CN101550576B - Zinc-nickel alloy nano multilayer film - Google Patents
Zinc-nickel alloy nano multilayer film Download PDFInfo
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- CN101550576B CN101550576B CN2009100943669A CN200910094366A CN101550576B CN 101550576 B CN101550576 B CN 101550576B CN 2009100943669 A CN2009100943669 A CN 2009100943669A CN 200910094366 A CN200910094366 A CN 200910094366A CN 101550576 B CN101550576 B CN 101550576B
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- nickel
- coating
- multilayer film
- zinc
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- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 21
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims description 42
- 238000000576 coating method Methods 0.000 claims description 42
- 239000002356 single layer Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 23
- 230000007797 corrosion Effects 0.000 abstract description 22
- 238000007747 plating Methods 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 8
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 description 17
- 239000008151 electrolyte solution Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 238000009713 electroplating Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 239000004141 Sodium laurylsulphate Substances 0.000 description 5
- 229910000831 Steel Chemical group 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 5
- 239000010959 steel Chemical group 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910007567 Zn-Ni Inorganic materials 0.000 description 3
- 229910007614 Zn—Ni Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000006193 liquid solution Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 229910020994 Sn-Zn Inorganic materials 0.000 description 1
- 229910009069 Sn—Zn Inorganic materials 0.000 description 1
- 229910007564 Zn—Co Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
The present invention discloses a nano multilayer film with zinc-nickel alloy plated on the surface, belong to surface treatment technique of components and metallic materials field. The plating layeris alternately overlayed by low nickel layer and high nickel layer, wherein nickel content of the low nickel layer is about 14%, and nickel content of the high nickel layer is about 78%, the modulati on wavelength is about 240 nm. The invention is provided with advantages of higher corrosion resistance, rigidity, compactness, wearing resistance, high-temperature resistance, easy solderability and pretty appearance.
Description
Technical field
The present invention relates to a kind of coating surface has zinc-nickel alloy nano multilayer film coating, belongs to iron and steel parts and metal material surface processing technology field.
Background technology
Corrosion and corrosion protection is related to Economic development and people's life safety, and surface engineering technology is to solve component of machine and material corrosion and most economical effective means of protection and method.Along with the develop rapidly of modern industry and science and technology, more and more higher to the performance requriements of component of machine and material surface, process for treating surface has also had development rapidly thereupon.Surface engineering technology can use chemistry, physics or electrochemical method to come component or material surface are handled, and makes its surface form various protective layers, improves the work-ing life of component or material.Alloy compound surface deposition (galvanic deposit or electroless plating) compare with the monometallic surface deposition because of it have higher solidity to corrosion, hardness, compactness, wear resistance, high thermal resistance, weldability and beautiful outward appearance, and obtained using widely.
In recent years, people have given very big concern to the research and development nano-multilayer film.On the basis of constantly improving the galvanic deposit nano-multilayer film, developed the nano-multilayer film product and the technology of better performances such as Cu/Ni, Co/Cu, Co/Pt, but many research as magnetic property, the rarely seen report of the research aspect corrosion resistance coating.
The admiro plating has obtained widespread use as the protective coating of iron and steel.In order to satisfy to component or material property requirements at the higher level, research and application have all been strengthened both at home and abroad to the plating of zinc base alloys such as Zn-Fe, Zn-Ni, Sn-Zn, Zn-Co, Zn-Mn, Zn-Cr, Zn-Ti, Zn-Co-Cr, Zn-Co-Fe, Zn-Ni-P, Zn-Fe-P, wherein therefore the admiro multilayer film is studied by numerous mechanisms because of having good solidity to corrosion.
Because the deposition of admiro belongs to unusual codeposition, traditional viewpoint is thought when nickel content reaches 13% in the zn-ni alloy deposits, the solidity to corrosion of coating is best, so the problem that conventional admiro additive mainly solves is exactly the zinc-nickel alloy electrolyte of managing unusual codeposition, when plating, nickel content is near to 13% in the control coating, but such additive is deleterious for the deposit multilayer film.What the multilayer film deposition required is the change that realizes nickel content in the coating under different deposition current in same plating bath, realize that to reach the different superpositions that contains nickel dam realizes multiple stratification when the ALT pulse, the outward appearance that guarantees coating simultaneously is bright and clean smooth, has certain ornamental.Corrosion resistance of coating is better, has higher hardness (for conventional zn-ni alloy deposits), wear resistance, and do not need to plate aftertreatment technology, save cost, efficient quick, handled easily.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of existing higher hardness, solidity to corrosion, wear resistance, pyro-oxidation resistance are provided, the zinc-nickel alloy nano multilayer film coating of high compactness, ornamental (outward appearance), high comprehensive performance is arranged again; Utilize electro-plating method and the electrolytic solution do not need Passivation Treatment, just can obtain high anti-corrosion, abrasion coating, technology simply, safety, handled easily.
Technology contents of the present invention is: this coating surface zinc-nickel alloy nano multilayer film, coating is the different admiro superposition layers that contain nickel dam.Nickel content is about 14% in the wherein low after testing nickel dam, and the nickel content of high nickel dam is about 78%, and modulation wavelength is 240nm, and thickness in monolayer is in this scope of 100-150nm.Thickness of coating and each constituent content are determined in given range according to actual needs.
