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Investigation of the nucleation and growth behavior of Ti2AlC and Ti3AlC nano-precipitates in TiAl alloys

  • Bo Hou , Aiqin Wang EMAIL logo , Pei Liu EMAIL logo and Jingpei Xie
Published/Copyright: February 10, 2023
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Nanotechnology Reviews
From the journal Nanotechnology Reviews Volume 12 Issue 1

Abstract

In this work, the nucleation and growth behavior of Ti2AlC and Ti3AlC nano-precipitates in Ti–44Al–1.2C alloys were systematically studied by observing their distribution, morphology, and interface atomic structure. The experiment results show that the needle-like C atom segregation zones in TiAl alloys are the nucleation site of Ti2AlC, and the long axis direction of segregation zones is parallel to the TiAl(111) plane. The rod-like Ti2AlC nano-precipitates mainly distribute at the TiAl/Ti3Al interface, and the orientation relationship between them is [ 1 ̅ 01 ]TiAl//[ 11 2 ̅ 0 ]Ti2AlC//[ 11 2 ̅ 0 ]Ti3Al, (111)TiAl//(0001)Ti2AlC//(0001)Ti3Al. The needle-like Ti3AlC nano-precipitates distribute in TiAl with the orientation relationship of [001]Ti3AlC//[001]TiAl, (100)Ti3AlC//(100)TiAl, (020)Ti3AlC//(020)TiAl, and (110)Ti3AlC//(110)TiAl during the nucleation stage. After growing into the rod-like, the orientation relationship between Ti3AlC precipitates and TiAl is [ 1 1 ̅ 0 ]Ti3AlC//[ 1 1 ̅ 0 ]TiAl, (001)Ti3AlC//(001)TiAl, (220)Ti3AlC//(220)TiAl, and (111)Ti3AlC//(111)TiAl. Both the needle- and rod-like Ti3AlC precipitates preferentially grow along the [001]TiAl direction. The crystal structure and lattice mismatch between Ti2AlC and Ti3AlC nano-precipitates and the TiAl matrix determine their distribution, morphology, and interface atomic structure.

Keywords: TiAl alloys; Ti2AlC and Ti3AlC nano-precipitates; nucleation and growth; interface atomic structure

1 Introduction

The requirements for engine performance have become increasingly stringent due to the rapid development of the aerospace and automotive fields in recent years, i.e., lighter, stronger, and higher. The development of new lightweight, high-temperature structural materials has become the key to improving engine performance and reducing energy consumption. TiAl alloys are expected to become the competitive high-temperature structural materials to replace nickel-based superalloys at the service temperature of 650–850°C due to their high melting point, low density, high specific strength, and specific modulus [1,2,3,4,5,6,7]. Nevertheless, the practical application of TiAl alloys at room temperature (<2%) was limited due to their poor ductility. To overcome the aforementioned shortcomings, researchers discovered that alloying technology is a reliable method to enhance the mechanical properties of TiAl alloys. In addition to the commonly used metallic elements (Nb, Cr, and B), the infinitesimal non-metallic elements (C, N, and O) can also have an effect on the microstructure and mechanical properties of TiAl alloys [8,9,10,11,12].

Domestic and foreign studies have shown that the C atom could refine the microstructure by changing the solidification path of TiAl alloys and could also improve their strength and creep resistance through solid solution strengthening and precipitation strengthening [13,14]. Noteworthy is the fact that the effect of precipitation strengthening is related to the C content. Wang et al. [15] found that the room temperature tensile properties of Ti–47Al–2Nb–2Cr could be significantly improved when the C content reaches 0.2 at.%. Li et al. [16] also found that 0.5 at.% C content could simultaneously improve the ultimate tensile strength and elongation of the Ti-43Al-6Nb-1Mo-1Cr alloy. Previous studies have shown that the C atom has a solid solution limit in TiAl alloys, and its solid solubility is greatly affected by factors such as temperature and alloying elements [17,18]. When the C content exceeds the solid solution limit of TiAl alloys, two kinds of carbides will precipitate, i.e., Ti2AlC and Ti3AlC. Schwaighofer et al. [19] found that the addition of C could cause the precipitation of the fine Ti2AlC carbides in TiAl alloys. Wu et al. [20] proved that both the fine Ti2AlC and Ti3AlC carbides could precipitate from C-containing TiAl alloys, and the carbide precipitates could also refine the microstructure of the TiAl matrix. Lapin et al. [21] studied the high-temperature deformation behavior of C-containing TiAl alloys and found that the fine Ti2AlC and Ti3AlC carbide precipitates could improve the creep resistance of TiAl alloys by hindering the movement of dislocations. Based on the aforementioned analysis, it could be seen that the precipitation of Ti2AlC and Ti3AlC carbides significantly improves the microstructure and mechanical properties of TiAl alloys, necessitating further research into their precipitation (nucleation and growth) behavior. However, according to our knowledge, the correlative investigation has not been reported up to date.

In the present work, the distribution, morphology, and interface atomic structure of Ti2AlC and Ti3AlC nano-precipitates in Ti–44Al–1.2C alloys were systematically observed using transmission electron microscopy (TEM), and the nucleation and growth behavior of two carbides in TiAl alloys were concluded. This study has a guiding significance for controlling the morphology and distribution of Ti2AlC and Ti3AlC nano-precipitates and contributes to optimizing the mechanical properties of TiAl alloys.

