CN1304633C - Chemical nickel-plating method on magnesium alloy surface - Google Patents
Chemical nickel-plating method on magnesium alloy surface Download PDFInfo
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- CN1304633C CN1304633C CNB021448345A CN02144834A CN1304633C CN 1304633 C CN1304633 C CN 1304633C CN B021448345 A CNB021448345 A CN B021448345A CN 02144834 A CN02144834 A CN 02144834A CN 1304633 C CN1304633 C CN 1304633C
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- chemical nickel
- magnesium alloy
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- plating
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- 238000007747 plating Methods 0.000 title claims abstract description 81
- 239000000126 substance Substances 0.000 title claims abstract description 68
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000008139 complexing agent Substances 0.000 claims abstract description 13
- 230000004913 activation Effects 0.000 claims abstract description 10
- 238000007781 pre-processing Methods 0.000 claims abstract description 6
- 239000003929 acidic solution Substances 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 24
- 150000002815 nickel Chemical class 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000001488 sodium phosphate Substances 0.000 claims description 15
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 15
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 15
- 238000007772 electroless plating Methods 0.000 claims description 14
- 239000011775 sodium fluoride Substances 0.000 claims description 12
- 235000013024 sodium fluoride Nutrition 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 230000002829 reductive effect Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 238000005554 pickling Methods 0.000 claims description 9
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 9
- 238000002203 pretreatment Methods 0.000 claims description 9
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005238 degreasing Methods 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 239000001632 sodium acetate Substances 0.000 claims description 8
- 235000017281 sodium acetate Nutrition 0.000 claims description 8
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 7
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 7
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 6
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229940095064 tartrate Drugs 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 229910000085 borane Inorganic materials 0.000 claims description 4
- VDTVZBCTOQDZSH-UHFFFAOYSA-N borane N-ethylethanamine Chemical compound B.CCNCC VDTVZBCTOQDZSH-UHFFFAOYSA-N 0.000 claims description 4
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 239000001433 sodium tartrate Substances 0.000 claims description 4
- 229960002167 sodium tartrate Drugs 0.000 claims description 4
- 235000011004 sodium tartrates Nutrition 0.000 claims description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 4
- 229940038773 trisodium citrate Drugs 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- BXBMHLIYMZRCNK-UHFFFAOYSA-H thallium(3+);trisulfate Chemical compound [Tl+3].[Tl+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BXBMHLIYMZRCNK-UHFFFAOYSA-H 0.000 claims description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 2
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 150000002222 fluorine compounds Chemical class 0.000 abstract 1
- 150000002506 iron compounds Chemical class 0.000 abstract 1
- 238000010415 tidying Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- 238000005406 washing Methods 0.000 description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 229960004249 sodium acetate Drugs 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910001096 P alloy Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 3
- 235000019263 trisodium citrate Nutrition 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000009996 mechanical pre-treatment Methods 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000004512 die casting Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
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Landscapes
- Chemically Coating (AREA)
Abstract
The present invention relates to a magnesium alloy surface treating technique, particularly to a chemical nickel-plating method on a magnesium alloy surface. The chemical nickel-plating method comprises the following steps: 1), activating or tidying up: magnesium alloy is activated in the temperature of 20 to 60 DEG C by an acidic solution containing fluoride after the magnesium alloy is polished or ground, degreased and washed in acid, and the activation time is within 0.5 to 5 minutes; 2), making chemical plating preprocessing: a water solution composed of fluorine compounds, iron compounds and a complexing agent is used for processing, the temperature is controlled within 15 to 45 DEG C, and the time is within 5 to 30 minutes; 3), making chemical nickel plating. A chemical nickel plating layer made by the chemical nickel-plating method has the advantages of even film thickness, strong binding force with a base and good corrosion resistance, and has metal appearance; the raw materials of the chemical nickel-plating method are easy to obtain and the cost is low; and the chemical nickel-plating method is suitable for commercial production, and reduces environmental pollution.
