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Article

Microscopic Characteristics and Properties of Fe-Based Amorphous Alloy Compound Reinforced WC-Co-Based Coating via Plasma Spray Welding

by
Yan Xu
1,2,
Yinfeng Wang
3,
Yi Xu
3,
Mingyong Li
3 and
Zheng Hu
3,*
1
China Research and Development Academy of Machinery Equipment, Beijing 100089, China
2
School of Mechanical and Vehicle Engineering, Beijing Institute of Technology, Beijing 100081, China
3
Science and Technology on Vehicle Transmission Laboratory, China North Vehicle Research Institute, Beijing 100072, China
*
Author to whom correspondence should be addressed.
Processes 2021, 9(1), 6; https://doi.org/10.3390/pr9010006
Submission received: 16 November 2020 / Revised: 18 December 2020 / Accepted: 21 December 2020 / Published: 22 December 2020
(This article belongs to the Special Issue Advances in Plasma Diagnostics and Applications)
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Abstract

:
Plasma spray welding, as one of the material surface strengthening techniques, has the advantages of low alloy material consumption, high mechanical properties and good coating compactness. Here, the Co alloy, WC and Fe-based amorphous alloy composite coating is prepared by the plasma spray welding method, and the coating characteristics are investigated. The results indicate that the coatings have a full metallurgical bond in the coating/substrate interface, and the powder composition influences the microstructures and properties of the coating. The hardness of coatings increases with the mass fraction of the Fe-based amorphous alloy. The spray welding layer has a much higher wear resistance compared with the carbon steel, and the Fe-20 exhibits a superior wear resistance when compared to others. The results indicate that the amorphous alloy powders are an effective additive to prepare the coating by plasma spray welding for improving the wear resistance of the coating.

1. Introduction

The rapid development of the industry has led to increasingly higher requirements for the performance and service life of various mechanical parts [1,2,3]. Wear and corrosion are the prime reasons for material failure during use, which seriously affect the performance quality and service life of mechanical products [4,5,6,7]. Therefore, improving the wear resistance of the material surface is of great significance to reduce costs and save resources [8,9]. In order to improve the service life of structural steel in harsh environments, the plasma spray welding is an effective method to modify and strengthen the surface of the steel to form a new alloy coating to improve the wear and corrosion resistance of the material and reduce the production cost [10,11,12,13].
In the plasma spray welding technique, suitable alloy powders are selected according to the actual conditions and requirements of surface properties [14,15,16]. A spray welding layer of cobalt-based alloy has an excellent high temperature impact wear resistance and outstanding high temperature oxidative stability [17,18]. By optimizing the plasma spray welding process parameters, the quality of the spray welding layer has been improved, and different methods were proposed to reduce the spray welding layer cracks [19,20,21,22]. By adding different materials to the alloy powder to make composite materials, the structure and performance of the plasma spray welding layer are improved [23,24]. Especially in the aspects of hardness, wear resistance, corrosion resistance and oxidation resistance, the spray welding layer has achieved excellent results [25,26].
Numerous studies have shown that a transition metal-based amorphous alloy can be used directly as alloy powder or added to a nickel base, cobalt base, iron base and other self-fluxing alloyed powders owing to the high melting point, high hardness and good abrasive resistance. For example, Fe45Cr16Mo18C18B5 amorphous coatings were deposited on the mild substrate by plasma spraying, and their corrosion in 3.5 wt.% NaCl solution was compared with those of the substrate and 316 stainless steel. The obtained results imply that the coating has a promising prospect for industrial applications [27]. Moreover, it has been reported that a WC-CoCr/35 wt.% amorphous Fe-based alloy composite coating was prepared by high velocity oxygen fuel spray, and, in comparison with the WC-CoCr coating, the WC-CoCr/35 wt.% amorphous Fe-based alloy composite coating exhibits excellent thermal stability and better corrosion resistance [28].
In this work, WC, Co and Fe-based alloy composite powders are selected to prepare a reinforced coating on the surface of 42CrMo steel using the plasma spray welding method. The Co-based amorphous alloy had excellent physicochemical properties, and the mechanical performance under high-temperature conditions was excellent [22,29]. The WC coating compounded with Co element has a high hardness value in a certain temperature range. At the same time, its impact resistance and toughness are very good, and the porosity of the coating is low, and it is combined with the substrate’s high strength [3,30,31]. The influence and mechanism of the added Fe-based amorphous powder amount on the microstructure and properties of the spray welding layer are discussed. The results clearly show that the hardness of coatings increases with the mass fraction of the Fe-based amorphous alloy. The spray welding layer has a much higher wear resistance compared with the carbon steel, and the Fe-20 exhibits a superior wear resistance when compared to others.

