Surface Chemistry of Oxide Scale on IN-738LC Superalloy: Effect of Long-Term Exposure in Air at 1173 K

The oxidation kinetics of IN-738LC at 1173 K in dry air up to 1500 hr followed parabolic law. Surface morphology and the oxide phases present in the scale were characterized by SEM, XRD, EDS, FIB, and XPS. FIB investigation exhibited a compact and adherent oxide layer. XRD analysis revealed the presence of NiO, NiAl₂O₄, NiCr₂O₄ spinel, and Al₂O₃ on the top scale surface formed at 1173 K in dry air. Extensive XPS analyses revealed the presence of Cr₂O₃, CrO₂, and CrO₃ on the top scale surface formed on IN-738LC after 10 hr of exposure. The presence of TiO₂, Al₂O₃, Cr₂O₃, NiO, and NiAl₂O₄ and NiCr₂O₄ spinels along with the oxides of Ta at the top surface of the scale was observed after 100 hr of oxidation. The TiO₂ content was high on the surface and the entire scale cross section was composed mostly of Cr₂O₃, NiO, TiO₂, and Al₂O₃ after 100 hr of exposure to dry air at 1173 K. The concentration of Al₂O₃ on the surface of the oxide scale was found to increase after 100 hr of exposure and remained constant thereafter. After 300 and 1500 hr of exposure, the surface oxide was mainly Al₂O₃ along with oxides of Ni, Ti, and Cr. The oxide scale cross section consisted mostly of Al₂O₃ along with other oxides such as Cr₂O₃, NiO, and TiO₂. The oxide-scale composition was found to vary significantly with the duration of exposure to dry air at 1173 K.     

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.     

Roles of Nb on the oxidation characteristics and oxide scale evolution of Fe-25Cr-35Ni-2.5Al-XNb alloys at 1000°C and 1100°C

The oxidation characteristics of Fe-25Cr-35Ni-2.5Al-_XNb (0, 0.6, and 1.2 wt%) alumina-forming austenitic alloys at 1000°C and 1100°C in air were investigated. Results show that Nb has an important effect on the high-temperature oxidation resistance. A bilayer oxide scale with a Cr₂O₃-rich outer layer and Al₂O₃-rich internal layer forms on the surface of the Nb-free alloy and exhibits a poor oxidation resistance at 1000°C and 1100°C. With Nb addition, both the 0.6Nb-addition and 1.2Nb-addition alloys exhibit better oxidation resistance at 1000°C. Because of the third element effect, Nb addition reduces the critical Al content and forms a single external protective Al₂O₃ scale, which greatly improves the oxidation resistance. After oxidation at 1100°C, niobium oxides (mainly Nb₂O₅) are formed on the surface of the 1.2Nb-addition alloy and destroy the integrity of the Al₂O₃ scale, which causes the formation of Cr-rich oxide nodules and eventually develops to be a loose bilayer oxide scale with NiCr₂O₄, Cr₂O₃, and Fe₂O₃ outer layers and Al₂O₃ inner layer.     

Oxide phase development upon high temperature oxidation of γ‐NiCrAl alloys

The amount of each oxide phase developed upon thermal oxidation of a γ‐Ni‐27Cr‐9Al (at.%) alloy at 1353 K and 1443 K and a partial oxygen pressure of 20 kPa is determined with in‐situ high temperature X‐ray Diffractometry (XRD). The XRD results are compared with microstructural observations from Scanning Electron Microscope (SEM) backscattered electron images, and model calculations using a coupled thermodynamic‐kinetic oxidation model. It is shown that for short oxidation times, the oxide scale consists of an outer layer of NiO on top of an intermediate layer of Cr₂O₃ and an inner zone of isolated α‐Al₂O₃ precipitates in the alloy. The amounts of Cr₂O₃ and NiO in the oxide scale attain their maximum values when successively continuous Cr₂O₃ and α‐Al₂O₃ layers are formed. Then a transition from very fast to slow parabolic growth kinetics occurs. During the slow parabolic growth, the total amount of non‐protective oxide phases (i.e. all oxide phases excluding α‐Al₂O₃) in the oxide scale maintain at an approximately constant value. The formation of NiCr₂O₄ and subsequently NiAl₂O₄ happens as a result of solid‐state reactions between the oxide phases within the oxide scale.     

