CN114606482A - Method for preparing Cu @ ZrC core-shell complex-phase particle material by chemical plating - Google Patents
Method for preparing Cu @ ZrC core-shell complex-phase particle material by chemical plating Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 60
- 239000002245 particle Substances 0.000 title claims abstract description 48
- 239000011258 core-shell material Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000000126 substance Substances 0.000 title claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 64
- 239000010949 copper Substances 0.000 claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052802 copper Inorganic materials 0.000 claims abstract description 56
- 239000011156 metal matrix composite Substances 0.000 claims abstract description 21
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 14
- 239000008187 granular material Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- 206010070834 Sensitisation Diseases 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 230000008313 sensitization Effects 0.000 claims description 6
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 6
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 4
- 239000006172 buffering agent Substances 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical group [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 4
- 229940038773 trisodium citrate Drugs 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000007772 electroless plating Methods 0.000 claims 9
- 239000011238 particulate composite Substances 0.000 claims 1
- 230000002787 reinforcement Effects 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000000919 ceramic Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000004663 powder metallurgy Methods 0.000 abstract description 3
- 229910026551 ZrC Inorganic materials 0.000 description 79
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 56
- 239000002131 composite material Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 239000011246 composite particle Substances 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- -1 hydroxide ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007550 Rockwell hardness test Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
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Images
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
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1642—Substrates other than metallic, e.g. inorganic or organic or non-conductive semiconductor
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1889—Multistep pretreatment with use of metal first
-
- 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
- C23C18/40—Coating with copper using reducing agents
Abstract
The invention discloses a method for preparing a Cu @ ZrC core-shell complex-phase granular material by chemical plating, and belongs to the technical field of powder metallurgy material manufacturing. The method comprises the following steps: the preparation method comprises the following steps of sequentially carrying out oil removal treatment, coarsening treatment, sensitizing treatment, activating treatment and dispersing treatment on ZrC powder to obtain ZrC powder to be plated with copper, and then carrying out chemical copper plating treatment on the ZrC powder to be plated with copper to obtain the Cu @ ZrC core-shell complex-phase granular material. The method can effectively improve the bonding property between the ZrC ceramic phase and the metal matrix, further can be used as a reinforcement to improve the mechanical property of the metal matrix composite, and provides a new reinforcement phase particle selection for the preparation of MMCs of the metal matrix composite.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy material manufacturing, and particularly relates to a method for preparing a Cu @ ZrC core-shell complex-phase granular material by chemical plating.
Background
Metal Matrix Composites (MMCs) are composites of metals and their alloys as matrices, artificially combined with one or more metallic or non-metallic reinforcing phases. The MMCs have the characteristics of high strength and high elasticity, and simultaneously have excellent performances of wear resistance, high temperature resistance and the like. The metal matrix composite material is mainly divided into a particle reinforced metal matrix composite material and a fiber reinforced metal matrix composite material, and compared with the fiber reinforced metal matrix composite material, the particle reinforced metal matrix composite material has more advantages in production process and cost and more uniform performance. Therefore, in the actual production process, the reinforcing particles are used for reinforcing the metal matrix composite material. ZrC is a high-temperature structural ceramic material with excellent performance, has high hardness, high strength, high wear resistance and high temperature resistance, is very suitable for being used as a reinforcing phase particle of a metal matrix composite, but is difficult to sinter due to small atomic diffusion coefficient, so that the ZrC is poor in combination with matrix metal, and the application of the ZrC is limited. Therefore, it is necessary to improve the dispersibility of ZrC particles and the bondability to the matrix metal by modifying ZrC.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for preparing a Cu @ ZrC core-shell complex phase particle material by chemical plating, wherein the Cu @ ZrC core-shell complex phase particle is obtained by uniformly plating copper on the surface of submicron ZrC powder by chemical plating, and the bonding property between a ZrC ceramic phase and a metal matrix is effectively improved.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes of the invention is a method for preparing a Cu @ ZrC core-shell complex-phase particle material by chemical plating, which comprises the following steps: the preparation method comprises the following steps of sequentially carrying out oil removal treatment, coarsening treatment, sensitizing treatment, activating treatment and dispersing treatment on ZrC powder to obtain ZrC powder to be plated with copper, and then carrying out chemical copper plating treatment on the ZrC powder to be plated with copper to obtain the Cu @ ZrC core-shell complex-phase granular material.
Further, the ZrC powder is submicron ZrC powder.
Further, the oil removal treatment specifically comprises the following operations: soaking ZrC powder in NaOH solution, filtering, cleaning and drying.
