CN114457325A - Method for controlling thickness of nickel layer of nickel-plated polymer microsphere - Google Patents
Method for controlling thickness of nickel layer of nickel-plated polymer microsphere Download PDFInfo
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- CN114457325A CN114457325A CN202111654511.1A CN202111654511A CN114457325A CN 114457325 A CN114457325 A CN 114457325A CN 202111654511 A CN202111654511 A CN 202111654511A CN 114457325 A CN114457325 A CN 114457325A
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- nickel
- plating
- solution
- microspheres
- buffer solution
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 224
- 239000004005 microsphere Substances 0.000 title claims abstract description 121
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 112
- 229920000642 polymer Polymers 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000007747 plating Methods 0.000 claims abstract description 114
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 239000007853 buffer solution Substances 0.000 claims description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 230000001276 controlling effect Effects 0.000 claims description 17
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 11
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 10
- 102000002260 Alkaline Phosphatase Human genes 0.000 claims description 10
- 108020004774 Alkaline Phosphatase Proteins 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229960001484 edetic acid Drugs 0.000 claims description 10
- 239000008055 phosphate buffer solution Substances 0.000 claims description 10
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 230000001502 supplementing effect Effects 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 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 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 8
- TWNDEXHSZJGRBX-UHFFFAOYSA-N boric acid;n-methylmethanamine Chemical compound CNC.OB(O)O TWNDEXHSZJGRBX-UHFFFAOYSA-N 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- 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 claims description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229920005553 polystyrene-acrylate Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000007788 roughening Methods 0.000 claims description 4
- XFWCDQMDZATIEY-UHFFFAOYSA-L benzenesulfonate;nickel(2+);hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1 XFWCDQMDZATIEY-UHFFFAOYSA-L 0.000 claims description 3
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
- OFWQYFSMYVEOSZ-UHFFFAOYSA-L nickel hypophosphite hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]P=O.[O-]P=O OFWQYFSMYVEOSZ-UHFFFAOYSA-L 0.000 claims description 3
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 3
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 34
- 238000009713 electroplating Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- -1 plasma Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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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
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
-
- 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
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
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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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1683—Control of electrolyte composition, e.g. measurement, adjustment
-
- 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
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
-
- 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
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/285—Sensitising or activating with tin based compound or composition
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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
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Organic Chemistry (AREA)
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- Chemically Coating (AREA)
Abstract
The invention discloses a nickel layer thickness control method of nickel-plated polymer microspheres, which comprises the following steps: coarsening the polymer microsphere, treating the surface of the polymer microsphere after coarsening, plating nickel on the surface of the activated polymer microsphere by a batch plating method, and plating nickel on the surface of the batch nickel-plated microsphere by a continuous plating method. The technical means of the invention is embodied in the chemical nickel plating stage, the method of batch plating and continuous plating is adopted, and the chemical nickel plating layer with controllable thickness, uniformity, compactness and strong binding force is obtained by controlling the replenishing frequency of the nickel plating solution and separating the continuous plating frequency.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for controlling the thickness of a nickel layer of nickel-plated high polymer microspheres.
Background
With the advancement of electronic packaging technology, electronic components are continuously being developed toward smaller, lighter, higher input/output number and more environmental protection, however, traditional tin-lead soldering has not been able to meet the requirements, and thus there is an increasing urgent need for new interconnection materials. Anisotropic Conductive Films (ACFs) have been developed to date as a connecting material as a substitute for tin-lead solder. Compared with tin-lead solder, the ACF has the advantages of environmental protection, narrower connectable distance, low working temperature and the like. The ACF is mainly composed of a resin binder and conductive particles, wherein the resin binder provides mechanical connection to the ACF, and the conductive properties of the ACF depend on the conductive particles therein. At present, the commonly used conductive particles are generally polymer/metal composite microspheres, that is, the polymer microspheres are used as cores, and a metal layer is plated on the surfaces of the polymer microspheres by adopting an electroplating or chemical plating process. Wherein, the polymer core layer is usually selected from monodisperse polystyrene microspheres, monodisperse polymethyl methacrylate microspheres and the like, and the shell layer is usually selected from metals such as gold, silver, nickel and the like.