Influence of Moisture on the oxidation of γ-TiAl

The influence of water vapour on the oxidation of Ti-50 at.% Al was studied at 900°C. Thick, well-adherent oxide scales were formed consisting of an outer TiO₂ layer and an inner heterogeneous mixture of TiO₂ and Al₂O₃. The interface between these layers is marked by large pores and Al₂O₃ particles embedded in TiO₂. No compact Al₂O₃ barrier layer was observed. The oxidation leads to formation of a two phase, oxygen enriched subsurface zone, which is Al-depleted by inner oxidation of Al to Al₂O₃. The oxidation kinetics were followed by continuous thermogravimetry. Exposure in moist oxygen leads to an accelerated attack compared with oxidation in dry oxygen. In moist oxygen the rate is linear after a short transition period. The oxidation rate is influenced by water partial pressure and oxygen partial pressure.     

Cyclic Oxidation Kinetics and Oxide Scale Morphologies Developed on the IN600 Superalloy

The oxidation behavior of the IN600 Ni?CCr?CFe superalloy was investigated in air at temperatures ranging from 750 to 950 °C, for up to 12 cycles. Oxidation kinetics and oxide scale morphologies were examined using weight gain measurements, SEM-EDS, and X-ray diffraction. The cyclic oxidation kinetic results suggested that the oxidation behavior of the IN600 alloy approximately followed a sub-parabolic rate and the scaling process was controlled by the formation of a chromia scale. At 850 °C, SEM-EDS observations indicated that the formed oxide scale was primarily composed of Cr₂O₃, and the internal oxidation of Cr and Ti occurred. At 950 °C, a fast initial stage with high weight gain was observed, followed by a steady-state stage with gradual weight gain. Additionally, a considerable change in the oxidation kinetic occurred. SEM-EDS observations and XRD results indicated that the external scale was relatively thick with a localized porous, preferential adherent, and a complex oxide scale was developed. This complex oxide scale consisted of an outermost thin layer composed of MnCr₂O₄?CCr₂O₃ mixed together with a small amount of isolated TiO₂, an intermediate relatively thick layer, composed of Cr₂O₃, and an innermost discrete layer formed at the scale/alloy interface, which enriched by Ni/NiO mixed with Ti-, Al-, and Fe-oxides. Finally, only the Al alloying element was internally oxidized to form Al₂O₃ fingers, which create a discrete and narrow internal oxidation zone. Al oxide was observed as a dark area and primarily grows along the alloy grain boundaries in the vicinity of the inward chromia pegs.     

High-Temperature Corrosion Behaviour of Aluminized-Coated and Uncoated Alloy 718 Under Cyclic Oxidation and Corrosion in NaCl Vapour at 750 °C

To evaluate the suitability of HR3C and 22Cr–25Ni–2.5Al AFA steels as the heat-resistant alloys, the oxidation behavior of them was investigated in air at 700, 800, 900 and 1000 °C. The evolution of oxide layer on the surface and subsurface was investigated using a combination of compositional/elemental (SEM, EDS) and structural (XRD, GDOES) techniques. A dense and continuous Cr₂O₃ healing layer on the HR3C was formed at the temperature of 700 or 800 °C, but the Cr₂O₃ oxide film on HR3C was unstable and partly converted into a less protective MnCr₂O₄ with the increase in temperature to 900 or 1000 °C. The composition and structure of oxide film of 22Cr–25Ni–2.5Al AFA steels are significantly different to the HR3C alloys. The outer layer oxides transformed from Cr₂O₃ to Al-containing oxides, leading to a better oxidation resistance at 700 or 800 °C compared to HR3C. Further, the oxide films consist of internal Al₂O₃ and AlN underneath the outer loose layer after 22Cr–25Ni–2.5Al AFA oxidized at 900 or 1000 °C. It can be proved that the internal oxidation and nitrogen would make 22Cr–25Ni–2.5Al AFA steels have worse oxidation resistance than HR3C alloys at 900 or 1000 °C.     

