CN114850472A - Method for coating ceramic particles and preparation method of composite material - Google Patents
Method for coating ceramic particles and preparation method of composite material Download PDFInfo
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- CN114850472A CN114850472A CN202210305408.4A CN202210305408A CN114850472A CN 114850472 A CN114850472 A CN 114850472A CN 202210305408 A CN202210305408 A CN 202210305408A CN 114850472 A CN114850472 A CN 114850472A
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- 239000002245 particle Substances 0.000 title claims abstract description 137
- 239000000919 ceramic Substances 0.000 title claims abstract description 120
- 238000000576 coating method Methods 0.000 title claims abstract description 118
- 239000011248 coating agent Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 105
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 78
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 73
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- 238000007747 plating Methods 0.000 claims abstract description 45
- 238000001994 activation Methods 0.000 claims abstract description 33
- 230000004913 activation Effects 0.000 claims abstract description 31
- 230000003213 activating effect Effects 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000000853 adhesive Substances 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims description 65
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 101710134784 Agnoprotein Proteins 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 238000009715 pressure infiltration Methods 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000011241 protective layer Substances 0.000 abstract description 2
- 229910003336 CuNi Inorganic materials 0.000 description 31
- 230000001681 protective effect Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 8
- 229910000365 copper sulfate Inorganic materials 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 5
- 229960001231 choline Drugs 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- OASOQJKCZXXDMI-UHFFFAOYSA-N ethane-1,2-diol;hydrochloride Chemical compound Cl.OCCO OASOQJKCZXXDMI-UHFFFAOYSA-N 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000001509 sodium citrate Substances 0.000 description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 5
- 229910001018 Cast iron Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 239000011153 ceramic matrix composite Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011156 metal matrix composite Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000080590 Niso Species 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- B22F1/18—Non-metallic particles coated with metal
-
- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
- C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1005—Pretreatment of the non-metallic additives
- C22C1/101—Pretreatment of the non-metallic additives by coating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Chemically Coating (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a method for coating ceramic particles and a preparation method of a composite material. The coating method comprises the following steps: mixing the ceramic particles with the adhesive, adding the coating powder, and stirring to obtain ceramic particles coated by the coating powder; mixing the ceramic particles coated with the coating powder with polyvinyl alcohol, and drying to obtain ceramic particles with the coating powder and the polyvinyl alcohol attached to the surfaces; and activating the ceramic particles with the coating powder and the polyvinyl alcohol attached to the surfaces, and performing chemical plating by using a plating solution after activation to obtain the ceramic particles coated by the coating powder-metal coating. The preparation method of the composite material comprises the following steps: preparing ceramic particles coated by the coating powder-metal coating; and carrying out non-pressure infiltration treatment on the ceramic particles coated with the coating powder-metal coating and the metal matrix to obtain the composite material. The method of the invention utilizes the protective layer formed by polyvinyl alcohol to enable the coating powder to be better coated on the surface of the ceramic particle, and enables the ceramic particle and the metal matrix to better form a reactive interface in the compounding process, and the bonding performance is better.
Description
Technical Field
The invention relates to the technical field of ceramic composite materials, in particular to a method for coating ceramic particles and a preparation method of a composite material.
Background
The ceramic particles have the advantages of low density, high strength, wear resistance and corrosion resistance, the metal material has good plasticity and toughness, and the ceramic/metal-based composite material which has the advantages of metal, the characteristics of ceramic, higher toughness, high hardness and high oxidation resistance can be produced by combining the ceramic particles with the metal material.
But the ceramic/metal matrix composite material is difficult to prepare due to poor wettability of the ceramic particles with the metal matrix. Attempts have been made to surface treat ceramic particles and then to composite them with a metal matrix to enhance their wettability. The chemical plating technology has the advantages of simple process, uniform plating layer, good bonding force with a substrate and the like, can plate on metal, can plate directly on the surface of non-conductors such as ceramics, plastics, glass and the like after pretreatment, and is a ceramic particle surface treatment technology widely applied at present, wherein Ni, Cu or Fe and alloys thereof are mainly plated. However, the above-mentioned plating elements diffuse into the molten metal at high temperatures and eventually disappear from the ceramic surface. Therefore, some ceramic powders, carbide powders, and coated powders such as metal powders (e.g., metallic titanium) that are stable at high temperature and react with molten metal at high temperature to form an interface have been considered as a new development direction of the "shell" in the core-shell material.