Description
Technical field
The present invention relates to magnesium alloy surface treatment, the method for chemical nickel plating on specifically a kind of magnesium alloy.
Background technology
Magnesium alloy proportion is little, specific tenacity and specific rigidity height, heat-conductivity conducting is good, has good damping shock absorption and electro-magnetic screen function simultaneously, store content is abundant in addition, be easy to recycle, as electronic product, as mobile communication, the shell structure part of hand-held computer etc., can substitute the plastics that are widely used at present, satisfy light, thin, the miniaturization of electronic product and the requirement of Highgrade integration, be used widely just day by day.The extensive application of magnesium alloy on car body especially can realize car lightization.According to measuring and calculating, automotive dead weight alleviates 10%, and its fuel efficiency can improve 5.5%, because the lighting of automobile has reduced fuel consumption, has reduced the automobile greenhouse gas emissions simultaneously, has reduced pollution, has more important meaning in environment protection.Therefore, magnesium and magnesium alloy have become the preferred material in fields such as Hyundai Motor, electronics, communication and aerospace, are described as " the green engineering material of 21st century ".
But, further enlarge the application of magnesium alloy on automobile and 3C Product, must solve the corrosion and protection problem of magnesium alloy.Magnesium is the highest metallic substance of chemical activity in the existing structure material, and its standard potential is-2.37 volts.The oxide film that the surface forms naturally in atmosphere is loose porous, does not have provide protection substantially.Under various envrionment conditionss, when especially chlorion existed, the corrosion failure of magnesium and alloy thereof was very serious.
Chemical plating of metal nickel coating on magnesium alloy carries out surface modification to magnesium alloy, is one of effective way that improves the corrosion resistance of magnesium alloy energy.Yet, because the height chemical activity of magnesium and alloy thereof, after workpiece enters chemical nickel-plating liquid, intensive corrosion and replacement(metathesis)reaction take place, and simultaneously with a large amount of liberations of hydrogen, cause coating and magnesium alloy substrate bonding force poor, the local foaming or the convex surface peeling appears, these defectives have had a strong impact on the quality of chemical plating, and the quality of follow-up electrolytic coating, can not guarantee the high anti-corrosion of coating.The pre-treating technology complexity of chemical nickel plating on traditional magnesium alloy generally will be through soaking steps such as zinc, cyanide electroplating, and especially cyanide electroplating liquid contains prussiate, and toxicity is very big.
Summary of the invention
In order to overcome above-mentioned deficiency, the object of the invention is to provide a kind of method with chemical nickel plating on the good magnesium alloy of high anti-corrosion and coating and basal body binding force.
To achieve these goals, technical scheme of the present invention is:
1) activation or arrangement: will polish or grind, degreasing, the magnesium alloy after the pickling is 20～60 ℃ in temperature, adopts fluorine-containing acidic solution activation, the time is 0.5～5 minute; Purpose is to remove metallic surface oxide film and pickling ash as thin as a wafer;
2) electroless plating pre-treatment: use the aqueous solution of being made up of fluorochemicals, iron containing compounds and complexing agent to handle, temperature is controlled between 15～45 ℃, and the time is 5～30 minutes; Purpose is to make Mg alloy surface form the fluorochemical protective membrane, has embedded the iron atom as the catalytic active center of next step chemical nickel plating in the film, has improved the bonding force of coating and matrix;
3) chemical nickel plating.
