3.2. Microstructure and Composition
Changes of the alloy’s grain size are usually related to the weld processing parameters. Interestingly, the interpass temperature and ultrasonic vibration could also effectively change the microstructure of the NAB alloy during WAAM when the weld processing parameters remain unchanged.
Figure 3 shows the OM micrographs of the microstructure between two adjacent ILB fabricated by WAAM in different interpass temperatures with and without UVA treatment (Y-Z plane, the observation position is shown in
Figure 1e). The microstructure of the Cu-8Al-2Ni-2Fe-2Mn alloys without UVA treatment is mainly composed of columnar dendrites, as shown in
Figure 3a1–a4,b1–b4. The size and morphology of the microstructure are quite different. The region of elongated columnar grains without secondary dendrite arms (SDA) growth along the deposition direction due to a high temperature gradient (G) and a slow growth rate (R) at the bottom of the molten pool delineated the ILB and is marked with a white arrow (
Figure 3a1,b1). With the decrease of the temperature gradient from the bottom to the top of the molten pool, the liquid metal becomes undercooled and leads to the destabilization of the solidification front [
28], the columnar grains turn to be coarser and gradually form SDA (
Figure 3a3,b3). The morphology of SDA is related to the cooling rate [
29]. More SDAs are found in the samples which undergo higher interpass temperatures. In fact, at the top of each deposited layer, the epitaxial growth of the columnar dendrites structure is blocked off by a random oriented equiaxed dendrites structure, the equiaxed dendrites with a thickness of about 200–300 μm (Insert picture in
Figure 4a). The transition character of the top region is revealed in a higher magnification (
Figure 4a). It is believable that the columnar to equiaxed transition occurs at the top of the molten pool due to the decrease of the temperature gradient and the increase of the interface moving velocity [
30]. There is no subsequent layers re-melting it, hence, only the top region shows this transition characteristic.
When the UVA treatment WAAM is under the interpass temperature of 400 °C, part of the columnar dendrites structure is fractured and the grain size is further decreased (as shown in
Figure 3c1–c3). At the top of the molten pool that is near the ILB, abundant columnar dendrites with SDAs are also found (
Figure 3c4). Hence, a mixed microstructure contains the coarse cellular dendrites, cellular grains and columnar dendrites, which are formed in UVA treatment WAAM samples with a higher interpass temperature. With further decrease of interpass temperature at 100 °C, the microstructure is refined to form a cellular structure and the grain boundaries are shortened (
Figure 3d1–d4). Similar microstructure evolution has been reported for fabrication using laser additive manufacturing [
23,
25] and welding process [
21,
31]. Ultrasonic vibration induces acoustic streaming and cavitation caused the stirring and mixing of liquid materials in the molten pool [
18,
32,
33]. Meanwhile, the effect of heating accumulation can be eliminated by controlling the interpass temperature. The actions of stirring and mixing lead to a homogenizing density and heat in the molten pool, which contribute to the uniform distribution of grains and the formation of a cellular structure with uniform grain boundaries.
The microstructure of some characteristic regions is shown in
Figure 4.
Figure 4b,c shows the comparisons of the deposition layers near the substrate. The C2 sample without UVA treatment presents the planar growth in the bonding interfaces due to the high temperature gradient and slow growth rate at the bottom of the molten pool near the substrate and is marked by a black arrow. With the decrease of G/R, random distribution of dendrites form into α-Cu matrix and then change to cellular structure (
Figure 4c). This cellular structure grows in the opposite direction to the temperature gradient and eventually forms columnar dendrites. Similar phenomena are obtained for the C3 sample.
