CN103451693B - A kind of alkaline zinc-nickel alloy pulse plating method of nickel stable content - Google Patents

A kind of alkaline zinc-nickel alloy pulse plating method of nickel stable content Download PDF

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CN103451693B
CN103451693B CN201310321460.XA CN201310321460A CN103451693B CN 103451693 B CN103451693 B CN 103451693B CN 201310321460 A CN201310321460 A CN 201310321460A CN 103451693 B CN103451693 B CN 103451693B
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nickel
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王玥
郭晓斐
孙焕喜
陈伟强
张龙龙
张志芳
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Shandong Jianzhu University
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Abstract

The invention belongs to electroplated zinc nickel alloy technical field, be specifically related to a kind of admiro pulse plating method of nickel stable content.The alkaline zinc-nickel alloy pulse plating method of nickel stable content of the present invention, comprises the following steps: (1) preparation Electroplate liquid of alkaline zinc-nickel alloy, (2) substrate pretreated, (3) pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath, (4) waste water reclamation and cleaning coating.Compared with direct current electrode position admiro, it is careful that pulse plating has coating crystallization, nickel stable content, and stress is low, porosity is low, the features such as excellent corrosion resistance, accomplishes alloy plating truly.

Description

A kind of alkaline zinc-nickel alloy pulse plating method of nickel stable content
Technical field
The invention belongs to electroplated zinc nickel alloy technical field, be specifically related to a kind of admiro pulse plating method of nickel stable content.
Background technology
Electroplated zinc nickel alloy is a kind of Anodic Type protective coating on steel substrate risen the eighties in 20th century.It typically refers to the low nickel content alloy of nickel content below 20%, not only solidity to corrosion is higher than zinc coating 7-10 doubly for this type of alloy layer, and there is low hydrogen embrittlement, good japanning, weldability and formability, be thus widely used in the steel protections such as automobile, space flight and aviation, light industry, household electrical appliances.Single with regard to adopting the automotive components of Zinc-nickel alloy electroplating layer, just in some American-European countries's schema, achieve stdn, more extensive in Japanese range of application.And China starts late, just have relevant research report the nineties in last century, put into production still thing in recent years, and constantly go wrong in process of production, and wherein in deposition layer, the control of nickel content is a large obstacle of restriction Zinc-nickel alloy electroplating development.
Current admiro sort of plating solution is mainly divided into acid and alkalescence two kinds of systems.
Acidic zinc-nickel alloy electroplating current efficiency is more than 90%, and coating deposition rate is fast, and can reach 1 μm/more than min, production run cost is low, the advantages such as bright in color.But the covering power of its plating solution is poor, thickness distribution is uneven, and in workpiece high and low current density district coating, nickel content difference is larger; In plating solution, composition transfer is large, and component need be analyzed at any time and adjust, especially the acidity of solution.Its Patent CN201110362502.5, namely CN200910094368.8, CN200680028815.4 relate to formula and the technique of Acidic zinc-nickel alloy plating, and form of power used is direct current.
It is good that Electrodeposition of Zn-ni Alloy In Alkaline Bath has covering power, and thickness of coating distribution is relatively uniform, and in very large current density range, alloy layer is relatively even, and technique such as easily to operate at the advantage.Along with the initial stage that this technique is using can ensure the homogeneous of different current density districts nickel content, but along with the continuous prolongation of production cycle, in alloy layer, nickel content presents downtrending, only have zinc in final settled layer, this is the subject matter that restriction Zinc-nickel alloy electroplating is able to sustainable development and heavy industrialization.For addressing this problem, study hotspot main at present concentrates on the optimization of alkali plating solution recipe ingredient, its Patent CN94100815.0, CN02142485.3, CN200510086235.8, CN200810120050.8, CN201010501430.3, namely CN201110424916.6, CN201210109208.8 relate to the formula of Electroplate liquid of alkaline zinc-nickel alloy, adopt technique to be direct current electrode position.
Compared with direct current electrode position, pulse plating has lot of advantages, by the adjustment of pulsewidth, cycle and dutycycle isopulse parameter, can obtain that porosity is low, crystallization is careful, low-stress, low hydrogen embrittlement and binding force of cladding material are good, the deposition layer of excellent corrosion resistance, pulse plating also can reduce concentration polarization simultaneously, improve the current density of negative electrode, thus reach the effect improving plating speed.Pulse plating early has application in precious metal, in recent years, also widely adopts in acid copper-plating, and reports very few in admiro electro-deposition techniques, also have no the patent report about admiro pulse plating.
