CN116334619A - Co-based alloy powder and WC ceramic powder synergistically reinforced composite coating and preparation method thereof - Google Patents
Co-based alloy powder and WC ceramic powder synergistically reinforced composite coating and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
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- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
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- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
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Abstract
The invention discloses a Co-based alloy powder and WC ceramic powder collaborative strengthening composite coating and a preparation method thereof, belonging to the technical field of composite coatings. According to the invention, co-based metal alloy powder and WC ceramic powder are mixed according to a certain proportion, wherein the mass ratio of the WC ceramic powder is more than 60%, the mass ratio of the Co-based metal alloy powder is up to 40%, an in-situ autogenous method and coaxial powder feeding are adopted, and a composite coating containing various hard reinforcing phases is prepared on the surface of 316L stainless steel by utilizing a laser cladding technology, so that the coating has excellent performances of high strength, high-temperature wear resistance, corrosion resistance and the like, and the problems of low strength, poor wear resistance, short service life and the like of a sink roll on a hot dip plating production line can be solved.
Description
Technical Field
The invention relates to the technical field of composite coatings, in particular to a Co-based alloy powder and WC ceramic powder synergistically reinforced composite coating and a preparation method thereof.
Background
Along with the expansion of industrial production scale and the rapid development of technology, the requirements for long-time effective stable operation of equipment and mechanical parts under various severe working conditions such as high pressure, high temperature and the like are gradually increased. At present, the traditional simple heat treatment mode is difficult to achieve higher requirements. On a hot dip plating production line, the service life of the sink roll is usually only 7-10 days, and the economic loss caused by starting and stopping each time is up to 30 ten thousand yuan, so that the reduction of the replacement times of various rolls is an important measure for improving the economic benefit.
At present, a wear-resistant and corrosion-resistant coating, such as a Co-12WC coating, is usually prepared by a thermal spraying method for prolonging the service life of the sink roll, but the coating prepared by thermal spraying has low bonding strength, poor surface quality and large dilution rate. The holes on the surface are easy to be passages for liquid metal such as aluminum, zinc and the like to contact the substrate, so that the performance of the coating is reduced, the difference between the thermal expansion rate of the coating and the thermal expansion rate of the metal substrate is often larger, the service life of the protective coating is shorter, and the protective coating is easy to be peeled off integrally. Therefore, a new technology and process are needed to prepare a coating with better output and wear resistance.
The laser cladding technology has the advantages of quick cooling, small dilution rate, controllable cladding area, easiness in automation and the like, and is greatly concerned and researched. Self-fluxing alloys such as: ni-based, co-based and Fe-based have better performance through laser cladding preparation. In particular, after laser cladding, the Co-based alloy coating shows excellent high temperature resistance and friction and wear resistance. The ceramic powder has the characteristics of high hardness, high melting point and corrosion resistance, and the ceramic powder and the Co-based alloy are uniformly mixed according to a certain proportion, so that the high-temperature-resistant, oxidation-resistant and friction-resistant composite coating can be prepared. The Co-Cr alloy composite coating added with WC hard phase has excellent effect on the combination of strength and toughness, and the corrosion resistance of Cr material is exerted.
However, such coatings prepared at present have the following disadvantages: firstly, the ceramic powder has lower quality, and the service life of the prepared coating is difficult to meet the requirement of actual production; secondly, the difference between the thermal expansion coefficients of the ceramic and the matrix material is large, so that large internal stress can be generated, defects such as cracks and holes are easy to generate on the cladding layer, and the coating performance is poor.
Through searching, patent publication No. CN 115029601A discloses a high-entropy alloy/hard ceramic synergistic reinforced composite coating and a preparation method thereof. In the application, fe and B element powder is added in five metal elements of high-entropy alloy powder Co, ni, mo, B, cr, a preset coating and an in-situ autogenous method are adopted to generate a plurality of ternary boride hard ceramic reinforcing phases by means of laser cladding treatment, the reinforcing phases are distributed in the high-entropy alloy, and the synergistic effect between the preset coating and the in-situ autogenous method is utilized to combine the limitation of the content of the ternary boride, so that the coating has good wear resistance and corrosion resistance. However, compared with the contrast, the abrasion loss and corrosion loss of the composite coating obtained by the application are not improved much, and the production and use requirements are difficult to meet.
