3.1. Microstructure of Laser-Cladded FeCrSiNiCoC Coating
The cross-sectional shape and elemental distribution of a covering made of FeCrSiNiCoC are shown in
Figure 2.
Figure 2a reveals that the surface of the FeCrSiNiCoC coating is good with no visible cracks.
Figure 2b displays the cross section of laser-cladded samples: from top to bottom it shows the FeCrSiNiCoC coating, heat-affected zone andsubstrate. Combined with the hardness distribution, it can be seen that the coating and heat-affected zone thicknesses are around 1.66 mm and 0.34 mm, respectively. Due to the slagging effect of Si element, when the coating melts, it moves freely and wets the steel substrate completely [
37]. Therefore, the FeCrSiNiCoC coating is fully dense and homogenous without pores. The EDS line scanning shown in
Figure 2c depicts the stable diffusion of alloying elements from the FeCrSiNiCoC coating to the 1Cr11Ni heat resistant steel substrate. It can be observed that the quality of bonding between the coating and the substrate is good.
Figure 3 presents the XRD profiles of the FeCrSiNiCoC coating at different temperatures. XRD findings indicate that, the FeCrSiNiCoC coating at 50 °C consists mostly of γ-Fe phase and Fe-Cr phase. SEM images and main elements distribution of the FeCrSiNiCoC coatings at 50 °C are shown in
Figure 4. Dendritic and eutectic structures can be found in
Figure 4, showing that the coating is made up of these types of structure. The EDS results show that coating components are evenly distributed with respect to Fe and Cr. The Fe and Cr contents in the dendrites are 66.47% and 16.04%, respectively. In the eutectic structures, the Fe and Cr contents are 36.02% and 41.09%, respectively. In conjunction with the XRD findings, the conclusion can be drawn that the dendritic structures contain γ-Fe and the eutectic structures contain intermetallic Fe-Cr. When the temperature was 300 °C, the phase of the FeCrSiNiCoC coating changed from γ-Fe, Fe-Cr to α-Fe, Fe-Cr. When the temperature was raised to 500 °C and 700 °C, carbides Cr
7C
3 precipitated from the grain boundary.
3.3. Effects of Temperature and Load on Tribological Properties of Coatings
Figure 6a shows the wear-test samples of the FeCrSiNiCoC coating at different temperatures (50 °C, 300 °C, 500 °C and 700 °C) under 200 N load.
Figure 6b reveals the surface morphology from the wear-test samples. Wear width, wear depth and wear rate of coatings at different temperatures are shown in
Table 3. As the temperature increases, the untreated surface of the coating changes from silver-white, then yellow to dark black No obvious oxide film is visible in
Figure 6a, which proves that the FeCrSiNiCoC coating has good high temperature oxidation resistance. As exhibited in
Figure 6b, the wear depth and wear width of the coating at 700 °C is greater than for the other test samples, and it can be seen that the coating is not suitable for working at too high a temperature. At 500 °C, the grain size of the coating is reduced and carbide Cr
7C
3 precipitated at the grain boundaries, resulting in an increase in the hardness of the coating and a significant improvement in wear performance (See
Figure 3 and
Supplemental Material for a discussion of the effect of temperature on the organization and properties of FeCrSiNiCoC coatings). Therefore, the coating at 500 °C exhibited the lowest wear breadth, the smallest wear depth, and the smallest wear rate.
Figure 6c depicts the temperature dependence of the coefficient of friction (COF) distance curves for 200N (50 °C, 300 °C, 500 °C and 700 °C). The wear-test samples at 50 °C, 300 °C and 500 °C reached stable wear stages around 240 m, 100 m and 100 m, respectively. However, the friction coefficient of the wear-test sample at 700 °C basically remains within a stable range, as the initial stage of wear is stable wear. The samples maintained a dynamic equilibrium during the wear process. Therefore, under the same load, the friction coefficients of the wear-test samples at 50 °C, 300 °C, 500 °C and 700 °C can be calculated as 0.76, 0.62, 0.50 and 0.29, respectively. When the temperature rises, the friction coefficient drops and the distance to the steady wear stage shortens. However, variations in temperature amplified fluctuations in the friction coefficient, which was caused by the wear surface softening and suffering serious plastic deformation under high temperature sliding friction; the worn surface was seriously bonded and a large amount of spalling occurred, thus resulting in the worn surface becoming uneven.
Figure 7a depicts the wear-test samples of the FeCrSiNiCoC coating at various loads (100 N, 200 N, 300 N, 400 N) under 500 °C temperature.
Figure 7b reveals the surface morphology from the wear test samples.
Table 4 displays the average wear breadth, wear depth, and wear rate of coatings over a range of temperatures. The wear width and wear depth of coating gradually increase with the increase of load, as illustrated in
Figure 7a. As can be observed in
Figure 7b, wear does not proportionally increase with a growing load, but shows a slowing trend.
