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Scientific Reports volume 14, Article number: 29410 (2024 ) Cite this article wear plates
FeCrMoCB amorphous coatings were prepared by detonation spraying technology. The coating microstructure, elements distribution, microhardness distribution, wear behaviors under various temperatures and the electrochemical corrosion resistance were discussed, respectively. It was found the amorphous content of the detonation sprayed Fe-based amorphous coating can reach 84.6%, higher than the other usual thermal spray technologies. The coating microhardness reached 900 HV0.5, and the wear rate of the amorphous coating was about 47 × 10− 6 mm3/N.m. The coating under 400 °C exhibited the strongest wear resistance among the coatings under various temperatures due to the oxidation appeared during the fabrication process, and several big cracks appeared in the coating under 600 °C because of the coating brittleness.
In the past few years, amorphous coatings have attracted much attention for their high hardness, excellent wear and resistance. Among the amorphous material categories, Fe-based amorphous coatings have been highly concerned and frequently applied due to the relative lower cost and higher performance than other amorphous coatings (like Ni-based, Cu-based and Zr-based).
Various coating technologies have been adopted to fabricate Fe-based amorphous coatings, among them, the thermal spray technologies obtain large potential of applying Fe-based amorphous coatings in the fields of industrial, marine and aviation for its easy operation and low cost1,2,3,4,5,6,7,8,9. For example, C. Zhang et al.10 fabricated FeCrMoCBY amorphous coating on mild steel substrate by HVOF with different feedstock powder size, and found the coatings sprayed with the finest powders showed the most compact structure; while the coating with the coarser powders exhibited a better corrosion resistance. Wenmin Guo et al.11 used high-velocity arc spraying technology to obtain Fe-based amorphous coating, and the results showed that the amorphous Fe-based coatings exhibited an attractive combination of high hardness (900–1100 HV0.3) and superior bonding strength (44.9–54.8 MPa) with a dense structure and a low porosity of only 2%. Z. Zhou et al.12 applied atmospheric plasma spraying technology to fabricate FeCrMoCBY amorphous coatings and investigated the electrochemical corrosion resistance. The results showed that the coatings exhibited extremely wide passive region and relatively low passive current density in 3.5% NaCl and 1 mol/L HCl solutions, which illustrated their superior ability to resist localized corrosion. Detonation spraying technology obtains high coating density, microhardness, and cooling speed which were fit for amorphous coating deposition and application, however, the detonation sprayed amorphous coatings were seldomly reported.
Wear and corrosion properties are the key points of coating application13,14,15,16,17,18,19,20,21,22,23,24. Pavan Bijalwan et al.25 fabricated FeCrSiBC amorphous coatings on mild steel substrate by atmospheric plasma spraying, and found the values of nanohardness increased to 12 GPa at high plasma power because amorphous content decreased from 93 to 89% and amount of hard intermetallic nanoparticles increased. Jiangbo Cheng et al.26 adopted air plasma spraying technology to obtain FeCrMoCBP amorphous coating under various powers, and the results showed that the coating wear rate with 42 kW is about 1.6 and 4.2 times lower than that with 28 kW and Eq. 70 marine steel in a 3.5 wt% NaCl solution, respectively. C. Zhang et al.27 prepared FeCrMoCBY amorphous coatings by HVOF and discussed its wear behavior. The results showed that the dominating wear mechanism of the Fe-based amorphous coating is oxidative wear coupled with delamination wear where the oxidation process is governed by inward diffusion of oxygen. At present, most research on coating deposition have been focused on room temperature wear resistance, but few on various temperatures, especially the wear behaviors of detonation sprayed amorphous coating under high temperatures. However, the coatings often suffer wear under high temperature, such as aircraft coating. Therefore, the wear behaviors under various high temperatures need to be studied.
In order to systematically investigate the microstructure, high temperature wear and corrosion behaviors of the detonation sprayed amorphous coatings, this work applied detonation spray technology to deposit FeCrMoCB amorphous coating on 304 stainless steel, and discussed the wear behavior and properties under various temperatures as well as the electrochemical corrosion behavior.
The amorphous powders were commercial high-purity Fe, Cr, Mo, C and B metal alloy powders with particle size ranging mostly between 20 and 60 μm, and the average size is 33.5 μm, as exhibited in Fig. 1a. The component alloy powders were gas atomized and sieved. Figure 1b and c display the morphologies of cross section of the powder particles. It can be seen that most particles show a circular shape and solid structure. The circular shape benefits to improve the powder flowability and maintain the fluency of spraying process. The solid structure is beneficial to the stability of powder melting degree during flying in the spray process.
The particle size distribution and cross-section morphology of the Fe-based amorhpous powder (a) powder particle size distribution (b) the cross section of powder particle (c) the magnification of powder particle.