2. Materials and Methods

2.1. Experimental Materials

42CrMo steel was adopted as the base material of plasma spray welding, and the 42CrMo chemical composition is shown in Table 1. WC (53–90 μm, 99.9 wt.%), Co alloy (53–165 μm) and Fe-based amorphous alloy (16–54 μm) are all products by Aidun Alloy Material Co., Ltd., Suzhou, China, and their chemical compositions are shown in Table 1.

2.2. Experimental Methods

Firstly, Co alloy, WC and Fe-based amorphous alloy powders are mixed with ball-milling in a certain ratio (20%WC + Co + 5%Fe, 20%WC + Co + 10%Fe, 20%WC + Co + 15%Fe and 20%WC + Co + 20%Fe marked as Fe-5, Fe-10, Fe-15 and Fe-20). Secondly, the 42CrMo steel was cut into a sample of 30 × 50 × 10 mm using a wire cutting machine. Before plasma spray welding, the sample was polished with coarse sandpaper to remove the oxide layer and adjust the roughness, and then cleaned ultrasonically for 30 min in a bath of acetone to remove the rust, organic and fatty contaminants. Finally, a plasma spray welding was used on the 42CrMo steel surface to prepare the plasma welding layer, and the layer was about 23 × 35 mm. The spray welding layer was arc-shaped and the thickness about 2.7 mm. The technological parameters of the plasma spray welding are shown in Table 2.

2.3. Detection and Analysis

Microstructure observations and a chemical analysis of the plasma spray welding layer were carried out by a field-emission scanning electron microscope (SEM, S-3000N, Hitachi, Tokyo, Japan) equipped with an energy-dispersive X-ray spectrometer (EDS). The phase composition of the sample was analyzed by the X-ray diffraction (XRD, D8 ADVANCE, BRUKER, Karlsruhe, Germany) and the parameters were set as follows: D/Max 2500PC, Cu Kα radiation, λ = 0.15418 nm, scan rate is 4°/min. Furthermore, the micro hardness of the sample was tested by adopting a micro-sclerometer (MH-3, Minks Testing Equipment Co., Ltd., Xi’an, China) for 10 s, with an applied load of 500g, and the test parameters were determined according to the composition of the material, the uniformity of the structure, the size and the surface roughness [32]. The wear resistance of the sample was tested by adopting an abrasive wear testing machine (ML-100, Jingcheng Testing Technology Co., Ltd., Jinan, China), with an applied load of 10 N. The stroke was 121.0 m and wear materials 600#SiC waterproof abrasive paper were used [33].

