CN104651888B - High corrosion resistance zinc-nickel alloy electroplating additive with weak acidity to neutrality and electroplating liquid - Google Patents
High corrosion resistance zinc-nickel alloy electroplating additive with weak acidity to neutrality and electroplating liquid Download PDFInfo
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- CN104651888B CN104651888B CN201510095955.4A CN201510095955A CN104651888B CN 104651888 B CN104651888 B CN 104651888B CN 201510095955 A CN201510095955 A CN 201510095955A CN 104651888 B CN104651888 B CN 104651888B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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Abstract
The invention discloses a high corrosion resistance zinc-nickel alloy electroplating additive with weak acidity to neutrality and an electroplating liquid. The high corrosion resistance zinc-nickel alloy electroplating additive comprises the following components in parts by volume: 60-90 parts of a complexing agent, 15-25 parts of brightener, and 1-5 parts of a change agent. The electroplating liquid prepared from the additive consists of 150-220g/L of potassium chloride, 35-70g/L of potassium acetate, 50-75g/L of zinc chloride, 55-80g/L of nickel chloride, 60-90ml/L of a complexing agent, 15-25ml/L of a brightener, 1-5ml/L of a change agent and the balance of water. The high corrosion resistance zinc-nickel alloy electroplating additive disclosed by the invention is free of boric acid and ammonium chloride, the current efficiency of the high corrosion resistance zinc-nickel alloy electroplating additive is as high as 95%, as the basic liquid is free of boric acid, the pH value is relatively high and can be stabilized to be 5.5-7, the nickel content of a layer formed by electroplating with the electroplating liquid with the additive is stabilized to be within 10-15%, and the electroplated layer is stable in gamma crystal phase and excellent in anti-corrosion property.
Description
Technical field
The present invention relates to field of metal surface treatment technology, has height more particularly to a kind of faintly acid to neutral
Corrosion resistance Zinc-nickel alloy electroplating additive and electroplate liquid.
Background technology
Electroplated zinc nickel alloy is a kind of iron and steel Anodic Type protective coating risen over nearly more than 20 years.Zn-ni alloy depositses are not only
Corrosion resistance more possesses good japanning, solderability and mouldability, with excellent anti-corrosive properties higher than traditional 5-10 times of zinc coat
And low hydrogen fragility, suitable plating requires endurance, such as spring, securing member and other structures part or use at relatively high temperatures zero
Part, thus it is widely used in the industries such as automobile, Aero-Space, light industry, household electrical appliances.
Admiro and tradition plating, also divide acidity and alkaline system.Alkaline zinc-nickel alloy has plating solution dispersion energy
Power is good, less to equipment and workpiece corrosion, and technological operation is easy.Faintly acid system has plating very simple, current efficiency
High, deposition velocity is fast, the advantages of the advantages of cost is relatively low.Admiro due to the difference of nickel content, its microcosmic crystal phase structure
Difference, causes its anti-corrosion gender gap larger.Research shows the anti-corrosive properties of admiro difference crystalline phase：γ phases>η+γ phases>α+γ
Phase, only when in zn-ni alloy depositses, nickel content is between 10-15%, at most, antiseptic property is best for gained coating phase containing γ.
Traditional protection type plating 70% or so is zinc-plated, but with the raising of industry requirement, tradition is zinc-plated much
Demand can not be met.Occur in that various Zinc alloy electroplating layers, such as zinc-iron, zinc-tin, zinc cobalt, admiro etc..With other alloys
Compare, admiro has higher anti-corrosive properties, wear resistance, thermal-shock resistance, and can substitute cadmium plating layer for space flight
Air equipment, thus be at home and abroad widely used, in protection type plating, shared proportion is also increasing year by year.
Zinc-nickel alloy electroplating develops popularization, but the simply Electrodeposition of Zn-ni Alloy In Alkaline Bath for developing, acid zinc-nickel rapidly in China
Alloy plating is not but accordingly developed, and the use ratio of two kinds of techniques of Zinc-nickel alloy electroplating should be with acid zinc plating and alkali according to reason
Property zinc-plated ratio approximately, and should not have the difference of great disparity.But domestic acidity Zinc-nickel alloy electroplating ratio is less than at present
10%.The reason for Acidic zinc-nickel alloy plating proportion is so low is that
Workpiece generally employ Electrodeposition of Zn-ni Alloy In Alkaline Bath technique at present.As Acidic zinc-nickel alloy cost is more alkaline low, also will not
Carbonate and cyanide is produced, the advantages of current efficiency is more alkaline high, this situation will can be changed from now on, acid zinc-nickel
Alloy plating process ratio can also gradually rise.
