CN110172684A - A kind of ABS Chrome-free coarsening solution and the preparation method and application thereof - Google Patents
A kind of ABS Chrome-free coarsening solution and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110172684A CN110172684A CN201910491387.8A CN201910491387A CN110172684A CN 110172684 A CN110172684 A CN 110172684A CN 201910491387 A CN201910491387 A CN 201910491387A CN 110172684 A CN110172684 A CN 110172684A
- Authority
- CN
- China
- Prior art keywords
- abs
- coarsening solution
- chrome
- roughening
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims description 13
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 70
- 238000007788 roughening Methods 0.000 claims abstract description 61
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 29
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 20
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 13
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 10
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229960004838 phosphoric acid Drugs 0.000 claims abstract description 3
- 229940032330 sulfuric acid Drugs 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 27
- 238000007747 plating Methods 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
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- 239000002253 acid Substances 0.000 claims description 11
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- 239000002994 raw material Substances 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
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- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
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- 238000006386 neutralization reaction Methods 0.000 claims description 3
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
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- 239000012286 potassium permanganate Substances 0.000 abstract description 9
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 abstract description 8
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 41
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 41
- 238000009713 electroplating Methods 0.000 description 14
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- 230000008569 process Effects 0.000 description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
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- XADCESSVHJOZHK-UHFFFAOYSA-N Meperidine Chemical compound C=1C=CC=CC=1C1(C(=O)OCC)CCN(C)CC1 XADCESSVHJOZHK-UHFFFAOYSA-N 0.000 description 5
- 241000209140 Triticum Species 0.000 description 5
- 235000021307 Triticum Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
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- 238000002386 leaching Methods 0.000 description 4
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- 239000000084 colloidal system Substances 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- 238000011056 performance test Methods 0.000 description 2
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- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical compound [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
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- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
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- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001174 tin-lead alloy Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- 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
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2093—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by electrochemical 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
- C23C18/18—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
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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
- C23C18/26—Roughening, e.g. by etching using organic liquids
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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
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
Abstract
The present invention provides a kind of ABS Chrome-free coarsening solution, the coarsening solution be containing manganese sulfate, sulfuric acid, phosphoric acid, methane sulfonic acid aqueous solution.The present invention also provides the method for roughening that such Chrome-free coarsening solution is used for ABS plastic, after above-mentioned configured Chrome-free coarsening solution is electrolysed with electrolysis unit, ABS plastic is put into coarsening solution and carries out chemical roughening, the Chrome-free coarsening solution needs to connect evaporation equipment to keep the specific gravity of solution.Coarsening solution provided by the invention has evaded the use of the conventional chromic acid roughening explosive materials such as bring environmental pollution and potassium permanganate, and the method for roughening provided improves coarsening solution and the stability for being roughened ability, has good roughening effect and industrial application value.
Description
Technical field
The present invention relates to plastic cement electroplating technologies, formula and its preparation more particularly, to a kind of ABS Chrome-free coarsening solution,
And application of the ABS Chrome-free coarsening solution in terms of being roughened ABS plastic；The invention further relates to a kind of methods for being roughened ABS plastic.
Background technique
ABS plastic (i.e. acrylonitrile-butadiene-styrene copolymer) is to be widely used in parts industry and defend
Bathe the plating grade resins material of industry.Its principle that can be electroplated is, in the coarsening solution of conventional chromic acid/sulfuric acid system, A-S
Backbone chemical stability is preferable, is not easy to be oxidized, and butadiene therein can be oxidized, and forms anchor chalaza, colloid palladium deposition
Wherein, after dispergation, atom palladium is exposed, to play catalytic action in chemical nickel, forms one layer on the surface of the material very
Thin electroless nickel layer that can be conductive, and then can be carried out subsequent functional and decorative electroplating.