At present, two preparation methods mainly exist for a core-shell structure, the first method is to ball mill metals with lower melting points such as Ni powder and the like, then mix the metals with ceramic particles, and then perform vacuum sintering, and a stable core-shell structure can be obtained by the method, but the method needs a long time in the ball milling and vacuum sintering processes and has the defect of long preparation time; in addition, the method is limited by experimental conditions of high temperature and vacuum, and has the defects of high preparation temperature, high energy consumption and small yield. The second method is to directly bond the coating powder to the surface of the ceramic particle using an adhesive. The method can obtain the core-shell material in large batch, but in the preparation process of the ceramic/metal matrix composite material, the coating powder which is simply and mechanically combined is directly contacted with flowing high-temperature metal, so that the coating powder on the surface layer can be washed away; in addition, the binder in the inner layer can be volatilized rapidly under the condition of long-time high temperature, and even fall off from the surface of the ceramic particle to the molten metal integrally, so that the integrity and uniformity of a coating layer formed by the coating powder can be influenced to different degrees.
Disclosure of Invention
In view of the defects in the prior art, an object of the present invention is to provide a method for obtaining a large amount of ceramic particles coated with a coating powder-metal coating at a low temperature in a short time, and to obtain a composite material with a complete and uniform interface by casting the obtained ceramic particles coated with the coating powder-metal coating with a metal matrix.
An aspect of the present invention provides a method of coating ceramic particles, which may include the steps of: mixing the ceramic particles with the adhesive, adding the coating powder, and stirring to obtain ceramic particles coated by the coating powder; mixing the ceramic particles coated with the coating powder with polyvinyl alcohol, and drying to obtain ceramic particles with the coating powder and the polyvinyl alcohol attached to the surfaces; and activating the ceramic particles with the coating powder and the polyvinyl alcohol attached to the surfaces, and then plating by using a plating solution, such as chemical plating, to obtain the ceramic particles coated with the coating powder-metal coating.
Another aspect of the present invention provides a method for preparing a composite material, which may include the steps of: preparing the ceramic particles coated by the coating powder-metal coating by the method for coating the ceramic particles; and casting the ceramic particles coated by the coating powder-metal coating and the metal base to obtain the composite material.
Compared with the prior art, the beneficial effects of the invention at least comprise at least one of the following:
(1) the method of the invention utilizes the protective layer formed by the polyvinyl alcohol to ensure that the coating powder is better coated on the surface of the ceramic particles, and the coating powder is prevented from being separated from the ceramic particles and dispersed into the activation solution.
(2) The method of the invention protects the coating powder by using the metal layer formed after the chemical plating, can avoid the influence on the integrity and uniformity of the coating layer caused by the direct contact of the ceramic particles coated by the coating powder and the metal-based liquid at high temperature, can better form a reactive interface in the compounding process of the ceramic particles and the metal base, has better bonding performance, and can improve the interface bonding strength of the ceramic particles and the metal base.
(3) The method can obtain the ceramic particles coated by the coating powder-metal coating in a short time at a low temperature in a large batch.
Drawings
The above and other objects and features of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 shows ZTA p Before and after Ti/PVA activation with ZTA p Comparison of the appearance before and after Ti activation.
FIG. 2 shows ZTA p -Ti and ZTA p Comparison of the microtopography before and after Ti/PVA activation.
FIG. 3 shows ZTA p -area profile of Ti/PVA @ CuNi cross-sectional elements.
FIG. 4 shows ZTA p -elemental surface profile at Ti/PVA @ CuNi/HCCI interface.
Detailed Description
Hereinafter, a method of coating ceramic particles and a method of preparing a composite material according to the present invention will be described in detail with reference to the accompanying drawings and exemplary embodiments.
