CN104805480A - Alkaline zinc-nickel electroplating liquid, preparation method and electroplating method - Google Patents

Alkaline zinc-nickel electroplating liquid, preparation method and electroplating method Download PDF

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Publication number
CN104805480A
CN104805480A CN201510263051.8A CN201510263051A CN104805480A CN 104805480 A CN104805480 A CN 104805480A CN 201510263051 A CN201510263051 A CN 201510263051A CN 104805480 A CN104805480 A CN 104805480A
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China
Prior art keywords
electroplate liquid
pyridine
nickel
electroplating
alkali zinc
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CN201510263051.8A
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Inventor
陈蔡喜
侯柏龙
罗迎花
牛艳丽
刘红霞
蔡志华
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GUANGDONG DAZHI ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
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GUANGDONG DAZHI ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
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Priority to CN201510263051.8A priority Critical patent/CN104805480A/en
Publication of CN104805480A publication Critical patent/CN104805480A/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys

Abstract

The invention relates to the technical field of electroplating and particularly relates to alkaline zinc-nickel electroplating liquid, a preparation method and an electroplating method. The alkaline zinc-nickel electroplating liquid disclosed by the invention is wide in working current density range, can be widely applied to rack plating or barrel plating and is wide in application range; the electroplating liquid is easy to maintain and high in electroplating efficiency; an electroplated layer electroplated by using the electroplating liquid is semi-bright or bright in appearance; an electroplate-deposited zinc-nickel alloy electroplated layer is extremely high in corrosion resistance, more than 1500 hours in red rust-free time in a neutral salt spray test and more than 500 hours in white rust-free time in the neutral salt spray test, and the service life of an electroplated work piece is greatly prolonged.