The curves of the coefficient of friction (COF) distance at 500 °C and various weights are shown in
Figure 7c (100 N, 200 N, 300 N, 400 N). The wear coefficient fluctuates relatively little for the 100 N and 200 N wear test samples after stable wear. Due to the increased load, the presence of plenty of wear debris caused the frictional wear curve of the 300 N and 400 N wear-test samples to change in the direction of increase after steady wear. All wear test samples enter the stable wear period at around 200 m. Thus, at the same temperature, the average friction coefficients of the wear-test specimens at 100 N, 200 N, 300 N and 400 N in stable wear can be calculated as 0.50, 0.60, 0.47 and 0.66, respectively. The coefficient of friction of the 400 N wear-test sample increased slightly and there were large fluctuations at the stable wear stage, which may be due to the serious plastic deformation of the coating induced by the high load and a large amount of debris.
According to the above results, the FeCrSiNiCoC coating has the best comprehensive wear performance at 200 N and 500 °C, with a wear rate of 2.3 × 10
−5 g/m. At this time, compared with the Fe
50Cr
40Si
10 coating, the wear rate of the FeCrSiNiCoC coating under higher load and higher temperature is about twice as low as that of the Fe
50Cr
40Si
10 coating [
39].
3.4. Wear Mechanism
To explore the wear mechanism of the FeCrSiNiCoC coating at various temperatures and loads, SEM and energy spectrum analysis were used to study the worn surface.
In
Figure 8, we see SEM pictures of the surface wear of 200 N-loaded wear-test specimens at 50 °C, 300 °C, 500 °C, and 700 °C.
Figure 8a shows that the worn surface is relatively flat, with more tiny grooves parallel to the sliding direction (pointed by red arrows). This results from the serious shearing of the coating surface under pressure, which causes it to be separated by the micro-cutting action. The soft metal phase in the coating is stripped by friction, thus making the surface uneven. This leads to an increase in contact pressure on the worn surface and a rise in temperature up to the melting point. Some of the debris may be pulled out by kinetic forces and others embedded in the grooves. As a result, the primary wear mechanisms in this instance were abrasive wear and adhesive wear.
Compared with
Figure 8a, the coating in
Figure 8b shows a little delamination (pointed to by pink arrows) and a substantial quantity of oxidized debris on the surface. The temperature of the contact surface of the friction pair rises as wear progresses and the coating surface partially softens or melts. The softened surface is plastically deformed by the pressure of the friction ring resulting in delamination. Meanwhile, some soft metal phases are stripped from the coating and gradually form oxidation debris as a result of extrusion and oxidation during wear. During the wear process of relative sliding, the surface cutting effect is reduced by the softened wear surface and a large amount of oxidized debris, resulting in a reduction in the friction coefficient and wear rate. As such, oxidation wear and adhesive wear were predominant at 300 °C.
As observed in
Figure 8c, the delamination of the surface is even more serious with higher temperatures, with massive accumulation of oxide wear debris on the part of coating near the wear track. However, a large quantity of oxidation debris is produced to replace the worn coating, and smoother wear markings serve to shield the coating from further damage, hence decreasing the friction coefficient and wear rate. In this case, the two most common types of wear are oxidation and adhesive.
Serious plastic deformation and delamination of coating surface can be observed in
Figure 8d (represented by the blue region). Under high temperature sliding friction, the worn surface melts and suffers from serious plastic deformation, resulting in serious bonding of the wear surface and massive spalling of hard metal silicide. This makes the wear rate much higher and the friction coefficient fluctuates significantly, but the friction coefficient is greatly reduced. The oxygen content of the worn surface has been reduced due to the peeling off of the hard phase (
Table 5). Consequently, the principal wear processes include three-body wear and oxidation wear.
The examination of worn surface shape and wear processes at various temperatures indicates that high-temperature friction leads to the softening of the coating surface and the production of extensive quantities of oxides; this significantly enhances the high-temperature wear resistance of the FeCrSiNiCoC coating. The wear mechanism of the coating shifts from abrasive wear, adhesive wear and oxidation wear to oxidation wear and three-body wear.
Figure 9 reveals worn surface images captured by scanning electron microscopy from wear-test specimens subjected to 100 N, 200 N, 300 N and 400 N at a temperature of 500 °C. From
Figure 9a–c, it is clear that the delamination of the wear surface is gradually becoming more serious and the surface oxidation debris is gradually increasing. As the positive pressure increases, the plastic deformation and flaking of the coating becomes more intense and produces more oxide debris. A large amount of oxidation debris separates coating from the friction ring and acts as a lubricant instead of wear, which causes the wear rate of the coating to gradually increase, but the coefficient of friction remains steady. Oxidation and adhesion wear were the coating’s wear processes.
Figure 9d shows that serious plastic deformation and fine grooves occur on the wear surface at 400 N. Under the combined effect of high temperatures and high loads, the interface between the coating and the friction ring generates high temperatures; this results in a possible softening and melting of coating and the friction ring, with a large number of fragments bonding and being pulled out of the wear interface. The wear process is thus a continuous bonding, peeling and discharging of the wear interface and, therefore, the coefficient of friction is the maximum. The low oxygen content of the surface analyzed according to the EDS (
Table 6) results indicates that the worn surface has flaked off before more serious oxidation has occurred. Therefore, three-body wear and abrasive wear were the primary wear mechanisms.
A higher load causes a greater rate of coated surface flaking and wear, as determined by an examination of worn surface morphology and wear processes under various loads. Shifting from adhesive wear and oxidation wear to three-body wear and abrasive wear is how the coating wears.