High temperature scaling of Ni-xSi-10 at.% Al alloys in 1 atm of pure O2

The oxidation of Ni-xSi-10Al alloys (with x = 0, 2, 4 and 6 at.%), has been studied at 900 and 1000 °C in 1 atm of pure O₂ to examine the effect of different silicon additions on the behavior of ternary Ni-Si-10Al alloys. The kinetic curves of Ni-10Al are approximately parabolic at both 900 and 1000 °C. Conversely, the kinetics of the ternary alloys at both temperatures correspond generally to a rate decrease faster than predicted by the parabolic rate law, except for the oxidation of Ni-6Si-10Al at 1000 °C, which exhibits a single nearly-parabolic stage. Oxidation of the binary alloy formed at both temperatures an internal oxidation zone beneath a layer of NiO. Oxidation of Ni-2Si-10Al at both temperatures and of the other two alloys at 900 °C formed initially a zone of internal oxidation of Al + Si. However, a layer of alumina forming at the front of internal oxidation after some time blocked the internal oxidation and produced a gradual conversion of the metal matrix of this region into NiO, with a simultaneous decrease of the oxidation rate. Conversely, the oxidation of Ni-4Si-10Al and Ni-6Si-10Al at 1000 °C did not produce an internal oxidation, but formed an alumina layer directly on the alloy surface after an initial stage when also Ni was oxidized. Therefore, silicon exerts the third-element effect by reducing the critical Al content needed for the transition from its internal to its external oxidation with respect to the corresponding Ni-Al alloy. This result is interpreted by means of an extension to ternary alloys of Wagner’s criterion for the same transition in binary alloys based on the attainment of a critical volume fraction of internal oxide.     

The oxidation of three Ni-6Si-xAl alloys in 1 atm O2 at 1000 °C

The oxidation of three ternary Ni-6Si-xAl alloys containing 6, 10 and 15 at.% Al and of the corresponding binary Ni-Al alloys has been studied at 1000 °C under 1 atm O₂ to examine the effect of different Al additions on the behavior of ternary Ni-Al-Si alloys containing 6 at.% Si. Of the three binary Ni-Al alloys only Ni-15Al was able to form external alumina scales. Conversely, all the three ternary alloys formed an innermost layer of alumina directly in contact with the alloy following very similar and approximately parabolic kinetics after a short faster initial stage due to transient formation of NiO. Thus, the presence of silicon is very effective to reduce the critical Al content needed to form exclusive alumina scales with respect to binary Ni-Al alloys. The third-element effect due to silicon is interpreted on the basis of an extension of Wagner’s criterion for the transition from the internal to the external oxidation of the most reactive component in binary alloys.     

The nature of the third-element effect in the oxidation of Fe-xCr-3 at.% Al alloys in 1 atm O2 at 1000 °C

The oxidation of an Fe-Al alloy containing 3 at.% Al and of four ternary Fe-Cr-Al alloys with the same Al content plus 2, 3, 5 or 10 at.% Cr has been studied in 1 atm O₂ at 1000 °C. Both Fe-3Al and Fe-2Cr-3Al formed external iron-rich scales associated with an internal oxidation of Al or of Cr+Al. The addition of 3 at.% Cr to Fe-3Al was able to stop the internal oxidation of Al only on a fraction of the alloy surface covered by scales containing mixtures of the oxides of the three alloy components, but not beneath the iron-rich oxide nodules which covered the remaining alloy surface. Fe-5Cr-3Al formed very irregular external scales where areas covered by a thin protective oxide layer alternated with others covered by thick scales containing mixtures of the oxides of the three alloy components, undergrown by a thin layer rich in Cr and Al, while internal oxidation was completely absent. Conversely, Fe-10Cr-3Al formed very thin, slowly-growing external Al₂O₃scales, providing an example of third-element effect (TEE). However, the TEE due to the Cr addition to Fe-3Al was not directly associated with a prevention of the internal oxidation of Al, but rather with the inhibition of the growth of external scales containing iron oxides. This behavior has been interpreted on the basis of a qualitative oxidation map for ternary Fe-Cr-Al alloys taking into account the existence of a complete solid solubility between Cr₂O₃ and Al₂O₃.     