2 Experimental methods

In this study, spherical Ti powder (99.95% purity, ∼25 μm), spherical Al powder (99.95% purity, ∼25 μm), and graphene nanosheets were used as raw materials for the preparation of carbon-containing TiAl alloys. The Ti/Al/C composite powders were obtained by a high-energy ball milling equipment with argon gas protection based on the atomic ratio of Ti–44Al–1.2C. Afterward, the composite powders placed in a graphite mold were compacted through the pneumatic press, and then the carbon-containing TiAl alloy sample was prepared by vacuum hot pressing sintering at 1,623 K with 40 MPa for 2 h. The TiAl alloy sample was cut into a sample of 10 × 10 × 10 mm3, and the solution was treated at 1,523 K for 20 h and aged at 1,173 K for 1 h. It is worth emphasizing that in order to prevent the alloy from oxidizing at high temperatures, the heat treatment process is carried out in a quartz tube filled with argon as a protective gas. The microstructure and element distribution were characterized by scanning electron microscopy (SEM, JSM-7800F) coupled with energy dispersive spectroscopy. The cylindrical specimens with the size of Φ6 mm × 9 mm were used for the room-temperature compression tests by an electronic universal material testing machine (ZUAG-I250 KN). The high-temperature compression tests of the TiAl alloys with the same cylindrical size were carried out on the Gleeble-3800 system with a strain rate of 0.001 s−1. The sample for TEM analysis was machined into 0.5 mm from the aged sample using wire-electrode cutting and mechanically ground to about 60 μm, then cut into 3-mm-diameter foils. The Gatan precision ion polishing system (Gatan Model 695) was used for further thinning, and morphology analysis and phase identification were carried out by TEM (JEM-2100) with an accelerating voltage of 300 kV.

3 Results and analysis

3.1 Microstructure and mechanical properties

Figure 1(a)–(c) shows the SEM microstructure and corresponding elemental point analysis of TiAl alloys after heat treatment, respectively, and it could be observed that the TiAl matrix consists of TiAl and Ti3Al phases in the form of lamellar colonies. Figure 1(d) shows the room-temperature compressive stress–strain curve of the TiAl alloys, and the results indicated that the compressive strength is about 1,591 MPa and the compressive strain is about 16.7%. As can be seen from the true stress–strain curve in the inset, the true stress increases with an increasing strain rate. The true stress increases sharply with the increase in deformation strain in the initial stage and then increases slowly to the highest point of true stress. In addition, as shown in Figure 1(e), the compressive strength of the TiAl alloys at 800°C is about 639 MPa. The room-temperature and high-temperature compressive performances of this work are at a middle level among the reported TiAl alloys and TiAl-based composites, which may be related to the carbon content, sintering temperature, and time.

Figure 1 The SEM microstructure and mechanical properties of TiAl alloys: (a) SEM image; (b) element composition of Point 1 in (a); (c) element composition of Point 2 in (a); (d) room-temperature compressive stress–strain curve; and (e) high-temperature compressive stress–strain curve.
Figure 1

The SEM microstructure and mechanical properties of TiAl alloys: (a) SEM image; (b) element composition of Point 1 in (a); (c) element composition of Point 2 in (a); (d) room-temperature compressive stress–strain curve; and (e) high-temperature compressive stress–strain curve.

3.2 Nucleation and growth behavior of Ti2AlC nano-precipitates in TiAl alloys

Figure 2(a) shows the high-resolution transmission electron microscopy (HRTEM) morphology of the needle-like C atom segregation zones in TiAl, and Figure 2(b) is the fast Fourier transform (FFT) pattern of the square area in Figure 2(a). According to the calibration result in Figure 2(b), it could be seen that quite a few segregation zones in Figure 1(a) distribute parallel to each other along the TiAl(111). It could be observed from the inverse FFT (IFFT) image in Figure 2(c) that the segregation zone is only a few unit cells wide and its lattice arrangement is distorted to a certain extent compared with the surrounding TiAl matrix. Based on the morphology and crystallographic knowledge, we consider that the C atom segregation zone nucleates on TiAl(111) and then grows along TiAl(111) to be needle-like. In addition, we also think that as C atoms continue to segregate, this region will transform into Ti2AlC nano-precipitates, which will be discussed in detail in Section 4.

Figure 2 The TEM analysis of C atom segregation in TiAl alloys. (a) HRTEM image of segregation zone; (b) FFT pattern; and (c) IFFT image of segregation zone.
Figure 2

The TEM analysis of C atom segregation in TiAl alloys. (a) HRTEM image of segregation zone; (b) FFT pattern; and (c) IFFT image of segregation zone.

Figure 3 shows the nucleation and growth behavior of rod-like Ti2AlC nano-precipitates precipitated from the TiAl/Ti3Al interface. As seen in Figure 3(a), the TiAl/Ti3Al matrix consists of lamellae γ-TiAl and lamellae α2-Ti3Al, and also found that a small number of rod-like Ti2AlC nano-precipitates distribute at the TiAl/Ti3Al interface. Figure 3(b) shows the HRTEM image of the square area in Figure 3(a), and it could be observed that the width of the Ti2AlC nano-precipitate is about 10 nm. Insets (b-1), (b-2), and (b-3) in Figure 3(b) are the FFT patterns corresponding to Ti3Al, Ti2AlC, and TiAl, respectively. According to the calibration results, it could be determined that inset (b-1) is the TiAl along the [ 1 ̅ 01 ] zone axis, inset (b-2) is the Ti2AlC along the [ 11 2 ̅ 0 ] zone axis, and inset (b-3) is the Ti3Al along the [ 11 2 ̅ 0 ] zone axis. The FFT pattern of the TiAl/Ti2AlC/Ti3Al interface is shown in Figure 3(c), and the corresponding indexed pattern of Figure 3(c) is shown in Figure 3(d). According to the calibration result in Figure 3(d), their orientation relationship is as follows:

Figure 3 The TEM analysis of rod-like Ti2AlC nano-precipitates at the TiAl/Ti3Al interface: (a) TEM image of TiAl/Ti3Al and rod-like Ti2AlC; (b) HRTEM image of the TiAl/Ti2AlC/Ti3Al interface; (c) FFT pattern of the TiAl/Ti2AlC/Ti3Al interface; (d) indexing of the FFT pattern in (c); (e) IFFT image of the Ti2AlC/TiAl interface; and (f) IFFT image of the Ti3Al/Ti2AlC interface.
Figure 3

The TEM analysis of rod-like Ti2AlC nano-precipitates at the TiAl/Ti3Al interface: (a) TEM image of TiAl/Ti3Al and rod-like Ti2AlC; (b) HRTEM image of the TiAl/Ti2AlC/Ti3Al interface; (c) FFT pattern of the TiAl/Ti2AlC/Ti3Al interface; (d) indexing of the FFT pattern in (c); (e) IFFT image of the Ti2AlC/TiAl interface; and (f) IFFT image of the Ti3Al/Ti2AlC interface.