Disclosure of Invention
1. Technical problem to be solved by the invention
Aiming at the problems of the background technology, the invention provides the Co-based alloy powder and WC ceramic powder synergic strengthening composite coating and the preparation method thereof.
2. Technical proposal
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
according to the Co-based alloy powder and WC ceramic powder cooperative reinforcement composite coating, co, cr, W, B, C, fe element powder is used as a raw material, a plurality of hard eutectic carbide reinforcing phases are distributed in the coating, the mass ratio of ceramic powder in the composite powder is more than 60%, and the balance is Co-based metal alloy powder.
Further, in the coating raw material, the metal alloy powder comprises the following chemical components in percentage by mass: 27 to 32 percent of Cr, 4 to 6 percent of W, less than or equal to 3.0 percent of Fe, less than or equal to 0.5 to 2.0 percent of Mn, less than or equal to 3 percent of Ni, 2.5 to 5.0 percent of Mo, 2.0 to 2.5 percent of B, 0.9 to 1.2 percent of C and the balance of Co.
Further, the WC ceramic powder comprises the following chemical components in percentage by mass: c5-8%, and the balance W.
Still further, the plurality of hard eutectic carbide reinforcing phases include (Co, cr, fe) 7 C 3 、(Co、Fe) 23 C 6 、(Co、Fe) 6 C、W 2 C, performing operation; the metal alloyThe composition includes a metal element Co, cr, W, fe, C.
Still further, the phases of the coating include the eutectic carbide, metal alloy, and elemental powders, the eutectic carbide, and the metal alloy being multi-dimensionally fused to the base material of the coating.
Still further, the elemental powders all have a purity of greater than 99.9%.
The invention relates to a preparation method of a Co-based alloy powder and WC ceramic powder collaborative strengthening composite coating, which comprises the following steps:
step 1: through an in-situ autogenous method, uniformly grinding and mixing raw material powder through a planetary ball mill, and then placing the raw material powder into a drying box for drying treatment;
step 2: polishing the base material until the smooth surface is exposed, cleaning the base material with alcohol, and preheating the base material in a resistance heating furnace;
step 3: irradiating the surface of the reaction material by adopting a laser cladding technology, wherein a matrix and raw material powder can react in situ in the laser cladding process to generate a hard phase which is distributed in the alloy, so as to form the metal alloy/WC ceramic cooperative reinforcement composite coating;
step 4: and (3) placing the prepared coating into a heating furnace, tempering at high temperature, and then cooling to room temperature along with the furnace.
Further, in the step 1, the ball mill stirs the mixed powder at a rotation speed of 300rpm-400rpm, and the mixed powder is fully and uniformly mixed; and (3) putting the mixed powder into a drying oven at the temperature of 100-120 ℃ for drying.
Further, in step 3, the laser cladding process parameters are: the diameter of the circular light spot is 4mm, the powder feeding amount is 16.2g/min, the laser power is 600-1200W, the scanning speed is 300-500mm/min, the lap joint rate is 40-50%, and the thickness of the obtained coating is 1-1.5mm.
Further, in step 2, the substrate is preheated to a temperature of 400 ℃; in step 4, the tempering temperature is 600 ℃, and the temperature is kept for 2 hours.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) The invention combines the advantages of the metal coating and the ceramic coating, the mass ratio of the ceramic powder in the composite powder reaches 60 percent, the wear resistance and corrosion resistance of the coating are further improved, and the service life of the product is prolonged. The failure mode of the coating is integral stripping, waste residues are not generated, and the quality of products on a production line is affected.
