CN110306174A - 胶体镍组合物及其应用 - Google Patents
胶体镍组合物及其应用 Download PDFInfo
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- CN110306174A CN110306174A CN201910690322.6A CN201910690322A CN110306174A CN 110306174 A CN110306174 A CN 110306174A CN 201910690322 A CN201910690322 A CN 201910690322A CN 110306174 A CN110306174 A CN 110306174A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 82
- 239000000084 colloidal system Substances 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 238000007747 plating Methods 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 20
- 229920003656 Daiamid® Polymers 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 150000002815 nickel Chemical class 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 229920000962 poly(amidoamine) Polymers 0.000 claims abstract description 14
- 239000000412 dendrimer Substances 0.000 claims abstract description 13
- 229920000736 dendritic polymer Polymers 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 amine salt Chemical class 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 claims description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 239000002280 amphoteric surfactant Substances 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000123 paper Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052763 palladium Inorganic materials 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000007769 metal material Substances 0.000 description 5
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 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 description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229920004934 Dacron® Polymers 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
- B01J31/064—Dendrimers
-
- B01J35/23—
-
- 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
-
- 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
-
- 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
- C23C18/405—Formaldehyde
Abstract
本发明公开了一种胶体镍组合物及其应用，胶体镍组合物包括原料如下：PAMAM聚酰胺胺树状聚合物分子、镍盐、将镍离子还原为零价镍的还原剂、以及水。本发明的胶体镍组合物，以PAMAM聚酰胺胺树状聚合物分子、镍盐及还原剂等原料制得，是一种纳米颗粒的稳定水溶液，稳定且催化性高，可用作非金属材料基材的化学金属镀覆的催化剂，极大的降低非金属材料基材的化学金属镀覆生产成本，解决了现有基于钯的系统的原材料价格及波动问题。
Description
技术领域
本发明涉及催化剂技术领域，尤其涉及一种胶体镍组合物及其应用。
背景技术
在非金属材料镀覆过程中，为了实现材料的导电化，最常用的方法是化学镀覆铜或镍磷合金，其利用甲醛、次磷酸钠等还原剂将铜、镍等金属还原至非金属材料表面。为了实现这一过程，采用数个处理步骤以确保在材料表面上覆盖催化剂材料。现有的用于将非金属材料表面处理中进行浸泡的催化剂液浴，以包含钯作为活性成分的胶体钯为主。多年来，钯的成本急剧增加。因此采用廉价的替代品取代含钯的催化剂溶液就成了化学镀覆工业一段时间以来的目标。
虽然许多无钯催化剂溶液也能够触发化学铜镀覆，但要取代现有的常用商业胶体钯系统的表现性能仍然被证明具有挑战性。影响替代的催化剂溶液的吸引力的最关键因素为：稳定性-催化剂液浴必须在加工温度下暴露于空气中历经数月的过程里保持它们的活性。
镍的使用解决了面临现有基于钯的系统时的原材料的价格及波动问题。目前有许多报道使用银胶体、铜胶体替代胶体钯的研究，但因体系稳定性、催化活性不足等原因未见大批量性商业化应用。
发明内容
本发明要解决的技术问题在于，提供一种稳定且催化性高的胶体镍组合物及其应用。
本发明解决其技术问题所采用的技术方案是：提供一种胶体镍组合物，包括包括原料如下：PAMAM聚酰胺胺树状聚合物分子、镍盐、将镍离子还原为零价镍的还原剂、以及水。
优选地，所述胶体镍组合物中，零价镍的量为500ppm-2500ppm，PAMAM聚酰胺胺树状聚合物分子的量为0.5g/L-100g/L，所述还原剂的量为0.1g/L-25g/L。
优选地，所述镍盐包括硝酸镍、氧化镍、醋酸镍、硫酸镍、氯化镍、柠檬酸镍和有机磺酸镍中的一种或多种。
优选地，所述还原剂包括硼氢化钠、硼氢化钾、次磷酸钠、葡萄糖和二甲基胺硼烷中的一种或多种。
优选地，所述胶体镍组合物还包括添加剂；所述添加剂包括表面活性剂、缓冲剂、pH调节剂和溶剂中的一种或多种。
优选地，所述表面活性剂包括阴离子型、非离子型、阳离子型和两性表面活性剂中一种或多种；
所述缓冲剂包括羧酸、羧酸盐、胺、胺盐、氨基酸、氨基酸盐、无机酸、无机酸盐和无机碱中的一种或多种。
优选地，所述胶体镍组合物为纳米颗粒的稳定水溶液，其中纳米颗粒的平均粒径为1nm-500nm。
优选地，所述胶体镍组合物的pH值为7-13。
本发明还提供一种胶体镍组合物的应用，用于非金属材料基材的化学金属镀覆。
优选地，所述非金属材料基材包括玻璃、陶瓷、树脂、玻璃纤维、纸、布和泡棉中的一种或多种。
本发明的胶体镍组合物，以PAMAM聚酰胺胺树状聚合物分子、镍盐及还原剂等原料制得，是一种纳米颗粒的稳定水溶液，稳定且催化性高，可用作非金属材料基材的化学金属镀覆的催化剂，极大的降低非金属材料基材的化学金属镀覆生产成本，解决了现有基于钯的系统的原材料价格及波动问题。
具体实施方式
本发明的胶体镍组合物，包括原料如下：PAMAM聚酰胺胺树状聚合物分子、镍盐、将镍离子还原为零价镍的还原剂、以及水。该胶体镍组合物适用作非金属材料化学镀的催化剂。
其中，水可以是任何类型的水，如自来水或者去离子水。PAMAM聚酰胺胺树状聚合物分子、镍盐以及还原剂均匀混合在水中，并通过还原剂将镍盐中的镍离子还原为零价镍(零价金属镍)，零价镍和PAMAM聚酰胺胺树状聚合物分子稳定化合形成纳米级颗粒，从而形成了纳米颗粒的稳定水溶液(胶体溶液)。