[ 1 ̅ 01 ]TiAl//[ 11 2 ̅ 0 ]Ti2AlC//[ 11 2 ̅ 0 ]Ti3Al, (111)TiAl//(0001)Ti2AlC//(0001)Ti3Al.

Figure 3(e) and (f) shows the IFFT images of the square area 1 and 2 in Figure 3(b), respectively. The IFFT images were marked to see the atomic arrangement of the interface more clearly, as shown in Figure 3(e)–(f), where the following red, purple, and blue circles represent the TiAl atoms, Ti2AlC atoms, and Ti3Al atoms, respectively. Figure 3(f) exhibits that the atomic stacking sequence of Ti2AlC can be regarded as the sequence of BABABAB along the [0001] direction, where the underlined letters correspond to Al layers and the non-underlined letters correspond to Ti layers, and the result is consistent with the previously studied layered crystal structure of Ti2AlC [22,23,24]. Furthermore, based on the arrangement of interface atoms, it could be concluded that both the Ti2AlC/TiAl interface and the Ti3Al/Ti2AlC interface show good atomic matching, indicating that these interfaces are coherent.

In addition to the precipitation of rod-like Ti2AlC at the TiAl/Ti3Al interface, the rod-like Ti2AlC nano-precipitate could also be observed in Ti3Al, as shown in Figure 4(a). Figure 4(b) shows the HRTEM image of the Ti3Al/Ti2AlC interface, and the insets (b-1) and (b-2) are the corresponding FFT patterns of Ti3Al and Ti2AlC, respectively. It could be determined from the calibration results that inset (b-1) is the Ti3Al along the [ 11 2 ̅ 0 ] zone axis and inset (b-2) is the Ti2AlC along the [ 11 2 ̅ 0 ] zone axis. Figure 4(c) shows the FFT pattern of the Ti3Al/Ti2AlC interface, and Figure 4(d) is the corresponding indexed pattern of Figure 4(c). Figure 4(e) and (f) is both IFFT images of the Ti3Al/Ti2AlC interface, and atomic arrangement results indicate that the orientation relationship between Ti3Al and Ti2AlC is the same as that in Figure 3(e), i.e., [ 11 2 ̅ 0 ]Ti3Al//[ 11 2 ̅ 0 ]Ti2AlC and (0001)Ti3Al//(0001)Ti2AlC.

Figure 4 The TEM analysis of rod-like Ti2AlC nano-precipitate in Ti3Al: (a) TEM image of Ti2AlC in Ti3Al; (b) HRTEM image of the Ti3Al/Ti2AlC interface; (c) FFT pattern of the Ti3Al/Ti2AlC interface; (d) indexing of the FFT pattern in (c); and (e and f) IFFT images of the Ti3Al/Ti2AlC interface.
Figure 4

The TEM analysis of rod-like Ti2AlC nano-precipitate in Ti3Al: (a) TEM image of Ti2AlC in Ti3Al; (b) HRTEM image of the Ti3Al/Ti2AlC interface; (c) FFT pattern of the Ti3Al/Ti2AlC interface; (d) indexing of the FFT pattern in (c); and (e and f) IFFT images of the Ti3Al/Ti2AlC interface.

3.3 Nucleation and growth behavior of Ti3AlC nano-precipitates in TiAl alloys

Apart from the distribution of Ti2AlC nano-precipitates in TiAl alloys, we also observed the precipitation of needle-like Ti3AlC, as shown in Figure 5(a). It could be seen that the high-density needle-like Ti3AlC nano-precipitates in TiAl alloys are distributed parallel to each other, and there are numerous dislocations around them. Figure 5(b) shows the HRTEM image of needle-like Ti3AlC nano-precipitates in TiAl, and Figure 5(c) is the FFT pattern of the square area in Figure 5(b). The calibration result shows that the TiAl corresponds to the [ 1 1 ̅ 0 ] zone axis, and it could be determined that the Ti3AlC nano-precipitates grow needle-like along the TiAl[001] direction according to the morphology in Figure 5(b).

Figure 5 The TEM analysis of needle-like Ti3AlC nano-precipitates in TiAl alloys: (a) TEM image of needle-like Ti3AlC in TiAl; (b) HRTEM image of needle-like Ti3AlC in TiAl; (c) FFT pattern of TiAl.
Figure 5

The TEM analysis of needle-like Ti3AlC nano-precipitates in TiAl alloys: (a) TEM image of needle-like Ti3AlC in TiAl; (b) HRTEM image of needle-like Ti3AlC in TiAl; (c) FFT pattern of TiAl.

Based on the aforementioned analysis, it could be observed that the needle-like Ti3AlC nano-precipitates grow along the TiAl[001] direction. Therefore, the needle-like Ti3AlC nano-precipitates show dot-like cross-sections when imaged along the TiAl[001] direction, and the corresponding TEM images were shown in Figure 6(a) and (b). Figure 6(c) shows the HRTEM image of the needle-like Ti3AlC nano-precipitates, where the TiAl is on the right side of the image. Figure 6(d) is the FFT pattern of the square area in Figure 6(c), and it can be seen that the diffraction spots of Ti3AlC appear between the diffraction spots of TiAl. The diffraction spots of Ti3AlC phase exist in the TiAl phase, which is due to the lattice parameters of Ti3AlC and TiAl being quite similar, thereby the diffraction spots of Ti3AlC appear at the superlattice position of TiAl with the face-centered tetragonal structure, which also proves the formation of Ti3AlC nano-precipitates from TiAl. The corresponding index pattern of Figure 6(d) is shown in Figure 6(e), and the calibration result shows that the Ti3AlC is along the [001] zone axis, the TiAl is along the [001] zone axis, the Ti3AlC(100) is parallel to the TiAl(100), the Ti3AlC(020) is parallel to the TiAl(020), and the Ti3AlC(110) is parallel to the TiAl(110). Therefore, the following orientation relationship results:

Figure 6 The TEM analysis of needle-like Ti3AlC nano-precipitates in TiAl alloys: (a and b) TEM images; (c) HRTEM image; (d) FFT pattern of the square area in (c); (e) indexing of the FFT pattern in (d); and (f) IFFT image of the square area in (c).
Figure 6

The TEM analysis of needle-like Ti3AlC nano-precipitates in TiAl alloys: (a and b) TEM images; (c) HRTEM image; (d) FFT pattern of the square area in (c); (e) indexing of the FFT pattern in (d); and (f) IFFT image of the square area in (c).