The nickel-plated polymer microspheres are favored in ACF application due to the advantages of good conductivity, high stability, low price and the like. ACFs are often prepared as conductive fillers for the attachment of display panels to flexible circuit boards for electronic calculators, liquid crystals, plasma, and various semiconductors. In the nickel plating process, the thickness of the nickel layer and the uniformity thereof are one of important indexes for measuring the quality of the nickel layer. The thickness of the nickel layer directly influences the performances such as corrosion resistance, wear resistance, porosity, conductivity and the like, so that the reliability and the service performance of the product are influenced to a great extent.
Chinese patent CN 102965702A discloses a method for improving the thickness uniformity of an electroplated nickel layer, which solves the problems of thin middle and thick edge of the electroplated nickel layer caused by the edge effect of electroplating in the process of electroplating nickel. The sand blasting procedure is added before the nickel electroplating, micron-sized pits with different directions are uniformly distributed on the surface of the alloy substrate, and the nickel electroplating layer can uniformly grow on the surface of the alloy substrate, so that the edge effect of the nickel electroplating is improved. However, the plating requires an applied current and an anode, and it is inevitable that the thickness is not uniform due to the non-uniform current distribution, and the plating layer is inferior in bonding strength to the electroless plating.
Chinese patent CN 103276376a discloses a method for chemically plating nickel on the surface of polymer microsphere. The polymer microsphere containing functional groups is used as a mother sphere, and under the combined action of mechanical stirring and ultrasonic waves, the composite redox nickel plating solution is adopted for chemical plating to obtain the monodisperse conductive microsphere with uniform and firm plating layer and the thickness of 1-100 nm. However, the nickel layer of the nickel-plated polymer microsphere with a low nickel layer thickness is easy to crack to cause surface defects, influence the performances such as corrosion resistance, conductivity and the like, and is not beneficial to subsequent application.
The nickel plating layer on the surface of the polymer microsphere is similar to patents CN 102176337A, CN 101415863A and CN 1936078A, but the defects of weak plating bonding force, poor uniformity, uncontrollable thickness and the like exist. Therefore, it is urgently needed to find an effective preparation method capable of controlling the thickness and uniformity of the nickel layer.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a method for controlling the thickness of a nickel layer of a nickel-plated polymer microsphere. The preparation method can overcome the defects of poor conductivity, uneven thickness of the electroplated nickel layer, weak binding force and the like caused by uncontrollable thickness of the traditional chemical nickel plating layer, and lays a foundation for preparing the ACF with excellent performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a nickel layer thickness control method of nickel-plated polymer microspheres comprises the following steps:
step one, coarsening polymer microspheres:
pouring a coarsening agent into a flask, adding polymer microsphere powder while stirring, stirring for a period of time after the polymer microspheres are completely soaked in the coarsening agent, performing centrifugal separation on suspension, washing with water and ethanol in sequence, and drying for later use;
step two, roughening the surface of the polymer microsphere:
dispersing the coarsened polymer microspheres in ultrapure water, adding a pH regulator and an activating agent, stirring, centrifuging, washing, adding a reducing agent, continuously stirring for a period of time, centrifuging, and washing to obtain activated polymer microspheres;
step three, plating nickel on the surface of the activated polymer microsphere by a batch plating method:
dispersing activated polymer microspheres in a buffer solution, heating to a certain temperature, adding a nickel plating solution into the activated polymer microsphere dispersion solution in batches under the action of mechanical stirring, adding a certain amount of nickel plating solution in the first batch, supplementing a certain amount of nickel plating solution after the reaction is finished, repeating the supplementing for several times, adjusting the pH value by using a pH regulator during the process, and performing centrifugal separation to obtain batch nickel plating microspheres;
step four, plating nickel on the surfaces of the batch nickel-plated microspheres by a continuous plating method:
dispersing the nickel-plated microspheres in batches in a buffer solution, heating to the same temperature of three phases in the step, adding a certain amount of nickel-plating solution into the nickel-plated microsphere dispersion in batches for several times, adding the nickel-plated microspheres in batches each time according to the step of batch plating, adjusting the pH value by adopting a pH regulator in the whole process, and separating, washing and drying to obtain the continuous nickel-plated microspheres.
Preferably, the coarsening agent in the step one is a strong oxidation substance, and the dosage is 10-50 mL; the polymer microsphere is one or a mixture of polystyrene and polymethyl methacrylate, and the dosage is 1-20 g; continuously stirring for 60-150 min; the rotating speed of the centrifuge is 1000-.