(2) The invention can avoid the problems of poor surface quality and short service life of the prepared coating by adopting the thermal spraying technology which is mainly adopted at present. The coating prepared by the laser cladding process has uniform appearance, distinct internal interface layers and good metallurgical bonding, so that the forming quality and surface continuity of the coating are good.
(3) According to the invention, through process optimization, the proportion of elements, such as the increase of the content of Mo and B elements, can be adjusted, so that the plasticity of the coating can be improved, and the crack sensitivity of the coating can be reduced, thereby having performance advantages.
Drawings
FIG. 1 is an SEM image of a coating according to an embodiment of the invention;
FIG. 2 is an XRD pattern of a coating in an embodiment of the invention;
FIG. 3 is a graph showing the hardness profile of a coating according to an embodiment of the present invention;
FIG. 4 is a graph of the frictional wear profile of a coating in an embodiment of the invention;
FIG. 5 is a graph of the corrosion profile of a coating in an embodiment of the invention.
Detailed Description
For a further understanding of the present invention, the present invention will be described in detail with reference to the drawings and examples.
316L stainless steel was used as a base material, and the element ratios and the process parameters of examples 1 to 3 and comparative examples were shown in Table 1.
TABLE 1 chemical composition of composite powder elements
Example 1
The preparation method of the Co-based alloy powder and WC ceramic powder collaborative strengthening composite coating comprises the following specific steps:
powder mixing: and (3) putting Co-based alloy powder and WC ceramic powder elements with corresponding mass fractions into a ball milling tank, ball milling the above powder for 4 hours by using a planetary ball mill at a rotation speed of 400rpm, fully and uniformly mixing and prealloying. The mixed powder was placed in a drying oven and dried at 120℃for 2 hours.
And (3) treating a base material: and then polishing the substrate until the smooth surface is exposed, cleaning the substrate with alcohol, and then heating the substrate in a resistance heating furnace for 2-3 hours until the temperature of the substrate is increased to 400 ℃.
And (3) laser cladding: the method adopts a semiconductor laser and adopts a coaxial powder feeding mode to prepare the coating, and the process parameters are as follows: the diameter of the circular light spot is 4mm, the powder feeding amount is 16.2g/min, the powder feeding air flow is 6L/min, the protection air flow is 10L/min, the protection air and the powder feeding air are respectively argon and helium with the purity of 99.99%, the cladding power and speed are respectively 600W and 500mm/min, the experiment is carried out by a multi-pass lap joint method, the lap joint rate is 50%, and the thickness of the obtained coating is 1.5mm.
Post-treatment: and (3) placing the prepared sample into a heating furnace, tempering at 600 ℃, preserving heat for 2 hours, and then cooling to room temperature along with the furnace.
Example 2
The preparation method of the Co-based alloy powder and WC ceramic powder collaborative strengthening composite coating comprises the following specific steps:
powder mixing: and (3) putting Co-based alloy powder and WC ceramic powder elements with corresponding mass fractions into a ball milling tank, ball milling the above powder for 4.5 hours by using a planetary ball mill at a rotating speed of 300rpm, fully and uniformly mixing and prealloying. The mixed powder was placed in a drying oven and dried at 100℃for 2.5 hours.
And (3) treating a base material: and then polishing the substrate until the smooth surface is exposed, cleaning the substrate with alcohol, and heating the substrate in a resistance heating furnace for 2-3h until the temperature of the substrate is increased to 400 ℃.
And (3) laser cladding: the method adopts a semiconductor laser and adopts a coaxial powder feeding mode to prepare the coating, and the process parameters are as follows: the diameter of the circular light spot is 4mm, the powder feeding amount is 16.2g/min, the powder feeding air flow is 6L/min, the protection air flow is 10L/min, the protection air and the powder feeding air are respectively argon and helium with the purity of 99.99%, the cladding power and speed are respectively 1200W and 300mm/min, the experiment is carried out by a multi-pass lap joint method, the lap joint rate is 50%, and the thickness of the obtained coating is 1.2mm.
