CN1928156A - Chemical plating method for Mg and its alloy - Google Patents
Chemical plating method for Mg and its alloy Download PDFInfo
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- CN1928156A CN1928156A CN 200510099104 CN200510099104A CN1928156A CN 1928156 A CN1928156 A CN 1928156A CN 200510099104 CN200510099104 CN 200510099104 CN 200510099104 A CN200510099104 A CN 200510099104A CN 1928156 A CN1928156 A CN 1928156A
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Abstract
The chemical plating process for magnesium-base material includes the following steps: 1. alkaline dewaxing the magnesium-base material; 2. activating with acid solution containing fluoric salt and no chlorine ion and in pH 2.0-5.0, and treating with alkaline neutralizing solution containing alkali metal salt of pyrophosphoric acid, fluoric salt and hypophosphite in pH 8.0-12.0; 3. chemical nickel pre-plating with the plating solution containing nickel salt in 10-80 g/L concentration, fluoric salt in 5-50 g/L concentration, pyrophosphite in 20-100 g/L concentration and no chlorine ion and in pH 5.0-9.0; 4. chemical nickel plating with the plating solution containing nickel salt in 10-100 g/L concentration, pyrophosphite in 10-80 g/L concentration and no chlorine ion and in pH 3-7; and 5. optional heat treatment. The said process can form homogeneous compact nickel layer with sufficient binding force on magnesium-base material.
Description
Invention field
The present invention relates to the chemical plating technology of magnesium or its alloy.Particularly, the present invention relates to by chemical plating technology, covering on the base material of the active magnesium of chemical property or its alloy has bottom layer nickel enough bonding forces, even and fine and close.
Background technology
Magnesium is light metal, and the reserves in earth metal are very big.At present, magnesium is becoming the third-largest metal engineering material after iron and steel, aluminium.It has the excellent physical properties at aspects such as intensity, toughness, lightweight, electric conductivitys.But,, be corroded easily, so limited its use for a long time because the chemical property of magnesium is active.Smelted along with magnesium in recent years, the breakthrough of forming technique, the application quantity of magnesium has very big development.Magnesium and alloy thereof with good damping shock absorption performance are Hyundai Motor loss of weight, energy-conservation, consumption reduction, light-weighted preferred material; Magnesium and alloy thereof have specific tenacity height, heat-conductivity conducting is strong, electromagnetic wave shielding is good advantage, for such as 3C Products such as computer, communication, consumer electronics, favourable its lightization, thinning, microminiaturization, highly integrated will be so will have more and more widely application in information industry.
For susceptibility-to-corrosion, the inflammableness that prevents magnesium and alloy thereof, need provide the protectiveness skin for goods based on magnesium and alloy thereof; Simultaneously,, also need the goods based on magnesium or its alloy are carried out surface treatment, attracting product appearance is provided for catering to the needs of market to products appearance.But present magnesium or its alloy surface are handled the spraying technology that only is confined to product surface mostly, as plasma spraying, spray paint, plastic-blasting material, spray pottery etc.The surface-treated shortcoming of this class is: if goods as functional component, have then lost metal scale character, for example performances such as the peculiar conduction of metal, heat conduction, welding, magnetic; If goods are as appearance part, then because the color in the spraying is stiff, not only buried the good hand and the texture of magnesium or its alloy, more the color and luster that can't obtain after electroplating through water law with the parts that present ABS plastic, zinc alloy, copper, iron etc. are made compares favourably.
The inventor is reaching two more than ten years zinc alloy, copper, iron, aluminium, ABS, PC plastics water law are electroplated on the empirical basis, in finding in the research to magnesium and alloy thereof in recent years, by following method of the present invention, can cover last layer on the base material of active magnesium of chemical and alloy thereof has underlying metal enough bonding forces, even and fine and close.With this underlying metal is media layer, can carry out conventional water law then and electroplate, thereby obtain the goods that have satisfactory appearance and keep the original character of metal.And the inventive method can reach the high rate of finished products more than 80%, has the industrial applicibility of height.