In comparison to the WAAM without UVA treatment (
Figure 4b), the UVA treatment WAAM produces a weaker bonding interface, as shown in
Figure 4d. Further, the pressure in the acoustic field made the solid-liquid interface morphologically unstable and fragmented the dendrites and epitaxial cellular tips [
33]. These dendrite tips are conveyed into the undercooled melt via convection. In the meantime, a large amount of grain nucleation is formed. Hence, the alloy fabricated with UVA treatment generated equiaxed grain in a smaller grain size (about 5–12 μm) at the bottom region. It can be discerned that there exist two kinds of morphology of ILB, which is an important feature. One is that the ILB exhibit typical columnar grains orient upwards, which often shows a little darker contrast compares with the surroundings under OM (the OM insert in
Figure 4e and macrostructure in
Figure 2a). The higher magnification observation of the microstructure (
Figure 4e,f) shows that the below ILB expresses the relatively larger primary dendrite arms (PDA) spacing with SDAs. In contrast, the secondary arms are partially re-melting in the ILB. The characteristics of ILB in the C2, C3 and U2 samples all conform to this formation rule. Other kinds of cambered bands in U3 sample shows the different size of cellular structure in ILB (
Figure 4g). With the micrograph in
Figure 3d1–d4, the microstructure of the U3 sample can be divided into three parts: ILB, fine cellular zone, and coarse cellular zone. The formation of ILB can be attributed to the partial re-melting of the previously deposited layers and complex thermal history experienced by the WAAM process. Zhu et al. [
34] also found that the ILB were spaced uniformly in the whole sample, which demonstrated that it was just a result of the depositing layer. Furthermore, the two adjacent ILB are 2.0–2.2 mm in separation, which corresponds to the average added layer height. It is easy to measure that the deposition height of the last layer is more than 2.4 mm for the convenience of explaining the ILB are re-melting structure.
Figure 4h shows a higher magnification of interdendritic structure from U3 sample. The microstructure consists of α-Cu matrix and perishable etch interdendritic κ phase. Besides, no evidence of retain β or acicular β′ martensite is observed in the UVA treatment WAAM sample, a similar result is reported in Dharmendra’s studies [
17]. However, SEM and OM are difficult to qualitatively evaluate the type of the precipitation phase in the UVA treatment WAAM samples. The TEM examination is discussed in detail below.
As we know, the microstructure is very sensitive to temperature, while the different locations of the deposited wall during the WAAM process undergo rapid melting and solidification with a complex thermal history, so it is necessary to observe the microstructure in different deposited heights.
Figure 5 shows the microstructure in the X-Z plane of each component is described in lower and upper regions (the location is shown in
Figure 1e). All of the samples without UVA treatment have coarse columnar dendrites grown epitaxially along the deposition direction, as shown in
Figure 5a–d, which accord with the observation in the Y-Z plane. Continuous columnar dendrites are blocked by UVA treatment in the U2 sample and the broken character can be seen more clearly in the high magnification SEM image (
Figure 5e,f). A similar cellular structure is found in the UVA treatment at an interpass temperature of 100 °C sample (
Figure 5g,h). It is important to point out that different vertical locations strongly effect PDA spacing. In the C2, C3, and U2 samples, the PDA spacing is coarsened with increasing deposition height. After analysis by the quantitative metallography method, the average PDA space of the C2, C3, U2, and U3 samples is around 28.5 ± 4.2 μm, 21.6 ± 3.6 μm, 26.8 ± 3.1 μm, and 18.6 ± 2.6 μm, respectively.
The typical microstructure of the X-Y plane is shown in
Figure 6 (the observation location is marked with a blue arrow in
Figure 1e). Since the microstructure grows epitaxial along the deposition direction (i.e., Z direction) in C2, C3 and U2 samples, it appears as coarse dendritic structure in C2 due to develop SDA (
Figure 6a,b). Typical equiaxed grains are found in C3 sample (
Figure 6c,d) in this section, which result in fewer SDAs at lower interpass temperatures. In the cross-section of the UVA treatment samples, the size of dendritic structure is further reduced (i.e., U2 sample in
Figure 6e,f), and the microstructure of the U3 sample is similar to that of the other two cross-sections (
Figure 6g,h), which also proves that the microstructure form in the U3 sample is more uniform.