[ 001 ]Ti3AlC//[ 001 ]TiAl, (100)Ti3AlC//(100)TiAl, (020)Ti3AlC//(020)TiAl, (110)Ti3AlC//(110)TiAl.

Figure 6(f) shows the IFFT image of the square area in Figure 6(c). As exhibited in Figure 6(f), the blue and red circles represent the TiAl and Ti3AlC atoms, respectively. According to the atomic stacking sequence and the interface structure of Ti3AlC and TiAl, it could be concluded that Ti3AlC remains the coherent interface with TiAl during the precipitation.

Figure 7(a) shows the TEM image of the rod-like Ti3AlC precipitate in TiAl alloys after growth. The selected area electron diffraction (SAED) pattern of the rod-like Ti3AlC precipitate and TiAl is shown in Figure 7(b), and Figure 7(c) is the indexing of the FFT pattern in Figure 7(b). It could be observed that the large, bright spots represent the electron diffraction of TiAl and the small, dark spots represent the electron diffraction of Ti3AlC. The calibration result indicates that the Ti3AlC is along the [ 1 1 ̅ 0 ] zone axis, the TiAl is along the [ 1 1 ̅ 0 ] zone axis, the Ti3AlC(001) is parallel to the TiAl(001), the Ti3AlC(220) is parallel to the TiAl(220), and the Ti3AlC(111) is parallel to the TiAl(111). Thus, the orientation relationship is as follows:

Figure 7 The TEM analysis of rod-like Ti3AlC precipitate after growth in TiAl alloys: (a) TEM image of Ti3AlC and TiAl; (b) SAED pattern of Ti3AlC and TiAl; (c) indexing of the FFT pattern in (b); (d) TEM image of rod-like Ti3AlC; (e) FFT pattern of Ti3AlC; and (f) IFFT image of Ti3AlC.
Figure 7

The TEM analysis of rod-like Ti3AlC precipitate after growth in TiAl alloys: (a) TEM image of Ti3AlC and TiAl; (b) SAED pattern of Ti3AlC and TiAl; (c) indexing of the FFT pattern in (b); (d) TEM image of rod-like Ti3AlC; (e) FFT pattern of Ti3AlC; and (f) IFFT image of Ti3AlC.

[ 1 1 ̅ 0 ]Ti3AlC//[ 1 1 ̅ 0 ]TiAl, (001)Ti3AlC//(001)TiAl, (220)Ti3AlC//(220)TiAl, (111)Ti3AlC//(111)TiAl.

Figure 7(d) is the HRTEM image of the rod-like Ti3AlC precipitate in Figure 7(a). Figure 7(e) and (f) shows the FFT pattern and IFFT image of the square area in Figure 7(d), respectively. It could be observed from Figure 7(e) that the interplanar spacing of Ti3AlC(001) and Ti3AlC(110) is 0.418 and 0.295 nm, respectively, which further proved that the rod-like precipitate is Ti3AlC.

4 Discussion

In a nutshell, the C atoms solid-dissolved in the TiAl alloys will generate Ti2AlC and Ti3AlC nano-precipitates during the aging process, and their distribution, morphology, and orientation relationship with TiAl are quite different. Therefore, in the following sections 4.1 and 4.2, we attempt to explain the different morphology, distribution and orientation relationship between Ti2AlC and Ti3AlC nano-precipitates by investigating their crystal structures and lattice mismatch. The crystal structure and lattice parameters of TiAl, Ti3Al, Ti2AlC, and Ti3AlC are demonstrated in Table 1.

Table 1

The crystal structure and lattice parameters of TiAl, Ti3Al, Ti2AlC, and Ti3AlC

Phase Crystal structure Space group a (nm) b (nm) c (nm)
TiAl Tetragonal P4/mmm (123) 0.4018 0.4018 0.4065
Ti3Al Hexagonal P63/mmc (194) 0.5780 0.5780 0.4647
Ti2AlC Hexagonal P63/mmc (194) 0.2968 0.2968 1.3223
Ti3AlC Cubic Pm-3m (221) 0.4156 0.4156 0.4156