Summary of the invention
The object of the present invention is to provide a kind of compositive lining layer treatment process of mg-based material, this method can make described compositive lining layer both have fabulous solidity to corrosion and wear resistance, has excellent electroconductibility again.Especially, this method has uniform hiding power and is not subjected to the influence of the hole of complicated shape on the base material.And conventional Electroplate Factory also need not to increase expensive equipment when implementing the inventive method.
In this application, except at embodiment or have at other the occasion of regulation, all numerical value of the amount of the expression composition that uses in specification sheets and claims, reaction conditions etc. all should be considered to available in all cases wording " approximately " and modify.Thereby unless otherwise prescribed, the numerical parameter that provides in following specification sheets and appended claims all is an approximation, can change according to the expected performance of being looked for by the present invention.At least each numerical parameter should be explained by using the common technology of rounding up according to the numerical value of the significant figure of being reported, yet this is not the restriction of attempting the doctrine of equivalents of the scope of claim.
Though wide region numerical range of the present invention as mentioned above and parameter are approximations, the numerical value that provides in specific embodiment is as far as possible accurately reported.Yet any numerical value contains inevitable by the certain error that standard deviation caused that exists in the experimental measurement separately at them inherently.
According to an aspect of the present invention, provide the method for magnesium or its alloy being carried out electroless plating, this method comprises:
A. pretreatment procedure:
Pretreatment procedure of the present invention mainly comprises selection, removed the step of thick-oxide and oil removing.
From improving the angle of plated item yield rate, at first make every effort to screening and be fit to galvanized qualified blank.Defective on the metallograph of blank, cold shut, water wave, loosen, be mingled with, husky hole, pore, component segregation, the not first-class defective of crystallite size be as mustn't go to correction, then may cause plating leakage, corrosion hole, the latter directly influences the yield rate of goods.The base material defective is the main source of coating hole, directly influences the solidity to corrosion of coating.And the defective on the blank also can influence the bonding force of coating and base material.Therefore, qualified blank is the precondition that reaches high rate of finished products and adapt to industrial applications.
The technician can choose or select by instrument known in the art the blank that does not have defective or less defective is arranged by hand; For the blank that less defective (for example a spot of husky hole, pore) arranged, can adopt water-based to fill up agent and under vacuum, seal.Be applicable to that water-based of the present invention fills up agent and include, but are not limited to water-soluble varnish, water-soluble closed dose, electrocoating paint, gelatin etc.According to the difference of blank forming method, can also optionally heat-treat the removal internal stress to it.For blank can also sandblast with being selected from, method such as vibration, barreling removed thick oxide film.
Blank through above-mentioned selection is carried out the sonochemistry oil removing.For example, but be not limited under 50-90 ℃, remove the cured aqueous solution (pH 9-12) to blank oil wax removal 2-3 minute with alkalescence.Be applicable to that Wax removal water solution of the present invention can select weakly alkaline prescriptions such as yellow soda ash, tertiary sodium phosphate, water glass, trisodium phosphate, sodium bicarbonate, OP emulsifying agent, tensio-active agent for use.
B. activation treatment operation:
Activation treatment operation of the present invention mainly comprises activation and neutralization procedure.
The activatory purpose is to remove the loose oxide film on magnesium or its alloy surface.Yet because the chemical property of magnesium is active, thereby how to make Mg alloy surface still can keep fresh magnesium based metal before forming chemical Ni-plating layer be the activatory key.
Adopt fluorine-containing salt, make passive films such as magnesium oxide on the magnesium matrix, magnesiumcarbonate, magnesium hydroxide all be replaced as uniform magnesium fluoride film.In order to ensure forming the good complete magnesium fluoride film of one deck, can adopt the thick film of pulse electrolysis with the oxide compound of assisting to remove workpiece surface and oxyhydroxide etc.The new magnesium fluoride film that forms can make whole magnesium workpiece surface that chemical nickel-plating liquid is uniform activity, thereby has avoided the erratic deposition of nickel.This is most important for good bonding force.
