CN1289718C - Zn-Ni-RE electroplating layer and its electroplating method and electrolytic liquor - Google Patents
Zn-Ni-RE electroplating layer and its electroplating method and electrolytic liquor Download PDFInfo
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- CN1289718C CN1289718C CN200410022601.9A CN200410022601A CN1289718C CN 1289718 C CN1289718 C CN 1289718C CN 200410022601 A CN200410022601 A CN 200410022601A CN 1289718 C CN1289718 C CN 1289718C
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- 238000009713 electroplating Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 47
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 33
- 239000010959 steel Substances 0.000 claims abstract description 33
- 238000005260 corrosion Methods 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 238000007747 plating Methods 0.000 claims abstract description 31
- 230000007797 corrosion Effects 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims description 63
- 238000000576 coating method Methods 0.000 claims description 63
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 42
- 239000011701 zinc Substances 0.000 claims description 38
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 21
- -1 rare-earth salts Chemical class 0.000 claims description 20
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- 239000008139 complexing agent Substances 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 9
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 9
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 8
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 8
- 235000012141 vanillin Nutrition 0.000 claims description 8
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 7
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 6
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 abstract description 39
- 238000005516 engineering process Methods 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 238000002161 passivation Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 125000001309 chloro group Chemical class Cl* 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 16
- 239000000956 alloy Substances 0.000 description 16
- 229910052684 Cerium Inorganic materials 0.000 description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 229910052773 Promethium Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052688 Gadolinium Inorganic materials 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 4
- 229910052706 scandium Inorganic materials 0.000 description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910007567 Zn-Ni Inorganic materials 0.000 description 3
- 229910007614 Zn—Ni Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 3
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 229910007570 Zn-Al Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- 229940029985 mineral supplement Drugs 0.000 description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 229910000346 scandium sulfate Inorganic materials 0.000 description 2
- QHYMYKHVGWATOS-UHFFFAOYSA-H scandium(3+);trisulfate Chemical compound [Sc+3].[Sc+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QHYMYKHVGWATOS-UHFFFAOYSA-H 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 2
- 101150058765 BACE1 gene Proteins 0.000 description 1
- 229910003317 GdCl3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910007564 Zn—Co Inorganic materials 0.000 description 1
- 229910007610 Zn—Sn Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- HWZAHTVZMSRSJE-UHFFFAOYSA-H praseodymium(iii) sulfate Chemical compound [Pr+3].[Pr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HWZAHTVZMSRSJE-UHFFFAOYSA-H 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The present invention relates to a steel component and part with the surface plated with Zn-Ni-RE composite plating layers, an electroplating method and an electrolytic solution, which belongs to the technical field of surface treatment of the steel component and part and a metal material. The surface of the component and part is plated with a corrosion-resistance Zn-Ni-RE composite plating layer; the electroplating method is adopted; plating liquids are the electrolytic solution which uses chlorine salts of Ni and Zn, and the electrolytic solution comprises rare earth. The Zn-Ni-RE composite plating layer is obtained by controlling the content of the Ni salts, the Zn salts and the rare earth, the PH value of the plating liquids and the current density. The present invention has the advantages of favorable corrosion resisting properties of the plating layer, favorable compactness and ornamental properties, favorable combination properties, large area for film formation, easy film formation, high film forming speed, easy control on film thickness, simple device and technology, no need for passivation, little environment pollution, high production safety, low integrative cost, easy popularization and use in production field, etc. The present invention can form films on uneven curved surfaces.
Description
Technical field: the present invention relates to a kind of Zn-Ni-RE electrolytic coating and electro-plating method thereof, belong to iron and steel parts and metal material surface processing technology field.
Technical background: the corrosion and protection of material is the great research field that is related to sustainable economic development and people's life safety, before and after the seventies in 20th century, the financial loss that most industrially developed country causes because of corrosion every year accounts for 1%～5% of various countries GNP, and wherein about 1/4th loss can be avoided by improving anticorrosive measure.In China, the loss that caused because of corrosion in 1998 has reached 2,800 hundred million yuan.Practice shows, the surface treatment of material is to solve material corrosion and one of protection most economical and effective means and method, it can be with chemical, physics or electrochemical method come component or material surface are handled, make its surface form various protective layers, improve the work-ing life of component or material, it is being promoted technological progress, save material, improve the product innovation performance, prolong product work-ing life, decorative environment, the effect of beautify life aspect performance is more and more outstanding, will enter among the Important Project or product design of all trades and professions, become the important component part of whole engineering or product design.
