CN106835087A - A kind of magnesium alloy surface chemical nickel plating method - Google Patents
A kind of magnesium alloy surface chemical nickel plating method Download PDFInfo
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- CN106835087A CN106835087A CN201611136546.5A CN201611136546A CN106835087A CN 106835087 A CN106835087 A CN 106835087A CN 201611136546 A CN201611136546 A CN 201611136546A CN 106835087 A CN106835087 A CN 106835087A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
Abstract
The invention discloses a kind of magnesium alloy surface chemical nickel plating method, comprise the following steps：Ultrasonic wave is cleaned；Alkali cleaning；Acid-wash activation：Using two step activation methods；Prepare plating solution：Nickel sulfate, sodium hypophosphite, sodium acetate, ammonium acetate and deionized water are mixed into solid dissolving, then hydrofluoric acid is eventually adding and is uniformly mixed to ammoniacal liquor is added dropwise in solution with the speed of 1 2ml/min, chemical plating fluid is obtained；Then AZ91D magnesium alloys are put into chemical plating fluid and are processed；Waste liquid after finally chemical nickel plating is processed carries out wastewater treatment and reclaims metallic nickel.The method can effectively improve the adhesion of coating and matrix, and nickel coating corrosion resistance is good, and mechanical performance is excellent, and heat endurance is good, and effectively reduce harm of the nickel-plating waste water to environment.
Description
Technical field：
The present invention relates to technical field of surface, a kind of magnesium alloy surface chemical nickel plating method is specifically related to.
Background technology：
Magnesium alloy has a specific strength and specific stiffness very high, good thermal conductivity, electric conductivity, damping vibration attenuation, electromagnetic shielding,
Be easily worked shaping and beneficial to reclaim the advantages of, have boundless application preceding in fields such as automobile, electronics, space flight and national defence
Scape.But, the chemism of magnesium alloy is high, and loose porous oxide-film, oxide film protection magnesium are easily oxidized to form in atmosphere
The ability of alloy is poor, therefore, the corrosion resisting property and anti-wear performance of magnesium alloy are very poor.Surface to magnesium alloy carries out certain change
And physical method treatment are the most direct, most efficient methods of corrosion resistance and the anti-wear performance difference for solving magnesium alloy.Contrast it
Its magnesium alloy surface treatment, chemical nickel plating has that thickness of coating is uniform, adhesion is good, the low advantage of porosity, very
It is multi-field to be widely used.
Chemical nickel plating is, by the use of nickel salt and hypophosphite as reducing agent, to be gone back by the autocatalysis and oxidation of metal
Original reaction, the technique that deposition obtains the alloy layers such as Ni-P.The chemical nickel plating of magnesium alloy mainly has pre-plating layer method and directly chemistry
Two methods of nickel plating.And chemical nickel plating has following characteristics：1. the coating for obtaining has the characteristics of fine and close, corrosion resistance is good, its coating
Performance is much better than electroless nickel layer；2. the hardness of chemical deposit is very high, and it is hard further to improve its by the heat treatment in later stage
Degree.So the wearability of chemical Ni-plating layer is very well, can be used instead of hard chrome in some cases；3. high temperature resistant, low resistance, pricker
Weldering performance is good；4. strong adaptability.Can uniformly be plated having on the part of the complicated shapes such as blind hole, deep hole, pipe fitting, turning
Layer, this point is also superior to plating.So, the applied chemistry coating technology on magnesium alloy can make magnesium alloy obtain range of application more
Extensively, and extend the service life of magnesium alloy, make to obtain preferably playing still with the performance characteristics of magnesium alloy, existing magnesium
The chemical plating nickel technology of alloy is generally chemical nickel plating again after middle preplating, and technique is cumbersome, is unfavorable for industrially using.On the other hand
The liquid waste processing of chemical nickel plating is more difficult, processes halfway words severe contamination environment.
The content of the invention：
In order to solve the above-mentioned technical problem, the invention provides a kind of magnesium alloy surface chemical nickel plating method, party's legal system
With basal body binding force firmly, corrosion resisting property is good, and mechanical performance is excellent for the nickel dam for obtaining, and heat endurance and electric conductivity are also preferable, and
Pollution problem of the chemical nickel-plating liquid to environment is this method solve, the good recovery of nickel is realized from waste liquid, it is cost-effective.