The WAAM process involves a larger melt pool diameter and layer height than power bed technologies, which generally lead to a greater microstructural heterogeneity and more severe ILB [
35]. Hence, the microstructure between two adjacent ILB changes regularly with the temperature gradient and growth rate, and the phenomenon is more obvious under the control of interpass temperature. The Cu-8Al-2Ni-2Fe-2Mn samples fabricated by WAAM without UVA treatment not only contain columnar dendrites, but also exhibit columnar to equiaxed dendrites transition. Kurz and Fisher [
36] established a solid-liquid interface model for instability criterion during solidification, which pointed out the ratio of G/R determined the growth morphology and G·V controlled the scale of the microstructure formed. Bermingham [
37] reported the thermal environment was dynamic during additive manufacturing and equiaxed grain formation was only achievable when temperature gradients decrease sufficiently to permit constitutional supercooling. With the decrease of G/R from the bottom to the top of the molten pool, the grain morphology might change from columnar dendrites to equiaxial dendrites due to serious constitutional undercooling. Forced control of the interpass temperature causes the deposited layer act as a mainly heat sink, which made the amounts of heat flux dissipates downward during the solidification process and results in regular changes in the microstructure between adjacent ILB.
As shown in
Figure 7a, the endothermic peaks in calorimetric curve reveal the melting point of the WAAM Cu-8Al-2Ni-2Fe-2Mn alloy is about 1020 °C. The typical thermal cycle measures in the WAAM built for a sequence of six added layers is shown in
Figure 7b. The first curve is the thermal cycle of thermocouple plunge into the melt pool. The peak temperature of the second curve is very close to the melting point measured by DSC. Hence, we can predict that the temperature of the arc melting pool is high enough to re-melt the equiaxed dendrites region (
Figure 4a), while the SDAs help to maintain the growth direction of primary dendrites in subsequent layers (
Figure 3a1–b4 and
Figure 4f), and finally forms the epitaxial growth.
Previous studies reveal that the microstructure of materials depends on both the nucleation condition and subsequent growth stage [
19,
26]. The UVA treatment WAAM at lower interpass temperature can hinder the growth of epitaxial columnar more effectively and promote the formation of new grains. The refinement of the microstructures mainly results from the actions of acoustic streaming and cavitation induced by ultrasonic vibration [
18,
32,
33]. The pressure in the acoustic streaming makes the solid-liquid interface morphologically unstable and fragments the columnar grain tips. With the assistance of instant high acoustic streaming, the primary coarse columnar grains are broken and fragmented because of the force. These dendrite tips are conveyed into the undercooled melt via convection and stirring. In the meantime, a large amount of grain nucleation is formed. With a lower interpass temperature of 100 °C, the effect of heat accumulation on the WAAM process is eliminated. Eventually, WAAM parts with refined grains are obtained UVA treatment at a lower interpass temperature process during the nucleation stage.
In order to reveal the various intermetallic phases in the interdendritic regions and α-Cu matrix, detailed TEM observations of the U3 sample were studied.
Figure 8 and
Figure 9 show the distribution features of elements at the interdendritic regions and α-Cu matrix. The interdendiritic regions display two types of intermetallic phases, κ
II phase in the different globular sizes (Range from some nanometers to tens nanometers) and κ
III phase in the lamellar morphology, and EDS elemental mapping distinctly reveals the morphology (
Figure 8). The κ
II and κ
III phase are found to be Fe
3Al and NiAl, respectively, based on the selected area diffraction pattern analysis, as shown in
Figure 10a,b,d,e. Some amounts are very fine to the sizes of κ
IV phase (Fe-rich, 5 to 10 nm in size) precipitate is observed in the α-Cu matrix (
Figure 9). The observation of fine Fe-rich precipitation and precipitation-free areas is distributing non-uniformly in the α-Cu matrix, which may be resulted by the different effects of thermal cycling of the WAAM on different locations. Selected area diffraction pattern analysis reveals the κ
IV precipitates have a composition and crystal structure is similar to that of κ
II based on Fe
3Al (
Figure 10c,f). It is possible that the κ
II and κ
IV are being precipitated at the same temperature from the same phase [
5]. The small and disperse κ
IV phases may inhibit grain boundary mobility, which beneficial for improving strength [
38], and also preventing grain growth [
4].