Alloy compound surface deposition technique (galvanic deposit or electroless plating) has higher solidity to corrosion because of comparing with the monometallic surface deposition, hardness, compactness, wear resistance, high thermal resistance, weldability and beautiful outward appearance, and has obtained using widely.The plating of metallic substance is one of surface diposition, also be one of four big fundamental technologies of China's mechanical industry, zinc-plated protective coating as iron and steel, aboundresources low price because of zinc, obtained widespread use, almost account for 1/3～1/2 of whole plated item, but the corrosion resistance of this coating can't reach industrial special requirement.Recent research for corrosion resistance coating, mainly concentrate on the alloy layer of the high etch resistant properties of exploitation, wherein zinc base alloy coating is one of alloy layer of studying at most, the zinc base alloy coating of having studied comprises Zn-Sn, Zn-Ni, Zn-Co, Zn-Fe, Zn-Fe-P, Zn-Ti, Zn-Mn etc., and what have is applied in the industrial production.
Since the twentieth century, the research of Zn-Ni alloy electroplating and application have obtained developing rapidly, on the basis of constantly improving the compound plating of galvanic deposit zinc-base, have developed Zn-TiO
2, Zn-Al
2O
3, Zn-SiO
2, etc. the composite deposite product and the technology of better performances, have better solidity to corrosion and other performances in order to make composite deposite, developed Zn-Fe-TiO in recent years again
2, Zn-Co-TiO
2, Zn-Ni-TiO
2Deng titanium is zinc bace composite coating layer.In the binary zinc base alloy, over-all properties the best of zinc nickel alloy electroplating layer, it is noticeable with the solidity to corrosion of excellence.Compare with other alloy platings, zinc-nickel alloy has the barrier propterty height, hydrogen embrittlement is little, good with matrix bond, weldability is good, good (coating hardness can reach 250～310Hv) to wear resistance, relative simple, the advantage such as solution dispersibility is good, be suitable for electroplating comparatively complicated parts, overall economic efficiency is better of the current density range broad of electroplating technology, plating bath, and its technology is comparative maturity also; But develop rapidly along with modern industry and science and technology, people have proposed more and more higher requirement to the surface property of material, specific function and to quality product, especially to the more requirement of high anti-corrosion and over-all properties, make the performance of traditional Z n-Ni alloy and the needs that technology can not satisfy modern industry and particular surroundings far away.Have various specific functions owing to contain the novel material of rare earth, rare earth is paid close attention to by people with the film preparing technology that contains rare earth, but to the research of rare earth and zinc base alloy galvanic deposit with use also seldom, and mostly be rare earth is improved the over-all properties technology of traditional coating (non-admiroes such as Zn-Al, Zn-Fe) or adopts hot plating technology to obtain containing novel material film (the non-admiro film) technology of rare earth as a kind of trace mineral supplement.Rare earth is adopted passivation technology as a kind of Technology Need of trace mineral supplement, and process procedure complexity, environmental pollution be big, be unfavorable for environment protection and safety in production; And the method that adopts hot plating technology to obtain containing the novel material film of rare earth have high-temperature sintering process, vacuum vapor deposition method, ion sputtering method, fusion electrolysis method, etc. hot plating technology and non-aqueous solution electrodip process, the Zn base i alloy layer that these methods obtain is a functional coating, though have good magnetic performance, electrocatalysis characteristic, photoelectricity conversion performance, optomagnetic memory performance and corrosion resistance nature etc., but film is bad with combining of component surface, and corrosion resisting property improves also limited; Use these method film forming difficulties,, film thickness control difficulty slow to component surface requirement height, film forming speed, and or technology complicated, preparation condition is had relatively high expectations, the production cost height has seriously restricted research and the application of rare earth technology aspect alloy layer.
Adopt electro-plating method, especially with rare earth directly as the deposition of elements in the coating, in the aqueous solution direct galvanic deposit " Zn-Ni-RE " ternary alloy, increase substantially the corrosion resisting property of coating and the research and the application of other over-all properties and yet there are no report.
