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Article

Wear Characteristics Caused by Ti3AlC2 Particles under Impact-Sliding Conditions in Marine Engine

by
Jie Liu
1,
Yan Shen
1,*,
Zhixiang Liu
1,
Baihong Yu
1,
Jinghao Qu
1,
Leize Li
1 and
Guogang Zhang
2
1
Key Laboratory of Ship-Machinery Maintenance & Manufacture, Dalian Maritime University, Dalian 116026, China
2
Dalian Marine Diesel Engine Co., Ltd., Dalian 116021, China
*
Author to whom correspondence should be addressed.
J. Mar. Sci. Eng. 2024, 12(10), 1777; https://doi.org/10.3390/jmse12101777 (registering DOI)
Submission received: 12 September 2024 / Revised: 30 September 2024 / Accepted: 1 October 2024 / Published: 7 October 2024
(This article belongs to the Section Ocean Engineering)
Browse Figures
Versions Notes

Abstract

:
With the marine industry’s demands for carbon reduction and increased reliability, the friction and wear performance of marine engines is becoming increasingly important. MAX phase materials show great potential in marine engine tribopair materials due to their unique microstructure and performance. The typical MAX phase material Ti3AlC2 was combined with MoDTC and added to the lubricant containing ZDDP additive for the tribopair composed of chromium-based ceramic composite coated steel (CKS) piston rings and cast iron cylinder liners under impact-sliding conditions. Compared to Ti3AlC2 alone, the friction coefficient and wear depth of the designed composite additive MoDTC/Ti3AlC2 were reduced by 36.9% and 41.4%, respectively. The worn surface lubricated with the Ti3AlC2/MoDTC composite additive showed fewer scratches with significantly less plastic deformation and clearer honing grooves. The multi-component tribofilm containing FeS, MoS2, MoO3, ZnO, TiO2, Al2O3, unoxidised particles, short-chain phosphates, and some ZnS was present on the worn cylinder liner surface. The synergistic effect of Ti3AlC2, MoDTC and ZDDP additives in the lubricant can isolate the mutual contact, generate a solid tribofilm and reduce the scratching. This can provide some guidance for the development of high-performance lubricant additives under impact-sliding conditions.

1. Introduction

With the improvement of energy saving and emission reduction standards for low-speed marine engines, the mechanical and thermal load on the piston ring and cylinder liner (PRCL) friction interface is increasing. Much attention has been paid to friction and wear issues, which have a significant impact on the mechanical efficiency, service life and reliability of the PRCL.
The Mn+1AXn (MAX) phase material is a ternary compound with a layer structure, which has the characteristics of high temperature resistance and self-lubrication, and has gradually attracted attention in the field of marine engines [1,2,3,4]. Previous studies have shown that the Ti3AlC2 particles of typical MAX phase materials have unique advantages that improve the friction and wear performance [5,6]. The Ti3AlC2 material can create the prepared coating with a high hardness, and can form a continuous self-lubricating tribofilm under the condition of high-temperature wear, thus having excellent wear resistance [7]. The doping of Mo causes Ti3AlC2 to form self-lubricating oxidation products such as MoO3 and Mo oxides, which effectively improve its tribological properties at high temperatures [8]. However, for the TiC/Ti3AlC2-Co cermet coatings, as the increase in the Ti3AlC2 content increases, the surface is scratched by Ti3AlC2 particles, resulting in abrasive wear and fatigue damage. As the Ti3AlC2 content increases further, the wear mechanism of the coating changes from abrasive wear to adhesive wear due to the influence of the Ti3AlC2 layer structures and residual content [9,10]. Although Ti3AlC2 has great potential in tribological applications, in-depth research is still required to understand the abrasive action of Ti3AlC2 during the friction process and the method of inhibiting the damage caused by abrasive wear.
In order to weaken the damage of the worn surface, molybdenum dialkyl dithiocarbamate (MoDTC) and zinc dialkyl dithiophosphate (ZDDP) are commonly used additives in commercial lubricants. MoDTC produces MoO3 and MoS2 on the tribological contact surfaces, where the formed MoS2 can effectively improve the friction and wear performance of the surface [11,12,13,14]. This is due to the strong covalent bonds between the MoS2 atoms and the weak van der Waals attraction between the lattice layers. MoS2 can convert the micro-asperities contact into sliding between the lattice layers, thus maintaining good tribological properties [15,16]. Adding a high concentration of MoDTC additive to the lubricant can effectively reduce the friction force of DLC-based coatings, but it increases the wear depth of the sample [17]. Under the conditions of a higher temperature and high additive concentration, the anti-friction effect of the MoDTC additive is the most effective, but the decomposition rate of the MoDTC additive is accelerated and the anti-friction effect is reduced under high-temperature conditions [18].
Adding ZDDP to the lubricant can reduce wear losses in the tribological pairs by generating tribofilms on the surfaces of the tribological pairs and reducing the direct contact of micro-asperities in boundary lubrication [19,20,21]. These tribofilms have multilayer structures consisting of zinc/iron sulfide layers and polyphosphate layers of different chain lengths [22]. Temperature has a certain effect on the decomposition of ZDDP and the growth of tribofilms. As the temperature increases, the growth rate of the tribofilms also increases [23]. Under boundary lubrication, physical parameters such as the temperature and pressure have significant effects on the durability of tribofilms. The consumption rate of ZDDP tribofilms can be higher than the growth rate with an increasing temperature and load, leading to serious friction and wear losses [24,25,26]. Under high-temperature and heavy load conditions, it is sometimes difficult for the tribofilms generated by adding ZDDP and/or MoDTC additives to achieve good anti-friction and wear resistance [27]. The effect of MoDTC and ZDDP additives on the impact of Ti3AlC2 particles on worn surfaces when Ti3AlC2 particles combined with MoDTC and ZDDP additives are used remains to be clarified.
In this paper, Ti3AlC2, MoDTC and Ti3AlC2/MoDTC composite additives were added to a same lubricant containing ZDDP, respectively. The friction and wear performance of the lubricants containing Ti3AlC2, MoDTC and Ti3AlC2/MoDTC composite additives were compared under different working conditions using an impact-sliding friction and wear test rig. The worn surface morphology, elemental distribution and tribofilms were used to analyze the differences among the different lubricant additives. This will provide some guidance on the application of MAX phase materials in the design of high-performance lubricant additives for low-speed marine engines.

