CN103215574A - Magnesium-alloy chemical nickel plating solution and nickel plating process thereof - Google Patents
Magnesium-alloy chemical nickel plating solution and nickel plating process thereof Download PDFInfo
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- CN103215574A CN103215574A CN2013101365713A CN201310136571A CN103215574A CN 103215574 A CN103215574 A CN 103215574A CN 2013101365713 A CN2013101365713 A CN 2013101365713A CN 201310136571 A CN201310136571 A CN 201310136571A CN 103215574 A CN103215574 A CN 103215574A
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- nickel plating
- chemical nickel
- magnesium alloy
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 262
- 238000007747 plating Methods 0.000 title claims abstract description 138
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 132
- 239000000126 substance Substances 0.000 title claims abstract description 92
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title abstract description 11
- 230000008569 process Effects 0.000 title abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000005516 engineering process Methods 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000007772 electroless plating Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 6
- 229940078494 nickel acetate Drugs 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 5
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 4
- 229940050410 gluconate Drugs 0.000 claims description 4
- 229940049920 malate Drugs 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003518 caustics Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims 4
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims 2
- 239000000174 gluconic acid Substances 0.000 claims 2
- 235000012208 gluconic acid Nutrition 0.000 claims 2
- 239000004310 lactic acid Substances 0.000 claims 2
- 235000014655 lactic acid Nutrition 0.000 claims 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 8
- 230000000536 complexating effect Effects 0.000 abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 3
- 230000037452 priming Effects 0.000 abstract 1
- 230000008719 thickening Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229960003975 potassium Drugs 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 229940120146 EDTMP Drugs 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical group OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- YKXCWZVUWWQSAV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O YKXCWZVUWWQSAV-BTVCFUMJSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UXZTTXYFUOYMTO-UHFFFAOYSA-N [K].P(=O)(O)OP(=O)O.OC=C Chemical compound [K].P(=O)(O)OP(=O)O.OC=C UXZTTXYFUOYMTO-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 239000001508 potassium citrate Substances 0.000 description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 229940001516 sodium nitrate Drugs 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 235000015870 tripotassium citrate Nutrition 0.000 description 2
- 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 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000006439 Lemna minor Nutrition 0.000 description 1
- 244000207740 Lemna minor Species 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004224 potassium gluconate Substances 0.000 description 1
- 235000013926 potassium gluconate Nutrition 0.000 description 1
- 229960003189 potassium gluconate Drugs 0.000 description 1
- 239000001415 potassium malate Substances 0.000 description 1
- SVICABYXKQIXBM-UHFFFAOYSA-L potassium malate Chemical compound [K+].[K+].[O-]C(=O)C(O)CC([O-])=O SVICABYXKQIXBM-UHFFFAOYSA-L 0.000 description 1
- 235000011033 potassium malate Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000019265 sodium DL-malate Nutrition 0.000 description 1
- 239000001394 sodium malate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
The invention discloses a magnesium-alloy chemical nickel plating solution and a nickel plating process thereof. The magnesium-alloy chemical nickel plating solution disclosed by the invention comprises alkaline chemical nickel plating liquid and neutral chemical nickel plating liquid; and a special complexing system is used in a plating liquid system, so that the corrosion action on magnesium metal is reduced, and the stability of plating liquid and the bonding force between a base material and a nickel layer are improved. The invention further provides a magnesium-alloy two-step chemical nickel plating process, wherein the alkaline chemical nickel plating liquid is used for priming, and then, the neutral chemical nickel plating liquid is used for carrying out thickening treatment. Furthermore, according to the nickel plating process, a pretreatment process of ultrasonic alkaline membrane removal is adopted before two-step chemical nickel plating, so that an oxidized membrane and a residual demolding agent on the surface of a magnesium-alloy workpiece are cleaned thoroughly, and then, the yield of nickel-plated products is further increased.
Description
Technical field
The invention belongs to the metal protection field, particularly magnesium alloy chemical nickel plating solution and nickel plating technology thereof.
