CN1181227C - 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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- CN1181227C CN1181227C CNB011291494A CN01129149A CN1181227C CN 1181227 C CN1181227 C CN 1181227C CN B011291494 A CNB011291494 A CN B011291494A CN 01129149 A CN01129149 A CN 01129149A CN 1181227 C CN1181227 C CN 1181227C
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Abstract
The present invention relates to a composite plating combination of which the total thickness is less than 13 um. The combination which has the advantages of high brightness, high corrosion resistance and high abrasion resistance is dark nickel nanometer composite nickel / bright nickel / chromium. The present invention is obtained by successively plating 1.5 to 2.0 um of dark nickel, 5 to 8 um of nanometer composite nickel, 3 to 4 um of bright nickel and 0.25 to 0.5 um of chromium with an electroplating method. 3 to 10% of composite oxide of which the particle diameter is from 40 to 80 nm is dispersed in nanometer composite nickel plating, and the composite oxide takes alpha-Al2O3 as a main crystal phase. The nanometer composite nickel plating is formed by electrodepositing 50 to 150 g/L of composite oxide slurry which takes alpha-Al2O3 as a main crystal phase and is added to conventional watt electrolytes. Compared with the conventional trinickel system of which the total thickness is 25 um, the plating combination of which the total thickness is 13 um has the advantages of considerable brightness and greatly enhanced abrasion resistance and erosion resistance, and is especially suitable for decorating and protecting objects impacted by high-speed particulates in moist salt spray atmosphere.
Description
One, 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.This coating is organized the usefulness that both can satisfy 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.
Two, 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.Plated in decorating with one 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.
Three, Fa Ming content
One of technical problem to be solved of the present invention is: a kind of promptly bright, wear-resisting, not only electrolytic coating combination of anti-corrosion but also flexible is provided, and the bright anticorrosive wear-resistant nickel base nanometer composite galvanized coating of promptly a kind of total thickness≤13 μ m makes up.
The present invention want the technical solution problem two be: a kind of technology for preparing above-mentioned nickel base nanometer 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 the bright anticorrosive wear-resistant nickel base nanometer composite galvanized coating combination of a kind of total thickness≤13 μ m, it is characterized by: electrolytic coating is combined as: dark nickel dam/nickel base nanometer composite deposite/bright nickel layer/chromium layer; Wherein, disperse has 3-10wt% with α-Al in the nickel base nanometer composite deposite of electrolytic coating combination
2O
3Be the nano composite oxides particulate of principal crystalline phase, contain the oxide compound of alkaline-earth metal in the described nano composite oxides particulate, as magnesium oxide 1-10wt%.
In above-mentioned total thickness≤13 μ m nickel base nanometer composite galvanized coatings combination, dark nickel coating is thick to be 1.5-2.0 μ m, the thick 5-8 μ of the compound nickel dam of nickel base nanometer m, the thick 3-4 μ of bright nickel coating m, the thick 0.25-0.5 μ of chromium coating m.
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 combination of nickel base nanometer composite galvanized coating, comprise plating conventional dark nickel dam 1.5-2.0 μ m, plating nickel-base nanometer composite layer 5-8 μ m, electroplate conventional bright nickel layer 3-4 μ m, electroplate conventional chromium layer 0.25-0.5 μ m; Wherein, the technology of plating nickel-base nanometer composite layer comprises: add α-Al in conventional watt electrolytic solution
2O
3It is nano composite slurry, former grain fineness number＜the 100nm of dispersed particle in the slurry, 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 4-5wt%.
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 solids/l
pH 3.5-4.6
Cathode current density D
k3-4A/dm
2
Temperature ℃ 55-65
Nickel base nanometer thickness of multiple plating 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 dam feel secure again nickel plating base nanometer composite layer, conventional bright nickel dam and chromium layer, 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 with half of three layers of nickel coating total thickness, even higher degree of protection, 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.
Four, 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 condition plating nickel-base nano-composite plate: 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 solids/l, pH:4.0, cathode current density Dk:3.5A/dm
2Temperature: 60 ℃, plating nickel-base nano-composite plate 7 μ m, 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) contains measures 80g solids/l, 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 dam/semi-bright nickel layer/high-sulfur nickel dam/bright nickel layer) 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 nickel base nanometer composite deposite of the present invention, and rate of wear is almost more than 100 times of nickel base nanometer composite deposite.