2. Materials and Methods

2.1. Experimental Materials

The Ti3AlC2 particles were sourced from Zhongxin New Materials Co., Ltd., Chiping County, Liaocheng City, China. Figure 1 shows the SEM and EDS of the Ti3AlC2 particle additive. The Ti3AlC2 additive with a layered structure had a length of about 10 µm and an average thickness of 1–2 µm. Red, yellow, green, and blue represent the distribution of C, O, Al, and Ti elements in the selected region, respectively. The MoDTC additive was purchased from Tongrun Information Technology Co., Ltd., China. Figure 2 shows the process of preparing the Ti3AlC2/MoDTC composite additive. First, Ti3AlC2 and MoDTC were added to 50 mL of deionized water in a mass ratio of 0.33:2 and stirred at 60 °C for 3 h at 600 rpm using a magnetic stirrer. Then, the composite additive sample was completely homogenized for 4 h using a probe ultrasonicator (power 93W, frequency 19.66 kHz, amplitude 60 %). Finally, the composite additive sample was shaken with an ultrasonic device (power 120 W, frequency 40 kHz) for 3 h to improve dispersion. The obtained product was centrifuged, washed, desiccated, ground, sieved and stored in a vacuum desiccator until use [28]. For the Ti3AlC2/MoDTC composite particle additive, it was found that the surface of the Ti3AlC2 particles contained a certain amount of S (light blue) and Mo (purple), which were derived from the MoDTC additive, as shown in Figure 3.
The selected lubricant (Great Wall Lubricants Company of China, 10 W-40 CF-4) was found to contain approximately 1 wt.% of the traditional antiwear additive ZDDP. The viscosity index of the lubricant is 139, and the kinematic viscosity is 103.7 mm2/s at 40 °C and 13.9 mm2/s at 100 °C. Prior to the friction and wear test, the mixture of additives in the lubricant should be treated to homogenize it. The concentrations of the Ti3AlC2, MoDTC and Ti3AlC2/MoDTC compound additives added to the lubricant were 0.33 wt%, 2 wt% and 2.33 wt%, respectively. The lubricant was first heated to 60 °C with a heater to ensure that the newly added additive could disperse more quickly in the lubricant. The additive was added to the lubricant and stirred for 1 h at 60 °C and 600 rpm using a magnetic stirrer. The sample was then completely homogenized for 2 h at 60 °C using a probe ultrasonicator (power 93 W, frequency 19.66 kHz, amplitude 60%). During the test, the magnetic stirrer was used for continuous stirring at 60 °C and 60 rpm to reduce the influence of the dispersion state of the lubricant suspension on the test. Figure 4 shows the suspension state and appearance of the lubricant samples with Ti3AlC2, MoDTC and Ti3AlC2/MoDTC additives. It can be seen that all the lubricant suspensions maintained a good dispersion state without the phenomenon of stratification during the period from 0 to 12 h. This guarantees the stability of the test results during the friction and wear test.
The tribopair consists of a chromium-based ceramic composite coated steel (CKS) piston ring and a cast iron cylinder liner, both of which are commonly used materials in low-speed marine engines. Figure 5 shows the surface morphology of the CKS piston ring and cast iron cylinder liner. The surface morphology of the CKS piston ring is shown in Figure 5a. Figure 5b shows the original honed textures machined into the surface morphology of the cast iron cylinder liner, which not only reduces the direct contact area, but can also store the lubricant. The sample parameters for the tests are shown in Table 1. The CKS piston ring is 11 mm long, 3 mm wide and 4 mm high. The cast iron cylinder liner is 43 mm long, 8.5 mm wide and 6 mm high. The CKS piston ring has a surface roughness (contour arithmetic mean deviation) of 0.24 µm and a hardness of 705 HV0.1. The cast iron cylinder liner has a surface roughness of 0.72 µm and a hardness of 238 HV0.1.