Summary of the invention: the objective of the invention is to overcome the deficiencies in the prior art, provide a kind of and have that high anti-corrosion, high compactness, ornamental (outward appearance) are good, iron and steel parts of high comprehensive performance surface Zn-Ni-RE composite galvanized coating, and do not need that Passivation Treatment, apparatus and process are simple, safety, comprehensive cost are low, environmental protection, the iron and steel parts Zn-Ni-RE method for electroplating surface low to the component surface requirement.
Technology contents of the present invention is: iron and steel parts surface Zn-Ni-RE electrolytic coating, its special character is that coating is the composite deposite (thickness of coating is generally 5～20 μ m) that contains zinc, iron and rare earth element, the content range of various metallic elements is zinc 86% to 92% by weight in the coating, nickel 2% to 8%, rare earth element 5% to 12%.Rare earth element can be any one or two kinds of arbitrary combination in all rare earth elements (that is: cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium), and thickness of coating and each constituent content are determined in given range according to actual needs.
Iron and steel parts surface Zn-Ni-RE composite electric plating method, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into the plating tank electroplate liquid again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from plating bath, electroplate liquid contain as the villaumite of the Zn of main salt and Ni, as conducting salt KCl or NaCl, as the H of buffer reagent
3BO
3, and rare-earth salts, its special character is also to contain complexing agent and additive in the plating bath, specifically consists of: ZnCl
210～25g/L, NiCl
26H
2O 15～30g/L, rare-earth salts 2～6g/L, KCl or NaCl 60～140g/L, H
3BO
315～45g/L, complexing agent 5～40g/L, additive 0.4～0.8g/L.Rare-earth salts is any one or two kinds of arbitrary combination (that is: the villaumite of lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu, yttrium Y, scandium Sc or any one or two kinds of arbitrary combination in the vitriol, as: Lanthanum trichloride, Cerium II Chloride, Yttrium trichloride, cerous sulfate, lanthanum sulfat, praseodymium sulfate, Cerium II Chloride, praseodymium chloride, Europium trichloride, Scium trichloride etc.) in rare earth villaumite, the rare earth sulfate; Additive is any or several arbitrary combination (available dehydrated alcohol is made solvent, and the dissolving back adds electrolytic solution) in piperonylaldehyde, sodium lauryl sulphate, Vanillin, tonka bean camphor, polyoxyethylene glycol, the thiocarbamide; Complexing agent is any or several arbitrary combination in citric acid, sodium ethylene diamine tetracetate, Seignette salt, the nitrilotriacetic acid(NTA); The pH value of plating bath is 1～5, and the current density of plating is 1～8A/dm
2, temperature is room temperature.The content of each constituent, processing parameter such as choose and plating time can be according to actual needs such as required thickness of coating, solidity to corrosions, the concrete selection determined.
Because the special electron structure of rare earth element makes it have outstanding chemically reactive; The adding of rare earth element can increase cathodic polarization, the galvanic deposit of resistance alloy when electroplating on the one hand, thereby crystal grain thinning alleviates the impurity element segregation, makes coating become smooth careful, and solidity to corrosion and ornamental (outward appearance) improve; Direct and the Zn-Ni formation coating of rare earth alloy element changes the alloy microtexture by effects such as alloying, qualitative changes on the other hand, forms metallic compound in coating, thereby the solidity to corrosion of coating is significantly improved.Rare earth can also remove the oxygen and the sulphur of accelerated corrosion effect, can produce favourable influence to chemical property by purifying crystal boundary, and in alloy, become surfactant, tendency with enrichment body surface, form fine and close zone of oxidation uniformly on the surface, can stop the introduced contaminants atom to the alloy internal divergence to a great extent, thereby delay oxidation and corrosion process.In addition, because the effect of coating middle-weight rare earths element, make coating not need Passivation Treatment just can reach higher solidity to corrosion and ornamental, simplified the production technique link greatly, reduced environmental pollution, improved production security.
