3.1. Microstructure and Crystal Structure
Figure 1 shows the microstructure and XRD patterns of the as-cast Al0.5CoCrFeNiTi
x HEAs. Based on the XRD results, the diffraction peak is narrow and sharp, indicating that the alloy exhibits high crystallinity. The intensity of the large angle diffraction peak is weak because the change in the atomic radius of multiple principal elements in the HEAs leads to lattice distortion and enhanced diffuse reflection, and the intensity of the diffraction peak decreases with increasing scanning angle.
Additionally, the Ti-0.3 alloy is mainly composed of the FCC phase and a small amount of the BCC phase. With increasing Ti content, the diffraction peak of BCC increases gradually. For alloy Ti-0.8, the diffraction peak intensity of the BCC phase is similar to the diffraction peak intensity of the FCC phase, indicating that the phase contents in the alloy are similar. The FCC phase is of the A1 type, with a = 3.5975 Å and the Pearson symbol of cF4. The BCC1 phase is of the A2 type, with a = 2.876 Å and the Pearson symbol of cl2. The BCC2 phase is of the B2 type, with a = 2.920 Å and a Pearson symbol of cP2. By comparing the XRD results of the three Al0.5CoCrFeNiTi
x HEAs, we found that the diffraction peak of the solid solution shifted slightly to the left with increasing Ti addition, indicating that the lattice parameters of the BCC phase increased slightly, and that lattice distortion occurred as more Ti with a large atomic radius dissolved into the BCC solid solution. Some previous studies have found the same phenomenon [
24,
25].
Based on the SEM results, Ti-0.3 and Ti-0.5 alloys are cellular structures. Inside the cell, the dark gray phase and light gray phase are arranged alternately. A dark gray phase was mainly observed between the cells. From the EDS results (
Table 2), Co is distributed uniformly in the alloy. Al, Ti and Ni are enriched in light gray phases (Areas 1-2 and 2-2), while Fe and Cr are enriched in dark gray phases, which can be explained by the mixing enthalpy between elements.
Table 3 shows that by comparing the mixing enthalpy between elements, the negative enthalpy of mixing between Al, Ni and Ti is lower. Thus, the metal binding force between AlTiNi is stronger, and the combination of these three elements forms the ordered BCC phase (AlNi2Ti). Cr and Fe are repelled from the light gray phases, which makes the dark gray phases rich in Cr and Fe. Many researchers have found element segregation in different phases in HEAs. Zhang et al. [
26] added Al to a CoCrFeNiTi alloy and found that significant element segregation occurred in the alloy. The dendrite region is rich in Co, Ni, Ti and Al, while the interdendrite region is rich in Fe and Cr. Saideep et al. [
21] found that the microstructure of AlCoCrFeNi
2.1 consists of a lamellar arrangement of L12 and B2 solid-solution phases. The two phases have different elemental compositions. The B2 phase was found to be rich in Ni and Al, while the L12 phase was rich in Co, Cr, and Fe. The above studies are similar to the studies in this paper. According to XRD and EDS analysis of Ti-0.3 and Ti-0.5 alloys, it is reasonable to infer that the light gray and dark gray phases are BCC (A2/B2) and FCC solid solutions, respectively.
With increasing Ti content, intermetallic compound σ precipitates gradually precipitated in the high-entropy alloys. According to the XRD results, the σ phase had formed within the Ti-0.5 alloy, but it is difficult to observe them from SEM images due to the small amount. With a further increase in the Ti content, the FCC phase and BCC phase in the Ti-0.8 alloy decrease significantly, and a large amount of intermetallic compound σ precipitates. The σ phase (Cr0.99Fe1.01) has a tetragonal structure, with a = 8.797 Å, c = 4.558 Å and the Pearson symbol tP30. According to the electron backscatter diffraction (EBSD) results in
Figure 2, the flower-like light gray phase is the BCC phase, which is rich in TiAlNi. Numerous σ phases are distributed in the gap between the BCC phases. The element distribution diagram shows that numerous Cr and Fe elements are enriched around the flower-like BCC phase. The content of Cr is up to 34.43%, almost twice the average content. A large amount of Cr contributes to the formation of the σ phase. In addition, Cr tends to decrease toward the cell wall. The mixing enthalpy of Cr and Fe with other elements is relatively high.
