CN1380446A - High-brightness high-corrosion-resistance high-wear resistance nano compound electroplating layer composition - Google Patents
High-brightness high-corrosion-resistance high-wear resistance nano compound electroplating layer composition Download PDFInfo
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- CN1380446A CN1380446A CN 01129149 CN01129149A CN1380446A CN 1380446 A CN1380446 A CN 1380446A CN 01129149 CN01129149 CN 01129149 CN 01129149 A CN01129149 A CN 01129149A CN 1380446 A CN1380446 A CN 1380446A
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Abstract
The present invention relates to a high-brightness high corrosion resistance high wearability composite plating layer composite whose total thickness is less than 13 micrometers includes dark nickel/nano composite nickel/bright nickel/chrome, and its electroplating method includes the following steps: firstly, plating dark nickel with thickness of 1.5-2.0 micrometers, plating nano composite nickel with thickness of 5-8 micrometers, plating bright nickel with thickness of 3-4 micrometers and plating chrome with thickness of 0.25-0.5 micrometer so as to obtain the invented plating layer composition, in which the nano composite nickel-plated layer contains 3-10% of composite oxide using alpha-Al2O3 as main crystal phase and with grain size of 40-80 nm, and is formed by means of electrodeposition in conventional electrolytic bath.
Description
(1), technical field
The present invention relates to a kind of new combination of coating and new process for electroplating thereof that can obtain to have concurrently decoration and corrosion-proof wear function.The combination of this coating both can have been satisfied the usefulness of high bright decorative plating, can satisfy high abrasion, high anti-corrosion or need the requirement of decoration protection of the goods of corrosion-proof wear simultaneously again.
(2), technical background
Since the sixties in last century, people are in order to obtain high anti-corrosion coating, and multi-layer plating has been invented by U.S. peace bit company, and three layers of nickel from two nickel one to today, four layers of nickel are to improve the anti-corrosion performance of decorative coating; In order to improve the function of electrolytic coating, the loyal husband of the Japan woods same period waits all one's effort propelling to develop composite plating, has set up multiple function composite plating systems such as wear-resisting, anti-oxidant, anti-attrition so far, has developed a plurality of function electroplating technologies.Be used for decorating plating afterwards and with compound plating, so nickel envelope and the face of forging nickel etc. are arranged, but still can not invest wear resistance simultaneously, fraction of particle then produces frosting phenomenon to increase its wear resistance in the coating if improve, can not obtain high bright coating, sometimes even run counter to desire, the coating embrittlement, solidity to corrosion also descends, so does not still have so far not only light, not only wear-resisting, not only anti-corrosion but also combined plating flexible appears on the market, and does not see that also the patent of related process even research paper report.
(3), Fa Ming content
One of technical problem to be solved of the present invention is: provide a kind of not only light, not only wear-resisting, the not only electrolytic coating combination of anti-corrosion but also flexible, promptly a kind of total thickness≤13 μ m high-brightness high-corrosion-resistance high-wear resistance nano compound electroplating layers combination.
The present invention want the technical solution problem two be: a kind of technology for preparing above-mentioned composite galvanized coating combination is provided.
Solving one of the technology of the present invention problem is by adopting such technical scheme to realize, be a kind of total thickness≤13 μ m high-brightness high-corrosion-resistance high-wear resistance nano compound electroplating layers combination, it is characterized by: electrolytic coating is combined as: dark plating/nano combined nickel/bright nickel/chromium; Wherein, disperse has 3-10% with α-Al in the composite deposite of electrolytic coating combination
2O
3Nano composite oxides particulate for principal crystalline phase; Contain alkaline-earth metal in the described nano composite oxides particulate, or/and cross metallizing 1～10%.
In above-mentioned total thickness≤13 μ m high-brightness high-corrosion-resistance high-wear resistance nano compound electroplating layers combination, dark coating is thick to be 1.5-2.0 μ m, the thick 5-8 μ of nano combined nickel dam m, bright nickel bed thickness 3-4 μ m, the thick 0.25-0.5 μ of chromium surface layer m.The alkaline-earth metal that contains in described nano composite oxides particulate comprises magnesium or magnesium oxide, crosses metallizing and comprises nickel or nickel oxide.