Preferably, the strong oxidizing substance is one or a mixture of concentrated sulfuric acid and potassium dichromate.
Preferably, the dosage of the coarsening polymer microspheres in the second step is 0.1-0.6 g; the dosage of the ultrapure water is 10-50 mL; the pH regulator is one or a mixture of hydrochloric acid, a sodium hydroxide solution, a potassium hydroxide solution and ammonia water, and the dosage is 1-10 mL; the activator is palladium salt, tin salt or mixed salt thereof, and the dosage is 0.01-0.1 g; the reducing agent is one or a mixture of more of dimethylamine borate, hydrazine, sodium borohydride, sodium hypophosphite and sodium citrate, and the dosage is 10-100 mL; stirring for 10-60 min; the rotating speed of the centrifuge for separation and purification is 1000-.
Preferably, the buffer solution with the pH value of 7-10 in the third step comprises one or more of phosphate buffer solution, ethylene diamine tetraacetic acid buffer solution, alkaline phosphatase buffer solution and tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution, and the dosage is 1-50 mL; the heating temperature is 30-70 ℃; the total dosage of the nickel plating solution is 20-100mL, and 10-50mL is added in the first batch; the addition amount is 5-25mL, and the repetition times are 1-3 times; the pH regulator is one or a mixture of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the pH value is regulated to 6-12; the rotating speed of the centrifuge is 1000-.
Preferably, the buffer solution with the pH value of 7-10 in the fourth step comprises one or more of phosphate buffer solution, ethylene diamine tetraacetic acid buffer solution, alkaline phosphatase buffer solution and tris-hydrochloric acid buffer solution, and the dosage is 1-50 mL; the pH regulator is one or a mixture of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the pH value is regulated to 6-12; the dosage of the nickel plating solution is 60-300 mL; the nickel plating solution is added for 1 to 3 times.
Preferably, the formula of the nickel plating solution in the third step and the fourth step is as follows: main salt, reducing agent and pH regulator;
the main salt is one or a mixture of nickel acetate tetrahydrate, nickel benzenesulfonate hexahydrate, nickel chloride hexahydrate, nickel hypophosphite hexahydrate and nickel sulfate hexahydrate;
the reducing agent is one or a mixture of more of dimethylamine borate, hydrazine, sodium borohydride, sodium hypophosphite and sodium citrate;
the pH regulator is one or more of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a method of batch plating and continuous plating, and obtains a chemical nickel plating layer with controllable thickness, uniformity, compactness and strong bonding force by controlling the replenishing times of the nickel plating solution and the separating continuous plating times; the technical means is embodied in the chemical nickel plating stage and mainly comprises the following two steps: firstly, in the chemical nickel plating process, after a first nickel layer is formed, other conditions are kept unchanged, and a proper amount of nickel plating solution is added in batches. Secondly, after the nickel plating waste liquid is supplemented in batches, the nickel plating waste liquid is separated from the microspheres, the first step is repeated according to the same conditions, and the nickel plating is continuously carried out on the surfaces of the microspheres, so that the thickness of a nickel layer is further increased. In the technical means, the purpose of controlling the thickness of the nickel layer can be achieved by controlling the replenishing times of the nickel plating solution and the continuous plating times of separation.
Drawings
In order to more particularly and intuitively illustrate an embodiment of the present invention or a prior art solution, a brief description of the drawings needed for use in the description of the embodiment or the prior art will be provided below.
FIG. 1 is a Scanning Electron Microscope (SEM) image of batch nickel plated microspheres;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the microspheres continuously plated with nickel.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example one
Referring to fig. 1-2, a method for controlling the thickness of a nickel layer of a nickel-plated polymer microsphere comprises the following steps:
step one, coarsening polymer microspheres:
pouring a coarsening agent into a flask, wherein the coarsening agent increases the surface micro roughness and the contact area to ensure that a plating layer has good adhesive force, adding polymer microsphere powder while stirring, after the polymer microspheres are completely soaked in the coarsening agent, stirring for a period of time, carrying out centrifugal separation on suspension, washing with water and ethanol in sequence, and drying for later use, wherein the coarsening agent is a strong oxidation substance and the dosage is 10 mL; the polymer microsphere is one or a mixture of polystyrene and polymethyl methacrylate, and the using amount is 1 g; continuously stirring for 60 min; the rotating speed of the centrifuge is 1000r/min, and the time is 3 min;
the strong oxidizing substance is one or a mixture of concentrated sulfuric acid and potassium dichromate.
