CN117107236B - Middle groove alloy coating and laser cladding process thereof - Google Patents
Middle groove alloy coating and laser cladding process thereof Download PDFInfo
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- CN117107236B CN117107236B CN202311364357.3A CN202311364357A CN117107236B CN 117107236 B CN117107236 B CN 117107236B CN 202311364357 A CN202311364357 A CN 202311364357A CN 117107236 B CN117107236 B CN 117107236B
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- 238000000576 coating method Methods 0.000 title claims abstract description 102
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000008569 process Effects 0.000 title claims abstract description 37
- 238000004372 laser cladding Methods 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 51
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 46
- 239000011247 coating layer Substances 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 34
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 24
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 238000005253 cladding Methods 0.000 claims abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 20
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- 238000001035 drying Methods 0.000 claims abstract description 17
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 16
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 16
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 241000779819 Syncarpia glomulifera Species 0.000 claims abstract description 10
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 claims abstract description 10
- 239000001739 pinus spp. Substances 0.000 claims abstract description 10
- 229940036248 turpentine Drugs 0.000 claims abstract description 10
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 8
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229950006389 thiodiglycol Drugs 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 238000005488 sandblasting Methods 0.000 claims description 10
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 7
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 7
- 229940009827 aluminum acetate Drugs 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 7
- 229940078494 nickel acetate Drugs 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 8
- 229910000617 Mangalloy Inorganic materials 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 oxalate ions Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The application relates to the technical field of high-entropy alloy coatings, and particularly discloses a middle groove alloy coating and a laser cladding process thereof, comprising the following steps: s1: pretreatment; s2: mixing metal acetate and absolute ethyl alcohol uniformly, then adding oxalic acid, triethylamine and 1, 3-propane sultone, stirring, and boiling to obtain a precursor liquid; s3: adding quaternary ammonium base and thiodiglycol into the precursor liquid, stirring, filtering, washing and drying to obtain a metal salt oligomer; s4: mixing turpentine, rosin and phosphatidylcholine to prepare a binder; then uniformly mixing metal salt oligomer, high-purity aluminum powder, high-purity cobalt powder, high-purity chromium powder, high-purity iron powder, high-purity nickel powder and high-purity copper powder to prepare high-entropy alloy powder; s5: uniformly mixing the binder and the high-entropy alloy powder, and coating the mixture on the surface of the middle groove to form a coating layer; s6: and carrying out cladding treatment on the coating layer. The middle groove alloy coating prepared by the method has the advantage of good mechanical property.
Description
Technical Field
The application relates to the technical field of alloy coating cladding, in particular to a middle groove alloy coating and a laser cladding process thereof.
Background
Coal is a very important energy source, mainly for the production of electricity or heat energy by combustion. Is also an important raw material in metallurgical and chemical industries, and is used for refining metals or producing chemical fertilizers and a plurality of chemical products. At present, in the coal transportation process, a scraper conveyor is generally adopted, a middle groove is an important component part of a chain transmission system of the scraper conveyor, and is directly contacted with coal, rock and gravel in the transportation operation process, because the resistance of the coal and the rock is overlarge and the stress is uneven, the stress at a plurality of positions on the surface of the middle groove can exceed the allowable stress under the full-load condition, so that the surface of the middle groove is damaged, and the service life of the middle groove can be directly influenced by the performance of the middle groove.
In order to reduce the damage of coal and other materials to the middle groove, a layer of alloy material is coated on the surface of the middle groove, a generally adopted coating method is laser cladding, and the alloy powder is melted and cooled by using the extremely high energy of laser to form a cladding alloy coating, so that the hardness and the wear resistance of the surface of the middle groove are improved. Moreover, the technical staff also carries out related researches on alloy materials to develop high-entropy alloy, wherein the high-entropy alloy consists of 5 or more elements, and the atomic fraction of each element is 5-35%, wherein the elements with higher utilization rate mainly comprise Al, co, cr, fe, mn, ni, ti and the like, and the hardness and corrosion resistance of the cladding alloy coating are further improved by adopting the high-entropy alloy as the cladding material.
The performance of the high-entropy alloy material is much better than that of the conventional alloy material, but in the process of forming the alloy, uneven distribution of metal elements can occur in the high-entropy alloy coating, and bad phenomena such as dislocation, segregation and the like can occur, so that the performance advantage of the high-entropy alloy material is not fully exerted.
Disclosure of Invention
In order to further improve the performance of the middle groove alloy coating, the application provides a middle groove alloy coating and a laser cladding process thereof.