One aspect of the present invention provides a method of coating ceramic particles. In one exemplary embodiment of the method of coating ceramic particles of the present invention, the following steps may be included:
and S01, mixing the ceramic particles with the adhesive, adding the coating powder, and stirring to obtain the ceramic particles coated by the coating powder.
And S02, mixing the ceramic particles coated by the coating powder with polyvinyl alcohol, and drying to obtain the ceramic particles coated by the coating powder and the polyvinyl alcohol.
And S03, activating the coating powder and the polyvinyl alcohol coated ceramic particles, and performing chemical plating by using a plating solution after activation to obtain the coating powder-metal coating coated ceramic particles.
Further, the ceramic particles may be metal oxide ceramic particles, carbide ceramic particles, or boride ceramic particles. For example, it may be ZTA ceramic particles (ZTA) p ）、Al 2 O 3 Ceramic particles, TiC particles, SiC particles, ZrO 2 Ceramic particles, TiB 2 Particles or SiO 2 Ceramic particles. Of course, the kind of the ceramic particles of the present invention is not limited thereto, and may be WC particles or the like.
Further, the adhesive may be a water glass adhesive, a polyvinyl alcohol (PVA) adhesive, or the like. The binder is used for adhering the coating powder to the surface of the ceramic particles.
Further, the coating powder can be one or a combination of metal powder, ceramic powder, carbide powder and boride powder. For example, the metal powder may be Ti powder, Ni powder, Cu powder, or a mixture thereof, and the like. For example, when the ceramic particles are ZTA p When the coating powder is Ti powder, the obtained ceramic particles coated by the coating powder are ZTA p -Ti. By the coating method, non-conductive ceramic powder, carbide powder and the like can be coated on the surface of the ceramic particles at low temperature and under the condition of simple process flow.
Further, the radial size of the coated powder can be 0.1-10 μm. The size of the coating powder is less than 0.1 mu m, and the coating layer formed on the surface of the ceramic particles is too compact, so that high-temperature molten metal cannot be cast and infiltrated during the preparation of the composite material, and the composite effect is influenced; the coated powder has too large size, which affects the coating uniformity. For example, the coated powder may have a radial dimension of 0.3 μm to 8 μm or 1 μm to 7 μm.
Furthermore, polyvinyl alcohol (PVA) is added to form a layer of protective film on the surface of the ceramic particles after the coating powder is coated, so that the coating powder can be prevented from being separated from the surface of the ceramic particles and dispersed in the activation liquid in the activation process, and the coating powder can be better attached to the surface of the ceramic particles to form a coating layer. Preferably, the mass concentration of PVA can be 1.5% -8.5%. If the mass concentration of PVA is lower than 1.5%, the formed protective film is too thin, and the coating powder can be separated from the surface of the ceramic particles and enter the activating solution during activation, so that the coating powder cannot be prevented from being separated from the surface of the ceramic particles, and the coating layer formed by the coating powder is influenced; if the mass concentration of PVA is higher than 8.5%, the formed protective film is too thick, the protective film cannot be completely dissolved during activation, the final plating effect is influenced, and the activation effect exists on the protective film due to the too thick protective film, so that the activation effect cannot be exerted on the coating powder, and the subsequent chemical plating is influenced. And a proper protective film thickness is formed, a part of the protective film is dissolved in the activation process, a part of the undissolved protective film plays a protective role, and the activated and residual film is mixed on the surface of the coated powder, so that the coated powder is complete and active. Preferentially, the mass concentration of PVA can be 2.5-3.5% (2.5-3.5 g/L), and within the mass concentration range, the formed protective film has moderate thickness, so that the activation effect of the coating powder can not be influenced while the coating powder can be well prevented from being separated from the ceramic particles. Here, the mass concentration of PVA is referred to as PVA mass/deionized water mass (for example, the mass concentration of PVA is 3%, and when the mass of deionized water is 100g, 3g of PVA are added). PVA may be prepared by stirring at 500rpm for 6 hours at 85 ℃ to give a viscous clear solution. Of course, the preparation of PVA of the present invention is not limited thereto, and PVA may be added to deionized water and stirred uniformly.