Summary of the invention
Object of the present invention is exactly the advantage utilizing pulse plating techniques, provides the method for pulse plating admiro under a kind of alkaline system.Solve the problem of nickel content instability in coating, realize crystal grain thinning simultaneously, reduce coating stress, and improve the solidity to corrosion of coating.The method belongs to pulse plating field, adopts monopulse electroplating technology, realizes above-mentioned purpose by changing each processing parameter of pulse plating.
The present invention is realized by following technical scheme:
An alkaline zinc-nickel alloy pulse plating method for nickel stable content, comprises the following steps:
(1) Electroplate liquid of alkaline zinc-nickel alloy is prepared: the often liter of electroplate liquid that consists of of the Electroplate liquid of alkaline zinc-nickel alloy of preparation gained comprises: 10g zinc oxide, 80g sodium hydroxide, 15g nickel sulfate hexahydrate, 15ml quadrol, 10ml tetraethylene pentamine, 30g Seignette salt, 10g Trisodium Citrate, 40ml trolamine, 1.5 ml OP-10,0.5 g Vanillin;
(2) substrate pretreated: first carry out dip rust removal to matrix, then carries out electrolytic degreasing to matrix, until Ex-all; After oil removing completes, first use 50 ~ 60 DEG C of hot water cleanings, then clean with flowing pure water; Finally at room temperature carry out impregnating active with 3-5% hydrochloric acid soln to matrix, soak time is 30 ~ 60s, and through pure washing after having activated, pre-treatment completes;
(3) pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath: first add the Electroplate liquid of alkaline zinc-nickel alloy that step (1) is prepared in plating tank, then matrix good for pre-treatment is connected with the negative electrode of the pulse power, anode adopts stainless steel plate, entirety puts into plating tank again, carry out pulse alloy plating under room temperature, wherein pulsation process condition is: average current density 0.72 ~ 5.45A/dm 2, pulsewidth 100 ~ 1000 μ s, cycle 1000 ~ 9000 μ s;
(4) waste water reclamation and cleaning coating: carry out waste water reclamation to alkali plating solution after step (3) completes, distilled water cleaning coating, to obtain final product.
OP-10 is nonionogenic tenside, the one of alkylphenol polyoxyethylene.
The alkaline zinc-nickel alloy pulse plating method of above-mentioned nickel stable content, in described step (1), the concrete steps of preparation Electroplate liquid of alkaline zinc-nickel alloy are as follows: load weighted sodium hydroxide and zinc oxide are stirred first respectively, the distilled water adding plating solution cumulative volume 1/5 dissolves, and abundant stirring and dissolving, until solution clear, redilution is to 1/3 of cumulative volume, and this solution is No. 1 solution; Again by load weighted nickel sulfate hexahydrate and Seignette salt, Trisodium Citrate dissolves respectively, then mixes, abundant stirring, add load weighted quadrol again, tetraethylene pentamine and trolamine, be uniformly mixed, this solution is No. 2 solution, finally slowly add in No. 1 solution by No. 2 solution, limit edged stirs, then adds Vanillin, OP-10, until plating solution is even, transparent bluish voilet, dilution constant volume is stand-by to cumulative volume.
In the alkaline zinc-nickel alloy pulse plating method of above-mentioned nickel stable content, body material described in step (2) is not easily liberation of hydrogen parts, described dip rust removal step is, at temperature 30 ~ 40 DEG C, carry out etch rust cleaning with pickling agent, through 2 road cold water cleanings after rust Ex-all; Then carry out electrolytic degreasing to matrix, under temperature 70 ~ 80 DEG C of conditions, carry out oil removing with degreaser, current density is 5 ~ 10A/dm 2, anode and cathode oil removing time ratio is 20:1, until Ex-all.
Not easily liberation of hydrogen parts refer to that the metallographic structure of part is even, smooth surface, without greasy dirt, are easy to the parts imposing metal plating.Common not easily liberation of hydrogen parts are made up of high overpotential of hydrogen evolution metal (as Pb, Cd, Zn, Sn) or usually as the component of upper layer, the iron and steel parts be made up of soft steel and low alloy steel forms for steel relative to other, can think not easily liberation of hydrogen parts.
