CN108570696A - A kind of acidic zinc nickel plating solution of resistance to high current density and its application - Google Patents
A kind of acidic zinc nickel plating solution of resistance to high current density and its application Download PDFInfo
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- CN108570696A CN108570696A CN201810361101.XA CN201810361101A CN108570696A CN 108570696 A CN108570696 A CN 108570696A CN 201810361101 A CN201810361101 A CN 201810361101A CN 108570696 A CN108570696 A CN 108570696A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
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Abstract
The invention discloses a kind of acidic zinc nickel plating solution of resistance to high current density and its applications.The acidic zinc nickel plating solution of this resistance to high current density, is made of raw material below:Zinc chloride, nickel chloride, alcamine compound, conductive salt, pH buffer, brightener, complexing agent and water.Also disclose that a kind of acidic zinc nickel plating solution using the resistance to high current density carries out electric plating method simultaneously.Ammonium chloride is not contained in the acidic zinc nickel plating solution of the resistance to high current density of the present invention, the intractability of waste water is alleviated, using NEW TYPE OF COMPOSITE additive, there is good wettability, with low bubble performance, even if normal production is nor affected on using air stirring and continuous filter unit, in 0~3A/dm2In wider current density range, coating nickel content can be stablized in a certain range, improve the uniformity of nickel content in height area coating well, while can bear more than 5A/dm2Current density is also not easy to burn.
Description
Technical field
The present invention relates to a kind of acidic zinc nickel plating solution of resistance to high current density and its applications.
Background technology
Protection for automobile parts, traditional method are to carry out zinc-plated, but the corrosion of electro-galvanized layer on its surface
Rate is excessively high, requires higher and higher, traditional electro-galvanized layer to have been unable to meet to corrosion proof in particular with auto parts and components
It is required that.Instead Zinc-nickel alloy electroplating, zn-ni alloy deposits excellent corrosion resistance, be 5 times of equal conditions zinc coating with
On, and Hydrogen Embrittlement is low, and weldability and toughness have prodigious advantage, due to these features of admiro, to it
Research it is also more and more, and the seventies in last century foreign countries be just applied to large batch of production.Electroplated zinc nickel alloy mainly has
Acid and alkaline solution system, alkaline system dispersion performance is good, and coating alloy ingredient is uniform in prodigious current density range,
But its current efficiency is low, and with hydrogen embrittlement is easily caused, smell is big in implementation process, and plating solution is not easily controlled and there are aging phenomenon, rows
The waste water put is more intractable.Acid system current efficiency is high, and cost low compared with alkaline system 50% compares the hydrogen embrittlement of steel substrate
It is small, the advantages that electroplating sewerage processing is simple, and aging phenomenon is not present in plating solution.Therefore, acid system has obtained quick development.
However, existing acidic solution system, has defect as is evident below:(1) during plating, ammonium chloride is commonly used
It keeps the pH and electric conductivity of solution, increases wastewater treatment difficulty;(2) plating process generally uses air stirring and continuous
Filter device, plating solution surface will produce a large amount of froth beds, so that overflowing coating bath, seriously affect production;(3) high in electroplating process
The ratio of nickel is uneven in low current area coating, when current density is more than 4A/dm2It is even easy to burn when high current density.
Invention content
It is an object of the invention to be directed to current Acidic zinc-nickel alloy, a kind of acidity of resistance to high current density is provided
Zinc-nickel electroplate liquid and its application, can be in 0~3A/dm using this electroplate liquid2It is electroplated, is plated in wider current density range
The ratio uniform of nickel content, can bear more than 5A/dm in layer2Current density is not burnt.
The technical solution used in the present invention is:
A kind of acidic zinc nickel plating solution of resistance to high current density, is made of raw material below:
In the acidic zinc nickel plating solution of resistance to high current density, the general structure of alcamine compound is:In general formula, R1Indicate the alkyl of H or C1~C4;R2Indicate H ,-CH3、-CH2OH、-
CH2CH2OH、-CH2NH2、-CH2CH2NH2;R3Indicate the alkylidene of C1~C5.
In the acidic zinc nickel plating solution of resistance to high current density, conductive salt is in potassium chloride, sodium chloride, potassium sulfate, sodium sulphate
At least one.
In the acidic zinc nickel plating solution of resistance to high current density, pH buffer is boric acid, borate, acetic acid, acetate, lemon
At least one of acid, citrate.