Produce this adoptable electro-plating method in iron and steel parts 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, electroplate liquid stirs or leaves standstill down and carries out galvanized step, also be included in and carry out taking out after the electrolysis step that described component are washed, dried from electroplate liquid, the electroplate liquid that is adopted includes as the salt of the Ni salt of main salt and Zn, as the NH of conducting salt
4Cl, as the H of buffer reagent
3BO
3, electroplate liquid consists of: NiCl
26H
2O100～180g/L, ZnCl
220～80g/L, NH
4Cl 180～220g/L, H
3BO
320～40g/L, additive 0.5～5g/L; Additive is one or more the arbitrary combination in peregal, asccharin, the sodium lauryl sulphate etc.The pH value of plating bath is 3～5, electroplate power supply mode and be the output pulse power supply, concrete parameter is: the control average current density is that 0.3A, first pulse duty factor are 0.01, working hour 20s, second duty of ratio is 0.5, working hour 40s, and reverse impulse output mean current all is 0.2A, dutycycle is 0.1, working hour 10ms; Temperature is a room temperature.
The content of each constituent or processing parameter such as choose and plating time can specifically be selected according to the required thickness of coating of reality, hardness, density etc. in providing scope.
The present invention adopts the laminated coating of zinc-nickel alloy nano multilayer film, thereby makes hardness, wear resistance, the significantly raising of coating; And owing to Ni in the electroplating bath solution
2+Quantity big, make in the coating Ni content bigger, make coating outward appearance light, the good compactness that has and the advantage of ornamental (outward appearance).In acidic medium, the reaction of coating and medium mainly is zinc, nickel and H
+Reaction, the solidity to corrosion of coating depends primarily on matrix metal nickel and H
+The speed degree of reaction, and the specific activity zinc of nickel in acid is poor, so higher Ni content improves its solidity to corrosion to acid in the coating.The multilayer alloy layer alternately exists, and the corrosion speed of having slowed down coating can hinder airborne O again
2In coating, permeate, thereby slowed down Zn greatly (OH)
2, Ni (OH)
2And Fe (OH)
3Generation, corrosion resistance of coating is improved greatly.Because the effect of higher Ni content makes coating not need Passivation Treatment just can reach higher solidity to corrosion in the coating, has simplified the production technique link greatly, has reduced environmental pollution, has improved production security.
Therefore, this coating surface has zinc-nickel alloy nano multilayer film to have the high advantage of hardness, solidity to corrosion, wear resistance, high-temperature oxidation, compactness and over-all properties.In addition, employed electroplating technology and electrolytic solution have does not need to plate aftertreatment technology, saves cost, efficient quick, the advantage of handled easily.
Description of drawings
Fig. 1 is a multi-layer film structure synoptic diagram of the present invention.White portion is represented high nickel dam among the figure, and black is partly represented low nickel dam.
Embodiment
Further specify flesh and blood of the present invention with example below, but content of the present invention is not limited to this.
Before electroplating to described component polish washing, oil removing, wash then, remove corrosion, again after washing, put into the plating tank electroplate liquid, electroplate to stir or leave standstill down and carry out at electroplate liquid, the described component of taking-up are washed, are dried from electroplate liquid after carrying out electrolysis.The electroplate liquid that adopts contains as the salt of the Ni salt of main salt and Zn, as the NH of conducting salt
4Cl, as the H of buffer reagent
3BO
3, consist of as electroplate liquid: NiCl
26H
2O 100～180g/L, ZnCl
220～80g/L, NH
4Cl 180～220g/L, H
3BO
320～40g/L, additive 0.5～5g/L; Additive is one or more the arbitrary combination in peregal, asccharin, the sodium lauryl sulphate etc.The pH value of plating bath is 3～5, electroplate power supply mode and be the output pulse power supply, concrete parameter is: the control average current density is that 0.3A, first pulse duty factor are 0.01, working hour 20s, second duty of ratio is 0.5, working hour 40s, and reverse impulse output mean current all is 0.2A, dutycycle is 0.1, working hour 10s; Temperature is a room temperature.
The content of each constituent or processing parameter such as choose and plating time also can specifically be selected according to the required thickness of coating of reality, hardness, density etc. in providing scope.
Embodiment 1: coating surface has the steel plate of zinc-nickel alloy nano multilayer film, and its coating is zinc-nickel alloy nano multilayer film, and the nickel content of low by weight nickel dam is 14.07% in the coating, the nickel content content of high nickel dam is 77.35%, and the thickness of coating is 8.0 * 10
-3Mm.
Concrete steps are: with steel plate before electroplating to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electroplate liquid and electrolytic solution stirred or leave standstill again, after carrying out electrolysis, from electrolytic solution, take out component and wash oven dry.The pH value of plating bath is 3.5, and the power supply mode of plating is that pulse output power supply, temperature are that room temperature, time are 25 minutes.