The application provides a middle groove alloy coating and a laser cladding process thereof, which adopts the following technical scheme:
in a first aspect, the present application provides a laser cladding process for a mid-groove alloy coating, comprising the steps of:
s1: pretreatment: performing sand blasting and polishing treatment on the surface of the middle groove to remove greasy dirt and rust impurities on the surface;
s2: according to weight portions, 30-50 portions of metal acetate and 200-300 portions of absolute ethyl alcohol are taken and placed into a reaction kettle to be uniformly mixed, then 60-75 portions of oxalic acid, 15-20 portions of triethylamine and 5-10 portions of 1, 3-propane sultone are added to be continuously stirred for 1-1.5 hours, and then the precursor liquid is obtained after the mixture is treated for 30-50 minutes under the boiling condition; the metal acetate consists of nickel acetate, cobalt acetate and aluminum acetate according to a molar ratio of 1:1:0.5;
s3: adding 1-2.5 parts of quaternary ammonium base and 3-5 parts of thiodiglycol into the precursor liquid, continuously stirring for 10-20min, and then filtering, washing and drying to obtain a metal salt oligomer;
s4: according to weight portions, 25 to 35 portions of turpentine, 7 to 12 portions of rosin and 2 to 3 portions of phosphatidylcholine are taken and evenly mixed to prepare the adhesive; then uniformly mixing metal salt oligomer, high-purity aluminum powder, high-purity cobalt powder, high-purity chromium powder, high-purity iron powder, high-purity nickel powder and high-purity copper powder to prepare high-entropy alloy powder;
s5: uniformly mixing a binder and high-entropy alloy powder to prepare a coating material, uniformly coating the coating material on the surface of a middle groove, and drying to form a coating layer;
s6: under the protection of inert gas, a plurality of laser cladding technologies are adopted to treat the coating layer, and the control process parameters are as follows: the laser power is 1.3-1.5KW, the scanning speed is 6-10mm/s, and the alloy coating is obtained after cladding the coating layer under the protection of inert gas.
Through adopting above-mentioned technical scheme, this application forms the coating at middle part groove surface earlier, makes the intensive mixing dispersion between each high entropy alloy raw materials, then adopts the mode of laser cladding, forms the alloy coating that has high element homogeneity to the performance advantage of full play high entropy alloy material obtains better mechanical properties.
In the preparation process of the coating layer, firstly, absolute ethyl alcohol is used for dissolving metal acetate to prepare a homogeneous system, then oxalic acid, triethylamine and 1, 3-propane sultone are added, a part of metal ions are combined with oxalate ions, and meanwhile, crystallization phase change is carried out under the mixing action of the triethylamine, so that a micro-nano crystal nucleus is formed as a growth center. Then adding quaternary ammonium base and thiodiglycol, and crystallizing and growing the rest metal ions and oxalic acid radical ions by taking the micro-nano crystal nucleus as the center to form the metal salt oligomer. In addition, in the growth process, the 1, 3-propane sultone forms a dynamic molecular resistance layer on the surface of the micro-nano crystal nucleus, delays the diffusion deposition rate of metal ions, refines the crystallization process, improves the distribution uniformity of each metal ion in the metal salt oligomer, thereby improving the compactness of the coating, reducing dendrite deflection, obtaining better element uniformity and microstructure stability and further improving the performance of the high-entropy alloy coating.
In addition, the adhesive is prepared by mixing turpentine, rosin and phosphatidylcholine, and then the adhesive is uniformly mixed with high-entropy alloy powder, wherein the high-entropy alloy powder can form anchoring sites in a turpentine-rosin solution system, choline is uniformly dispersed around the anchoring sites, the effect of stabilizing a cladding material system is achieved through the physical and chemical effects among molecules, the migration speed of metal elements is regulated and controlled in a proper range, the interaction and lattice distortion among metal atoms are weakened to a certain extent, the reduction of the stacking fault energy and the increase of the flow stress are realized, the diffusivity and the phase change speed of solid solutions are improved, and nano twin crystals are activated, so that the formed alloy coating exerts more excellent mechanical properties.
Preferably, in the step S3, the quaternary ammonium base is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
By adopting the technical scheme, the variety composition of the quaternary ammonium base is optimized and adjusted, the end capping effect and the steric hindrance effect of the quaternary ammonium base molecule are balanced, the crystallization state of the metal salt oligomer is improved, and the element uniformity of the alloy coating is further improved.
Preferably, in the step S3, the quaternary ammonium base is composed of tetramethylammonium hydroxide and tetrabutylammonium hydroxide according to a mass ratio of 1:0.5.