Further, after the ceramic particles coated with the coating powder are mixed with polyvinyl alcohol, the drying temperature can be 50-70 ℃. Drying in the above temperature range can form a protective film on the surface of the ceramic particles with the polyvinyl alcohol, and prevent the ceramic particles from being bonded to each other due to the presence of the polyvinyl alcohol, thereby preventing the bonding surfaces between the ceramic particles from being effectively plated. The drying time can be 1 min-2 min.
Further, the activation of the coating powder and the polyvinyl alcohol-coated ceramic particles may include activation at a temperature of 150 to 200 ℃ using an activation liquid, for example, the activation may be performed at 170 ℃. The purpose of activation is to provide the surface of the particles with metal active sites to better plate the metal contained in the plating solution onto the surface of the ceramic particles. The activating solution may be Ni (Ac) 2 An activating solution of Ni (Ac) 2 The activating solution may be composed of Ni (Ac) 2 、NaH 2 PO 2 、C 2 H 6 O and H 2 O composition of, wherein, Ni (Ac) 2 、NaH 2 PO 2 、C 2 H 6 O and H 2 The mass concentration ratio of O may be 1 (0.5-1.5) to 10-20 to 1-3. For example, it may be 1:1:15: 2. The activation time is only required to activate all the ceramic particles coated by the coating powder, and can be adjusted according to the yield and the completeness of the activation, for example, the activation time can be 20min to 30min, for example, 25 min. Specifically, ceramic particles ZTA having titanium powder and polyvinyl alcohol adhered to their surfaces p Activation of Ti/PVA, possibly with Ni (Ac) 2 :NaH 2 PO 2 :C 2 H 6 O:H 2 Activating the components with the mass concentration ratio of O =1:1:15:2 for 25min at 170 ℃ to obtain Ni-activated ZTA p -Ti/PVA/Ni 2+ . Of course, the activating solution may also be PbCl 2 Activating solutions or AgNO 3 An activating solution.
Further, the plating solution may be a plating solution containing an Ni element and/or a Cu element. For example, the plating solution may contain nickel sulfate, or copper sulfate, or a mixture of nickel sulfate and copper sulfate.
For example, in the case of a CuNi alloy as the metal plating layer,the plating solution may contain nickel sulfate (NiSO) 4 ·6H 2 O), copper sulfate (CuSO) 4 ·5H 2 O), sodium citrate (C) 6 H 5 Na 3 O 7 •2H 2 O), sodium hypophosphite (NaH) 2 PO 2 •H 2 O), boric acid (H) 3 BO 3 ) And choline chloride-ethylene glycol (ChCl-EG), wherein the concentration of nickel sulfate in the plating solution can be 25-35 g/L, and copper sulfate (CuSO) 4 ·5H 2 O) with a concentration of 25-35 g/L, sodium citrate (C) 6 H 5 Na 3 O 7 •2H 2 O) with a concentration of 28-33 g/L, sodium hypophosphite (NaH) 2 PO 2 •H 2 O) at a concentration of 27 to 38g/L, boric acid (H) 3 BO 3 ) The concentration of (b) may be 13g/L to 17g/L and the concentration of choline chloride-ethylene glycol (ChCl-EG) may be 0g/L to 40 g/L. And mixing the coating powder and the polyvinyl alcohol coated ceramic particles with the plating solution, adjusting the pH to 9-10, and chemically plating for 30-70 min at the rotation speed of 80-120 rpm and the temperature of 50-80 ℃. For example, the concentration of nickel sulfate in the plating solution may be 30g/L, copper sulfate (CuSO) 4 ·5H 2 O) concentration may be 30g/L, sodium citrate (C) 6 H 5 Na 3 O 7 •2H 2 O) may be 30g/L, sodium hypophosphite (NaH) 2 PO 2 •H 2 O) may be 32g/L, boric acid (H) 3 BO 3 ) The concentration of (b) may be 15g/L and the concentration of choline chloride-ethylene glycol (ChCl-EG) may be 25 g/L. And mixing the coating powder and the polyvinyl alcohol coated ceramic particles with the plating solution, adjusting the pH to 9.2, and performing chemical plating for 50min at the rotation speed of 100rpm and the temperature of 65 ℃. For example, for Ni activated ZTA p -Ti/PVA/Ni 2+ The Ti-CuNi coated ZTA, namely ZTA, can be obtained after plating by the plating solution p -Ti/PVA@CuNi。
In another aspect of the invention, a method for preparing a composite material is provided. In one exemplary embodiment of the method of making a composite material of the present invention, the method may comprise the steps of:
and S100, mixing the ceramic particles with the adhesive, adding the coating powder, and stirring to obtain the ceramic particles coated by the coating powder.