Background technology
Magnesium alloy is described as the green metal structured material of 21 century, has that density is low, specific tenacity and a specific rigidity height, and damping and amortization, machinability, castability are superior, have obtained increasingly extensive application on automotive industry, space flight and aviation industry, electronic industry.
Yet magnesium alloy chemical character is active, and corrosion-resistant need be carried out anti-corrosive treatment to its surface, and is ion implantation etc. as plating, electroless plating, conversion coating, anodic oxidation, thermospray and vapour deposition.Wherein, chemically coated nickel method also can obtain the uniform coating of thickness because of obviously improving the solidity to corrosion and the wear resistance of magnesium alloy on complicated plating piece surface, becomes the prefered method of magnesium alloy surface protective.
Because the Standard Electrode Potentials of nickel and magnesium differs bigger, therefore on magnesium alloy, directly carry out chemical nickel plating, gained coating and basal body binding force are relatively poor.In order to address this problem, before chemical nickel plating, soak zinc, alkaline activation usually, method such as acidic activated is carried out surface preparation, plays certain improvement effect.With soaking the zinc pretreatment mode, between magnesium alloy and nickel dam, come transition exactly with zinc-impregnating layer, improving the chemical Ni-plating layer bonding force, but in the chemical nickel plating bath, the dissolving of zinc metal can be shortened chemical nickel work-ing life.Great majority adopt acidic activated pre-treatment at present, make Mg alloy surface generate the moderate MgF of one deck thickness
2Protective membrane directly carries out chemical nickel plating, MgF then
2Protective membrane plays control chemical nickel sedimentation velocity, can improve the chemical nickel bonding force, but need the chemical nickel plating time longer relatively, and production efficiency is low.
Magnesium alloy chemical nickel medicament all is special-purpose, and with the supporting use of corresponding flow process, big portion chemical nickel plating bath is slightly acidic or neutrality, the pH value is controlled at 5.5～8 interior (Mao Zexu etc. of scope, AZ91D magnesium alloy direct chemical nickel-plating technology, material protection, 2010 the 5th phases; Bang duckweed etc., magnesium alloy direct chemical nickel-plating technology and coating performance are electroplated and covering with paint, 2011 the 2nd phases), advantage is that sedimentation velocity is fast, helps plating on the chemical nickel.Protect magnesium alloy not to be subjected to etch though in the chemical nickel plating bath, add a large amount of hydrofluoric acid or fluorochemical, still corroded easily under the high temperature neutrallty condition.Especially the magnalium AZ-91D die casting that uses of actual production because segregation mutually and the local corrosion phenomenon can appear in the surface composition skewness in the chemical nickel plating bath, can't completely be gone up nickel, causes and produces the yield instability.And when on this electroless nickel layer, continuing electroplating other metals coating, with the increase of thickness, the bonding force between coating and base material worse and worse, its major cause is that sedimentation velocity is fast, the big institute of nickel dam stress causes, and makes that this technology limitation in actual production is bigger.
Summary of the invention
The objective of the invention is to overcome existing deficiency, magnesium alloy chemical nickel plating solution and nickel plating technology thereof are provided.
The technical solution used in the present invention is:
A kind of magnesium alloy chemical nickel plating solution comprises alkaline electroless plating nickel solution and neutral chemical nickel-plating solution:
By mass percentage, the alkaline chemical nickel-plating solution composition is as follows:
Surplus is a deionized water, and is 10.0～11.5 with the pH of pH regulator agent regulator solution;
By mass percentage, neutral chemical nickel-plating solution is composed as follows:
Surplus is a deionized water, and is 5.5～7.0 with the pH value of pH regulator agent regulator solution.
Preferably, by mass percentage, the alkaline chemical nickel-plating solution composition is as follows:
Surplus is deionized water and an amount of pH regulator agent;
Preferably, by mass percentage, neutral chemical nickel-plating solution is composed as follows:
Surplus is deionized water and an amount of pH regulator agent.