By adopting the technical scheme, the composition ratio of the quaternary ammonium base is further screened and tested, the crystallization process is further refined, and the metal salt oligomer with more disordered and uniform crystallization morphology is obtained.
Preferably, in the step S4, the molar ratio of the metal salt oligomer to the high-purity aluminum powder to the high-purity cobalt powder to the high-purity chromium powder to the high-purity iron powder to the high-purity nickel powder to the high-purity copper powder is controlled to be (0.3-0.6): 1:1:1:1:1:1, based on oxalic acid root.
By adopting the technical scheme, the molar ratio of the metal salt oligomer, the high-purity aluminum powder, the high-purity cobalt powder, the high-purity chromium powder, the high-purity iron powder and the high-purity nickel powder is optimized and adjusted, the vacancy diffusion process among metal atoms in the solid solution is improved, the average energy after diffusion is balanced, the diffusivity and the phase change speed of the solid solution are further improved, and the performance of the alloy coating is improved.
Preferably, in the step S5, the mass ratio of the binder to the high-entropy alloy powder is (0.08-0.12): 1.
By adopting the technical scheme, too much binder is added, more pores are easily generated in the cladding process, so that the alloy coating is cracked, and when the binder is excessively added, no perfect point contact is formed among particles of the high-entropy alloy powder, so that the alloy coating is easy to dent, and therefore, the mass ratio of the binder to the high-entropy alloy powder is tested and screened, and the structural state of the alloy coating is further improved.
Preferably, in the step S5, the drying is performed by heating from 20 ℃ to 100 ℃ at a heating rate of 8 ℃/min, and preserving heat at 100 ℃ for 120min; then heating from 100 ℃ to 200 ℃ at a heating rate of 12 ℃/min, and preserving heat for 10min at the temperature of 200 ℃; then cooling from 200 ℃ to 120 ℃ at a cooling rate of 8.5 ℃/min, and finally naturally cooling to room temperature.
By adopting the technical scheme, the drying temperature is optimized and adjusted, the microstructure state of the coating layer is improved, and the element uniformity is improved.
Preferably, in the step S4, the average particle size of the high-purity aluminum powder, the high-purity cobalt powder, the high-purity chromium powder, the high-purity iron powder, the high-purity nickel powder, and the high-purity copper powder is 10-20 μm.
By adopting the technical scheme, the average particle size of the high-purity aluminum powder, the high-purity cobalt powder, the high-purity chromium powder, the high-purity iron powder and the high-purity nickel powder is optimized and adjusted, so that the specific surface area of the solid particles is moderate, the rheological property is better, and the forming and cladding are facilitated.
Preferably, in the step S1, the surface roughness Ra of the middle groove after sand blasting and polishing treatment is less than or equal to 0.25 μm.
Preferably, in the step S5, the thickness of the coating layer is 0.8-1.5mm.
In a second aspect, the present application provides a middle trough alloy coating disposed on a surface of a middle trough substrate, the middle trough alloy coating being made by the laser cladding process described above.
In summary, the present application has the following beneficial effects:
1. according to the preparation method, the metal salt oligomer is prepared by adopting a phase-change crystallization process, then the metal salt oligomer is uniformly mixed with high-purity aluminum powder, high-purity cobalt powder, high-purity chromium powder, high-purity iron powder and high-purity nickel powder to prepare high-entropy alloy powder, a coating layer with high dispersion uniformity is formed after the high-entropy alloy powder is mixed with a binder, an alloy coating layer with high element uniformity and microstructure stability is obtained through a laser cladding technology, the advantages of high-entropy alloy are fully exerted, and the mechanical property of the alloy coating layer is further improved.
2. The composition of the quaternary ammonium hydroxide is optimized and regulated, the molar ratio of the metal salt oligomer to the high-purity aluminum powder to the high-purity cobalt powder to the high-purity chromium powder to the high-purity iron powder to the high-purity nickel powder and the mass ratio of the binder to the high-entropy alloy powder are further improved, the dispersion uniformity of the metal element in the coating layer is further improved, and the diffusivity and the phase change speed of the solid solution in the cladding process are improved, so that the mechanical property of the alloy coating layer is improved.
3. The middle groove alloy coating prepared by the laser cladding process of the middle groove alloy coating has good mechanical properties, and the wear resistance and hardness are greatly improved, so that the service life of the middle groove can be prolonged.
Drawings
Fig. 1: SEM test chart of the mid-groove alloy coating of example 1 of the present application.
Fig. 2: SEM test chart of the mid-groove alloy coating of example 2 of the present application.
Fig. 3: SEM test chart of the mid-groove alloy coating of example 3 of the present application.