304 stainless steel plates were wire cut into specimens with dimensions of 100 mm×100 mm×4 mm for use. Before detonation spray, the substrate surface was sandblasted under pressure of 0.5 MPa using silica sand to activate the surface and remove the grease. Then they were ultrasonic cleaned and dried in air. The surface roughness of sandblasted substrate specimens was controlled to about Ra = 3.2 μm.
The spray experiments were conducted using commercially available detonation spray equipment (Plackart-Ob-D2 equipment, Plackart, Russia). The powder injection point was located about 400 mm from the open end of the barrel. The injection was carried out by a powder feeder. Barrel length and diameter was 1000 mm and 25 mm, respectively. The filling ratio of the charge of gas mixture into the barrel was 58%. Nitrogen was adopted as the carrier gas. Compressed N2 was used to cool the substrate during the spray process to reduce oxidation and crystallization. The working gas was the mixture of O2 and C2H2. Oxygen flow was 1.2 m3/h, acetylene flow was 1.0 m3/h. Spray distance was 150 mm, powder feed rate was 40 g/min, and the working frequency was 4 times per second. The coating thickness was ranged between 300 and 600 μm.
Microhardness of the coatings were examined on polished cross sections using a Vickers microhardness indenter (HX-1000, Shanghai Second Optical Instrument Factory, China) under 500 g load for duration of 15 s. Ten measurements for each coating specimen were obtained and the average value was calculated, as well as the standard deviation. Friction and wear experiments were conducted under dry condition from room temperature to 600 °C using a ball-on-disk sliding apparatus (HT-1000, Zhongke Kaihua Company, China). Chromium steel balls with a diameter of 9.525 mm, a hardness of 50 HRC and a mean surface roughness of around 50 nm were adopted as the counterpart material. New ball was used for each test.
Before the wear friction experiment, all specimens were grinded, polished to a mirror surface and cleaned. The sliding duration was 30 min, the load was 20 N, and the sliding velocity was 0.1, 0.2 and 0.3 m/s for each specimen. The wear rate Ws of the coating was estimated by the equation of Ws = V/DL, V is the volume loss, D is the sliding distance, and L is the applied load on the specimen. The volume loss V = m/ρ, where ρ is the specimen material density, m is the mass loss during each test run. The worn surfaces of substrate and coatings were compared by SEM.
The electrochemical corrosion behaviors of the amorphous coatings and stainless steel were investigated by polarization method in 3.5 mass% NaCl solution at room temperature using an electrochemical workstation (CHI660E, Shanghai Chenhua Instrument Co., Ltd., China). The specimens were polished to mirror surface, and sealed by epoxy resin to expose an area of 1 cm × 1 cm for the corrosion test. During the corrosion test, a conventional three-electrode cell was used. The coating sample, saturated calomel electrode (SCE), and platinum foil were adopted as working electrode, reference electrode and auxiliary electrode, respectively. The potential was scanned at sweep rate of 1 mV/s from − 700 to 1500 mV relative to open-circuit potential (OCP).
Scanning electron microscopy (SEM, Quanta 250 FEG, FEI) was used to examine the morphologies of the amorphous powder and coatings. The phase structure was investigated by X-ray diffraction (XRD, Rigaku D/max − 2550VB) using Cu Kα irradiation, with the diffraction angle set from 20° to 80°. The coating porosity was evaluated by applying the Image Pro-Plus 6.0 software. At least fifteen cross-sectional SEM images at the magnification of 1000 times were randomly selected for the porosity measurement of each coating.
Figure 2 exhibits the cross-section morphologies of the detonation sprayed Fe-based amorphous coating. From the Fig. 2a, the thickness of the coating reached 500 μm, which can meet the requirements of the wear and corrosion protection coatings on thickness in industry. Moreover, the coating thickness uniformly distributes, indicating the flying and impacting states of the powder particles were similar, which was mainly dependent on the particle size distribution and spray equipment stability. From Fig. 2b, the interface of coating and substrate displays a compact bonding, and several embedding regions are found. This can be explained that the detonation energy was huge which sustained heating and accelerating the powder particles to impact the substrate. The powder particles obtained high temperature and velocity, resulting in the softening of substrate, then the powder particles embedded into the substrate. The coating obtains a high density according to the Fig. 2a and c. The typical lamellar structure in most thermal sprayed coating was found in detonation sprayed coating, but less than the plasma sprayed coatings. It can be inferred that during plasma spraying, the powder particles possessed higher temperature and lower impacting speed than detonation spray due to the characteristic of plasma flame, leading more lamellar structure which is mainly promoted by temperature gradient and impeded by impacting speed. From Fig. 2d, several tiny pores can be seen in the lamellar structure, which are supposed to be generated by the gas escaping from melted particle when impacting substrate and spreading. Moreover, a small amount of unmelted particle can be observed in the coating, which can be attributed that the coarse powder particles may not be fully melted in the detonation spraying process and a part of the particles retained in the formed coating.