At present, on market Zinc-nickel alloy electroplating additive product is most of to trust external import, domestic admiro
Additive is also immature, and various aspects of performance is also not sufficiently stable.And external import virtually increased the cost of admiro.With
Electrodeposition of Zn-ni Alloy In Alkaline Bath basal liquid species single (basal liquid is by Zinc Oxide, sodium hydroxide) is different, Acidic zinc-nickel alloy plating
Liquid species can be divided into sulfate type, chloride type, sulfate-chloride type, pyrophosphate-type, sulfamic acid salt form, cyanide
Type etc..Wherein with the combination property of chloride type preferably, research is most wide, and performance is also most stable, Acidic zinc-nickel alloy on the market
Substantially chloride type is, typically with boric acid as buffer agent, ammonium chloride is conducting salt.
Chinese Patent Application No.：Although CN201110362502.5 compositions are simpler, steel substrate surface is can only be used to,
PH relatively low (less than 5, between 3-4), it is larger to the corrosivity of equipment, have a strong impact on service life of equipment.Chinese patent application
Number：Although CN201210451680.X pH are higher, less to equipment corrosion, its electroplating temperature is 30-40 DEG C, using temperature
It is narrower, and electroplating process need to carry out preplating and multiple plating, operation technological process is more complicated.Both of which boric acid containing buffer agent and conducting salt
Ammonium chloride, belongs to conventional Zinc-nickel alloy electroplating, and boric acid mainly plays cushioning effect near cathode surface as buffer agent, in order to
Maintain stable pH, its consumption generally large (10-40g/L).But boric acid water solublity is bad, dissolving need to be with more than 70 DEG C heat
Water, and temperature easily separated out when relatively low, electroplating temperature must be more than 30 DEG C, and boric acid separates out unstable, the shadow that also results in plating solution pH
Coating nickel content is rung, and also stain can be formed in coating surface affects coating performance.
The content of the invention
The present invention proposes that a kind of faintly acid has high corrosion-resistant Zinc-nickel alloy electroplating additive and electroplate liquid to neutral, and this adds
Plus the faintly acid of the electroplate liquid of agent and preparation not boronic acid containing and ammonium chloride, its current efficiency may be up to more than 95%, gene basis liquid
In not boronic acid containing, more preferably, the coating nickel content electroplated out is stable between 10-15%, and coating is formed for the relatively high and stable property of pH
Stable γ crystalline phases, with excellent antiseptic property.And the additive system plating working condition is loose, can be at 20-50 DEG C
Within the temperature range of electroplated without there is crystallization to separate out, upper plating is fast, current efficiency up to more than 95%, coating antiseptic property
Excellent, gained coating only needs 8 μm or so neutral salt spray tests to can reach more than 850h.
What the present invention was realized particular by technical scheme below：
A kind of faintly acid has high corrosion-resistant Zinc-nickel alloy electroplating additive, calculates according to parts by volume, including chelating agent 60-
90 parts, brightener 15-25 parts, walk agent 1-5 parts.
Further, the chelating agent in parts by weight, is consisted of：Aspirin 5-10%, heterocyclic amine chemical combination
Thing 30-50%, balance of water；
Further, the heterocyclic amine compound be caprolactam, azetidinone, imidazoles, in 4- nitroimidazoles
One or more；
Further, the brightener in parts by weight, is consisted of：Sulfonate 10-30%, diaminourea polymer 1-
5%, balance of water；
Further, the sulfonate be sodium hydroxymethane sulfonate, sulfonate be methylol potassium sulfonate, propargyl sodium sulfonate,
Propargyl potassium sulfonate, sodium allylsulfonate, allyl sulphonic acid potassium, ethoxy-c epoxide block compound sodium sulfonate, ethoxy-c
One or more in epoxide block compound sodium sulfonate potassium；
Further, it is described to walk agent in parts by weight, consist of：Maleic anhydride 4-8%, dispersant NNO 1-
6%, nicotinic acid and its derivant 8-16%, balance of water；
Further, the nicotinic acid and its derivant be nicotinic acid, niacinamide usp, 2- chlorine apellagrins, the one kind in methyl nicotinate or
It is several.