The alkaline zinc-nickel alloy pulse plating method of above-mentioned nickel stable content, body material described in step (2) is easy liberation of hydrogen parts, described dip rust removal step is, at temperature 30 ~ 40 DEG C, carry out etch rust cleaning with pickling agent, through 2 road cold water cleanings after rust Ex-all; Then carry out electrolytic degreasing to matrix, under temperature 70 ~ 80 DEG C of conditions, carry out oil removing with degreaser, current density is 5 ~ 10A/dm 2, only carry out anode oil removing, until Ex-all.
Easy liberation of hydrogen parts refer to that there are the parts of greasy dirt on the large or surface of part metallographic structure inequality, surface irregularity, stress, as spring steel (high carbon steel), high quality steel, weldment, riveting parts, cast iron, thin-wall part etc.
In the alkaline zinc-nickel alloy pulse plating method of above-mentioned nickel stable content, described in step (2), pickling agent comprises the hydrochloric acid soln that mass concentration is 15% ~ 20%, 0.5 ~ 5g/L urotropine.
In the alkaline zinc-nickel alloy pulse plating method of above-mentioned nickel stable content, described in step (2), degreaser comprises sodium hydroxide 20g for often liter of degreaser, sodium carbonate 20g, sodium phosphate 20g, water glass 3g, and surplus is water.
Preferably, in the alkaline zinc-nickel alloy pulse plating method of above-mentioned nickel stable content, the pulsation process condition in step (3) is: average current density 1 ~ 3A/dm 2, pulsewidth 100 ~ 500 μ s, cycle 1000 μ s ~ 5000 μ s.
Preferred, in the alkaline zinc-nickel alloy pulse plating method of above-mentioned nickel stable content, the pulsation process condition in step (3) is: average current density 2 ~ 2.5A/dm 2, pulsewidth 100 ~ 300 μ s, cycle 1000 μ s ~ 3000 μ s.
The invention has the beneficial effects as follows: compared with direct current electrode position admiro, it is careful that pulse plating has coating crystallization, nickel stable content, stress is low, porosity is low, the features such as excellent corrosion resistance, accomplish alloy plating truly, for the industrial sustainable development of Zinc-nickel alloy electroplating provides technical support.
Specific experiment Comparative result below by pulse plating method of the present invention and direct current electrode position method is described in detail.
When the pulsation process condition adopting Zinc-nickel alloy electroplating method of the present invention is average current density 2.5A/dm 2, pulsewidth 100 μ s, cycle 1000 μ s, under the alloy layer obtained after cold galvanising 10min and DC condition, cathode current density is 2.5A/dm 2, cold galvanising 10min gained alloy layer is compared as follows shown in table 1.
Table 1: Comparative result
Project Mean porosities (individual/cm 2) Binding force of cladding material Microscopic appearance Corrosion potential (V)
Pulse plating 0 Meet the requirements Crystal grain is tiny, evenly -0.765
Direct current electrode position 11 Slight peeling Crystal grain is comparatively large, has crackle -0.816
Under pulse and direct current electrode position, the scanning electron microscope diagram sheet of Zinc-nickel alloy electroplating layer is as shown in Figure 1-2, and wherein Fig. 1 is pulsed electrical coating surface SEM pattern, Fig. 2 is direct current coating surface SEM pattern,
By Fig. 1 and Fig. 2 compare can obtain impulsive condition under the crystallization that obtains more tiny, crystallization is evenly distributed, flawless, and this is the major cause that its solidity to corrosion is strengthened.And the coating crystal grain obtained under DC condition is thicker, distribution is also even relatively not, has obvious crack and transgranular fracture, and illustrate that the coating stress under direct current electrode position is larger, this is the reason causing its solidity to corrosion to decline.
The alkaline zinc-nickel alloy pulse plating method of a kind of nickel stable content of the present invention, belong to Zinc-nickel alloy electroplating, the present invention changes Traditional DC electric plating method, adopting monopulse technology to realize the codeposition of admiro, is that the series of parameters by changing the pulse power obtains the zn-ni alloy deposits that bonding force is good, low-stress, porosity are low, crystallization is careful.Replace direct current plating method with pulsive electroplating, in raising coating performance, there is obvious advantage.
Accompanying drawing explanation
Fig. 1 is zn-ni alloy deposits surface topography under a scanning electron microscope in the specific embodiment of the invention;
Fig. 2 is the zn-ni alloy deposits surface topography under a scanning electron microscope of direct current electrode position.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, so that those skilled in the art more understands the present invention, but does not therefore limit the present invention.
