3.1. Composition and Microstructure
The surface morphologies of both the ground TC4 and the MAO coatings with different concentrations of Si
3N
4/TaC particles are shown in
Figure 2. As shown in
Figure 2, there were some scratches and small pores of 1–2 μm on the surface of the ground TC4 alloy (
Figure 2a); regardless of the Si
3N
4/TaC particles, there were many crater-like holes of different sizes in the coatings formed by the spark discharge and gas bubbles throughout the discharge channels during the MAO process, where the melted materials were expelled by the discharge and could not flow back to fill the discharge channels before their solidification [
37,
38]. Moreover, some significant changes could also be observed on the surface of the MAO coatings with the addition of the Si
3N
4/TaC particles (
Figure 2c–e). For example, there were some microcracks in the MAO coatings with the Si
3N
4/TaC particles, which may be attributed to the fact that the particle additions block the flow of the melted metal, thus leading to the formation of the microcracks. On the other hand, it was found that some bright particles adhered to the surfaces of the coatings and that both the number and the size of the bright particles increased with the increasing Si
3N
4/TaC particle concentration (
Figure 2c–e), indicating that the Si
3N
4 or TaC particles might be involved in the reaction of the MAO process. To further reveal the effect of the addition of the Si
3N
4/TaC particles on the MAO coatings, the number density and the size of microholes, the number density of the bright particles, and the thickness of the MAO coatings were quantified. The results are given in
Figure 3 and
Table 2, showing that the thickness of the composite MAO coatings gradually increased with the increment of the concentration of Si
3N
4/TaC particles (
Figure 3), which probably resulted from the inert or partly reactive incorporation of Si
3N
4/TaC particles into the oxide layer [
21,
27,
29,
30]. Compared with the MAO coating without Si
3N
4/TaC particles, the addition of Si
3N
4/TaC particles made the porosity significantly decrease. However, further increasing the concentration of Si
3N
4/TaC particles gave rise to a slight increment in the porosity (
Figure 3). The previous studies also reported that the addition of the ceramic particles to the electrolyte reduced the porosity and average size of the micropores in the MAO coatings [
25,
27,
30,
31,
32,
33]. With increasing the concentration of Si
3N
4/TaC particles, the microarc discharge was more intense and allowed the particles to sinter together, which was evident by the observation of the larger bright particles in the coating with a higher concentration of Si
3N
4/TaC particles (
Figure 2e). Meanwhile, a high concentration of Si
3N
4/TaC particles caused the ability of the particles to fill the microholes weaken during the MAO process and thus a slightly higher porosity, number density, and average size of the microholes were observed in the MAO coating with a high concentration of Si
3N
4/TaC particles. This well explained why the coatings with 1 g/L Si
3N
4 + 0.5 g/L TaC particles had the relevantly flat surface with the lowest porosity, the smallest average size, and number density of the microholes. Ding et al. [
36] reported that the addition of TaC particles was beneficial to fill the micropores formed by the spark discharge during MAO process to make the surface become flat. Similar results were also reported in the MAO coatings incorporated by some hard particles (Cr
2O
3, Al
2O
3, etc.) [
26,
27,
39].
The EDS mappings of the MAO coatings in
Figure 4, especially in the enlarged image in
Figure 4d, confirm that the bright particles were enriched with Ta and Si, which supported the incorporation of some Si
3N
4/TaC particles in the composite coatings that caused the number of the holes to decrease and the surface flatten.
Table 3 shows the average compositions of the surfaces of the MAO coatings with different concentrations of Si
3N
4/TaC particles.
Table 4 presents the EDS results of regions A (bright particle 1), B (bright particle 2), and C in the MAO coatings with the addition of 4 g/L Si
3N
4 + 2 g/L TaC particles, showing that some bright particles were enriched in Si, while others were enriched in Ta. As the plasma temperature during the MAO process was lower than the melt temperature of Si
3N
4 (1900 °C) and TaC (3880 °C), Si
3N
4 or TaC particles might be inertly absorbed onto or sintered to the MAO coatings. However, the size of the Si-rich particle in region A in
Figure 4d was about 800 nm, which was much larger than the average size of the Si
3N
4 particles (about 50 nm). This suggested that the Si
3N
4 particles were very likely melted during the MAO process. In fact, it was reported that the melting point of the nano-sized particles decreased with the decreasing particle size [
40,
41]. It was likely that the nano-sized Si
3N
4 particles were reactively incorporated into the MAO coatings.
The phase constituents of the MAO coatings with different contents of Si
3N
4/TaC particles were investigated by XRD. The results are illustrated in
Figure 5, and they show that the MAO coatings formed in the absence of Si
3N
4/TaC particles were mainly composed of anatase-type TiO
2 and rutile-type TiO
2, while both the TaC phase and Si
3N
4 phases could be detected in the coatings with the addition of the Si
3N
4/TaC particles. Moreover, by increasing the concentration of Si
3N
4/TaC particles, the peak intensity of rutile TiO
2 and TaC gradually increased, which was confirmed by the SEM results, i.e., the amounts of the Si-rich or Ta-rich bright particles increased with the increasing concentration of the Si
3N
4/TaC particles (
Figure 2c–e). The formation of Al
4Ti
2SiO
12 may be associated with high temperature and high pressure during the MAO process. Wang et al. [
27] found that Al
2TiO
5 in the Si
3N
4/Al
2O
3 composite coatings formed on TC4 alloy by MAO in the electrolyte with Al
2O
3 particles. The occurrence of Al
4Ti
2SiO
12 and the decrease in the metastable anatase-TiO
2 suggested that Al
2TiO
5 might react with Si
3N
4 to form Al
4Ti
2SiO
12 during localized high temperature and high pressure in the process of MAO. Aliofkhazraei et al. [
33] fabricated Si
3N
4/TiO
2 nanocomposite coatings on commercially pure Ti and found the existence of Si
4Al
2O
2N
6 in the composite coatings.