In order to preferably solve above-mentioned technical problem, the present invention uses following technical scheme：
A kind of magnesium alloy surface chemical nickel plating method, comprises the following steps：
(1) ultrasonic wave cleaning：AZ91D magnesium alloys are immersed in acetone soln, under 400-800W power, room temperature cleaning
5-15min, is then cleaned up with deionized water；
(2) alkali cleaning：NaOH, sodium phosphate and deionized water are well mixed, soda-wash solution is obtained, will be by ultrasonic wave
AZ91D magnesium alloys after cleaning are immersed in soda-wash solution, and 10-20min is cleaned at 60-70 DEG C；Then it is clear with deionized water
Wash clean；
(3) acid-wash activation：AZ91D magnesium alloys after alkali cleaning is processed are immersed in the mixed solution of phosphoric acid and nitric acid,
1-2min is processed at room temperature, is then cleaned up with deionized water；Then by the AZ91D magnesium alloys after pickling in phosphoric acid solution
Activation process 3-7min, taking-up is cleaned up with deionized water, then the activation process 2-5min in ammonium hydrogen fluoride solution, then
Dried after being cleaned up with deionized water, it is stand-by；
(4) plating solution is prepared：Nickel sulfate, sodium hypophosphite, sodium acetate, ammonium acetate and deionized water are mixed into solid
Dissolving, is then eventually adding hydrofluoric acid and is uniformly mixed with the speed of 1-2ml/min to ammoniacal liquor is added dropwise in solution, preparedization
Plating solution is learned, its pH is 4.5-5.5；
(5) will be put into chemical plating fluid obtained in step (4) by the AZ91D magnesium alloys after step (3) treatment, 85-95
1-2h is processed at DEG C, then AZ91D deionized waters used for magnesium alloy is cleaned up, dried, nickel plating is completed；
(6) waste liquid in nickel process is collected, the pH value of chemical nickel plating waste solution is then adjusted to 4-6, by compound extraction
Agent is taken after diluting dilution agent, counter-current extraction is carried out to above-mentioned chemical nickel plating waste solution, obtain rich nickel organic phase；
(7) by above-mentioned rich nickel organic phase stripped with mineral acid, organic phase and inorganic phase are obtained, will be compound in organic phase
Extractant is recycled, and water is through being concentrated by evaporation, crystallizing, centrifugal dehydration, obtains metallic nickel.
Used as the preferred of above-mentioned technical proposal, in step (2), the NaOH, the concentration of sodium phosphate are respectively：15-
30g/L、10-22g/L。
As the preferred of above-mentioned technical proposal, in the mixed solution of step (3) phosphoric acid and nitric acid, the concentration of phosphoric acid and nitric acid
Respectively：100-200ml/L、20-50ml/L.
Used as the preferred of above-mentioned technical proposal, in step (3) described phosphoric acid solution, the concentration of phosphoric acid is 120-160ml/L.
Used as the preferred of above-mentioned technical proposal, in step (3) described ammonium hydrogen fluoride solution, the concentration of ammonium acid fluoride is 50-
80g/L。
Used as the preferred of above-mentioned technical proposal, in step (4), in the chemical plating fluid, the concentration of each component is：Nickel sulfate
14-21g/L, sodium hypophosphite 15-20g/L, sodium acetate 10-20mg/L, ammonium acetate 20-25mg/L, ammoniacal liquor 20-28ml/L, hydrogen
Fluoric acid 10-15ml/L.
Used as the preferred of above-mentioned technical proposal, in step (6), the composite extractant is by organo phosphoric extractant and aldehyde
Oximes extractant constitute, wherein, organic extractant be P204, P507 and C272, the aldoxime kind of extractants be lix63 and
The volume ratio of N902, organic extractant and aldoxime kind of extractants is (1-5)：1.
Used as the preferred of above-mentioned technical proposal, in step (6), the diluent is in sulfonated kerosene, aviation kerosine
Kind, the percent by volume of organo phosphoric extractant is 20-50% after dilution.
Used as the preferred of above-mentioned technical proposal, in step (7), the inorganic acid is the sulfuric acid or hydrochloric acid of 0.5-4mol/L.
Compared with prior art, the invention has the advantages that：
The present invention processes magnesium by rationally control pickling, the formula of alkali cleaning treatment fluid using the method for re-activation
Alloy, effectively increases the adhesion of coating and matrix；
The present invention adds sodium acetate and ammonium acetate as buffer in chemical plating fluid, and rationally controls the consumption of the two,
Effectively improve the stability of plating solution, obtained coating good mechanical property, excellent anti-corrosion performance；
The present invention is rationally processed the waste liquid in nickel process, and reclaim nickel, to environment non-secondary pollution, nothing
The new three wastes are produced, low cost.
