CN117568793B - Preparation method of ZnO nanoparticle reinforced copper-zinc alloy-based composite coating - Google Patents
Preparation method of ZnO nanoparticle reinforced copper-zinc alloy-based composite coating Download PDFInfo
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- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 116
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000000576 coating method Methods 0.000 title claims abstract description 90
- 239000011248 coating agent Substances 0.000 title claims abstract description 88
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 82
- 239000011812 mixed powder Substances 0.000 claims abstract description 44
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- 239000007921 spray Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000010288 cold spraying Methods 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- 238000005507 spraying Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- 239000004927 clay Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 abstract description 32
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 10
- 238000011049 filling Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004372 laser cladding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
Classifications
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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
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/09—Mixtures of metallic powders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
- C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention relates to the technical field of composite coatings, in particular to a preparation method of a ZnO nanoparticle reinforced copper-zinc alloy-based composite coating. Mixing large-scale copper-zinc alloy powder and small-scale copper-zinc alloy powder, and performing ball milling to obtain mixed powder; taking the mixed powder as spraying powder, and performing high-pressure cold spraying to obtain a cold-sprayed copper-zinc alloy coating; and (3) carrying out high-temperature micro-oxygen heat treatment on the coating under a closed condition to obtain the ZnO nanoparticle reinforced copper-zinc alloy-based composite coating. The powder can be quickly and uniformly mixed on the premise of not influencing the shape and the particle size of the powder by adjusting the ball milling parameters, and the high-purity high-compactness high-quality cold-sprayed copper-zinc alloy coating is prepared by adopting high-pressure cold spraying. The Zn phase in the cold spray copper zinc alloy coating is subjected to in-situ reaction to generate ZnO nano particles by adopting high-temperature micro-oxygen heat treatment, so that the aim of preparing the high-performance ZnO nano particle reinforced cold spray copper zinc alloy base composite coating is fulfilled.
Description
Technical Field
The invention relates to the technical field of composite coatings, in particular to a preparation method of a ZnO nanoparticle reinforced copper-zinc alloy-based composite coating.
Background
Various water treatment technologies have been developed, and metallic materials have been widely used in water treatment technologies by virtue of their unique advantages. Copper-zinc alloys have been used in water treatment for their good corrosion resistance, fatigue resistance, superelasticity, cavitation resistance, wear resistance, impact resistance, and the like. The copper-zinc alloy filter material can effectively reduce or remove chlorine and heavy metals in water and effectively control microorganisms and scale; the method has good effects in the aspects of removing iron, reducing fluoride, nitrate, carbonate, sulfate and the like; and the maintenance is convenient, the comprehensive performance is good, but the cost of using the copper-zinc alloy block as a whole is higher. In addition, the filter material is easy to cause that the pore is blocked, the filter material loss is caused in the water treatment process, and the water treatment capacity is further reduced. The high-performance copper-zinc alloy coating or copper-zinc alloy composite coating is expected to solve the problem that common copper-zinc alloy filter materials are easy to block in water treatment, reduce the cost for using the copper-zinc alloy materials in a whole, and have remarkable advantages in the aspects of energy conservation, emission reduction, environmental protection and the like.
Cold spraying has significant advantages in the field of surface coating preparation. Cold spraying is a process in which particles of micrometer size (5-50 μm) are fed into a high-velocity gas stream, accelerated to a high velocity (300-1200 m·s -1), and then collide with a substrate in a completely solid state (< 1000 ℃) form, and the coating is produced by plastic deformation of the particles and the substrate/deposited particles together. Compared with the coating preparation processes based on melting and resolidification, such as thermal spraying, laser cladding, selective laser cladding and the like, the cold spraying has the remarkable characteristic of low particle temperature, so that the non-oxidation preparation of a metal deposit can be realized in the atmosphere, and the phenomena of thermal effect of a matrix, burning loss of metal powder components and the like are avoided. The cold spray metal coating has potential excellent properties such as mechanical properties, electrical properties, oxidation resistance, corrosion resistance, abrasion resistance and the like, so that the cold spray metal coating has wide application prospects in the fields of aerospace, electronic and electric appliances, medical appliances, workpiece repair and automobile manufacturing, additive manufacturing (3D printing) and the like. At present, cold spraying is used for preparing a copper-zinc alloy coating, but a main method adopted is low-pressure cold spraying, and the prepared copper-zinc alloy coating is poor in performance and low in strength. Therefore, the preparation of the high-performance cold-spraying copper-zinc alloy composite coating has important potential application value.
