CN115216768B - Method for preparing composite wear-resistant coating by laser cladding and application thereof - Google Patents
Method for preparing composite wear-resistant coating by laser cladding and application thereof Download PDFInfo
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- CN115216768B CN115216768B CN202211125209.1A CN202211125209A CN115216768B CN 115216768 B CN115216768 B CN 115216768B CN 202211125209 A CN202211125209 A CN 202211125209A CN 115216768 B CN115216768 B CN 115216768B
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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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
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Abstract
The application belongs to the field of laser cladding, and particularly relates to a method for preparing a composite wear-resistant coating by laser cladding, which comprises the steps of carrying out laser cladding repair by adopting prefabricated alloy powder to obtain a cladding layer, wherein the prefabricated alloy powder is a mixture of CoCrFeNiAlx and WO3, and the cladding layer has a BCC-phase and FCC-phase dual-phase structure and contains Al2O3 particles and W particles synthesized in situ. The method solves the technical problem that the cutter and the blade of the shredder are difficult to repair. The method for repairing the cutter of the shredder has the advantages of simple process, controllable cost and reliable performance.
Description
Technical Field
The invention belongs to the field of laser cladding, and particularly relates to the field of preparing a composite wear-resistant coating by laser cladding and the field of repairing hot work die steel by laser cladding.
Background
A double-shaft scrap steel shredder is characterized in that a pair of cutters on one device comprises a plurality of blades, a plurality of shearing cutting edges are distributed on one blade, and the blades are made of high-strength, high-hardness and high-toughness alloy steel and are expensive. When the cutter is used for shearing metal steel, the working environment is extremely severe, and the cutter is required to bear strong friction, extrusion and impact, so that the material still can keep high impact toughness under the condition of high hardness.
Once the cutting edge of the cutter blade of the shredder is large in wear resistance or is locally cracked, the shredder can be sheared continuously or integrally, the reject ratio of the sheared and discharged finished products is reduced, the whole cutter or the whole cutter needs to be scrapped, and the cutter needs to be replaced by a new cutter. Therefore, in fact, the cutting edge only occupies a small part of the whole material weight of the blade, if the whole blade is replaced due to the damaged cutting edge, the maintenance and use cost is too high for a client, so that the problem that how to repair the damaged cutting edge of the blade and the repair cost are controlled at the same time becomes a problem which needs to be solved urgently in the industry.
Therefore, aiming at the failure part of the shredder cutter, the problem of the industry is that the effective surface modification technology can repair the die steel more effectively, prolong the service life of the die steel and ensure the service quality of the shredder cutter after repair.
The laser cladding technique is a surface modification technique in which a cladding material (wire or powder) is melted and solidified on the surface of a substrate simultaneously with the surface layer of the substrate using a high-energy laser beam. It has many advantages, such as: the coating and the substrate are bonded in a metallurgical bonding mode, so that the bonding strength is high; the input power is high, but the total input energy is low, the heat influence on the matrix is small, and the matrix is not easy to deform; when the cladding material is powder, the powder can be prepared according to the needs, and the materials are widely selected. By virtue of the advantages, laser cladding is widely applied to new material preparation, metal part manufacturing and failed metal part repair.
The concept of high-entropy alloy was originally proposed by taiwan academician She Junwei, and the biggest difference from the traditional alloy is that five or more elements are used as basic components instead of one or two elements, and the mole fraction of each element is between 5% and 35%. Due to the particularity of the components of the high-entropy alloy, the high-entropy alloy has a high-entropy effect, a lattice distortion effect, a delayed diffusion effect and a 'cocktail' mixed effect. Due to the characteristics, the high-entropy alloy has excellent performances of high strength and hardness, good wear resistance, good corrosion resistance and the like. The laser cladding technology is utilized to prepare a layer of high-entropy alloy coating on the surface of the hot-work die steel, or repair the hot-work die, and the service life of the alloy coating is expected to be greatly prolonged.