A kind of faintly acid has high corrosion-resistant Zinc-nickel alloy electroplating liquid, consisting of：
Potassium chloride 150-220g/L；
Potassium acetate 35-70g/L；
Zinc chloride 50-75g/L；
Nickel dichloride. 55-80g/L；
Chelating agent：60–90ml/L；
Brightener：15-25ml/L；
Walk agent：1-5ml/L；
Remaining is water.
What the present invention was produced has the beneficial effect that：In above-mentioned electroplate liquid, potassium acetate replacement boric acid plays a part of buffered pH value,
Be highly soluble in water, can dissolve without the need for heating, unlike boric acid needs to be heated to more than 70 DEG C to dissolve, and temperature it is relatively low when
Easily separate out.Make pH buffer with potassium acetate, pH makees compared with boric acid that buffer agent is higher, can reduce the corrosion to equipment；Operating temperature
Wider range, can electroplate at normal temperatures without the need for heating, can electroplate at 15-50 DEG C, and the addition of potassium acetate, can increase electricity
Current density scope, electric current density 0.5-5A/dm2The zn-ni alloy depositses of uniform light can be obtained down.
Chelating agent can guarantee the stability of plating solution and alloy distribution in whole current density range, make zinc-nickel ratio in plating solution
1.0-1.5：1, coating nickel content is between 10-15%.Brightener can crystallization of refinement, improve low area's electric current density and covering power
Meanwhile, increase the bright property of coating.Without nicotinic acid and its during derivant, binding force of cladding material is poor, and Jing quenchings are easy to foaming, adds cigarette
After acid and its derivant, the adhesion of coating is remarkably reinforced.
Above-mentioned Zinc-nickel alloy electroplating basal liquid and additive can be used to prepare γ phase zinc of the nickel content between 10-15%
Nickel alloy coating, which uses the flow process to be：Metal base → alkali electroless oil removing (oil removing spirit) → hot water wash → acid deoiling rust cleaning
→ cleaning → flowing cool water washes → and Acidic zinc-nickel alloy plating → reclaim → cleaning → passivation → cleaning → closing (inessential) →
Dry solidification (60-70 DEG C).Its using method is：First metal base is cleaned with alkaline degreaser, washing removes substrate surface
Greasy dirt, then use hydrochloric acid degreasing and rust removal, then rinsed with water again, clean base material is directly in the basal liquid added with additive
Temperature is 15-50 DEG C, after plating 10-60min, you can obtains zinc-nickel of the coating nickel content of different-thickness between 10-15% and closes
Gold plate.The coating antiseptic property is excellent, and when thickness of coating is more than 8 μm, coating appears above red rust in 850h.Additive can
Use at 15-50 DEG C, optimal use temperature is 25-35 DEG C, electric current density 0.5-5A/dm2.Electroplating time is generally 10-
60min, when requiring relatively thin or thicker to thickness of coating, can suitably shorten as needed or extend electroplating time.
Electroplated zinc nickel alloy basal liquid provided by the present invention and additive are stable in properties, and usage cycles are long, can be various
Metal base includes that the metallic substrate surfaces such as iron and steel, magnesium alloy, aluminium alloy form admiro of the nickel content between 10-15%
Coating.The zn-ni alloy depositses have fabulous Corrosion Protection, and have low hydrogen is crisp, wear-resistant, heat shock resistance is good etc.
Excellent properties.And, there is provided the faintly acid of a kind of not boronic acid containing and ammonium chloride has high corrosion-resistant zn-ni alloy depositses with efficiently
Basal liquid and additive, its electroplating current efficiency may be up to more than 95%.Not boronic acid containing in the liquid of gene basis is very good with dissolubility
Potassium acetate replace needing the boric acid of hot water dissolving, make the relatively high and stable property of electroplate liquid pH more preferably, reduce the corrosion to equipment, increase
Oil (gas) filling device service life.And due to the introducing of potassium acetate, the additive system can be in 0.5-5A/dm2Broad electric current density
Scope, is electroplated within the temperature range of 20-50 DEG C without there is crystallization to separate out, and upper plating is fast, current efficiency up to more than 95%,
Coating antiseptic property is excellent.Gained coating only needs 8 μm or so neutral salt spray tests to can reach more than 850h.
Specific embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below in conjunction with the embodiment of the present invention,
Obviously, described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.Based in the present invention
Embodiment, the every other embodiment obtained under the premise of creative work is not made by those of ordinary skill in the art, all
Belong to the scope of protection of the invention.