Specific embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solution
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of magnesium alloy surface chemical nickel plating method, comprises the following steps：
(1) ultrasonic wave cleaning：AZ91D magnesium alloys are immersed in acetone soln, under 400W power, room temperature cleaning
5min, is then cleaned up with deionized water；
(2) alkali cleaning：NaOH, sodium phosphate and deionized water are well mixed, soda-wash solution is obtained, wherein, hydroxide
Sodium, the concentration of sodium phosphate are respectively：15g/L, 10g/L, are immersed in alkali cleaning molten by the AZ91D magnesium alloys after ultrasonic wave is cleaned
In liquid, 10min is cleaned at 60-70 DEG C；Then cleaned up with deionized water；
(3) acid-wash activation：AZ91D magnesium alloys after alkali cleaning is processed are immersed in the mixed solution of phosphoric acid and nitric acid,
1-2min is processed at room temperature, and the wherein concentration of phosphoric acid is 100ml/L, and the concentration of nitric acid is 20ml/L, then clear with deionized water
Wash clean；Then by the AZ91D magnesium alloys after pickling in the phosphoric acid solution of 120ml/L activation process 3min, taking-up spend from
Sub- water is cleaned up, then the activation process 2min in the ammonium hydrogen fluoride solution of 50g/L, after then being cleaned up with deionized water
Dry, it is stand-by；
(4) plating solution is prepared：Nickel sulfate, sodium hypophosphite, sodium acetate, ammonium acetate and deionized water are mixed into solid
Dissolving, is then eventually adding hydrofluoric acid and is uniformly mixed with the speed of 1ml/min to ammoniacal liquor is added dropwise in solution, and chemistry is obtained
Plating solution, its pH is 4.5-5.5；Wherein, the concentration of each component is respectively in chemical plating fluid：Nickel sulfate 14g/L, sodium hypophosphite
15g/L, sodium acetate 10mg/L, ammonium acetate 20mg/L, ammoniacal liquor 20ml/L, hydrofluoric acid 10ml/L；
(5) will be put into chemical plating fluid obtained in step (4) by the AZ91D magnesium alloys after step (3) treatment, 85-95
1h is processed at DEG C, then AZ91D deionized waters used for magnesium alloy is cleaned up, dried, nickel plating is completed；
(6) waste liquid in nickel process is collected, the pH value of chemical nickel plating waste solution is then adjusted to 4-6, by organophosphor
After the sulfonated kerosene cutback of composite extractant of acid extraction agent and aldoxime kind of extractants composition, above-mentioned chemical nickel plating waste solution is carried out
Counter-current extraction, obtains rich nickel organic phase；Wherein, the volume ratio of organo phosphoric extractant and aldoxime kind of extractants is 1：1, after dilution
The percent by volume of organo phosphoric extractant is 20%；
(7) above-mentioned rich nickel organic phase is stripped with the sulfuric acid of 0.5mol/L, organic phase and inorganic phase is obtained, by organic phase
In composite extractant recycle, water through be concentrated by evaporation, crystallization, centrifugal dehydration, obtain metallic nickel.
Embodiment 2
A kind of magnesium alloy surface chemical nickel plating method, comprises the following steps：
(1) ultrasonic wave cleaning：AZ91D magnesium alloys are immersed in acetone soln, under 500W power, room temperature cleaning
7min, is then cleaned up with deionized water；
(2) alkali cleaning：NaOH, sodium phosphate and deionized water are well mixed, soda-wash solution is obtained, wherein, hydroxide
Sodium, the concentration of sodium phosphate are respectively：18g/L, 14g/L, are immersed in alkali cleaning molten by the AZ91D magnesium alloys after ultrasonic wave is cleaned
In liquid, 13min is cleaned at 60-70 DEG C；Then cleaned up with deionized water；
(3) acid-wash activation：AZ91D magnesium alloys after alkali cleaning is processed are immersed in the mixed solution of phosphoric acid and nitric acid,
1-2min is processed at room temperature, and the wherein concentration of phosphoric acid is 120ml/L, and the concentration of nitric acid is 30ml/L, then clear with deionized water
Wash clean；Then by the AZ91D magnesium alloys after pickling in the phosphoric acid solution of 130ml/L activation process 4min, taking-up spend from
Sub- water is cleaned up, then the activation process 3min in the ammonium hydrogen fluoride solution of 60g/L, after then being cleaned up with deionized water
Dry, it is stand-by；
(4) plating solution is prepared：Nickel sulfate, sodium hypophosphite, sodium acetate, ammonium acetate and deionized water are mixed into solid
Dissolving, is then eventually adding hydrofluoric acid and is uniformly mixed with the speed of 1.2ml/min to ammoniacal liquor is added dropwise in solution, preparedization
Plating solution is learned, its pH is 4.5-5.5；Wherein, the concentration of each component is respectively in chemical plating fluid：Nickel sulfate 17g/L, sodium hypophosphite
16g/L, sodium acetate 12mg/L, ammonium acetate 21mg/L, ammoniacal liquor 22ml/L, hydrofluoric acid 11ml/L；
(5) will be put into chemical plating fluid obtained in step (4) by the AZ91D magnesium alloys after step (3) treatment, 85-95
1.2h is processed at DEG C, then AZ91D deionized waters used for magnesium alloy is cleaned up, dried, nickel plating is completed；
(6) waste liquid in nickel process is collected, the pH value of chemical nickel plating waste solution is then adjusted to 4-6, by organophosphor
After the sulfonated kerosene cutback of composite extractant of acid extraction agent and aldoxime kind of extractants composition, above-mentioned chemical nickel plating waste solution is carried out
Counter-current extraction, obtains rich nickel organic phase；Wherein, the volume ratio of organo phosphoric extractant and aldoxime kind of extractants is 2：1, after dilution
The percent by volume of organo phosphoric extractant is 30%；
(7) above-mentioned rich nickel organic phase is stripped with the sulfuric acid of 1.5mol/L, organic phase and inorganic phase is obtained, by organic phase
In composite extractant recycle, water through be concentrated by evaporation, crystallization, centrifugal dehydration, obtain metallic nickel.