Disclosure of Invention
The invention provides a method for laser cladding coating and a method for repairing a shredder cutter by using the method, which have the advantages of simple process, controllable cost and reliable performance.
A method for preparing a composite wear-resistant coating by laser cladding,
performing laser cladding repair by adopting prefabricated alloy powder to obtain a cladding layer; wherein the laser deposition process comprises the steps of controlling the laser power to be 2200-4200W, controlling the scanning speed of inert protective gas flow to be 1-30L/min to be 12-20 mm/s, and carrying out four-point coaxial powder feeding with the powder feeding amount of 2.5-6.5 g/s and the lap joint amount of 50-55%; the pre-alloyed powder is CoCrFeNiAl x With WO 3 A mixture of (a); said WO 3 Coating of nanoparticlesIn the CoCrFeNiAl x On the particles.
CoCrFeNiAl in the pre-alloyed powder x X of (b) is 1.0 to 1.5.
The cladding layer has a BCC phase and a FCC phase and contains in-situ synthesized Al 2 O 3 Particles and W particles.
The preparation process of the pre-alloyed powder comprises the following steps:
1) Adding CoCrFeNiAlx medium entropy alloy powder into an ammonium tungstate solution according to a set proportion to obtain a mixed solution;
2) Heating the mixed solution to 60-80 ℃, adding citric acid, and stirring for 4-8h, wherein the molar ratio of the citric acid to the ammonium tungstate is 2.5-3.5: 1, then carrying out vacuum drying to obtain a mixed precursor;
3) Placing the mixed precursor obtained in the step 2) in an inert atmosphere for calcination treatment to obtain pre-alloy powder;
in step 1), coCrFeNiAl x The molar ratio of the ammonium tungstate to the ammonium tungstate in the solution is 1:0.1 to 0.5;
in step 1), coCrFeNiAl x The average particle size of the medium-entropy alloy powder is 30-75 mu m;
in the step 2), the vacuum drying temperature is 60-80 ℃, and the drying time is 16-24 h;
in the step 3), calcining is carried out in an argon atmosphere, wherein the calcining temperature is 520-650 ℃;
conversion of ammonium tungstate in mixed precursors to nano-WO by calcination 3 Thereby obtaining a surface coated with WO 3 Nanoparticulate CoCrFeNiAl x And (3) granules.
In addition, the invention also provides a method for repairing the cutter of the shredder through laser cladding, which comprises the following steps
a) The method comprises the following steps Carrying out pretreatment such as cleaning, sand blasting and the like on the surface of a die to be repaired;
b) The method comprises the following steps Performing stress relief annealing on the die, preserving heat at 220-300 ℃ for 1-24 hours to perform stress relief annealing, and releasing internal stress of the die in the working and damage processes;
c) The method comprises the following steps By adopting the method for preparing the composite wear-resistant coating by laser cladding, cladding repair is carried out on the surface of the cutter of the shredder;
d) And repairing the die for subsequent treatment, and grinding the cladding layer of the repaired die to achieve the designed size and precision of the die.
The invention selects CoCrFeNiAl x On one hand, the medium-entropy alloy has low melting point and large atomic radius of Al element, and can cause lattice distortion of the high-entropy alloy when the Al element is added into a coating, the lattice distortion can hinder the diffusion of atoms and further contribute to refining crystal grains, the lattice distortion in the high-entropy alloy is aggravated along with the increase of the content of the Al element, the phase structure of the alloy is changed from FCC (fluid catalytic cracking) to BCC (cubic carbon black), and the strength and hardness of the high-entropy alloy are greatly strengthened. On the other hand, in the laser cladding process, coCrFeNiAl x Granules and coated WO 3 In-situ reaction between nano particles and Al reduction of WO 3 Tungsten in (1) to Al 2 O 3 Particles and W. Al (Al) 2 O 3 The particles are formed and uniformly dispersed and distributed as hard ceramic particles, so that the hardness and the wear resistance of the remelted layer are effectively improved. W enters the high-entropy alloy layer after being reduced, so that the lattice distortion effect of the heavy-entropy alloy layer is increased, the element disorder effect in the high-entropy alloy is increased, and the hardness of the cladding layer is further increased. Meanwhile, W can improve the tempering stability of the cladding layer and effectively improve the wear resistance of the cladding layer in the working environment of the cutter of the shredder.