The present invention is owing to adopt water-soluble Zn-Ni-RE electroplate liquid and electro-plating method, utilize China's abundant and the cheap rare earth resources of cost, directly obtain the iron and steel parts that coating surface has Zn-Ni-RE coating, directly in Zn, Ni hypothallus, increased rare earth element, thus have can the big area film forming, can be on uneven curved surface film forming, film forming is easy, film forming speed is fast, film thickness is controlled easily, apparatus and process is simple, easy to operate, energy consumption cost is low, be easy to advantage such as promote the use of at production field.
Description of drawings: accompanying drawing is a process flow sheet of the present invention.
Embodiment: essence of the present invention is described further below in conjunction with drawings and Examples.
Embodiment 1: be plated on the Zn-Ni-Ce electrolytic coating of steel tube surface, contain zinc, nickel and cerium (Ce) element, the thickness of coating is 5 μ m, and the content of various metallic elements is zinc 86% by weight in the coating, nickel 8%, cerium 6%.
The electro-plating method of this steel tube surface Zn-Ni-Ce coating, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution; The pH value of the electrolytic solution that uses is 2, and galvanized current density is 2A/dm
2, temperature is room temperature, electroplating time is 0.2 hour.
This Zn-Ni-Ce electrolytic solution comprise as the villaumite of the Zn of main salt and Ni, as conducting salt KCl, as the H of buffer reagent
3BO
3, Cerium II Chloride, also contain citric acid complexing agent and Vanillin additive; It consists of: ZnCl
210g/L, NiCl
26H
2O 30g/L, Cerium II Chloride 3g/L, KCl 60g/L, H
3BO
315g/L, citric acid 10g/L, Vanillin 0.45g/L.
Embodiment 2: be plated on the Zn-Ni-La composite galvanized coating on guardrail surface, contain zinc, nickel and lanthanum (La) element, the thickness of coating is 20 μ m, and the content of various metallic elements is zinc 86% by weight in the coating, nickel 2%, lanthanum 12%.
The electro-plating method of this guardrail surface Zn-Ni-La coating, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution; The pH value of the electrolytic solution that uses is 5, and galvanized current density is 8A/dm
2, temperature is room temperature, electroplating time is 1 hour.
This Zn-Ni-La electrolytic solution comprise the villaumite that contains as the Zn of main salt and Ni, as conducting salt NaCl, as the H of buffer reagent
3BO
3, and rare-earth salts, also contain Seignette salt complexing agent and thiourea additives, it consists of: ZnCl
210g/L, NiCl
26H
2O 15g/L, Lanthanum trichloride 6g/L, NaCl 140g/L, H
3BO
345g/L, Seignette salt 40g/L, thiocarbamide 0.8g/L.
Embodiment 3: be plated on rolling screen door surface Zn-Ni-Y-Gd composite galvanized coating, contain zinc, nickel and yttrium (Y), gadolinium (Gd) element, the thickness of coating is 10 μ m, and the content of various metallic elements is zinc 88% by weight in the coating, nickel 4%, rare earth 8% (yttrium 5%, gadolinium 3%).
The electro-plating method of this rolling screen door surface Zn-Ni-Y-Gd coating, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution; The pH value of the electrolytic solution that uses is 4, and galvanized current density is 4A/dm
2, temperature is room temperature, electroplating time is 0.4 hour.
This Zn-Ni-Y-Gd electrolytic solution include as the villaumite of the Zn of main salt and Ni, as conducting salt KCl, as the H of buffer reagent
3BO
3, and rare-earth salts, also contain Seignette salt complexing agent and thiourea additives, it consists of: ZnCl
220g/L, NiCl
26H
2O 20g/L, rare-earth salts 4.5g/L (Yttrium trichloride 3g/L, Gadolinium trichloride 1.5g/L), KCl140g/L, H
3BO
330g/L, nitrilotriacetic acid(NTA) 30g/L, polyoxyethylene glycol 0.5g/L.
Embodiment 4: the Zn-Ni-Ce-La electrolytic coating that is plated on the decorative steel plate surface, contain zinc, nickel and cerium (Ce), lanthanum (La) element, the thickness of coating is 15 μ m, and the content of various metallic elements is zinc 92% by weight in the coating, nickel 3%, rare earth 5% (lanthanum 3%, cerium 2%).
The Zn-Ni-Ce-La method for electroplating surface of this steel plate, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution; The pH value of the electrolytic solution that uses is 1, and galvanized current density is 5A/dm
2, temperature is room temperature, electroplating time is 0.5 hour.