Further, the concentration of the NaOH solution was 15 vol.%.
Further, the drying temperature in the oil removing treatment is 50 ℃ and the time is 10 hours.
Further, the specific operation of the coarsening process is as follows: the ZrC powder after the oil removal treatment is put in HNO3Ultrasonic treatment in solution, filtering, cleaning and drying, wherein the HNO is prepared by3The concentration of the solution was 40 vol.%.
Further, the drying temperature in the coarsening treatment is 50 ℃ and the time is 10 h.
Further, the specific operations of the sensitization treatment are as follows: performing ultrasonic treatment on the coarsened ZrC powder in a sensitizing solution, cleaning and filtering, wherein the sensitizing solution is SnCl2And a mixed solution of HCl.
Further, SnCl in the sensitizing solution2The concentration of (2) was 20g/L and the concentration of HCl was 20 g/L.
Further, the specific operations of the activation treatment are as follows: the sensitized ZrC powder is placed in AgNO3Ultrasonic treatment in solution, filtering and washing to neutrality, wherein the AgNO is3The concentration of the solution was 5 g/L.
Further, the dispersion treatment specifically includes: and performing dispersion treatment on the activated ZrC powder by using a dispersing agent to obtain the ZrC powder to be plated with copper, wherein the dispersing agent is a mixed solution of sodium pyrophosphate and water glass, and the concentration of sodium pyrophosphate in the dispersing agent is 0.5 wt.%.
Further, the dispersion treatment specifically includes: and adding the activated ZrC powder into a dispersing agent, and performing ultrasonic dispersion treatment for 0.5h, wherein the power of the ultrasonic dispersion treatment is 40 kHz.
Furthermore, the mass volume ratio of the activated ZrC powder to the dispersing agent is 1g:10 ml.
Further, the specific operation of the electroless copper plating treatment is as follows: sequentially adding copper sulfate, a complexing agent, a buffering agent and a catalyst into water to obtain a mixed solution, adjusting the pH value of the mixed solution to 11, then sequentially adding ZrC powder to be plated with copper and a reducing agent to obtain a chemical copper plating reaction system, reacting the chemical copper plating reaction system at the temperature of 60 ℃, filtering, cleaning and drying after the reaction is finished to obtain the Cu @ ZrC core-shell complex phase granular material.
Further, the complexing agent is trisodium citrate, the buffering agent is boric acid, the catalyst is nickel chloride hexahydrate, the reducing agent is sodium hypophosphite, and the mass ratio of copper sulfate: and (3) after copper plating of ZrC powder: sodium hypophosphite 40:20: 15; the pH value of the electroless copper plating reaction system is maintained at 10.5-11.5 in the whole reaction process.
Further, copper sulfate: trisodium citrate: boric acid: nickel chloride hexahydrate: and (3) after copper plating of ZrC powder: sodium hypophosphite 40:258:15:23.8:20: 15.
Further, the mass volume ratio of the copper sulfate to the water is 40g: 300-700 ml.
The reaction principle of electroless copper plating is as follows:
the chemical copper plating reaction is more violent, the pH value of the solution is gradually reduced during the reaction, and hydroxide ions in the system are gradually reduced, so that the chemical copper plating reaction is slowed down or even can not be carried out due to the lack of the hydroxide ions, therefore, sodium hydroxide solution is required to be continuously added to adjust the pH value, and the pH value of the plating solution is kept at about 11.
Further, the reaction time is 1-4 h.
The second technical scheme of the invention is that the Cu @ ZrC core-shell complex-phase particle material is prepared by the method for preparing the Cu @ ZrC core-shell complex-phase particle material by chemical plating.
Further, the core of the Cu @ ZrC core-shell complex phase particle material is a ZrC particle, and the shell is a Cu layer.
The third technical scheme of the invention is the application of the Cu @ ZrC core-shell complex-phase particle material prepared by chemical plating in a metal matrix composite.
Further, the Cu @ ZrC core-shell complex phase particle material prepared by chemical plating is used as a reinforcement of the metal matrix composite, the addition amount of the Cu @ ZrC core-shell complex phase particle material in the metal matrix composite is 20 vol.%, and the volume ratio of zirconium carbide to copper metal in the Cu @ ZrC core-shell complex phase particle material is 1: 2.