Disclosure of Invention
The invention aims to provide a preparation method of a ZnO nanoparticle reinforced copper-zinc alloy-based composite coating, which aims to solve the problems in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a ZnO nanoparticle reinforced copper-zinc alloy matrix composite coating, which comprises the following steps:
Step 1), mixing large-scale copper-zinc alloy powder and small-scale copper-zinc alloy powder, and performing ball milling to obtain mixed powder;
step 2) taking the mixed powder as spraying powder, and performing high-pressure cold spraying to obtain a cold-sprayed copper-zinc alloy coating;
And 3) carrying out high-temperature micro-oxygen heat treatment on the cold spray copper-zinc alloy coating under a closed condition to obtain the ZnO nanoparticle reinforced copper-zinc alloy-based composite coating.
Preferably, the average grain size of the large-scale copper-zinc alloy powder in the step 1) is 150-350 mu m, and the average grain size of the small-scale copper-zinc alloy powder is 10-30 mu m; the dimensions of the large-scale copper-zinc alloy powder and the small-scale copper-zinc alloy powder are different by more than 10 times.
Preferably, the volume ratio of the large-scale copper-zinc alloy powder to the small-scale copper-zinc alloy powder in the step 1) is 1-3:1-7.
Preferably, the ball milling time in the step 1) is 1-10 h, and the rotating speed is 50-100 rpm.
Preferably, the copper zinc alloy powder comprises an H80 single phase copper zinc alloy or an H59 dual phase copper zinc alloy.
Preferably, the pressure of the high-pressure cold spraying in the step 2) is 4-7 MPa, the temperature is 700-900 ℃, and the working gas is N 2.
Preferably, the step 3) is to put the cold sprayed copper-zinc alloy coating into a closed crucible container, fill oxide mixed powder into the crucible container to provide oxygen partial pressure for the system, and put the closed crucible container into a high-temperature furnace to carry out high-temperature micro-oxygen heat treatment.
Preferably, the oxide mixed powder consists of 30% of CuO, 40% of Cu 2 O and 30% of ZnO powder by mass percent respectively, and is filled into a crucible container after being dried, and then the crucible container is sealed by adopting refractory clay; drying the sealed crucible in an oven at 100-200 ℃ for 0.5-2 h, and then loading the crucible into a furnace for high-temperature micro-oxygen heat treatment.
Preferably, the temperature of the high-temperature micro-oxygen heat treatment is 800-1000 ℃ and the time is 5-10 h.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts ball milling technology to prepare a series of uniformly distributed mixed powder which consists of large-scale spherical copper-zinc alloy powder and small-scale spherical copper-zinc alloy powder and has different contents, and the powder can be quickly and uniformly mixed on the premise of not influencing the appearance and the particle size of the powder by adjusting ball milling parameters. Taking the mixed powder as spraying powder, adopting high-pressure cold spraying, utilizing the influence of particle size on the accelerating performance of powder particles to accelerate the small-scale powder particles to be above the critical deposition speed, and then depositing the small-scale powder particles on a substrate to form a copper-zinc alloy coating; the large-scale powder particles rebound due to the fact that the critical deposition speed is not reached, the compaction strengthening effect is achieved on the deposited coating, and the preparation of the high-purity high-density high-quality cold-spraying copper-zinc alloy coating is achieved. The Zn phase in the cold spray copper zinc alloy coating is subjected to in-situ reaction under a certain oxygen partial pressure and high temperature condition by adopting high-temperature micro-oxygen heat treatment to generate ZnO nano particles, so that the aim of preparing the high-performance ZnO nano particle reinforced cold spray copper zinc alloy matrix composite coating is fulfilled.