S101, mixing the ceramic particles coated by the coating powder with polyvinyl alcohol, and drying to obtain the coating powder and polyvinyl alcohol-coated ceramic particles.
S102, activating the coating powder and the ceramic particles coated by the polyvinyl alcohol, and carrying out chemical plating by using a plating solution containing metal to obtain the ceramic particles coated by the coating powder-metal plating layer.
S103, casting the ceramic particles coated by the coating powder-metal coating and the metal base to obtain the composite material.
The steps S100 to S102 are the same as the above-mentioned steps S01 to S03, and a description thereof will not be repeated. At present, in the process of preparing a ceramic/metal matrix composite material in the prior art, coating powder is directly bonded on the surface of ceramic particles by using an adhesive and then is directly cast with a metal matrix, and the method has the following problems: on one hand, the coating powder which is simply and mechanically combined is directly contacted with flowing high-temperature metal, so that the coating powder on the surface layer can be washed away; on the other hand, the adhesive can be volatilized rapidly under a long-time high-temperature condition, and even fall off from the surface of the ceramic particle to the high-temperature molten metal integrally, so that the integrity and the uniformity of the coating layer can be influenced to different degrees. The ceramic particles coated with the coating powder-metal coating layer prepared in the steps S100 to S102 can be completely and uniformly coated with the coating powder on the surfaces of the ceramic particles. After the chemical plating, a metal coating can be formed on the surface of the coating layer, so that the coating powder is prevented from directly contacting with flowing high-temperature metal, the coating powder is prevented from being washed away by metal liquid, the coating powder and the metal layer formed after the chemical plating can enable ceramic particles and a metal base to better form a reactive interface in a composite process, and the bonding performance is better.
Further, the metal matrix may be titanium, copper, iron or steel based, for example, the metal matrix may be HCCI high chromium cast iron. Of course, the metal base of the present invention is not limited thereto, and for example, a vanadium base, an aluminum base, and the like are also possible.
Further, the casting treatment may be a pressureless infiltration treatment.
For a better understanding of the present invention, the following further illustrates the contents of the present invention with reference to specific examples, but the contents of the present invention are not limited to the following examples.
Example 1
Step 2, mixing ZTA p Mixing Ti with PVA with the mass concentration of 3%, and drying at 60 ℃ for 1min to obtain coated powder Ti and PVA-coated ZTA p I.e. ZTA p -Ti/PVA。
Step 3, mixing ZTA p -Ti/PVA with Ni (Ac) 2 Mixing the activating solutions, and activating at 170 deg.C for 25min to obtain activated ceramic particles ZTA p -Ti/PVA/Ni 2+ Wherein, Ni (Ac) 2 The activating solution is Ni (Ac) 2 、NaH 2 PO 2 、C 2 H 6 O and H 2 And the mass concentration ratio of O is 1:1:15: 2.
And 4, preparing the CuNi plating solution. Nickel sulfate (NiSO) in CuNi plating solution 4 ·6H 2 O) concentration of 30g/L, copper sulfate (CuSO) 4 ·5H 2 O) concentration may be 30g/L, sodium citrate (C) 6 H 5 Na 3 O 7 •2H 2 O) may be 30g/L, sodium hypophosphite (NaH) 2 PO 2 •H 2 O) may be 32g/L, boric acid (H) 3 BO 3 ) The concentration of (b) may be 15g/L and the concentration of choline chloride-ethylene glycol (ChCl-EG) may be 10 g/L.