2.2. Friction and Wear Tests

An impact-sliding friction and wear test rig was used to simulate the influence of the peak pressure on the tribo-surface [29,30]. A schematic diagram of the impact-sliding test rig is shown in Figure 6. In this apparatus, a normal load is measured by the load sensor and the value of the normal load is displayed in real time on the instrument. The load is applied to the cam and a peak impact load is generated at the dead center. The crank-connecting rod mechanism drives the heating block in a reciprocating motion and the heating block heats the tribo-surface. The friction forces generated between the samples is transmitted to a pressure sensor, which converts the pressure into an electrical signal. The charge amplifier then converts the tiny charge signal into a larger electrical signal. Finally, the friction forces are displayed on the screen. Table 2 shows the friction and wear test parameters. The rotational speed of the crankshaft in the test was 200 rpm, which is commonly used for low-speed marine engines. The speed mode of the heating block was sinusoidal and the movement amplitude was 30 mm. The peak pressure at the dead center was determined by the ratio of the normal force to the projected normal area (25.5 mm2). When the normal force was 255 N, the peak pressure was 10 MPa, and when the normal force was 1275 N, the peak pressure was 50 MPa. The tests were carried out at 150 °C under the low-load running-in regime (10 MPa), and the wear time was 10 min. Under the high-load wear regime (50 MPa), the test temperature was 150 °C, 200 °C and 250 °C, and the wear time under this condition was 180 min. During the test, a micro-peristaltic pump was used to deliver lubricant to the samples at a rate of 0.1 mL/min. To investigate the effect of various lubricant additives on the tribopairs, friction and wear tests were carried out under different temperatures and a peak impact load of 50 MPa (1275 N).
When the test reached a steady state, the coefficient of friction was obtained according to the ratio of the maximum friction force in the stroke to the peak impact load at the dead center. The wear depth of the tribopair was measured using the OLYMPUS LEXT OLS 3100 laser scanning confocal surface characterization microscope (Olympus Corporation, Tokyo, Japan). The magnification was 20× when measuring the wear depth of the samples. At the dead center, the height difference between the worn surface and the unworn surface was the wear depth. The test was performed at least three times to ensure that the results of the friction coefficient and wear depth were as consistent as possible, with a variation of less than 10%. The worn surface morphology and elemental distribution were analyzed using a SUPRA 55 SAPPHIRE scanning electron microscope (SEM, Carl Zeiss NTS GmbH, Oberkochen, Germany) and energy-dispersive X-ray spectroscopy (EDS, Carl Zeiss NTS GmbH, Oberkochen, Germany), respectively. The main test parameters for the SEM and EDS included magnifications of 200×, 500×, 5.00 KX and 10.00 KX, acceleration voltages of 3.00 kV and 10.00 kV, and a working distance of approximately 10.00 mm. A K-Alpha 1063 X-ray photoelectron spectroscope (XPS, Thermo Fisher Scientific, Waltham, MA, USA) was used to determine the surface chemistry of the cast iron cylinder liner lubricated with different additives. The test results were post-processed using Advantage software (version number v5.9921) to identify and fit the spectral peaks and to evaluate the peaks according to their position, shape and intensity.