Step two, roughening the surface of the polymer microsphere:
dispersing the coarsened polymer microspheres in ultrapure water, adding a pH regulator and an activating agent, adsorbing active particles by the activating agent to form active sites, fully reacting, stirring, centrifuging, washing, adding a reducing agent, continuously stirring for a period of time, centrifuging, and washing to obtain activated polymer microspheres, wherein the dosage of the coarsened polymer microspheres is 0.1 g; the dosage of ultrapure water is 10 mL; the pH regulator is one or a mixture of hydrochloric acid, a sodium hydroxide solution, a potassium hydroxide solution and ammonia water, and the dosage is 1 mL; the activator is palladium salt, tin salt or mixed salt thereof, and the dosage is 0.01 g; the reducing agent is one or a mixture of more of dimethylamine borate, hydrazine, sodium borohydride, sodium hypophosphite and sodium citrate, and the dosage is 10 mL; stirring for 10 min; the rotation speed of the centrifuge for separation and purification is 1000r/min, and the time is 3min
Step three, plating nickel on the surface of the activated polymer microsphere by a batch plating method:
dispersing activated polymer microspheres in a buffer solution, heating to a certain temperature, adding a nickel plating solution into the activated polymer microsphere dispersion solution in batches under the action of mechanical stirring, adding a certain amount of nickel plating solution in the first batch, supplementing a certain amount of nickel plating solution after the reaction is finished, repeating the supplementing for several times, adjusting the pH value by using a pH regulator during the process, and performing centrifugal separation to obtain batch nickel plating microspheres;
the buffer solution has a pH value of 7, the buffer solution keeps the pH value of the system stable and comprises one or more of phosphate buffer solution, ethylene diamine tetraacetic acid buffer solution, alkaline phosphatase buffer solution and tris-hydroxymethyl aminomethane-hydrochloric acid buffer solution, and the dosage is 1 mL; the heating temperature is 30 ℃; the total dosage of the nickel plating solution is 20mL, and 10mL is added in the first batch; the addition amount is 5mL, and the repetition frequency is 1 time; the pH regulator is one or a mixture of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the pH value is regulated to 6; the rotating speed of the centrifuge is 1000-.
Step four, plating nickel on the surfaces of the batch nickel-plated microspheres by a continuous plating method:
dispersing the nickel-plated microspheres in batches in a buffer solution, heating to the same temperature of three phases in the step, adding a certain amount of nickel-plating solution into the nickel-plated microsphere dispersion in batches for several times, adding the nickel-plated microspheres in batches each time according to the step of batch plating, adjusting the pH value by adopting a pH regulator in the whole process, and separating, washing and drying to obtain continuous nickel-plated microspheres;
the buffer solution with the pH value of 7 comprises one or more of phosphate buffer solution, ethylene diamine tetraacetic acid buffer solution, alkaline phosphatase buffer solution and tris-hydrochloric acid buffer solution, and the dosage is 1 mL; the pH regulator is one or a mixture of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the pH value is regulated to 6; the dosage of the nickel plating solution is 60 mL; the number of times of adding the nickel plating solution was 1.
Example two
Referring to fig. 1-2, a method for controlling the thickness of a nickel layer of a nickel-plated polymer microsphere comprises the following steps:
step one, coarsening polymer microspheres:
pouring a coarsening agent into a flask, wherein the coarsening agent increases the surface micro roughness and the contact area to ensure that a plating layer has good adhesive force, adding polymer microsphere powder while stirring, after the polymer microspheres are completely soaked in the coarsening agent, stirring for a period of time, carrying out centrifugal separation on suspension, washing with water and ethanol in sequence, and drying for later use, wherein the coarsening agent is a strong oxidation substance and is used in an amount of 30 mL; the polymer microsphere is one or a mixture of polystyrene and polymethyl methacrylate, and the using amount is 10.5 g; continuously stirring for 105 min; the rotating speed of the centrifuge is 4500r/min, and the time is 3 min;
the strong oxidizing substance is one or a mixture of concentrated sulfuric acid and potassium dichromate.