4.1 Nucleation and growth mechanism of Ti2AlC nano-precipitates

Previous research has shown that C atoms are inevitably solid-dissolved in the TiAl matrix during the aging process, and the concentration of C atoms in Ti3Al is higher than that in TiAl. As reported by Menand et al. [25] using the advanced Atom Probe Technique (APT), the solid solution of C atom in Ti3Al (0.15%, molar fraction) is 3–5 times higher than in TiAl. They tentatively concluded that the difference in solid solubility of C atom in Ti3Al and TiAl is mainly due to the different interstitial vacancies occupied by C atom in the two-phase lattice. Scheu et al. [18] further investigated the interstitial vacancies of TiAl and Ti3Al, and found that the C atom are mainly solidified in the octahedral interstitial of the TiAl and Ti3Al, and the Ti6-type is the best solid solution interstitial vacancy structure. Among them, Ti3Al with D019 structure possesses this Ti6-type octahedral interstitial, while the TiAl with L10 structure contains Al4Ti2 and Al2Ti4-type octahedral interstitial, thus resulting in relatively higher solid solubility of C atoms in Ti3Al. During the solid-phase transition stage, the lamellae of TiAl were first formed in Ti3Al, and the TiAl/Ti3Al lamellar colony was finally formed when the system reached the equilibrium state [26,27]. Because more defects distribute at the two-phase interface and the arrangement of atoms is loose, which is more beneficial to the enrichment of C atoms, the Ti2AlC nano-precipitate tends to nucleate at the TiAl/Ti3Al interface [28]. The formation process of the Ti2AlC precipitate at the TiAl/Ti3Al interface can be described as follows: Ti3Al → TiAl + Ti3Al → TiAl + Ti2AlC, and the process will be described in detail later through the schematic diagram of the atomic model. Furthermore, a small number of C atoms have segregated before diffusing to the grain boundary due to the effects of kinetics and thermodynamics, resulting in the precipitation of Ti2AlC in TiAl and Ti3Al. For the precipitation of Ti2AlC in TiAl, the C atoms precipitate and form the segregation zone parallel to TiAl(111), which then promotes the nucleation of Ti2AlC in this zone, as shown in Figure 2. The specific atomic planes of Ti2AlC and TiAl(111) have a good match in the interface structure after nucleation. While for the precipitation in Ti3Al, both the Ti2AlC and Ti3Al are hexagonal crystal structure and their chemical compositions have similar ratios of Ti and Al elements, thereby the Ti2AlC with thermodynamically stable phase also tend to precipitate from Ti3Al, as shown in Figure 4. It is worth noting that the precipitation of Ti2AlC from Ti3Al or TiAl is nucleated on the close-packed planes between them to minimize the interfacial energy.

Based on typical interface precipitation, Figure 8 shows the schematic diagram of the nucleation and growth behavior of Ti2AlC nano-precipitates precipitated from the TiAl/Ti3Al interface. Figure 8(a) is the atomic model of the TiAl/Ti3Al interface, the red cube represents TiAl, the hexamorphic column represents Ti3Al, and the blue cube represents the Ti6-type octahedral interstice. First, the solid solubility of interstitial C atoms in Ti3Al decreases with the decrease in temperature, thus making it easy to precipitate from the TiAl/Ti3Al interface with more defects. Then, with the continuous precipitation of C atoms, under the influence of thermodynamics and kinetics, Ti2AlC carbides are formed with the interface as the nucleation point, as shown in Figure 8(b). According to the crystal structure and the minimization of elastic strain energy, Ti2AlC tend to form a good atomic matching with a coherent interface with the TiAl(111) and Ti3Al(0001), i.e., TiAl(111)//Ti2AlC(0001)//Ti3Al(0001). Finally, the Ti2AlC grow rod-like along the TiAl(111)/Ti3Al(0001) interface, as shown in Figure 8(c). The formation reason for the rod-like morphology could be explained through the interface atomic model in Figure 8(d), the atomic models of closely packed TiAl(111) surface, Ti2AlC(0001) surface, and Ti3Al(0001) surface, and TiAl/Ti2AlC/Ti3Al interface. It could be seen that the Ti2AlC(0001) is composed of the same kind of atoms, while along the [0001] direction it is composed of different kinds of atoms, and every two Ti6C octahedra are separated by an Al layer along the [0001] direction. Due to the layered atomic arrangement, the growth rate of Ti2AlC parallel to the (0001) plane is higher than that along the [0001] direction. In addition, it is worth mentioning that the Ti2AlC precipitated at the TiAl/Ti3Al interface can inhibit the further growth of the lamellae, thereby improving the stability of the structure, which is conducive to effectively improving the mechanical properties of the TiAl alloy [29,30].

Figure 8 The schematic illustration for the nucleation and growth mechanism of Ti2AlC nano-precipitates: (a) the TiAl/Ti3Al interface and Ti3Al with Ti6-type octahedral interstice; (b) the nucleation of Ti2AlC; (c) the growth of Ti2AlC; and (d) the surface of TiAl(111), Ti2AlC(0001), and Ti3Al(0001) and the Ti3Al/Ti2AlC/TiAl interface.
Figure 8

The schematic illustration for the nucleation and growth mechanism of Ti2AlC nano-precipitates: (a) the TiAl/Ti3Al interface and Ti3Al with Ti6-type octahedral interstice; (b) the nucleation of Ti2AlC; (c) the growth of Ti2AlC; and (d) the surface of TiAl(111), Ti2AlC(0001), and Ti3Al(0001) and the Ti3Al/Ti2AlC/TiAl interface.

4.2 Nucleation and growth mechanism of Ti3AlC nano-precipitates

The Ti3AlC nano-precipitates in this article preferentially grow into needle- and rod-like structures along the [001]TiAl during the nucleation and growth stage. Figure 9 shows the schematic diagram of the nucleation and growth of Ti3AlC in TiAl. First, the dissolution of interstitial C atoms in the TiAl matrix tends to form the TiAl(C) solid solution with Al2Ti4-type octahedral interstices, as shown in Figure 9(a). Afterward, since the crystal structure and atomic arrangement of Ti3AlC and TiAl(C) solid solution are quite close, as the thermodynamics gradually tends to the equilibrium state, the upper and lower Al atoms of the octahedral interstice are easily replaced by Ti atoms to form the initial Ti3AlC with the TiAl(001) plane as the nucleation site. The Ti3AlC precipitates maintain a coherent atomic correspondence with the interface between TiAl during the initial nucleation process, as shown in Figure 9(b). Figure 9(c) shows the growth model of Ti3AlC and the needle-like direction corresponding to the TiAl[001]. The formation of needle-like morphology is mainly due to the fact that Ti3AlC and TiAl have a lower lattice mismatch in the [001] direction than in the [100] and [010] directions. Li et al. [31] have calculated that the lattice mismatch between Ti3AlC and TiAl is 3.13% along the [100] and [010] directions and 2.16% along the [001] direction. Therefore, it could be concluded that the morphology of Ti3AlC in TiAl is determined by the lattice mismatch between them. Furthermore, the lattice mismatch of the Ti3AlC and TiAl is different at different precipitation stages. Considering the strain energy, the lattice mismatch between Ti3AlC and TiAl is lower during the nucleation stage, and the elastic strain field between Ti3AlC and TiAl is almost isotropic due to the small size of Ti3AlC. The lattice mismatch further increases as the growth of the Ti3AlC precipitates; thus, in order to decrease the strain energy at the interface, the Ti3AlC needs to grow along the [001]TiAl direction, where the lattice mismatch is much lower. Figure 9(d) shows the atomic models of TiAl and Ti3AlC, and it can be clearly seen that the atomic arrangements between them are quite similar, which further verifies the above phase transition process.