With the reduction of Cr, some acicular phase formed in the cell wall (Area 3-3). The same acicular phase is observed in the cell wall of the Ti-0.5 alloy (Area 2-3). The above two regions have high Ti and Ni contents, possibly due to the high mixing enthalpy between Ti and Ni, which easily combine to form intermetallic compounds. Wu et al. [
24] also found this acicular phase when they studied FeCoCrAlNiTi1.5 and FeCoCrAlNiTi2 HEA coatings on 304 stainless steel. They considered this needle-like phase to be the (Ti, Ni) intermetallic compound phase. Thomas Lindner et al. [
27] found that for the Al
xCoCrFeNiTi alloy, a bright acicular phase precipitated between the cell wall when
x = 0.2 and 0.8. They believed that the acicular phase was the intermetallic compound phase η with space Group P63/mmc (194) and hcp (D024) structures. However, they and Chuang et al. [
28] found that the η phase could not be detected clearly by XRD analysis, consistent with the XRD results of this study, as it is difficult to observe the peak of this intermetallic compound phase.
SEM and XRD results for the Al
xCoCrFeNiTi0.5 HEAs are shown in
Figure 3. The microstructure and phase composition of the Al-0.3 and Al-0.8 alloys are significantly different from the microstructure and phase composition of the Ti-0.5 alloy. The phase composition of the Al-0.3 alloy is relatively simple. The XRD results show that the phase composition contains an FCC phase and a small amount of BCC phase. However, we observed by SEM that acicular intermetallic compounds precipitate in the cell walls (Area 4-3). At present, only Ti-0.5, Ti-0.8 and Al-0.3 HEAs contain this phase among the 13 HEAs in this study. These three HEAs have a common characteristic, i.e., high Ti contents. The weight ratio of Ti in these HEAs ranges from 5.67 to 13.81 wt %, and the content of Ti in these three alloys ranges from 9.11 to 13.81 wt %, while the content of Ti in other alloys is less than 9 wt %.
Other studies [
24,
27,
28] also found that in AlCoCrFeNiTi or CoCrFeNiTi HEAs, the acicular η phase, which is the (Ti, Ni) intermetallic compound phase, gradually precipitated in the AlCoCrFeNiTi HEAs with increasing Ti content. The acicular η phase can also be observed in many nickel-based superalloys [
29,
30,
31], which was attributed to elemental segregation. Long et al. [
31] calculated the partitioning coefficient of each element when studying nickel-based superalloys. If the partitioning coefficient of an element is greater than the unity, the element tends to segregate more in the dendrite core than in the liquid and vice versa. They found that Ti had a lower partition coefficient than that of other elements, so Ti has a strong segregation tendency to the liquid phase. As a result, the content of Ti in the interdendrite region of the nickel-based superalloy is higher, and it is easier to form the η phase with the main element Ni. In fact, in the solidification process of many multicomponent alloys, element segregation easily occurs. Some elements tend to segregate into the dendrite nuclei, while others tend to accumulate in the interdendrite. This results in micro-segregation of elements between dendrite and interdendrite regions. In this paper, the EDS results show that Ti-0.5, Ti-0.8 and Al-0.3 alloys also show similar element distributions. It can be inferred that when the three above HEAs solidify, the cell structure forms crystal nuclei, and Ti is segregated into the liquid phase. When the content of Ti is higher than the solution limit, Ti and Ni combine to form the (Ti, Ni)-rich intermetallic compound phase between cell walls. In addition, low Al content may be another factor influencing the formation of the η phase. Thomas Lindner et al. [
27] believe that the Al content is also among the factors affecting the formation of the η phase. They found that with the further reduction of aluminum in the
x = 0.2 alloy, the η phase precipitates. An increase in aluminum content prevents the the η phase from precipitating. The same phenomenon has been found in nickel-based superalloys. It has been reported that a high Ti/Al ratio favors the nucleation and growth of the η phase during solidification of superalloys [
32,
33].
The EDS results (
Table 4) show that Al is enriched in the cell. The lattice constant of the FCC phase increases when Al is enriched inside the cell, and the alloy produces lattice distortion, leading to instability of the FCC phase. Since the atomic arrangement density of the BCC structure is lower than the atomic arrangement density of the FCC and HCP structures, it is easier to adapt the BCC structure to larger solute atoms. Therefore, adding too much Al will change the crystal structure of FCC to BCC and reduce the lattice distortion energy of the alloy. The BCC phase obviously increases with increasing Al content. When studying CoCrFeNiTiAl
x HEAs, Zhang et al. [
26] also found that the XRD pattern of the Al-1.0 alloy was similar to the diffraction pattern of the Al-0.5 alloy, but its reflected light shifted slightly to the left. The reflection shift can be attributed to the increase in the lattice constant caused by the solid solution of Al. As Al has a large atomic radius, the solid solution of Al will lead to lattice deformation and lattice expansion; thus, the lattice constant increases, and a reflection shift occurs [
34]. Yu et al. [
35] found that adding Al atoms can also slightly decrease the lattice parameters of FeNiCoCr HEA. This may be due to the distinct ionic size of aluminum atoms. In this paper, when the Al atom ratio reaches 0.8, numerous σ phases precipitate within the Al-0.8 alloy. In addition, the Al-0.8 alloy contains a small amount of FCC and BCC phases.