Be fit to the example that contains villiaumite of the present invention and include, but are not limited to Neutral ammonium fluoride, Sodium Fluoride, hydrofluoric acid, ammonium bifluoride.Preferably containing villiaumite is ammonium bifluoride.According to a specific embodiments of the present invention, this amount that contains villiaumite can be 50-300 according to the magnesium alloy of the different trades mark, is preferably 100g/L.
According to a specific embodiments of the present invention, activation solution is the above-mentioned acidic solution that contains villiaumite, and its pH is 1.0-5.0, preferred fluorinated hydrogen ammonium.Also contain inhibiter 20-200g/L in this solution, preferred 50g/L; Catalyzer 50-200g/L, preferred 150g/L; No chlorion.Be applicable to that inhibiter of the present invention includes, but are not limited to two phosphorus toluene thiocarbamides, thiocarbamide, urea, hexamethylenetetramine, sulfuration animal proteinum, Chinese honey locust leach liquor etc.Hexamethylenetetramine is preferred inhibiter.Be applicable to that accelerator activator of the present invention includes, but are not limited to phosphoric acid, chromic anhydride, acetic acid, citric acid, boric acid, oxysuccinic acid etc., especially preferably phosphoric acid.
The activatory temperature is not particularly limited, usually can be at 20～70 ℃, carry out under preferred 40 ℃, and for example 8-15 minute, preferred 10 minutes.In reactivation process, can apply voltage of alternating current and carry out electrolysis, to promote activation.This voltage of alternating current frequency is not particularly limited, for example can be 50 hertz, 3～5V carried out 1～2 minute.
The neutral purpose is that lax blocked up fluoride films allows the surface soak into reductive agent equably, and it is believed that neutralizing agent can also form very thin protective membrane on the surface of magnesium workpiece, temporary transient secluding air, thus protect established fluoride films.Preferably needn't wash through neutral magnesium workpiece, can directly move into the pre-plating with electroless nickel groove.
The example that is fit to neutralizing agent of the present invention includes, but are not limited to vitriolate of tartar, dipotassium hydrogen phosphate, potassium pyrophosphate, Tripotassium Citrate, sodium tetraborate, Seignette salt.Preferred neutralizing agent comprises potassium pyrophosphate, Tripotassium Citrate, more preferably potassium pyrophosphate.According to a specific embodiments of the present invention, the amount of this neutralizing agent can be 50-200g/L, is preferably 80g/L.
According to a specific embodiments of the present invention.Neutralizing agent is alkalescence (pH is 8-12), alkali metal pyrophosphate salts: 50-100g/L, particular certain cancers or sylvite, more preferably potassium pyrophosphate; Contain villiaumite 5-100g/L, preferred fluorinated hydrogen ammonium; Hypophosphite 5-100g/L, preferred inferior sodium phosphate; Water-soluble organic colloid protective material 5-20g/L, preferred gelatin; Buffer reagent 10-50g/L, optimization citric acid sodium; No chlorion.Contain villiaumite and comprise Neutral ammonium fluoride, Sodium Fluoride, hydrofluoric acid, ammonium bifluoride.Preferably containing villiaumite is ammonium bifluoride.Preimpregnation reductive agent (hypophosphite) is prepared for the reduction operation that goes on foot chemical nickel plating down, preferred inferior sodium phosphate.Reductive agent is decided with chemical nickel plating in the reduction operation, includes but not limited to inferior sodium phosphate, sodium borohydride, dimethyamine borane, diethylamine borane, hydrazine.Water-soluble organic colloid protective material comprises gelatin, phosphorous acid nickel, preferred gelatin; Buffer reagent comprises Seignette salt, propanedioic acid hydrogen sodium, Soduxin, Trisodium Citrate, optimization citric acid sodium.