3. Result and Discussion

The results of the XRD analysis of the 20%WC + Co spray welding layer with different contents of Fe-based amorphous alloy are shown in Figure 1. It was found that the spray welding layer is mainly composed of carbides such as WC, Cr,Fe,Ni,Co(W,C) and (Cr,Fe,Ni,Co)3W3C, as well as the alloy phase of Cr, Fe, Ni and Co. Cr,Fe,Ni,Co(W,C) is an fcc solid solution of W and C in the metal lattice with a larger lattice parameter, whereas (Cr,Fe,Ni,Co)3W3C is a metastable sub-stoichiometric ternary carbide called η-phase (M6C, where M = metal). Since the Cr, Fe and Co elements have a strong affinity with the C element, they could form carbides easily. The carbides have both a high hardness and excellent wear resistance and can be used as a hard phase supporting matrix, which can greatly improve the hardness and wear resistance of the spray welding layer [34]. Figure 1b shows the XRD analysis results of Fe-20. Compared to Fe-5, a much harder phase was formed on the surface of the substrate. This can be attributed to the fact that an increase of the Fe content would generate a harder phase in the spray welding process, which is conducive to comprehensively improving the hardness, wear resistance and other mechanical properties of the spray-welding layer.
The typical surface morphology of the coatings with a different Fe-based amorphous alloy content are characterized by SEM, as shown in Figure 2. The Fe-based amorphous alloy content of 5% is shown in Figure 2a, where it can be clearly seen that the white phase is the carbide phase, which is the main existing style of carbide particles in the spray welding layer, and the dark gray phase is mainly the matrix solid solution phase. As shown in Figure 2, the white carbide phase mainly exists in the form of regular dendrites in the spray welding layer. As the Fe-based amorphous alloy content increases, the number and size of dendritic solidification structures also increase, as shown in Figure 2b. It is worth noting that few WC particles are observed in the coating surface, which is due to the different melting points and densities of WC and the metal phase during the rapid cooling rate in the plasma spray welding process. The WC melting point, which is the highest compared to that of the metal phase, is about 2870 °C. During the process of coating formation, the metal phase is melted into liquid owing to the higher hot plasma energy, while the WC powder is hard to melt. Then, the WC powder with a high density would sink down inward because of gravity. In order to confirm the main phase in the coating surface, the elemental composition of the surface of the spray welding layer was analyzed, and the results of points 1–4 are shown in Table 3. It can be clearly seen that points 1 and 3 have the same elements, including C, Si, Cr, Fe, Co, W and Ni. And so do points 2 and 4, compared with points 1 and 3, which lack the Si element. The results indicate that the white area’s chemical component in the dendritic crystal is composed of WC and that the dendritic crystal is mainly composed of (Cr,Fe,Ni,Co)3W3C, while the matrix’s solid solution phase is mainly composed of Cr,Fe,Co,Ni(C). Moreover, it was found that the Fe, Cr, Ni and Co elements in the carbide phase are significantly less than that in the matrix, while the W elements in the carbide phase are more numerous than that in the matrix.
Figure 3 shows the SEM of the cross-section of the samples’ spray welding layer. The result shows that the coating has a dense microstructure and the thermal plasma beam can ensure metallurgical bonding between the coating and the 42CrMo steel. As shown in Figure 3a,e, it was found that the WC particles are not evenly distributed. There are few WC particles in the surface zone of coating, while the WC particles are concentrated in the fusion zone nearing the steel surface. The microstructures of the surface zone are shown in Figure 3b,f. It is clear that most of the carbide phases are dendritic structures, some of which are irregular in shape and distributed among the dendritic structures. Figure 3c,g show the microstructures of the middle zone. Compared with the surface zone, the irregular WC particles in the middle zone increase and the carbide phases with dendritic structure decrease. Figure 3d,h shows the structure of the fusion zone. It can be clearly seen that there are plenty of WC particles with a surrounded dendritic structure. This is due to the plasma spray welding process. The melting point of WC is too high, and the WC exists in a semi-melted form in the liquid metal. The semi-melted WC particles can be used as nucleation particles in the liquid phase solidification process to promote non-uniform nucleation, causing the local segregation of alloy components and promoting the growth of nucleation particles in the form of dendrites during the solidification of the liquid phase metal [35]. In a certain crystal grain range, the hardness decreases with the increase of WC crystal grains. This is due to the small size effect of fine grain WC, large surface energy, effective flow for liquid phase diffusion during the spray welding process, uniform grain growth and high densification, which improves the mechanical properties [36,37]. As shown in Figure 3c,d, it was found that the crystal grain of WC is bigger than tin Figure 3g,h indicating that the properties of Fe-20 are superior to those of Fe-5.When the grains have an uneven distribution and an irregular growth, the mechanical properties of the coating are reduced. It can be seen that the grains’ uneven distribution in Fe-5 and Fe-20 affect the performance of the coating. Besides, the shape of the carbide phase is significantly different