Figure 4 shows that the addition of Co can significantly change the phase composition and morphology of Al0.5Co
xCrFeNiTi0.5 HEAs. The addition of Co makes the original BCC/FCC lamellar structure gradually disappear, and the microstructure gradually changes from a cellular structure to a dendritic structure. XRD analysis shows that both Co-1.5 and Co-2 alloys are composed of a large amount of the FCC phase and a small amount of the BCC phase. From the EDS results (
Table 5), the overall element distribution of the Co-1.5 alloy is relatively uniform. The contents of Al and Ti in Area 6-2 are slightly higher, which may be due to the formation of a small amount of the BCC phase in this region. The Co-2 alloy shows the same distribution characteristics of elements. A small amount of BCC phase may form in the 7-2 region.
With increasing Cr content, the Cr-1.5 and Cr-2 alloys change from lamellae to equiaxed and flower-like structures (
Figure 5). According to the SEM images at high magnification and low magnification (
Figure 5a,b) of the Cr-1.5 alloy, lamellar structures are distributed around the equiaxed or flower-like phase, which are composed of an alternating white phase (8-2-W) and black phase (8-2-B). EDS analysis (
Table 6) shows that the black phase is a high Cr phase, which can be inferred to be the σ phase. The white phase is low in Al and Ti and high in Fe and Cr, and Ni and Co are at the average level, which should be the FCC phase. The equiaxed and flower-like phase rich in AlTiNi is the BCC phase. The XRD results showed that the increase in Cr content promoted the precipitation of σ. With the increase in Cr content, the peak values of the BCC and FCC solid solution phases decreased significantly, while the peak values of the σ phase increased significantly. By comparing the mixing enthalpy of Cr and other elements, the absolute value of the mixing enthalpy of Cr and Fe was determined to be the smallest, which is −1. In theory, intermetallic compounds formed by CrFe easily precipitate, consistent with the EDS results.
Figure 6 shows the microstructure and XRD patterns of the as-cast Al0.5CoCrFe
xNiTi0.5 alloys. The microstructures of the Fe-1.5 and Fe-2 alloys are similar to the microstructure of the Ti-0.5 alloy, both of which are cellular structures. With increasing Fe content, the phase composition of the Al0.5CoCrFe
xNiTi0.5 alloys showed little change. However, the XRD peak value of the BCC phase decreases with increasing Fe content. The EDS results (
Table 7) show that Co, Cr, Fe and Ni are enriched in the dark gray area (Areas 10-1 and 11-1) in the Fe-1.5 and Fe-2 alloys, which should be the FCC phase. Al and Ti are enriched in the light gray area (Areas 10-2 and 11-2), and they easily form the BCC phase when combined with Ni. The light gray area decreases with increasing Fe content, while the dark gray area increases, consistent with the XRD results.
The XRD patterns and microstructure of AlCoCrFeNi
xTi alloys with Ni additions are shown in
Figure 7. With the increase in Ni, the microstructure of Al0.5CoCrFeNi
xTi0.5 HEAs change significantly. The microstructure of Ti-0.5 is BCC/FCC lamellae distributed in the cell, while Ni-1.5 and Ni-2 alloys are typical dendrite structures. Moreover, the dendrite phase obviously coarsened with increasing Ni. The EDS results (
Table 8) show that the dendrite phase (Areas 12-1 and 13-1) contains less Al and Ti but is enriched in Co, Cr, Fe and Ni, forming a typical FCC phase. The interdendritic area (Areas 12-2 and 13-2) is rich in Al, Ti and Ni, forming the BCC phase. Based on the XRD results, the peak value of the FCC phase with chemical composition FeNi is enhanced, indicating that the Ni element promoted the formation of the FCC phase.
From the high-magnification SEM images (
Figure 8a–c), some submicron microstructures can be found within the Co2, Ni1.5 and Ni2 alloys (indicated by arrows). All three alloys have typical dendrite structures. The dendrite phase is the FCC phase and the BCC phase. However, in the BCC phase, the distribution of the smile needle structure can be observed. Qiu et al. [
36] analyzed the BCC phase of Al0.6CoCrFeNi alloy by the SAED pattern of TEM. As seen in the TEM figure (
Figure 8d), the brighter phase is the B2 (ordered BCC) phase, while the darker phase is the BCC (disordered BCC) phase. The widths of both the BCC and B2 phases are approximately 100 nm. Lee et al. [
37] also discovered this structure when studying the interdendrite bcc phase of Al0.5CoCrFe1.5NiTi0.5 alloy. They believed that this was a eutectic structure consisting of disordered BCC and ordered BCC phases.