High temperature oxidation resistance of Ni-(5∼13)Co-(10∼16)Cr-(5∼9)W-5Al-(1∼1.5)Ti-(3∼6)Ta alloys

The oxidation behavior of Ni-based superalloys was examined by cyclic oxidation tests at 850 and 1000 °C. The present study focused on the investigation of two newly developed and three commercial alloys (GTD-111, IN738LC, and CM247LC). The oxidation resistance of the superalloys were evaluated by the oxidation rate constants and the mass gains. The oxidation scales mainly consisted of outer Cr₂O₃ and inner Al₂O₃ layers at both temperatures, as well as oxides of minor elements such as TiO₂, NiCr₂O₄, CrTaO₄, HfO₂, and TaO. The oxidation resistance of the alloys containing larger amounts of Al, W, and Ta and lower Mo and Ti concentrations was higher than those of the other alloys. The ranking of oxidation resistance for the alloys corresponded to the statistical prediction drawn from a response surface analysis. Furthermore, these alloys contained more Ta oxides, such as CrTaO₄ and TaO, suggesting that Ta oxides had an active role in improving the oxidation resistance.     

High Temperature Oxidation of the Haynes 282© Nickel-Based Superalloy

Nickel-based superalloys are used in applications where corrosion and oxidation resistance at high temperatures are required together with microstructural stability. Superalloys with different metallurgical characteristics are therefore currently being developed; the high temperature behaviour of these systems must be evaluated. In this investigation, the isothermal oxidation resistance of a Haynes 282^© nickel-based superalloy was studied by gravimetric means in the temperature range 800–1,000 °C for relatively short exposure times up to 150 h. The results from the tests suggest that the parabolic rate law describes the oxidation kinetics of the alloy. The chemical composition of the oxides present in the scale comprised an outer TiO₂ layer and an inner Cr₂O₃ layer, with the latter located at the metal/oxide interface_. In addition, the formation of an internal oxidation zone of Al₂O₃ and TiO₂ was also observed at all temperatures. The role of oxide formation on microstructural changes experienced by the alloy is discussed.     

Cyclic Oxidation Behavior of IN 718 Superalloy in Air at High Temperatures

Ni-base superalloy IN 718 was cyclically oxidized in laboratory air at temperatures ranging from 750 to 950 °C for up to 12 cycles (14 h/cycle). The kinetic behaviour as well as the surface morphology, and the oxide phases of the scales were characterized by means of weight gain measurements, cyclic oxidation kinetics, scanning electron microscopy equipped with energy dispersive spectroscopy (SEM-EDS), and X-ray diffraction (XRD) analysis techniques. The results showed that as the oxidation temperature increased, the oxidation rate, the external scale thickness, and internal oxidation zone increased. It was suggested that the oxidation rate was controlled by the diffusion of substrate elements in the alloy and the inward diffusion of oxygen through the oxide scale. The oxidation kinetics followed a sub-parabolic rate law and, the activation energy of oxidation was 249 ± 20 kJ mol^?1. The scaling process was controlled mainly by the diffusion of chromium, titanium, manganese, and oxygen ions through the chromia scale. IN 718 showed low weight gain and very slow reaction rates of substrate elements at 750 °C. At 850 °C, a continuous and very thin oxide scale was formed. At 950 °C, XRD and EDS-elemental mapping analysis revealed that a complex oxide scale had formed. It consisted of an outermost layer of TiO₂?CMnCr₂O₄ spinels, inner layer of Cr₂O₃, and the inner most layer composed of Ni₃Nb enriched with Nb, Ti and Al oxides underneath the chromia layer. The oxide scale at this temperature seemed to be thicker layer, significant spallation and volatilization had apparently occurred, and greater internal corrosion was identified. The doping effect of titanium was observed, where it was found to be diffused through the chromia scale to form TiO₂ at the oxide-gas interface as well as internally and at the oxide alloy interface. The amount of rutile (TiO₂) at the oxide surface increased with temperature. In view of Mn contents in the alloy, the manganese?Cchromium spinel oxide was inferred to have played an important role in cyclic oxidation behaviour of IN 718, where the change in oxidation kinetic was noted. The Al contents would cause internal Al-rich oxide formation at grain boundaries.     