Solving two of the technology of the present invention problem is by adopting such technical scheme to realize, be a kind of technology for preparing the high-brightness high-corrosion-resistance high-wear resistance nano compound electroplating layer combination, the technology of its composite plating comprises: the α-Al that adds 50-150g/L in conventional watt electrolytic solution
2O
3It is the composite Nano slurry, former grain fineness number＜the 100nm of dispersed particle in the slurry, be preferably 40nm-80nm, it is a kind of α all stable in soda acid-crystalline state particle, can not reunite in the medium-term and long-term dispersion state that keeps of electroplating process, it can be scattered in equably with the sub-state of former crystal grain among the coating when electroplating, and dispersed granules content is 4-5% (Wt).
According to technique scheme, the composition and the processing condition of the electrolytic solution that uses in the technology of the present invention are as follows:
Single nickel salt 350-380g/L
Boric acid 40-45g/L
Sodium-chlor 12-16g/L
α-Al
2O
3Composite nano slurry 50-150g/L (Gu)
PH 3.5-4.6
Dk 3-4A/dm
2
t℃ 55-65
Nano composite plating layer thickness 5-8 μ m
In the technology, anode pure nickel electrode, pneumatic blending, stirring velocity is with all particles suspension degree of being in the slurries.Newly join groove and must stir 6 hours slaking tank liquors.
According to above-mentioned technology, use conventional dark nickel bottoming to plate nano combined nickel, conventional bright nickel and chromium again, under the situation of total thickness＜13 μ m, obtain to be better than the solidity to corrosion of conventional three layers of nickel 25 μ m-30 μ m, and have high wear resistance.
Superiority of the present invention is conspicuous: at first, will be in soda acid all stable, optically with light plating coupling, can homodisperse in plating bath, can even dispersion in coating with α-Al
2O
3For the made slurry of the composite nano particle of principal crystalline phase makes an addition in the conventional watt electrolytic solution, by electroplating the nano-composite plate that obtains metallic nickel, this kind coating has special construction: the nanometer amorphous nickel of short range order is multi-hole state in 15 dust to 20 dust (1.5-2.0nm) scopes, its aperture＜100nm, α-Al
2O
3Composite nano particle is uniformly distributed among these holes, thus constitute a kind of have high abrasion, high rigidity, high anti-corrosion, have flexible half bright coating, a very easily bright dipping.Compare in three layers of nickel, the solidity to corrosion of new combination increases substantially, only can obtain to equate even higher degree of protection with half of three layers of nickel coating total thickness, it demonstrates special solidity to corrosion in the etch of antisaturation salt solution, concentrated nitric acid, nitration mixture, high chromic acid content and even chloroazotic acid, and its wear resistant is 100 times of three layers of nickel.Electroplate so replace three nickel with it, not only material is saved half, and the energy, man-hour also saves half, greatly reduces its production cost, and because of reducing half its three wastes of easier improvement of operation liquid.
Another superiority of the present invention also is the wear resistant that it is high, can make light lasting, especially outdoor, in the extreme climate environment of humidity, saliferous, acid rain, more demonstrates its superiority when having high speed dust to impact again.
The 3rd superiority of the present invention is that it very easily is converted into nano composite plating with three layers of nickel plating, it only need move negative electrode and change pneumatic blending into, oil (gas) filling device no longer in addition, after former three nickel tank liquors are removed various brightening agents and tensio-active agent with gac, oxidation is filtered and can be used, can not cause waste, very easily promote.
(4), embodiment
Below with example by contrast more detailed description the present invention, used technical recipe is an indefiniteness.
Embodiment 1: plate dark nickel 1.5 μ m with standard watt electrolytic solution, then by following technical recipe and the composite electroplated nickel of condition: single nickel salt (NiSO
46H
2O) 350g/L, boric acid 40g/L, sodium-chlor 15g/L, α-Al
2O
3Composite nano slurry (the former grain fineness number 65nm of nanoparticle) 120g/L (Gu), PH4.0, Dk3.5A/dm
2T ℃ 60, composite electroplated nickel coating 7 μ m, single nickel salt 350g/l, bright nickel technological specification electroplating bright nickel dam 4 μ m routinely again, last chromium plating 0.25 μ m, gained coating is 9/8 through the anti-corrosion grade of 24hCASS test evaluation, defect area 0.07%, rate of wear 0.003%, micro-vickers hardness value (HV0.1) 597.
Embodiment 2: process of the test is identical with example 1, wherein α-Al
2O
3Composite nano slurry (the former grain fineness number 65nm of nanoparticle) contain measure 80g/L (Gu), gained coating is 9/8 through the anti-corrosion grade of 24hCASS test evaluation, defect area 0.08%, rate of wear 0.006%, micro-vickers hardness value (HV0.1) 596, its solidity to corrosion and hardness are almost constant, and only rate of wear slightly increases.