Description

A kind of alkali zinc nickel electroplate liquid, preparation method and electro-plating method
Technical field
The present invention relates to electroplating technology field, be specifically related to a kind of alkali zinc nickel electroplate liquid, preparation method and electro-plating method.
Background technology
Electro-galvanized layer is as the positive polarity protective coating of steel substrate; almost account for whole plated item 20 ~ 30%; at present, the corrosion resistance of this coating can't reach high performance requirement of shelter, as neutral salt spray test reaches 500 hours more than (produce white rust time).In recent years, for the research of erosion resistance coating, mainly concentrate on the alloy layer of exploitation high corrosion resistance, wherein zinc base alloy coating is one of alloy layer studying at most, comprise zinc-nickel, zinc cobalt, zinc-iron etc., the normally used zinc coating of these alloy ratios has more excellent barrier propterty.Wherein the over-all properties of zn-ni alloy deposits is best, and application is the most general, have excellent erosion resistance (erosion resistance of the zinc-nickel alloy layer of nickeliferous 10-18% is 4 ~ 7 times of pure zinc coating), weldability, can the premium properties such as mechanical workout.
In alkali zinc nickel electroplating technology of the prior art, coating nickel content is unstable, can not obtain the workpiece with homogeneous coating, thus cause the corrosion resistance of workpiece poor, cannot meet plating requirement.
Summary of the invention
The present invention's first object provides a kind of alkali zinc nickel electroplate liquid for the deficiencies in the prior art, the zn-ni alloy deposits of light or half light is obtained after plating, in alloy layer, nickel content is between 10 ~ 18%, solves the problem of the nickeliferous instability of coating in prior art neutral and alkali zinc-nickel electroplating technology; Zinc-nickel alloy electroplating layer after electroplating deposition has high resistance to corrosion, and neutral salt spray test reaches more than 1500 hours without the red rust time, reaches more than 500 hours without the white rust time, substantially increases the work-ing life of electroplating parts.
Another object of the present invention is the preparation method and the electro-plating method that provide a kind of alkali zinc nickel electroplate liquid for the deficiencies in the prior art, the preparation method of electroplate liquid is simple, easy to operate, working current density wide ranges in electroplating process, can be applicable to rack plating or barrel plating, applied widely, plating solution is easily safeguarded, electroplating efficiency is high.
In order to realize above object, the invention provides following technical scheme:
A kind of alkali zinc nickel electroplate liquid, described electroplate liquid comprises following component:
Wherein, described auxiliary brightener is any one or the two or more mixture in organic amine, organic aldehyde and polyvinyl alcohol.
As preferably, described organic amine is any one or two or more mixtures in quadrol, TEPA tetraethylene pentamine, polymine.
As preferably, described organic aldehyde is any one or two or more mixtures in formaldehyde, acetaldehyde, certain herbaceous plants with big flowers aldehyde.
Wherein, the general formula of described polyvinyl alcohol is [C 2h 4o] n, molecular weight is 3000 ~ 3500.
Wherein, described brightening agent is the mixture of pyridine-3,4-dicarboxylic acid or pyridine-3,4-dicarboxylate or pyridine-3,4-dicarboxylic acid and pyridine-3,4-dicarboxylate.
As preferably, described brightening agent is the mixture of pyridine-3,4-dioctyl phthalate or pyridine-3,4-dioctyl phthalate disodium or pyridine-3,4-dioctyl phthalate and pyridine-3,4-dioctyl phthalate disodium.
Wherein, described nickel complexing agent is any two or the two or more mixture in Seignette salt, Trisodium Citrate, tetrasodium ethylenediamine tetraacetate, triethylene tetramine.
Prepare a method for described alkali zinc nickel electroplate liquid, comprise the following steps:
(1) basal liquid preparation: to prepare 1L electroplate liquid, precise zinc oxide 5 ~ 20g, sodium hydroxide 40 ~ 220g, in beaker, add appropriate amount of deionized water, the sodium hydroxide taken slowly is poured into, is stirred to and dissolves completely, slowly add the zinc oxide taken again, until dissolve obtained basal liquid completely, be cooled to room temperature, for subsequent use;
(2) auxiliary brightener preparation: accurately take any one or the two or more mixture 250g in organic amine, organic aldehyde and polyvinyl alcohol, appropriate amount of deionized water is added in beaker, the said components taken slowly is poured into, 1L is settled to again with ionized water, obtained auxiliary brightener, for subsequent use;
(3) preparation of brightening agent: brightening agent is the mixture of pyridine-3,4-dicarboxylic acid or pyridine-3,4-dicarboxylate or pyridine-3,4-dicarboxylic acid and pyridine-3,4-dicarboxylate;
(4) preparation of nickel complexing agent: accurately take any two in Seignette salt, Trisodium Citrate, tetrasodium ethylenediamine tetraacetate, triethylene tetramine or two or more mixture 200g, be dissolved in appropriate amount of deionized water, 1L is settled to again, obtained nickel complexing agent with deionized water, for subsequent use;
(5) accurately take nickel complexing agent 10-50g prepared by step (4), accurately take single nickel salt 2.2-13.5g and add in the complexing agent taken, form mixed solution;
(6) auxiliary brightener 1-5g prepared by step (2) is accurately taken, and add in mixed solution prepared by step (5), and then take brightening agent 0.2-1g prepared by step (3) and add mixed solution, deionized water is finally utilized to be settled to 1L, obtained alkali zinc nickel electroplate liquid.
Apply an electro-plating method for described alkali zinc nickel electroplate liquid, comprise the following steps:
(1) mild steel plate is put into described alkali zinc nickel electroplate liquid, as anode;
(2) pending workpiece is put into described alkali zinc nickel electroplate liquid, as negative electrode;
(3) direct supply is passed into, cathode current density 0.5-5 ampere/square decimeter, electroplating temperature 15-40 DEG C, electroplating time 10-30 minute.