High Temperature Oxidation Behavior of Alloy 617 and Haynes 230 in Impurity-Controlled Helium Environments

The high temperature oxidation behavior of alloy 617 and Haynes 230 have been investigated for VHTR intermediate heat exchanger applications. Oxidation tests were carried out for up to 500 h at 900 °C and 1000 °C in impure helium environments containing H₂, H₂O, CO, CO₂, and CH₄. The oxidation kinetics of the alloys followed a parabolic rate law in all cases. In the impure helium environments with very low oxygen, the external oxides of alloy 617 were composed of a Cr₂O₃ layer, TiO₂ ridges on the grain boundaries, and isolated MnCr₂O₄ grains on top of the Cr₂O₃ layer. On the other hand, those of Haynes 230 consisted of a Cr₂O₃ inner layer and a protective MnCr₂O₄ outer layer, which increased the oxidation resistance. The effect of small amounts of CH₄ and H₂ on the oxidation kinetics of the alloys was insignificant. Irregular oxide morphology, such as cellular Cr₂O₃ oxides for alloy 617 and MnCr₂O₄ platelets for Haynes 230, was formed in the impure helium environment at 900 °C. For Haynes 230, along with platelets, whiskers were frequently found at the tip of the MnCr₂O₄ oxide crystals.     

High Temperature Oxidation Resistance of CrAlYN-Coated Ti45Al8Nb

The oxidation behaviour of Cr_0.45Al_0.53Y_0.02N (at.%) thin film deposited on ??-TiAl based alloy Ti?C45Al?C8Nb (at.%) was carried out. The tests were performed in the temperature range 750?C950???C for 500?h. The materials showed good corrosion resistance only at temperatures of 750 and 850???C where Al₂O₃ and Cr₂O₃ phases developed as a top oxide scale. A lack of corrosion resistance was observed at 950???C where a thick scale (100???m) that developed consisted of alternate layers of TiO₂ and Al₂O₃ phases. To investigate the oxidation behaviour, the corrosion kinetics were determined by means of discontinuous gravimetry of the exposed samples. Surface and cross-sectional analyses of exposed samples were conducted using scanning electron microscopy (SEM) and energy X-ray dispersive spectroscopy (EDS).     

Transient Oxidation of a γ-Ni–28Cr–11Al Alloy

γ-NiCrAl alloys with relatively low Al contents tend to form a layered oxide scale during the early stages of oxidation, rather than an exclusive α-Al₂O₃ scale, the so-called “thermally grown oxide” (TGO). A layered oxide scale was established on a model γ-Ni–28Cr–11Al (at.%) alloy after isothermal oxidation for several minutes at 1100°C. The layered scale consisted of an NiO layer at the oxide/gas interface, an inner Cr₂O₃ layer, and an α-Al₂O₃ layer at the oxide/alloy interface. The evolution of such an NiO/Cr₂O₃/Al₂O₃ layered structure on this alloy differs from that proposed in earlier work. During heating, a Cr₂O₃ outer layer and a discontinuous inner layer of Al₂O₃ initially formed, with metallic Ni particles dispersed between the two layers. A rapid transformation occurred in the scale shortly after the sample reached maximum temperature (1100°C), when two (possibly coupled) phenomena occurred: (i) the inner transition alumina transformed to α-Al₂O₃, and (ii) Ni particles oxidized to form the outer NiO layer. Subsequently, NiO reacted with Cr₂O₃ and Al₂O₃ to form spinel. Continued growth of the oxide scale and development of the TGO was dominated by growth of the inner α-Al₂O₃ layer.     