Embodiment 3
A kind of magnesium alloy surface chemical nickel plating method, comprises the following steps：
(1) ultrasonic wave cleaning：AZ91D magnesium alloys are immersed in acetone soln, under 600W power, room temperature cleaning
9min, is then cleaned up with deionized water；
(2) alkali cleaning：NaOH, sodium phosphate and deionized water are well mixed, soda-wash solution is obtained, wherein, hydroxide
Sodium, the concentration of sodium phosphate are respectively：18g/L, 16g/L, are immersed in alkali cleaning molten by the AZ91D magnesium alloys after ultrasonic wave is cleaned
In liquid, 15min is cleaned at 60-70 DEG C；Then cleaned up with deionized water；
(3) acid-wash activation：AZ91D magnesium alloys after alkali cleaning is processed are immersed in the mixed solution of phosphoric acid and nitric acid,
1-2min is processed at room temperature, and the wherein concentration of phosphoric acid is 140ml/L, and the concentration of nitric acid is 35ml/L, then clear with deionized water
Wash clean；Then by the AZ91D magnesium alloys after pickling in the phosphoric acid solution of 140ml/L activation process 5min, taking-up spend from
Sub- water is cleaned up, then the activation process 3min in the ammonium hydrogen fluoride solution of 65g/L, after then being cleaned up with deionized water
Dry, it is stand-by；
(4) plating solution is prepared：Nickel sulfate, sodium hypophosphite, sodium acetate, ammonium acetate and deionized water are mixed into solid
Dissolving, is then eventually adding hydrofluoric acid and is uniformly mixed with the speed of 1.4ml/min to ammoniacal liquor is added dropwise in solution, preparedization
Plating solution is learned, its pH is 4.5-5.5；Wherein, the concentration of each component is respectively in chemical plating fluid：Nickel sulfate 17/L, sodium hypophosphite
17g/L, sodium acetate 14mg/L, ammonium acetate 22mg/L, ammoniacal liquor 24ml/L, hydrofluoric acid 12ml/L；
(5) will be put into chemical plating fluid obtained in step (4) by the AZ91D magnesium alloys after step (3) treatment, 85-95
1.4h is processed at DEG C, then AZ91D deionized waters used for magnesium alloy is cleaned up, dried, nickel plating is completed；
(6) waste liquid in nickel process is collected, the pH value of chemical nickel plating waste solution is then adjusted to 4-6, by organophosphor
After the sulfonated kerosene cutback of composite extractant of acid extraction agent and aldoxime kind of extractants composition, above-mentioned chemical nickel plating waste solution is carried out
Counter-current extraction, obtains rich nickel organic phase；Wherein, the volume ratio of organo phosphoric extractant and aldoxime kind of extractants is 3：1, after dilution
The percent by volume of organo phosphoric extractant is 20-50%；
(7) above-mentioned rich nickel organic phase is stripped with the hydrochloric acid of 2.5mol/L, organic phase and inorganic phase is obtained, by organic phase
In composite extractant recycle, water through be concentrated by evaporation, crystallization, centrifugal dehydration, obtain metallic nickel.
