistance to oxidation increases with the concentration of alloying element in the range of the concentrations investigated in the work; (2) the high resistance to oxidation of the coatings is a result of the thin α-Al₂O₃ layer formation on the surface of the substrate during oxidation; (3) the formation of dense and uniform α-Al₂O₃ layer on the coating surface is due to a fine-crystalline structure of the magnetron deposited γ-TiAlW coating.     

Effects of Chromia Coatings on the High-Temperature Behavior of F17Ti Stainless Steel in Air: Analytical Studies of the Effect of Rare-Earth-Element Oxides

The MOCVD deposition of neodymium oxide and/orchromium oxide provided beneficial effects both onisothermal- and cyclic high-temperature behavior ofcommercial F17Ti stainless steel. Fracture crosssections provided information about the morphology ofthe oxide scales formed on bare steel and coatedspecimens. The chromia scales developed small equiaxedgrains on the Nd₂O₃-coated samplesand columnar grains on the uncoated ones. Neo dymium segregatedwithin a surface layer composed ofMn_1.5Cr_1.5O₄ spineloxide. A complex phase (close to the structure ofCeTi₂₁O₃₈) was identified in thiszone. It could act as a source of neodymium ions, which couldsegregate to the grain boundaries of the chromia scale.Polished cross sections associated with X-ray mappingstudies confirmed the scale structure and the location of the rare-earth element in the outer part ofthe oxide layer.     

Influence of niobium additions on high-temperature-oxidation behavior of Ti3Al alloys and coatings

In this study, the oxidation properties of Ti₃Al+Nb bulk alloys, as well as IMI 829 alloy, coated with a Ti₃Al+Nb layer, have been considered. Model alloys have been prepared, with 5–25 at.% niobium contents; 50-m-thick Ti₃Al+10 at.% Nb coatings have also been deposited on IMI 829 by triode sputtering. Bulk alloys and coated substrates have been exposed to cyclic and isothermal oxidation in air between 700 and 800°C. Niobium additions generally caused the oxidation rate of Ti₃Al to decrease significantly. In all cases rutile is the main oxide formed. It is believed that the ability of niobium to dissolve in the rutile lattice, and therefore to lower the oxygen diffusion rate through the oxide layer, is a contribution to the observed oxidation resistance enhancement. The formation of niobium oxide has also been envisaged for this matter.     

The influence of alloying elements on the development and maintenance of protective scales

Some of the important principles that determine the establishment, growth and long-term maintenance of protective Cr₂O₃, Al₂O₃ and SiO₂ scales on hightemperature iron-, nickel- and cobalt-base alloys are reviewed and discussed. Emphasis is placed on the effects of alloying elements and other additions, such as third elements and reactive elements or oxide dispersions, on each of these processes. Particular attention is paid to transport processes in the scales and the importance of short-circuit paths. Some of the important parameters that influence the long-term mechanical stability of such scales are considered and evaluated.     

Electroless ternary Ni-W-P alloys containing micron size Al2O3 particles

In the present investigation electroless ternary NiWP-Al₂O₃ composite coatings were prepared using an electroless nickel bath. Second phase alumina particles (1 µm) were used to codeposit in the NiWP matrix. Nanocrystalline ternary NiWP alloys and composite coatings were obtained using an alkaline citrate based bath which was operated at pH 9 and temperature at 88 ± 2 °C. Mild steel was used as a substrate material and deposition was carried out for about 4 h to get a coating thickness of 25 ± 3 µm. Metallographic cross-sections were prepared to find out the coating thickness and also the uniform distribution of the aluminum oxide particles in NiWP matrix. Surface analysis carried out on both the coatings using scanning electron microscope (SEM) showed that particle incorporation in ternary NiWP matrix has increased the nodularity of composite coatings compared to fine nodular NiWP deposits. Elemental analysis of energy dispersive X-ray (EDX) results showed that codeposited P and W elements in plain NiWP deposit were 13 and 1.2 wt.%, respectively. There was a decrease in P content from 13 to 10 wt.% with a marginal variation in the incorporated W (1.01 wt.%) due to the codeposition of aluminum oxide particles in NiWP matrix. X-ray diffraction (XRD) studies carried out on as-plated deposits showed that both the deposits are X-ray amorphous with a grain size of around 3 nm. Phase transformation studies carried out on both the coatings showed that composite coatings exhibited better thermal stability compared to plain NiWP deposits. From the XRD studies it was found that metastable phases such as NiP and Ni₅P₂ present in the composite coatings heat treated at major exothermic peak temperature. Annealed composite coatings at various temperatures revealed higher microhardness values compared to plain NiWP deposits.