Step 5, activating the ceramic particles ZTA p -Ti/PVA/Ni 2+ Mixing with CuNi plating solution, and chemically plating at a rotation speed of 100rpm and a temperature of 65 deg.C for 50min under the condition of pH adjusted to 9.5 to obtain CuNi-coated ZTA p Ti/PVA, i.e. ZTA p -Ti/PVA@CuNi。
Step 6, ZTA p Carrying out non-pressure infiltration treatment on the-Ti/PVA @ CuNi and the high-chromium cast iron to obtain the composite material ZTA p -Ti/PVA@CuNi/HCCI。
Comparative example 1
Step 100, particles of ZTA (ZTA) p ) Mixing with water glass adhesive, adding Ti powder with particle size of 4 μm, mechanically stirring to obtain powder-coated Ti-coated ZTA granule, i.e. ZTA p -Ti。
Step 200, ZTA p -Ti with Ni (Ac) 2 Mixing the activating solutions, and activating at 170 deg.C for 25min to obtain activated ceramic particles ZTA p -Ti/Ni 2+ Wherein, Ni (Ac) 2 The activating solution is Ni (Ac) 2 、NaH 2 PO 2 、C 2 H 6 O and H 2 And the mass concentration ratio of O is 1:1:15: 2.
Step 300, preparing CuNi plating solution. The concentration of nickel sulfate in the CuNi plating solution is 30g/L, and copper sulfate (CuSO) 4 ·5H 2 O) concentration may be 30g/L, sodium citrate (C) 6 H 5 Na 3 O 7 •2H 2 O) may be 30g/L, sodium hypophosphite (NaH) 2 PO 2 •H 2 O) may be 32g/L, boric acid (H) 3 BO 3 ) The concentration of (b) may be 15g/L and the concentration of choline chloride-ethylene glycol (ChCl-EG) may be 10 g/L.
Step 400, activating the ceramic particles ZTA p -Ti/Ni 2+ Mixing with CuNi plating solution, and chemically plating at a rotation speed of 100rpm and a temperature of 65 deg.C for 50min under the condition of pH adjusted to 9.5 to obtain Ti-CuNi coated ZTA, i.e. ZTA p -Ti@CuNi。
Step 500, ZTA p Carrying out non-pressure infiltration treatment on the-Ti @ CuNi and the high-chromium cast iron to obtain the composite material ZTA p -Ti@CuNi/HCCI。
Comparative example 1 compared to example 1, the difference being that comparative example 1 did not perform step 2 of example 1, i.e. ZTA was not applied p Ti is mixed with PVA, the other steps being identical.
As shown in FIG. 1, FIG. 1 shows the ZTA of example 1 p ZTA before and after activation of Ti/PVA and comparative example 1 p Comparison of appearance and morphology before and after Ti activation. White is a small crucible, fig. (a) 1 And c 1 ) The green liquid is the activating liquid. Picture (a)Is the original ceramic particles and is grey white. After step 1 (or step 100), the ZTA particles become gray black after coating Ti powder, as shown in fig. (b). And after step 2, in ZTA p After coating a layer of PVA on the basis of Ti particles, the ceramic still has a grey black color, but the surface has a distinct gloss, as shown in the graph (c). When not coated with PVA, Ti powder will be detached from the surface of ZTA ceramic particles as shown in (b) 1 ) The activation solution turned black as shown. And PVA-coated ZTA p Ti, the color of the activation solution is still pale green, as shown in (c) 1 ) Shown in (a) when not coated with titanium 1 ) The color is consistent, and the PVA film is proved to well protect the Ti powder coated by the ZTA particles. After sintering at a high temperature of 30min, the color of the sintered ZTA ceramic particles was observed (a) 2 ) The original ZTA particles are gray due to Ni (Ac) in the activation solution 2 After reduction with sodium hypophosphite, Ni is activated. And (b) 2 ) Mixing of Ti powder into the activating solution without PVA protection results in sintered ZTA p Is black in color. FIG. C 2 ) Middle, ZTA p Color of Ti-coated PVA after activation and (a) 2 ) No difference, therefore, it indicates that PVA can be applied to ZTA at high temperature p Ti plays a role of protection and does not influence the activation thereof so as to carry out the next electroless plating process.