Basal liquid is prepared：The solid of the potassium chloride of amount of calculation, potassium acetate, zinc chloride and nickel oxide is added in coating bath, plus
2/3 water is stirred to after being completely dissolved, and is sufficiently stirred for；After adding the desired amount of additive, moisturizing is equal to final volume stirring
It is even, you can to obtain weak acid to neutral Zinc-nickel alloy electroplating liquid.
Embodiment 1
Basal liquid is consisted of：Potassium chloride 150g/L, potassium acetate 35g/L, zinc chloride 54g/L, Nickel dichloride. 57g/L.To above-mentioned
Weak acid adds chelating agent into neutral basal liquid：62ml/L, brightener：23ml/L, walk agent：3ml/L, obtains after stirring
Obtain Zinc-nickel alloy electroplating liquid.
Wherein, 62ml/L chelating agent composition (mass fraction) is aspirin 7%, and caprolactam 42%, water are surplus.
Wherein, 23ml/L brighteners composition (mass fraction) are：Methylol potassium sulfonate 20%, diaminourea polymer 5%,
Water is surplus.
Wherein, 3ml/L walks agent composition (mass fraction) for maleic anhydride 6%, dispersant NNO (di-2-ethylhexylphosphine oxide naphthalenes
Sodium sulfonate) 3.5%, nicotinic acid 16%, water are surplus.
Embodiment 2
Basal liquid is consisted of：Potassium chloride 176g/L, potassium acetate 38g/L, zinc chloride 50g/L, Nickel dichloride. 67.5g/L.Upwards
State weak acid chelating agent is added into neutral basal liquid：60ml/L, brightener：24ml/L, walk agent：3.5ml/L, after stirring
Zinc-nickel alloy electroplating liquid is obtained.
Wherein, 60ml/L chelating agent constitutes (mass fraction) for aspirin 7.5%, azetidinone 35%, and water is
Surplus.
Wherein, 24ml/L brighteners composition (mass fraction) are：Propargyl sodium sulfonate 29%, diaminourea polymer
4.2%, water is surplus.
Wherein, 3.5ml/L walks agent composition (mass fraction) for maleic anhydride 5%, dispersant NNO (di-2-ethylhexylphosphine oxides
Sodium naphthalene sulfonate) 5.4%, niacinamide usp 10%, water are surplus.
Embodiment 3
Basal liquid is consisted of：Potassium chloride 168g/L, potassium acetate 43g/L, zinc chloride 58g/L, Nickel dichloride. 55g/L.To above-mentioned
Weak acid adds chelating agent into neutral basal liquid：82ml/L, brightener：25ml/L, walk agent：4ml/L, obtains after stirring
Obtain Zinc-nickel alloy electroplating liquid.
Wherein, 82ml/L chelating agent composition (mass fraction) is aspirin 5%, and imidazoles 30%, water are surplus.
Wherein, 25ml/L brighteners composition (mass fraction) are：Sodium allylsulfonate 18%, diaminourea polymer
2.6%, water is surplus.
Wherein, 4ml/L walks agent composition (mass fraction) for maleic anhydride 8%, dispersant NNO (di-2-ethylhexylphosphine oxide naphthalenes
Sodium sulfonate) 4%, 2- chlorine apellagrins 13%, water is surplus.
Embodiment 4
Basal liquid is consisted of：Potassium chloride 185g/L, potassium acetate 70g/L, zinc chloride 62.5g/L, Nickel dichloride. 62g/L.Upwards
State weak acid chelating agent is added into neutral basal liquid：74ml/L, brightener：20ml/L, walk agent：3.8ml/L, after stirring
Zinc-nickel alloy electroplating liquid is obtained.
Wherein, 74ml/L chelating agent composition (mass fraction) is aspirin 8%, and 4- nitroimidazoles 50%, water are remaining
Amount.
Wherein, 20ml/L brighteners composition (mass fraction) are：Ethoxy-c epoxide block compound potassium sulfonate 10%, two
Amino urea polymers 1.4%, water are surplus.
Wherein, 3.8ml/L walks agent composition (mass fraction) for maleic anhydride 7.3%, dispersant NNO (methylene
Double sodium naphthalene sulfonates) 1%, methyl nicotinate 8%, water are surplus.
Embodiment 5
Basal liquid is consisted of：Potassium chloride 214g/L, potassium acetate 52.5g/L, zinc chloride 75g/L, Nickel dichloride. 69g/L.Upwards
State weak acid chelating agent is added into neutral basal liquid：90ml/L, brightener：17ml/L, walk agent：1ml/L, after stirring i.e.