The roughening of ABS is not enough or roughening is excessive, the binding force of substrate and coating can be caused bad, particularly with automobile
The plastic cement of components industry is electroplated, and binding force is and its one of important reference performance.The roughening system of chromic acid/sulfuric acid system,
The advantages that because of its technical maturity, component is simple, low in cost is widely used in current plastic electroplating.But six in chromic acid
Valence chromium has carcinogenic teratogenesis, and wastewater treatment is more difficult, has very big harmfulness to environment and operator.
The research about the roughening of ABS Chrome-free plastics is broadly divided into optically catalytic TiO 2 processing, plasma treatment both at home and abroad
It is easy to operate wherein chemically treated method is low in cost with three directions of chemical treatment, it is feasible with industrialized production
Property.Again with potassium permanganate system, the most study of titanium dioxide manganese systems in chemical treatment, experimental result, which is shown, has preferable roughening effect
Fruit.For the coarsening solution of manganese dioxide system, manganese dioxide is minimal amount of to be dissolved in solution, remaining is with powdered dispersion solution
In, product surface can be attached in coarsening process, lead to product locally and cannot be roughened or be roughened not enough, cause plating leakage, blistering and
The non-uniform defect of binding force；For the coarsening solution of potassium permanganate system, titanium dioxide will form after being reduced in coarsening process
Manganese, equally has the shortcomings that above-mentioned, and furthermore potassium permanganate, which belongs to, easily makes quick-fried chemicals, it is more difficult to realize that batch in the industry is raw
It produces.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, this application provides a kind of ABS Chrome-free coarsening solutions and preparation method thereof
And application.Coarsening solution provided by the invention has evaded the conventional chromic acid roughening explosive original such as bring environmental pollution and potassium permanganate
The use of material, the method for roughening provided improve coarsening solution and the stability for being roughened ability, have good roughening effect and work
Industry application value.
Technical scheme is as follows:
A kind of ABS Chrome-free coarsening solution, the raw material including following concentration:
The content of manganese sulfate is 20-80g/L, and the content of sulfuric acid is 500-600ml/L, and the content of phosphoric acid is 50-200ml/L, first
The content of base sulfonic acid is 50-200ml/L.
Present invention also provides the preparation methods of the ABS Chrome-free coarsening solution, comprising the following steps:
(1) manganese sulfate is soluble in water, it is stirred well to dissolution, is slowly added to phosphoric acid and first thereto under conditions of cold bath
Base sulfonic acid, is finally slowly added to sulfuric acid；So that the concentration of manganese sulfate, sulfuric acid, phosphoric acid, methane sulfonic acid be respectively 20-80g/L,
500-600ml/L,50-200ml/L,50-200ml/L；
(2) solution that step (1) obtains is placed in electrolysis unit and is electrolysed to get ABS Chrome-free coarsening solution.
Preferably, the anode of step (2) described electrolysis is the platinum electrode that niobium is electroplated, and the thickness of coating of niobium is 1-5 microns thick；
Electrolysis cathode is stainless steel C276；The anode current of electrolysis is 1-5ASD.
Preferably, the content of Mn oxide is 2-8g/L in resulting ABS Chrome-free coarsening solution after step (2) electrolysis.
Preferably, the manganese sulfate raw material is Manganous sulfate monohydrate；The sulfuric acid is the sulfuric acid of concentration 98%；The phosphoric acid
For the phosphoric acid of concentration 85%.
Present invention also provides a kind of methods for being roughened ABS plastic, are roughened ABS using the ABS Chrome-free coarsening solution
Plastics；The method of roughening are as follows: ABS plastic is put into the ABS Chrome-free coarsening solution that temperature is 60-70 DEG C and is impregnated 5-15 minutes.