Embodiment 4
A kind of magnesium alloy surface chemical nickel plating method, comprises the following steps：
(1) ultrasonic wave cleaning：AZ91D magnesium alloys are immersed in acetone soln, under 700W power, room temperature cleaning
10min, is then cleaned up with deionized water；
(2) alkali cleaning：NaOH, sodium phosphate and deionized water are well mixed, soda-wash solution is obtained, wherein, hydroxide
Sodium, the concentration of sodium phosphate are respectively：25g/L, 18g/L, are immersed in alkali cleaning molten by the AZ91D magnesium alloys after ultrasonic wave is cleaned
In liquid, 15min is cleaned at 60-70 DEG C；Then cleaned up with deionized water；
(3) acid-wash activation：AZ91D magnesium alloys after alkali cleaning is processed are immersed in the mixed solution of phosphoric acid and nitric acid,
1-2min is processed at room temperature, and the wherein concentration of phosphoric acid is 160ml/L, and the concentration of nitric acid is 40ml/L, then clear with deionized water
Wash clean；Then by the AZ91D magnesium alloys after pickling in the phosphoric acid solution of 150ml/L activation process 6min, taking-up spend from
Sub- water is cleaned up, then the activation process 4min in the ammonium hydrogen fluoride solution of 70g/L, after then being cleaned up with deionized water
Dry, it is stand-by；
(4) plating solution is prepared：Nickel sulfate, sodium hypophosphite, sodium acetate, ammonium acetate and deionized water are mixed into solid
Dissolving, is then eventually adding hydrofluoric acid and is uniformly mixed with the speed of 1.7ml/min to ammoniacal liquor is added dropwise in solution, preparedization
Plating solution is learned, its pH is 4.5-5.5；Wherein, the concentration of each component is respectively in chemical plating fluid：Nickel sulfate 19g/L, sodium hypophosphite
18g/L, sodium acetate 16mg/L, ammonium acetate 23mg/L, ammoniacal liquor 26ml/L, hydrofluoric acid 13ml/L；
(5) will be put into chemical plating fluid obtained in step (4) by the AZ91D magnesium alloys after step (3) treatment, 85-95
1.6h is processed at DEG C, then AZ91D deionized waters used for magnesium alloy is cleaned up, dried, nickel plating is completed；
(6) waste liquid in nickel process is collected, the pH value of chemical nickel plating waste solution is then adjusted to 4-6, by organophosphor
After the composite extractant of acid extraction agent and aldoxime kind of extractants composition dilutes through aviation kerosine, above-mentioned chemical nickel plating waste solution is carried out
Counter-current extraction, obtains rich nickel organic phase；Wherein, the volume ratio of organo phosphoric extractant and aldoxime kind of extractants is 4：1, after dilution
The percent by volume of organo phosphoric extractant is 20-50%；
(7) above-mentioned rich nickel organic phase is stripped with the sulfuric acid of 3.5mol/L, organic phase and inorganic phase is obtained, by organic phase
In composite extractant recycle, water through be concentrated by evaporation, crystallization, centrifugal dehydration, obtain metallic nickel.
Embodiment 5
A kind of magnesium alloy surface chemical nickel plating method, comprises the following steps：
(1) ultrasonic wave cleaning：AZ91D magnesium alloys are immersed in acetone soln, under 800W power, room temperature cleaning
15min, is then cleaned up with deionized water；
(2) alkali cleaning：NaOH, sodium phosphate and deionized water are well mixed, soda-wash solution is obtained, wherein, hydroxide
Sodium, the concentration of sodium phosphate are respectively：30g/L, 22g/L, are immersed in alkali cleaning molten by the AZ91D magnesium alloys after ultrasonic wave is cleaned
In liquid, 20min is cleaned at 60-70 DEG C；Then cleaned up with deionized water；
(3) acid-wash activation：AZ91D magnesium alloys after alkali cleaning is processed are immersed in the mixed solution of phosphoric acid and nitric acid,
1-2min is processed at room temperature, and the wherein concentration of phosphoric acid is 200ml/L, and the concentration of nitric acid is 50ml/L, then clear with deionized water
Wash clean；Then by the AZ91D magnesium alloys after pickling in the phosphoric acid solution of 160ml/L activation process 7min, taking-up spend from
Sub- water is cleaned up, then the activation process 5min in the ammonium hydrogen fluoride solution of 80g/L, after then being cleaned up with deionized water
Dry, it is stand-by；
(4) plating solution is prepared：Nickel sulfate, sodium hypophosphite, sodium acetate, ammonium acetate and deionized water are mixed into solid
Dissolving, is then eventually adding hydrofluoric acid and is uniformly mixed with the speed of 2ml/min to ammoniacal liquor is added dropwise in solution, and chemistry is obtained
Plating solution, its pH is 4.5-5.5；Wherein, the concentration of each component is respectively in chemical plating fluid：Nickel sulfate 21g/L, sodium hypophosphite
20g/L, sodium acetate 20mg/L, ammonium acetate 25mg/L, ammoniacal liquor 28ml/L, hydrofluoric acid 15ml/L；
(5) will be put into chemical plating fluid obtained in step (4) by the AZ91D magnesium alloys after step (3) treatment, 85-95
2h is processed at DEG C, then AZ91D deionized waters used for magnesium alloy is cleaned up, dried, nickel plating is completed；
(6) waste liquid in nickel process is collected, the pH value of chemical nickel plating waste solution is then adjusted to 4-6, by organophosphor
After the sulfonated kerosene cutback of composite extractant of acid extraction agent and aldoxime kind of extractants composition, above-mentioned chemical nickel plating waste solution is carried out
Counter-current extraction, obtains rich nickel organic phase；Wherein, the volume ratio of organo phosphoric extractant and aldoxime kind of extractants is 5：1, after dilution
The percent by volume of organo phosphoric extractant is 50%；
(7) above-mentioned rich nickel organic phase is stripped with the hydrochloric acid of 4mol/L, organic phase and inorganic phase is obtained, by organic phase
Composite extractant recycle, water through be concentrated by evaporation, crystallization, centrifugal dehydration, obtain metallic nickel.