This Zn-Ni-Ce-La electrolytic solution include as the villaumite of the Zn of main salt and Ni, as conducting salt KCl, as the H of buffer reagent
3BO
3, and Cerium II Chloride and Lanthanum trichloride, also contain complexing agent (citric acid, nitrilotriacetic acid(NTA)) and additive (thiocarbamide, Vanillin, tonka bean camphor), it consists of: ZnCl
225g/L, NiCl
26H
2O 18g/L, rare-earth salts 2g/L (Cerium II Chloride 1g/L, Lanthanum trichloride 1g/L), KCl 80g/L, H
3BO
325g/L, complexing agent 5g/L (citric acid 3g/L, nitrilotriacetic acid(NTA) 2g/L), additive 0.4g/L (thiocarbamide 0.2g/L, Vanillin 0.1g/L, tonka bean camphor 0.1g/L; Make solvent with dehydrated alcohol, the dissolving back adds electrolytic solution).
Embodiment 5: be plated on the Zn-Ni-Pr-Pm electrolytic coating of shaped steel workpiece surface, contain zinc, nickel and praseodymium (Pr), promethium (Pm) element, the thickness of coating is 8 μ m, the content of various metallic elements is zinc 87% by weight in the coating, nickel 3%, rare earth 10% (praseodymium 6%, promethium 4%).
The Zn-Ni-Pr-Pm coating electro-plating method on this shaped steel surface, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution; The pH value of the electrolytic solution that uses is 4, and galvanized current density is 6A/dm
2, temperature is room temperature, electroplating time is 0.3 hour.
This Zn-Ni-Pr-Pm electrolytic solution contain as the villaumite of the Zn of main salt and Ni, as conducting salt KCl, as the H of buffer reagent
3BO
3, and rare-earth salts, also contain complexing agent (citric acid, sodium ethylene diamine tetracetate, Seignette salt, nitrilotriacetic acid(NTA)) and additive (piperonylaldehyde, thiocarbamide, Vanillin, tonka bean camphor, polyoxyethylene glycol), it consists of: ZnCl
215g/L, NiCl
26H
2O 18g/L, rare-earth salts 5g/L (praseodymium chloride 3g/L, sulfuric acid promethium 2g/L), KCl 100g/L, H
3BO
335g/L, complexing agent 30g/L (citric acid 10g/L, sodium ethylene diamine tetracetate 6g/L, Seignette salt 10g/L, nitrilotriacetic acid(NTA) 4g/L), additive 0.7g/L (piperonylaldehyde 0.3g/L, thiocarbamide 0.1g/L, Vanillin 0.1g/L, tonka bean camphor 0.1g/L, polyoxyethylene glycol 0.1g/L; Make solvent with dehydrated alcohol, the dissolving back adds electrolytic solution).
Embodiment 6: the Zn-Ni-Nd-Sc electrolytic coating that is plated on the shaped steel workpiece surface, contain zinc, nickel and neodymium (Nd), scandium (Sc) element, the thickness of coating is 12 μ m, and the content range of various metallic elements is zinc 89% by weight in the coating, nickel 4%, rare earth 7% (neodymium 5%, scandium 2%).
The electro-plating method of this shaped steel surface Zn-Ni-Nd-Sc coating, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution; The pH value of the electrolytic solution that uses is 2, and galvanized current density is 5A/dm
2, temperature is room temperature, electroplating time is 0.45 hour.
This Zn-Ni-Nd-Sc electrolytic solution include as the villaumite of the Zn of main salt and Ni, as conducting salt KCl, as the H of buffer reagent
3BO
3, and Neodymium trichloride and scandium sulfate, also contain complexing agent (sodium ethylene diamine tetracetate, Seignette salt) and additive (piperonylaldehyde, tonka bean camphor), it consists of: ZnCl
220g/L, NiCl
26H
2O 22g/L, rare-earth salts 3.5g/L (Neodymium trichloride 2.5g/L, scandium sulfate 1g/L), KCl 70g/L, H
3BO
325g/L, complexing agent 15g/L (sodium ethylene diamine tetracetate 5g/L, Seignette salt 10g/L), additive 0.5g/L (piperonylaldehyde 0.3g/L, tonka bean camphor 0.2g/L; Make solvent with dehydrated alcohol, the dissolving back adds electrolytic solution).