Present invention also provides a kind of ABS electric plating methods, comprising the following steps:
(1) cleaning step, the cleaning step successively include: oil removing, pre- roughening, acid preimpregnation；
(2) the step of roughening ABS plastic as claimed in claim 6；
(3) chemical pretreatment step, the chemical pretreatment step successively include: neutralization, preimpregnation, palladium activation, dispergation, chemical plating
Nickel；
(4) plating step, the plating step successively include: nickel preplating, sour copper, semi-gloss nickel, bright nickel/sand fourth nickel, microporous nickel,
The white black chromium of chromium/trivalent of trivalent.
Preferably, the reagent of step (1) the pre- roughening is pre- coarsening solution, by the 1- first of the sodium hydroxide of 90g, 103g
- 2 pyrrolidones of base, 18g butyl glycol ether be dissolved in deionized water, be settled to 1L, be configured to pre- roughening solution.
Preferably, the ABS Chrome-free coarsening solution further includes commercially available fog inhibitor or foaming agent.It is furthermore preferred that the suppression
The additive amount range of mist agent or foaming agent is 1 ~ 3 ml/L.
The present invention is beneficial to be had the technical effect that
Traditional coarsening solution is directly used after mixing raw material, and the present invention then joined electrolysis step, makes raw material by electrolysis
Performance changed and and interaction.In coarsening solution of the invention, the trivalent and tetravalence that are formed after manganese sulfate electrolysis
Manganese is main oxidant, in acid condition can double bond in oxygenated butadiene, oxidisability is not enough to destroy the A-S in ABS
Framework forms anchor chalaza in ABS surface after roughening, plays the role of good roughening.
In coarsening solution of the invention, the effect one of sulfuric acid is to provide acidic environment, and two are to provide oxidisability, with shape after electrolysis
At value Mn serve chemical cooperated, the pit that is formed is uniformly distributed after guaranteeing roughening, improves the binding force of coating.Phosphoric acid
Effect one is to provide acid condition, second is that the Manganic ion formed after complexing electrolysis, plays stabilizing trivalent manganese ion, prevents
The only generation of disproportionated reaction.
Methane sulfonic acid is a kind of organic acid and non-oxidizing acid, frequently as solvent, alkylation and esterifying reagent application
In organic synthesis, it is also used on tin and tin-lead alloy electroplating in recent years.Utilization principle and alkyl of the present invention to methane sulfonic acid
Sulfonate electroplate liquid is different, is to reduce solution using a small amount of manganese dioxide generated in complex reaction the characteristics of its chemical structure
Precipitating.The present invention also adjusts acidity by methane sulfonic acid, under conditions of sulfuric acid and certain phosphoric acid concentration, changes methyl sulphur
The dosage of acid makes roughening liquid acidity be limited in 23.7N ~ 24.3N.In addition, methane sulfonic acid also has certain corrosivity, can help
It is roughened ABS plastic.
Coarsening solution provided by the invention does not contain Cr VI, potassium permanganate and manganese dioxide precipitate, reduces to environment
Pollution, reduces the injury to operator；Chrome-free method of roughening provided by the invention, raw material components control are stablized, raw material group
Divide consumption few, the addition frequency is low, reduces supplies consumption cost and human input cost, is conducive to improve product yield.
Raw material of the present invention is easy to get, low in cost, and preparation method is simple, Environmental Safety.Value Mn is generated by electrolytic method,
The use that potassium permanganate easily makes quick-fried drug is avoided, there is good uniform roughening ability to ABS plastic, and without heavy in coarsening process
Starch generates.The divalent manganesetion that generates after value Mn reaction in coarsening process, can be regenerated by electrolysis value Mn from
Son, implementation recycle, and the roughening service life is high, have good industrial production value.