Compared with prior art, the beneficial effect that the present invention has is: the working current density wide ranges of alkali zinc nickel electroplate liquid of the present invention, can be applicable to rack plating or barrel plating, and applied widely, plating solution is easily safeguarded, electroplating efficiency is high; Deposit appearance after the plating of application electroplate liquid is half light or bright, Zinc-nickel alloy electroplating layer after electroplating deposition has high resistance to corrosion, neutral salt spray test reaches more than 1500 hours without the red rust time, reach more than 500 hours without the white rust time, substantially increase the work-ing life of electroplating parts.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but any limitation of the invention do not formed.
Embodiment 1.
The alkali zinc nickel electroplate liquid of the present embodiment comprises following component:
Embodiment 2.
The alkali zinc nickel electroplate liquid of the present embodiment comprises following component:
Embodiment 3.
The alkali zinc nickel electroplate liquid of the present embodiment comprises following component:
Embodiment 4.
The present embodiment provides basal liquid preparation method: to prepare 1L electroplate liquid, precise zinc oxide 5 ~ 20g, sodium hydroxide 40 ~ 220g, appropriate amount of deionized water is added in beaker, the sodium hydroxide taken slowly is poured into, be stirred to and dissolve completely, more slowly add the zinc oxide taken, until dissolve obtained basal liquid completely.
Embodiment 5.
The present embodiment provides the preparation method of auxiliary brightener: accurately take any one or the two or more mixture 250g in mixed amines, organic aldehyde and polyvinyl alcohol, appropriate amount of deionized water is added in beaker, the said components taken slowly is poured into, 1L is settled to again, obtained auxiliary brightener with ionized water.
Described organic amine is any one or two or more mixtures in quadrol, TEPA tetraethylene pentamine, polymine.
As preferably, described organic aldehyde is any one or two or more mixtures in formaldehyde, acetaldehyde, certain herbaceous plants with big flowers aldehyde.
Wherein, the general formula of described polyvinyl alcohol is [C 2h 4o] n, molecular weight is 3000-3500.
Embodiment 6.
The present embodiment provides the preparation method of brightening agent: brightening agent is the mixture of pyridine-3,4-dicarboxylic acid or pyridine-3,4-dicarboxylate or pyridine-3,4-dicarboxylic acid and pyridine-3,4-dicarboxylate.
As preferably, described brightening agent is the mixture of pyridine-3,4-dioctyl phthalate or pyridine-3,4-dioctyl phthalate disodium or pyridine-3,4-dioctyl phthalate and pyridine-3,4-dioctyl phthalate disodium.
Embodiment 7.
The present embodiment provides the preparation method of nickel complexing agent: accurately take any two in Seignette salt, Trisodium Citrate, tetrasodium ethylenediamine tetraacetate, triethylene tetramine or two or more mixture 200g, be dissolved in appropriate amount of deionized water, 1L is settled to again, obtained nickel complexing agent with deionized water.
Embodiment 8.
The present embodiment provides a kind of preparation method of alkali zinc nickel electroplate liquid: accurately take single nickel salt 2.2g and add in the nickel complexing agent of 10g, obtained mixed solution, auxiliary brightener 3g is added in mixed solution, and then add brightening agent 0.5g wherein, deionized water is finally utilized to be settled to 1L, obtained alkali zinc nickel electroplate liquid.
Embodiment 9.
The present embodiment provides the preparation method of another kind of alkali zinc nickel electroplate liquid: accurately take single nickel salt 5g and add in the nickel complexing agent of 30g, obtained mixed solution, auxiliary brightener 1g is added in mixed solution, and then add brightening agent 0.2g wherein, deionized water is finally utilized to be settled to 1L, obtained alkali zinc nickel electroplate liquid.
Embodiment 10.
The present embodiment provides the preparation method of another kind of alkali zinc nickel electroplate liquid: accurately take single nickel salt 13.5g and add in the nickel complexing agent of 50g, obtained mixed solution, auxiliary brightener 1g is added in mixed solution, and then add brightening agent 1g wherein, deionized water is finally utilized to be settled to 1L, obtained alkali zinc nickel electroplate liquid.
Embodiment 11.
The present embodiment provides a kind of electro-plating method applying described alkali zinc nickel electroplate liquid, comprises the following steps:
(1) mild steel plate is put into described alkali zinc nickel electroplate liquid, as anode;
(2) pending workpiece is put into described alkali zinc nickel electroplate liquid, as negative electrode;
(3) direct supply is passed into, cathode current density 0.5-5 ampere/square decimeter, electroplating temperature 15-40 DEG C, electroplating time 10-30 minute.
Embodiment 12.
Electroplate liquid prepared by the present embodiment Application Example 8-10, according to the electro-plating method of embodiment 11, test piece is electroplated, and plating result is detected, comprise the following steps:
(1) mild steel plate is put into described alkali zinc nickel electroplate liquid, as anode;
(2) test piece (iron plate) is put into described alkali zinc nickel electroplate liquid, as negative electrode;
(3) pass into direct supply, cathode current density 1 ampere/square decimeter, electroplating temperature 30 DEG C, electroplating time 20 minutes, obtain the test piece after electroplating processes.
Table 1: to electroplate liquid coating composition in embodiment 8 ~ 10 and coating protection performance test results
Above test-results shows: the Deposit appearance applied after electroplate liquid of the present invention plating is half light or bright, Zinc-nickel alloy electroplating layer after electroplating deposition has high resistance to corrosion, neutral salt spray test reaches more than 1500 hours without the red rust time, reach more than 500 hours without the white rust time, substantially increase the work-ing life of electroplating parts.
The above embodiments are only the preferred embodiments of the present invention, can not limit interest field of the present invention with this, and therefore, the equivalent variations done according to the present patent application the scope of the claims, still belongs to the scope that the present invention is contained.