Embodiment 1
(1) Electroplate liquid of alkaline zinc-nickel alloy is prepared: 10g zinc oxide will be taken first respectively, 80g sodium hydroxide, 15g nickel sulfate hexahydrate, 15ml quadrol, 10ml tetraethylene pentamine, 30g Seignette salt, 10g Trisodium Citrate, 40ml trolamine, 1.5 ml nonionogenic tensides, 0.5 g Vanillin.The sodium hydroxide taken and zinc oxide are stirred, the distilled water adding plating solution cumulative volume 1/5 dissolves, and abundant stirring and dissolving, until solution clear, redilution is to 1/3 of cumulative volume, and this solution is No. 1 solution; Again by load weighted nickel sulfate hexahydrate and Seignette salt, Trisodium Citrate dissolves respectively, then mixes, abundant stirring, add load weighted quadrol again, tetraethylene pentamine and trolamine, be uniformly mixed, this solution is No. 2 solution, finally slowly add in No. 1 solution by No. 2 solution, limit edged stirs, then adds Vanillin, non-ionic surfactant OP-10, until plating solution is even, transparent bluish voilet, dilution constant volume is stand-by to cumulative volume;
(2) substrate pretreated: body material is soft steel, first carry out dip rust removal to matrix, at temperature 30 ~ 40 DEG C, carry out etch rust cleaning with pickling agent, pickling agent used comprises 20%(massfraction) hydrochloric acid soln, 0.5g/L urotropine, through 2 road cold water cleanings after rust Ex-all; Then carry out electrolytic degreasing to matrix, under temperature 70 ~ 80 DEG C of conditions, carry out oil removing with degreaser, degreaser used comprises sodium hydroxide 20g for often liter of degreaser, sodium carbonate 20g, sodium phosphate 20g, water glass 3g, and current density is 5 ~ 10A/dm 2, the anode and cathode oil removing time, than being 20:1, until Ex-all, first being used 50 ~ 60 DEG C of hot water cleanings, then cleans with flowing pure water after oil removing completes; Finally at room temperature use 3%(massfraction) hydrochloric acid soln carries out impregnating active to matrix, and soak time is 30 ~ 60s, has activated after washing, and pre-treatment completes;
(3) pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath: first add the alkaline electrolyte that step (1) is prepared in plating tank, is then connected matrix good for pre-treatment with the negative electrode of the pulse power, and anode adopts stainless steel plate.Entirety puts into plating tank again, carries out pulse alloy plating under room temperature.Wherein pulsation process condition is: average current density 2.5A/dm 2, pulsewidth 100 μ s, cycle 1000 μ s, plating 10min.
(4) waste water reclamation and cleaning coating: carry out waste water reclamation to alkali plating solution after step (3) completes, distilled water cleaning coating, to obtain final product.
Embodiment 2
(1) Electroplate liquid of alkaline zinc-nickel alloy is prepared: 10g zinc oxide will be taken first respectively, 80g sodium hydroxide, 15g nickel sulfate hexahydrate, 15ml quadrol, 10ml tetraethylene pentamine, 30g Seignette salt, 10g Trisodium Citrate, 40ml trolamine, 1.5 ml nonionogenic tensides, 0.5 g Vanillin.The sodium hydroxide taken and zinc oxide are stirred, the distilled water adding plating solution cumulative volume 1/5 dissolves, and abundant stirring and dissolving, until solution clear, redilution is to 1/3 of cumulative volume, and this solution is No. 1 solution; Again by load weighted nickel sulfate hexahydrate and Seignette salt, Trisodium Citrate dissolves respectively, then mixes, abundant stirring, add load weighted quadrol again, tetraethylene pentamine and trolamine, be uniformly mixed, this solution is No. 2 solution, finally slowly add in No. 1 solution by No. 2 solution, limit edged stirs, then adds Vanillin, non-ionic surfactant OP-10, until plating solution is even, transparent bluish voilet, dilution constant volume is stand-by to cumulative volume;
(2) substrate pretreated: body material is spring steel, first carry out dip rust removal to matrix, at temperature 30 ~ 40 DEG C, carry out etch rust cleaning with pickling agent, pickling agent used comprises 15%(massfraction) hydrochloric acid soln, 5g/L urotropine, through 2 road cold water cleanings after rust Ex-all; Then carry out electrolytic degreasing to matrix, under temperature 70 ~ 80 DEG C of conditions, carry out oil removing with degreaser, degreaser used comprises sodium hydroxide 20g for often liter of degreaser, sodium carbonate 20g, sodium phosphate 20g, water glass 3g, and current density is 5 ~ 10A/dm 2, only carry out anode oil removing, until Ex-all, after oil removing completes, first use 50 ~ 60 DEG C of hot water cleanings, then clean with flowing pure water; Finally at room temperature use 5%(massfraction) hydrochloric acid soln carries out impregnating active to matrix, and soak time is 30 ~ 60s, has activated after washing, and pre-treatment completes;
(3) pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath: first add the alkaline electrolyte that step (1) is prepared in plating tank, is then connected matrix good for pre-treatment with the negative electrode of the pulse power, and anode adopts stainless steel plate.Entirety puts into plating tank again, carries out pulse alloy plating under room temperature.Wherein pulsation process condition is: average current density 2A/dm 2, pulsewidth 100 μ s, cycle 1000 μ s, plating 15min;
(4) waste water reclamation and cleaning coating: carry out waste water reclamation to alkali plating solution after step (3) completes, distilled water cleaning coating, to obtain final product.