Detailed description of the invention
Fig. 1 is the SEM scan image after the embodiment of the present invention and comparative example roughening.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.Obviously, described embodiment is only this
Invention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art exist
Every other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
ABS roughening solution and method of roughening provided by the invention can be adapted for various plating grade ABS, the plating
The ABS of grade is plating grade ABS well known to those skilled in the art, i.e. B content in ABS is in 15%-30%.Such as the trade mark is
0160R(Samsung), 0670R(Samsung), the odd beauty in the Taiwan 727(), P2MC(Styrolution), MG37EPX(Sabic), 3001M
(Japanese UMG) etc..It is the ABS template of the sea 160T day injection molding machine injection molding using the sample of use in embodiment, long 120mm is wide
90mm, thick 3mm.Fog inhibitor or foaming agent select commercial product, such as 928 fog inhibitors of ten thousand Xiang chemical industry, ten thousand Xiangs or wheat dolantin
Foaming agent, model F-19,858ht etc..
The whole set process process of embodiment 1:ABS roughening
1, oil removing
Using degreasing fluid disclosed in commercially available or this field, such as the ENPREP provided using wheat dolantin Enthone Chemistry Inc.
The degreasing fluid that 142 degreasing powders are prepared.ABS template is immersed in prepared degreasing fluid, after being stirred oil removing 7 minutes at 60 DEG C,
Cleaned up with pure water, it is therefore an objective to the greasy dirt on ABS plastic surface of going out makes roughening reaction more evenly, improve substrate and coating it
Between binding force.
2, pre- roughening
Using pre- roughening solution disclosed in commercially available or this field, or the pre- coarsening solution of self-control.Such as by the sodium hydroxide of 90g, 103g
- 2 pyrrolidones of 1- methyl, the butyl glycol ether of 18g is dissolved in deionized water, is settled to 1L, is configured to pre- roughening solution.
The ABS plastic workpiece cleaned after oil removing is placed in one, pre- roughening treatment 3 minutes under the conditions of 40 DEG C, then spend
Ionized water wash clean.The effect being roughened in advance is the organic polymer chain being swollen in substrate, is easier to carry out roughening, while can be with
The roughening effect on the ABS resin surface of next step is improved, aperture and the density for such as forming micropore are more uniform, so as to improve microetch
Effect enhances the binding force of coating and substrate.
3, acidleach
(1) it prepares coarsening solution: 20g Manganous sulfate monohydrate being dissolved in 200ml water, dissolution is stirred well to, in the item of cold bath
100ml concentrated phosphoric acid and 200ml methane sulfonic acid are slowly added under part thereto, is finally slowly added to the concentrated sulfuric acid of 500ml.It is described dense
The concentration of sulfuric acid is 98%；The concentration of the concentrated phosphoric acid is 85%.After preparation, fog inhibitor, additive amount range 2ml/ are added
L finally obtains ABS Chrome-free coarsening solution.
(2) electrolyzing and coarsening liquid: constant coarsening solution temperature is electrolysed at 70 DEG C.Electrolytic anode is the platinum electrode that niobium is electroplated,
The thickness of coating of niobium is 3 microns of thickness；Electrolysis cathode is stainless steel C276；The anode current of electrolysis is 2ASD.Electrolysis time is control
Coarsening solution processed to Mn oxide therein reaches 2g/L.
(3) solution after taking 20 parts of Chrome-free roughening electrolysis, is diluted to 100 parts with deionized water.After above-mentioned pre- roughening
Workpiece is placed in this acid dip solution, temperature room temperature, and the time 30 seconds.Acidleach effect first is that adjust product surface hydrophily, two
It is to be conducive to keep the acidity in subsequent Chrome-free roughening solution.
4, it is roughened
Workpiece after above-mentioned acidleach is immersed in the coarsening solution after electrolysis 15 minutes, then is cleaned up with pure water.
5, it neutralizes
It takes 0.4g hydroxylamine hydrochloride and 50ml hydrochloric acid to be added in pure water, is settled to 1L.It will be in the ABS template immersion after above-mentioned roughening
In liquid, stir 2 minutes under room temperature, then cleaned up with pure water.The effect of neutralization is by the remaining high price of sample surface
Manganese ion is reduced into bivalent manganese, prevents it from influencing subsequent palladium activation reconciliation adhesive process.