Claims (3)
1, a kind of bright anticorrosive wear-resistant nickel base nanometer composite galvanized coating combination, it is characterized by: electrolytic coating is combined as: dark nickel dam/nickel base nanometer composite deposite/bright nickel coating/chromium coating; In its electrolytic coating, dark nickel dam is thick to be 1.5-2.0 μ m, the thick 5-8 μ of the compound nickel coating of nickel base nanometer m, and the thick 3-4 μ of bright nickel coating m, the thick 0.25-0.5 μ of chromium coating m, and disperse has 3-10wt% with α-Al in the nickel base nanometer composite galvanized coating of electrolytic coating combination
2O
3Nanocomposite oxide fine particle for principal crystalline phase; The oxide compound that contains the alkaline-earth metal of 1-10wt% in the described nanocomposite oxide fine particle; Total thickness≤13 μ the m of electrolytic coating combination.
2, bright anticorrosive wear-resistant nickel base nanometer composite galvanized coating combination according to claim 1, it is characterized by: the oxide compound that contains alkaline-earth metal in the described nanocomposite oxide fine particle is a magnesium oxide.
3, the technology of the bright according to claim 1 anticorrosive wear-resistant nano composite galvanized coating combination of a kind of preparation is characterized in that: comprise plating conventional dark nickel dam 1.5-2.0 μ m, plating nickel-base nanometer composite layer 5-8 μ m, electroplate conventional bright nickel layer 3-4 μ m, electroplate conventional chromium layer 0.25-0.5 μ m; Wherein, the technology of plating nickel-base nanometer composite layer comprises: add α-Al in conventional watt nickel electrolyte
2O
3Be the composite Nano slurry, the former crystal grain footpath＜100nm of dispersed particle in the slurry, 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 solids/l
pH 3.5-4.6
Cathode current density D
k3-4A/dm
2
Temperature ℃ 55-65
Nickel base nanometer thickness of multiple plating 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.
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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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|---|---|---|---|
| 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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| CN1380446A CN1380446A (en) | 2002-11-20 |
| CN1181227C true CN1181227C (en) | 2004-12-22 |
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| WO2007021980A2 (en) | 2005-08-12 | 2007-02-22 | Isotron Corporation | Compositionally modulated composite materials and methods for making the same |
| CN100345996C (en) * | 2005-10-28 | 2007-10-31 | 福州大学 | Nanometer crystal-micro crystal layered composite material and its preparation method |
| BR122013014464B1 (en) | 2009-06-08 | 2020-10-20 | Modumetal, Inc | corrosion resistant multilayer coating on a substrate and electrodeposit method for producing a coating |
| CN102181896A (en) * | 2011-05-08 | 2011-09-14 | 黄明华 | Electroplated plowshare |
| BR112015022078B1 (en) | 2013-03-15 | 2022-05-17 | Modumetal, Inc | Apparatus and method for electrodepositing a nanolaminate coating |
| EA201500949A1 (en) | 2013-03-15 | 2016-02-29 | Модьюметл, Инк. | METHOD OF FORMING A MULTILAYER COATING, A COATING FORMED BY THE ABOVE METHOD, AND A MULTILAYER COATING |
| WO2014145771A1 (en) | 2013-03-15 | 2014-09-18 | Modumetal, Inc. | Electrodeposited compositions and nanolaminated alloys for articles prepared by additive manufacturing processes |
| CN105283587B (en) | 2013-03-15 | 2019-05-10 | 莫杜美拓有限公司 | Nano-stack coating |
| CN103276419A (en) * | 2013-06-08 | 2013-09-04 | 沈阳化工大学 | Preparation method of composite pulse high-temperature protection coat |
| CN103334146B (en) * | 2013-06-14 | 2015-06-24 | 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 |
| EA201790643A1 (en) | 2014-09-18 | 2017-08-31 | Модьюметал, Инк. | METHOD AND DEVICE FOR CONTINUOUS APPLICATION OF NANO-LAYERED METAL COATINGS |
| AR102068A1 (en) | 2014-09-18 | 2017-02-01 | Modumetal Inc | METHODS OF PREPARATION OF ITEMS BY ELECTRODEPOSITION AND ADDITIVE MANUFACTURING PROCESSES |
| BR112019004508A2 (en) | 2016-09-08 | 2019-06-04 | Modumetal Inc | methods for obtaining laminated coatings on workpieces and articles made therefrom |
| EP3601641A1 (en) | 2017-03-24 | 2020-02-05 | Modumetal, Inc. | Lift plungers with electrodeposited coatings, and systems and methods for producing the same |
| CA3060619A1 (en) | 2017-04-21 | 2018-10-25 | Modumetal, Inc. | Tubular articles with electrodeposited coatings, and systems and methods for producing the same |
| CN112272717B (en) | 2018-04-27 | 2024-01-05 | 莫杜美拓有限公司 | Apparatus, system, and method for producing multiple articles with nanolaminate coatings using rotation |
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