Embodiment 3
(1) Electroplate liquid of alkaline zinc-nickel alloy is prepared: 10g zinc oxide will be taken first respectively, 80g sodium hydroxide, 15g nickel sulfate hexahydrate, 15ml quadrol, 10ml tetraethylene pentamine, 30g Seignette salt, 10g Trisodium Citrate, 40ml trolamine, 1.5 ml nonionogenic tensides, 0.5 g Vanillin.The sodium hydroxide taken and zinc oxide are stirred, the distilled water adding plating solution cumulative volume 1/5 dissolves, and abundant stirring and dissolving, until solution clear, redilution is to 1/3 of cumulative volume, and this solution is No. 1 solution; Again by load weighted nickel sulfate hexahydrate and Seignette salt, Trisodium Citrate dissolves respectively, then mixes, abundant stirring, add load weighted quadrol again, tetraethylene pentamine and trolamine, be uniformly mixed, this solution is No. 2 solution, finally slowly add in No. 1 solution by No. 2 solution, limit edged stirs, then adds Vanillin, non-ionic surfactant OP-10, until plating solution is even, transparent bluish voilet, dilution constant volume is stand-by to cumulative volume;
(2) substrate pretreated: body material is thin-wall part, first carry out dip rust removal to matrix, at temperature 30 ~ 40 DEG C, carry out etch rust cleaning with pickling agent, pickling agent used comprises 18%(massfraction) hydrochloric acid soln, 2.5g/L urotropine, through 2 road cold water cleanings after rust Ex-all; Then carry out electrolytic degreasing to matrix, under temperature 70 ~ 80 DEG C of conditions, carry out oil removing with degreaser, degreaser used comprises sodium hydroxide 20g for often liter of degreaser, sodium carbonate 20g, sodium phosphate 20g, water glass 3g, and current density is 5 ~ 10A/dm 2, only carry out anode oil removing, until Ex-all, first with hot water cleaning after oil removing completes, then clean with flowing pure water; Finally at room temperature use 4%(massfraction) hydrochloric acid soln carries out impregnating active to matrix, and soak time is 30 ~ 60s, has activated after washing, and pre-treatment completes;
(3) pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath: first add the alkaline electrolyte that step (1) is prepared in plating tank, is then connected matrix good for pre-treatment with the negative electrode of the pulse power, and anode adopts stainless steel plate.Entirety puts into plating tank again, carries out pulse alloy plating under room temperature.Wherein pulsation process condition is: average current density 2.5A/dm 2, pulsewidth 200 μ s, cycle 2000 μ s, plating 10min;
(4) waste water reclamation and cleaning coating: carry out waste water reclamation to alkali plating solution after step (3) completes, distilled water cleaning coating, to obtain final product.
Embodiment 4
Pulsation process condition in step pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath is: average current density 2A/dm 2, pulsewidth 200 μ s, cycle 2000 μ s, plating 15min.Other steps are identical with embodiment 1.
Embodiment 5
Pulsation process condition in step pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath is: average current density 2.5A/dm 2, pulsewidth 300 μ s, cycle 3000 μ s, plating 10min.Other steps are identical with embodiment 1.