6, it presoaks
ABS template with after among the above, is immersed in the hydrochloric acid solution of 200ml/L, and room temperature leaching is set 1 minute.The purpose of preimpregnation is
Influence of the medical fluid of previous process to subsequent palladium activating process is prevented, guarantees the acidity in palladium activating process.
7, palladium activates
Template after above-mentioned pre-preg, is immersed in palladium activated solution 3 minutes, wherein palladium water concentration 30ppm, stannous chloride
7g/L, hydrochloric acid 300ml/L, 30 DEG C of temperature.Template after activation is cleaned up with pure water.
8, dispergation
Sol solution is solved using disclosed in commercially available or this field, such as the 887 dispergation systems of wheat dolantin Enthone Chemistry Inc..It will be upper
Template after stating palladium activation is placed in solution sol solution, temperature 45 C, and the time 1.5 minutes.The effect of dispergation is to remove colloid palladium week
The stannous chloride hydrolysate enclosed, exposes palladium core, forms a catalytic center, is conducive to the progress of subsequent chemistry nickel plating.
Template after dispergation, is cleaned up with pure water.
9, chemical nickel plating
Above-mentioned dispergation treated template is disclosed using this field or commercially available electroless nickel solution carries out chemical nickel plating, such as will
The electroless nickel solution for 891 systems that above-mentioned template is provided with wheat dolantin Enthone Chemistry Inc. carries out chemical nickel plating, temperature 30
DEG C, the time 7 minutes.Template after chemical nickel plating is cleaned up with pure water.
10, nickel preplating
Template after above-mentioned chemical nickel plating is placed in pre-nickel plating solution and is electroplated, 55 DEG C of temperature, 5 clock of time, current density
0.5A/dm2, wherein nickel sulfate content 260g/L, chlorination nickel content 45g/L, boric acid 45g/L.The effect of nickel preplating is in chemistry
One layer of thin electroplated layer is electroplated in low current on nickel layer, first is that increasing electric conductivity, second is that preventing the electro-coppering in subsequent high current
Middle chemistry nickel coating is breakdown.Template after nickel preplating needs to be cleaned up with pure water.
11, sour copper
Template after above-mentioned nickel preplating is placed in sour copper solution and is electroplated, 27 DEG C of temperature, time 2h, current density 3.5A/
Dm2, wherein sulfuric acid copper content 200g/L, sulfuric acid content 36ml/L, chloride ion content 80ppm, brightener used are happy for wheat dolantin
Think Chemical Co., Ltd. provides 1550 serial brighteners.Template after electroplating acid copper is complete is used after dilute potassium bichromate passivation
After pure water rinsing is clean, drying.
Finally obtain the ABS sample of the bright smooth copper electroplating layer with a thickness of 40 microns.
Embodiment 2: change coarsening solution composition
Coarsening solution composition in the step 3 of embodiment 1 is changed to: 50g Manganous sulfate monohydrate being dissolved in 200ml water, is sufficiently stirred
It mixes to dissolution, is slowly added to 150ml concentrated phosphoric acid and 150ml methane sulfonic acid thereto under conditions of cold bath, it is last slowly to add
Enter the concentrated sulfuric acid of 500ml.After preparation, fog inhibitor is added, makes its concentration 1ml/L.Constant coarsening solution temperature is at 65 DEG C, electricity
Solution coarsening solution to Mn oxide therein reaches 5g/L.Sample after above-mentioned acidleach is immersed in the coarsening solution after electrolysis 10 points
Clock, then cleaned up with pure water.
Finally obtain the ABS sample of the bright smooth copper electroplating layer with a thickness of 40 microns.