Figure 9 The schematic illustration for the nucleation and growth mechanism of Ti3AlC nano-precipitates: (a) the atomic model of TiAl(C) solid solution with Al2Ti4-type octahedral interstice; (b) the nucleation of Ti3AlC; (c) the growth of Ti3AlC; and (d) the atomic model of TiAl and Ti3AlC.
Figure 9

The schematic illustration for the nucleation and growth mechanism of Ti3AlC nano-precipitates: (a) the atomic model of TiAl(C) solid solution with Al2Ti4-type octahedral interstice; (b) the nucleation of Ti3AlC; (c) the growth of Ti3AlC; and (d) the atomic model of TiAl and Ti3AlC.

Based on the above analysis, the Ti2AlC and Ti3AlC nano-precipitates form the coherent interface (low-energy interface) with the TiAl matrix during precipitation, thereby reducing the overall free energy. It is worth mentioning that Ti3AlC is a metastable phase, and the decomposition of Ti3AlC at high temperatures will promote the nucleation and growth of Ti2AlC with the increase in aging temperature and time. Therefore, it will be an interesting point to investigate the effect of carbide morphology evolution on the mechanical properties of TiAl alloys in the future.

5 Conclusions

In this article, the nucleation and growth behavior of Ti2AlC and Ti3AlC nano-precipitates were investigated by observing their distribution, morphology, and interface structure. The conclusions could be summarized as follows:

  1. The needle-like C atom segregation zones in TiAl are the nucleation sites of Ti2AlC precipitates, and the long axis direction of the segregation zones is parallel to the TiAl(111) plane.

  2. The rod-like Ti2AlC nano-precipitates mainly distribute at the TiAl/Ti3Al interface, and the orientation relationship between them is [ 1 ̅ 01 ]TiAl//[ 11 2 ̅ 0 ]Ti2AlC//[ 11 2 ̅ 0 ]Ti3Al and (111)TiAl//(0001)Ti2AlC//(0001)Ti3Al. Both the Ti2AlC/TiAl interface and the Ti3Al/Ti2AlC interface show good atomic matching, indicating that these interfaces are coherent.

  3. The needle-like Ti3AlC nano-precipitates distribute in TiAl with the orientation relationship of [001]Ti3AlC//[001]TiAl, (100)Ti3AlC//(100)TiAl, (020)Ti3AlC//(020)TiAl, and (110)Ti3AlC//(110)TiAl during the nucleation stage. While the orientation relationship between rod-like Ti3AlC and TiAl is [ 1 1 ̅ 0 ]Ti3AlC//[ 1 1 ̅ 0 ]TiAl, (001)Ti3AlC//(001)TiAl, (220)Ti3AlC//(220)TiAl, and (111)Ti3AlC//(111)TiAl.

  4. The lattice mismatch of Ti3AlC and TiAl in the [001] direction is lower than in other directions during the nucleation and growth stages, thus both the needle- and rod-like Ti3AlC precipitates grow preferentially along the [001]TiAl direction.

  1. Funding information: The authors acknowledge financial support from the National Natural Science Foundation of China (Grant No. 52101174).

  2. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors state no conflict of interest.

  4. Data availability statement: All data generated or analyzed during this study are included in this published article.

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Received: 2022-07-11
Revised: 2022-11-29
Accepted: 2023-01-03
Published Online: 2023-02-10

© 2023 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/ntrev-2022-0510
Keywords for this article
TiAl alloys; Ti2AlC and Ti3AlC nano-precipitates; nucleation and growth; interface atomic structure
Creative Commons
BY 4.0