Embodiment 6
Pulsation process condition in step pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath is: average current density 2A/dm 2, pulsewidth 300 μ s, cycle 3000 μ s, plating 15min.Other steps are identical with embodiment 1.
Embodiment 7
Pulsation process condition in step pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath is: average current density 0.7A/dm 2, pulsewidth 1000 μ s, cycle 9000 μ s, plating 15min.Other steps are identical with embodiment 1.
Embodiment 8
Pulsation process condition in step pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath is: average current density 5A/dm 2, pulsewidth 100 μ s, cycle 1000 μ s, plating 15min.Other steps are identical with embodiment 1.
Embodiment 9
Pulsation process condition in step pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath is: average current density 3A/dm 2, pulsewidth 500 μ s, cycle 5000 μ s, plating 15min.Other steps are identical with embodiment 1.
Embodiment 10
Pulsation process condition in step pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath is: average current density 4A/dm 2, pulsewidth 700 μ s, cycle 7000 μ s, plating 15min.Other steps are identical with embodiment 1.
Aforesaid method changes the structure of coating, makes coating level and smooth, careful, bright; Reduce porosity and the stress of coating, realize the stable of nickel content.
Although above-mentioned, the specific embodiment of the present invention is described; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.

Claims (3)

1. an alkaline zinc-nickel alloy pulse plating method for nickel stable content, comprises the following steps:
(1) Electroplate liquid of alkaline zinc-nickel alloy is prepared: the often liter of electroplate liquid that consists of of the Electroplate liquid of alkaline zinc-nickel alloy of preparation gained comprises: 10g zinc oxide, 80g sodium hydroxide, 15g nickel sulfate hexahydrate, 15ml quadrol, 10ml tetraethylene pentamine, 30g Seignette salt, 10g Trisodium Citrate, 40ml trolamine, 1.5 ml OP-10,0.5 g Vanillin;
(2) substrate pretreated: first carry out dip rust removal to matrix, then carries out electrolytic degreasing to matrix, until Ex-all; After oil removing completes, first use 50 ~ 60 DEG C of hot water cleanings, then clean with flowing pure water; Last is at room temperature that 3-5% hydrochloric acid soln carries out impregnating active to matrix with mass percent concentration, and soak time is 30 ~ 60s, and through pure washing after having activated, pre-treatment completes;
(3) pulse Electrodeposition of Zn-ni Alloy In Alkaline Bath: first add the Electroplate liquid of alkaline zinc-nickel alloy that step (1) is prepared in plating tank, then matrix good for pre-treatment is connected with the negative electrode of the pulse power, anode adopts stainless steel plate, entirety puts into plating tank again, carry out pulse alloy plating under room temperature, wherein pulsation process condition is: average current density 0.72 ~ 5.45A/dm 2, pulsewidth 100 ~ 1000 μ s, cycle 1000 ~ 9000 μ s;
(4) waste water reclamation and cleaning coating: carry out waste water reclamation to alkali plating solution after step (3) completes, distilled water cleaning coating, to obtain final product.
2. the alkaline zinc-nickel alloy pulse plating method of nickel stable content according to claim 1, it is characterized in that, in described step (1), the concrete steps of preparation Electroplate liquid of alkaline zinc-nickel alloy are as follows: load weighted sodium hydroxide and zinc oxide are stirred first respectively, the distilled water adding plating solution cumulative volume 1/5 dissolves, and abundant stirring and dissolving, until solution clear, redilution is to 1/3 of cumulative volume, and this solution is No. 1 solution; Again by load weighted nickel sulfate hexahydrate and Seignette salt, Trisodium Citrate dissolves respectively, then mixes, abundant stirring, add load weighted quadrol again, tetraethylene pentamine and trolamine, be uniformly mixed, this solution is No. 2 solution, finally slowly add in No. 1 solution by No. 2 solution, limit edged stirs, then adds Vanillin, OP-10, until plating solution is even, transparent bluish voilet, dilution constant volume is stand-by to cumulative volume.
3. the alkaline zinc-nickel alloy pulse plating method of nickel stable content according to claim 1, is characterized in that, the pulsation process condition in step (3) is: average current density 1 ~ 3A/dm 2, pulsewidth 100 ~ 500 μ s, cycle 1000 μ s ~ 5000 μ s.
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