3. Results

3.1. Friction and Wear Performance of Ti3AlC2, MoDTC and Ti3AlC2/MoDTC Composite Additives

Figure 7 shows the variation in the coefficient of friction with temperature for lubrication with the Ti3AlC2, MoDTC and Ti3AlC2/MoDTC composite additives at 50 MPa. The coefficients of friction of all three additive lubricants are reduced to different degrees with the gradual increase in temperature. The coefficient of friction of the Ti3AlC2 additive is higher at 150 °C, but the difference in the coefficient of friction between the MoDTC and Ti3AlC2/MoDTC composite additive is not significant. At 200 °C, the coefficients of friction of the three additives are significantly different. At 250 °C, the difference in the coefficient of friction between the MoDTC and the Ti3AlC2/MoDTC composite additives is not obvious. The Ti3AlC2, MoDTC and Ti3AlC2/MoDTC composite additives present very different friction performances at the tribo-surface under different temperatures, especially at 200 °C.
Figure 8 shows the variation in the friction coefficient and wear depth for the tribopair lubricated with different additives at the impact position at 200 °C. It can be seen from Figure 8a that the friction coefficient of the lubricant using the Ti3AlC2 additive is about 0.084. The friction coefficients of the lubricants containing the MoDTC and Ti3AlC2/MoDTC composite additives are 0.057 and 0.053, respectively, a reduction of 32.1% and 36.9% compared to the Ti3AlC2 additive. In Figure 8b, the wear depth of the cast iron cylinder liner lubricated with the Ti3AlC2 additive is approximately 1.62 µm, while the corresponding wear depths for the MoDTC and Ti3AlC2/MoDTC composite additives are approximately 1.01 µm and 0.95 µm, respectively. Compared to the Ti3AlC2, the MoDTC and Ti3AlC2/MoDTC composite additives reduce the wear depths by 37.7% and 41.4%, respectively. The variation in the wear depth of the CKS piston ring is similar to that of the cast iron cylinder liner. The wear depth of the CKS piston ring for the Ti3AlC2/MoDTC composite additive shows a reduction of 71.9% and 7.8% compared to the Ti3AlC2 and MoDTC additives.

3.2. Worn Surfaces Analysis

Figure 9 shows the worn surface of the cast iron cylinder liner lubricated with the Ti3AlC2 additive. As a result of the damage caused by hard particles, the worn surface shows a large number of scratches in the sliding direction [31]. It produces the most severe plastic deformation caused by the abrasive wear, and the plastic deformation layer almost covers the original honing grooves (Figure 9a,b) [32]. The EDS results show that P, S and Zn elements produced by the tribochemical reaction of ZDDP can be detected on the worn platform (Positions 1, 2). There are also small amounts of Al and Ti on individual platform positions (position 1, 2). C, O, Fe and Si elements from the cast iron cylinder liner composition are found in the severely damaged honing grooves (Position 3).
Figure 10 shows the worn surface of the cast iron cylinder liner lubricated with the MoDTC additive. A few scratches caused by the abrasive particles are distributed on the platform along the sliding direction (Figure 10a). Many plastically deformed flakes are present at the edge of the honing grooves (Figure 10b). P, S, and Zn elements from ZDDP are also found on the worn platform (Positions 4, 5). Mo from the MoDTC additive is also present. In the plastic deformation flakes distributed in the honing grooves, elements C, O, Fe and Si from the cast iron cylinder liner composition are found (Position 6).
Figure 11 shows the worn surface of the cast iron cylinder liner lubricated with the Ti3AlC2/MoDTC composite additive. It has the smallest plastic deformation area, which mainly exists on the worn honing platforms. Small scratches are scattered across the platform (Figure 11a). The honing grooves are still well preserved (Figure 11b). Slightly higher amounts of the elements P, S, Zn and Mo are detected on the worn platform, and the elements Al and Ti are also found on the worn platform (Positions 7, 8). The elements C, O, Fe and Si from the cast iron cylinder liner composition are still found in the honing grooves (Position 9).
Figure 12 shows the worn surfaces of the CKS piston ring lubricated with different additives. For the Ti3AlC2 additive (Figure 12a), many large scratches of uniform length are distributed along the sliding direction on the worn CKS piston ring surface. For the MoDTC additive (Figure 12b), the worn CKS piston ring surface is relatively smooth and flat. For the Ti3AlC2/MoDTC composite additive (Figure 12c), only a few small scratches of uniform length are distributed along the sliding direction. The EDS results show that P, S, and Zn elements are detected on all the worn surfaces (Positions 10, 11, 13, 15). Al and Ti elements are not detected on the worn CKS piston ring surfaces lubricated with the Ti3AlC2 and Ti3AlC2/MoDTC composite additives. Mo is found on the CKS piston ring surface lubricated with the Ti3AlC2/MoDTC composite additive (Position 15). This indicates that the tribochemical products generated by the ZDDP additive always provide protection to the CKS piston ring surface, regardless of the other additives.
Figure 13 and Figure 14 show the microscopic morphology and elemental distribution of the Ti3AlC2 and Ti3AlC2/MoDTC composite additives collected from the used lubricant. For the Ti3AlC2 additive, the lubricated particles have significantly fewer layers with smaller dimensions. It is observed that there are large interlayer gaps between the particle layers (Figure 13a,b). It shows that Ti3AlC2 particles with a multilayer structure are gradually exfoliated by the cyclic impact on the reciprocating tribo-surface. The exfoliated sheets from the Ti3AlC2 particles easily cause many small, uniformly distributed scratches on the tribo-surface, as shown in Figure 9. The elemental distribution shows that small amounts of P, S (from the tribofilm) and Fe (from the matrix material) are adhered on the surface of the Ti3AlC2 particles. Some Ti3AlC2 particles might scratch the tribofilms and matrix material at the tribological interface, resulting in severe abrasive wear and the consumption of the tribofilms.
For the Ti3AlC2/MoDTC composite additive, the Ti3AlC2 particles remain in a dense layered distribution with little peeling (Figure 14a,b). The elemental distribution shows that the contents of P (from the tribofilm) and Fe (from the matrix material) adhering to the surface of the Ti3AlC2 particles are relatively low, while the increase in the content of S (from the tribofilm or MoDTC) is relatively small, and a certain amount of Mo (from MoDTC) is detected on the surface of the Ti3AlC2 particles. With the help of the MoDTC additive, the Ti3AlC2 particles reduce the peeling of the layered structure. The likelihood of the Ti3AlC2 particles scraping off the tribofilms and matrix material at the tribo-surface is reduced. The abrasive interaction between the Ti3AlC2 particles and the sliding surface is greatly improved.