Embodiment 3: change coarsening solution composition
Coarsening solution composition in the step 3 of embodiment 1 is changed to: 80g Manganous sulfate monohydrate being dissolved in 200ml water, is sufficiently stirred
It mixes to dissolution, is slowly added to 200ml concentrated phosphoric acid and 100ml methane sulfonic acid thereto under conditions of cold bath, it is last slowly to add
Enter the concentrated sulfuric acid of 500ml.After preparation, fog inhibitor is added, makes its concentration 3ml/L.Constant coarsening solution temperature is at 60 DEG C, electricity
Solution coarsening solution to Mn oxide therein reaches 8g/L.Sample after above-mentioned acidleach is immersed in the coarsening solution after electrolysis 5 minutes,
It is cleaned up again with pure water.
Finally obtain the ABS sample of the bright smooth copper electroplating layer with a thickness of 40 microns.
Embodiment 4: change coarsening solution composition
Coarsening solution composition in the step 3 of embodiment 1 is changed to: 20g Manganous sulfate monohydrate being dissolved in 200ml water, is sufficiently stirred
It mixes to dissolution, is slowly added to 50ml concentrated phosphoric acid and 150ml methane sulfonic acid thereto under conditions of cold bath, is finally slowly added to
The concentrated sulfuric acid of 600ml.After preparation, foaming agent is added, makes its concentration 1ml/L.Constant coarsening solution temperature is at 60 DEG C, electrolysis
Coarsening solution to Mn oxide therein reaches 2g/L.Sample after above-mentioned acidleach is immersed in the coarsening solution after electrolysis 5 minutes, then
It is cleaned up with pure water.
Finally obtain the ABS sample of the bright smooth copper electroplating layer with a thickness of 40 microns.
Embodiment 5: change coarsening solution composition
Coarsening solution composition in the step 3 of embodiment 1 is changed to: 50g Manganous sulfate monohydrate being dissolved in 200ml water, is sufficiently stirred
It mixes to dissolution, is slowly added to 100ml concentrated phosphoric acid and 100ml methane sulfonic acid thereto under conditions of cold bath, it is last slowly to add
Enter the concentrated sulfuric acid of 600ml.After preparation, foaming agent is added, makes its concentration 2ml/L.Constant coarsening solution temperature is at 65 DEG C, electricity
Solution coarsening solution to Mn oxide therein reaches 5g/L.Sample after above-mentioned acidleach is immersed in the coarsening solution after electrolysis 10 points
Clock, then cleaned up with pure water.
Finally obtain the ABS sample of the bright smooth copper electroplating layer with a thickness of 40 microns.
Embodiment 6: change coarsening solution composition
Coarsening solution composition in the step 3 of embodiment 1 is changed to: 80g Manganous sulfate monohydrate being dissolved in 200ml water, is sufficiently stirred
It mixes to dissolution, is slowly added to 150ml concentrated phosphoric acid and 50ml methane sulfonic acid thereto under conditions of cold bath, is finally slowly added to
The concentrated sulfuric acid of 600ml.After preparation, foaming agent is added, makes its concentration 3ml/L.Constant coarsening solution temperature is at 70 DEG C, electrolysis
Coarsening solution to Mn oxide therein reaches 8g/L.Sample after above-mentioned acidleach is immersed in the coarsening solution after electrolysis 15 minutes,
It is cleaned up again with pure water.
Finally obtain the ABS sample of the bright smooth copper electroplating layer with a thickness of 40 microns.
Comparative example 1: change preprocess method and coarsening solution composition
Compared with Example 1, pre- roughening and acid leaching process are not needed, coarsening solution and method of roughening are also different.
Coarsening solution used by this comparative example: the chromic anhydride of 400g, the concentrated sulfuric acid of 380g, 2ml ethanol solution are added to pure
In water, it is settled to 1L, it is agitated to be configured to roughening solution.Sample after oil removing is immersed to 12min in 68 DEG C of coarsening solution, then is used
Pure water cleans up.
Finally obtain the ABS sample of the bright smooth copper electroplating layer with a thickness of 40 microns.
Comparative example 2: change preprocess method and coarsening solution composition
Compared with Example 1, pre- roughening and acid leaching process are not needed, coarsening solution and method of roughening are also different.