Comparative example 1
A kind of magnesium alloy surface chemical nickel plating method, comprises the following steps：
(1) ultrasonic wave cleaning：AZ91D magnesium alloys are immersed in acetone soln, under 400W power, room temperature cleaning
5min, is then cleaned up with deionized water；
(2) alkali cleaning：NaOH, sodium phosphate and deionized water are well mixed, soda-wash solution is obtained, wherein, hydroxide
Sodium, the concentration of sodium phosphate are respectively：15g/L, 10g/L, are immersed in alkali cleaning molten by the AZ91D magnesium alloys after ultrasonic wave is cleaned
In liquid, 10min is cleaned at 60-70 DEG C；Then cleaned up with deionized water；
(3) acid-wash activation：AZ91D magnesium alloys after alkali cleaning is processed are immersed in the mixed solution of phosphoric acid and nitric acid,
1-2min is processed at room temperature, and the wherein concentration of phosphoric acid is 100ml/L, and the concentration of nitric acid is 20ml/L, then clear with deionized water
Wash clean；Then it is the AZ91D magnesium alloys after pickling is living in the phosphoric acid of 120ml/L and the ammonium acid fluoride mixed solution of 50g/L
Change treatment 5min, taking-up deionized water is dried after cleaning up, stand-by；
(4) plating solution is prepared：Nickel sulfate, sodium hypophosphite, sodium acetate, ammonium acetate and deionized water are mixed into solid
Dissolving, is then eventually adding hydrofluoric acid and is uniformly mixed with the speed of 1ml/min to ammoniacal liquor is added dropwise in solution, and chemistry is obtained
Plating solution, its pH is 4.5-5.5；Wherein, the concentration of each component is respectively in chemical plating fluid：Nickel sulfate 14g/L, sodium hypophosphite
15g/L, sodium acetate 10mg/L, ammonium acetate 20mg/L, ammoniacal liquor 20ml/L, hydrofluoric acid 10ml/L；
(5) will be put into chemical plating fluid obtained in step (4) by the AZ91D magnesium alloys after step (3) treatment, 85-95
1h is processed at DEG C, then AZ91D deionized waters used for magnesium alloy is cleaned up, dried, nickel plating is completed；
(6) waste liquid in nickel process is collected, the pH value of chemical nickel plating waste solution is then adjusted to 4-6, by organophosphor
After the sulfonated kerosene cutback of composite extractant of acid extraction agent and aldoxime kind of extractants composition, above-mentioned chemical nickel plating waste solution is carried out
Counter-current extraction, obtains rich nickel organic phase；Wherein, the volume ratio of organo phosphoric extractant and aldoxime kind of extractants is 1：1, after dilution
The percent by volume of organo phosphoric extractant is 20%；
(7) above-mentioned rich nickel organic phase is stripped with the sulfuric acid of 0.5mol/L, organic phase and inorganic phase is obtained, by organic phase
In composite extractant recycle, water through be concentrated by evaporation, crystallization, centrifugal dehydration, obtain metallic nickel.