Post-treatment: and (3) placing the prepared sample into a heating furnace, tempering at 600 ℃, preserving heat for 2 hours, and then cooling to room temperature along with the furnace.
Example 3
The preparation method of the Co-based alloy powder and WC ceramic powder collaborative strengthening composite coating comprises the following specific steps:
powder mixing: and (3) putting Co-based alloy powder and WC ceramic powder elements with corresponding mass fractions into a ball milling tank, ball milling the above powder for 4 hours by using a planetary ball mill at a rotating speed of 350rpm, fully and uniformly mixing and prealloying. The mixed powder was placed in a drying oven and dried at 120℃for 2 hours.
And (3) treating a base material: and then polishing the substrate until the smooth surface is exposed, cleaning the substrate with alcohol, and heating the substrate in a resistance heating furnace for 2-3h until the temperature of the substrate is increased to 400 ℃.
And (3) laser cladding: the method adopts a semiconductor laser and adopts a coaxial powder feeding mode to prepare the coating, and the process parameters are as follows: the diameter of the circular light spot is 4mm, the powder feeding amount is 16.2g/min, the powder feeding air flow is 6L/min, the protection air flow is 10L/min, the protection air and the powder feeding air are respectively argon and helium with the purity of 99.99%, the cladding power and the cladding speed are respectively 1000W and 400mm/min, the experiment is carried out by a multi-pass lap joint method, the lap joint rate is 50%, and the thickness of the obtained coating is 1.5mm.
Post-treatment: and (3) placing the prepared sample into a heating furnace, tempering at 600 ℃, preserving heat for 2 hours, and then cooling to room temperature along with the furnace.
Referring to fig. 1, the microscopic morphology of the cladding layer can be found to be of better quality in the cross section of the coating, free of cracks and more pronounced voids, and the unmelted WC particles are more evenly distributed throughout the coating. A strip is generated in the transition areaThe bright bond band indicates that the coating bonds well overall, forming a good metallurgical bond. As a result of analysis of the phase compositions of Sample2 and Sample2 in FIG. 2, the phase composition of the coating layer was mainly (Co, cr, fe) 7 C 3 、(Co、Fe) 23 C 6 、(Co、Fe) 6 C、W 2 C eutectic carbide, achieving the desired result. The microhardness results in FIG. 3 show that the average hardness value reaches 679.8HV, up to 732.6HV, 3.4 times the hardness of the substrate. The addition of the hard phase elements refines the grains in the coating, the hardness of the cladding layer is improved, and the high-temperature friction and wear test of fig. 4 shows that the wear amount of the base material reaches 117.4mg, the wear amount of the composite coating is only 7.6mg, the wear mechanism is adhesive wear and oxidative fatigue wear, the wear morphology of the coating is obviously improved compared with the surface of the base material, and the wear resistance of the composite coating can be obviously improved. FIG. 5 is a graph of surface topography after 15 days of corrosion in Zn-Al solution, with a Stellite6-60WC coating corrosion rate of only 4.45X10 after 15 days of corrosion -3 mg·cm -2· h -1 The corrosion rate of 316L stainless steel is about 0.062 mg.cm -2 ·h -1 The corrosion resistance is improved by about 13.9 times. The composition of the composite coating is very stable, which indicates that Zn-Al liquid does not permeate into the matrix yet, and the coating does not fail yet. From the results of performance tests and analyses of the coatings of examples 1 to 3 and the comparative example in Table 2, the mechanical properties of the composite coating are improved by several times, which shows that the addition of the hard ceramic reinforcing phase obviously enhances the hardness and strength of the alloy. Compared with the comparative example, the high-temperature wear resistance and corrosion resistance of the experimental example are improved to different degrees.
Table 2 coating property distribution tables of examples 1 to 3 and comparative example
The invention and its embodiments have been described above by way of illustration and not limitation, and the invention is illustrated in the accompanying drawings and described in the drawings in which the actual structure is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the structural mode and the embodiments similar to the technical scheme are not creatively designed without departing from the gist of the present invention.