Coarsening solution used by this comparative example: the sodium hydroxide of the potassium permanganate of 30g, 20g are added in pure water, constant volume
It is agitated to be configured to roughening solution to 1L.Sample after oil removing is immersed to 12min in 68 DEG C of coarsening solution, then is cleaned with pure water
Completely.
Finally obtain the ABS sample of the bright smooth copper electroplating layer with a thickness of 40 microns.
Comparative example 3: change preprocess method and coarsening solution composition
Compared with Example 1, pre- roughening and acid leaching process are not needed, coarsening solution and method of roughening are also different.
Coarsening solution used by this comparative example: the manganese dioxide of 30g, the 800ml concentrated sulfuric acid are added in 200ml pure water,
It is configured to roughening solution.Sample after oil removing is immersed to 12min in 68 DEG C of coarsening solution, then is cleaned up with pure water.
Finally obtain the ABS sample of the bright smooth copper electroplating layer with a thickness of 40 microns.
Performance test
1, SEM is tested
Template after roughening is cut into 1cm × 1cm size, is tested using scanning electron microscope its pattern after metal spraying.
The Inspect F50 of FEI company, scanning electron microscope model U.S. production.SEM after embodiment and comparative example roughening is swept
Tracing is as shown in Figure 1.It will be seen from figure 1 that the surface of ABS template all forms after using coarsening solution roughening of the invention
The hole of dense uniform, is conducive to the deposition of colloid palladium, to increase the binding force between substrate and coating.
2, adhesive force is tested
Adhesive force test is carried out according to the peel test force in the testing standard GMW14668 of General Motors, after having plated sour copper
Test board is cut into 12cm long, and the strip of 2.5cm wide, detachment rate 100mm/min, used equipment is Suzhou power the Supreme People's Procuratorate
The computermatic universal testing machine of measurement equipment Co., Ltd production.Peeling force >=9N/cm of standard requirements ABS.
3, cooling thermal impact is tested
Cooling thermal impact experiment is carried out according to the quick-cooling, heating shock-testing in the testing standard GMW14668 of General Motors, by sample
It is quickly transferred to be kept for 1 hour in 90 ± 3 DEG C of high temperature experimental box after being kept for 1 hour in -40 ± 3 DEG C of low temperature storage box,
The above are a cycles, repeat 4 circulations, after the completion 2 hours visual results of room temperature.Standard requirements appearance is without change
Change.
It should be noted that adhesive force is not the bigger the better, and bigger binding force means that cold under actual production conditions
After thermal cycle, substrate is bigger by the risk of coating drawing crack, influences the performance test of workpiece；Main and conventional chromic acid roughening herein
And the more example with certain volume production feasibility of existing research compares, binding force is roughened closer to chromic acid,
Effect is better.
The test result of adhesive force and thermal shock experiment is as shown in table 1.
Table 1
| Adhesive force (N/cm) | Cooling thermal impact | |
| Embodiment 1 | 9.62 | Appearance is unchanged |
| Embodiment 2 | 11.08 | Appearance is unchanged |
| Embodiment 3 | 11.32 | Appearance is unchanged |
| Embodiment 4 | 10.51 | Appearance is unchanged |
| Embodiment 5 | 11.82 | Appearance is unchanged |
| Embodiment 6 | 10.67 | Appearance is unchanged |
| Comparative example 1 | 12.63 | Appearance is unchanged |
| Comparative example 2 | 3.24 | There is blistering |
| Comparative example 3 | 7.96 | Appearance is unchanged |
As it can be seen from table 1 be roughened using the binding force of the ABS template after roughening solution roughening of the invention close to chromic acid
Binding force is better than the roughening effect using potassium permanganate and manganese dioxide system.