Step two, surface treatment of the coarsened polymer microspheres:
dispersing the coarsened polymer microspheres in ultrapure water, adding a pH regulator and an activating agent, adsorbing active particles by the activating agent to form active sites, fully reacting, stirring, centrifuging, washing, adding a reducing agent, continuously stirring for a period of time, centrifuging, and washing to obtain activated polymer microspheres, wherein the dosage of the coarsened polymer microspheres is 0.35 g; the using amount of ultrapure water is 30 mL; the pH regulator is one or a mixture of hydrochloric acid, a sodium hydroxide solution, a potassium hydroxide solution and ammonia water, and the dosage is 5.5 mL; the activator is palladium salt, tin salt or mixed salt thereof, and the dosage is 0.525 g; the reducing agent is one or a mixture of more of dimethylamine borate, hydrazine, sodium borohydride, sodium hypophosphite and sodium citrate, and the dosage is 55 mL; stirring for 35 min; the rotation speed of the centrifuge for separation and purification is 4500r/min, and the time is 3min
Step three, plating nickel on the surface of the activated polymer microsphere by a batch plating method:
dispersing activated polymer microspheres in a buffer solution, heating to a certain temperature, adding a nickel plating solution into the activated polymer microsphere dispersion solution in batches under the action of mechanical stirring, adding a certain amount of nickel plating solution in the first batch, supplementing a certain amount of nickel plating solution after the reaction is finished, repeating the supplementing for several times, adjusting the pH value by using a pH regulator during the process, and performing centrifugal separation to obtain batch nickel plating microspheres;
the buffer solution has the pH value of 8.5, the buffer solution keeps the pH value of the system stable and comprises one or more of phosphate buffer solution, ethylene diamine tetraacetic acid buffer solution, alkaline phosphatase buffer solution and tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution, and the dosage is 25.5 mL; the heating temperature is 50 ℃; the total dosage of the nickel plating solution is 60mL, and 30mL is added in the first batch; the addition amount is 15mL, and the repetition times is 2 times; the pH regulator is one or a mixture of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the pH value is regulated to 9; the rotating speed of the centrifuge is 4500r/min, and the time is 3 min.
Step four, plating nickel on the surfaces of the batch nickel-plated microspheres by a continuous plating method:
dispersing the nickel-plated microspheres in batches in a buffer solution, heating to the same temperature of three phases in the step, adding a certain amount of nickel-plating solution into the nickel-plated microsphere dispersion in batches for several times, adding the nickel-plated microspheres in batches each time according to the step of batch plating, adjusting the pH value by adopting a pH regulator in the whole process, and separating, washing and drying to obtain continuous nickel-plated microspheres;
the buffer solution with the pH value of 8.5 comprises one or more of phosphate buffer solution, ethylene diamine tetraacetic acid buffer solution, alkaline phosphatase buffer solution and tris-hydroxymethyl aminomethane-hydrochloric acid buffer solution, and the dosage is 25.5 mL; the pH regulator is one or a mixture of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the pH value is regulated to 9; the dosage of the nickel plating solution is 180 mL; the number of times of adding the nickel plating solution was 2.
EXAMPLE III
Referring to fig. 1-2, a method for controlling the thickness of a nickel layer of a nickel-plated polymer microsphere comprises the following steps:
step one, coarsening polymer microspheres:
pouring a coarsening agent into a flask, wherein the coarsening agent increases the surface micro roughness and the contact area to ensure that a plating layer has good adhesive force, adding polymer microsphere powder while stirring, after the polymer microspheres are completely soaked in the coarsening agent, stirring for a period of time, carrying out centrifugal separation on suspension, washing with water and ethanol in sequence, and drying for later use, wherein the coarsening agent is a strong oxidation substance and the dosage is 50 mL; the polymer microsphere is one or a mixture of polystyrene and polymethyl methacrylate, and the using amount is 20 g; the continuous stirring time is 150 min; the rotating speed of the centrifuge is 8000r/min, and the time is 3 min;
the strong oxidizing substance is one or a mixture of concentrated sulfuric acid and potassium dichromate.