Wherein said activation or arrangement are chosen weight concentration 1%～15% hydrofluoric acid usually with fluorine-containing acidic solution, weight concentration 1%～20% silicofluoric acid, wherein a kind of or its compound of 20～80g/l acid ammonium fluoride; Fluorochemical in the described electroless plating preprocessing solution is chosen weight concentration 1%～20% hydrofluoric acid usually, weight concentration 1%～25% silicofluoric acid, 10～30g/l acid ammonium fluoride, 1～15g/l Potassium monofluoride, wherein a kind of or its compound of 1～10g/l Sodium Fluoride; Usually the iron containing compounds of choosing is 1～10g/l ferrous sulfate, 1～12g/l iron protochloride, and 1～15g/l Iron nitrate, 1～12g/l ferrous ammonium sulphate, 1～20g/l Tripotassium iron hexacyanide, 1～15g/l thionamic acid iron is one or more compound wherein; Described complexing agent is chosen concentration 1～20g/l citric acid usually, 1～15g/l Trisodium Citrate, and 1～10g/l tartrate, 1～12g/l soluble tartrate, 3～20g/l sodium tartrate is one or more compound wherein.
Wherein said chemical nickel plating divided for two steps carried out, and detailed process is as follows:
1) a step chemical nickel plating: will immerse through pretreated magnesium alloy member and contain nickel salt, reductive agent, inhibiter, in the chemical nickel-plating solution of stablizer and organic acid and/or complexing agent, controlled temperature is 50～100 ℃, soak time is 10～60 minutes.
2) two step chemical nickel platings: will immerse and contain nickel salt through the magnesium alloy member of step chemical nickel plating processing, reductive agent, in the chemical nickel-plating solution of complexing agent, controlled temperature is 60～95 ℃, soak time is 30～360 minutes.
Nickel salt is chosen concentration 7～35g/l basic nickel carbonate, 10～40g/l single nickel salt, wherein a kind of or its compound of 10～35g/l nickel acetate usually in the wherein said step chemical nickel-plating solution; Usually the reductive agent of choosing is concentration 10～60g/l inferior sodium phosphate, 0.1～2.0g/l sodium borohydride, 1～10g/l dimethyamine borane, wherein a kind of or its compound of 1～5g/l diethylamine borane; Usually the complexing agent of choosing is 20～70g/l quadrol, 20～50g/l ammonium hydroxide, 20～45g/l sodium acetate, wherein a kind of or its compound of 50～100g/l trolamine; Usually the stablizer of choosing is concentration 0.1～2mg/l thiocarbamide, 0.2～1.8mg/l lead, 5～20mg/l molybdic oxide, 0.04～4mg/l thallic sulfate, 0.2～2mg/l Thiovanic acid, 0.05～0.2mg/l Gelucystine, 0.5～2mg/l K
2S
2O
5Wherein a kind of; Usually the organic acid of choosing is concentration 0.5～5g/l propionic acid, 3～10g/l acetate, 5～35g/l lactic acid, 3～40g/l citric acid, wherein a kind of or its compound of 5～25g/l oxysuccinic acid; Usually the inhibiter of choosing is concentration 10～40g/l Potassium monofluoride, 2～10g/l Sodium Fluoride, 5～20g/l Neutral ammonium fluoride, wherein a kind of or its compound of 2～8g/l fluoroboric acid; Nickel salt is chosen concentration 10～40g/l basic nickel carbonate, 15～45g/l single nickel salt, wherein a kind of or its compound of 15～45g/l nickel acetate usually in the described two step chemical nickel-plating solutions; Usually the reductive agent of choosing is concentration 8～50g/l inferior sodium phosphate, 0.5～3.0g/l sodium borohydride, 3～15g/l dimethyamine borane, wherein a kind of or its compound of 2～8g/l diethylamine borane; Usually the complexing agent of choosing is concentration 20～70g/l quadrol, 20～50g/l ammonium hydroxide, 20～45g/l sodium acetate, wherein a kind of or its compound of 50～100g/l trolamine.