Described pH regulator agent is sodium hydroxide, potassium hydroxide or ammoniacal liquor.
A kind of magnesium alloy nickel plating technology may further comprise the steps:
1) pre-treatment: the magnesium alloy sample is carried out oil removing, pickling, activation treatment;
2) chemical nickel plating: use magnesium alloy chemical nickel plating solution that the magnesium alloy sample is carried out bottoming of alkaline electroless plating nickel solution and neutral chemical nickel-plating solution nickel plating successively;
3) aftertreatment: behind the chemical nickel plating, toast dehydrogenation, activation treatment;
4) electroplate: carry out follow-up conventional the plating;
Used magnesium alloy chemical nickel plating solution as mentioned above.
Preferably, the treatment temp of alkaline electroless plating nickel solution bottoming is 45～52 ℃, and the treatment temp of neutral chemical nickel-plating solution nickel plating is 68～78 ℃.
Preferably, the treatment time of alkaline electroless plating nickel solution bottoming is 30～50min, and the treatment time of neutral chemical nickel-plating solution nickel plating is 15～55min.
Preferably, the pH value of alkaline electroless plating nickel solution is 10.5～11.5, and the pH value of neutral chemical nickel-plating solution is 5.5～7.0.
Preferably, in the step 1), after the pickling, after the membrane removal of ultrasonic wave alkalescence, carry out activation treatment; Alkalescence is removed consisting of of film: caustic alkali 10～30g/L, and yellow soda ash or salt of wormwood 5～10g/L, potassium pyrophosphate 10～25g/L, water-soluble citrate 10～20g/L, organic polyphosphonic acid salt 10～30g/L, surplus is a deionized water.
Ultrasonic wave alkalescence membrane removal treatment condition are: 55～65 ℃ of temperature, time 0.5～3min, ultrasonic frequency 20～40KHz.
The invention has the beneficial effects as follows:
Magnesium alloy chemical nickel plating solution provided by the invention, comprise that pH is that 10.0～11.5 alkali electroless nickel plating bath and pH are 5.5～7.0 neutral chemical nickel plating bath, in bath system, used special complex system, reduction is to the effect of magnesium corrosion of metal, improve the stability of plating bath and the bonding force of base material and nickel dam, obtained good, fine and close electroless nickel layer when making nickel plating.The present invention also provides the technology of magnesium alloy two-step chemical plating nickel, at first with the bottoming of alkali electroless nickel plating bath, re-uses neutral chemical nickel plating bath and thickeies processing, makes it reach desired thickness.
Further, the present invention is before two-step chemical plating nickel, adopt the pre-treating technology of ultrasonic wave alkalescence membrane removal, use a kind of alkalescence that does not contain hazardous materials such as sexavalent chrome, fluorochemical to remove film, under the ultrasonic wave booster action, it is clean that magnesium alloy work-piece surface oxide film and residual releasing agent are thoroughly handled, thereby further improved the nickel plating yield of products.
Embodiment
Adopt nickel acetate to provide nickel ion in the alkaline chemical nickel-plating solution system of the present invention,, improved the good article rate of suitability for industrialized production, reduced the risk that material is scrapped because of corrosion with to use single nickel salt to compare corrodibility littler as main salt.Simultaneously, adopted multiple special complexing agent synergy, as: Citrate trianion, metal is played complexing action, the control sedimentation velocity, and make solution-stabilized; Gluconate plays auxiliary complexing action, and the foreign metal that the complexing magnesium alloy is dissolved out further makes solution-stabilized; Malate plays the stable performance effect, makes solution-stabilized; And introduced organic polyphosphonic acid salt especially, and can promote the dissolving of substrate surface metal oxide film, the activation base material improves the bonding force of chemical Ni-plating layer and base material, and the effect with auxiliary complexing metal, has improved the stability of plating bath greatly.In addition, adopt aminocarboxylic acid, promote the nickel deposition effect, reduce nickel dam stress simultaneously as the bath stability agent.This system has not only solved the stability of plating bath under high pH value condition, and can suppress the corrosive nature of magnesium alloy, guarantees the enough even compacts of electroless nickel layer, has guaranteed to avoid when the magnesium alloy material is thickeied processing in the neutral chemical nickel plating bath in second road corrosion.