The oxidation of two ternary Fe-Cu-10 at.% Al alloys in 1 atm of pure O2 at 800-900 °C

The oxidation of two ternary Fe-Cu-Al alloys containing 10 at.% Al (Fe-65Cu-10Al and Fe-30Cu-10Al) has been studied at 800-900 °C under 1 atm O₂. Under all conditions both alloys show an initial faster stage during which Fe-65Cu-10Al corrodes more rapidly at 800 °C than at 900 °C, while Fe-30Cu-10Al follows nearly identical kinetics at both temperatures. As oxidation proceeds, a continuous alumina layer is eventually established on the surface of the two alloys, thus decreasing significantly their oxidation rates. Altogether, the Fe-rich alloy Fe-30Cu-10Al oxidizes slightly faster than the Cu-rich alloy Fe-65Cu-10Al at both temperatures. The possible reasons for the decrease in the critical Al content needed to form external alumina scales for the Cu-rich alloy in comparison with binary Cu-Al alloys are examined.     

Oxidation of a quaternary three-phase Cu-20Ni-20Cr-5Fe alloy at 700-900 °C in 1 atm of pure O2

The oxidation of a quaternary Cu-Ni-Cr-Fe alloy containing approximately 20 at.% Ni, 20 at.% Cr and 5 at.% Fe, balance Cu (Cu-20Ni-20Cr-5Fe), was studied at 700-900 °C in 1 atm of pure oxygen. The alloy is composed of a mixture of three phases, where the lightest α phase with the largest Cu content forms the matrix, while the other two, much richer in Cr, form a dispersion of isolated particles. At variance with the ternary three-phase Cu-20Ni-20Cr alloy examined previously, which was unable to form protective chromia scales over the alloy surface even after an extended period of oxidation, the present alloy formed complex external scales containing mixtures of the oxides of the various components plus a deep internal region containing a mixture of alloy and oxide phases. With time, a very irregular and thin but essentially continuous chromia layer formed at the bottom of the mixed internal oxidation region, producing a gradual decrease of the oxidation rate. Thus, the addition of 5 at.% Fe to Cu-20Ni-20Cr alloy is able to decrease the critical Cr content required to form the most stable oxide and promotes the formation of a continuous chromia scale under a lower Cr content in spite of the simultaneous presence of three different phases.     

Criteria for the formation of protective Al2O3 scales on Fe-Al and Fe-Cr-Al alloys

The conditions for the formation of external alumina scales on binary Fe-Al alloys and the nature of the third-element effect due to chromium additions have been investigated by studying the oxidation at 1000 °C in 1 atm O₂ of a binary Fe-10 at.% Al alloy (Fe-10Al) and of two ternary Fe-Cr-10 at.% Al alloys containing 5 and 10 at.% chromium (Fe-5Cr-10Al and Fe-10Cr-10Al, respectively). An Al-rich scale developed initially on Fe-10Al was subsequently replaced by a multi-layered scale containing mixtures of Fe and Al oxides plus a large number of Fe-rich oxide nodules: internal aluminum oxidation was essentially absent from this alloy. Addition of 5 at.% chromium to Fe-10Al did not suppress the formation of nodules, but they were eventually healed by the growth of an alumina layer at their base, resulting in a significant reduction of the oxidation rate. Finally, the alloy with 10 at.% Cr formed continuous external alumina scales without any Fe-rich nodule. Thus, the addition of sufficient amounts of chromium to Fe-10Al produces a third-element effect as expected. However, the process found in this alloy system does not involve a prevention of the internal oxidation of Al. Instead, it shows a transition from the growth of mixed Fe- and Al-rich external scales directly to an external Al₂O₃ scale formation. An interpretation of this kind of mechanism involving a third-element is presented along with a prediction of the critical Al contents required to produce the various possible scaling modes on binary Fe-Al alloys.     

Synthesis and oxidation behavior of platinum-enriched γ + γ′ bond coatings on Ni-based superalloys

Simple Pt-enriched γ + γ′ coatings were synthesized on René 142 and René N5 Ni-based superalloys by electroplating a thin layer of Pt followed by a diffusion treatment at 1150-1175 °C. The Al content in the resulting γ + γ′ coating was in the range of 16-19 at.% on superalloys with 13-14 at.% Al. After oxidation testing, alumina scale adherence to these γ + γ′ coatings was not as uniform as to the β-(Ni,Pt)Al coatings on the same superalloy substrates. To better understand the effect of Al, Pt and Hf concentrations on coating oxidation resistance, a number of Ni-Pt-Al cast alloys with γ + γ′ or β phase were cyclically oxidized at 1100 °C. The Hf-containing γ + γ′ alloys with 22 at.% Al and 10-30 at.% Pt exhibited similar oxidation resistance to the β alloys with 50 at.% Al. An initial effort was made to increase the Al content in the Pt-enriched γ + γ′ coatings by introducing a short-term aluminizing process via chemical vapor deposition or pack cementation. However, too much Al was deposited, leading to the formation of β or martensitic phase on the coating surface.     