Step two, roughening the surface of the polymer microsphere:
dispersing the coarsened polymer microspheres in ultrapure water, adding a pH regulator and an activating agent, adsorbing active particles by the activating agent to form active sites, fully reacting, stirring, centrifuging, washing, adding a reducing agent, continuously stirring for a period of time, centrifuging, and washing to obtain activated polymer microspheres, wherein the dosage of the coarsened polymer microspheres is 0.6 g; the dosage of ultrapure water is 50 mL; the pH regulator is one or a mixture of more of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the dosage is 10 mL; the activator is palladium salt, tin salt or mixed salt thereof, and the dosage is 0.1 g; the reducing agent is one or a mixture of more of dimethylamine borate, hydrazine, sodium borohydride, sodium hypophosphite and sodium citrate, and the dosage is 100 mL; stirring for 60 min; the rotation speed of the centrifuge for separation and purification is 8000r/min, and the time is 3min
Step three, plating nickel on the surface of the activated polymer microsphere by a batch plating method:
dispersing activated polymer microspheres in a buffer solution, heating to a certain temperature, adding a nickel plating solution into the activated polymer microsphere dispersion solution in batches under the action of mechanical stirring, adding a certain amount of nickel plating solution in the first batch, supplementing a certain amount of nickel plating solution after the reaction is finished, repeating the supplementing for several times, adjusting the pH value by using a pH regulator during the process, and performing centrifugal separation to obtain batch nickel plating microspheres;
the buffer solution has a pH value of 10, the buffer solution keeps the pH value of the system stable and comprises one or more of phosphate buffer solution, ethylene diamine tetraacetic acid buffer solution, alkaline phosphatase buffer solution and tris-hydroxymethyl aminomethane-hydrochloric acid buffer solution, and the dosage is 50 mL; the heating temperature is 70 ℃; the total dosage of the nickel plating solution is 100mL, and 50mL is added in the first batch; the addition amount is 25mL, and the repetition times is 3 times; the pH regulator is one or a mixture of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the pH value is regulated to 12; the rotation speed of the centrifuge is 8000r/min, and the time is 3 min.
Step four, plating nickel on the surfaces of the batch nickel-plated microspheres by a continuous plating method:
dispersing the nickel-plated microspheres in batches in a buffer solution, heating to the same temperature of three phases in the step, adding a certain amount of nickel-plating solution into the nickel-plated microsphere dispersion in batches for several times, adding the nickel-plated microspheres in batches each time according to the step of batch plating, adjusting the pH value by adopting a pH regulator in the whole process, and separating, washing and drying to obtain continuous nickel-plated microspheres;
the buffer solution with the pH value of 10 comprises one or more of phosphate buffer solution, ethylene diamine tetraacetic acid buffer solution, alkaline phosphatase buffer solution and tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution, and the dosage is 50 mL; the pH regulator is one or a mixture of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the pH value is regulated to 12; the dosage of the nickel plating solution is 300 mL; the number of times of adding the nickel plating solution was 3.
In the embodiment, the formula of the nickel plating solution in the third step and the fourth step is as follows: main salt, reducing agent and pH regulator; the main salt is one or a mixture of nickel acetate tetrahydrate, nickel benzenesulfonate hexahydrate, nickel chloride hexahydrate, nickel hypophosphite hexahydrate and nickel sulfate hexahydrate; the reducing agent is one or a mixture of more of dimethylamine borate, hydrazine, sodium borohydride, sodium hypophosphite and sodium citrate; the pH regulator is one or more of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water.
In the scheme, in the chemical nickel plating process, the thickness of the nickel layer is controlled by controlling the times of batch plating and continuous plating, and the metal nickel layer with the thickness of dozens of to hundreds of nanometers and uniform and compact distribution is obtained.