The results of TEM observation shows that the twins and dislocations can be found near the interdendritic region of the sample with UVA treatment. In the specimen process with UVA treatment at interpass temperature of 100 °C, the coexistence of twins and interdendritic is shown in
Figure 11a. The high-resolution HRTEM micrograph and corresponding selected area electron diffraction are inserted in
Figure 11a, which further verifies the structure of twins. The areas between the twin bands, which are tens of nanometers in thickness, seem to be parallel to each other, and EDS elemental mapping indicates that this parallel twinning may rely on κ
III precipitates (NiAl) in the interdendritic region (
Figure 12).
Figure 11b presents a density of dislocations in the U3 sample. The dislocations form rectangular blocks of 50–120 nm in size. EDS elemental mapping reveals that there is no obvious precipitated phase in the dislocations (
Figure 13). Meanwhile, the microstructure, that is without UVA treatment, specimens is simpler, as no obvious twins and dislocations occurs in the C3 specimen, as shown in
Figure 11c. Hence, combining previous studies [
39,
40] and the results obtained in this study, it can be concluded that the action of UVA treatment WAAM solidification process can help to create twins and dislocations. The twins and dislocations may contribute to strengthening of the WAAM NAB alloy by acting as a grain boundary and blocking the lattice dislocation motion [
41,
42].
3.3. Nano-Hardness and Tensile Properties
To acknowledge the variation of nano-hardness and modulus by the ultrasonic vibration and interpass temperature, the nano-indentation tests are conducted on the interdendritic region, ILB, α-Cu matrix lower and upper the ILB, respectively. Typical load-depth cures for four regions in C2, C3, U2 and U3 samples are plotted in
Figure 14a–d. It can be seen that the contract depth, maximum depth and final depth in the interdendritic region are shallower than those in the α-Cu matrix and ILB, which could partly reflect a greater nano-hardness of the interdendritic region. Besides, the ILB exhibits the maximum depth, which means that the nano-hardness value of the area is the minimum. In addition, the indentation test curves indicate a good repeatability with UVA treatment under interpass temperature of 100 °C samples (
Figure 14d).
The variation trends of both nano-hardness and modulus in four samples are shown in
Figure 14e,f. Each position nano-hardness value represents an average of at least 8 measurements. With the interpass temperature decreasing (C3 sample) and UVA treatment under interpass temperature of 100 °C (U3 sample), the nano-hardness of α-Cu matrix and ILB is increase, and the nano-hardness in the interdendritic region is decreases (
Figure 14b,d). Apart from the enhancement in nano-hardness, the modulus also slightly increases in α-Cu matrix and ILB, and decreases in the interdendritic region. It is often desirable to have more uniform nano-hardness in the material. With UVA treatment under interpass temperature of 100 °C, the nano-hardness in interdendritic region, ILB zone, the α-Cu matrix upper the ILB, the α-Cu matrix lower the ILB are 2.28 ± 0.09 GPa, 2.11 ± 0.02 GPa, 2.24 ± 0.03 GPa and 2.22 ± 0.02 GPa, while the four modulus are 129.4 ± 3.80 GPa, 122.4 ± 1.48 GPa, 126.4 ± 2.22 GPa and 126.1 ± 2.06 GPa, respectively. The nano-hardness and modulus of the WAAM Cu-8Al-2Ni-2Fe-2Mn alloy in U3 sample is relatively close, which indicates that the Cu-8Al-2Ni-2Fe-2Mn alloy fabricated by UVA treatment under interpass temperature of 100 °C is more stable. The uniform and increase of the α-Cu matrix and ILB in U3 sample is mainly attributed to two reasons: (i) based on the Hall-Petch law, the nano-hardness increases with the decreases of the grain size which is caused by UVA treatment [
43]. (ii) according to the TEM results, the precipitation of κ
IV phase in the α-Cu matrix may increase the mean nano-hardness [
17,
44].