3.3. XPS Study of the Tribofilm on the Surface of the Worn Cast Iron Cylinder Liner Using the Ti3AlC2/MoDTC Composite Additive

For elements such as P, S and Zn detected by EDS, the XPS technique is used to analyze the tribo-chemical reaction products at the peak pressure position of the cast iron cylinder liner. The tribofilms of the Ti3AlC2/MoDTC composite additive are compared and analyzed. The rules for split-peak fitting need to be strictly constrained, such as the peak area ratio, difference between the binding energies of the doublets, and full-width at half-maximum (FWHM). Spin-orbit splitting results in 2p signals for P, S, Zn, Fe, Ti and Al, with double peaks of 2p3/2 and 2p1/2, with an area ratio of 2:1. The signals of Mo from the 3d orbitals also show two peaks, 3d5/2 and 3d3/2, with a double peak area ratio of 3:2. The difference between the binding energies of the doublets is fixed for most elements, but the Al–Ti–C bond is 6.0 eV and the Ti–O bond is 5.7 eV for Ti elements [33]. The FWHMs of the same element should be the same or similar [34].
Figure 15 shows the signals in the tribofilms generated by the Ti3AlC2/MoDTC composite additive on the worn surface of a cast iron cylinder liner captured by XPS. For the P element (Figure 15a), the peaks of P2p3/2 with binding energies at 134.02 eV and 134.82 eV correspond to phosphates and all belong to short-chain phosphates [35].
For the O element (Figure 15b), the O1s peak around 530.2 ± 0.1 eV belongs to metal oxides, which may contain MoO3, ZnO, Fe2O3, TiO2, Al2O3, etc. [36]. The O1s peak near to 532.6 eV corresponds to sulfate (iron sulfate, ferrous sulfate) [37]. The O1s spectra can further confirm the presence of short-chain phosphates. NBO (531.6 ± 0.3 eV) and BO (533.3 ± 0.3 eV) are the signals that are closely related to phosphate in the O1s spectra, and the smaller ratio of BO to NBO indicates the shorter chain length of phosphate [38,39]. The ratio for the Ti3AlC2/MoDTC composite additive lubricant is 0.08. This shows that the Ti3AlC2, MoDTC and ZDDP additives have a synergistic effect and promote the depolymerization process of ZDDP.
For the S element (Figure 15c), an S2p3/2 signal with a binding energy of 161.87 ± 0.1 eV is obtained, indicating that it is FeS [40]. The S2p3/2 peak at 161.13 eV is considered to be ZnS, which can be associated with the peak of Zn2p3/2. The S2p3/2 peak at 163.4 ± 0.1 eV corresponds to the chemical state of MoS2 [41]. The S2p3/2 peak at 168.1 ± 0.1 eV corresponds to metal sulfate [34].
For the Zn element (Figure 15d), the Zn2p3/2 peak at 1021.5 eV corresponds to ZnO. The peaks of Zn2p3/2 at 1023.57 ± 0.1 eV are phosphates [37]. In addition, the Zn2p3/2 peak at 1022.27 eV is identified as ZnS [42].
For the Mo element (Figure 15e), the Mo3d5/2 peak at 229.13 ± 0.1 eV corresponds to the chemical state of MoS2, which is consistent with the results of the S2p3/2 split-peak fitting [43]. The Mo3d5/2 peak near 231.06 ± 0.1 eV is considered to be unreacted MoDTC additive [44]. The Mo3d5/2 peak at 232.5 ± 0.1 eV corresponds to the chemical state of MoO3 [11]. The results indicate that the MoDTC additive is involved in the tribo-chemical reaction at the tribo-surface and generates MoS2 and MoO3.
For the Fe element (Figure 15f), the Fe2p3/2 peak at 710.2 ± 0.1 eV corresponds to iron oxide [45]. The Fe2p3/2 peak at 711.8 ± 0.3 eV is considered to be iron phosphate [13]. The Fe2p3/2 peak at 713.3 ± 0.1 eV corresponds to the chemical state of iron sulfate [41]. This indicates that the iron-based material is involved in the tribo-chemical reaction and generates tribofilms.
For the Ti and Al elements, the Ti2p3/2 peak at 458.43 ± 0.1 eV (Figure 15g) is considered to be TiO2 [46]. The Ti2p3/2 peaks at 454.85 ± 0.1 eV and 456.28 ± 0.1 eV correspond to the chemical state of unoxidized Ti3AlC2 particles, which is in contrast to the Al2p3/2 peak at 72.2 ± 0.1 eV (Figure 15h) [47]. The Al2p3/2 peak at 74.23 ± 0.1 eV (Figure 15h) is considered to be Al2O3 [48]. This shows that Ti3AlC2 particles decompose at the tribo-surface to form TiO2 and Al2O3, which are also part of the tribofilms.