Drawings
FIG. 1 is a cross-sectional microstructure of a spray-coated H80 single-phase copper-zinc alloy coating prepared from a mixed powder having a large-scale powder volume fraction of 20%;
FIG. 2 is a cross-sectional microstructure of a spray-coated H80 single-phase copper-zinc alloy coating prepared from a mixed powder having a large-scale powder volume fraction of 50%;
FIG. 3 is a graph showing the internal microstructure of the H80 single-phase copper-zinc alloy coating of example 1 after high-temperature micro-oxygen heat treatment.
Detailed Description
The invention provides a preparation method of a ZnO nanoparticle reinforced copper-zinc alloy matrix composite coating, which comprises the following steps:
Step 1), mixing large-scale copper-zinc alloy powder and small-scale copper-zinc alloy powder, and performing ball milling to obtain mixed powder;
step 2) taking the mixed powder as spraying powder, and performing high-pressure cold spraying to obtain a cold-sprayed copper-zinc alloy coating;
And 3) carrying out high-temperature micro-oxygen heat treatment on the cold spray copper-zinc alloy coating under a closed condition to obtain the ZnO nanoparticle reinforced copper-zinc alloy-based composite coating.
In the present invention, the average particle diameter of the large-scale copper-zinc alloy powder in the step 1) is 150 to 350. Mu.m, preferably 180 to 320. Mu.m, more preferably 200 to 300. Mu.m, still more preferably 250. Mu.m; the average particle diameter of the small-sized copper-zinc alloy powder is 10 to 30. Mu.m, preferably 15 to 25. Mu.m, more preferably 18 to 23. Mu.m, still more preferably 20. Mu.m; the large-scale copper-zinc alloy powder and the small-scale copper-zinc alloy powder have a difference in scale of more than 10 times, preferably 12.5 times.
In the present invention, the volume ratio of the large-scale copper-zinc alloy powder to the small-scale copper-zinc alloy powder in the step 1) is 1-3:1-7, preferably 1.5-2.8:2-6, more preferably 1.8-2.5:3-5, and even more preferably 2-2.2:3.5-4.5.
In the present invention, the time of the ball milling in the step 1) is 1 to 10 hours, preferably 2 to 9 hours, more preferably 3 to 8 hours, still more preferably 5 to 5.5 hours, and the rotation speed is 50 to 100rpm, preferably 60 to 90rpm, still more preferably 70 to 80rpm.
In the present invention, the copper zinc alloy powder comprises an H80 single-phase copper zinc alloy or an H59 dual-phase copper zinc alloy, preferably an H59 dual-phase copper zinc alloy.
In the present invention, the pressure of the high-pressure cold spraying in the step 2) is 4 to 7MPa, preferably 5 to 6MPa, more preferably 5.5MPa, the temperature is 700 to 900 ℃, preferably 750 to 850 ℃, more preferably 800 ℃, and the working gas is N 2.
In the invention, the step 3) is to put the cold spray copper zinc alloy coating into a closed crucible container, fill oxide mixed powder into the crucible container to provide oxygen partial pressure for the system, and put the closed crucible container into a high temperature furnace to carry out high temperature micro oxygen heat treatment.
In the invention, the oxide mixed powder consists of 30 percent of CuO, 40 percent of Cu 2 O and 30 percent of ZnO powder in percentage by mass respectively, and is filled into a crucible container after being dried, and then the crucible container is sealed by adopting refractory clay; the sealed crucible is dried in an oven at 100-200 ℃, preferably 120-180 ℃, more preferably 150 ℃ for 0.5-2 hours, preferably 1-1.5 hours, and then is charged into a furnace for high-temperature micro-oxygen heat treatment.