from the difference in local alloy composition carbides and temperature gradient. Furthermore, the EDS analysis results of the middle zone in Fe-20 are shown in Figure 3i–l. It is obvious that the W elements are mainly distributed in the WC phase and the carbide phase, while the Fe, Cr, Ni and Co elements in the matrix are more numerous than the carbide phase. Several points are selected to further explore the chemical composition in the fusion zone, and the results of the electronic probe are shown in Table 4. It was found that point 1 only contains the C and W elements, indicating that the place of the point is WC. Points 2 and 3 contain the same elements, including C, Si, Cr, Fe, Co, W and Ni. It is confirmed that the WC particles are surrounded by a carbide phase with a dendritic structure. However, the distribution of elements in the carbide phase is quite different at different positions. The carbide phase near the WC phase has more W elements than those away from the WC phase. The reason is that, during the plasma spray welding process, WC gradually melts and releases W elements which would induce a high concentration of W around the WC particles, while these W elements would form a (Cr,Fe,Ni,Co)3W3C phase. In addition, the results of EDS component analysis show that the Fe content in point 3 is significantly higher than that in point 2. This is because the melting of the sub-matrix will cause the elements in the matrix to enter the molten pool. As a result, the Fe content is much higher, while the other elements in the fusion zone are diluted.
The influence of the contents of Fe-based amorphous alloys on the binding quality, microhardness and wear resistance property of the spray welding layer was further studied. Figure 4 shows the binding quality of the coating to the substrate. It can be seen that when the Fe-based amorphous alloy content is 20%, the spray welding layer can be well combined with the substrate, and when the Fe-based amorphous alloy content is relatively lower, the spray welding layer cannot form an excellent cladding with the substrate. When the content of the Fe-based amorphous alloy is 5%, the spray welding current is relatively too large to meet the requirement of the spray welding, so that the spray welding layer cannot be well fused with the substrate, resulting in spray welding defects. The microhardness distribution ranging from substrate to coating is shown in Figure 5a. It can be clearly seen that the hardness of the 42CrMo steel substrate is about 320 HV and the hardness of the spray welding layer is about 650–750 HV. The microhardness of the coating is about two times higher than that of the substrate for each coating. The microhardness of the spray welding layer fluctuates slowly, which may be caused by the difference in the size and quantity distribution of the hard phase. It was found that the hardness gradient in the bonding domain is large, which is a typical characteristic of the hardness distribution of the spray welding layer. This is the result of the sprayed liquid alloy and the matrix, which diffuse and penetrate each other, and the C element in the alloy power plays a solid solution strengthening effect [38,39]. Besides, as the content of Fe-based amorphous alloys increases, the microhardness of the spray welding layer increases, and has a great relationship with the microstructure. The increase of the carbide phase in the spray welding layer and the distribution lead to an increase in the hardness of the spray welding layer [40,41,42].
Wear mass loss is an important factor in characterizing the wear resistance of a material. The results of the wear mass loss are shown in Figure 5b. The wear mass loss of the spray welding layer of Fe-5, Fe-10 and Fe-15 is more than that of Fe-20. The smaller the wear loss rate, the better the wear resistance of the spray welding layer. When the amount of the Fe-based amorphous alloy added is 20%, the spray welding layer has better wear resistance. When the amount of the Fe-based amorphous alloy added is 5–15%, the microhardness and wear resistance are reduced. This is because when a small amount of Fe-based amorphous alloy is added, it can only play a solid solution strengthening effect [33,43]. Additionally, as shown in Figure 4b, the wear mass loss of the following three frictions and wear experiments is relatively balanced, while the wear mass loss of the first time is relatively high. This is because the surface is the outermost in the first wear experiment, which has a lower degree of bonding than the inside.
To further explore the influence of different Fe-based amorphous alloys on the wear resistance of the spray welding layer, frication and wear experiments were carried out on the samples. The morphologies of the worn surfaces of the coatings are shown in Figure 6. Figure 6a–c shows the SEM images of Fe-5, Fe-10 and Fe-15. Deep furrows and scratches are clearly visible on the sample surface, caused by the splashing and agglomeration of Fe-based amorphous alloys. The powder fails to effectively bond with the matrix when it is melted, resulting in a decrease in the Fe-based amorphous alloys content in the spray welding layer and an increase in the austenite phase content. The spray welding layer becomes soft, causing the furrows to deepen. Figure 6d shows the wear morphology of the Fe-20 spray welding layer. Fewer scratches and spalling pits were found, and there are almost no deep furrows in the spray welding layer’s wear scars. Meanwhile, more hard phases are scattered in the spray welding layer. The structure is small and uniform, and the hardness and toughness reach a good level. Therefore, the spray welding layer has a better wear resistance.