In the acidic zinc nickel plating solution of resistance to high current density, brightener is benzylideneacetone, two benzylideneacetones, aromatic third
Ketone, methyl acetonaphthone, methyl naphthalene acetone, o-chlorocinnamic acid, o-chlorobenzaldehyde, cinnamic acid, cumarin, polyethylene glycol, three ethyl alcohol
At least one of amine.
In the acidic zinc nickel plating solution of resistance to high current density, complexing agent is malic acid, gluconic acid, sodium tartrate, lemon
Sour sodium, sodium gluconate, potassium tartrate, potassium citrate, K-IAO, ammonium tartrate, malic acid ammonium, ammonium citrate, grape
At least one of saccharic acid ammonium, monoethanolamine, trien, tetren.
A method of plating zinc-nickel is carried out to base material using the acidic zinc nickel plating solution of above-mentioned resistance to high current density
Plating.
The beneficial effects of the invention are as follows:
Ammonium chloride is not contained in the acidic zinc nickel plating solution of the resistance to high current density of the present invention, the processing for alleviating waste water is difficult
Degree, using NEW TYPE OF COMPOSITE additive, there is good wettability, has low bubble performance, even if using air stirring and continuous mistake
Filter device nor affects on normal production, in 0~3A/dm2In wider current density range, coating nickel content can be stablized certain
In range, improve the uniformity of nickel content in height area coating well, while can bear more than 5A/dm2Current density is not yet
It is easy to burn.
It is specific as follows:
1, not containing ammonium chloride in electroplate liquid of the invention, alleviates the intractability of waste water, great amount of cost is saved for enterprise;
2, the various additives that the present invention uses have excellent performance, have preferable wettability, even if being stirred in air
It mixes and stirs under connection filter device, a large amount of bubbles will not be generated;
3, additive of the invention having the technical effect that containing alcamine compound improves the ratio unevenness of nickel content in coating
It is even, make the nickel content in coating in 0~3A/dm2Wider current density range keeps stable state, while can bear more than 5A/
dm2High current do not burn, show more excellent performance.
Specific implementation mode
A kind of acidic zinc nickel plating solution of resistance to high current density, is made of raw material below:
It is further preferred that a kind of acidic zinc nickel plating solution of resistance to high current density, is made of raw material below:
Preferably, in the acidic zinc nickel plating solution of resistance to high current density, the general structure of alcamine compound is:In general formula, R1Indicate the alkyl of H or C1~C4;R2Indicate H ,-CH3、-CH2OH、-
CH2CH2OH、-CH2NH2、-CH2CH2NH2;R3Indicate the alkylidene of C1~C5;The alkyl or alkylidene is linear chain or branched chain
Alkyl chain;It is further preferred that in general formula, R1Indicate H, methyl, ethyl, n-propyl or isopropyl, R2Indicate H ,-CH2OH
Or-CH2CH2OH, R3Indicate methylene or ethylidene.
Preferably, in the acidic zinc nickel plating solution of resistance to high current density, conductive salt is potassium chloride, sodium chloride, potassium sulfate, sulphur
At least one of sour sodium.
Preferably, in the acidic zinc nickel plating solution of resistance to high current density, pH buffer is boric acid, borate, acetic acid, acetic acid
At least one of salt, citric acid, citrate.
Preferably, in the acidic zinc nickel plating solution of resistance to high current density, brightener is benzylideneacetone, two benzylideneacetones, virtue
Fragrant same clan's acetone, methyl acetonaphthone, methyl naphthalene acetone, o-chlorocinnamic acid, o-chlorobenzaldehyde, cinnamic acid, cumarin, poly- second two
At least one of alcohol, triethanolamine.
Preferably, in the acidic zinc nickel plating solution of resistance to high current density, complexing agent is malic acid, gluconic acid, tartaric acid
Sodium, sodium citrate, sodium gluconate, potassium tartrate, potassium citrate, K-IAO, ammonium tartrate, malic acid ammonium, citric acid
At least one of ammonium, ammonium gluconate, monoethanolamine, trien, tetren.
A method of plating zinc-nickel is carried out to base material using the acidic zinc nickel plating solution of above-mentioned resistance to high current density
Plating.
Electric plating method is:Chemical high temperature oil removing → washing → anode electrolysis → washing → pickling → washing → ultrasonic wave removes
Oil → washing → anode electrolysis → washing → hydrochloric acid activation → washing → plating acidity zinc-nickel → washing → passivation → washing → envelope
It closes → dries.
Preferably, it is electroplated in the method for zinc-nickel, electroplating parameter is as follows:0~3A/dm of current density2(being not 0A), pH value is
5.2-5.8, electroplating time 30min~60min, 30 DEG C~40 DEG C of electroplating temperature.
