3.3.2. Microstructure of the Oxidated Layers
The XRD patterns of the surface oxidation products of CoCrNiAl
X alloys at 1100 °C are shown in
Figure 10. The elemental composition represented by each color in the figure has been marked on the left. Oxidation products are formed on the surface of CoCrNiAl
X alloys after 100 h oxidation. The surfaces of Al
0 and Al
0.1 alloys contain Cr
2O
3 and spinel oxides NiCrO
3, NiCr
2O
4, and CoCr
2O
4. The surfaces of Al
0.3, Al
0.5, and Al
0.7 mainly contain two oxides, Al
2O
3 and Cr
2O
3. According to the XRD phase analysis, after high-temperature oxidation at 1100 °C for 100 h, the Al
0 and Al
0.1 alloys have fcc phase diffraction peaks, which is mainly due to poor adhesion and excessive peeling of the Cr
2O
3 oxide layer, resulting in the exposure of the fcc phase matrix. The surfaces of the Al
0.5 and Al
0.7 alloys have not only the characteristic peaks of the matrix fcc but also the diffraction peaks of the bcc. This phenomenon indicates that the thickness of the oxide layer formed by the three alloys at this oxidation temperature is relatively thin, resulting in the XRD rays penetrating the oxide layer to make the fcc phase detected. The appearance of the matrix fcc phase in the alloy and the increasing intensity of the diffraction peaks indicate that the addition of Al improves the oxidation resistance of the alloy greatly. Some researches have shown [
33] have shown that Al can also react selectively with N at high temperature. However, this phenomenon was not found in this paper. This may be due to the different preparation methods which cause differences in microstructure.
In order to confirm the formation mechanism of high-temperature oxides of CoCrNiAl
X alloys, the oxidized surface of the alloys after oxidation at 1100 °C for 100 h were analyzed by XPS and the results are shown in
Figure 11. All four elements exist in relatively stable valence states (Co
2+, Cr
3+, Ni
2+, Al
3+) on the oxidized surface, and the XPS spectra of the core levels were fitted to the peaks using Thermo Advantage. Combining the XRD analysis results with XPS, it can be seen that Cr
2O
3 and NiCrO
3 correspond to the Cr
3+ peaks in the schematic diagram of the second column in
Figure 11. CoCr
2O
4 and NiCr
2O
4 match the peaks of Co
2+ and Ni
2+ in the schematic diagrams in the first and third columns of
Figure 11, respectively. Al
2O
3 corresponds to the single peak of Al
3+ in the schematic diagram in the fourth column of
Figure 11. The above results show that the analysis results of XPS are consistent with the results of XRD, that is, after oxidation at 1100 °C for 100 h, the surface oxides exist in the form of Cr
2O
3, Al
2O
3, and stable metal oxo-acid salts. The results of XPS further prove that when the Al content is low, the Cr element first undergoes selective oxidation, forming Cr-containing oxides attached to the surface of the alloy; while when the Al content gradually increases, Al firstly undergoes selective oxidation, mainly forming Al
2O
3, which covers the surface of the alloy to avoid further oxidation by oxygen elements [
34].
The surface oxidation morphology of CoCrNiAl
X (X = 0, 0.1, 0.3, 0.5, 0.7) is shown in
Figure 12. It can be seen that there is a clear difference among the alloys. As shown in
Figure 12a,b, the oxide layer of the Al
0 and Al
0.1 alloys has a loose hollow structure, resulting in large-scale spalling on the oxidized surface, as shown by the yellow arrows in the picture. The insets in
Figure 12a,b are the magnified morphology of regions A and C. Regions A and C are regions where spinel phases exist. Combining the chemical compositions of different regions of the oxidized surface in
Table 6 and the XRD analysis of the surface oxidation products in
Figure 10, spinel phases dominated by (Co, Ni) Cr
2O
4 and NiCrO
3 were formed. The B area contains more Cr and O elements, mainly Cr
2O
3. As the Al content increases, Al
2O
3 particles begin to appear in the D area, and then a dense Al
2O
3 film begins to form, preventing further oxidation of the matrix by oxygen, and the spalling situation is alleviated. A large number of Al
2O
3 particles is formed on the surface of the Al
0.3 alloy, as shown in
Figure 12c, indicating that Al diffuses rapidly from the matrix to the surface of the oxide layer. The E, G, and I regions are the regions where Cr
2O
3 and the matrix phase exist according to
Table 6. The F and H regions are film, which are Al
2O
3 phases in combination with the XRD analysis in
Figure 10. As the Al content increases to Al
0.5 and Al
0.7, under the action of high temperature, a dense but discontinuous alumina film is formed, which effectively prevents further oxidation of the matrix.
The SEM section image of CoCrNiAl
X oxidized at 1100 °C for 100 h is shown in
Figure 13. When the Al content is low, the oxidation depth is large and the structure is loose, resulting in a rougher cross-section of the oxidized substrate-oxide film. The selective oxidation of Al and Cr elements with oxygen occurs due to their high affinity for the element [
35,
36,
37]. In order to further determine the sequences and products of oxidation, the Gibbs free energy of the products of several oxidation at 1100 °C was calculated using the formula shown in [
38]. The formula is as follows:
ni is the amount of substance i in each substance participating in the reaction, ∅
i is the Gibbs free energy of substance i in each substance participating in the reaction, and the values of each parameter can be obtained from [
39].
T represents the reaction temperature.
is the reaction Gibbs free energy function,
is the Gibbs free energy, and
is the relative reaction enthalpy difference. The calculation results are shown in
Figure 14. It can be seen that the Gibbs free energy values of the oxidation products Al
2O
3 and Cr
2O
3 at 1100 °C are −1237.47 KJ/mol and −769.72 KJ/mol, respectively, which are the lowest among all oxidation products. This result indicates that Al and Cr selective oxidation occurs first, and the reaction is also spontaneous.
In contrast, the Al
0 alloy does not contain Al, but only Cr, which makes it difficult to form a dense oxide layer. According to the EDS mapping of the oxidation cross-section shown in
Figure 13f, it can be seen that the oxide layer is mainly composed of loose Cr
2O
3, and the spinel phase of (Co, Ni) Cr
2O
4 is attached to its outer layer. The poor adhesion of Cr
2O
3 results in continuous peeling during the oxidation process [
36,
37]. A dense oxide film cannot be formed, so the oxidation process is mainly the oxidation of the rate-controlled gas–metal interface reaction [
38]. Other elements in the matrix diffuse into the outer layer from the voids generated by shedding, thereby forming the spinel phase of (Co, Ni) Cr
2O
4 and NiCrO
3. The Al
0.1 alloy contains less Al, so the existence of Al
2O
3 cannot be detected in XRD. Combined with the EDS mapping of the oxidation cross-section shown in
Figure 13g, its oxidation process mainly depends on the diffusion of Cr, and the oxidation mechanism is the same as that of the Al
0 alloy. When the Al content increases to 0.3, no obvious segregation of elements such as oxygen is found in
Figure 13h–j. As shown in
Figure 12, Al
2O
3 particles begin to form on the surface of the Al
0.3 alloy. Under the action of high temperature, a dense but discontinuous Al
2O
3 film is formed on the surface of the Al
0.5 and Al
0.7 alloys, which blocks the intrusion of oxygen elements and avoids further oxidation of the matrix.
During the oxidation process, the diffusion of Al and Cr plays a key role, and the slow diffusion may also be partly responsible for the apparent stability of HEA [
40]. The high temperature causes a slow and steady diffusion of Al and Cr elements from the matrix to the surface of the oxide scale, and then reacts with oxygen to form oxides.