该胶体镍组合物为纳米颗粒(含纳米颗粒)的稳定水溶液，用于催化非金属材料基材的金属化学沉积。所谓“稳定”是指在室温下贮存时，3个月后没有可肉眼观察到的沉淀物形成。在室温贮存下，胶体镍组合物优选在6个月后、更优选1年后没有沉积物可见。术语“稳定的”也是指该纳米颗粒水溶液在加工温度下保持其催化的活性；通常的加工温度为20℃以上，优选20℃-50℃。
在胶体镍组合物中，该纳米颗粒可以有多种粒径；如果粒径变得太大，则组合物会不稳定，即可能会产生沉淀。作为选择，胶体镍组合物中的纳米颗粒的平均粒径为1nm-500nm，优选1nm-250nm，更优选1nm-100nm。纳米颗粒的粒径可以通过光散射法或透射电子显微镜进行确定。
在胶体镍组合物中，PAMAM聚酰胺胺树状聚合物分子作为稳定剂，其含量可为0.5g/L-100g/L，优选0.5g/L-25g/L，更优选为5g/L-15g/L。该PAMAM聚酰胺胺树状聚合物分子通常可以通过市售获得，或者可以通过本领域中已知的方法来制备获得。
镍盐提供镍离子，被还原剂还原为零价的金属镍(零价镍)存在于胶体镍组合物中。零价镍在胶体镍组合物中的量为25ppm-5000ppm，优选为500ppm-2500ppm。
镍盐可以是一种或多种，只要具有足够的水溶性均可。镍盐可包括但不限于硝酸镍、氧化镍、醋酸镍、硫酸镍、氯化镍、柠檬酸镍和有机磺酸镍中的一种或多种。在制备胶体镍组合物时，镍盐使用的量取决于镍盐的水溶性，例如可以是5mg/L-50mg/L。
还原剂具有将镍离子还原为零价镍的电势，其包括但不限于硼氢化钠、硼氢化钾、次磷酸钠、葡萄糖和二甲基胺硼烷中的一种或多种。该还原剂按照将镍离子还原成金属镍的量添加进组合物中并可能过量添加，超过的量以使得基本上组合物中所有的镍离子都被还原成金属镍即Ni。其中，可通过硼氢化钠等将镍离子还原成零价镍形成镍胶体，通过合适的过量次磷酸钠保护镍胶体避免其氧化失效。
在胶体镍组合物中，还原剂的量至少为0.1g/L，优选0.1g/L-25g/L，更优选优选1g/L-20g/L。
本发明的胶体镍组合物，pH值为7-13，优选9-13。
进一步地，本发明的胶体镍组合物还可以包括一种或多种化学镀覆催化剂组分中常见的添加剂。添加剂包括表面活性剂、缓冲剂、pH调节剂和溶剂中的一种或多种。其中，表面活性剂包括阴离子型、非离子型、阳离子型和两性表面活性剂中一种或多种；根据胶体镍组合物的重量，表面活性剂的量可以是0-25ppm，可优选为0.5-25ppm，更优选1-10ppm。
缓冲剂包括羧酸、羧酸盐、胺、胺盐、氨基酸、氨基酸盐、无机酸(如硼酸)、无机酸盐和无机碱(如碳酸氢钠)中的一种或多种；羧酸如柠檬酸、酒石酸、琥珀酸、苹果酸、丙二酸、马来酸、乳酸和乙酸。
pH调节剂包括但不限于碱金属氢氧化物，如氢氧化钠、氢氧化钾和酸(如矿物酸)。在使用时，使用可选的缓冲剂和pH值调节剂将胶体镍组合物的pH值充分调节至所需的范围内。
本发明的胶体镍组合物制备时，各原料可以按任意顺序添加。通常情况下，水溶性的镍盐先被溶于一定量的水中形成盐溶液，然后将该盐溶液加入到PAMAM聚酰胺胺树状聚合物分子的水溶液中，在室温下搅拌混合并调节所需的pH值形成混合物。通常在少量例如200ml时可以利用搅拌棒搅拌，在更大的量时采用搅拌器如磁力搅拌器和机械搅拌器。搅拌混合速率可以是200-1000转/分钟。最后在混合物中添加一种或多种还原剂的水溶液并继续搅拌。在还原反应之后，生成了含有PAMAM聚酰胺胺树状聚合物分子和零价镍的纳米颗粒的稳定水溶液。
本发明的胶体镍组合物可用于非金属材料基材的化学金属镀覆，作为催化剂。非金属材料基材包括有机和无机材料，如玻璃、陶瓷、瓷器、树脂、玻璃纤维、纸、布、和泡棉中一种或多种。
本发明的胶体镍组合物，由于包含一零价镍即Ni，因此在非金属材料基材的化学金属镀覆中省去了在化学金属镀覆之前的还原的步骤。另外，该胶体镍组合还使金属对非金属材料基材具有良好的粘附性且沉积均匀。此外，金属化时避免了在使用胶体钯时所需的解胶步骤，从而消除了现有的金属化的一个常规步骤。
下面通过具体实施例对本发明作进一步说明。
实施例1
制备胶体镍组合物：
在1L含有500毫升的去离子水的玻璃烧杯中加入13.6gPAMAM聚酰胺胺树状聚合物分子，在室温下搅拌使之完全溶解成溶液，加入溶解好的含8g六水硫酸镍的镍溶液，镍溶液的加入导致颜色立即变化成棕黑色。搅拌均匀，缓慢加入含5g/L NaOH和20g/L NaBH4的溶液400ml，均匀搅拌2小时以上直至反应气泡完全消失。