The technical means is embodied in the chemical nickel plating stage and mainly comprises the following two steps: firstly, in the chemical nickel plating process, after a first nickel layer is formed, other conditions are kept unchanged, and a proper amount of nickel plating solution is added in batches. Secondly, after the batch nickel plating is supplemented, the nickel plating waste liquid is separated from the microspheres, the first step is repeated according to the same conditions, and the nickel plating is continuously carried out on the surfaces of the microspheres, so that the thickness of a nickel layer is further increased.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A method for controlling the thickness of a nickel layer of a nickel-plated polymer microsphere is characterized by comprising the following steps:
step one, coarsening polymer microspheres:
pouring a coarsening agent into a flask, adding polymer microsphere powder while stirring, stirring for a period of time after the polymer microspheres are completely soaked in the coarsening agent, performing centrifugal separation on suspension, washing with water and ethanol in sequence, and drying for later use;
step two, roughening the surface of the polymer microsphere:
dispersing the coarsened polymer microspheres in ultrapure water, adding a pH regulator and an activating agent, stirring, centrifuging, washing, adding a reducing agent, continuously stirring for a period of time, centrifuging, and washing to obtain activated polymer microspheres;
step three, plating nickel on the surface of the activated polymer microsphere by a batch plating method:
dispersing activated polymer microspheres in a buffer solution, heating to a certain temperature, adding a nickel plating solution into the activated polymer microsphere dispersion solution in batches under the action of mechanical stirring, adding a certain amount of nickel plating solution in the first batch, supplementing a certain amount of nickel plating solution after the reaction is finished, repeating the supplementing for several times, adjusting the pH value by using a pH regulator during the process, and performing centrifugal separation to obtain batch nickel plating microspheres;
step four, plating nickel on the surfaces of the batch nickel-plated microspheres by a continuous plating method:
dispersing the nickel-plated microspheres in batches in a buffer solution, heating to the same temperature of three phases in the step, adding a certain amount of nickel-plating solution into the nickel-plated microsphere dispersion in batches for several times, adding the nickel-plated microspheres in batches each time according to the step of batch plating, adjusting the pH value by adopting a pH regulator in the whole process, and separating, washing and drying to obtain the continuous nickel-plated microspheres.
2. The method for controlling the thickness of the nickel layer of the nickel-plated polymer microsphere according to claim 1, wherein in the first step, the coarsening agent is a strong oxidation substance, and the dosage is 10-50 mL; the polymer microsphere is one or a mixture of polystyrene and polymethyl methacrylate, and the dosage is 1-20 g; continuously stirring for 60-150 min; the rotating speed of the centrifuge is 1000-.
3. The method of claim 2, wherein the strongly oxidizing substance is one or a mixture of concentrated sulfuric acid and potassium dichromate.
4. The method for controlling the thickness of the nickel layer of the nickel-plated polymer microspheres according to claim 3, wherein the dosage of the coarsened polymer microspheres in the second step is 0.1-0.6 g; the dosage of the ultrapure water is 10-50 mL; the pH regulator is one or a mixture of hydrochloric acid, a sodium hydroxide solution, a potassium hydroxide solution and ammonia water, and the dosage is 1-10 mL; the activator is palladium salt, tin salt or mixed salt thereof, and the dosage is 0.01-0.1 g; the reducing agent is one or a mixture of more of dimethylamine borate, hydrazine, sodium borohydride, sodium hypophosphite and sodium citrate, and the dosage is 10-100 mL; stirring for 10-60 min; the rotating speed of the centrifuge for separation and purification is 1000-.
5. The method for controlling the thickness of the nickel layer of the nickel-plated polymer microspheres according to claim 4, wherein the buffer solution with the pH of 7-10 in the third step comprises one or more of phosphate buffer solution, ethylene diamine tetraacetic acid buffer solution, alkaline phosphatase buffer solution and tris-hydrochloric acid buffer solution, and the amount of the buffer solution is 1-50 mL; the heating temperature is 30-70 ℃; the total dosage of the nickel plating solution is 20-100mL, and 10-50mL is added in the first batch; the addition amount is 5-25mL, and the repetition times are 1-3 times; the pH regulator is one or a mixture of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the pH value is regulated to 6-12; the rotating speed of the centrifuge is 1000-.
6. The method for controlling the thickness of the nickel layer of the nickel-plated polymer microspheres according to claim 5, wherein the buffer solution with the pH of 7-10 in the fourth step comprises one or more of phosphate buffer solution, ethylene diamine tetraacetic acid buffer solution, alkaline phosphatase buffer solution and tris-hydrochloric acid buffer solution, and the dosage is 1-50 mL; the pH regulator is one or a mixture of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the pH value is regulated to 6-12; the dosage of the nickel plating solution is 60-300 mL; the nickel plating solution is added for 1 to 3 times.
7. The method for controlling the thickness of the nickel layer of the nickel-plated polymer microsphere according to claim 6, wherein the formula of the nickel plating solution in the third step and the fourth step is as follows: main salt, reducing agent and pH regulator;
the main salt is one or a mixture of nickel acetate tetrahydrate, nickel benzenesulfonate hexahydrate, nickel chloride hexahydrate, nickel hypophosphite hexahydrate and nickel sulfate hexahydrate;
the reducing agent is one or a mixture of more of dimethylamine borate, hydrazine, sodium borohydride, sodium hypophosphite and sodium citrate;
the pH regulator is one or more of hydrochloric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia water.
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