Claims (10)

1. an alkali zinc nickel electroplate liquid, is characterized in that: described electroplate liquid comprises following component:
2. alkali zinc nickel electroplate liquid according to claim 1, is characterized in that: described auxiliary brightener is any one or two or more mixtures in organic amine, organic aldehyde and polyvinyl alcohol.
3. alkali zinc nickel electroplate liquid according to claim 2, is characterized in that: described organic amine is any one or two or more mixtures in quadrol, TEPA tetraethylene pentamine, polymine.
4. alkali zinc nickel electroplate liquid according to claim 2, is characterized in that: described organic aldehyde is any one or two or more mixtures in formaldehyde, acetaldehyde, certain herbaceous plants with big flowers aldehyde.
5. alkali zinc nickel electroplate liquid according to claim 2, is characterized in that: the general formula of described polyvinyl alcohol is [C 2h 4o] n, molecular weight is 3000 ~ 3500.
6. alkali zinc nickel electroplate liquid according to claim 1, is characterized in that: described brightening agent is the mixture of pyridine-3,4-dicarboxylic acid or pyridine-3,4-dicarboxylate or pyridine-3,4-dicarboxylic acid and pyridine-3,4-dicarboxylate.
7. alkali zinc nickel electroplate liquid according to claim 6, is characterized in that: described brightening agent is the mixture of pyridine-3,4-dioctyl phthalate or pyridine-3,4-dioctyl phthalate disodium or pyridine-3,4-dioctyl phthalate and pyridine-3,4-dioctyl phthalate disodium.
8. alkali zinc nickel electroplate liquid according to claim 1, is characterized in that: described nickel complexing agent is any two or two or more mixtures in Seignette salt, Trisodium Citrate, tetrasodium ethylenediamine tetraacetate, triethylene tetramine.
9. prepare a method for the alkali zinc nickel electroplate liquid described in claim 1-8 any one, it is characterized in that, comprise the following steps:
(1) basal liquid preparation: to prepare 1L electroplate liquid, precise zinc oxide 5 ~ 20g, sodium hydroxide 40 ~ 220g, in beaker, add appropriate amount of deionized water, the sodium hydroxide taken slowly is poured into, is stirred to and dissolves completely, slowly add the zinc oxide taken again, until dissolve obtained basal liquid completely, be cooled to room temperature, for subsequent use;
(2) auxiliary brightener preparation: accurately take any one or the two or more mixture 250g in organic amine, organic aldehyde and polyvinyl alcohol, appropriate amount of deionized water is added in beaker, the said components taken slowly is poured into, 1L is settled to again with ionized water, obtained auxiliary brightener, for subsequent use;
(3) preparation of brightening agent: brightening agent is the mixture of pyridine-3,4-dicarboxylic acid or pyridine-3,4-dicarboxylate or pyridine-3,4-dicarboxylic acid and pyridine-3,4-dicarboxylate;
(4) preparation of nickel complexing agent: accurately take any two in Seignette salt, Trisodium Citrate, tetrasodium ethylenediamine tetraacetate, triethylene tetramine or two or more mixture 200g, be dissolved in appropriate amount of deionized water, 1L is settled to again, obtained nickel complexing agent with deionized water, for subsequent use;
(5) accurately take nickel complexing agent 10-50g prepared by step (4), accurately take single nickel salt 2.2-13.5g and add in the complexing agent taken, form mixed solution;
(6) auxiliary brightener 1-5g prepared by step (2) is accurately taken, and add in mixed solution prepared by step (5), and then take brightening agent 0.2-1g prepared by step (3) and add mixed solution, deionized water is finally utilized to be settled to 1L, obtained alkali zinc nickel electroplate liquid.
10. application rights requires an electro-plating method for the alkali zinc nickel electroplate liquid described in 1-8 any one, it is characterized in that, comprises the following steps:
(1) mild steel plate is put into described alkali zinc nickel electroplate liquid, as anode;
(2) pending workpiece is put into described alkali zinc nickel electroplate liquid, as negative electrode;
(3) direct supply is passed into, cathode current density 0.5-5 ampere/square decimeter, electroplating temperature 15-40 DEG C, electroplating time 10-30 minute.
CN201510263051.8A 2015-05-21 2015-05-21 Alkaline zinc-nickel electroplating liquid, preparation method and electroplating method Pending CN104805480A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105442000A (en) * 2015-11-26 2016-03-30 贵阳华科电镀有限公司 Alkaline zinc-iron alloy electroplate liquid, preparation method and electroplating process
CN106637315A (en) * 2015-11-02 2017-05-10 株洲时代新材料科技股份有限公司 Chromium-ion-free zinc-nickel alloy automatic electroplating process
CN106841073A (en) * 2017-04-20 2017-06-13 广州超邦化工有限公司 The analysis method of nickel content in a kind of alkaline zinc-nickel alloy plating solution
CN107101959A (en) * 2017-05-25 2017-08-29 广州超邦化工有限公司 The analysis method of cobalt chloride in chloride zinc-cobalt alloy plating solution
CN108220870A (en) * 2018-01-23 2018-06-29 滁州英诺信电器有限公司 A kind of handware surfacecti proteon treatment process
CN113502514A (en) * 2021-06-28 2021-10-15 重庆信人科技发展有限公司 Zinc-nickel alloy electroplating solution and electroplating process thereof