The contrast experiment: high routinely anti-corrosion three layers of nickel technology (dark nickel/semi-bright nickel/high-sulfur nickel/bright nickel) plating total thickness is the coating of 25 μ m, plate the chromium layer of 0.25 μ m again, gained coating is 7/6 through the anti-corrosion grade of 24hCASS test evaluation, defect area 0.3%, rate of wear 0.65%, micro-vickers hardness value (HV0.1) 462, its solidity to corrosion and hardness are significantly less than composite deposite of the present invention, and rate of wear is almost more than 100 times of nano composite plating.
Claims (4)
1, a kind of total thickness≤13 μ m high-brightness high-corrosion-resistance high-wear resistance nano compound electroplating layers combination, it is characterized by: electrolytic coating is combined as: dark plating/nano combined nickel/bright nickel/chromium; Wherein, disperse has 3-10% with α-Al in the composite deposite of electrolytic coating combination
2O
3Nano composite oxides particulate for principal crystalline phase; Contain alkaline-earth metal in the described nano composite oxides particulate, or/and cross metallizing 1～10%.
2, high-brightness high-corrosion-resistance high-wear resistance nano compound electroplating layer combination according to claim 1, it is characterized by: in the electrolytic coating, dark coating is thick to be 1.5-2.0 μ m, the thick 5-8 μ of nano combined nickel dam m, bright nickel bed thickness 3-4 μ m, the thick 0.25-0.5 μ of chromium surface layer m.
3, high-brightness high-corrosion-resistance high-wear resistance nano compound electroplating layer combination according to claim 1, it is characterized by: in described nano composite oxides particulate, the alkaline-earth metal that contains comprises magnesium or magnesium oxide, crosses metallizing and comprises nickel or nickel oxide.
4, a kind of technology for preparing the high-brightness high-corrosion-resistance high-wear resistance nano compound electroplating layer combination, it is characterized in that: the technology of its composite plating comprises: the α-Al that adds 50-150g/L in conventional watt electrolytic solution
2O
3Be the composite Nano slurry, the former grain fineness number＜100nm of dispersed particle is preferably 40nm-80nm in the slurry, and the composition and the processing condition of the electrolytic solution that uses in the technology are as follows:
Single nickel salt 350-380g/L
Boric acid 40-45g/L
Sodium-chlor 12-16g/L
α-Al
2O
3Composite nano slurry 50-150g/L (Gu)
PH 3.5-4.6
Dk 3-4A/dm
2
t℃ 55-65
Nano composite plating layer thickness 5-8 μ m
In the technology, anode pure nickel electrode, pneumatic blending, stirring velocity is with all particles suspension degree of being in the slurries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011291494A CN1181227C (en) | 2001-12-04 | 2001-12-04 | High-brightness high-corrosion-resistance high-wear resistance nano compound electroplating layer composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011291494A CN1181227C (en) | 2001-12-04 | 2001-12-04 | High-brightness high-corrosion-resistance high-wear resistance nano compound electroplating layer composition |
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| Publication Number | Publication Date |
|---|---|
| CN1380446A true CN1380446A (en) | 2002-11-20 |
| CN1181227C CN1181227C (en) | 2004-12-22 |
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|---|---|---|---|
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| CN100345996C (en) * | 2005-10-28 | 2007-10-31 | 福州大学 | Nanometer crystal-micro crystal layered composite material and its preparation method |
| CN102181896A (en) * | 2011-05-08 | 2011-09-14 | 黄明华 | Electroplated plowshare |
| CN102639758A (en) * | 2009-06-08 | 2012-08-15 | 莫杜美拓有限责任公司 | Electrodeposited, nanolaminate coatings and claddings for corrosion protection |
| CN103276419A (en) * | 2013-06-08 | 2013-09-04 | 沈阳化工大学 | Preparation method of composite pulse high-temperature protection coat |
| CN103334146A (en) * | 2013-06-14 | 2013-10-02 | 西安理工大学 | Electroplating method of wear-resisting nano composite plate |