Fig. 4: SEM test chart of the mid-groove alloy coating of comparative example 1 of the present application.
Fig. 5: SEM test chart of the mid-groove alloy coating of comparative example 2 of the present application.
Fig. 6: SEM test chart of the mid-groove alloy coating of comparative example 3 of the present application.
Detailed Description
The present application is described in further detail below with reference to examples.
The raw materials of the examples and comparative examples herein are commercially available in general unless otherwise specified.
Examples
Example 1
The laser cladding process of the middle groove alloy coating of the embodiment comprises the following steps:
s1: pretreatment: taking a middle groove sample made of 16 manganese steel, carrying out sand blasting on the surface of the middle groove, and then carrying out sand sanding and polishing treatment to remove greasy dirt and rust oxide impurities on the surface of the middle groove, so that the roughness Ra of the surface of the middle groove is less than or equal to 0.25 mu m;
s2: placing 300g of metal acetate and 2000g of absolute ethyl alcohol into a reaction kettle with a stirring and temperature control device, uniformly mixing, adding 600g of oxalic acid, 200g of triethylamine and 50g of 1, 3-propane sultone, continuously stirring for 1h, and then treating for 30min under a boiling condition to obtain a precursor solution; the metal acetate consists of nickel acetate, cobalt acetate and aluminum acetate according to the mol ratio of 1:1:0.5;
s3: adding 10g of quaternary ammonium base and 50g of thiodiglycol into the precursor liquid, continuously stirring for 10min, and then filtering, washing and drying to obtain a metal salt oligomer;
s4: according to the weight parts, taking 350g of turpentine, 70g of rosin powder and 20g of phosphatidylcholine, uniformly mixing in a beaker, and filtering to prepare a clear adhesive; then uniformly mixing metal salt oligomer, high-purity aluminum powder, high-purity cobalt powder, high-purity chromium powder, high-purity iron powder, high-purity nickel powder and high-purity copper powder according to a molar ratio of 0.3:1:1:1:1:1:1 to obtain high-entropy alloy powder, wherein the molar amount of the metal salt oligomer is calculated by oxalic acid root;
s5: taking a binder and high-entropy alloy powder according to the mass ratio of 0.12:1, placing the binder and the high-entropy alloy powder in a sealed stirring tank under a dry environment, uniformly mixing to prepare a mud-shaped coating, uniformly coating the coating on the surface of a middle groove, heating the coating from 20 ℃ to 100 ℃ at the heating rate of 10 ℃/min, and drying the coating at the temperature of 100 ℃ for 3 hours to form a coating layer, so that the surface of the cladding layer is kept flat and smooth, and the thickness of the coating layer is 0.8mm;
s6: the coating layer is treated by adopting a multi-channel laser cladding technology under the protection of argon, and the technological parameters are controlled as follows: the laser power is 1.3KW, the scanning speed is 10mm/s, the spot diameter is 3mm, and the alloy coating is obtained after cladding the coating layer under the protection of argon.
Wherein the quaternary ammonium base is tetraethylammonium hydroxide. The purity of the high-purity aluminum powder, the high-purity cobalt powder, the high-purity chromium powder, the high-purity iron powder, the high-purity nickel powder and the high-purity copper powder is 4N, and the average grain diameter is 10 mu m. The rosin powder has a particle size of 200 mesh.