Cross-section morphologies of the Fe-based amorphous coating.
Figure 3 displays EDS of the cross-section of Fe-based amorphous coating. It can be seen the elements Fe, Mo and Cr uniformly distribute in the coating which exhibit light grey in the photo, indicating a homogeneous structure. The dark grey region represents the Cr and O rich structure, which may improve the coating hardness due to the high hardness of Cr oxides generated from the reaction of Cr and O.
EDS of the cross-section of Fe-based amorphous coating.
Figure 4 exhibits the EDS of the cross-section of lamellar structures. It can be seen the lamellar structure is mainly formed by Fe, Mo and Cr. The Cr oxides locate within the lamellar structure, according with the above results. The oxides between the lamellar structures are mainly due to the reaction between metal elements and oxygen when the powder particles were melted during detonation spray.
EDS of the cross-section of lamellar structures.
Figure 5 shows the XRD patterns of the amorphous powder and detonation sprayed coating. The powder exhibits broad diffused scattering peaks, indicating the most structure is amorphous. The high amorphous content is due to the rapid cooling of melted powder particle in the powder manufacturing process. After detonation spraying, Fe3Mo, Cr15Fe7C6 and Cr23C6 compounds appeared in the coating according to the sharp peaks in the coating pattern. The generation of crystalline can be explained that explosive energy was huge enough to melt the powder particles to reach the noncrystalline forming demand of cooling speed, but in the meantime, the high heat increased the crystalline when the high temperature powder particles impacted the formed coating. Comparing the XRD patterns of the coatings by detonation spraying, HVOF28 and laser cladding29, the detonation sprayed amorphous coating obtains the highest amorphous content which is calculated to be 84.6% by the software MDI JADE 5.0. This can be explained that the coating deposition in detonation spray mainly depends on the higher impacting particle velocity than HVOF and laser cladding but less heat input which is beneficial to improve amorphous content. What’s more, the peaks of oxides don’t exist in the coating XRD pattern, indicating the content of oxides is low, so the diffraction intensity is weak.
XRD patterns of the amorphous powder and detonation sprayed coating.
Figure 6 exhibits the microhardness distribution in the coating and substrate. The detonation sprayed Fe-based amorphous coating displays super high hardness of about 900 HV0.5, which can be due to the unique amorphous attribute and dense structure by detonation spray. The interface of coating and substrate shows the hardness of about 580 HV0.5. This can be attributed to the tiny pores and gaps in the bonding area due to the thermal incompatibility between the coating material and substrate during spray process. The coating hardness is much higher than the substrate, so it may keep the substrate from severe wear friction and strike.
Micro-hardness distribution of the coating and substrate.
Figure 7 exhibits the friction coefficients of the detonation sprayed Fe-based amorphous coatings at sliding velocity of 0.2 m/s under different wear temperature. From the curves, it can be seen the friction coefficient of the coating under RT (room temperature) is approximately 0.85. The coefficient comes to about 0.8 when the wear temperature is 200 °C, and the curve is more stable. When the wear temperature rises to 400 °C, the coefficient is increased to about 0.75. The coefficient reaches to the smallest of 0.73 when the temperature grows up to 600 °C. This phenomenon indicates that as the wear temperature increased, the wear resistance of the coating seemed to be stronger, and the wear friction process became more stable.
Friction coefficients of the coatings at sliding velocity of 0.2 m/s under different wear temperature.
Figure 8 shows the wear rates of the coatings and steel substrate at different sliding velocity under various temperatures. It can be found the detonation sprayed Fe-based amorphous coating exhibits much stronger wear resistance than the steel substrate, even two times stronger. At the same sliding velocity, the wear rate variation trend of the coatings under different temperature is similar, and the coating under 400 °C exhibits the best wear performance, the coating under RT displays the worst among the coatings, but the wear resistance of the coatings under different temperatures are close relative to the steel substrate. What’s more, as the sliding velocity increases, the wear rate of all the coatings and substrate rises, especially the sliding velocity of 0.3 m/s obviously aggravates the wear friction of the all the specimens.
Figure 9 displays the friction profiles of the coatings after wear test under various temperatures. It can be seen the friction profile of the coating under RT is the deepest among them, reaching nearly 100 μm. As the wear temperature rises, the depth and width of the wear pit gradually decreases, and reaches to approximately 10 μm. The depth and width data indicate the material volume loss during the wear test. From this result, the coating exhibits stronger wear resistance under the higher wear temperature, which is completely in accordance with the above results.