| CN103451695A (en) * | 2013-09-30 | 2013-12-18 | 烟台星辉航空液压机械有限公司 | High corrosion resistance nano nickel and crack-free micro hard chrome composite plating layer electroplate liquid and electroplated layer manufacturing technology |
| US10513791B2 (en) | 2013-03-15 | 2019-12-24 | Modumental, Inc. | Nanolaminate coatings |
| US10781524B2 (en) | 2014-09-18 | 2020-09-22 | Modumetal, Inc. | Methods of preparing articles by electrodeposition and additive manufacturing processes |
| US10808322B2 (en) | 2013-03-15 | 2020-10-20 | Modumetal, Inc. | Electrodeposited compositions and nanolaminated alloys for articles prepared by additive manufacturing processes |
| US10844504B2 (en) | 2013-03-15 | 2020-11-24 | Modumetal, Inc. | Nickel-chromium nanolaminate coating having high hardness |
| US10961635B2 (en) | 2005-08-12 | 2021-03-30 | Modumetal, Inc. | Compositionally modulated composite materials and methods for making the same |
| US11180864B2 (en) | 2013-03-15 | 2021-11-23 | Modumetal, Inc. | Method and apparatus for continuously applying nanolaminate metal coatings |
| US11286575B2 (en) | 2017-04-21 | 2022-03-29 | Modumetal, Inc. | Tubular articles with electrodeposited coatings, and systems and methods for producing the same |
| US11293272B2 (en) | 2017-03-24 | 2022-04-05 | Modumetal, Inc. | Lift plungers with electrodeposited coatings, and systems and methods for producing the same |
| US11365488B2 (en) | 2016-09-08 | 2022-06-21 | Modumetal, Inc. | Processes for providing laminated coatings on workpieces, and articles made therefrom |
| US11519093B2 (en) | 2018-04-27 | 2022-12-06 | Modumetal, Inc. | Apparatuses, systems, and methods for producing a plurality of articles with nanolaminated coatings using rotation |
| US11692281B2 (en) | 2014-09-18 | 2023-07-04 | Modumetal, Inc. | Method and apparatus for continuously applying nanolaminate metal coatings |
-
2001
- 2001-12-04 CN CNB011291494A patent/CN1181227C/en not_active Expired - Fee Related
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| CN100345996C (en) * | 2005-10-28 | 2007-10-31 | 福州大学 | Nanometer crystal-micro crystal layered composite material and its preparation method |
| US10253419B2 (en) | 2009-06-08 | 2019-04-09 | Modumetal, Inc. | Electrodeposited, nanolaminate coatings and claddings for corrosion protection |
| CN102639758A (en) * | 2009-06-08 | 2012-08-15 | 莫杜美拓有限责任公司 | Electrodeposited, nanolaminate coatings and claddings for corrosion protection |
| US11242613B2 (en) | 2009-06-08 | 2022-02-08 | Modumetal, Inc. | Electrodeposited, nanolaminate coatings and claddings for corrosion protection |
| US10544510B2 (en) | 2009-06-08 | 2020-01-28 | Modumetal, Inc. | Electrodeposited, nanolaminate coatings and claddings for corrosion protection |
| CN105839157B (en) * | 2009-06-08 | 2019-06-14 | 莫杜美拓有限公司 | For etch-proof electroplating nano laminated coating and covering |
| CN102639758B (en) * | 2009-06-08 | 2016-05-18 | 莫杜美拓有限公司 | For etch-proof electroplating nano laminated coating and covering |
| CN105839157A (en) * | 2009-06-08 | 2016-08-10 | 莫杜美拓有限公司 | Electrodeposited, nanolaminate coatings and claddings for corrosion protection |
| CN102181896A (en) * | 2011-05-08 | 2011-09-14 | 黄明华 | Electroplated plowshare |
| US11851781B2 (en) | 2013-03-15 | 2023-12-26 | Modumetal, Inc. | Method and apparatus for continuously applying nanolaminate metal coatings |
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| US11168408B2 (en) | 2013-03-15 | 2021-11-09 | Modumetal, Inc. | Nickel-chromium nanolaminate coating having high hardness |
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| CN103334146B (en) * | 2013-06-14 | 2015-06-24 | 西安理工大学 | Electroplating method of wear-resisting nano composite plate |
| CN103334146A (en) * | 2013-06-14 | 2013-10-02 | 西安理工大学 | Electroplating method of wear-resisting nano composite plate |
| CN103451695B (en) * | 2013-09-30 | 2016-02-10 | 山东星辉航空液压机械有限公司 | High corrosion resistance nano nickel adds flawless micro-hard chrome composite deposite electroplate liquid and electrolytic coating production technique |
| CN103451695A (en) * | 2013-09-30 | 2013-12-18 | 烟台星辉航空液压机械有限公司 | High corrosion resistance nano nickel and crack-free micro hard chrome composite plating layer electroplate liquid and electroplated layer manufacturing technology |
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