Present disclosure is described in further detail below by way of specific embodiment.It is former used in embodiment
Material unless otherwise specified, can be obtained from routine business approach.
Embodiment 1:
The acidic zinc nickel plating solution of the resistance to high current density of embodiment 1 is made of raw material below:Zinc chloride 40g/L, chlorine
Change nickel 90g/L, conductive salt 200g/L, pH buffer 60g/L, brightener 1mL/L, complexing agent 12mL/L, alcamine compound
10g/L (R in alcamine compound general formula1For H, R2For-CH2OH, R3For ethylidene), surplus is distilled water.
Raw material used in conductive salt, pH buffer, brightener and complexing agent is above-mentioned disclosed raw material, is this field
Routine techniques.Conductive salt, pH buffer, brightener and complexing agent composition used in the embodiment of the present invention and comparative example is identical.
Comparative example 1:
The zinc-nickel electroplate liquid of comparative example 1 is made of raw material below:Zinc chloride 40g//L, nickel chloride 90g/L, conductive salt
200g//L, pH buffer 60g//L, brightener 1mL/L, complexing agent 12mL/L, surplus are distilled water.
Embodiment 2:
The acidic zinc nickel plating solution of the resistance to high current density of embodiment 2 is made of raw material below:Zinc chloride 50g/L, chlorine
Change nickel 100g/L, conductive salt 210g/L, pH buffer 50g/L, brightener 1mL/L, complexing agent 12mL/L, alcamine compound
10g/L (R in alcamine compound general formula1For H, R2For-CH2OH, R3For ethylidene), surplus is distilled water.
Comparative example 2:
The zinc-nickel electroplate liquid of comparative example 2 is made of raw material below:Zinc chloride 50g/L, nickel chloride 100g/L, conductive salt
210g/L, pH buffer 50g/L, brightener 1mL/L, complexing agent 12mL/L, surplus are distilled water.
Application Example 1:
Plating experiment is carried out in the slot of the Hulls 267mL with the zinc-nickel electroplate liquid of embodiment 1, substrate material is standard steel, ruler
Very little is 100mm*60mm, and plating conditions are current density 1A, electroplating time 10min, 35 DEG C of temperature, pH value 5.4.
The nickel content of coating is measured using XDL type X- fluorescence layer thickness meter (German Fischer companies).With standard film water
The center line of plane draws a straight line, and using left margin as starting point, measures the nickel content of 2cm, 4cm, 6cm, 8cm, 9cm respectively, with
Solution electric current height area coating nickel content.Observation caliber piece left margin is that size of current is 5.1A/ at starting point 1cm simultaneously
dm2Electroplating conditions, and inflate plating solution under state the case where generating bubble.
As a result it shows:Under electroplating process inflates state, it is considerably less that plating solution generates bubble, it was demonstrated that this plating solution has low
Steep performance.Observation caliber piece whole region brightness is all higher, and there is no burn.Standard film difference galvanic areas coating
In nickel content it is as shown in table 1, high/low currents region nickel content is visibly homogeneous.
The plating result of 1 embodiment 1 of table
L (criterion distance piece Far Left distance cm) | Coating nickel content (wt%) |
2 | 13.2 |
4 | 12.7 |
6 | 13.1 |
8 | 12.6 |
9 | 14.1 |
Comparison study example 1:
It is electroplated using the zinc-nickel electroplate liquid of comparative example 1, electro-plating method is identical as Application Example 1.
As a result it shows:Under electroplating process inflates state, it is considerably less that plating solution generates bubble, it was demonstrated that this plating solution has low
Steep performance.Observation caliber piece brightness is higher, but standard film left margin is that left side presence slightly burns phenomenon at starting point 1cm.Mark
Nickel content in quasi- piece difference galvanic areas coating is as shown in table 2, and high/low currents region nickel content is very uneven.
The plating result of 2 comparative example 1 of table
L (criterion distance piece Far Left distance cm) | Coating nickel content (wt%) |
2 | 11.2 |
4 | 13.2 |
6 | 9.8 |
8 | 16.6 |
9 | 19.1 |
Application Example 2:
It is electroplated with the zinc-nickel electroplate liquid of embodiment 2, electro-plating method is identical as Application Example 1.
As a result it shows:Under electroplating process inflates state, it is few that plating solution generates bubble, it was demonstrated that this plating solution has low bubble
Energy.Observation caliber piece whole region brightness is all higher, and there is no burn.In standard film difference galvanic areas coating
Nickel content is as shown in table 3, and high/low currents region nickel content is visibly homogeneous.