Although the embodiments of the present invention have been disclosed as above, but its listed fortune not only in the description and the implementation
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, for this field
Those of ordinary skill for, without departing from the principles and spirit of the present invention can to these embodiments carry out it is a variety of
Change, modification, replacement and modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention
It is not limited to specific details.
Claims (10)
1. a kind of ABS Chrome-free coarsening solution, it is characterised in that the raw material including following concentration:
The content of manganese sulfate is 20-80g/L, and the content of sulfuric acid is 500-600ml/L, and the content of phosphoric acid is 50-200ml/L, first
The content of base sulfonic acid is 50-200ml/L.
2. a kind of preparation method of ABS Chrome-free coarsening solution described in claim 1, it is characterised in that the following steps are included:
(1) manganese sulfate is soluble in water, it is stirred well to dissolution, is slowly added to phosphoric acid and first thereto under conditions of cold bath
Base sulfonic acid, is finally slowly added to sulfuric acid；So that the concentration of manganese sulfate, sulfuric acid, phosphoric acid, methane sulfonic acid be respectively 20-80g/L,
500-600ml/L,50-200ml/L,50-200ml/L；
(2) solution that step (1) obtains is placed in electrolysis unit and is electrolysed to get ABS Chrome-free coarsening solution.
3. according to the method described in claim 2, it is characterized in that the anode of step (2) described electrolysis is the platinum electricity that niobium is electroplated
Pole, the thickness of coating of niobium are 1-5 microns thick；Electrolysis cathode is stainless steel C276；The anode current of electrolysis is 1-5ASD.
4. according to the method described in claim 2, it is characterized in that manganese in resulting ABS Chrome-free coarsening solution after step (2) electrolysis
The content of oxide is 2-8g/L.
5. ABS Chrome-free coarsening solution according to claim 1 or 2, it is characterised in that the manganese sulfate raw material is a hydration sulphur
Sour manganese；The sulfuric acid is the sulfuric acid of concentration 98%；The phosphoric acid is the phosphoric acid of concentration 85%.
6. ABS Chrome-free coarsening solution according to claim 1 or 2, it is characterised in that the ABS Chrome-free coarsening solution further includes city
The fog inhibitor or foaming agent sold.
7. ABS Chrome-free coarsening solution according to claim 6, it is characterised in that the additive amount of the fog inhibitor or foaming agent
Range is 1 ~ 3 ml/L.
8. a kind of method for being roughened ABS plastic, it is characterised in that using ABS Chrome-free coarsening solution of any of claims 1 or 2 come thick
Change ABS plastic；The method of roughening are as follows: ABS plastic is put into the ABS Chrome-free coarsening solution that temperature is 60-70 DEG C and impregnates 5-15
Minute.
9. a kind of ABS electric plating method, it is characterised in that the following steps are included:
(1) cleaning step, the cleaning step successively include: oil removing, pre- roughening, acid preimpregnation；
(2) the step of roughening ABS plastic as claimed in claim 6；
(3) chemical pretreatment step, the chemical pretreatment step successively include: neutralization, preimpregnation, palladium activation, dispergation, chemical plating
Nickel；
(4) plating step, the plating step successively include: nickel preplating, sour copper, semi-gloss nickel, bright nickel/sand fourth nickel, microporous nickel,
The white black chromium of chromium/trivalent of trivalent.
10. according to the method described in claim 9, it is characterized in that the reagent of step (1) the pre- roughening is pre- coarsening solution, general
The sodium hydroxide of 90g, -2 pyrrolidones of 1- methyl of 103g, 18g butyl glycol ether be dissolved in deionized water, be settled to 1L,
It is configured to pre- roughening solution.
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| CN112941585A (en) * | 2021-01-27 | 2021-06-11 | 重庆安创材料科技有限公司 | Chromium-free coating process |
| WO2022043241A1 (en) | 2020-08-25 | 2022-03-03 | Atotech Deutschland GmbH & Co. KG | Method for metallizing a non-metallic substrate and pre-treatment composition |
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