Compared with the prior art, the invention has the following beneficial effects:
(1) the Cu @ ZrC core-shell complex phase particle reinforced material is prepared by uniformly plating copper on the surface of ZrC powder through oil removal treatment, roughening treatment, sensitizing treatment, activating treatment, dispersing treatment and chemical copper plating treatment, impurities such as oil stains and the like on the surface of the ZrC powder can be removed through the oil removal treatment and roughening treatment, the specific surface area and the roughness of the ZrC powder are improved, the adhesion force of a copper plating layer on the ZrC powder is improved, agglomeration of the ZrC powder can be prevented through the sensitizing treatment, the activating treatment and the dispersing treatment, the uniformity and the quality of the copper plating layer are improved, and the Cu @ ZrC core-shell complex phase particle reinforced material with high dispersibility and uniformity is prepared through the synergistic cooperation of the steps. The method can effectively improve the bonding property between the ZrC ceramic phase and the metal matrix, further can be used as a reinforcement to improve the mechanical property of the metal matrix composite, and provides a new reinforcement phase particle selection for the preparation of MMCs of the metal matrix composite.
(2) The excellent properties of MMCs are largely influenced by the interfacial state characteristics, in addition to being largely dependent on the structure and properties of the components. In order to obtain a metal matrix composite material with excellent properties and capable of meeting various requirements, a proper interface is required so that the reinforcement and the matrix have good physicochemical and mechanical compatibility. According to the invention, copper is coated on the surface of the reinforcing particles to modify the reinforcing particles to prepare the core-shell composite particles, so that the interface wettability and the chemical compatibility between the ZrC ceramic particle reinforcement and a matrix can be improved, the uniform dispersion among different-phase particles is realized, and the excellent characteristics of the different-phase particles are fully exerted.
(3) The method adopts a chemical plating mode to plate copper on the surfaces of the ZrC ceramic particles, compared with electroplating, the chemical plating does not need an external power supply, metal ions are reduced into metal by using a reducing agent in a solution and are deposited on the surface of a substrate to form a plating layer, and the method is convenient to operate, simple in process, uniform in plating layer, small in porosity and good in appearance. Compared with the conventional chemical plating process, the method avoids the corrosion of the component to be plated by adopting virulent HF, and is safe and environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an SEM image of ZrC powder without being subjected to surface copper plating;
FIG. 2 is an SEM image of Cu @ ZrC core-shell composite particles after being subjected to surface copper plating prepared in example 1;
FIG. 3 is a schematic view of the microstructure of the Cu @ ZrC core-shell composite particle after being subjected to the surface copper plating treatment, prepared in example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
(1) Oil removal treatment: adding 20g of submicron ZrC powder (with the particle size of 3-5 microns) into 100ml of NaOH solution with the concentration of 15 vol.%, soaking for 1h, removing oil stains on the surface of the powder, repeatedly filtering and cleaning for 3 times by using the NaOH solution with the concentration of 15 vol.%, repeatedly filtering and cleaning for 3 times by using distilled water, and drying for 10h at 50 ℃ in a vacuum drying oven.
(2) Roughening treatment: the ZrC powder after oil removal treatment is subjected to HNO with the concentration of 40 Vol%3Carrying out medium ultrasonic treatment for 2 hours (ultrasonic frequency is 40kHz), filtering after powder is settled, repeatedly cleaning for 3 times by using distilled water, and then drying for 10 hours in a vacuum drying oven at 50 ℃ for later use; the surface of the coarsened ZrC powder is relatively rough.
(3) Sensitization treatment: putting the coarsened ZrC powder into 100ml of LSnCl with the concentration of 20g/LSnCl2Carrying out ultrasonic treatment for 1h (the ultrasonic frequency is 40kHz) in a mixed sensitizing solution of +20g/L HCl, continuously stirring by using a glass rod in the sensitizing process to prevent ZrC powder from depositing at the bottom of a beaker, and filtering and cleaning for 3 times by using distilled water after the sensitizing treatment is finished; the shape of the sensitized ZrC powder particles is more rugged than that of the non-sensitized surface, and the particle size is not obviously changed.
(4) Activation treatment: putting the sensitized ZrC powder into 100ml AgNO with the concentration of 5g/L3Performing ultrasonic treatment in the solution for 30min (ultrasonic frequency is 40kHz), washing with distilled water to neutrality, and drying in a vacuum drying oven at 50 deg.C for 5 h; the shape and structure of the ZrC powder after activation treatment have no obvious change.
(5) And (3) dispersion treatment: selecting a mixed solution of sodium pyrophosphate and water glass (the concentration of the sodium pyrophosphate is 0.5 wt.%) as a dispersing agent, and performing dispersion treatment on the submicron ZrC powder, wherein the mass-volume ratio of the activated ZrC powder to the dispersing agent is 1g:10 ml; and (3) adding the activated ZrC powder into a dispersing agent, and performing ultrasonic dispersion treatment for 0.5h (ultrasonic frequency is 40kHz), wherein the ZrC powder after the dispersion treatment is well dispersed, and no obvious agglomeration phenomenon exists among particles.