The plating result of 3 embodiment 2 of table
L (criterion distance piece Far Left distance cm) | Coating nickel content (wt%) |
2 | 12.6 |
4 | 12.7 |
6 | 12.1 |
8 | 13.7 |
9 | 13.4 |
Comparison study example 2:
It is electroplated using the zinc-nickel electroplate liquid of comparative example 2, electro-plating method is identical as Application Example 1.
As a result it shows:Under electroplating process inflates state, it is few that plating solution generates bubble, it was demonstrated that this plating solution has low bubble
Energy.Observation caliber piece brightness is higher, but standard film left margin is that left side presence slightly burns phenomenon at starting point 1cm.Standard film
Nickel content in different galvanic areas coating is as shown in table 4, and high/low currents region nickel content is very uneven.
The plating result of 4 comparative example 2 of table
L (criterion distance piece Far Left distance cm) | Coating nickel content (wt%) |
2 | 10.4 |
4 | 12.7 |
6 | 11.8 |
8 | 15.7 |
9 | 18.4 |
Compared with prior art, the present invention has the following advantages that:
1. not containing ammonium chloride in the electroplate liquid of the present invention, the intractability of waste water is alleviated.
2. using NEW TYPE OF COMPOSITE additive, there is good wettability, there is low bubble performance, though using air stirring and
Connection filter device, which will not cause plating solution to overflow coating bath, influences normal production.
3. in 0~3A/dm2In wider current density range, the ratio uniform of nickel content in coating can be born more than 5A/
dm2Current density is not burnt.
Claims (7)
1. a kind of acidic zinc nickel plating solution of resistance to high current density, it is characterised in that:It is made of raw material below:
2. a kind of acidic zinc nickel plating solution of resistance to high current density according to claim 1, it is characterised in that:Alcamines
Close object general structure be:In general formula, R1Indicate the alkyl of H or C1~C4;R2Table
Show H ,-CH3、-CH2OH、-CH2CH2OH、-CH2NH2、-CH2CH2NH2;R3Indicate the alkylidene of C1~C5.
3. a kind of acidic zinc nickel plating solution of resistance to high current density according to claim 1, it is characterised in that:Conductive salt is
At least one of potassium chloride, sodium chloride, potassium sulfate, sodium sulphate.
4. a kind of acidic zinc nickel plating solution of resistance to high current density according to claim 1, it is characterised in that:PH buffer
For at least one of boric acid, borate, acetic acid, acetate, citric acid, citrate.
5. a kind of acidic zinc nickel plating solution of resistance to high current density according to claim 1, it is characterised in that:Brightener is
Benzylideneacetone, two benzylideneacetones, aromatic acetone, methyl acetonaphthone, methyl naphthalene acetone, o-chlorocinnamic acid, o-chlorobenzaldehyde,
At least one of cinnamic acid, cumarin, polyethylene glycol, triethanolamine.
6. a kind of acidic zinc nickel plating solution of resistance to high current density according to claim 1, it is characterised in that:Complexing agent is
Malic acid, gluconic acid, sodium tartrate, sodium citrate, sodium gluconate, potassium tartrate, potassium citrate, K-IAO, wine
In stone acid ammonium, malic acid ammonium, ammonium citrate, ammonium gluconate, monoethanolamine, trien, tetren extremely
Few one kind.
7. a kind of method of plating zinc-nickel, it is characterised in that:Use the resistance to high current density of claim 1~6 any one of them
Acidic zinc nickel plating solution base material is electroplated.
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Cited By (3)
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CN109609979A (en) * | 2019-02-19 | 2019-04-12 | 广州睿邦新材料科技有限公司 | A kind of multi layer nickel plating additive improving stability |
CN112481667A (en) * | 2020-11-03 | 2021-03-12 | 张琪 | Zinc-nickel alloy electroplating process |
CN114525555A (en) * | 2022-02-22 | 2022-05-24 | 太仓鑫天健环保科技有限公司 | Acidic zinc-nickel alloy electroplating additive and electroplating solution |
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CN114525555A (en) * | 2022-02-22 | 2022-05-24 | 太仓鑫天健环保科技有限公司 | Acidic zinc-nickel alloy electroplating additive and electroplating solution |
CN114525555B (en) * | 2022-02-22 | 2023-12-01 | 太仓鑫天健环保科技有限公司 | Acidic zinc-nickel alloy electroplating additive and electroplating solution |
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