In the present invention, the high temperature micro-oxygen heat treatment is performed at a temperature of 800 to 1000 ℃, preferably 850 to 950 ℃, more preferably 900 ℃, for a time of 5 to 10 hours, preferably 6 to 9 hours, more preferably 7 to 8 hours.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Step 1) aiming at an H80 single-phase copper-zinc alloy system, placing the H80 single-phase copper-zinc alloy with the average particle sizes of 20 mu m and 250 mu m in a ball milling tank according to the volume ratio of 4:1, and performing ball milling for 5 hours at the rotating speed of 80rpm to obtain mixed powder with the volume fraction of 20% of large-scale powder.
And 2) taking the mixed powder as spraying powder, taking copper as a matrix, adopting high-pressure cold spraying to prepare the H80 copper-zinc alloy coating, wherein the working gas is high-purity N 2 in the spraying process, the pressure is 5MPa, and the temperature is 800 ℃. FIG. 1 is a cross-sectional microstructure of a cold spray H80 copper zinc alloy coating prepared from a mixed powder with a large-scale powder volume fraction of 20%, and as can be seen from FIG. 1, polygonal pores formed by inter-particle interfaces are locally formed in the coating, and the interface bonding quality is poor.
Step 3) placing the cold spray H80 copper zinc alloy coating in a closed crucible container, filling oxide mixed powder in the crucible container to provide oxygen partial pressure for a system, wherein the oxide mixed powder consists of 30% of CuO, 40% of CuO, 30% of Cu 2 O and ZnO powder in percentage by mass respectively, filling the dried powder into the crucible container, and sealing the crucible container by adopting refractory clay; drying the sealed crucible in an oven at 150 ℃ for 1h, and then placing the sealed crucible container in a high-temperature furnace for high-temperature micro-oxygen heat treatment at 900 ℃ for 5h;
After the cold spray H80 copper zinc alloy coating prepared by adopting the mixed powder with the volume fraction of 20% of the large-scale powder is subjected to high-temperature micro-oxygen heat treatment, polygonal pores in the coating are evolved into spherical pores, znO nano-particles appear near the interfaces among particles in the coating, and the nano-particles are shown in a figure 3 with high resolution. The corresponding coating strength is 100MPa, and the high-performance ZnO nanoparticle reinforced H80 single-phase copper-zinc alloy composite coating is successfully prepared.
Example 2
Step 1) aiming at an H80 single-phase copper-zinc alloy system, placing the H80 single-phase copper-zinc alloy with the average particle sizes of 20 mu m and 250 mu m in a ball milling tank according to the volume ratio of 1:1, and carrying out ball milling for 5 hours at the rotating speed of 80rpm to obtain mixed powder with the volume fraction of 50% of large-scale powder uniformly distributed.
And 2) taking the mixed powder as spraying powder, taking copper as a matrix, adopting high-pressure cold spraying to prepare the H80 copper-zinc alloy coating, wherein the working gas is high-purity N 2 in the spraying process, the pressure is 5MPa, and the temperature is 800 ℃. FIG. 2 is a cross-sectional microstructure of a cold spray H80 copper zinc alloy coating prepared from a mixed powder with a 50% large scale powder volume fraction, and as can be seen from FIG. 2, the coating is relatively dense, no large scale pores are observed in the coating, and the interface bonding quality is good.
Step 3) placing the cold spray H80 copper zinc alloy coating in a closed crucible container, filling oxide mixed powder in the crucible container to provide oxygen partial pressure for a system, wherein the oxide mixed powder consists of 30% of CuO, 40% of CuO, 30% of Cu 2 O and ZnO powder in percentage by mass respectively, filling the dried powder into the crucible container, and sealing the crucible container by adopting refractory clay; drying the sealed crucible in an oven at 150 ℃ for 1h, and then placing the sealed crucible container in a high-temperature furnace for high-temperature micro-oxygen heat treatment at 900 ℃ for 5h;
after the cold spray H80 copper-zinc alloy coating prepared by adopting mixed powder with the volume fraction of 50% of the large-scale powder is subjected to high-temperature micro-oxygen heat treatment, only a small amount of dot-shaped pores are observed in the coating, znO nano particles appear near the inter-particle interface in the coating, the corresponding coating strength is 150MPa, and the high-performance ZnO nano particle reinforced H80 single-phase copper-zinc alloy composite coating is successfully prepared.