Isothermal oxidation behavior of Ti3Al-based alloy at 700–1000 °C in air

The isothermal oxidation behavior of a Ti₃Al-based alloy (Ti-24Al-14Nb-3V-0.5Mo-0.3Si, molar fraction, %) at 700– 1 000 °C in air was investigated. The oxidation kinetics of tested alloy approximately obeys the parabolic law, which shows that the oxidation process is dominated by the diffusion of ions. The oxidation diffusion activity energy is 241.32 kJ/mol. The tested alloy exhibits good oxidation resistance at 700 °C. However, when the temperature is higher than 900 °C, the oxidation resistance becomes poor. The XRD results reveal that the oxide product consists of a mixture of TiO₂ and Al₂O₃. Serious crack and spallation of oxide scale occur during cooling procedure after being exposed at 1 000 °C in air for 16 h. According to the analysis of SEM/EDS and XRD, it is concluded that the Al₂O₃ oxide forms at the initially transient oxidation stage and most of it keeps in the outer oxide layer during the subsequent oxidation procedure.     

Cyclic oxidation behavior of Ni3Al-7.8% Cr-1.3% Zr-0.8% Mo-0.025% B between 900 and 1100°C

A Ni₃Al-based alloy, the composition of which was Ni-16.0% Al-7.8% Cr-1.3% Zr-0.8% Mo-0.025%B, was cyclically oxidized in the temperature range of 900 to 1100°C in air for up to 500 hr. The alloy displayed good cyclic oxidation resistance up to 1000°C, with little scale spallation. It, however, lost cyclic oxidation resistance during oxidation at 1100°C after about 200 hr, displaying large weight losses due to serious scale spallation. NiO, α-Al₂O₃, NiAl₂O₄ and ZrO₂ were formed. The oxide scales consisted primarily of an outer Ni-rich layer which was prone to spallation, and (Al, Cr, Zr, Mo, Ni)-containing internal oxides which were adherent due mainly to the formation of (Al₂O₃, ZrO₂)-containing oxides that keyed the oxide scale to the matrix alloy.     

High‐temperature oxidation of Ti3Al0.7Si0.3C2 compound at 900 and 1000 °C in air

The compound, Ti₃Al_0.7Si_0.3C₂, was synthesized by hot pressing a powder mixture of TiC_X (x = 0.6), Al and Si. Its oxidation at 900 and 1000 °C in air for up to 50 h resulted in the formation of rutile‐TiO₂, α‐Al₂O₃ and amorphous SiO₂. The oxide scales formed consisted of triple layers, viz, an outer TiO₂ layer containing Al₂O₃ particles, an intermediate Al₂O₃ layer, and an inner mixed layer that was rich in TiO₂, but deficient in Al₂O₃ and SiO₂. During oxidation, Ti diffused outwards to form the outer TiO₂ layer, and oxygen was transported inwards to form the inner mixed layer. At the same time, carbon was liberated from Ti₃Al_0.7Si_0.3C₂. Ti₃Al_0.7Si_0.3C₂ oxidized slower than the TiO₂‐forming kinetics, but faster than the (α‐Al₂O₃ or SiO₂)‐forming kinetics.     

Si对625合金激光熔覆层高温氧化特性的影响

利用循环氧化法,研究了不同Si含量（0%,1%,3%,质量分数）的625合金熔覆层在700、800、900 ℃下氧化144 h后的高温氧化行为。用XRD分析了氧化物相。通过SEM/EDS研究了氧化物表面和截面的形貌、元素组成和氧化膜的厚度。结果表明,不同温度下试样的氧化动力学都保持抛物线规律,随着温度的升高,氧化增重逐渐增加。通过观察,在900 ℃时,0% Si含量的625合金熔覆层出现了氧化膜大面积剥落的情况,3% Si含量的合金熔覆层氧化膜保持完整。在700 ℃时,随着Si含量增加,氧化膜表面的氧化颗粒尺寸减小且更加致密,同时促进了Cr₂O₃氧化物的生成。在700 ℃下,0 % Si含量的试样出现了大片的内氧化区域;1% Si含量的试样基体部分出现了2处条状的含Ni,Cr,Mo的氧化物相区;而3% Si含量的试样氧化后由于生成了富Si的内氧化层,这阻止了内氧化的发生。外层Cr₂O₃氧化膜和内层SiO₂的联合作用既阻止了O阴离子的渗入也抑制了Fe等金属离子的扩散,提高了合金熔覆层的抗氧化性。     