实施例2
制备胶体镍组合物：
在1L含有500毫升的去离子水的玻璃烧杯中加入13.6gPAMAM聚酰胺胺树状聚合物分子，在室温下搅拌使之完全溶解成溶液，加入溶解好的含8g六水硫酸镍的镍溶液，镍溶液的加入导致颜色立即变化成棕黑色。搅拌均匀，缓慢加入含15g次磷酸钠的水溶液，混合均匀，然后加入5g/L NaOH和20g/L NaBH4的溶液300ml，均匀搅拌2小时以上直至反应气泡完全消失。
实施例3
取280T方格纺织涤纶布，除浆处理，经200g/L NaOH溶液于70℃粗化10分钟，浸涂于实施例1所制得的胶体镍组合物中1分钟，清水漂洗干净，放入48℃的化学镀铜溶液镀覆30分钟，得到导电良好的具有良好电磁屏蔽性能的导电布。导电布的表面方阻可达30毫欧以下。
上述的化学镀铜溶液包含5-15g/L的五水硫酸铜、20-40g/L的EDTA、10g/L的NaOH和2-5ml/L的甲醛以及微量稳定剂。
实施例4
取330T平纹纺织涤纶布，除浆处理，经200g/L NaOH溶液于70℃粗化10分钟，浸涂于实施例2所制得的胶体镍组合物中1分钟，清水漂洗干净，放入48℃的化学镀铜溶液镀覆30分钟，可得到导电良好的具有良好电磁屏蔽性能的导电布。导电布的表面方阻可达30毫欧以下。
上述的化学镀铜溶液包含5-15g/L的五水硫酸铜、20-40g/L的EDTA、10g/L的NaOH和2-5ml/L的甲醛以及微量稳定剂。
实施例5
取2mm厚高密度涤纶泡棉，经150g/L NaOH溶液于60℃粗化10分钟，浸涂于实施例2所制得的胶体镍组合物中1分钟，清水漂洗干净，放入35℃的化学镀镍溶液镀覆8分钟，然后于电镀镍溶液中以2A/dm2的电流电镀10分钟，可得到导电良好的具有良好电磁屏蔽性能的和良好回弹性的导电泡棉。导电泡棉的表面方阻可达500毫欧以下，垂直电阻小于50毫欧。
上述的化学镀镍溶液包含5-15g/L的六水硫酸镍、30-60g/L的柠檬酸钠、10-30g/L的次磷酸钠和2-5g/L的氯化铵以及微量稳定剂。上述的电镀镍溶液包含250-350g/L的氨基磺酸镍、20-50g/L的硼酸、10-30g/L的氯化镍。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。
Claims (10)
1.一种胶体镍组合物，其特征在于，包括原料如下：PAMAM聚酰胺胺树状聚合物分子、镍盐、将镍离子还原为零价镍的还原剂、以及水。
2.根据权利要求1所述的胶体镍组合物，其特征在于，所述胶体镍组合物中，零价镍的量为500 ppm -2500ppm，PAMAM聚酰胺胺树状聚合物分子的量为0.5g/L-100g/L，所述还原剂的量为0.1g/L-25g/L。
3.根据权利要求1所述的胶体镍组合物，其特征在于，所述镍盐包括硝酸镍、氧化镍、醋酸镍、硫酸镍、氯化镍、柠檬酸镍和有机磺酸镍中的一种或多种。
4.根据权利要求1所述的胶体镍组合物，其特征在于，所述还原剂包括硼氢化钠、硼氢化钾、次磷酸钠、葡萄糖和二甲基胺硼烷中的一种或多种。
5.根据权利要求1所述的胶体镍组合物，其特征在于，所述胶体镍组合物还包括添加剂；所述添加剂包括表面活性剂、缓冲剂、pH调节剂和溶剂中的一种或多种。
6.根据权利要求5所述的胶体镍组合物，其特征在于，所述表面活性剂包括阴离子型、非离子型、阳离子型和两性表面活性剂中一种或多种；
所述缓冲剂包括羧酸、羧酸盐、胺、胺盐、氨基酸、氨基酸盐、无机酸、无机酸盐和无机碱中的一种或多种。
7.根据权利要求1所述的胶体镍组合物，其特征在于，所述胶体镍组合物为纳米颗粒的稳定水溶液，其中纳米颗粒的平均粒径为1nm-500nm。
8.根据权利要求1-7任一项所述的胶体镍组合物，其特征在于，所述胶体镍组合物的pH值为7-13。
9.一种权利要求1-8任一项所述的胶体镍组合物的应用，其特征在于，用于非金属材料基材的化学金属镀覆。
10.根据权利要求8所述的应用，其特征在于，所述非金属材料基材包括玻璃、陶瓷、树脂、玻璃纤维、纸、布和泡棉中的一种或多种。
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