Obtain Zinc-nickel alloy electroplating liquid.
Wherein, 90ml/L chelating agent constitutes (mass fraction) for aspirin 10%, 48% (oneself of heterocyclic amine compound
Lactams, imidazoles), water is surplus.
Wherein, 17ml/L brighteners composition (mass fraction) are：15% (the methylol sulfonic acid of sulfonate of organics modifications
Potassium, allyl sulphonic acid potassium), diaminourea polymer 1%, water are surplus.
Wherein, 1ml/L walks agent composition (mass fraction) for maleic anhydride 6.4%, dispersant NNO (di-2-ethylhexylphosphine oxides
Sodium naphthalene sulfonate) 6%, nicotinic acid and its derivant (nicotinic acid, methyl nicotinate) 12%, water is surplus.
Embodiment 6
Basal liquid is consisted of：Potassium chloride 220g/L, potassium acetate 68g/L, zinc chloride 61g/L, Nickel dichloride. 80g/L.To above-mentioned
Weak acid adds chelating agent into neutral basal liquid：82ml/L, brightener：16ml/L, walk agent：5ml/L, obtains after stirring
Obtain Zinc-nickel alloy electroplating liquid.
Wherein, 82ml/L chelating agent constitutes (mass fraction) for aspirin 9%, 34% (oneself of heterocyclic amine compound
Lactams, azetidinone), water is surplus.
Wherein, 16ml/L brighteners composition (mass fraction) are：30% (the methylol sulfonic acid of sulfonate of organics modifications
Sodium, propargyl sodium sulfonate), diaminourea polymer 3%, water are surplus.
Wherein, 5ml/L walks agent composition (mass fraction) for maleic anhydride 4.8%, dispersant NNO (di-2-ethylhexylphosphine oxides
Sodium naphthalene sulfonate) 1.8%, nicotinic acid and its derivant (nicotinic acid, 2- chlorine apellagrins) 11%, water is surplus.
Embodiment 7
Basal liquid is consisted of：Potassium chloride 200g/L, potassium acetate 62g/L, zinc chloride 72g/L, Nickel dichloride. 73g/L.To above-mentioned
Weak acid adds chelating agent into neutral basal liquid：80ml/L, brightener：15ml/L, walk agent：1.6ml/L, after stirring i.e.
Obtain Zinc-nickel alloy electroplating liquid.
Wherein, 80ml/L chelating agent constitutes (mass fraction) for aspirin 6.6%, heterocyclic amine compound 36%
(imidazoles, 4- nitroimidazoles), water is surplus.
Wherein, 15ml/L brighteners composition (mass fraction) are：28% (the allyl sulphonic acid of sulfonate of organics modifications
Sodium, propargyl potassium sulfonate), diaminourea polymer 3.2%, water are surplus.
Wherein, 1.6ml/L walks agent composition (mass fraction) for maleic anhydride 5.4%, dispersant NNO (methylene
Double sodium naphthalene sulfonates) 5.1%, nicotinic acid and its derivant (niacinamide usp, nicotinic acid) 9%, water is surplus.
Embodiment 8
Basal liquid is consisted of：Potassium chloride 180g/L, potassium acetate 50g/L, zinc chloride 65g/L, Nickel dichloride. 76g/L.To above-mentioned
Weak acid adds chelating agent into neutral basal liquid：75ml/L, brightener：18ml/L, walk agent：2.0ml/L, after stirring i.e.
Obtain Zinc-nickel alloy electroplating liquid.
Wherein, 75ml/L chelating agent constitutes (mass fraction) for aspirin 7.2%, heterocyclic amine compound 45%
(caprolactam, azetidinone, imidazoles), water is surplus.
Wherein, 18ml/L brighteners composition (mass fraction) are：26% (the methylol sulfonic acid of sulfonate of organics modifications
Sodium, propargyl sodium sulfonate, allyl sulphonic acid potassium), diaminourea polymer 3.8%, water are surplus.
Wherein, 2.0ml/L walks agent composition (mass fraction) for maleic anhydride 5.8%, dispersant NNO (methylenes
The double sodium naphthalene sulfonate of base) 2.8%, nicotinic acid and its derivant (2- chlorine apellagrins, niacinamide usp) 14%, water is surplus.