The neutral temperature is not particularly limited.Usually, lesser temps need carry out the long period, preferably carries out under 50～80 ℃ 3～5 minutes.
C. pre-chemical plating nickel operation
After workpiece was gone into groove, unsettled magnesium fluoride film was selected active fluorine very soon, exposes fresh magnesium based metal, the chemical immediately plating of nickel.If plating in time, magnesium will be subjected to bath corrosion.Both just afterwards plated nickel, bonding force is also very poor, can't obtain qualified product.
If after plating piece is gone into groove 60 seconds, even 30 seconds, deposition does not go up nickel, promptly can not be corroded.For this reason, if do not see yet in 15 seconds when bubble is overflowed, thereby can use the energising of metallic cathode plate contact magnesium workpiece to excite; Or with laser, uviolizing or improve the pH of plating bath, for example bring up to 6-9, preferred 7.0.
According to a specific embodiments of the present invention, pre-chemical plating nickel liquid comprises: nickel salt 10-80g/L, preferred 25g/L; Contain villiaumite 5-50g/L, preferred 10g/L; Hypophosphite 10-80g/L, preferred 25g/L; In addition, also can add one or more following additives: buffer reagent 5-50g/L, preferred 10g/L; Complexing agent 10-30g/L, preferred 15g/L; Wetting agent 2-20g/L, preferred 10g/L; Stablizer 0.1-5g/L, preferred 0.5g/L; Catalyzer 1-100g/L, preferred 5g/L; No chlorion.
The pH of above-mentioned plating bath is 5.0-9.0, preferred 7.The preferred pH that uses ammoniacal liquor to regulate pre-plating bath.
Be applicable to that nickel salt of the present invention includes, but are not limited to single nickel salt, nickelous carbonate, nickel acetate, ortho phosphorous acid nickel, nickel sulfamic acid, methylsulphonic acid nickel, preferred ortho phosphorous acid nickel, more preferably single nickel salt; Contain villiaumite and include, but are not limited to Neutral ammonium fluoride, Sodium Fluoride, hydrofluoric acid, ammonium bifluoride, preferred fluorinated hydrogen ammonium; Reductive agent includes, but are not limited to inferior sodium phosphate, ortho phosphorous acid potassium, sodium borohydride, dimethyamine borane, diethylamine borane, hydrazine etc., preferred inferior sodium phosphate; Buffer reagent includes, but are not limited to acetate/sodium acetate, Succinic Acid/borax, sodium bisuccinate/Soduxin, natrium hydrocitricum/sodium hydroxide, propanedioic acid hydrogen sodium/sodium hydroxide, potassium primary phosphate/borax, borax/boric acid, ammonia chloride/ammoniacal liquor, or its combination, preferred ammoniacal liquor, more preferably natrium hydrocitricum; Complexing agent includes, but are not limited to acetic acid, lactic acid, succsinic acid, oxyacetic acid, oxysuccinic acid, citric acid, glycine, L-Ala, or its combination, preferred lactic acid; Wetting agent includes, but are not limited to dodecyl sulfate, dodecane sulfonate, n-octyl sodium sulfate, preferred dodecyl sulfate; Stablizer comprises, but is not limited to thiocarbamide, Potassium Iodate, toxilic acid, Sulfothiorine, preferred thiocarbamide, more preferably Potassium Iodate.Catalyzer comprises, but is not limited to propanedioic acid, Succinic Acid, Padil, propionic acid, Sodium Fluoride, Sodium Glutamate, rare-earth elements of lanthanum La, neodymium Nd, preferred Sodium Glutamate, rare earth neodymium.
For obtaining the coating of even bonding force, need control chemical nickel plating self-catalyzed reaction start time.The present invention has underlying metal excellent bonding force, even and fine and close by controlling above-mentioned start time, can having accessed.