4. Conclusions

In summary, Fe-based amorphous alloy reinforced WC-Co-based coating was prepared on 42CrMo steel by plasma spray welding. The results indicate that the coatings have a full metallurgical bond in coating/substrate interface and the powder composition influences the microstructures and properties of the coating. The main components of the coating are WC, Cr,Fe,Ni,Co(W,C), (Cr,Fe,Ni,Co)3W3C and the alloy phase of Cr, Fe, Ni and Co. Experimental result shows that the interface between the spray welding layer and matrix has a large amount of WC, and there is a gradient distribution of WC from internal to external in the cross section. The spray welding layer would enhance the hardness and wear resistance of the 42CrMo steel. The hardness of the coatings increased with the mass fraction of the Fe-based amorphous alloy. The spray welding layer has a much higher wear resistance compared with the carbon steel, and Fe-20 exhibits a superior wear resistance when compared to others.

Author Contributions

Data curation, Y.W. and Y.X. (Yi Xu); formal analysis, M.L.; investigation, Y.X. (Yan Xu) and Y.X. (Yi Xu); project administration, Y.X. (Yi Xu) and Z.H. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Innovation Program (237099000000170004).

Acknowledgments

The authors would like to acknowledge the financial supports of the Innovation Program (237099000000170004).

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. XRD patterns of the coatings with different Fe-based amorphous alloy contents. (a) 5%, (b) 20%.
Figure 1. XRD patterns of the coatings with different Fe-based amorphous alloy contents. (a) 5%, (b) 20%.
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Figure 2. Surface SEM images of different coatings: (a) Fe-5 and (b) Fe-20.
Figure 2. Surface SEM images of different coatings: (a) Fe-5 and (b) Fe-20.
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Figure 3. SEM images of (a–d) the cross-section of the Fe-5 coating, (e–h) SEM images of the cross-section of the Fe-20 coating and (i–l) EDS images of the middle zone in the Fe-20 coating.
Figure 3. SEM images of (a–d) the cross-section of the Fe-5 coating, (e–h) SEM images of the cross-section of the Fe-20 coating and (i–l) EDS images of the middle zone in the Fe-20 coating.
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Figure 4. The different contents of the Fe-based amorphous alloy of the binding quality to the substrate (a) Fe-5 (b) Fe-10 (c) Fe-15 (d) Fe-20.
Figure 4. The different contents of the Fe-based amorphous alloy of the binding quality to the substrate (a) Fe-5 (b) Fe-10 (c) Fe-15 (d) Fe-20.
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Figure 5. The influence of the Fe-based amorphous alloy content on the mechanical properties of the plasma spray welding layer: (a) microhardness and (b) wear mass loss.
Figure 5. The influence of the Fe-based amorphous alloy content on the mechanical properties of the plasma spray welding layer: (a) microhardness and (b) wear mass loss.
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Figure 6. The morphologies of worn coatings: (a) Fe-5, (b) Fe-10, (c) Fe-15 and (d) Fe-20.
Figure 6. The morphologies of worn coatings: (a) Fe-5, (b) Fe-10, (c) Fe-15 and (d) Fe-20.
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Table
Table 1. Chemical composition (wt.%) of the raw material.
Table 1. Chemical composition (wt.%) of the raw material.
PowderCSiMnCrMoNiPSWBFeCo
42CrMo0.450.370.81.20.250.030.030.03----rest--
Co-Based Alloy3.21.01.026.0--22.5----5.0--3.0rest
Fe-Based Amorphous Alloy1.71.8--4.0--7.5------3.0rest--
Table
Table 2. The plasma spray welding parameters.
Table 2. The plasma spray welding parameters.
Delivering Powder Gas Flow Rate (mL/min)Plasma Gas Flow Rate
(mL/min)		Feeding Voltage (V)Standoff Distance (mm)Powder Delivery Amount (g/min)Current (A)Bead Diameter (mm)
4003002010201252
Table
Table 3. Chemical composition (at %) of the surface of the spray welding layer.
Table 3. Chemical composition (at %) of the surface of the spray welding layer.
CSiCrFeCoWNi
116.961.7615.697.7321.2225.5611.08
215.07--22.428.9836.092.2115.23
319.212.9314.949.5920.7922.969.58
417.74--19.710.6135.152.0514.75
Table
Table 4. Chemical composition (at %) of the points in the fusion zone.
Table 4. Chemical composition (at %) of the points in the fusion zone.
CSiCrFeCoWNi
145.62--------54.38--
217.312.0314.248.2919.428.5210.21
315.251.2612.0226.5918.7117.698.48
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Xu, Y.; Wang, Y.; Xu, Y.; Li, M.; Hu, Z. Microscopic Characteristics and Properties of Fe-Based Amorphous Alloy Compound Reinforced WC-Co-Based Coating via Plasma Spray Welding. Processes 2021, 9, 6. https://doi.org/10.3390/pr9010006

AMA Style

Xu Y, Wang Y, Xu Y, Li M, Hu Z. Microscopic Characteristics and Properties of Fe-Based Amorphous Alloy Compound Reinforced WC-Co-Based Coating via Plasma Spray Welding. Processes. 2021; 9(1):6. https://doi.org/10.3390/pr9010006

Chicago/Turabian Style

Xu, Yan, Yinfeng Wang, Yi Xu, Mingyong Li, and Zheng Hu. 2021. "Microscopic Characteristics and Properties of Fe-Based Amorphous Alloy Compound Reinforced WC-Co-Based Coating via Plasma Spray Welding" Processes 9, no. 1: 6. https://doi.org/10.3390/pr9010006

APA Style

Xu, Y., Wang, Y., Xu, Y., Li, M., & Hu, Z. (2021). Microscopic Characteristics and Properties of Fe-Based Amorphous Alloy Compound Reinforced WC-Co-Based Coating via Plasma Spray Welding. Processes, 9(1), 6. https://doi.org/10.3390/pr9010006

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