Example 2
The laser cladding process of the middle groove alloy coating of the embodiment comprises the following steps:
s1: pretreatment: taking a middle groove sample made of 16 manganese steel, carrying out sand blasting on the surface of the middle groove, and then carrying out sand sanding and polishing treatment to remove greasy dirt and rust oxide impurities on the surface of the middle groove, so that the roughness Ra of the surface of the middle groove is less than or equal to 0.25 mu m;
s2: putting 500g of metal acetate and 3000g of absolute ethyl alcohol into a reaction kettle with a stirring and temperature control device, uniformly mixing, adding 750g of oxalic acid, 150g of triethylamine and 100g of 1, 3-propane sultone, continuously stirring for 1.5h, and then treating for 50min under the boiling condition to obtain a precursor solution; the metal acetate consists of nickel acetate, cobalt acetate and aluminum acetate according to the mol ratio of 1:1:0.5;
s3: adding 25g of quaternary ammonium base and 30g of thiodiglycol into the precursor liquid, continuously stirring for 20min, and then filtering, washing and drying to obtain a metal salt oligomer;
s4: according to the weight parts, mixing 250g of turpentine, 120g of rosin powder and 30g of phosphatidylcholine uniformly in a beaker, and filtering to prepare a clear adhesive; then uniformly mixing metal salt oligomer, high-purity aluminum powder, high-purity cobalt powder, high-purity chromium powder, high-purity iron powder, high-purity nickel powder and high-purity copper powder according to a molar ratio of 0.6:1:1:1:1:1:1 to obtain high-entropy alloy powder, wherein the molar amount of the metal salt oligomer is calculated by oxalic acid root;
s5: taking a binder and high-entropy alloy powder according to the mass ratio of 0.08:1, placing the binder and the high-entropy alloy powder in a sealed stirring tank under a dry environment, uniformly mixing to prepare a mud-shaped coating material, uniformly coating the coating material on the surface of a middle groove, heating the coating material from 20 ℃ to 100 ℃ at a heating rate of 8 ℃/min, and preserving heat for 120min at a temperature of 100 ℃; then heating from 100 ℃ to 200 ℃ at a heating rate of 12 ℃/min, and preserving heat for 10min at the temperature of 200 ℃; then cooling from 200 ℃ to 120 ℃ at a cooling speed of 8.5 ℃/min, and naturally cooling to room temperature to form a coating layer, so that the surface of the cladding layer is kept smooth, and the thickness of the coating layer is 1.5mm;
s6: the coating layer is treated by adopting a multi-channel laser cladding technology under the protection of argon, and the technological parameters are controlled as follows: the laser power is 1.5KW, the scanning speed is 6mm/s, the spot diameter is 3mm, and the alloy coating is obtained after cladding the coating under the protection of argon.
Wherein the quaternary ammonium base is tetrapropylammonium hydroxide. The purity of the high-purity aluminum powder, the high-purity cobalt powder, the high-purity chromium powder, the high-purity iron powder, the high-purity nickel powder and the high-purity copper powder is 4N, and the average grain diameter is 20 mu m. The rosin powder has a particle size of 200 mesh.
Example 3
The laser cladding process of the middle groove alloy coating of the embodiment comprises the following steps:
s1: pretreatment: taking a middle groove sample made of 16 manganese steel, carrying out sand blasting on the surface of the middle groove, and then carrying out sand sanding and polishing treatment to remove greasy dirt and rust oxide impurities on the surface of the middle groove, so that the roughness Ra of the surface of the middle groove is less than or equal to 0.25 mu m;
s2: putting 350g of metal acetate and 2500g of absolute ethyl alcohol into a reaction kettle with a stirring and temperature control device, uniformly mixing, adding 700g of oxalic acid, 175g of triethylamine and 80g of 1, 3-propane sultone, continuously stirring for 1.5h, and then treating for 50min under a boiling condition to obtain a precursor solution; the metal acetate consists of nickel acetate, cobalt acetate and aluminum acetate according to the mol ratio of 1:1:0.5;
s3: adding 30g of quaternary ammonium base and 35g of thiodiglycol into the precursor liquid, continuously stirring for 15min, and then filtering, washing and drying to obtain a metal salt oligomer;
s4: according to the weight parts, 300g of turpentine, 100g of rosin powder and 25g of phosphatidylcholine are uniformly mixed in a beaker, and a clear adhesive is prepared after filtration; then uniformly mixing metal salt oligomer, high-purity aluminum powder, high-purity cobalt powder, high-purity chromium powder, high-purity iron powder, high-purity nickel powder and high-purity copper powder according to a molar ratio of 0.36:1:1:1:1:1:1 to obtain high-entropy alloy powder, wherein the molar amount of the metal salt oligomer is calculated by oxalic acid root;
s5: taking a binder and high-entropy alloy powder according to the mass ratio of 0.1:1, placing the binder and the high-entropy alloy powder in a sealed stirring tank under a dry environment, uniformly mixing to prepare a mud-shaped coating material, uniformly coating the coating material on the surface of a middle groove, heating the coating material from 20 ℃ to 100 ℃ at a heating rate of 8 ℃/min, and preserving heat for 120min at a temperature of 100 ℃; then heating from 100 ℃ to 200 ℃ at a heating rate of 12 ℃/min, and preserving heat for 10min at the temperature of 200 ℃; then cooling from 200 ℃ to 120 ℃ at a cooling speed of 8.5 ℃/min, and naturally cooling to room temperature to form a coating layer, so that the surface of the cladding layer is kept smooth, and the thickness of the coating layer is 0.95mm;
s6: the coating layer is treated by adopting a multi-channel laser cladding technology under the protection of argon, and the technological parameters are controlled as follows: the laser power is 1.5KW, the scanning speed is 6mm/s, the spot diameter is 3mm, and the alloy coating is obtained after cladding the coating under the protection of argon.