In the plating bath of above-mentioned two step chemical nickel platings, also can add organic acid and/or inhibiter; Adding the organic acid of choosing usually in the plating bath of two step chemical nickel platings is concentration 0.3～4g/l propionic acid, 5～15g/l acetate, 5～25g/l lactic acid, 3～40g/l citric acid, wherein a kind of or its compound of 3～20g/l oxysuccinic acid; Usually the inhibiter of choosing is concentration 5～20g/l Potassium monofluoride, 5～10g/l Sodium Fluoride, and 5～15g/l Neutral ammonium fluoride, 5～10g/l fluoroboric acid are wherein planted or its compound;
Superficial Foreign Body is removed in described polishing or grinding (being mechanical pre-treatment), reduces surfaceness; Described degreasing is to adopt usually that alkaline solution is concentration 5～40g/l sodium hydroxide, 5～35g/l potassium hydroxide, 10～25g/l water glass, 10～30g/l yellow soda ash, 10～20g/l sodium phosphate is wherein a kind of or its compound, its wash temperature is controlled between 50～95 ℃, and the time is 5～15 minutes; Described pickling is that to adopt solution usually be the combination solution of a kind of acid or multiple acid in concentration 5～20g/l hydrofluoric acid, 5～15g/l nitric acid, 5～25g/l sulfuric acid, the 5～40g/l phosphoric acid, removes oxide on surface with its washing; Temperature is controlled at 20～60 ℃, and the time is 0.5～5 minute;
When magnesium alloy sample greasy dirt is serious, before the inventive method above-mentioned (alkali lye) degreasing, can adopt petroleum-type, aromatic species, hydro carbons or chloride kind solvent to carry out solvent treatment, to reach best degreasing effect; And all need wash after each operation steps of the present invention.
The present invention has following advantage:
1. adopt treatment process of the present invention,, reduce pollution environment without soaking electroless plating pre-treatment steps such as zinc and cyanide electroplating.
2. the chemical Ni-plating layer that adopts the present invention to make, thicknesses of layers is even, and is strong with basal body binding force, and solidity to corrosion is good, has metal appearance.
3. electroless plating pretreatment process of the present invention; make magnesium alloy member in pretreatment fluid, form in the fluorochemical protective membrane; replacement(metathesis)reaction takes place; the iron atom that displaces is mixed in the protective membrane; after workpiece enters chemical plating fluid; iron atom triggers electroless plating reaction as catalytic center, and coating is embedded in the protective membrane, has improved the bonding force of coating and matrix greatly.The coating peeling that has solved coating and basal body binding force difference in the chemically coating nickel by magnesium-alloy process and caused and the problem of bubbling have guaranteed the solidity to corrosion of coating and carrying out smoothly of follow-up processes such as plating.
4. electroless plating pretreatment technology of the present invention, solution composition is simple, is easy to control, does not contain easy decomposition composition, process stabilizing.
5. the present invention adopts two-step chemical plating nickel technology, and workpiece triggers reaction earlier and forms pre-plating layer in containing the plating bath of stablizer, thicken in the plating bath that does not contain stablizer subsequently, both can guarantee the smooth plating of workpiece, can guarantee thickness of coating and quality again.
6. raw material of the present invention is easy to get, and cost is low, is suitable for suitability for industrialized production.
Below in conjunction with embodiment in detail the present invention is described in detail.