With conventional direct addition of Al 2 O 3 Ceramic particles compared to Al in the present invention 2 O 3 The WO in the pre-alloyed powder is generated by direct reaction in the laser cladding process and has small size, and the WO in the pre-alloyed powder is prepared by a water-phase cladding method 3 Uniformly coated with CoCrFeNiAl x The surface of the particles can ensure Al generated by reaction in the cladding process 2 O 3 Can be uniformly dispersed and distributed, and avoids directly adopting Al 2 O 3 Al in the cladding layer after cladding when ceramic particles are mixed with powder 2 O 3 The ceramic particles are agglomerated, and the ceramic phase is distributed unevenly, so that the wear resistance of the coating is effectively improved.
Drawings
FIG. 1: and (5) carrying out a photo of the appearance of the coating after laser cladding.
FIG. 2 is a drawing: and (5) a picture of the wear appearance of the coating after the wear test.
Detailed Description
Example 1
Preparing the precast alloy powder for cladding:
1) According to the molar ratio of 1:0.2 adding CoCrFeNiAl medium entropy alloy powder into ammonium tungstate solution to obtain mixed solution;
2) Heating the mixed solution to 60 ℃, adding citric acid, and stirring for 5 hours, wherein the molar ratio of the citric acid to the ammonium tungstate is 2.8:1, then carrying out vacuum drying to obtain a mixed precursor;
3) And (3) calcining the mixed precursor obtained in the step 2) for 0.5h at 550 ℃ in an inert atmosphere to obtain the pre-alloyed powder.
Cladding is carried out on the surface of the H13 hot-work die steel, and the laser cladding process of the surface of the hot-work die steel is as follows:
a) The method comprises the following steps Cleaning the surface of the H13 die steel;
b) The method comprises the following steps And 3) performing laser deposition repair by adopting the prefabricated alloy powder prepared in the step 3), wherein the laser deposition process comprises the steps of controlling the laser power to be 2800W, controlling the scanning speed of inert protective gas to be 13mm/s at the flow rate of 15L/min, and testing the cladding layer by four-point coaxial powder feeding with the powder feeding amount of 4.5g/s and the lap joint amount of 50%, and the specific result is shown in Table 1.
Example 2
Preparing prefabricated alloy powder for cladding:
1) According to the formula CoCrFeNiAl 1.2 The molar ratio of ammonium tungstate in the solution is 1:0.3 adding CoCrFeNiAl 1.2 Adding the medium-entropy alloy powder into an ammonium tungstate solution to obtain a mixed solution;
2) Heating the mixed solution to 70 ℃, adding citric acid, and stirring for 6 hours, wherein the molar ratio of the citric acid to the ammonium tungstate is 3:1, then carrying out vacuum drying to obtain a mixed precursor;
3) And 3) calcining the mixed precursor obtained in the step 2) for 0.5h at 520 ℃ in an inert atmosphere to obtain the pre-alloy powder.
Cladding is carried out on the surface of the H13 hot-work die steel, and the laser cladding process of the surface of the hot-work die steel is as follows:
a) The method comprises the following steps Cleaning the surface of the H13 die steel;
b) The method comprises the following steps Performing laser cladding repair by adopting prefabricated alloy powder to obtain a sample 1; in the laser cladding process, the laser power is 3200W, the scanning speed is 15mm/s by controlling the inert shielding gas flow to be 17L/min, the powder feeding amount is 5.5g/s by four-point coaxial powder feeding, the lap joint amount is 55%, and the cladding layer is tested, wherein the specific result is shown in Table 1.