Wherein the quaternary ammonium base consists of tetramethyl ammonium hydroxide and tetrabutyl ammonium hydroxide according to the mass ratio of 1:0.5. The purity of the high-purity aluminum powder, the high-purity cobalt powder, the high-purity chromium powder, the high-purity iron powder, the high-purity nickel powder and the high-purity copper powder is 4N, and the average grain diameter is 15 mu m. The rosin powder has a particle size of 200 mesh.
Comparative example
Comparative example 1
The laser cladding process of the middle groove alloy coating of the comparative example comprises the following steps:
s1: pretreatment: taking a middle groove sample made of 16 manganese steel, carrying out sand blasting on the surface of the middle groove, and then carrying out sand sanding and polishing treatment to remove greasy dirt and rust oxide impurities on the surface of the middle groove, so that the roughness Ra of the surface of the middle groove is less than or equal to 0.25 mu m;
s2: according to the weight parts, taking 350g of turpentine, 70g of rosin powder and 20g of phosphatidylcholine, uniformly mixing in a beaker, and filtering to prepare a clear adhesive; then uniformly mixing high-purity aluminum powder, high-purity cobalt powder, high-purity chromium powder, high-purity iron powder, high-purity nickel powder and high-purity copper powder according to a molar ratio of 1:1:1:1:1:1 to obtain high-entropy alloy powder;
s3: taking a binder and high-entropy alloy powder according to the mass ratio of 0.12:1, placing the binder and the high-entropy alloy powder in a sealed stirring tank under a dry environment, uniformly mixing to prepare a mud-shaped coating, uniformly coating the coating on the surface of a middle groove, heating the coating from 20 ℃ to 100 ℃ at the heating rate of 10 ℃/min, and drying the coating at the temperature of 100 ℃ for 3 hours to form a coating layer, so that the surface of the cladding layer is kept flat and smooth, and the thickness of the coating layer is 0.8mm;
s4: the coating layer is treated by adopting a multi-channel laser cladding technology under the protection of argon, and the technological parameters are controlled as follows: the laser power is 1.3KW, the scanning speed is 10mm/s, the spot diameter is 3mm, and the alloy coating is obtained after cladding the coating layer under the protection of argon.
Wherein, the purity of the high-purity aluminum powder, the high-purity cobalt powder, the high-purity chromium powder, the high-purity iron powder, the high-purity nickel powder and the high-purity copper powder is 4N, and the average grain diameter is 10 mu m. The rosin powder has a particle size of 200 mesh.
Comparative example 2
The laser cladding process of the middle groove alloy coating of the comparative example comprises the following steps:
s1: pretreatment: taking a middle groove sample made of 16 manganese steel, carrying out sand blasting on the surface of the middle groove, and then carrying out sand sanding and polishing treatment to remove greasy dirt and rust oxide impurities on the surface of the middle groove, so that the roughness Ra of the surface of the middle groove is less than or equal to 0.25 mu m;
s2: placing 300g of metal acetate and 2000g of absolute ethyl alcohol into a reaction kettle with a stirring and temperature control device, uniformly mixing, adding 600g of oxalic acid, continuously stirring for 1h, and then treating for 30min under the boiling condition to obtain a precursor liquid; the metal acetate consists of nickel acetate, cobalt acetate and aluminum acetate according to the mol ratio of 1:1:0.5;
s3: adding 10g of quaternary ammonium base and 50g of thiodiglycol into the precursor liquid, continuously stirring for 10min, and then filtering, washing and drying to obtain a metal salt oligomer;
s4: according to the weight parts, taking 350g of turpentine, 70g of rosin powder and 20g of phosphatidylcholine, uniformly mixing in a beaker, and filtering to prepare a clear adhesive; then uniformly mixing metal salt oligomer, high-purity aluminum powder, high-purity cobalt powder, high-purity chromium powder, high-purity iron powder, high-purity nickel powder and high-purity copper powder according to a molar ratio of 0.3:1:1:1:1:1:1 to obtain high-entropy alloy powder, wherein the molar amount of the metal salt oligomer is calculated by oxalic acid root;
s5: taking a binder and high-entropy alloy powder according to the mass ratio of 0.12:1, placing the binder and the high-entropy alloy powder in a sealed stirring tank under a dry environment, uniformly mixing to prepare a mud-shaped coating, uniformly coating the coating on the surface of a middle groove, heating the coating from 20 ℃ to 100 ℃ at the heating rate of 10 ℃/min, and drying the coating at the temperature of 100 ℃ for 3 hours to form a coating layer, so that the surface of the cladding layer is kept flat and smooth, and the thickness of the coating layer is 0.8mm;
s6: the coating layer is treated by adopting a multi-channel laser cladding technology under the protection of argon, and the technological parameters are controlled as follows: the laser power is 1.3KW, the scanning speed is 10mm/s, the spot diameter is 3mm, and the alloy coating is obtained after cladding the coating layer under the protection of argon.