Embodiment 9
Basal liquid is consisted of：Potassium chloride 190g/L, potassium acetate 55g/L, zinc chloride 68g/L, Nickel dichloride. 79g/L.To above-mentioned
Weak acid adds chelating agent into neutral basal liquid：68ml/L, brightener：19ml/L, walk agent：4ml/L, obtains after stirring
Obtain Zinc-nickel alloy electroplating liquid.
Wherein, 68ml/L chelating agent constitutes (mass fraction) for aspirin 7.8%, heterocyclic amine compound 41%
(azetidinone, imidazoles, 4- nitroimidazoles), water is surplus.
Wherein, 19ml/L brighteners composition (mass fraction) are：22% (the propargyl sulfonic acid of sulfonate of organics modifications
Sodium, allyl sulphonic acid potassium, ethoxy-c epoxide block compound sodium sulfonate), diaminourea polymer 4.6%, water are surplus.
Wherein, 4ml/L walks agent composition (mass fraction) for maleic anhydride 4%, dispersant NNO (di-2-ethylhexylphosphine oxide naphthalenes
Sodium sulfonate) 3.6%, nicotinic acid and its derivant (2- chlorine apellagrins, methyl nicotinate) 15%, water is surplus.
Test example 1
In embodiment, take Zinc-nickel alloy electroplating liquid 1-9 and identical steel substrate electroplated, plating conditions be 25 DEG C,
20min, electric current density 1A/dm2, at identical conditions passivation, after sealing treatment, carry out neutral salt spray test (according to salt fog
Experimental standard ASTM-B-117 is performed).And thickness and the nickel content of coating same area is determined with X-Ray, as a result such as following table：
Embodiment 1-3 thickness of coating, nickel content, corrosion resistance are similar, embodiment 4-6 thickness of coating, nickel content, corrosion resistance phase
Seemingly, embodiment 7-9 corrosion resistance is similar, and above-mentioned three groups of embodiment corrosion resistances are incremented by.Embodiment 7-9 best results.
Under the same terms, embodiment 7-9 current efficiency highest, preferably, performance is most for the anti-corrosive properties of gained zn-ni alloy depositses
It is excellent.
Test example 2
Prepare and 1,5,6 identical admiro electroplate liquid of embodiment, difference is to be not added with caprolactam in chelating agent
And other heterocyclic amine compounds, and the Zinc-nickel alloy electroplating liquid pair of caprolactam and other heterocyclic amine compounds will be not added with
Identical metal base is electroplated, plating conditions be 25 DEG C, 20min, electric current density 1A/dm2, thickness of coating is determined respectively
(according to GB/T16921-1997) and neutral salt spray test (are performed according to salt mist experiment standard ASTM-B-117), and embodiment 1,
5th, 6 comparing result such as following table：
When not containing heterocyclic amine compound in invention complexing agent, under the same terms, gained thickness of coating is 5.3 μm, neutral
Salt mist experiment time average is 528h, and coating nickel content obtained by the sample of addition heterocyclic amine compound is 7.8 μm, neutral salt
Mist experimental period average out to 791h.Heterocyclic amine compound is added as chelating agent, is remarkably improved current efficiency, is plated on coating
Faster, production efficiency is significantly improved.
Prepare and 1,5,6 identical admiro electroplate liquid of embodiment, difference is to be not added with caprolactam in chelating agent
And other heterocyclic amine compounds, and the Zinc-nickel alloy electroplating liquid pair of caprolactam and other heterocyclic amine compounds will be not added with
Identical metal base is electroplated, and plating conditions are 25 DEG C, electric current density 1A/dm2, gained thickness of coating is 8 μm, respectively
Determine coating nickel content (according to GB/T17359-2012) and neutral salt spray test (is held according to salt mist experiment standard ASTM-B-117
OK), and embodiment 1,5,6 comparing result such as following table：
When not containing heterocyclic amine compound in invention complexing agent, gained coating nickel content is 9%, during neutral salt spray test
Between average out to 492h, and add heterocyclic amine compound sample obtained by coating nickel content be 13.6%, during neutral salt spray test
Between average out to 878h.Heterocyclic amine compound is added as chelating agent, is remarkably improved coating nickel content, is obtained nickel content and is existed
Single γ phases zn-ni alloy depositses between 10-15%, so that obtain more preferable anti-corrosion effects.