3.4. Failure Mechanism Analysis for Ti3AlC2, MoDTC and Ti3AlC2/MoDTC Composite Additives

The results of the friction and wear tests show that the Ti3AlC2/MoDTC composite additive in the lubricant has a better friction and wear performance than either the Ti3AlC2 or MoDTC additive. Figure 16 shows the effect of the Ti3AlC2, MoDTC and Ti3AlC2/MoDTC composite additives on the honing cast iron cylinder liner surfaces. For the respective Ti3AlC2 and MoDTC additives, the plastic deformation layers are gradually extruded from the honing platform surfaces. The plastic flakes gradually accumulate, fill and cover the honing grooves. But the honing textures can be well preserved, with less plastic deformation for the Ti3AlC2/MoDTC composite particle additive. In addition, the worn surface morphology indicates that the formation of scratches is mainly caused by the Ti3AlC2 particles, but the MoDTC encapsulated on the surface of the particles reduces the number of scratches to some extent.
With regard to the tribofilm of the Ti3AlC2/MoDTC composite additive, the XPS detection results show that the MoS2 and MoO3 tribofilms generated by the decomposition of the MoDTC encapsulated on the Ti3AlC2 particles can act as solid lubricants. The tribofilms of the short-chain phosphates and ZnS generated by the decomposition of ZDDP can inhibit the direct contact of micro-asperities. The multilayer structure of Ti3AlC2 slides easily on the worn surface and also has a good self-lubricating performance. TiO2 and Al2O3 generated by the decomposition of the Ti3AlC2 particles can further isolate the direct contact of the tribo-surface. These synergistic effects reduce the exfoliation of the Ti3AlC2 layer structure, as well as the disruption of its lamellar structure. The possibility of Ti3AlC2 particles scraping the tribofilm and the matrix material at the friction interface is greatly reduced. This is beneficial for the rational distribution of multi-component tribofilms.
Compared to the addition of Ti3AlC2 particles alone, the number of scratches, the friction coefficient and the wear depth were reduced to a certain extent after the encapsulation of MoDTC on the surface of Ti3AlC2 particles [49]. Further work should be carried out to investigate the effect of various additives in combination with Ti3AlC2 particles on the lubricant properties. More effective ways to reduce the scraping effect of the Ti3AlC2 particles on the tribofilms and the matrix material should be found.