Embodiment 7: be plated on the Zn-Ni-Eu electrolytic coating of steel tube surface, contain zinc, nickel and europium (Eu) element, the thickness of coating is 6 μ m, and the content of various metallic elements is zinc 87% by weight in the coating, nickel 7%, cerium 6%.
The electro-plating method of this steel tube surface Zn-Ni-Eu coating, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution; The pH value of the electrolytic solution that uses is 1.5, and galvanized current density is 1A/dm
2, temperature is room temperature, electroplating time is 0.25 hour.
This Zn-Ni-Eu electrolytic solution comprise as the villaumite of the Zn of main salt and Ni, as conducting salt KCl, as the H of buffer reagent
3BO
3, Europium trichloride, also contain citric acid complexing agent; It consists of: ZnCl
215g/L, NiCl
26H
2O 25g/L, Europium trichloride 3g/L, KCl 70Nag/L, H
3BO
315g/L, citric acid 8g/L.
Embodiment 8: be plated on the Zn-Ni-Er electrolytic coating of steel tube surface, contain zinc, nickel and bait (Er) element, the thickness of coating is 7 μ m, and the content of various metallic elements is zinc 87% by weight in the coating, nickel 6%, cerium 7%.
The electro-plating method of this steel tube surface Zn-Ni-Er coating, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution; The pH value of the electrolytic solution that uses is 2, and galvanized current density is 2A/dm
2, temperature is room temperature, electroplating time is 0.3 hour.
This Zn-Ni-Er electrolytic solution comprise as the villaumite of the Zn of main salt and Ni, as conducting salt NaCl, as the H of buffer reagent
3BO
3, the chlorination bait, also contain citric acid complexing agent; It consists of: ZnCl
215g/L, NiCl
26H
2O 25g/L, chlorination bait 3.5g/L, NaCl 75g/L, H
3BO
320g/L, citric acid 15g/L.
Claims (8)
1, a kind of iron and steel parts surface electrical coating is characterized in that described electrolytic coating is the Zn-Ni-RE composite galvanized coating that contains zinc, nickel and rare earth element.
2, electrolytic coating as claimed in claim 1 is characterized in that the content range of various metallic elements in the coating is zinc 86% to 92%, nickel 2% to 8%, rare earth element 5% to 12% by weight.
3, electrolytic coating as claimed in claim 1 or 2 is characterized in that described rare earth element can be any one or two kinds of arbitrary combination in all rare earth elements.
4, a kind of iron and steel parts method for electroplating surface, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into the plating tank electroplate liquid again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from plating bath, electroplate liquid include as the villaumite of the Zn of main salt and Ni, as conducting salt KCl or NaCl, as the H of buffer reagent
3BO
3, and rare-earth salts, it is characterized in that also containing in the electroplate liquid complexing agent and additive.
5, electro-plating method according to claim 4 is characterized in that the content of each constituent in the electroplate liquid is: ZnCl
210～25g/L, NiCl
2.6H
2O 15～30g/L, rare-earth salts 2～6g/L, KCl or NaCl 60～140g/L, H
3BO
315～45g/L, complexing agent 5～40g/L, additive 0.4～0.8g/L.
6, electro-plating method according to claim 5 is characterized in that described rare-earth salts is any one or two kinds of arbitrary combination in rare-earth chlorination salt, the rare earth sulfate.
7, according to claim 4 or 5 described electro-plating methods, it is characterized in that described additive is any or several arbitrary combination in piperonylaldehyde, sodium lauryl sulphate, Vanillin, tonka bean camphor, polyoxyethylene glycol, the thiocarbamide, complexing agent is any or several arbitrary combination in citric acid, sodium ethylene diamine tetracetate, Seignette salt, the nitrilotriacetic acid(NTA).
8, according to each described electro-plating method of claim 4～6, the pH value that it is characterized in that plating bath is 1～5, and galvanized current density is 1～8A/dm
2, temperature is room temperature.
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| CN101348934B (en) * | 2008-08-28 | 2010-04-21 | 上海应用技术学院 | Method for electroplating nickel rare earth-titanium diboride composite coating |
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