Example 3
Step 1) aiming at an H59 double-phase copper-zinc alloy system, placing the H59 double-phase copper-zinc alloy with the average particle sizes of 20 mu m and 250 mu m in a ball milling tank according to the volume ratio of 7:3, and carrying out ball milling for 5 hours at the rotating speed of 80rpm to obtain mixed powder with the volume fraction of 30% of large-scale powder uniformly distributed.
Step 2) taking the mixed powder as spraying powder, taking copper as a matrix, adopting high-pressure cold spraying to prepare the H59 copper-zinc alloy coating, wherein the working gas is high-purity N 2 in the spraying process, the pressure is 5.5MPa, and the temperature is 850 ℃. A small amount of triangular pores formed by interfaces among particles are locally formed in the cold spray H59 copper-zinc alloy coating prepared from mixed powder with the volume fraction of 30% of large-scale powder, and the interface bonding quality is poor.
Step 3) placing the cold spray H59 copper zinc alloy coating in a closed crucible container, filling oxide mixed powder in the crucible container to provide oxygen partial pressure for a system, wherein the oxide mixed powder consists of 30% of CuO, 40% of CuO, 30% of Cu 2 O and ZnO powder in percentage by mass respectively, filling the dried powder into the crucible container, and sealing the crucible container by adopting refractory clay; drying the sealed crucible in an oven at 150 ℃ for 1h, and then placing the sealed crucible container in a high-temperature furnace for high-temperature micro-oxygen heat treatment, wherein the treatment temperature is 950 ℃ and the treatment time is 8h;
after the cold spray H59 copper-zinc alloy coating prepared by adopting mixed powder with the volume fraction of large-scale powder of 30 percent is subjected to high-temperature micro-oxygen heat treatment, triangular pores in the coating are evolved into spherical pores, znO nano-particles appear at inter-particle interfaces and in particles in the coating, the corresponding coating strength is 120MPa, and the high-performance ZnO nano-particle reinforced H59 double-phase copper-zinc alloy composite coating is successfully prepared.
Example 4
Step 1) aiming at an H59 double-phase copper-zinc alloy system, placing the H59 double-phase copper-zinc alloy with the average particle sizes of 20 mu m and 250 mu m in a ball milling tank according to the volume ratio of 2:3, and carrying out ball milling for 5 hours at the rotating speed of 80rpm to obtain mixed powder with the volume fraction of 60% of large-scale powder uniformly distributed.
Step 2) taking the mixed powder as spraying powder, taking copper as a matrix, adopting high-pressure cold spraying to prepare the H59 copper-zinc alloy coating, wherein the working gas in the spraying process is N 2, the pressure is 5.5MPa, and the temperature is 850 ℃. The cold spray H59 copper-zinc alloy coating prepared by adopting the mixed powder with the volume fraction of the large-scale powder of 60 percent is relatively compact, no large-scale pores are observed in the coating, and the interface bonding quality is good.
Step 3) placing the cold spray H59 copper zinc alloy coating in a closed crucible container, filling oxide mixed powder in the crucible container to provide oxygen partial pressure for a system, wherein the oxide mixed powder consists of 30% of CuO, 40% of CuO, 30% of Cu 2 O and ZnO powder in percentage by mass respectively, filling the dried powder into the crucible container, and sealing the crucible container by adopting refractory clay; drying the sealed crucible in an oven at 150 ℃ for 1h, and then placing the sealed crucible container in a high-temperature furnace for high-temperature micro-oxygen heat treatment, wherein the treatment temperature is 950 ℃ and the treatment time is 8h;
After the cold spray H59 copper-zinc alloy coating prepared by adopting the mixed powder with the volume fraction of the large-scale powder of 60 percent is subjected to high-temperature micro-oxygen heat treatment, only a small amount of dot-shaped pores are observed in the coating, znO nano particles appear at the inter-particle interface and the particle inside of the coating, the corresponding coating strength is 180MPa, and the high-performance ZnO nano particle reinforced H59 double-phase copper-zinc alloy composite coating is successfully prepared.