4. Conclusions

In this study, the tribological performance of Ti3AlC2 particles in CKS piston rings and cast iron cylinder liners were evaluated on an impact-sliding friction and wear test rig. The Ti3AlC2 additive, the MoDTC additive and the prepared Ti3AlC2/MoDTC composite additive lubricants were tested at different temperatures at 50 MPa. After analyzing the synergistic action of Ti3AlC2, MoDTC and ZDDP additives in the lubricant, the following conclusions can be drawn:
(1) The Ti3AlC2/MoDTC composite additive showed the best friction and wear performance. Compared to Ti3AlC2 alone, the friction coefficient and wear depth of the designed composite additive MoDTC/Ti3AlC2 were reduced by 36.9% and 41.4%, respectively. The worn surfaces lubricated with the Ti3AlC2/MoDTC composite additive were smoother, with fewer scratches. The plastic deformed flake existed only on the edge of the platform, better preserving the honing grooves.
(2) For the worn surface lubricated with the Ti3AlC2/MoDTC composite additive, EDS detection showed that the contents of elements P, S, Zn and Mo were slightly higher on the worn platform. XPS further found the presence of FeS, MoS2, MoO3, ZnO, TiO2, Al2O3 and unoxidized particles; short-chain phosphates and some ZnS were also detected on the surface of the cast iron cylinder liner.
(3) The MoDTC encapsulated on the Ti3AlC2 particles formed a solid tribofilm that reduced the stripping of the Ti3AlC2 layer structure and inhibited the possibility of Ti3AlC2 particles scraping the tribofilm and the matrix material at the friction interface.

Author Contributions

Conceptualization, Y.S.; methodology, Y.S. and J.L.; validation, J.Q.; formal analysis, J.L., Y.S., L.L., J.Q. and G.Z.; investigation, J.L., Y.S., Z.L., B.Y. and L.L.; writing—original draft preparation, J.L.; writing—review and editing, Y.S.; supervision, Y.S.; funding acquisition, Y.S. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the Study on Tribology and Lubrication Technology of the Marine Low-Speed Engine (Grant No. 202123J-2), the National Natural Science Foundation of China (Grant No. 51979018), the Natural Science Foundation of Liaoning Province in China (Grant No. 2024-MS-011) and the Fundamental Research Funds for the Central Universities (Grant No. 3132023515).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data will be made available upon request.

Conflicts of Interest

Author Guogang Zhang was employed by the company Dalian Marine Diesel Engine Co., Ltd. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