Embodiment 1
Chemical nickel plating on the magnesium alloy
Sample is extruding attitude AZ31D magnesium alloy, and its concrete operations step is:
1. mechanical pretreatment: grind with sandblast or sand paper, remove deburring, firm oxide compound, extruding with lubricator, releasing agent, casting model powder, cutting wet goods foreign matter, reduce surfaceness; Washing;
2. degreasing:, remove lubricant that general dirt, sintering adhere to, cutting agent etc. with 10g/l sodium hydroxide, 15g/l sodium phosphate, the washing of 15g/l yellow soda ash combination solution; Temperature is controlled at 70 ℃, and the time is 5 minutes; Washing;
3. pickling:, remove lubricant, the lubricant of bringing into, steel grit, casting model powder and other dirts that oxide skin, corrosion product, the sintering do not removed in the degreasing adhere to the composite acid solution washing of dense hydrofluoric acid, phosphoric acid 1: 1 by volume; Temperature is 30 ℃, and the time is 1 minute; Washing;
4. activation or arrangement: normal temperature, adopt 5% hydrofluoric acid solution, remove metallic surface oxide film as thin as a wafer, remove the pickling ash, the time is 1 minute; Washing;
5. electroless plating pre-treatment:
To immerse through the magnesium alloy sample of pre-treatment in the described electroless plating preprocessing solution, solution is by silicofluoric acid, Sodium Fluoride, and ferrous sulfate and Trisodium Citrate are formed (silicofluoric acid 15%, Sodium Fluoride 3g/l, ferrous sulfate 7g/l and Trisodium Citrate 8g/l).Controlled temperature is 40 ℃, soak time 10 minutes, and can obtain color is silver-gray fluoride films; Washing;
6. one go on foot chemical nickel plating: will immerse through pretreated workpiece and contain basic nickel carbonate 25g/l, inferior sodium phosphate 35g/l, propionic acid 4g/l, in the chemical nickel-plating liquid of Sodium Fluoride 7g/l and plumbic acetate 2.4mg/l, controlled temperature is 75 ℃, the pH value is 5.5, and the immersion time is 30 minutes, can obtain to have the nickel-phosphorus alloy pre-plating layer of metalluster.Coating and matrix bond are firm, and phosphorus content is 9%, presents amorphous structure.
7. two go on foot chemical nickel platings: will be through the magnesium alloy member of nickel preplating phosphorus alloy, immersion contains single nickel salt, lactic acid, inferior sodium phosphate, (single nickel salt 30tg/l in the chemical nickel-plating solution of Potassium monofluoride and sodium-acetate, lactic acid 20g/l, inferior sodium phosphate 22g/l, Potassium monofluoride 10g/l and sodium-acetate 30g/l), 90 ℃ of controlled temperature, the pH value is 5,120 minutes immersion time.Thickness of coating is 50 μ m.
According to standard GB/T13913-92: " autocatalytic nickel-phosphorus technical requirements and experimental technique ", for the experiment detection method of coating and basal body binding force; The thermal shock experiment is with the heating of the workpiece behind the chemical nickel plating one hour, drops in the cold water again, and whether observe coating has peeling and bubbling phenomenon; The file experiment is to make file become miter angle with coating, and whether the moving file of file is observed between coating and matrix and peeled off.The magnesium alloy workpiece of present embodiment gained nickel plating has passed through thermal shock and file experiment, meets standard GB/T13913-92 requirement fully.
Embodiment 2
Pre-treating process is identical with embodiment 1.
Difference from Example 1 is: adopt die casting AZ91D magnesium alloy;
Skimming temp is controlled at 90 ℃, and the time is 10 minutes; Pickling temperature is 20 ℃, and the time is 5 minutes; Activation or arrangement temperature are 30 ℃, 2 minutes time.
1. electroless plating pre-treatment: will immerse in the electroless plating preprocessing solution through the magnesium alloy sample of pre-treatment, solution is by hydrofluoric acid, Potassium monofluoride, and Iron nitrate and sodium tartrate are formed (silicofluoric acid 12%, Sodium Fluoride 2g/l, Iron nitrate 9g/l and sodium tartrate 10g/l).Controlled temperature is 30 ℃, soak time 15 minutes, and can obtain color is gray fluoride films; Washing;
2. one go on foot chemical nickel plating: will immerse through pretreated workpiece and contain basic nickel carbonate, inferior sodium phosphate, citric acid, lactic acid, Sodium Fluoride and K
2S
2O
5Chemical nickel-plating liquid in (basic nickel carbonate 15g/l, inferior sodium phosphate 20g/l, citric acid 35g/l, lactic acid 30g/l, Sodium Fluoride 5g/l and K
2S
2O
51.2mg/l), controlled temperature is 70 ℃, and the pH value is 6.0, and the immersion time is 40 minutes, can obtain to have the nickel pre-plating layer of metalluster.Coating and matrix bond are firm.