Example 3
Preparing prefabricated alloy powder for cladding:
1) According to CoCrFeNiAl 1.5 The molar ratio of ammonium tungstate in the solution is 1:0.4 CoCrFeNiAl 1.5 Adding the medium-entropy alloy powder into an ammonium tungstate solution to obtain a mixed solution;
2) Heating the mixed solution to 80 ℃, adding citric acid, and stirring for 5 hours, wherein the molar ratio of the citric acid to the ammonium tungstate is 3.5:1, then carrying out vacuum drying to obtain a mixed precursor;
3) And (3) calcining the mixed precursor obtained in the step 2) for 0.5h at 650 ℃ in an inert atmosphere to obtain the pre-alloyed powder.
Cladding is carried out on the surface of the H13 hot-work die steel, and the laser cladding process of the surface of the hot-work die steel is as follows:
a) The method comprises the following steps Cleaning the surface of the H13 die steel;
b) The method comprises the following steps Performing laser cladding repair by adopting prefabricated alloy powder to obtain a sample 1; in the laser deposition process, the laser power is 3500W, the scanning speed of the inert protective gas flow is controlled to be 25L/min and 18mm/s, the powder feeding amount is 6.5g/s and the lap joint amount is 55 percent by four-point coaxial powder feeding, and the specific results are shown in table 1.
Comparative example 1
The CoCrFeNi intermediate entropy powder is adopted to clad on the surface of the H13 hot-work die steel, and the laser cladding process of the surface of the hot-work die steel is the same as that of the embodiment 1.
Comparative example 2
Adopts CoCrFeNi medium entropy powder alloy powder and Al 2 O 3 The mixed powder is clad on the surface of H13 hot-work die steel, and the laser cladding process of the surface of the hot-work die steel is the same as that in the embodiment 1. Wherein in the mixed powder, the average grain size of the CoCrFeNi intermediate entropy alloy powder is 35-65 mu m, and Al 2 O 3 The average grain size of the powder alloy powder is 50-100 mu m, and 10wt% of Al is added into the CoCrFeNi medium entropy powder alloy powder 2 O 3 Mixing the powders, and repeatedly mixing the powders in a planet ball mill for 6 hours to obtain CoCrFeNi entropy-containing powder alloy powder and Al for cladding 2 O 3 The mixed powder of (1).
And (3) carrying out phase structure analysis on the surface of the laser remelting high-entropy alloy coating by adopting a D/MAX2500PC type X-ray diffractometer (XRD). And (3) performing a coating friction wear test by using a high-frequency reciprocating friction wear testing machine, wherein the grinding wheel is made of GCr15 steel, the load is 8N, and the testing time is 30 min. The hardness of the sample was measured by using an HV-1000 type microhardness tester, and 15 sets of data were measured at different points of the remelted layer, respectively, and the average value was determined as the surface microhardness value.
TABLE 1
The samples of examples 1-3 and comparative examples 1-2 were incubated at 800 ℃ for 8 hours to simulate the high temperature tempering stability. See table 2 for specific results.
TABLE 2
As can be seen from the table 1, the hardness and the wear resistance of the substrate of the laser deposited high-entropy alloy coating are obviously improved compared with those of the H13 substrate. Compared with the comparative example 1 in which CoCrFeNi intermediate entropy alloy powder is only adopted for remelting, the hardness and the wear resistance of the embodiments 1-3 of the invention are both obviously improved, on one hand, due to the addition of Al, the high entropy alloy coating has a dual-phase structure of FCC + BCC, and the hardness is increased; on the other hand also benefit from laserAl generated in situ during deposition 2 O 3 Hard particles, and W strengthening. In comparison with comparative example 2, in which the hard phase was also added, the microhardness of examples 1 to 3 according to the present invention was substantially equal to that of comparative example 2, but the wear resistance was significantly improved as compared with comparative example 2. This is mainly due to Al in comparative example 2 2 O 3 The mixed powder is adopted, the dispersion uniformity is obviously reduced compared with the invention, agglomeration phenomenon exists, the agglomeration can cause local brittleness increase, the hard strengthening phase can fall off in the abrasion process, and the friction coefficient and the abrasion loss are increased.