The Effect of Si Additions on the High-Temperature Oxidation of a Ternary Ni–10Cr–4Al Alloy in 1 ATM O2 AT 900–1000 °C

The oxidation of four Ni–10Cr–ySi–4Al alloys has been studied in 1 atm O₂ at 900 and 1000 °C to examine the effects of various Si additions on the behavior of the ternary alloy Ni–10Cr–4Al, which during an initial stage formed external NiO scales associated with an internal oxidation of Cr + Al, later replaced by the growth of a chromia layer at the base of the scale plus an internal oxidation of Al. The addition of 2 at.% Si was able to prevent the oxidation of nickel already from the start of the test, but was insufficient to form external alumina scales at 1000 °C, while at 900 °C alumina formed only over a fraction of the alloy surface. At 1000 °C the addition of 4 at.% Si produced external chromia scales plus a region of internal oxidation of Al and Si, a scaling mode which formed over a fraction of the alloy surface in combination with alumina scales also by oxidation at 900 °C. Conversely, the presence of about 6 at.% Si produced external alumina scales over the whole sample surface at 900 °C, but only over about 60 % of the alloy surface at 1000 °C. The changes in the oxidation modes of the ternary Ni–10Cr–4Al alloy produced by Si additions have been interpreted by extending to these quaternary alloys the mechanism of the third-element effect based on the attainment of the critical volume fraction of internal oxides needed for the transition to the external oxidation of the most-reactive-alloy component, already proposed for ternary alloys.     

Comparison of the oxidation of high-sulfur Ni-25Cr-5Al alloys in as-cast and as-sputtered states

To understand the effect of sulfur on the oxidation of nanocrystalline (NC) alloys, a high-sulfur alloy having a chemical composition similar to a coarse-grained (CG) cast alloy of Ni-25Cr-5Al-1S (wt.%) was fabricated using magnetron sputtering. The oxidation of the two alloys in isothermal and cyclic conditions in air at 1000 °C shows that the alumina scale formed on the cast alloy was susceptible to spallation, whereas the alumina scale on the sputtered alloy was intrinsically adhesive. The result indicates that the nanocrystallization of alloys helps to eliminate the detrimental “sulfur effect” on oxidation, through minimizing the segregation of sulfur to the scale/alloy interface.     

Effect of Hf and Y alloy additions on aluminide coating performance

Iron- and Ni-base alloys, with and without Hf or Hf and Y alloy additions, were aluminized by chemical vapor deposition to study the potential for minor alloy additions to improve oxidation resistance of coated alloys. Compared to uncoated specimens, the coated specimens showed improved cyclic oxidation resistance at 1100° and 1150 °C. However, alumina scale spallation was observed at relatively short times and, particularly for the Ni-base alloy X, the aluminized lab-cast alloy with Hf tended to have poor coating performance compared to the commercial alloy without Hf. Internal oxidation of Hf at 1150 °C and rapid Al depletion in the relatively thin aluminide coatings contributed to the observed detrimental Hf effect. For the Ni-base alloys, the increased scale spallation could be attributed to much higher S contents (10-50 ppma) in the laboratory-cast alloys. Oxide scale spallation from the coating surface was minimized when Hf and Y were added to a casting and the [Y]/[S] content ratio was ∼ 1.     

Pitting behavior of a bulk Ni-18 wt.% Fe nanocrystalline alloy

Three electrodeposited Ni-18 wt.% Fe samples were annealed at 400 °C for 3 h (hrs), 8 h, and 24 h to study the effects of grain size on the electrochemical properties of bulk Ni-18 wt.% Fe in 3.5 wt.% NaCl. The electrochemical results from the annealed samples are compared with those measured for the as-received Ni-18 wt.% Fe material consisting of an average grain size of 23 nanometers (nm). Of the four materials studied, the as-received nanocrystalline alloy less sensitive to localized corrosion.     