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Figure 1. SEM and EDS images of the Ti3AlC2 particle additive.
Figure 1. SEM and EDS images of the Ti3AlC2 particle additive.
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Figure 2. Schematic diagram of the preparation of the Ti3AlC2/MoDTC composite particle additive.
Figure 2. Schematic diagram of the preparation of the Ti3AlC2/MoDTC composite particle additive.
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Figure 3. SEM and EDS images of the Ti3AlC2/MoDTC composite particle additive.
Figure 3. SEM and EDS images of the Ti3AlC2/MoDTC composite particle additive.
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Figure 4. Suspension and appearance of the lubricant samples with Ti3AlC2, MoDTC and Ti3AlC2/MoDTC additives.
Figure 4. Suspension and appearance of the lubricant samples with Ti3AlC2, MoDTC and Ti3AlC2/MoDTC additives.
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Figure 5. Surface morphology of the (a) CKS piston ring and (b) cast iron cylinder liner.
Figure 5. Surface morphology of the (a) CKS piston ring and (b) cast iron cylinder liner.
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Figure 6. Schematic diagram of an impact-sliding test rig.
Figure 6. Schematic diagram of an impact-sliding test rig.
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Figure 7. Relationship between coefficient of friction and temperature of different additives at 50 MPa.
Figure 7. Relationship between coefficient of friction and temperature of different additives at 50 MPa.
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Figure 8. (a) Friction coefficient, and (b) wear depth for the tribopair lubricated with different additives at the impact position at 200 °C.
Figure 8. (a) Friction coefficient, and (b) wear depth for the tribopair lubricated with different additives at the impact position at 200 °C.
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Figure 9. Worn surface of the cast iron cylinder liner lubricated with the Ti3AlC2 additive. (a) magnification 200× (b) position A magnification 500×.
Figure 9. Worn surface of the cast iron cylinder liner lubricated with the Ti3AlC2 additive. (a) magnification 200× (b) position A magnification 500×.
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Figure 10. Worn surface of the cast iron cylinder liner lubricated with the MoDTC additive. (a) magnification 200× (b) position B magnification 500×.
Figure 10. Worn surface of the cast iron cylinder liner lubricated with the MoDTC additive. (a) magnification 200× (b) position B magnification 500×.
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Figure 11. Worn surface of the cast iron cylinder liner lubricated with the Ti3AlC2/MoDTC composite additive. (a) magnification 200× (b) position C magnification 500×.
Figure 11. Worn surface of the cast iron cylinder liner lubricated with the Ti3AlC2/MoDTC composite additive. (a) magnification 200× (b) position C magnification 500×.
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Figure 12. Worn surfaces of the CKS piston ring lubricated with the (a) Ti3AlC2 additive, (b) MoDTC additive, and (c) Ti3AlC2/MoDTC composite additive.
Figure 12. Worn surfaces of the CKS piston ring lubricated with the (a) Ti3AlC2 additive, (b) MoDTC additive, and (c) Ti3AlC2/MoDTC composite additive.
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Figure 13. Microscopic morphology and elemental distribution of the Ti3AlC2 additive at (a) 5.00 KX, and (b) 10.00 KX magnification after the lubrication of the tribopair.
Figure 13. Microscopic morphology and elemental distribution of the Ti3AlC2 additive at (a) 5.00 KX, and (b) 10.00 KX magnification after the lubrication of the tribopair.
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Figure 14. Microscopic morphology and elemental distribution of the Ti3AlC2/MoDTC composite additive at (a) 5.00KX and (b) 10.00KX magnification after the lubrication of the tribopair.
Figure 14. Microscopic morphology and elemental distribution of the Ti3AlC2/MoDTC composite additive at (a) 5.00KX and (b) 10.00KX magnification after the lubrication of the tribopair.
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Figure 15. XPS captures the tribofilm signal: (a) P 2p, (b) O 1s, (c) S 2p, (d) Zn 2p, (e) Mo 3d, (f) Fe 2p, (g) Ti 2p; (h) Al 2p generated by the Ti3AlC2/MoDTC compound additive on the worn surface of the cast iron cylinder liner.
Figure 15. XPS captures the tribofilm signal: (a) P 2p, (b) O 1s, (c) S 2p, (d) Zn 2p, (e) Mo 3d, (f) Fe 2p, (g) Ti 2p; (h) Al 2p generated by the Ti3AlC2/MoDTC compound additive on the worn surface of the cast iron cylinder liner.
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Figure 16. Schematic diagram of the different additives on the honing cast iron cylinder liner surfaces.
Figure 16. Schematic diagram of the different additives on the honing cast iron cylinder liner surfaces.
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Table 1. Sample parameters for friction and wear testing.
Table 1. Sample parameters for friction and wear testing.
SampleSample Parameters
Long
(mm)		Wide
(mm)		High
(mm)		Roughness
(µm)		Hardness
(HV0.1)
CKS piston ring11340.24705
Cast iron cylinder liner438.560.72238
Table 2. Friction and wear test parameters.
Table 2. Friction and wear test parameters.
Test StageSpeed
(rpm)		Frequency
(Hz)		Stroke
(mm)		Peak Impact Load
(MPa)		Temperature
(°C)		Time
(min)		Lubricant
Feed Rate
(mL/min)
Low load 2003.333010150100.1
High load 2003.333050150/200/2501800.1
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MDPI and ACS Style

Liu, J.; Shen, Y.; Liu, Z.; Yu, B.; Qu, J.; Li, L.; Zhang, G. Wear Characteristics Caused by Ti3AlC2 Particles under Impact-Sliding Conditions in Marine Engine. J. Mar. Sci. Eng. 2024, 12, 1777. https://doi.org/10.3390/jmse12101777

AMA Style

Liu J, Shen Y, Liu Z, Yu B, Qu J, Li L, Zhang G. Wear Characteristics Caused by Ti3AlC2 Particles under Impact-Sliding Conditions in Marine Engine. Journal of Marine Science and Engineering. 2024; 12(10):1777. https://doi.org/10.3390/jmse12101777

Chicago/Turabian Style

Liu, Jie, Yan Shen, Zhixiang Liu, Baihong Yu, Jinghao Qu, Leize Li, and Guogang Zhang. 2024. "Wear Characteristics Caused by Ti3AlC2 Particles under Impact-Sliding Conditions in Marine Engine" Journal of Marine Science and Engineering 12, no. 10: 1777. https://doi.org/10.3390/jmse12101777

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