From the above examples, the present invention provides a method for preparing a ZnO nanoparticle reinforced copper-zinc alloy matrix composite coating. A series of evenly distributed mixed powder with different contents, which is composed of spherical copper-zinc alloy powder with average particle diameters of 20 mu m and 250 mu m respectively, is prepared by adopting a ball milling process, and the powder can be quickly and evenly mixed on the premise of not influencing the appearance and the particle diameter of the powder by adjusting ball milling parameters. Taking the mixed powder as spraying powder, adopting high-pressure cold spraying, utilizing the influence of particle size on the accelerating performance of powder particles to accelerate the small-scale powder particles to be above the critical deposition speed, and then depositing the small-scale powder particles on a substrate to form a copper-zinc alloy coating; the large-scale powder particles rebound due to the fact that the critical deposition speed is not reached, the compaction strengthening effect is achieved on the deposited coating, and the preparation of the high-purity high-density high-quality cold-spraying copper-zinc alloy coating is achieved. The Zn phase in the cold spray copper zinc alloy coating is subjected to in-situ reaction under a certain oxygen partial pressure and high temperature condition by adopting high-temperature micro-oxygen heat treatment to generate ZnO nano particles, so that the aim of preparing the high-performance ZnO nano particle reinforced cold spray copper zinc alloy matrix composite coating is fulfilled.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (3)
1. The preparation method of the ZnO nanoparticle reinforced copper-zinc alloy-based composite coating is characterized by comprising the following steps of:
Step 1), mixing large-scale copper-zinc alloy powder and small-scale copper-zinc alloy powder, and performing ball milling to obtain mixed powder;
step 2) taking the mixed powder as spraying powder, and performing high-pressure cold spraying to obtain a cold-sprayed copper-zinc alloy coating;
step 3) carrying out high-temperature micro-oxygen heat treatment on the cold spray copper-zinc alloy coating under a closed condition to obtain the ZnO nanoparticle reinforced copper-zinc alloy-based composite coating;
the average grain diameter of the large-scale copper-zinc alloy powder in the step 1) is 150-350 mu m, and the average grain diameter of the small-scale copper-zinc alloy powder is 10-30 mu m; the scale difference of the large-scale copper-zinc alloy powder and the small-scale copper-zinc alloy powder is more than 10 times;
The ball milling time in the step 1) is 1-10 hours, and the rotating speed is 50-100 rpm;
The pressure of the high-pressure cold spraying in the step 2) is 4-7 MPa, the temperature is 700-900 ℃, and the working gas is N 2;
the step 3) is to put the cold spray copper zinc alloy coating into a closed crucible container, the inside of the crucible container is filled with oxide mixed powder to provide oxygen partial pressure for the system, and the closed crucible container is put into a high-temperature furnace for high-temperature micro-oxygen heat treatment;
The oxide mixed powder consists of 30% of CuO, 40% of Cu 2 O and 30% of ZnO powder by mass percent respectively, and is filled into a crucible container after being dried, and then the crucible container is sealed by adopting refractory clay; drying the sealed crucible in an oven at 100-200 ℃ for 0.5-2 hours, and then charging the crucible into a furnace for high-temperature micro-oxygen heat treatment;
the temperature of the high-temperature micro-oxygen heat treatment is 800-900 ℃ and the time is 5-10 h.
2. The preparation method of the ZnO nanoparticle reinforced copper-zinc alloy-based composite coating according to claim 1, wherein the volume ratio of the large-scale copper-zinc alloy powder to the small-scale copper-zinc alloy powder in the step 1) is 1-3:1-7.
3. The method of preparing a ZnO nanoparticle-reinforced copper-zinc alloy-based composite coating according to claim 1, wherein the copper-zinc alloy powder comprises H80 single-phase copper-zinc alloy or H59 dual-phase copper-zinc alloy.
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