3. two go on foot chemical nickel platings: will immerse and contain single nickel salt, inferior sodium phosphate through the magnesium alloy member of nickel preplating, (single nickel salt 35g/l, inferior sodium phosphate 12g/l, sodium-acetate 25g/l in the chemical nickel-plating solution of sodium-acetate, 85 ℃ of controlled temperature, pH value are 4.5,200 minutes immersion time.Thickness of coating is 70 μ m.
The magnesium alloy workpiece of present embodiment gained nickel plating has passed through thermal shock and file experiment, meets standard GB/T13913-92 requirement fully.
Embodiment 3
Pre-treating process is identical with embodiment 1.
Difference from Example 1 is: adopt sample to be extruding attitude AM60 magnesium alloy;
Skimming temp is controlled at 70 ℃, and the time is 7 minutes; Pickling temperature is 60 ℃, and the time is 0.5 minute; Activation or arrangement temperature are 25 ℃, and the time is 10 minutes;
1. electroless plating pre-treatment: will immerse in the described electroless plating preprocessing solution through the magnesium alloy sample of pre-treatment, solution is by silicofluoric acid, acid ammonium fluoride, and ferrous ammonium sulphate and tartrate are formed (silicofluoric acid 8%, acid ammonium fluoride 15g/l, ferrous ammonium sulphate 10g/l and tartrate 5g/l).Controlled temperature is 30 ℃, soak time 12 minutes, and can obtain color is linen fluoride films; Washing;
2. one go on foot chemical nickel plating: will immerse through pretreated workpiece and contain single nickel salt 20g/l, inferior sodium phosphate 32g/l, citric acid 15g/l, oxysuccinic acid 8g/l, in the chemical nickel-plating liquid of Neutral ammonium fluoride 7g/l and thiocarbamide 0.5mg/l, controlled temperature is 95 ℃, the pH value is 5.3, and the immersion time is 20 minutes, can obtain to have the nickel-phosphorus alloy pre-plating layer of metalluster; Coating and matrix bond are firm.
3. two go on foot chemical nickel platings: will immerse and contain single nickel salt, sodium borohydride through the magnesium alloy member of nickel preplating phosphorus alloy, in the chemical nickel-plating solution of quadrol (single nickel salt 20g/l, sodium borohydride 1.2g/l, quadrol 25g/l), 90 ℃ of controlled temperature, pH value are 4.0,90 minutes immersion time.Thickness of coating is 30 μ m.
The magnesium alloy workpiece of present embodiment gained nickel plating has passed through thermal shock and file experiment, meets standard GB/T13913-92 requirement fully.
Claims (10)
1. the method for chemical nickel plating on the magnesium alloy is characterized in that, as follows operation:
1) activation or arrangement: will polish or grind, degreasing, the magnesium alloy after the pickling is 20～60 ℃ in temperature, adopts fluorine-containing acidic solution activation, the time is 0.5～5 minute;
2) electroless plating pre-treatment: use the aqueous solution of being made up of fluorochemicals, iron containing compounds and complexing agent to handle, temperature is controlled between 15～45 ℃, and the time is 5～30 minutes;
3) chemical nickel plating.
2. according to chemical nickel plating method on the described magnesium alloy of claim 1, it is characterized in that: described activation or arrangement are weight concentration 1%～15% hydrofluoric acid with fluorine-containing acidic solution, weight concentration 1%～20% silicofluoric acid, wherein a kind of or its compound of 20～80g/l acid ammonium fluoride.