Electrolytic solution contains as the salt of the Ni of main salt and Zn, as the NH of conducting salt
4Cl, as the H of buffer reagent
3BO
3, it specifically consists of: NiCl
26H
2O140g/L, ZnCl
250g/L, NH
4Cl220g/L, H
3BO
330g/L, peregal 0.3g/L, asccharin 0.015g/L, sodium lauryl sulphate 0.03g/L.
Embodiment 2: coating surface has the nut of zinc-nickel alloy nano multilayer film, and its coating is zinc-nickel alloy nano multilayer film, and the nickel content of low by weight nickel dam is 14.20% in the coating, the nickel content content of high nickel dam is 76.8%, and the thickness of coating is 7.5 * 10
-3Mm.
The method for electroplating surface of this nut, comprise nut before electroplating to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electroplate liquid and electrolytic solution stirred or leave standstill again, after carrying out electrolysis, from electrolytic solution, take out component and wash oven dry.The pH value of plating bath is 3.5, and the power supply mode of plating is that pulse output power supply, temperature are that room temperature, time are 20 minutes.
Electrolytic solution contains as the salt of the Ni of main salt and Zn, as the NH of conducting salt
4Cl, as the H of buffer reagent
3BO
3, it specifically consists of: NiCl
26H
2O 140g/L, ZnCl
250g/L, NH
4Cl 220g/L, H
3BO
330g/L, peregal 0.3g/L, asccharin 0.015g/L, sodium lauryl sulphate 0.03g/L.
Embodiment 3: coating surface has the pump chamber liner of zinc-nickel alloy nano multilayer film, and its coating is zinc-nickel alloy nano multilayer film, and the nickel content of low by weight nickel dam is 13.9% in the coating, the nickel content content of high nickel dam is 77.5%, and the thickness of coating is 8.5 * 10
-3Mm.
The method for electroplating surface of this pump chamber liner, comprise the pump chamber liner before electroplating to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electroplate liquid and electrolytic solution stirred or leave standstill again, after carrying out electrolysis, from electrolytic solution, take out component and wash oven dry.The pH value of plating bath is 3.5, and the power supply mode of plating is that pulse output power supply, temperature are that room temperature, time are 30 minutes.
Electrolytic solution contains as the salt of the Ni of main salt and Zn, as the NH of conducting salt
4Cl, as the H of buffer reagent
3BO
3, it specifically consists of: NiCl
26H
2O 140g/L, ZnCl
250g/L, NH
4Cl 220g/L, H
3BO
330g/L, peregal 0.3g/L, asccharin 0.015g/L, sodium lauryl sulphate 0.03g/L.
Zinc-nickel alloy nano multilayer film coating of the present invention and Zn, Zn-Ni coating is corrosion proof comparative result (equal thickness) in 5%NaCl solution:
| The coating classification | Begin the time of getting rusty/h |
| ?Zn | 13 |
| ?Zn-Ni(Ni％＝13.2％) | 66 |
| Zinc-nickel alloy nano multilayer film | 172 |
Claims (2)
1. zinc-nickel alloy nano multilayer film, it is characterized in that: coating alternately is formed by stacking by low nickel dam and high nickel dam, and wherein low nickel dam nickel content is 14%, and the nickel content of high nickel dam is 78%, and modulation wavelength is the multilayer film of 240nm.
2. zinc-nickel alloy nano multilayer film according to claim 1 is characterized in that: the thickness in monolayer of described low nickel dam and high nickel dam is at 100-150nm, and the thickness of coating is (8～9) * 10
-3Mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100943669A CN101550576B (en) | 2009-04-17 | 2009-04-17 | Zinc-nickel alloy nano multilayer film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100943669A CN101550576B (en) | 2009-04-17 | 2009-04-17 | Zinc-nickel alloy nano multilayer film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101550576A CN101550576A (en) | 2009-10-07 |
| CN101550576B true CN101550576B (en) | 2011-05-18 |
Family
ID=41155057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100943669A Expired - Fee Related CN101550576B (en) | 2009-04-17 | 2009-04-17 | Zinc-nickel alloy nano multilayer film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101550576B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102383155A (en) * | 2011-11-16 | 2012-03-21 | 中国船舶重工集团公司第七二五研究所 | Zinc-nickel alloy electrolyte and preparation method of plating layer thereof |
| JP6813692B2 (en) * | 2017-09-27 | 2021-01-13 | 株式会社日立製作所 | Film laminate and its manufacturing method |
-
2009
- 2009-04-17 CN CN2009100943669A patent/CN101550576B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| I. IVANOV et al..Corrosion resistance of compositionally modulated Zn–Ni multilayers electrodeposited from dual baths.Journal of Applied Electrochemistry.2002,32 * |
| 张英杰.电沉积金属多层膜的研究现状.材料保护.2007,40(8), * |
| 李振明.调制波长对铜-镍纳米多层膜磨损性能的影响.烟台大学学报(自然科学与工程版).1999,12(3), * |
| 费敬银.电沉积法制备组分调制Zn-Ni合金多层镀层.腐蚀科学与防护技术.2006,18(1), * |
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| Publication number | Publication date |
|---|---|
| CN101550576A (en) | 2009-10-07 |
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