Tensile properties of specimen U2, C3 and U3 are tested according to the effective area of deposition (
Table 1) and the finer grain size (
Figure 3). The typical stress-strain curves for the three conditions of the WAAM samples and cast C95220 alloys, as well as the tensile properties determine from these curves, are compared in
Figure 15. It can be seen that all of the WAAM samples are found to exhibit considerably higher yield strength (YS) and elongation (EL) as compared to the cast samples. The cast C95220 alloys has higher ultimate tensile strength (UTS) than that of WAAM samples due to more contents of Al, Ni and Fe elements (the microstructure of C95220 alloys is shown in the inserted picture at the top left). The figures demonstrate that though the nature of the flow curves of the U2, C3 and U3 samples are similar, there is a marked difference in their properties. The yield strength of the U3 samples (224–227 MPa) are higher than that of the C3 (200–204 MPa) and U2 samples (189–193 MPa). In the perspective of NAB component engineering design, yield strength is more relevant than ultimate tensile strength. On the other hand, the ultimate tensile strength of U3 (515–518 MPa) samples are also higher than C3 (434–458 MPa) and U2 samples (387–438 MPa). The anisotropy of UTS exists in C3 and U2 samples. Regarding ductility, the elongation of U3 samples (40.56–41.42%) are comparable to that of the C3 samples (39.95–42.8%), while specimens prepared from U2 samples exhibit higher ductility (42.2–50.87%). The detailed results of the average tensile properties in the vertical direction (V) and horizontal direction (H) within the UTS, YS and EL are listed in
Table 2.
In order to study the interpass temperature and UVA treatment effects on different locations along the deposition direction on the tensile properties of the fabricated wall, the tensile properties at different heights along the deposition direction are tested. Experimental results are shown in
Figure 16. In the U2 and C3 samples, the UTS is more sensitive to the locations within the build and decreasing along the build height. The near to substrate sample shows the highest UTS, which is caused by the finer microstructure in the bottom region. In addition, although the UTS of the samples at different heights differ, no clear trend can be identified in YS and ductility in the U2 and C3 samples. In addition, when a low interpass temperature of 100 °C is used, less decrease of UTS is generated along the deposited direction in C3 samples. After UVA treatment under an interpass temperature of 100 °C, the tensile properties of the samples at different heights tend to be stable. Hence, from both horizontal and vertical tensile properties consequences, it is considered that the tensile properties are symmetrical within the U3 samples. The UTS, YS, and EL of the U3 samples are 517.0 ± 0.89 MPa, 226.2 ± 0.95 MPa, and 41.01 ± 0.29%, respectively. Among all the test samples, anisotropy is well controlled in the samples with UVA treatment at an interpass temperature of 100 °C, and the increase of UTS and YS is not accompanied by any drop in the ductility.
Figure 17 shows that SEM micrographs of the tensile fracture surfaces for the Cu-8Al-2Ni-2Fe-2Mn alloy fabricated with and without UVA treatment under different interpass temperature. The fracture surface morphology of the U2 and C3 samples exhibits a transgranular ductile failure mode (
Figure 17a–f). In U2-H direction samples, the slip separation (marked by the white arrow in
Figure 17a,b) and dimples mix in the boundaries so that the PDA is clearly observed. The U2-V direction is mainly dominated by slip separation in fracture characteristics (
Figure 17c). However, there are a large number of small and deep dimples aligned along the PAD boundaries when the UVA treatment is not applied (
Figure 17d–f), implying a ductile type of fracture. With the UVA treatment under the interpass temperature of 100 °C, the grains sizes are greatly reduced, as grain boundaries become ambiguous in the fracture surface of the U3 samples and abundant finer dimples can be observed, as shown in
Figure 17g–i, which also indicates a ductile failure mode. In addition, in the horizontal tensile fracture morphologies of the U2 and C3 samples, the PDA spacing in the fracture increases with different heights along the deposition direction, which is consistent with the results of microstructure observation (
Figure 5) and also explains the tensile strength decreases with deposited height (
Figure 16). The consistency of these tensile test results is in agreement with the changes in grain size observed in the microstructure, suggesting that UVA treatment under an interpass temperature of 100 °C is beneficial to the material properties of WAAM fabricated Cu-8Al-2Ni-2Fe-2Mn alloy components.