(6) Chemical copper plating treatment: 40g of copper sulfate was weighed into a 1L beaker, and 500ml of distilled water was added, followed by dissolution by mechanical stirring in a 60 ℃ constant temperature water bath. 258g complexing agent trisodium citrate is added to the copper sulphate solution, after which 15g buffer boric acid, 23.8g catalyst nickel chloride hexahydrate (NiCl) are added in succession2·6H2O), when the reagent is completely dissolved, adding sodium hydroxide to adjust the pH value to 11, adding 20g of dispersed ZrC powder after adjustment, and finally adding 15g of reducing agent sodium hypophosphite to obtain a chemical copper plating reaction system. The temperature of the chemical copper plating reaction system is constant at 60 ℃, and the reaction lasts for 3 hours. The chemical copper plating reaction is violent, the pH value of the solution is gradually reduced while the chemical copper plating reaction is violent, and sodium hydroxide solution is continuously added in the process to adjust the pH value, so that the pH value of the plating solution is kept at about 11 (10.5-11.5). And (3) after the reaction is finished, closing the stirrer and the water bath, cleaning the copper-plated ZrC powder for 6 times by using distilled water, and drying in an air-blast drying oven at the temperature of 80 ℃ for 5 hours to obtain the Cu @ ZrC core-shell complex-phase granular material.
ZrC powder raw materials which are not subjected to surface copper plating treatment (oil removal treatment, coarsening treatment, sensitization treatment, activation treatment and dispersion treatment are not carried out, namely any treatment is not carried out) and the Cu @ ZrC core-shell complex-phase particle materials which are prepared in the example 1 and are subjected to surface copper plating treatment are respectively taken to carry out electron microscope scanning, wherein the figure 1 is an SEM picture of ZrC powder which is not subjected to surface copper plating treatment, the figure 2 is an SEM picture of Cu @ ZrC core-shell complex-phase particles which are prepared in the example 1 and are subjected to surface copper plating treatment, and as can be seen from the figures 1 and 2, the ZrC powder still has good dispersibility and no obvious agglomeration phenomenon after copper plating, while the ZrC powder which is not subjected to surface copper plating treatment has obvious agglomeration phenomenon and uneven dispersion.
The schematic microstructure of the Cu @ ZrC core-shell complex phase particle material subjected to the surface copper plating treatment prepared in example 1 is shown in fig. 3, and as can be seen from fig. 3, the Cu @ ZrC core-shell complex phase particle prepared in example 1 has a core-shell structure, and a uniform copper layer is formed on the surface of the ZrC particle.
Comparative example 1
The difference from example 1 is that the Cu @ ZrC powder after activation treatment was used as it is without dispersion treatment to perform electroless copper plating treatment.
Comparative example 2
The difference from example 1 is that the Cu @ ZrC powder after sensitization treatment was dried and then directly subjected to dispersion treatment and electroless copper plating treatment without activation treatment.
Effect verification
The Cu @ ZrC core-shell complex-phase particle materials prepared in the embodiment 1 and the comparative examples 1-2 of the invention and ZrC powder raw materials which are not subjected to surface copper plating treatment (oil removal treatment, coarsening treatment, sensitization treatment, activation treatment and dispersion treatment, namely, no treatment) are respectively taken as reinforcements to prepare the titanium-based composite material, and the addition amount of the reinforcements is 20 vol% of the metal-based composite material. The preparation method comprises the following steps:
firstly, mixing Ti powder, 6Al-4V alloy powder and ZrC powder or Cu @ ZrC core-shell complex phase particles which are not subjected to surface copper plating according to a formula by ball milling according to a certain proportion, and carrying out ball milling at a rotating speed of 80r/min for 20 min. Ball milling, placing the mixed powder into a mold, cold isostatic pressing at 300MPa to obtain a cylindrical blank, and vacuum sintering the blank in a vacuum resistance furnace to obtain a vacuum degree of 5 × 10-2And (4) Pa above, raising the temperature to 1500 ℃ at the speed of 20 ℃/min, and preserving the temperature for 3h to prepare the powder metallurgy titanium-based composite material block.