Comparative example 2
A kind of magnesium alloy surface chemical nickel plating method, comprises the following steps：
(1) ultrasonic wave cleaning：AZ91D magnesium alloys are immersed in acetone soln, under 400W power, room temperature cleaning
5min, is then cleaned up with deionized water；
(2) alkali cleaning：NaOH, sodium phosphate and deionized water are well mixed, soda-wash solution is obtained, wherein, hydroxide
Sodium, the concentration of sodium phosphate are respectively：15g/L, 10g/L, are immersed in alkali cleaning molten by the AZ91D magnesium alloys after ultrasonic wave is cleaned
In liquid, 10min is cleaned at 60-70 DEG C；Then cleaned up with deionized water；
(3) acid-wash activation：AZ91D magnesium alloys after alkali cleaning is processed are immersed in the mixed solution of phosphoric acid and nitric acid,
1-2min is processed at room temperature, and the wherein concentration of phosphoric acid is 100ml/L, and the concentration of nitric acid is 20ml/L, then clear with deionized water
Wash clean；Then by the AZ91D magnesium alloys after pickling in the phosphoric acid solution of 120ml/L activation process 3min, taking-up spend from
Sub- water is cleaned up, then the activation process 2min in the ammonium hydrogen fluoride solution of 50g/L, after then being cleaned up with deionized water
Dry, it is stand-by；
(4) plating solution is prepared：Nickel sulfate, sodium hypophosphite and deionized water are mixed into solid dissolving, then with
The speed of 1ml/min is eventually adding hydrofluoric acid and is uniformly mixed to ammoniacal liquor is added dropwise in solution, and chemical plating fluid is obtained, and its pH is
4.5-5.5；Wherein, the concentration of each component is respectively in chemical plating fluid：Nickel sulfate 14g/L, sodium hypophosphite 15g/L, ammoniacal liquor
20ml/L, hydrofluoric acid 10ml/L；
(5) will be put into chemical plating fluid obtained in step (4) by the AZ91D magnesium alloys after step (3) treatment, 85-95
1h is processed at DEG C, then AZ91D deionized waters used for magnesium alloy is cleaned up, dried, nickel plating is completed；
(6) waste liquid in nickel process is collected, the pH value of chemical nickel plating waste solution is then adjusted to 4-6, by organophosphor
After the sulfonated kerosene cutback of composite extractant of acid extraction agent and aldoxime kind of extractants composition, above-mentioned chemical nickel plating waste solution is carried out
Counter-current extraction, obtains rich nickel organic phase；Wherein, the volume ratio of organo phosphoric extractant and aldoxime kind of extractants is 1：1, after dilution
The percent by volume of organo phosphoric extractant is 20%；
(7) above-mentioned rich nickel organic phase is stripped with the sulfuric acid of 0.5mol/L, organic phase and inorganic phase is obtained, by organic phase
In composite extractant recycle, water through be concentrated by evaporation, crystallization, centrifugal dehydration, obtain metallic nickel.
The coating to embodiment 1-5 and comparative example 1-2 carries out performance test below.
1st, the measure of binding force of cladding material
The adhesion of detection coating is tested by thermal shock, according to《The temperature of 100 class environmental test methods of GJB360B-2009 107
Degree impact test》Standard：Muffle furnace inside holding 1h of the sample at 220 DEG C, after taking-up in rapid input cold water, 5 experiments repeatedly,
Whether observation coating has the phenomenons such as foaming, crackle and peeling.
2nd, corrosion resistance of coating is determined
The corrosion resisting property of coating is detected with salt spray test, according to《The salt of 100 class environmental test methods of GJB360B-2009 101
Mist is tested》Standard：Sample placed 72h in salt fog cabinet.Sample is continuously sprayed by 36h, interval 36h, on specimen surface
The spot corrosion of appearance accounts for the percentage of total surface area.Further according to GB GB/T 6461-2002《On metallic matrix metal and its
His inorganic cover layer through sample and test specimen after corrosion test grading》Choose the grade of coating.
Test result is as shown in the table.
The corrosion of coating rating method of table 1
| Rate of corrosion (%) | Anti-corrosion grade |
| 0 | 10 |
| 0~0.25 | 9 |
| 0.25~0.5 | 8 |
| 0.5~1 | 7 |
| 1~2 | 6 |
| 2~4 | 5 |
| 4~8 | 4 |
| 8~16 | 3 |
| 16~32 | 2 |
| 32~64 | 1 |
| 64~ | 0 |
The test result of table 2
| Adhesion | Corrosion resisting property | |
| Embodiment 1 | Flawless and peeling phenomenon | 8 |
| Embodiment 2 | Flawless and peeling phenomenon | 9 |
| Embodiment 3 | Flawless and peeling phenomenon | 8 |
| Embodiment 4 | Flawless and peeling phenomenon | 8 |
| Embodiment 5 | Flawless and peeling phenomenon | 9 |
| Embodiment 6 | Flawless and peeling phenomenon | 9 |
| Comparative example 1 | There are obvious crackle and skin effect phenomenon | 2 |
| Comparative example 2 | There are obvious peeling and peeling phenomenon | 3 |
From the point of view of above table, comparative example 1,2 is compared, and the obtained coating of the present invention is strong with the adhesion of matrix, corrosion resistance
Can be good.