Below in conjunction with embodiment, further set forth the present invention, but be not limited thereto.
Following examples adopt the AZ-91D magnesium alloy as sample, and its chemical constitution is as shown in table 1:
The chemical constitution of table 1AZ-91D magnesium alloy
Adopt the ultrasonic wave deoiling method to carry out oil removing among the embodiment, the degreaser prescription is: sodium hydroxide 5～10g/L, and sodium phosphate 5～10g/L, OP series emulsifying agent 1～5g/L, surplus is a water;
Embodiment 1
Press the composition of table 2 neutral and alkali chemical nickel-plating solution, take by weighing each component, each component is dissolved in deionized water, and transfer pH to 10.5, complement to 100% with deionized water then with sodium hydroxide;
Press the composition of neutral chemical nickel-plating solution in the table 2, each component is dissolved in deionized water, and transfer pH to 6.0, complement to 100% with deionized water then with ammoniacal liquor.
Get magnesium alloy sample, carry out Nickel Plating Treatment, may further comprise the steps:
1) ultrasonic wave oil removing: treatment temp is 50～60 ℃, and the time is 3～6min;
2) pickling: phosphoric acid 5～10g/L, citric acid 10～15g/L, urotropine 0.1～0.5g/L, surplus is a water; Temperature is 20～30 ℃, and the time is 1～2min;
3) activation: potassium pyrophosphate 10～15g/L, Sodium Fluoride 3～5g/L, SODIUMNITRATE 3～5g/L, glucose sodium saccharate 20～30g/L, organic phosphonate 50～80g/L, surplus is a water; Temperature is 50～60 ℃, and the time is 0.5～1min;
4) alkaline electroless plating nickel solution bottoming: sample is immersed in the plating bath, and keeping temperature is 45 ℃, plating 30min;
5) neutral chemical nickel-plating solution nickel plating: sample is immersed in the plating bath, and keeping temperature is 68 ℃, plating 55min;
6) aftertreatment: the sample behind the chemical nickel plating is toasted dehydrogenation, under 200 ℃ of temperature, handle 80min; After the cooling, carry out acid activation with 2% sulfuric acid again;
7) electroplate: last, carry out conventional electro-coppering, nickel, chromium processing successively, make its thickness of coating be respectively 15～20 μ m, nickel dam 10～15 μ m, trivalent chromium layer 0.2～0.5 μ m.
Certainly, when magnesium alloy workpiece is handled through above steps, all need clean with pure water between each step and clean, guarantee to clean up, prevent each step soup crossed contamination through the twice tap water.
The bonding force detection method: the AZ-91D magnesium alloy sample that will plate after trivalent chromium is handled toasted 1 hour under 200 ℃, and immerse room temperature water immediately and cool off, the observation coating surface, not having foaming or peeling is that detection is qualified.
Implementation result: alkalescence bottoming chemical nickel sedimentation velocity reaches 3.5 μ m/h, and neutral chemical nickel deposition speed reaches 8 μ m/h, and the electroless nickel layer total thickness is about 8.5 μ m; The follow-up conventional bonding force of electroplating detects, and qualification rate is 85%.
Embodiment 2
The preparation of alkaline electroless plating nickel solution, neutral chemical nickel-plating solution is with embodiment 1.
The composition that alkalescence is removed film 1# sees Table 3.