Test example 3
Prepare and 1,6,8 identical admiro electroplate liquid of embodiment, difference is to be not added with sulfonate in brightener, and
The admiro for being not added with sulfonate is electroplated to identical metal base with electroplate liquid.Zinc-nickel alloy electroplating condition is 25
DEG C, 20min, electric current density 1A/dm2, measure height area's thickness of coating (according to GB/T16921-1997), and embodiment 1 respectively,
5th, 6 comparing result such as following table：
When not containing sulfonate in invention, gained coating average thickness is 6.9 μm, and height area thickness is than generally 2.8-3：1,
And coating average thickness obtained by the sample of addition sulfonate is 7.8 μm, height area thickness is than generally 1.8-2.2：1.Sulfonate
Add as brightener main component, be remarkably improved coating uniformity, strengthen low area and walk, improve covering power.
Test 4
Prepare and 1,5,7 identical admiro electroplate liquid of embodiment, difference is the nicotinic acid that be not added with agent that walks, and will
The admiro for being not added with nicotinic acid is electroplated to identical metal base with electroplate liquid.Zinc-nickel alloy electroplating condition be 25 DEG C,
Electric current density 1A/dm2, gained thickness of coating is 8 μm, and the adhesion of embodiment 1,5,7 is contrasted, using heating (quenching)
Sample is incubated 1h in 300 DEG C of baking ovens by test method(s), is cooled down in then being put into 15 DEG C of cold water, and observation whether there is foaming,
As a result it is as follows：
When not containing nicotinic acid and its derivant in invention, binding force of cladding material is poor, and Jing quenchings are easy to foaming, adds nicotinic acid and its spreads out
After biology, adhesion is remarkably reinforced.
In patent of invention, selected potassium acetate substitutes boric acid as pH buffer, not only can stablize pH value, can also increase
Current density range during power-up plating, reduction burn.Selected special heterocyclic amine compound, sulfonate compound, nicotinic acid and its
Derivant is remarkably improved current efficiency, makes current efficiency reach more than 95%, and it is stable between 10-15% to obtain nickel content
Zn-ni alloy depositses.Coating height area thickness ratio is can be controlled between 1.8-2.2, and covering power is excellent.These compounds
Cooperatively act on other components in additive, the additive system can be in 0.5-5A/dm2Broad current density range,
The weak acid of 5.5-7 is electroplated to neutral pH range, within the temperature range of 20-50 DEG C without there is crystallization to separate out, and upper plating is fast, electricity
, up to more than 95%, coating antiseptic property is excellent for stream efficiency high.It is little to equipment corrosion, and basal liquid prepare without the need for first with 70 DEG C with
On hot water dissolving's boric acid after re-dissolved other components, directly all components can be dissolved together at normal temperatures, electroplating temperature exists
There will not be crystal when less than 30 DEG C and separate out affects plating solution and coating performance.Gained coating only needs 8 μm or so neutral salt spray tests
More than 850h is can reach.
Test example 5
Take in the electroplating additive addition basal liquid of Atotech and elegant rich production, electroplated at T=25 DEG C, gained plating
Layer is respectively product 1 and product 2 and project implementation example 8, and thickness of coating is 8 μm, in 2 electroplate liquid of product 1 and product with
Boric acid is pH buffer, embodiment not boronic acid containing and ammonium chloride, makees buffer agent with potassium acetate, carry out neutral salt spray test (according to
Salt mist experiment standard ASTM-B-117 is performed), comparing result such as following table：
Upper table illustrates that the Zinc-nickel alloy electroplating liquid current density range of the present invention is wider；The more commercially available Zinc-nickel alloy electroplatings of pH
Liquid pH is higher, the corrosivity of equipment is reduced, and pH is more stable when electroplating；Its corrosion resistance of coating is better than foreign same type product；
According to 50021 SS neutral salt spray testing standards of ASTMB-117 and DIN, more than 250h starts nascent white rust, and 8 μm of coating is red
Generally up to more than 850-1000h, when thickness of coating increases, the salt mist experiment time also accordingly can increase rust salt mist experiment, anti-corrosion
Property is more preferable.Compared with the Zinc-nickel alloy electroplating additive of external report, obtained by Project Product, zn-ni alloy depositses corrosion resistance has
Clear superiority, and cost is lower.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (5)
1. a kind of faintly acid has high corrosion-resistant Zinc-nickel alloy electroplating additive to neutral, it is characterised in that according to parts by volume meter
Calculate, including chelating agent 60-90 parts, brightener 15-25 parts, walk agent 1-5 parts；The chelating agent in parts by weight, is consisted of：
Aspirin 5-10%, heterocyclic amine compound 30-50%, balance of water；The brightener in parts by weight, is constituted
For：Sulfonate 10-30%, diaminourea polymer 1-5%, balance of water；It is described to walk agent in parts by weight, consist of：
Maleic anhydride 4-8%, dispersant NNO 1-6%, nicotinic acid and its derivant 8-16%, balance of water.