D. chemical nickel plating operation
The purpose of chemical nickel plating is the fine and close and nickel alloy layer uniformly at plating on the magnesium of above-mentioned pre-chemical plating nickel or its alloy.
The key of electroless plating operation is how to control the uniform density of coating.If the nickel self-catalyzed reaction speed of the magnesium workpiece in the plating bath is out of control, form easily loose bottom, can be in subsequent handling cause magnesium matrix to be corroded, to dissolve in entering other coating bath the time.Like this, not only can not electroplate the numerous plating baths in also can the contaminate subsequent operation.Thereby, need the coating of control chemical nickel plating self-catalyzed reaction speed, and guarantee carrying out smoothly of subsequent handling with the acquisition even compact.
According to a specific embodiments of the present invention, solution composition comprises: nickel salt 10-100g/L, preferred 25g/L; Hypophosphite 10-80g/L, preferably approximately 25g/L; Complexing agent, buffer reagent, catalyzer, stablizer, each 1-50g/L of wetting agent, preferably approximately 25g/L; No chlorion.The pH of chemical plating fluid is generally 3-7, preferably approximately 5.Transfer described pH with ammoniacal liquor.Wherein, nickel salt, hypophosphite, complexing agent, buffer reagent, catalyzer, stablizer, selecting for use of wetting agent can be referring to above-mentioned description.
Chemical nickel plating especially is fit to complex-shaped workpiece, at positions such as groove, blind hole, deep holes, all can obtain the uniform coating of thickness and avoid plating leakage effectively simultaneously, and magnesium alloy parts can be used in than rugged environment in acid, alkali, corrosion such as wet; And to be subjected to the influence of electric field distribution and dielectric behavior unlike anodic oxidation, little lonely oxidation and electroplating technology, and the latter causes the male and fomale(M﹠F) thickness of coating difference of magnesium workpiece very big, and wherein the coating of concave surface low potential is thinner, can influence the whole anti-corrosion effect of workpiece.
Therefore, use the above-mentioned advantage of electroless plating can advantageously prolong the work-ing life of magnesium workpiece better.In case of necessity, can apply the bonding force that vibration of ultrasonic wave increases nickel dam and magnesium matrix.The ultrasonic wave strong agitation tank liquor, reduced the concentration difference of reaction interface, make hydrogen be not easy to be detained simultaneously at workpiece surface; Cavitation effect of ultrasonic waves provides activation evergy in addition, has increased surface dislocation density and nucleation centre, improves nucleation rate, helps the crystallization refinement, has increased the coating density.In addition, apply laser, ultraviolet ray also can provide activation evergy, promotes the carrying out of chemical reaction.
After chemical nickel plating, can with the plating of routine, for example water law electroplate to be connected.
E. toast heat treatment step
In time removal moisture can prevent to form galvanic cell between magnesium matrix and the chemical nickel and corrode; Can prevent simultaneously because the hydrogen in statu nascendi that magnesium and water reaction generate forms hydrogen embrittlement in the slit.Thereby workpiece preferably toasts thermal treatment timely after taking out from the chemical nickel plating groove, remove moisture.
Thermal treatment can also change into amorphous chemical nickel the tiny primary crystal of granularity, thereby increases density.Can adjust heat treated temperature and time according to the workpiece size.Usually, baking thermal treatment can be advantageously at 100～300 ℃, carry out preferably approximately 120 minutes 30～200 minutes under 200 ℃ of the preferably approximatelies.
F. electroplate front activating
Alkaline electrolysis, acid immersion etc. all can be removed the oxide film that thermal treatment produces.In addition, utilize acid soak whether evolving gas also can check the density of chemical nickel coating.Be applicable to that acid of the present invention includes, but are not limited to sulfuric acid, citric acid, boric acid, hydroflouric acid or its combination, preferably sulfuric acid, or the combination of boric acid and hydrofluoric acid.