As can be seen from Table 2, the wear resistance of inventive examples 1-3 after high temperature incubation was significantly better than the substrates of comparative examples 1, 2 and H13 due to the addition of W. This indicates that W plays a significant role in improving the high temperature tempering resistance of the coating.
The invention has been described above by way of example, and it is obvious that the specific implementation of the invention is not limited to the above-mentioned manner, and the invention can be used for repairing the plane of a blade or the edge with a special-shaped structure. The invention is in the scope of protection only if various improvements are made by the method conception and the technical scheme of the invention, or the method is directly applied to other occasions without improvement.
Claims (8)
1. A method for preparing a composite wear-resistant coating by laser cladding is characterized by comprising the following steps:
performing laser cladding repair by adopting prefabricated alloy powder to obtain a cladding layer; wherein the laser deposition process comprises the steps of controlling the laser power to be 2200-4200W, controlling the scanning speed of inert protective gas flow to be 1-30L/min to be 12-20 mm/s, and carrying out four-point coaxial powder feeding with the powder feeding amount of 2.5-6.5 g/s and the lap joint amount of 50-55%; the pre-alloyed powder is CoCrFeNiAl x With WO 3 A mixture of (a); said WO 3 Coating the CoCrFeNiAl with nanoparticles x On particles, wherein CoCrFeNiAl is in the pre-alloy powder x X of (b) is 1.0 to 1.5.
2. The laser cladding prepared composite wear-resistant coating of claim 1Wherein the cladding layer has a BCC phase and a FCC phase and contains nano Al synthesized in situ 2 O 3 Particles and W particles.
3. The method for preparing the composite wear-resistant coating by laser cladding according to claim 2, wherein the preparation process of the pre-alloyed powder comprises the following steps:
1) Adding CoCrFeNiAlx medium-entropy alloy powder into an ammonium tungstate solution according to a set proportion to obtain a mixed solution;
2) Heating the mixed solution to 60-80 ℃, adding citric acid, and stirring for 4-8h, wherein the molar ratio of the citric acid to the ammonium tungstate is 2.5-3.5: 1, then carrying out vacuum drying to obtain a mixed precursor;
3) And (3) placing the mixed precursor obtained in the step 2) in an inert atmosphere for calcination treatment to obtain the pre-alloyed powder.
4. The method for laser cladding composite wear-resistant coating according to claim 3, wherein in step 1), coCrFeNiAl x The molar ratio of the ammonium tungstate to the ammonium tungstate in the solution is 1:0.1 to 0.5.
5. The method for laser cladding composite wear-resistant coating according to claim 3, wherein in step 1), coCrFeNiAl x The average particle size of the medium entropy alloy powder is 30-75 μm.
6. The method for preparing the composite wear-resistant coating by laser cladding according to claim 3, wherein in the step 2), the vacuum drying temperature is 60-80 ℃, and the drying time is 16-24 h.
7. The method for preparing the composite wear-resistant coating by laser cladding according to claim 3, wherein in the step 3), the calcination is performed in an argon atmosphere, and the calcination temperature is 520-650 ℃.
8. A method of repairing shredder cutters by laser cladding includes the following steps
a) The method comprises the following steps Cleaning and sandblasting the cutter surface of the shredder to be repaired;
b) The method comprises the following steps Performing stress relief annealing on the cutter, and performing stress relief annealing at 220-300 ℃ for 1-24 hours to release internal stress of the cutter in the working and damage processes;
c) The method comprises the following steps The method for preparing the composite wear-resistant coating by laser cladding according to any one of claims 1 to 7, wherein cladding repair is carried out on the surface of a cutter of a shredder;
d) The method comprises the following steps And repairing the cutter of the shredder for subsequent treatment, and grinding the melt-coated layer of the repaired cutter of the shredder to reach the designed size and precision of the cutter.
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