Claims (10)
1. A Co-based alloy powder and WC ceramic powder cooperative reinforcement composite coating is characterized in that: the Co, cr, W, B, C, fe element powder is used as a raw material, a plurality of hard eutectic carbide reinforcing phases are distributed in the coating, the mass ratio of ceramic powder in the composite powder is more than 60%, and the balance is Co-based metal alloy powder.
2. The Co-based alloy powder and WC ceramic powder Co-strengthened composite coating according to claim 1, wherein: the coating raw material comprises the following chemical components in percentage by mass: 27 to 32 percent of Cr, 4 to 6 percent of W, less than or equal to 3.0 percent of Fe, less than or equal to 0.5 to 2.0 percent of Mn, less than or equal to 3 percent of Ni, 2.5 to 5.0 percent of Mo, 2.0 to 2.5 percent of B, 0.9 to 1.2 percent of C and the balance of Co.
3. The Co-based alloy powder and WC ceramic powder Co-strengthened composite coating according to claim 2, wherein: the WC ceramic powder comprises the following chemical components in percentage by mass: c5-8%, and the balance W.
4. A Co-based alloy powder and WC ceramic powder Co-strengthened composite coating according to claim 3, wherein: the reinforcing phases of the plurality of hard eutectic carbides comprise (Co, cr, fe) 7 C 3 、(Co、Fe) 23 C 6 、(Co、Fe) 6 C、W 2 C, performing operation; the composition of the metal alloy includes a metal element Co, cr, W, fe, C.
5. The Co-based alloy powder and WC ceramic powder Co-strengthened composite coating according to claim 4, wherein: the phases of the coating include the eutectic carbide, metal alloy, elemental powders, multi-dimensional fusion of the eutectic carbide and metal alloy with the matrix material of the coating.
6. The Co-based alloy powder and WC ceramic powder Co-strengthened composite coating according to claim 5, wherein: the purity of the elemental powders is greater than 99.9%.
7. The preparation method of the Co-based alloy powder and WC ceramic powder collaborative strengthening composite coating is characterized by comprising the following steps:
step 1: uniformly grinding and mixing raw material powder through a planetary ball mill by an in-situ autogenous method, prealloying, and then placing into a drying box for drying treatment;
step 2: polishing the base material until the smooth surface is exposed, cleaning the base material with alcohol, and preheating the base material in a resistance heating furnace;
step 3: irradiating the surface of the reaction material by adopting a laser cladding technology, wherein a matrix and raw material powder can react in situ in the laser cladding process to generate a hard phase which is distributed in the alloy, so as to form the metal alloy/WC ceramic cooperative reinforcement composite coating;
step 4: and (3) placing the prepared coating into a heating furnace, tempering at high temperature, and then cooling to room temperature along with the furnace.
8. The method for preparing the Co-based alloy powder and WC ceramic powder collaborative strengthening composite coating, which is characterized in that: in the step 1, the ball mill stirs the mixed powder at a rotation speed of 300rpm-400rpm, and the mixed powder is fully and uniformly mixed; and (3) putting the mixed powder into a drying oven at the temperature of 100-120 ℃ for drying.
9. The method for preparing the Co-based alloy powder and WC ceramic powder collaborative strengthening composite coating, which is characterized in that: in step 3, the laser cladding process parameters are as follows: the diameter of the circular light spot is 4mm, the powder feeding amount is 16.2g/min, the laser power is 600-1200W, the scanning speed is 300-500mm/min, the lap joint rate is 40%, and the thickness of the obtained coating is 1-1.5mm.
10. The method for preparing the Co-based alloy powder and WC ceramic powder collaborative strengthening composite coating, which is characterized in that: in the step 2, preheating the base material at a preheating temperature of 400 ℃; in step 4, the tempering temperature is 600 ℃, and the temperature is kept for 2 hours.
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