2. a kind of faintly acid as claimed in claim 1 has high corrosion-resistant Zinc-nickel alloy electroplating additive, its feature to neutral
It is that the heterocyclic amine compound is caprolactam, azetidinone, imidazoles, one or more in 4- nitroimidazoles.
3. a kind of faintly acid as claimed in claim 1 has high corrosion-resistant Zinc-nickel alloy electroplating additive, its feature to neutral
It is that the sulfonate is sodium hydroxymethane sulfonate, methylol potassium sulfonate, propargyl sodium sulfonate, propargyl potassium sulfonate, pi-allyl sulphur
Sour sodium, allyl sulphonic acid potassium, ethoxy-c epoxide block compound sodium sulfonate, ethoxy-c epoxide block compound sodium sulfonate potassium
In one or more.
4. a kind of faintly acid as claimed in claim 1 has high corrosion-resistant Zinc-nickel alloy electroplating additive, its feature to neutral
It is that the nicotinic acid and its derivant are nicotinic acid, niacinamide usp, 2- chlorine apellagrins, one or more in methyl nicotinate.
5. a kind of faintly acid using as described in any one of claim 1-4 there is high corrosion-resistant Zinc-nickel alloy electroplating to add to neutral
Plus electroplate liquid prepared by agent, it is characterised in that consisting of：
Potassium chloride 150-220g/L；
Potassium acetate 35-70g/L；
Zinc chloride 50-75g/L；
Nickel dichloride. 55-80g/L；
Chelating agent：60–90ml/L；
Brightener：15-25ml/L；
Walk agent：1-5ml/L；
Remaining is water.
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| CN105002532A (en) * | 2015-08-21 | 2015-10-28 | 哈尔滨工业大学 | Low-bubble weak-acid chloride zinc-nickel alloy electroplate liquid |
| CN105063686A (en) * | 2015-08-31 | 2015-11-18 | 武汉吉和昌化工科技股份有限公司 | Auxiliary brightening agent for subacidity system electroplated bright zinc-nickel alloy and electroplating technology thereof |
| CN105970254A (en) * | 2016-06-24 | 2016-09-28 | 武汉吉和昌化工科技股份有限公司 | Electroplate liquid having acidic all-chloride system for electroplating bright zinc-nickel alloys and electroplating process thereof |
| CN107173349A (en) * | 2017-06-13 | 2017-09-19 | 超品贸易（上海）有限公司 | It is unleaded to fish pendant and preparation method thereof |
| CN110760907A (en) * | 2019-12-05 | 2020-02-07 | 佛山市南海高益美环保实业有限公司 | Alkaline cyanide-free electroplating zinc-nickel alloy additive and electroplating solution |
| CN111593378A (en) * | 2020-04-20 | 2020-08-28 | 常州新纪元材料科技有限公司 | Preparation of high corrosion-resistant alkaline zinc-nickel alloy electroplating solution and components of additive |
| CN111647916A (en) * | 2020-07-14 | 2020-09-11 | 华业金属表面处理(五莲)有限公司 | Production process of alkaline electrogalvanizing |
| CN114134544A (en) * | 2021-12-31 | 2022-03-04 | 三门峡毕昇制版科技股份有限公司 | Alkaline copper plating additive for electronic engraving printing gravure |
| 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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| US4388160A (en) * | 1980-02-20 | 1983-06-14 | Rynne George B | Zinc-nickel alloy electroplating process |
| CN101273157A (en) * | 2005-06-20 | 2008-09-24 | 百富可公司 | Zinc-nickel alloy electroplating system |
| HUE026918T2 (en) * | 2006-07-13 | 2016-07-28 | Enthone Incorporated | Electrolyte composition und process for the deposition of a zinc-nickel alloy layer on a cast iron or steel substrate |
| CN103806038A (en) * | 2012-11-12 | 2014-05-21 | 无锡三洲冷轧硅钢有限公司 | Preparation method for low-hydrogen fragile zinc-nickel alloy electroplated layer |
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