Generation of copper nanoparticles during alkaline etching of an Al-30 at.%Cu alloy

A mechanism of formation of copper nanoparticles is proposed for alkaline etching of a sputtering-deposited Al-30 at.%Cu alloy, simulating the equilibrium θ phase of 2000 series aluminium alloys. Their formation involves enrichment of copper in the alloy beneath a thin alumina film, clustering of copper atoms, and occlusion of the clusters, due to growth of alumina around the clusters, to form nanoparticles. The proposed mechanism is supported by medium energy ion scattering, Rutherford backscattering spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy of the alloy following immersion in the sodium hydroxide solution, which disclose the enrichment of copper and the generation of the nanoparticles in the etching product of hydrated alumina. The generation of the nanoparticles is dependent upon the enrichment of copper in the alloy in a layer of a few nanometres thickness, with no requirement for bulk de-alloying of the alloy.     

Effect of silicon on oxidation of Ni-15Al alloy

1　INTRODUCTIONChromium, aluminum, and silicon can formsatisfactory protective scales on Ni based alloys.Chromium is expensive and not suitable for use attemperatures above 1 000℃ due to the evaporationof CrO3. It has also been well established that theincorporation of Si in many alloy systems has abeneficial effect on their oxidation resistance[1, 2].In addition, silicon is abundant and cheap. More over, Si has one of the largest solubility in Ni3Alwhere it …     

Corrosion behaviour of dc magnetron sputtered Fe1−xMgx alloy films in 3 wt% NaCl solution

Fe_1−xMg_x alloy films (with x ? 43.4 at.% Mg) were deposited by dc magnetron sputtering onto glass slide substrates. The objective of this study was to characterise the corrosion properties of these alloys in saline solution for application as new friendly environmentally sacrificial coatings in the protection of steel structures. The morphological and structural properties of the alloys were systematically studied prior to electrochemical experiments, and then the degraded surfaces were analysed to determine the composition and nature of corrosion products. Alloys with <25  at.% Mg were single-phase body-centred cubic (bcc) with enlarged lattice parameters, whereas for magnesium contents above 25 at.%, amorphisation occurred. The reactivity of the alloys in saline solution is strongly dependent on the Mg content and the alloy structure. The incorporation of magnesium leads to an open circuit potential shift of the alloy towards more negative values, that confers an attractive interest of these alloys as sacrificial coatings. A transition in corrosion activity is observed at 25 at.% Mg from which the reactivity decreases with the magnesium content increase. The evolution of the alloy corrosion behaviour is discussed in terms of structural and corrosion products evolution versus magnesium content.     

The oxidation of two ternary Ni-Cu-10 at.% Al alloys in 1 atm of pure O2 at 800-900 °C

The oxidation of the ternary alloys Ni-45Cu-10Al and Ni-30Cu-10Al has been studied at 800-900 °C under 1 atm O₂. The presence of 10 at.% Al reduces significantly the oxidation rate of the corresponding Cu-Ni alloys during the initial oxidation stages, even before the establishment of a complete Al₂O₃ layer. The weight of individual sample of the two ternary Ni-Cu-10Al alloys at 800 °C increases more rapidly than at 900 °C during the initial oxidation stage. As oxidation proceeds, the weight gain at 800 °C slows down to a degree that the total weight gain after 24 h oxidation at 800 °C is less than that at 900 °C. Due to a faster formation of the Al₂O₃ layer, which suppresses earlier the further oxidation of Cu and Ni, the external region of the scales grown on Ni-45Cu-10Al contain much less Cu and Ni oxides than those grown on Ni-30Cu-10Al. The transition from the internal oxidation to the selective external oxidation of the most reactive component Al in Ni-Cu-Al alloys is favored by higher values of the Al content, of temperature and of the Cu/Ni ratio.     

An electrochemical study of the effect of Li on the corrosion behavior of Ni3Al intermetallic alloy in molten (Li + K) carbonate

A study of the effect of lithium content (1, 3 and 5 wt.%) and heat treatment (400 °C during 144 h) on the corrosion behavior of Ni₃Al alloy has been carried out in a 62 mol.%Li₂CO₃-38 mol.%K₂CO₃ mixture at 650 °C using electrochemical techniques. Employed electrochemical techniques included potentiodynamic polarization curves, linear polarization resistance, LPR, electrochemical impedance spectroscopy, EIS, and electrochemical noise, measurements EN. Results have shown that the alloys exhibited an active-passive behavior regardless of the heat treatment. For alloys without heat treatment, the most corrosion resistant was the Ni₃Al base alloy, but when they were heat treated, the most corrosion resistant was the alloy containing 3%Li. EIS results showed that for short immersion tests, the corrosion process was under diffusion control, but for longer exposure times, the presence of a protective scale was evident. All the alloys were highly susceptible to a localized type of corrosion according to EN measurements and supported by SEM micrographs.     