Early-Stage Oxidation Behavior of Pt-Modified γ′-Ni3Al-Based Alloys with and without Hf Addition

The early-stage oxidation behavior in air of Pt-modified γ′-Ni₃Al-based alloys of composition (in at.%) Ni–22Al–30Pt with and without 0.5Hf was investigated in terms of oxidation kinetics, scale evolution and Al₂O₃ phase transformation. Oxidation exposures included heating to and short-term holds at 1,150 °C. Hafnium addition did not appear to affect microstructural evolution and growth rate of the oxide scales during heating to 1,150 °C; however, it was found that Hf delayed the metastable-to-α-Al₂O₃ phase transformation, thus allowing continued fast growth of oxide scale. After the transient oxidation stage of up to about 10 min (including heating time), Ni-rich metallic particles precipitated in the lower part of the metastable Al₂O₃ layer, due to a decrease in the oxygen potential resulting from scale evolution. The present results indicated that the period of oxide phase transformation was followed by the establishment of steady-state oxidation kinetics. However, the steady-state kinetics were different for the two alloy systems. Specifically, after complete phase transformation to α-Al₂O₃, rapid growth of oxide grains occurred on the Hf-free alloy; whereas, the oxide grain size remained small for the Hf-containing alloy. Such a difference of transformation and subsequent grain-growth behavior greatly affected oxide thickening kinetics.     

High-Temperature Scaling of Cu–Al and Cu–Cr–Al Alloys: An Example of a Non-Classical Third-Element Effect

The oxidation of three Cu–xCr–2Al and three Cu–xCr–4Al alloys (x ≅ 0,4,8 at.%) has been investigated at 800°C in 1 atm O₂. Oxidation of a binary Cu–Al alloy containing 2.2 at.% Al produced external scales composed mainly of copper oxides with small amounts of Al-rich oxide in the inner region, while the internal oxidation of Al was almost absent. The addition of 3.9 at.% Cr to this alloy was able to decrease the oxidation rate but was insufficient to prevent the oxidation of copper. Conversely, addition of 8.1 at.% Cr to the same binary alloy promoted the rather fast formation of a protective Al₂O₃ layer in contact with the metal substrate, with a simultaneous large decrease in the oxidation rate, producing a form of third-element effect. On the contrary, all the Cu–xCr–4Al alloys formed an internal Al₂O₃ layer after an initial stage during which all the alloy components were oxidized, so that the only effect of the presence of chromium was to decrease the duration of the fast initial stage. The third-element effect due to chromium additions to Cu–2Al is related to a transition from the formation of external scales composed of mixtures of Cu and Al oxides to the external growth of Al₂O₃–rich scales as a consequence of a thermodynamic destabilization of copper oxides associated with the formation of solid solutions between Al₂O₃ and Cr₂O₃.     

Cyclic Oxidation Behavior of the Ti–6Al–4V Alloy

The cyclic oxidation behavior of the Ti–6Al–4V alloy has been studied under heating and cooling conditions within a temperature range from 550 to 850 °C in air for up to 12 cycles. The mass changes, phase, surface morphologies, cross-sectional morphologies and element distribution of the oxide scales after cyclic oxidation were investigated using electronic microbalance, X-ray diffractometry, scanning electron microscopy and energy dispersive spectroscopy. The results show that the rate of oxidation was close to zero at 550 °C, obeyed parabolic and linear law at 650 and 850 °C, respectively, while at 750 °C, parabolic—linear law dominated. The double oxide scales formed on surface of the Ti–6Al–4V alloy consisted of an inner layer of TiO₂ and an outer layer of Al₂O₃, and the thickness of oxide scales increased with an increasing oxidation temperature. At 750 and 850 °C, the cyclic oxidation resistance deteriorated owing to the formation of voids, cracks and the spallation of the oxide scales.