3. according to chemical nickel plating method on the described magnesium alloy of claim 1, it is characterized in that: the fluorochemical in the described electroless plating preprocessing solution is weight concentration 1%～20% hydrofluoric acid, weight concentration 1%～25% silicofluoric acid, 10～30g/l acid ammonium fluoride, 1～15g/ Potassium monofluoride, wherein a kind of or its compound of 1～10g/l Sodium Fluoride; Iron containing compounds is 1～10g/l ferrous sulfate, 1～12g/l iron protochloride, 1～15g/l Iron nitrate, 1～12g/l ferrous ammonium sulphate, 1～20g/l Tripotassium iron hexacyanide, the compound that 1～15g/l thionamic acid iron is wherein a kind of or youngster plants; Described complexing agent is concentration 1～20g/l citric acid, 1～15g/l Trisodium Citrate, and 1～10g/l tartrate, 1～12g/l soluble tartrate, 3～20g/l sodium tartrate is one or more compound wherein.
4. according to chemical nickel plating method on the described magnesium alloy of claim 1, it is characterized in that wherein said chemical nickel plating divided for two steps carried out, detailed process is as follows:
1) a step chemical nickel plating: will immerse through pretreated magnesium alloy member and contain nickel salt, reductive agent, inhibiter, in the chemical nickel-plating solution of stablizer and organic acid and/or complexing agent, controlled temperature is 50～100 ℃, soak time is 10～60 minutes.
2) two step chemical nickel platings: will immerse and contain nickel salt through the magnesium alloy member of step chemical nickel plating processing, reductive agent, in the chemical nickel-plating solution of complexing agent, controlled temperature is 60～95 ℃, soak time is 30～360 minutes.
5. according to chemical nickel plating method on the described magnesium alloy of claim 4, it is characterized in that: nickel salt is concentration 7～35g/l basic nickel carbonate in the described step chemical nickel-plating solution, 10～40g/l single nickel salt, wherein a kind of or its compound of 10～35g/l nickel acetate; Reductive agent is concentration 10～60g/l inferior sodium phosphate, 0.1～2.0g/l sodium borohydride, 1～10g/l dimethyamine borane, wherein a kind of or its compound of 1～5g/l diethylamine borane; Complexing agent is 20～70g/l quadrol, 20～50g/l ammonium hydroxide, 20～45g/l sodium acetate, wherein a kind of or its compound of 50～100g/l trolamine; Stablizer is concentration 0.1～2mg/l thiocarbamide, 0.2～1.8mg/l lead, 5～20mg/l molybdic oxide, 0.04～4mg/l thallic sulfate, 0.2～2mg/l Thiovanic acid, 0.05～0.2mg/l Gelucystine, 0.5～2mg/lK
2S
2O
5Wherein a kind of; Organic acid is concentration 0.5～5g/l propionic acid, 3～10g/l acetate, 5～35g/l lactic acid, 3～40g/l citric acid, wherein a kind of or its compound of 5～25g/l oxysuccinic acid; Inhibiter is concentration 10～40g/l Potassium monofluoride, 2～10g/l Sodium Fluoride, 5～20g/l Neutral ammonium fluoride, wherein a kind of or its compound of 2～8g/l fluoroboric acid.
6. according to chemical nickel plating method on the described magnesium alloy of claim 4, it is characterized in that: nickel salt is concentration 10～40g/l basic nickel carbonate in the described two step chemical nickel-plating solutions, 15～45g/l single nickel salt, wherein a kind of or its compound of 15～45g/l nickel acetate; Reductive agent is concentration 8～50g/l inferior sodium phosphate, 0.5～3.0g/l sodium borohydride, 3～15g/l dimethyamine borane, wherein a kind of or its compound of 2～8g/l diethylamine borane; Complexing agent is concentration 20～70g/l quadrol, 20～50g/l ammonium hydroxide, 20～45g/l sodium acetate, wherein a kind of or its compound of 50～100g/l trolamine.
7. according to chemical nickel plating method on the described magnesium alloy of claim 4, it is characterized in that: in the plating bath of two step chemical nickel platings, add organic acid and/or inhibiter.