Get magnesium alloy sample, carry out Nickel Plating Treatment, may further comprise the steps:
1) ultrasonic wave oil removing: treatment temp is 50～60 ℃, and the time is 3～6min;
2) pickling: phosphoric acid 5～10g/L, citric acid 10～15g/L, urotropine 0.1～0.5g/L, surplus is a water; Temperature is 20～30 ℃, and the time is 1～2min;
3) ultrasonic wave alkalescence membrane removal: treatment temp is 55～65 ℃, and the time is 0.5～3min, and ultrasonic frequency is 20～40KHz;
4) activation: potassium pyrophosphate 10～15g/L, Sodium Fluoride 3～5g/L, SODIUMNITRATE 3～5g/L, glucose sodium saccharate 20～30g/L, organic phosphonate 50～80g/L, surplus is a water; Temperature is 50～60 ℃, and the time is 0.5～1min;
5) alkaline electroless plating nickel solution bottoming: sample is immersed in the plating bath, and keeping temperature is 45 ℃, plating 30min;
6) neutral chemical nickel-plating solution nickel plating: sample is immersed in the plating bath, and keeping temperature is 68 ℃, plating 55min;
7) aftertreatment: the sample behind the chemical nickel plating is toasted dehydrogenation, under 200 ℃ of temperature, handle 80min; After the cooling, carry out acid activation with 2% sulfuric acid again;
8) electroplate: last, carry out conventional electro-coppering, nickel, chromium processing successively, make its thickness of coating be respectively 15～20 μ m, nickel dam 10～15 μ m, trivalent chromium layer 0.2～0.5 μ m.
The bonding force detection method: the AZ-91D magnesium alloy sample that will plate after trivalent chromium is handled toasted 1 hour under 200 ℃, and immerse room temperature water immediately and cool off, the observation coating surface, not having foaming or peeling is that detection is qualified.
Implementation result: alkalescence bottoming chemical nickel sedimentation velocity reaches 3.5 μ m/h, and neutral chemical nickel deposition speed reaches 8 μ m/h, and the electroless nickel layer total thickness is about 8.5 μ m; The follow-up conventional bonding force of electroplating detects, and qualification rate is 100%.
Embodiment 3～8
The processing parameter of embodiment 3～8 is similar to embodiment 2.Employed chemical nickel-plating solution composition is as shown in table 2 among each embodiment, and it is as shown in table 3 that alkalescence is removed the film composition, and processing parameter and nickel plating effect are as shown in table 4.
The composition of chemical nickel-plating solution among each embodiment of table 2
Annotate:
1, used hypophosphite is a sodium hypophosphite among alkaline chemical nickel-plating liquid: the embodiment 1～4, is potassium hypophosphite among the embodiment 5～8; Used water-soluble citrate is a Trisodium Citrate among the embodiment 1～5, is Tripotassium Citrate among the embodiment 6～8; Used water-soluble gluconate is a Sunmorl N 60S among the embodiment 1～4, is Potassium Gluconate among the embodiment 5～8; Used malate is a sodium malate among the embodiment 1～5, is potassium malate among the embodiment 6～8; Used organic polyphosphonic acid salt is Amino Trimethylene Phosphonic Acid potassium among the embodiment 1,2, be ethylenediamine tetramethylene phosphonic acid potassium among the embodiment 3,4, being Amino Trimethylene Phosphonic Acid potassium and ethylenediamine tetramethylene phosphonic acid potassium (mass ratio 1:2) among the embodiment 5, is hydroxy ethylene diphosphonic acid potassium among the embodiment 6～8.
2, used hypophosphite is a sodium hypophosphite among neutral chemical nickel-plating liquid: the embodiment 1～4, is potassium hypophosphite among the embodiment 5～8.
Table 3 embodiment 2～8 neutral and alkalis remove the composition of film
Annotate: the caustic alkali that removes among film 1#～5# is sodium hydroxide, is potassium hydroxide among 6#, the 7#;
Except that water-soluble citrate among film 1#～5# is a Trisodium Citrate, among 6#, the 7# Tripotassium Citrate;
Except that organic polyphosphonic acid salt among the film 1# is Amino Trimethylene Phosphonic Acid potassium, among 2#, the 3# ethylenediamine tetramethylene phosphonic acid potassium, being Amino Trimethylene Phosphonic Acid potassium and ethylenediamine tetramethylene phosphonic acid potassium (mass ratio 1:2) among the 4#, is ethylenediamine tetramethylene phosphonic acid potassium and hydroxy ethylene diphosphonic acid potassium (mass ratio 1:1) among 5#～7#.