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JP2012246554A (en) * 2011-05-30 2012-12-13 Nippon Hyomen Kagaku Kk Zinc-nickel alloy plating liquid and plating method
CN103451693A (en) * 2013-07-29 2013-12-18 山东建筑大学 Pulse electroplating method for alkaline zinc-nickel alloy with stable nickel content
CN104120465A (en) * 2013-04-28 2014-10-29 国家电网公司 Alkaline zinc-nickel alloy electroplating solution as well as preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
JPH01298192A (en) * 1988-05-27 1989-12-01 Ebara Yuujiraito Kk Zinc-nickel alloy plating solution
CN101240437A (en) * 2008-03-20 2008-08-13 北京航空航天大学 Method for plating zinc-nickel alloy in alkaline electroplate liquid
CN102171386A (en) * 2008-10-17 2011-08-31 麦克德米德股份有限公司 Zinc alloy electroplating baths and processes
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106637315A (en) * 2015-11-02 2017-05-10 株洲时代新材料科技股份有限公司 Chromium-ion-free zinc-nickel alloy automatic electroplating process
CN105442000A (en) * 2015-11-26 2016-03-30 贵阳华科电镀有限公司 Alkaline zinc-iron alloy electroplate liquid, preparation method and electroplating process
CN105442000B (en) * 2015-11-26 2018-08-31 贵阳华科电镀有限公司 A kind of alkalinity Zn-Fe alloy electroplating liquid, preparation method and electroplating technology
CN106841073A (en) * 2017-04-20 2017-06-13 广州超邦化工有限公司 The analysis method of nickel content in a kind of alkaline zinc-nickel alloy plating solution
CN107101959A (en) * 2017-05-25 2017-08-29 广州超邦化工有限公司 The analysis method of cobalt chloride in chloride zinc-cobalt alloy plating solution
CN107101959B (en) * 2017-05-25 2019-06-04 广州超邦化工有限公司 The analysis method of cobalt chloride in chloride zinc-cobalt alloy plating solution
CN108220870A (en) * 2018-01-23 2018-06-29 滁州英诺信电器有限公司 A kind of handware surfacecti proteon treatment process
CN113502514A (en) * 2021-06-28 2021-10-15 重庆信人科技发展有限公司 Zinc-nickel alloy electroplating solution and electroplating process thereof

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Application publication date: 20150729