The wear rate of the coatings and steel substrate at different sliding velocity under various temperatures.
The friction profiles of the coatings after wear test at sliding velocity of 0.2 m/s under various temperatures.
The SEM photos of the wear surfaces of detonation sprayed coatings under various friction temperatures are exhibited in Fig. 10. It can be seen that a lot of humps appear on the friction surface of the coating under room temperature wear friction, accompanied by big flake-like abrasive dust. Moreover, several minor cracks can be found from the magnified photo. As the friction temperature increased, the humps decreased as well as the volume of the abrasive dust. However, big cracks appeared when the temperature rose to 600 °C. This phenomenon can be attributed to the oxides production during the high temperature wear friction. During the high temperature wear friction, oxides of Fe and Cr gradually increased and enhanced the coating microhardness but decreased the toughness due to the relation of hardness and toughness which generated the cracks.
Surface morphology SEM photos of the coatings after wear friction test at sliding velocity of 0.2 m/s under different temperatures.
Figure 11 shows the surface morphology SEM photos of the grinding balls after wear friction under various wear temperatures. It’s obvious that the wear profile decreased as the wear temperature rose, which is in agreement with the above wear friction results. It’s remarkable that the circumference of wear profile exhibits the brighter color than inner area, illustrating the edge of contact area suffered the worst severe wear which can be due to the stress concentration.
Surface morphology SEM photos of the grinding balls after wear friction at sliding velocity of 0.2 m/sunder various wear temperatures.
Figure 12 exhibits the potentiodynamic polarization curves of the detonation sprayed amorphous coating and substrate in 3.5 wt% NaCl solution. The corrosion potential of the coating is -253 mV, higher than the substrate of -268 mV, indicating the coating obtains the weaker corrosion trend in 3.5 wt% NaCl solution. The corrosion current of the amorphous coating is 1.8 × 10− 6 A/cm2, lower than the substrate of 6.4 × 10− 6 A/cm2, indicating the coating corrosion speed is slower than the steel substrate. The difference of corrosion resistance can be attributed to the corrosion resistance of amorphous material and density of the coating.
Potentiodynamic polarization curves for the detonation sprayed amorphous coating and substrate in 3.5 wt% NaCl.
Figure 13 exhibits the corrosion surfaces of the amorphous coating and steel substrate. It can be found the steel was seriously corroded, several big cracks and holes appeared at local area. On the contrary, the coating displays a uniform surface after corrosion test, and no cracks are found, but some tiny corrosion pits can be seen due to the intense corrosivity of Cl− ion. This phenomenon completely agrees with the above conclusions.
Morphology SEM photos of the corrosion surface of the steel substrate and coating.
In this work, FeCrMoCB amorphous coatings were prepared by detonation spray technology. The thickness of detonation sprayed Fe-based amorphous coating reached 300–500 μm, exhibiting the typical lamellar structure of thermal sprayed coatings, moreover, several embedding regions, unmelted particles and tiny pores were found in the coating. Uniform structure and element distribution of the coating can be found from EDS analysis. The Fe-based amorphous coating exhibits a high amorphous content of 84.6%, indicating the detonation spray is an appropriate deposition technology to get amorphous coating. What’s more, the coating obtains the hardness of about 900 HV0.5, which is much higher than steel substrate and common materials. The coating under 400 °C exhibits the best wear resistance than those under RT, 200 °C and 600 °C from the wear friction results, which can be due to the Fe and Cr oxides generated during the wear process providing the further high hardness. Moreover, the detonation sprayed Fe-based amorphous coating displayed the better electricalchemical corrosion resistance than the steel substrate. The corrosion potential and the corrosion current of the coating are − 253 mV and 1.8 × 10− 6 A/cm2, and those of substrate are − 268 mV and 6.4 × 10− 6 A/cm2.
Data is provided within the manuscript.
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This work was supported by Natural Science Foundation of Hunan Province (2021JJ50025); Key R&D Plan Project of Hunan Province (2022GK2030).
School of Management Engineering, Jiangsu Urban and Rural Construction Vocational College, Changzhou, 213147, People’s Republic of China
Hunan Provincial Key Defense Laboratory of High Temperature Wear-resisting Materials and Preparation Technology, Hunan University of Science and Technology, Xiangtan, 411201, People’s Republic of China
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Author Lu Xie wrote the main manuscript and finished the expriment of corrosion test. Author Yueming Wang finished the experiment of coating fabrication, wear friction test and manuscript review.
The authors declare no competing interests.
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Xie, L., Wang, Y. High temperature wear and corrosion behavior of detonation sprayed Fe-based amorphous coatings. Sci Rep 14, 29410 (2024). https://doi.org/10.1038/s41598-024-80308-2
DOI: https://doi.org/10.1038/s41598-024-80308-2
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