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  27. NIR-II window absorbing graphene oxide-coated gold nanorods and graphene quantum dot-coupled gold nanorods for photothermal cancer therapy
  28. Nonlinear three-dimensional stability characteristics of geometrically imperfect nanoshells under axial compression and surface residual stress
  29. Investigation of different nanoparticles properties on the thermal conductivity and viscosity of nanofluids by molecular dynamics simulation
  30. Optimized Cu2O-{100} facet for generation of different reactive oxidative species via peroxymonosulfate activation at specific pH values to efficient acetaminophen removal
  31. Brownian and thermal diffusivity impact due to the Maxwell nanofluid (graphene/engine oil) flow with motile microorganisms and Joule heating
  32. Appraising the dielectric properties and the effectiveness of electromagnetic shielding of graphene reinforced silicone rubber nanocomposite
  33. Synthesis of Ag and Cu nanoparticles by plasma discharge in inorganic salt solutions
  34. Low-cost and large-scale preparation of ultrafine TiO2@C hybrids for high-performance degradation of methyl orange and formaldehyde under visible light
  35. Utilization of waste glass with natural pozzolan in the production of self-glazed glass-ceramic materials
  36. Mechanical performance of date palm fiber-reinforced concrete modified with nano-activated carbon
  37. Melting point of dried gold nanoparticles prepared with ultrasonic spray pyrolysis and lyophilisation
  38. Graphene nanofibers: A modern approach towards tailored gypsum composites
  39. Role of localized magnetic field in vortex generation in tri-hybrid nanofluid flow: A numerical approach
  40. Intelligent computing for the double-diffusive peristaltic rheology of magneto couple stress nanomaterials
  41. Bioconvection transport of upper convected Maxwell nanoliquid with gyrotactic microorganism, nonlinear thermal radiation, and chemical reaction
  42. 3D printing of porous Ti6Al4V bone tissue engineering scaffold and surface anodization preparation of nanotubes to enhance its biological property
  43. Bioinspired ferromagnetic CoFe2O4 nanoparticles: Potential pharmaceutical and medical applications
  44. Significance of gyrotactic microorganisms on the MHD tangent hyperbolic nanofluid flow across an elastic slender surface: Numerical analysis
  45. Performance of polycarboxylate superplasticisers in seawater-blended cement: Effect from chemical structure and nano modification
  46. Entropy minimization of GO–Ag/KO cross-hybrid nanofluid over a convectively heated surface
  47. Oxygen plasma assisted room temperature bonding for manufacturing SU-8 polymer micro/nanoscale nozzle
  48. Performance and mechanism of CO2 reduction by DBD-coupled mesoporous SiO2
  49. Polyarylene ether nitrile dielectric films modified by HNTs@PDA hybrids for high-temperature resistant organic electronics field
  50. Exploration of generalized two-phase free convection magnetohydrodynamic flow of dusty tetra-hybrid Casson nanofluid between parallel microplates
  51. Hygrothermal bending analysis of sandwich nanoplates with FG porous core and piezomagnetic faces via nonlocal strain gradient theory
  52. Design and optimization of a TiO2/RGO-supported epoxy multilayer microwave absorber by the modified local best particle swarm optimization algorithm
  53. Mechanical properties and frost resistance of recycled brick aggregate concrete modified by nano-SiO2
  54. Self-template synthesis of hollow flower-like NiCo2O4 nanoparticles as an efficient bifunctional catalyst for oxygen reduction and oxygen evolution in alkaline media
  55. High-performance wearable flexible strain sensors based on an AgNWs/rGO/TPU electrospun nanofiber film for monitoring human activities
  56. High-performance lithium–selenium batteries enabled by nitrogen-doped porous carbon from peanut meal
  57. Investigating effects of Lorentz forces and convective heating on ternary hybrid nanofluid flow over a curved surface using homotopy analysis method
  58. Exploring the potential of biogenic magnesium oxide nanoparticles for cytotoxicity: In vitro and in silico studies on HCT116 and HT29 cells and DPPH radical scavenging
  59. Enhanced visible-light-driven photocatalytic degradation of azo dyes by heteroatom-doped nickel tungstate nanoparticles
  60. A facile method to synthesize nZVI-doped polypyrrole-based carbon nanotube for Ag(i) removal
  61. Improved osseointegration of dental titanium implants by TiO2 nanotube arrays with self-assembled recombinant IGF-1 in type 2 diabetes mellitus rat model
  62. Functionalized SWCNTs@Ag–TiO2 nanocomposites induce ROS-mediated apoptosis and autophagy in liver cancer cells
  63. Triboelectric nanogenerator based on a water droplet spring with a concave spherical surface for harvesting wave energy and detecting pressure
  64. A mathematical approach for modeling the blood flow containing nanoparticles by employing the Buongiorno’s model
  65. Molecular dynamics study on dynamic interlayer friction of graphene and its strain effect
  66. Induction of apoptosis and autophagy via regulation of AKT and JNK mitogen-activated protein kinase pathways in breast cancer cell lines exposed to gold nanoparticles loaded with TNF-α and combined with doxorubicin
  67. Effect of PVA fibers on durability of nano-SiO2-reinforced cement-based composites subjected to wet-thermal and chloride salt-coupled environment
  68. Effect of polyvinyl alcohol fibers on mechanical properties of nano-SiO2-reinforced geopolymer composites under a complex environment
  69. In vitro studies of titanium dioxide nanoparticles modified with glutathione as a potential drug delivery system
  70. Comparative investigations of Ag/H2O nanofluid and Ag-CuO/H2O hybrid nanofluid with Darcy-Forchheimer flow over a curved surface
  71. Study on deformation characteristics of multi-pass continuous drawing of micro copper wire based on crystal plasticity finite element method
  72. Properties of ultra-high-performance self-compacting fiber-reinforced concrete modified with nanomaterials
  73. Prediction of lap shear strength of GNP and TiO2/epoxy nanocomposite adhesives
  74. A novel exploration of how localized magnetic field affects vortex generation of trihybrid nanofluids
  75. Fabrication and physicochemical characterization of copper oxide–pyrrhotite nanocomposites for the cytotoxic effects on HepG2 cells and the mechanism
  76. Thermal radiative flow of cross nanofluid due to a stretched cylinder containing microorganisms
  77. In vitro study of the biphasic calcium phosphate/chitosan hybrid biomaterial scaffold fabricated via solvent casting and evaporation technique for bone regeneration
  78. Insights into the thermal characteristics and dynamics of stagnant blood conveying titanium oxide, alumina, and silver nanoparticles subject to Lorentz force and internal heating over a curved surface
  79. Effects of nano-SiO2 additives on carbon fiber-reinforced fly ash–slag geopolymer composites performance: Workability, mechanical properties, and microstructure
  80. Energy bandgap and thermal characteristics of non-Darcian MHD rotating hybridity nanofluid thin film flow: Nanotechnology application
  81. Green synthesis and characterization of ginger-extract-based oxali-palladium nanoparticles for colorectal cancer: Downregulation of REG4 and apoptosis induction
  82. Abnormal evolution of resistivity and microstructure of annealed Ag nanoparticles/Ag–Mo films
  83. Preparation of water-based dextran-coated Fe3O4 magnetic fluid for magnetic hyperthermia