8. according to chemical nickel plating method on the described magnesium alloy of claim 7, it is characterized in that: adding organic acid in the plating bath of two step chemical nickel platings is concentration 0.3～4g/l propionic acid, 5～15g/l acetate, 5～25g/l lactic acid, 3～40g/l citric acid, wherein a kind of or its compound of 3～20g/l oxysuccinic acid; Inhibiter is concentration 5～20g/l Potassium monofluoride, 5～10g/l Sodium Fluoride, 5～15g/l Neutral ammonium fluoride, wherein a kind of or its compound of 5～10g/l fluoroboric acid.
9. according to chemical nickel plating method on the described magnesium alloy of claim 1, it is characterized in that: it is concentration 5～40g/l sodium hydroxide, 5～35g/l potassium hydroxide, 10～25g/l water glass, 10～30g/l yellow soda ash that alkaline solution is adopted in described degreasing, 10～20g/l sodium phosphate is wherein a kind of or its compound, its wash temperature is controlled between 50～95 ℃, and the time is 5～15 minutes; It is the combination solution of a kind of acid or multiple acid in concentration 5～20g/l hydrofluoric acid, 5～15g/l nitric acid, 5～25g/l sulfuric acid, the 5～40g/l phosphoric acid that solution is adopted in described pickling, and its wash temperature is controlled at 20～60 ℃, and the time is 0.5～5 minute.
10. according to chemical nickel plating method on claim 1,4, one of the 9 described magnesium alloy, it is characterized in that: all need wash after described each operation steps.
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| CN1303250C (en) * | 2004-08-05 | 2007-03-07 | 广州杰赛科技股份有限公司 | Magnesium alloy non cyanogen plating copper chemical plating nickle and its plating process |
| CN100462479C (en) * | 2005-09-05 | 2009-02-18 | 李克清 | Chemical plating method for Mg and its alloy |
| CN100451165C (en) * | 2005-09-30 | 2009-01-14 | 佛山市顺德区汉达精密电子科技有限公司 | Magnesium-alloy chemical nickel coating method |
| CN100451170C (en) * | 2006-11-21 | 2009-01-14 | 东北大学 | Process for preparing pretreatment layer and coating on magnesium and magnesium alloy surface |
| US20110192316A1 (en) * | 2010-02-05 | 2011-08-11 | E-Chem Enterprise Corp. | Electroless plating solution for providing solar cell electrode |
| CN102732865A (en) * | 2012-04-11 | 2012-10-17 | 中国电子科技集团公司第五十五研究所 | Chemical nickel plating solution and aluminum silicon carbide plating method |
| CN103882492B (en) * | 2014-02-24 | 2016-08-24 | 哈尔滨工程大学 | Metallic matrix chemical plating pre-treating method |
| CN105566676A (en) * | 2015-12-30 | 2016-05-11 | 南通万德科技有限公司 | Highly conductive elastomer based on chemical plating and preparation method thereof |
| CN105839083B (en) * | 2016-05-23 | 2018-09-07 | 深圳市瑞世兴科技有限公司 | A kind of magnesium alloy nickel plating process |
| CN106994507B (en) * | 2017-03-23 | 2018-11-16 | 西安飞机工业（集团）有限责任公司 | One kind can increase the active method of copper sheet surface nickel coating |
| CN106937491A (en) * | 2017-04-05 | 2017-07-07 | 广东浪潮大数据研究有限公司 | One kind is based on pcb board card gold finger galvanizing nickel and plating gold process and its application |
| CN107058988A (en) * | 2017-04-20 | 2017-08-18 | 上海丰豫新材料科技有限公司 | A kind of chemical nickel plating tungsten phosphorus formula |
| CN108441846B (en) * | 2018-02-08 | 2020-08-11 | 中山市鑫鸿顺新材料有限公司 | Gold vat additive and preparation method thereof |
| CN109898074A (en) * | 2019-04-11 | 2019-06-18 | 上海应用技术大学 | A kind of method of chemically coating nickel by magnesium-alloy-boron layer |
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