It was found that the tensile properties are anisotropic between the horizontal and vertical directions in U2 and C3 samples. Previous studies have shown that the strength is related to the growth of columnar grains along the deposition direction [
45]. Due to the different orientations of the tensile specimens, horizontal samples contain more grain boundaries, while the vertical samples contain more columnar grains (as shown the test samples pictures are inserted in
Figure 15). Since the strength resulting from the grain boundaries is higher than the strength of the grains themselves, the strength of the horizontal tensile specimen is higher than the vertical one, and the elongation of the vertical sample is higher than that of the horizontal sample [
46]. In addition, as the inserted test samples pictures are shown in
Figure 15, the vertical samples show more obvious uniform elongation and necking when compared with the horizontal samples, which means vertical samples have greater plastic deformation and leading to a large amount of slip separations on the fracture (
Figure 17c). As the strength increases and elongation decreases, fractures change to a mixture of slip separation and dimples (
Figure 17a,b,d–f). In the U3 samples, the microstructure is cellular, and the relationship between the tensile force and grain boundaries is shown in
Figure 15 (insert test samples pictures), where the number of dimples is increasing and the size is smaller than other samples.
Aside from the anisotropy of mechanical properties, when compared the U2 with C3 samples, the U3 sample fabricate with UVA treatment under an interpass temperature of 100 °C have remarkably larger tensile strength and yield strength. The mean values of these properties increase by 19.7% and 13.3% in UTS, and 15.8% and 11.1% in YS, respectively. In contrast, the elongation decreases by 9.4% in U2 samples, which is almost the same as elongation of C3 samples. The main factors contribute to higher strength are as follows: the grain refinement, the formation of twins and dislocations structure, and the presence of precipitating phase in α-Cu matrix. Firstly, it is clearly seen that U3 samples have fine grains than other parameters samples (
Figure 3 and
Figure 5). This fine cellular structure is the direct outcome of UVA treatment under an interpass temperature of 100 °C and is observed in many other UVA treatments for manufacturing of processed materials [
25]. The grain size reduced significantly, and the material is strengthened according to the Hall-Petch effect [
47]. Further, Wang et al. [
48] also made it clear that the fine cellular structure significantly enhanced the strength of additive manufacturing samples. Secondly, due to the UVA treatment WAAM process, the twins and dislocations form, coherent twins have a strengthening effect that is similar to the influence of grain boundaries [
41]. The generated twins act as additional grain boundaries and interrupt dislocation gliding, resulting in the dynamic Hall-Petch effect [
49]. Thirdly, the results of TEM confirm the existence of the precipitate κ
IV phase in the α-Cu matrix (
Figure 9). The precipitates are bypassed through the dislocation looping mechanism, which increases in strength [
41]. It may be noted that the WAAM process under UVA at an interpass temperature of 100 °C probably restricts the solid-state transformation of κ
IV phase due to more superior cooling rates. However, in fact, this process may reduce the formation of interdendritic (more κ
II phase, composed of Fe-rich), and promote the distribution of Fe into the α-Cu matrix. During the WAAM process, the previous layers are subjected to re-heating by the thermal cycle of the subsequent deposition. The temperature range of 500 to 600 °C would result in homogeneous κ
IV precipitation in the α-Cu matrix [
17]. In this temperature range, the WAAM process has a significant reduction in cooling rate and this condition can be retained for a long time (
Figure 7b), and when Fe is sufficient, more κ
IV phase will precipitate in α-Cu matrix. Moreover, it can maintain good ductility in U3 sample that is fabricated by UVA treatment WAAM under interpass temperature of 100 °C methods could be mainly due to the formation of cellular structure [
42]. Furthermore, the fact that the fracture morphology develops from the slip separation of high interpass temperature to fine dimples at the lower interpass temperature, which also verify the general trend of increasing strength and keep ductility. In addition, compared with the U2 samples, the tensile strength of the C3 samples increase slightly, which mainly results in the refinement of the columnar dendrites.