Nickel Plating Treatment processing parameter and nickel plating effect among each embodiment of table 4
When the present invention is directed to present suitability for industrialized production, chemically coating nickel by magnesium-alloy can corrode the problem of material, has researched and developed magnesium alloy chemical nickel plating solution, comprises that pH is that 10.0～11.5 alkali electroless nickel plating bath and pH are 5.5～7.0 neutral chemical nickel plating bath.
The present invention also provides a kind of treatment process of two-step chemical plating nickel, be that 10.0～11.5 alkali electroless nickel plating bath is as prime coat at first with pH, mainly be because pH is lower than at 10.0 o'clock, the relatively poor magnesium alloy material of pressure injection is easily by the plating bath etch, higher pH value can be avoided plating bath etch material, so that make chemical nickel evenly go up plating, complete covering, nickel deposition speed is slower under this pH simultaneously, liberation of hydrogen is less, helps the careful porosity of nickel dam low.And then to use pH be that 5.5～7.0 neutral chemical nickel plating bath is thickeied processing, mainly is to utilize its fast deposition nickel dam, increases the density of nickel layer, avoids follow-up plating to cause corrosion.The alkali electroless nickel plating bath adopts multiple special complexing agent synergy, introduced organic polyphosphonic acid salt especially, the stability of plating bath and the bonding force of base material and nickel dam have been improved greatly, this system has not only solved the stability of plating bath under high pH value condition, and has a corrosive nature that suppresses magnesium alloy, guarantee the enough even compacts of electroless nickel layer, guarantee in the neutral chemical nickel plating bath in second road, to thicken when handling, avoid material to be corroded.The present invention simultaneously uses nickel acetate to provide the nickel metal as main salt, with to use single nickel salt to compare corrodibility littler, has improved the good article rate of suitability for industrialized production, has reduced the risk that material is scrapped because of corrosion.
Further, the present invention is before two-step chemical plating nickel, adopt the pre-treating technology of ultrasonic wave alkalescence membrane removal, use a kind of alkalescence that does not contain hazardous materials such as sexavalent chrome, fluorochemical to remove film, under the ultrasonic wave booster action, it is clean that magnesium alloy work-piece surface oxide film and residual releasing agent are thoroughly handled, thereby further improved the nickel plating yield of products.
Because the nickel plating magnesium alloy bonding force of this prepared is good, after the plating chemical nickel, handle through dehydrogenation, can on nickel dam, electroplate other functional, ornamental coating arbitrarily, the electroplating assembly line that is particularly useful for complex-shaped workpieces uses, and effect is better than traditional prussiate electroplating technology.
Claims (9)
1. magnesium alloy chemical nickel plating solution comprises alkaline electroless plating nickel solution and neutral chemical nickel-plating solution:
By mass percentage, the alkaline chemical nickel-plating solution composition is as follows:
Nickel acetate 1～4%
Water-soluble hypophosphite 1～6%
Yellow soda ash or salt of wormwood 0.1～2%
Water-soluble citrate 1～6%
Water-soluble gluconate 1～6%
Water-soluble malate 0.5～5%
Organic polyphosphonic acid salt 0.1～2%
Sodium Fluoride or Potassium monofluoride 0.5～5%
Aminocarboxylic acid 0.1～1%
Surplus is a deionized water, and is 10.0～11.5 with the pH of pH regulator agent regulator solution;
By mass percentage, neutral chemical nickel-plating solution is composed as follows:
Nickel acetate 1～3%
Water-soluble hypophosphite 1～6%
Citric acid 0.2～1.5%
Lactic acid 0.5～5%
Gluconic acid 0.5～3%
Oxysuccinic acid 0.5～3%
Aminocarboxylic acid 0.1～1%
Sodium dodecylbenzene sulfonate 0.1～0.5%
Ammonium bifluoride 1～5%
Surplus is a deionized water, and is 5.5～7.0 with the pH value of pH regulator agent regulator solution.