Claims (9)
1. a kind of magnesium alloy surface chemical nickel plating method, it is characterised in that comprise the following steps：
(1) ultrasonic wave cleaning：AZ91D magnesium alloys are immersed in acetone soln, under 400-800W power, room temperature cleaning 5-
15min, is then cleaned up with deionized water；
(2) alkali cleaning：NaOH, sodium phosphate and deionized water are well mixed, soda-wash solution is obtained, will be cleaned by ultrasonic wave
AZ91D magnesium alloys afterwards are immersed in soda-wash solution, and 10-20min is cleaned at 60-70 DEG C；Then clean dry with deionized water
Only；
(3) acid-wash activation：AZ91D magnesium alloys after alkali cleaning is processed are immersed in the mixed solution of phosphoric acid and nitric acid, in room temperature
Lower treatment 1-2min, is then cleaned up with deionized water；Then the AZ91D magnesium alloys after pickling are activated in phosphoric acid solution
Treatment 3-7min, taking-up is cleaned up with deionized water, and then the activation process 2-5min in ammonium hydrogen fluoride solution, then spends
Ionized water is dried after cleaning up, stand-by；
(4) plating solution is prepared：Nickel sulfate, sodium hypophosphite, sodium acetate, ammonium acetate and deionized water are mixed into solid molten
Solution, is then eventually adding hydrofluoric acid and is uniformly mixed with the speed of 1-2ml/min to ammoniacal liquor is added dropwise in solution, and chemistry is obtained
Plating solution, its pH is 4.5-5.5；
(5) will be put into chemical plating fluid obtained in step (4) by the AZ91D magnesium alloys after step (3) treatment, at 85-95 DEG C
Treatment 1-2h, then cleans up AZ91D deionized waters used for magnesium alloy, dries, and nickel plating is completed；
(6) waste liquid in nickel process is collected, the pH value of chemical nickel plating waste solution is then adjusted to 4-6, by composite extractant
After diluting dilution agent, counter-current extraction is carried out to above-mentioned chemical nickel plating waste solution, obtain rich nickel organic phase；
(7) by above-mentioned rich nickel organic phase stripped with mineral acid, organic phase and inorganic phase are obtained, by the compound extracting in organic phase
Agent is recycled, and water is through being concentrated by evaporation, crystallizing, centrifugal dehydration, obtains metallic nickel.
2. a kind of magnesium alloy surface chemical nickel plating method as claimed in claim 1, it is characterised in that：In step (2), the hydrogen
Sodium oxide molybdena, the concentration of sodium phosphate are respectively：15-30g/L、10-22g/L.
3. a kind of magnesium alloy surface chemical nickel plating method as claimed in claim 1, it is characterised in that：Step (3) phosphoric acid and nitre
In the mixed solution of acid, the concentration of phosphoric acid and nitric acid is respectively：100-200ml/L、20-50ml/L.
4. a kind of magnesium alloy surface chemical nickel plating method as claimed in claim 1, it is characterised in that：Step (3) described phosphoric acid
In solution, the concentration of phosphoric acid is 120-160ml/L.
5. a kind of magnesium alloy surface chemical nickel plating method as claimed in claim 1, it is characterised in that：Step (3) described fluorination
In hydrogen ammonium salt solution, the concentration of ammonium acid fluoride is 50-80g/L.
6. a kind of magnesium alloy surface chemical nickel plating method as claimed in claim 1, it is characterised in that：In step (4), describedization
Learn in plating solution, the concentration of each component is：Nickel sulfate 14-21g/L, sodium hypophosphite 15-20g/L, sodium acetate 10-20mg/L, vinegar
Sour ammonium 20-25mg/L, ammoniacal liquor 20-28ml/L, hydrofluoric acid 10-15ml/L.
7. a kind of magnesium alloy surface chemical nickel plating method as claimed in claim 1, it is characterised in that：It is described multiple in step (6)
Close extractant be made up of organo phosphoric extractant and aldoxime kind of extractants, wherein, organic extractant be P204, P507 and
C272, the aldoxime kind of extractants is lix63 and N902, and the volume ratio of organic extractant and aldoxime kind of extractants is (1-5)：1.
8. a kind of magnesium alloy surface chemical nickel plating method as claimed in claim 1, it is characterised in that：It is described dilute in step (6)
It is the one kind in sulfonated kerosene, aviation kerosine to release agent, and the percent by volume of organo phosphoric extractant is 20-50% after dilution.
9. a kind of magnesium alloy surface chemical nickel plating method as claimed in claim 1, it is characterised in that：In step (7), the nothing
Machine acid is the sulfuric acid or hydrochloric acid of 0.5-4mol/L.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314848A (en) * | 2008-07-16 | 2008-12-03 | 中山大学 | Non-ammonia type plating solution for chemical nickel plating |
| CN104962888A (en) * | 2015-05-29 | 2015-10-07 | 东南大学 | Method for treating chemical nickel plating concentrated waste liquid by solvent extraction method and ion exchange method |
-
2016
- 2016-12-12 CN CN201611136546.5A patent/CN106835087A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314848A (en) * | 2008-07-16 | 2008-12-03 | 中山大学 | Non-ammonia type plating solution for chemical nickel plating |
| CN104962888A (en) * | 2015-05-29 | 2015-10-07 | 东南大学 | Method for treating chemical nickel plating concentrated waste liquid by solvent extraction method and ion exchange method |
Non-Patent Citations (2)
| Title |
|---|
| 唐锐: "AZ91D镁合金二次活化化学镀镍新工艺的研究", 《中国优秀硕士学位论文全文数据库，工程科技Ⅰ辑》 * |
| 马荣骏: "《萃取冶金》", 31 August 2009, 冶金工业出版社 * |
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