Wherein the quaternary ammonium base is tetraethylammonium hydroxide. The purity of the high-purity aluminum powder, the high-purity cobalt powder, the high-purity chromium powder, the high-purity iron powder, the high-purity nickel powder and the high-purity copper powder is 4N, and the average grain diameter is 10 mu m. The rosin powder has a particle size of 200 mesh.
Comparative example 3
The laser cladding process of the middle groove alloy coating of the comparative example comprises the following steps:
s1: pretreatment: taking a middle groove sample made of 16 manganese steel, carrying out sand blasting on the surface of the middle groove, and then carrying out sand sanding and polishing treatment to remove greasy dirt and rust oxide impurities on the surface of the middle groove, so that the roughness Ra of the surface of the middle groove is less than or equal to 0.25 mu m;
s2: placing 300g of metal acetate and 2000g of absolute ethyl alcohol into a reaction kettle with a stirring and temperature control device, uniformly mixing, adding 600g of oxalic acid, 200g of triethylamine and 50g of 1, 3-propane sultone, continuously stirring for 1h, treating for 30min under the boiling condition, and then filtering, washing and drying to obtain a metal salt oligomer; the metal acetate consists of nickel acetate, cobalt acetate and aluminum acetate according to the mol ratio of 1:1:0.5;
s3: according to the weight parts, taking 350g of turpentine, 70g of rosin powder and 20g of phosphatidylcholine, uniformly mixing in a beaker, and filtering to prepare a clear adhesive; then uniformly mixing metal salt oligomer, high-purity aluminum powder, high-purity cobalt powder, high-purity chromium powder, high-purity iron powder, high-purity nickel powder and high-purity copper powder according to a molar ratio of 0.3:1:1:1:1:1:1 to obtain high-entropy alloy powder, wherein the molar amount of the metal salt oligomer is calculated by oxalic acid root;
s4: taking a binder and high-entropy alloy powder according to the mass ratio of 0.12:1, placing the binder and the high-entropy alloy powder in a sealed stirring tank under a dry environment, uniformly mixing to prepare a mud-shaped coating, uniformly coating the coating on the surface of a middle groove, heating the coating from 20 ℃ to 100 ℃ at the heating rate of 10 ℃/min, and drying the coating at the temperature of 100 ℃ for 3 hours to form a coating layer, so that the surface of the cladding layer is kept flat and smooth, and the thickness of the coating layer is 0.8mm;
s5: under the protection of argon, C0 is adopted 2 The coating layer is treated by a multi-channel laser cladding technology, and the control process parameters are as follows: the laser power is 1.3KW, the scanning speed is 10mm/s, the spot diameter is 3mm, and the coating layer is obtained after cladding under the protection of argonTo the alloy coating.
Wherein, the purity of the high-purity aluminum powder, the high-purity cobalt powder, the high-purity chromium powder, the high-purity iron powder, the high-purity nickel powder and the high-purity copper powder is 4N, and the average grain diameter is 10 mu m. The rosin powder has a particle size of 200 mesh.
Performance test
The middle groove samples of examples 1-3 and comparative examples 1-3 were taken, the alloy coating was polished with 1000# water-resistant sandpaper, and after polishing, the vickers hardness test was performed, each sample was randomly measured for 10 positions, and the average value was taken, and the test results are shown in table 1.
TABLE 1 hardness test results for the mid-tank alloy coatings of examples 1-3 and comparative examples 1-3
The middle tank samples of examples 1-3 and comparative examples 1-3 were cut into 7X 25mm samples to be tested, and the wear resistance was tested using an MMV-1 wear tester with the following parameters: dry-grinding sliding friction, load of 5kg, rotating speed of 200r/min and test time of 1h, then using electronic weighing to test the mass of the sample to be tested before and after, calculating the loss weight to evaluate the wear resistance, and the test results are shown in Table 2.
TABLE 2 results of wear resistance test of the mid-groove alloy coatings of examples 1-3 and comparative examples 1-3
Taking the middle groove samples of examples 1-3 and comparative examples 1-3, and polishing the alloy coating for later use; the etching solution is prepared by uniformly mixing 500g of ferric chloride, 1L of concentrated nitric acid, 300ml of concentrated hydrochloric acid and 8.5L of absolute ethyl alcohol, the etching solution is used for etching the alloy coating, and SEM test is carried out after the alloy coating is purged cleanly, and the test results are shown in figures 1-6.