2. magnesium alloy chemical nickel plating solution according to claim 1 is characterized in that:
By mass percentage, the alkaline chemical nickel-plating solution composition is as follows:
Nickel acetate 1.5～2%
Water-soluble hypophosphite 1.5～4%
Yellow soda ash or salt of wormwood 0.4～1%
Water-soluble citrate 1.5～4%
Water-soluble gluconate 1.5～4%
Water-soluble malate 1～3%
Organic polyphosphonic acid salt 0.5～1%
Sodium Fluoride or Potassium monofluoride 1～3%
Aminocarboxylic acid 0.1～0.5%
Surplus is deionized water and an amount of pH regulator agent;
By mass percentage, neutral chemical nickel-plating solution is composed as follows:
Nickel acetate 1.5～2%
Water-soluble hypophosphite 1.5～4%
Citric acid 0.2～1.5%
Lactic acid 0.8～3.5%
Gluconic acid 1.5～2%
Oxysuccinic acid 1.5～2%
Aminocarboxylic acid 0.1～0.5%
Sodium dodecylbenzene sulfonate 0.2～0.3%
Ammonium bifluoride 2～3%
Surplus is deionized water and an amount of pH regulator agent.
3. magnesium alloy chemical nickel plating solution according to claim 1 and 2 is characterized in that: the pH regulator agent is sodium hydroxide, potassium hydroxide or ammoniacal liquor.
4. magnesium alloy nickel plating technology may further comprise the steps:
1) pre-treatment: the magnesium alloy sample is carried out oil removing, pickling, activation treatment;
2) chemical nickel plating: use magnesium alloy chemical nickel plating solution that the magnesium alloy sample is carried out bottoming of alkaline electroless plating nickel solution and neutral chemical nickel-plating solution nickel plating successively;
3) aftertreatment: behind the chemical nickel plating, toast dehydrogenation, activation treatment;
4) electroplate: carry out follow-up conventional the plating;
Used magnesium alloy chemical nickel plating solution is as described in any one of the claim 1～3.
5. a kind of magnesium alloy nickel plating technology according to claim 4 is characterized in that: the treatment temp of alkaline electroless plating nickel solution bottoming is 45～52 ℃, and the treatment temp of neutral chemical nickel-plating solution nickel plating is 68～78 ℃.
6. a kind of magnesium alloy nickel plating technology according to claim 5 is characterized in that: the treatment time of alkaline electroless plating nickel solution bottoming is 30～50min, and the treatment time of neutral chemical nickel-plating solution nickel plating is 15～55min.
7. according to any described a kind of magnesium alloy nickel plating technology of claim 4～6, it is characterized in that: the pH value of alkaline electroless plating nickel solution is 10.5～11.5, and the pH value of neutral chemical nickel-plating solution is 5.5～7.0.
8. according to any described a kind of magnesium alloy nickel plating technology of claim 4～6, it is characterized in that: in the step 1), after the pickling, after the membrane removal of ultrasonic wave alkalescence, carry out activation treatment;
Alkalescence is removed consisting of of film:
Caustic alkali 10～30 g/L, yellow soda ash or salt of wormwood 5～10 g/L, potassium pyrophosphate 10～25 g/L, water-soluble citrate 10～20 g/L, organic polyphosphonic acid salt 10～30 g/L, surplus is a deionized water.
9. a kind of magnesium alloy nickel plating technology according to claim 8 is characterized in that: ultrasonic wave alkalescence membrane removal treatment condition are: 55～65 ℃ of temperature, time 0.5～3min, ultrasonic frequency 20～40KHz.
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