  84. Statistical investigations and morphological aspects of cross-rheological material suspended in transportation of alumina, silica, titanium, and ethylene glycol via the Galerkin algorithm
  85. Effect of CNT film interleaves on the flexural properties and strength after impact of CFRP composites
  86. Self-assembled nanoscale entities: Preparative process optimization, payload release, and enhanced bioavailability of thymoquinone natural product
  87. Structure–mechanical property relationships of 3D-printed porous polydimethylsiloxane films
  88. Nonlinear thermal radiation and the slip effect on a 3D bioconvection flow of the Casson nanofluid in a rotating frame via a homotopy analysis mechanism
  89. Residual mechanical properties of concrete incorporated with nano supplementary cementitious materials exposed to elevated temperature
  90. Time-independent three-dimensional flow of a water-based hybrid nanofluid past a Riga plate with slips and convective conditions: A homotopic solution
  91. Lightweight and high-strength polyarylene ether nitrile-based composites for efficient electromagnetic interference shielding
  92. Review Articles
  93. Recycling waste sources into nanocomposites of graphene materials: Overview from an energy-focused perspective
  94. Hybrid nanofiller reinforcement in thermoset and biothermoset applications: A review
  95. Current state-of-the-art review of nanotechnology-based therapeutics for viral pandemics: Special attention to COVID-19
  96. Solid lipid nanoparticles for targeted natural and synthetic drugs delivery in high-incidence cancers, and other diseases: Roles of preparation methods, lipid composition, transitional stability, and release profiles in nanocarriers’ development
  97. Critical review on experimental and theoretical studies of elastic properties of wurtzite-structured ZnO nanowires
  98. Polyurea micro-/nano-capsule applications in construction industry: A review
  99. A comprehensive review and clinical guide to molecular and serological diagnostic tests and future development: In vitro diagnostic testing for COVID-19
  100. Recent advances in electrocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid: Mechanism, catalyst, coupling system
  101. Research progress and prospect of silica-based polymer nanofluids in enhanced oil recovery
  102. Review of the pharmacokinetics of nanodrugs
  103. Engineered nanoflowers, nanotrees, nanostars, nanodendrites, and nanoleaves for biomedical applications
  104. Research progress of biopolymers combined with stem cells in the repair of intrauterine adhesions
  105. Progress in FEM modeling on mechanical and electromechanical properties of carbon nanotube cement-based composites
  106. Antifouling induced by surface wettability of poly(dimethyl siloxane) and its nanocomposites
  107. TiO2 aerogel composite high-efficiency photocatalysts for environmental treatment and hydrogen energy production
  108. Structural properties of alumina surfaces and their roles in the synthesis of environmentally persistent free radicals (EPFRs)
  109. Nanoparticles for the potential treatment of Alzheimer’s disease: A physiopathological approach
  110. Current status of synthesis and consolidation strategies for thermo-resistant nanoalloys and their general applications
  111. Recent research progress on the stimuli-responsive smart membrane: A review
  112. Dispersion of carbon nanotubes in aqueous cementitious materials: A review
  113. Applications of DNA tetrahedron nanostructure in cancer diagnosis and anticancer drugs delivery
  114. Magnetic nanoparticles in 3D-printed scaffolds for biomedical applications
  115. An overview of the synthesis of silicon carbide–boron carbide composite powders
  116. Organolead halide perovskites: Synthetic routes, structural features, and their potential in the development of photovoltaic
  117. Recent advancements in nanotechnology application on wood and bamboo materials: A review
  118. Application of aptamer-functionalized nanomaterials in molecular imaging of tumors
  119. Recent progress on corrosion mechanisms of graphene-reinforced metal matrix composites
  120. Research progress on preparation, modification, and application of phenolic aerogel
  121. Application of nanomaterials in early diagnosis of cancer
  122. Plant mediated-green synthesis of zinc oxide nanoparticles: An insight into biomedical applications
  123. Recent developments in terahertz quantum cascade lasers for practical applications
  124. Recent progress in dielectric/metal/dielectric electrodes for foldable light-emitting devices
  125. Nanocoatings for ballistic applications: A review
  126. A mini-review on MoS2 membrane for water desalination: Recent development and challenges
  127. Recent updates in nanotechnological advances for wound healing: A narrative review
  128. Recent advances in DNA nanomaterials for cancer diagnosis and treatment
  129. Electrochemical micro- and nanobiosensors for in vivo reactive oxygen/nitrogen species measurement in the brain
  130. Advances in organic–inorganic nanocomposites for cancer imaging and therapy
  131. Advancements in aluminum matrix composites reinforced with carbides and graphene: A comprehensive review
  132. Modification effects of nanosilica on asphalt binders: A review
  133. Decellularized extracellular matrix as a promising biomaterial for musculoskeletal tissue regeneration
  134. Review of the sol–gel method in preparing nano TiO2 for advanced oxidation process
  135. Micro/nano manufacturing aircraft surface with anti-icing and deicing performances: An overview
  136. Cell type-targeting nanoparticles in treating central nervous system diseases: Challenges and hopes
  137. An overview of hydrogen production from Al-based materials
  138. A review of application, modification, and prospect of melamine foam
  139. A review of the performance of fibre-reinforced composite laminates with carbon nanotubes
  140. Research on AFM tip-related nanofabrication of two-dimensional materials
  141. Advances in phase change building materials: An overview
  142. Development of graphene and graphene quantum dots toward biomedical engineering applications: A review
  143. Nanoremediation approaches for the mitigation of heavy metal contamination in vegetables: An overview
  144. Photodynamic therapy empowered by nanotechnology for oral and dental science: Progress and perspectives
  145. Biosynthesis of metal nanoparticles: Bioreduction and biomineralization
  146. Current diagnostic and therapeutic approaches for severe acute respiratory syndrome coronavirus-2 (SARS-COV-2) and the role of nanomaterial-based theragnosis in combating the pandemic
  147. Application of two-dimensional black phosphorus material in wound healing
  148. Special Issue on Advanced Nanomaterials and Composites for Energy Conversion and Storage - Part I
  149. Helical fluorinated carbon nanotubes/iron(iii) fluoride hybrid with multilevel transportation channels and rich active sites for lithium/fluorinated carbon primary battery
  150. The progress of cathode materials in aqueous zinc-ion batteries
  151. Special Issue on Advanced Nanomaterials for Carbon Capture, Environment and Utilization for Energy Sustainability - Part I
  152. Effect of polypropylene fiber and nano-silica on the compressive strength and frost resistance of recycled brick aggregate concrete
  153. Mechanochemical design of nanomaterials for catalytic applications with a benign-by-design focus
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