Analysis of results
As can be seen from analysis of examples 1-3 and comparative examples 1-3 in combination with tables 1-2, the middle trough alloy coating prepared by the method has better mechanical properties, hardness and wear resistance, can fully exert the advantages of the high-entropy alloy material, can prolong the service life of the middle trough when applied to coal mine transportation, reduces the production cost, and is suitable for popularization and application.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. The laser cladding process of the middle groove alloy coating is characterized by comprising the following steps of:
s1: pretreatment: performing sand blasting and polishing treatment on the surface of the middle groove to remove greasy dirt and rust impurities on the surface;
s2: according to weight portions, 30-50 portions of metal acetate and 200-300 portions of absolute ethyl alcohol are taken and placed into a reaction kettle to be uniformly mixed, then 60-75 portions of oxalic acid, 15-20 portions of triethylamine and 5-10 portions of 1, 3-propane sultone are added to be continuously stirred for 1-1.5 hours, and then the precursor liquid is obtained after the mixture is treated for 30-50 minutes under the boiling condition; the metal acetate consists of nickel acetate, cobalt acetate and aluminum acetate according to a molar ratio of 1:1:0.5;
s3: adding 1-2.5 parts of quaternary ammonium base and 3-5 parts of thiodiglycol into the precursor liquid, continuously stirring for 10-20min, and then filtering, washing and drying to obtain a metal salt oligomer;
s4: according to weight portions, 25 to 35 portions of turpentine, 7 to 12 portions of rosin and 2 to 3 portions of phosphatidylcholine are taken and evenly mixed to prepare the adhesive; then uniformly mixing metal salt oligomer, high-purity aluminum powder, high-purity cobalt powder, high-purity chromium powder, high-purity iron powder, high-purity nickel powder and high-purity copper powder to prepare high-entropy alloy powder;
s5: uniformly mixing a binder and high-entropy alloy powder to prepare a coating material, uniformly coating the coating material on the surface of a middle groove, and drying to form a coating layer;
s6: under the protection of inert gas, a plurality of laser cladding technologies are adopted to treat the coating layer, and the control process parameters are as follows: the laser power is 1.3-1.5kW, the scanning speed is 6-10mm/s, and the alloy coating is obtained after cladding the coating layer under the protection of inert gas.
2. The process of claim 1, wherein in step S3, the quaternary ammonium base is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
3. The laser cladding process of claim 2, wherein in step S3, the quaternary ammonium base is composed of tetramethylammonium hydroxide and tetrabutylammonium hydroxide in a mass ratio of 1:0.5.
4. The laser cladding process of a middle trough alloy coating according to claim 1, wherein in the step S4, the molar ratio of the metal salt oligomer to the high-purity aluminum powder to the high-purity cobalt powder to the high-purity chromium powder to the high-purity iron powder to the high-purity nickel powder to the high-purity copper powder is controlled to be (0.3-0.6): 1:1:1:1:1:1:1, based on oxalic acid root.
5. The process of claim 1, wherein in step S5, the mass ratio of the binder to the high-entropy alloy powder is (0.08-0.12): 1.
6. The laser cladding process of a middle trough alloy coating according to claim 1, wherein in step S5, the drying is performed by heating from 20 ℃ to 100 ℃ at a heating rate of 8 ℃/min, and maintaining the temperature at 100 ℃ for 120min; then heating from 100 ℃ to 200 ℃ at a heating rate of 12 ℃/min, and preserving heat for 10min at the temperature of 200 ℃; then cooling from 200 ℃ to 120 ℃ at a cooling rate of 8.5 ℃/min, and finally naturally cooling to room temperature.
7. The laser cladding process of a middle trough alloy coating according to claim 1, wherein in the step S4, the average grain size of the high-purity aluminum powder, the high-purity cobalt powder, the high-purity chromium powder, the high-purity iron powder, the high-purity nickel powder and the high-purity copper powder is 10-20 μm.
8. The laser cladding process of a middle groove alloy coating according to claim 1, wherein in the step S1, the surface roughness Ra of the middle groove after the sand blasting and polishing treatment is less than or equal to 0.25 μm.
9. The laser cladding process of a middle tank alloy coating according to claim 1, wherein in the step S5, the thickness of the coating layer is 0.8-1.5mm.
10. A mid-tank alloy coating, characterized in that the mid-tank alloy coating is provided on the surface of a mid-tank substrate, said mid-tank alloy coating being produced by the laser cladding process of any one of claims 1-9.
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