The Effect of Silicon on the Oxidation of a Ni-6 at.% Al Alloy in 1 atm of pure O2 at 900°C

The oxidation behavior of a binary Ni–6Al alloy and of three ternary Ni–xSi–6Al alloys containing 2, 4 and 6 at.% Si has been studied at 900°C under 1 atm of pure O₂. The addition of 2 at.% Si to Ni–6Al increases the short-time oxidation rate of Ni–6Al, which is subsequently reduced and becomes similar to that of the binary alloy. However, the presence of this silicon level is already able to stop after some time the coupled internal oxidation of Al+Si by forming a healing oxide layer rich of alumina at the front of internal oxidation. The addition of 4 at.% Si to the same alloy permits a more rapid inhibition of the internal oxidation and the formation of a steady-state, inner alumina-rich scale. Finally, the addition of 6 at.% Si prevents the internal oxidation completely and leads to an earlier growth of a protective oxide layer in contact with the alloy as well as to a further reduction in the scaling rate. The role of Si in promoting the formation of protective scales in comparison with the binary alloy is examined on the basis of an extension to ternary alloys of a criterion proposed by Wagner for the transition between the internal and external oxidation of the most reactive component in binary alloys.     

KCl-induced high temperature corrosion of the austenitic Fe-Cr-Ni alloys 304L and Sanicro 28 at 600 °C

The influence of KCl(s) on the high temperature oxidation of the austenitic alloys 304L and Sanicro 28 at 600 °C in O₂ + H₂O environment is reported. 0.10 mg/cm² KCl(s) was added before exposure. The samples are investigated by grazing angle XRD, SEM/EDX, and AES. In the absence of KCl, both alloys show protective behaviour in dry O₂. In O₂ + H₂O environment, alloy 304L suffers local breakaway corrosion while Sanicro 28 still shows protective behaviour. The oxidation of both alloys is strongly accelerated by KCl. KCl reacts with chromium in the normally protective corundum-type oxide, forming K₂CrO₄. This depletes the scale in chromia and leads to the formation of a non-protective, iron-rich scale. The significance of KCl-induced corrosion in real applications is discussed and the oxidation behaviour of the two steels is compared.     

Electrochemical passive properties of AlxCoCrFeNi (x = 0, 0.25, 0.50, 1.00) alloys in sulfuric acids

This study investigates the electrochemical passive properties of Al_xCoCrFeNi alloys in H₂SO₄ by potentiodynamic polarization, EIS, and weight loss tests from 20 to 65 °C. Experimental results indicate that Al harms the corrosion resistance in H₂SO₄ at temperatures exceeding 27 °C owing to the porous and inferior nature of the protection oxide film of Al in these alloys. Closely examining the Arrhenius plots of corrosion current density reveals that both pre-exponential factor A and activation energy E_a increase with Al content. However, A affects corrosion current density more significantly than E_a at higher temperatures and, conversely, at lower temperatures.     

Effect of ambient air pressure on the oxidation kinetics of Fe-6 at.% Si alloy

Surface oxidation of Fe-6 at.% Si alloy was investigated during annealing in ambient air of various pressures with simultaneous isothermal resistivity registrations. Measurements have been done in the temperature range 500-540 °C. Chemical and phase compositions of the samples were analyzed using X-ray photoelectron spectroscopy, conversion electron Mössbauer spectroscopy (CEMS), transmission Mössbauer spectroscopy (TMS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Phase analysis showed that during isothermal resistivity measurement in a low pressure air 100 mbar a protective film of hematite α-Fe₂O₃ was formed on the surface of FeSi substrate. By decreasing pressure to 10⁻² mbar the time dependence of the resistivity exhibits an increase due to the transformation of hematite to magnetite Fe₃O₄. The activation energy for this transformation is 115 ± 5 kJ/mol. By regressive increasing the pressure back from 10⁻² to 100 mbar a non-protective oxide scale of hematite + magnetite was formed. The results were interpreted in the light of the iron-oxygen phase diagram.