3.3. Deformation Mechanisms of AlCoCrFeNiTi HEAs
According to the above analysis, the complex phase composition of AlCoCrFeNiTi HEAs has a direct effect on their mechanical properties. However, the influence of the microstructure on the mechanical properties cannot be obtained only through fracture morphology analysis. In this study, the deformation behavior of AlCoCrFeNiTi HEAs with different microstructures was studied, and the effect of the microstructure on crack initiation and propagation was observed. Due to the complex phase composition, large phase size and low intermetallic compound phase content of AlCoCrFeNiTi HEAs, we did not adopt transmission electron microscopy with a small observation area but rather observed the deformed samples by SEM to analyze the mechanical behavior of AlCoCrFeNiTi HEAs.
By observing the deformation samples of AlCoCrFeNiTi HEAs, more slip lines, including single slip and cross slip, can be observed in the FCC phase of the alloys regardless of the cell structure or dendrite structure. We can infer that the FCC phase bears the most deformation of the alloy. These dislocation motions carry a large amount of deformation in the alloy, providing plasticity for the material, and these dislocation rows are fixed to specific slip planes related to the short-range order in HEAs. When dislocation crosses the short-range ordered region of the slip plane, the distribution of solute atoms can be randomized, and the relative friction force of dislocation sliding on the specific slip plane can be reduced. At the initial stage of deformation, when the stress is low, a single slip system starts, but with the increase in deformation, multiple slip systems start. Faults in multiple directions begin to appear, and the extended width of these faults is very wide; as a result, intersections of faults in different slip systems are more likely to occur. These slip lines are also at an angle of 45–50° with the deformation direction.
For the AlCoCrFeNiTi HEAs with cellular structures, if the alloy is only composed of a solid solution phase, such as Ti-0.3 (
Figure 12a), Co-1.5 (
Figure 12d), Fe-1.5 (
Figure 12f) and Fe-2 (
Figure 12g) alloys, the FCC/BCC lamellae are distributed alternately in the cell, and the BCC lamellae with higher strength are smaller. During deformation, in addition to the deformation of the intercellular FCC phase, the FCC/BCC lamellae in the cell were also distorted, and some slip lines across the lamellae could be observed in some areas (indicated by arrows in
Figure 12g), showing that the deformation of FCC + BCC HEAs with cellular structures is uniform. Therefore, Ti-0.3, Co-1.5, Fe-1.5 and Fe-2 alloys exhibit great ductility. At the same time, the appropriate BCC phase also plays a strengthening role, so that the fracture strength of Ti-0.3 and Fe-2 alloys is above 2500 MPa.
Ti-0.5 (
Figure 12b) and Al-0.3 (
Figure 12c) alloys also have cellular structures, but from the high-magnification SEM, the shape and size of the BCC phase in the cell are greatly different from Ti-0.3, Co-1.5, Fe-1.5 and Fe-2 alloys. Ti-0.5 and Al-0.3 alloys contain numerous equiaxed BCC phases. According to the properties and microstructure, the structure of Ti-0.5 and Al-0.3 alloys is not conducive to uniform deformation of materials. The thin BCC/FCC lamella bends and distorts as a whole, but the equiaxed BCC or thick lamellar BCC/FCC does not easily bend under the action of an external force due to its large size. In addition to equiaxed BCC and thick lamellar BCC/FCC, Ti-0.5 and Al-0.3 alloys also contain intermetallic compound phases. Due to these difficult-to-deform phases, it easy for dislocations to plug up at the phase boundaries, resulting in local nonuniform deformation, which leads to cracks. The crack continues to propagate along the boundary of the least resistance, as indicated by the arrow in
Figure 12b. Simultaneously, the primary crack expands to the secondary crack, and the secondary crack also expands along the phase boundary. Therefore, for Ti-0.5 and Al-0.3 alloys, due to the characteristics of the microstructure, the plasticity and strength are much lower than the plasticity and strength of Ti-0.3, Co-1.5, Fe-1.5 and Fe-2 alloys.
AlCoCrFeNiTi HEAs with dendrite structures, such as Co-2, Ni-1.5 and Ni-2 alloys, contain FCC dendrites and intergranular BCC phases. During deformation, cracks easily form at the boundary due to the large difference in the properties of the two phases. When the crack expands to the ductile phase FCC, the FCC encounters plastic deformation to relax the local stress and release the elastic energy, which hinders the formation and propagation of the crack. Compared with dendritic FCC, the interdendritic BCC phase has lower plasticity, so the critical stress needed for crack instability propagation in the BCC phase is relatively small. Cracks at the FCC/BCC boundary are more likely to propagate inward to the BCC.
Figure 12e,h,i show that most cracks formed in the BCC phase are parallel to the direction of the external force. Some BCC phase cracks completely under the action of an external force. However, the crack passes when it extends to the FCC/BCC phase boundary. In addition, many short slip lines are observed in the BCC phase (inset of
Figure 12e), indicating that the interdendritic BCC phase also yields and participates in plastic deformation.