This indicated that the Si
3N
4 particles were partially reactively incorporated into the composite MAO coatings, which was inconsistent with the results from Lu et al. [
32].
Figure 3 shows that with an increasing Si
3N
4/TaC concentration, the thickness of the coatings increased slightly from 20.2 μm for the coating without Si
3N
4/TaC particles to 22.0 μm for the coating with the addition of 4 g/L Si
3N
4 + 2 g/L TaC particles, which contributed to the incorporation of the Si
3N
4 and TaC particles into the composite coatings during the process of MAO. Similar results were also reported in some studies [
26,
27,
30], i.e., the excessive addition of the particles produced a large number of particles in the composite coatings and a thicker coating.
3.2. Tribological Properties
Figure 6 presents the friction coefficient of both the TC4 alloy and the composite MAO coatings with different concentrations of Si
3N
4/TaC particles against the GCr15 steel ball in the artificial seawater, which showed that the friction coefficient of the TC4 alloy fluctuated significantly and reached about 0.5 after nearly 5 min. The friction coefficients of the MAO coatings with different concentrations of Si
3N
4/TaC particles all first increased due to the high initial surface roughness and then decreased due to the improvement of the surface contact condition between the protrusions and the GCr15 steel ball with the sliding time [
27,
30]. For the high hardness of the MAO coatings, their friction coefficients were lower and experienced less fluctuation compared to the TC4 alloy. It was also observed from
Figure 6 that the MAO coatings, without the addition of the Si
3N
4/TaC particles, had the lowest friction coefficient of about 0.15, and the friction coefficient of the composite MAO coatings slightly increased with the concentration of Si
3N
4/TaC particles. Previous research [
34] revealed that Si
3N
4 addition could improve the wear resistance of the MAO coatings and significantly reduce the friction coefficient, which was attributed to Si
3N
4 having excellent lubrication. Thus, the friction coefficient of the composite MAO coatings was a little higher than that of the MAO coatings in the absence of Si
3N
4/TaC particles, which may be associated with the addition of hard TaC particles. In order to reveal wear damages to the coatings, SEM was used to examine the worn surfaces. The morphologies of their worn surfaces are illustrated in
Figure 7, showing that the TC4 alloy had the widest wear scar of 787.8 μm with a lot of furrows along the wear direction. This was ascribed to the fact that the TC4 alloy has a much lower hardness than the MAO coatings [
42,
43]. The wear width of the MAO coatings ranged from 358.2 to 445.3 μm, which is significantly lower than the wear width of the TC4 alloy. This indicated that the MAO coatings greatly improved the tribological properties of the TC4 alloy, regardless of the addition of Si
3N
4/TaC particles. The wear width of the composite MAO coatings was lower than that of the particle-free coatings and slightly increased with the concentration of Si
3N
4/TaC particles.
3.3. Corrosion Resistance
The potentiodynamic polarization curves of the TC4 alloy and the composite MAO coatings with the different concentrations of Si
3N
4/TaC particles in the artificial seawater were plotted in
Figure 8 and
Figure 9, respectively. The relevant electrochemical data are listed in
Table 5. It could be easily found from
Figure 8 and
Figure 9 and
Table 5 that the addition of Si
3N
4/TaC particles caused the corrosion potential (
Ecorr) of the composite coatings to move to a positive direction and the current densities decrease by about three orders of magnitude, indicating that the corrosion resistance of the composite coatings was significantly improved compared with the TC4 alloy substrate. Moreover, as can be seen from
Figure 8 and
Figure 9 and
Table 5, the corrosion potential of the particle-free MAO coatings reached −0.176 V
SCE, which was significantly higher than that of the TC4 alloy substrate, with a minimum corrosion potential of −1.229 V
SCE. The corrosion current densities (
Icorr) of the particle-free coatings were a little bit higher than that of the TC4 alloy substrate, which was attributed to the fact that the particle-free coatings have high porosity (19.5%) (
Figure 4). In general, the corrosion resistance of the MAO coatings mainly depends on the porosity, thickness, and composition of the coating. Chen et al. [
29] investigated the corrosion resistance of the MoS
2-modified MAO coatings on the titanium alloy with different MoS
2 concentrations of 0, 2, 4, 6, and 8 g/L in a 3.5 wt. % NaCl solution and the results showed that the addition of MoS
2 could significantly improve the corrosion resistance of the MAO coating and that the MoS
2-modified MAO coating with an additional amount of 4 g/L possessed the minimum porosity and average pore size and hence showed the best corrosion resistance. Therefore, it was easily understood that for the minimum porosity of 11.5%, the composite MAO coatings incorporated with the concentration of 1 g/L Si
3N
4 + 0.5 g/L TaC particles had the optimal corrosion properties in the artificial seawater.