FIG. 2 shows ZTA of example 1 p ZTA before and after activation of Ti/PVA and comparative example 1 p Comparison of the microtopography before and after Ti activation. The ZTA particles (fig. a) are coated with Ti powder p The Ti powder on the surface of the Ti particles is loose (fig. b), in ZTA p After a layer of PVA is coated on the basis of Ti particles, Ti powder is coated in the Ti particles, and only a smooth PVA film is presented on the surface of the Ti particles. ZTA without PVA coating p The surface of the-Ti @ CuNi particles is observed to be CuNi alloy spherical particles and a naked ZTA surface (shown in a figure b) 1 ) (ii) a And ZTA obtained by coating PVA p The surface of the-Ti @ CuNi particle is uniformly coated by CuNi alloy spherical particles (as shown in a figure c) 1 ). It can also be seen from the cross section that ZTA obtained by coating with PVA p -Ti @ CuNi particles, the Ti powder being coated on the ZTA particle sheet in a complete and uniform thicknessNoodle (see figure c) 2 ) ZTA plated without PVA coating p -Ti @ CuNi particles, substantial loss of Ti powder (FIG. b) 2 ）。
FIG. 3 shows ZTA prepared in example 1 p -area profile of Ti/PVA @ CuNi cross-sectional elements. Panel (a) is ZTA prepared by step 5 p -Ti/PVA @ CuNi particles appearance morphology, copper-nickel coated ZTA p The Ti particles are smooth on the surface and have a red metallic luster. As can be seen from the surface distribution of the elements in the graph (b), the mixture of Ti powder and water glass is uniformly coated on the surface of ZTA particles by the CuNi coating.
FIG. 4 shows ZTA prepared in example 1 p -element area profile at Ti @ CuNi/HCCI interface. FIG. (a) is ZTA prepared in step 6 p -the appearance of Ti @ CuNi/HCCI composite material, the composite material has no pore defects. As can be seen from the graph (b) and the surface distribution of the elements, under the casting infiltration effect of the high-temperature molten iron, the CuNi coating is melted and reacts with Ti powder, and forms a uniform and stable reactive interface with the elements in the high-chromium cast iron.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method of coating ceramic particles, comprising the steps of:
mixing the ceramic particles with the adhesive, adding the coating powder, and stirring to obtain ceramic particles coated by the coating powder;
mixing the ceramic particles coated with the coating powder with polyvinyl alcohol, and drying to obtain ceramic particles with the coating powder and the polyvinyl alcohol attached to the surfaces;
and activating the ceramic particles with the coating powder and the polyvinyl alcohol attached to the surfaces, and plating by using a plating solution after activation to obtain the ceramic particles coated by the coating powder-metal coating.
2. The method of claim 1, wherein the drying temperature is 50 ℃ to 70 ℃.
3. The method of claim 1 or 2, wherein the coating powder is one or more of metal powder, ceramic powder, carbide powder and boride powder.
4. The method of claim 1 or 2, wherein the coating powder has a radial dimension of 0.1 μm to 10 μm.
5. The method of claim 1 or 2, wherein the polyvinyl alcohol is present in a concentration of 1.5% to 8.5% by mass.
6. A method of coating ceramic particles according to claim 1 or 2, wherein the plating solution is one or a mixture of two of a nickel-containing plating solution and a copper-containing plating solution.
7. The method of claim 1 or 2, wherein the activating the ceramic particles with the surface coating powder and the polyvinyl alcohol comprises mixing the ceramic particles with the surface coating powder and the polyvinyl alcohol with an activating solution, and then activating at a temperature of 150 ℃ to 200 ℃.
8. The method of claim 7, wherein the activating liquid is Ni (Ac) 2 Activating solution, PbCl 2 Activating solutions or AgNO 3 An activating solution.
9. A preparation method of a composite material is characterized by comprising the following steps:
coating powder-metal coating-coated ceramic particles prepared by the method for coating ceramic particles according to any one of claims 1 to 8;
and casting the ceramic particles coated by the coating powder-metal coating and the metal base to obtain the composite material.
10. The method of producing a composite material according to claim 9, wherein the metal base is titanium base, copper base, iron base, or steel base.
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