The following performance tests were performed on the titanium-based composite material and the titanium alloy material, using the titanium-based composite material prepared using the Cu @ ZrC core-shell complex-phase particles prepared in example 1 and comparative examples 1 to 2 as corresponding examples 1 and 1 to 2, using the ZrC powder without surface copper plating as a reinforcement as a control 1, and using the titanium alloy material prepared without reinforcement as a blank control 2 (the titanium alloy preparation method is the same as the titanium-based composite material preparation method except that no reinforcement is added).
(1) Mechanical Property test
The titanium-based composite material of example 1, comparative examples 1-2 and control 1 and the titanium alloy material of blank control 2 were measured for the density of the sintered material according to the method specified in GB/T10421-2002 (determination of density of sintered metal friction material), the tensile strength performance was measured according to the GB/T228-2002 metal material room temperature tensile test method, and the Rockwell hardness test was performed using a digital display Rockwell hardness tester, with the test results shown in Table 1:
TABLE 1
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for preparing a Cu @ ZrC core-shell complex-phase particle material by chemical plating is characterized by comprising the following steps: the preparation method comprises the following steps of sequentially carrying out oil removal treatment, coarsening treatment, sensitizing treatment, activating treatment and dispersing treatment on ZrC powder to obtain ZrC powder to be plated with copper, and then carrying out chemical copper plating treatment on the ZrC powder to be plated with copper to obtain the Cu @ ZrC core-shell complex-phase granular material.
2. The method for preparing the Cu @ ZrC core-shell complex phase particle material by the electroless plating process according to claim 1, wherein the oil removing process comprises the following specific operations: soaking ZrC powder in NaOH solution, filtering, cleaning and drying; the specific operation of the coarsening treatment is as follows: the ZrC powder after the oil removal treatment is put in HNO3Ultrasonic treatment in solution, filtering, cleaning and drying, wherein the HNO is prepared by3The concentration of the solution was 40 vol.%.
3. The method for preparing the Cu @ ZrC core-shell complex phase particle material by the electroless plating according to claim 1, wherein the specific operations of the sensitization treatment are as follows: carrying out ultrasonic treatment on the coarsened ZrC powder in a sensitizing solution, cleaning and filtering; the sensitizing solution is SnCl2And HCl.
4. The method for preparing the Cu @ ZrC core-shell complex-phase particle material by electroless plating according to claim 3, wherein SnCl in the sensitizing solution2The concentration of (2) was 20g/L and the concentration of HCl was 20 g/L.
5. The method for preparing the Cu @ ZrC core-shell complex-phase particle material by electroless plating according to claim 1, wherein the specific operations of the activation treatment are as follows: the sensitized ZrC powder is placed in AgNO3Ultrasonic treatment in solution, filtering and washing to neutrality, wherein the AgNO is3The concentration of the solution was 5 g/L.
6. The method for preparing the Cu @ ZrC core-shell complex phase particle material by the electroless plating according to claim 1, wherein the dispersion treatment comprises the following specific operations: and performing dispersion treatment on the activated ZrC powder by using a dispersing agent to obtain the ZrC powder to be plated with copper, wherein the dispersing agent is a mixed solution of sodium pyrophosphate and water glass, and the concentration of sodium pyrophosphate in the dispersing agent is 0.5 wt.%.
7. The method for preparing the Cu @ ZrC core-shell complex-phase granular material by electroless plating according to claim 1, wherein the electroless copper plating treatment comprises the following specific operations: adding copper sulfate, a complexing agent, a buffering agent and a catalyst into water to obtain a mixed solution, adjusting the pH value of the mixed solution to 11, then adding ZrC powder to be plated with copper and a reducing agent to obtain a chemical copper plating reaction system, reacting the chemical copper plating reaction system at the temperature of 60 ℃, filtering, cleaning and drying after the reaction is finished to obtain the Cu @ ZrC core-shell complex-phase granular material.
8. The method for preparing the Cu @ ZrC core-shell complex-phase granular material by electroless plating according to claim 7, wherein the complexing agent is trisodium citrate, the buffering agent is boric acid, the catalyst is nickel chloride hexahydrate, the reducing agent is sodium hypophosphite, and the weight ratio of copper sulfate: and (3) after copper plating of ZrC powder: sodium hypophosphite 40:20: 15; the pH value of the electroless copper plating reaction system is maintained at 10.5-11.5 in the whole reaction process.
9. The Cu @ ZrC core-shell complex-phase particle material prepared by the method for preparing the Cu @ ZrC core-shell complex-phase particle material through electroless plating according to any one of claims 1 to 8.
10. The use of the electroless plating prepared Cu @ ZrC core-shell composite particulate material as defined in claim 9 in a metal matrix composite.
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