Thermal treatment temp height, time length may produce thicker oxide film, therefore preferably separate activation with neutral nickel preplating sun.
G. electroplating work procedure
Electroplate the good metal that walks earlier, for example neutral burnt copper or neutral nickel, until the shrinkage pool that covers workpiece, and the metal plating of thickening low potential on the shrinkage pool is to needed thickness, to ensure the solidity to corrosion at workpiece low potential place.
Preferably, electroplate liquid is applied ultrasonic wave.Hyperacoustic applying except reducing concentration difference and improving the nucleation rate, importantly also reduce because of bubble hydrogen be clipped in cause in the coating of growth ooze hydrogen and hydrogen embrittlement.
Subsequently, can electroplating bright acid copper to pave slick surface.Formed certain thickness copper layer has good ductility, can be as the buffer layer of various stress.In addition, can the anticorrosion nickel dam of plating to satisfy the corrosion-resistant requirement of any goods.
In electroplating work procedure of the present invention, the preferred charged cylinder of going into of workpiece.Like this, can prevent chemical Ni-plating layer when having tiny penetrance pore, the very negative magnesium of current potential (the mark Huaihe River electropotential of magnesium for-2.36V) or its alloy can produce pitting attack.
Above-mentioned electroplating work procedure can carry out according to methods known in the art.
H. last, randomly, can in different look cylinders, electroplate needed color and luster according to the goods design requirements.For example, can electroplate pearl chromium, bright chromium, bronze, black chromium, bronze, Gu Xi, gold, silver etc. are to reach satisfied products appearance.
Description of drawings
Fig. 1 is the synoptic diagram of process flow of the present invention.
Embodiment
Below, specify the present invention by exemplary embodiment.Should be appreciated that scope of the present invention should not be limited to the scope of embodiment.Any variation or change that does not depart from purport of the present invention can be understood by those skilled in the art.Protection scope of the present invention is determined by the scope of claims.
Except as otherwise noted, percentage ratio that is occurred among the embodiment and umber are all based on weight.
The preparation of preparation embodiment A activation treatment liquid (A-1, A-2)
1.PIN-1 consisting of of additive
| PIN-1 forms | Hexamethylenetetramine | Phosphoric acid |
| Volume % | 100 | 300 |
The phosphoric acid of 300ml and the hexamethylenetetramine of 100ml are dissolved in the 300ml pure water, obtain 2 times of concentrated solutions of PIN-1 additive.
2.PIN-2 consisting of of additive
| PIN-2 forms | Hexamethylenetetramine | Trisodium Citrate |
| Weight g/L | 100 | 120 |
Take by weighing above gram number, be dissolved in 4 times of concentrated solutions that obtain the PIN-2 additive in 1 liter of pure water.
3.1 rise the preparation of activation treatment liquid:
Take by weighing 100 gram ammonium bifluorides, be dissolved in the 200ml pure water, after the stirring and dissolving, add 2 times of concentrated solutions of 500ml PIN-1 additive, mend pure water and to 1000ml, obtain activation treatment liquid A-1 liquid.
4.1 rise the preparation of activation treatment liquid:
Take by weighing 100 gram ammonium bifluorides, be dissolved in the 200ml pure water, after the stirring and dissolving, add 4 times of concentrated solutions of 500ml PIN-2 additive, mend pure water and to 1000ml, obtain activation treatment liquid A-2 liquid.
The preparation of preparation Embodiment B neutralizing treatment liquid B-1
1.PIN-3 consisting of of additive
| PIN-3 forms | Inferior sodium phosphate | Ammonium bifluoride | Trisodium Citrate |
| Weight g/L | 200 | 40 | 120 |
Take by weighing above gram number, be dissolved in 4 times of concentrated solutions that obtain the PIN-3 additive in 1 liter of pure water.
2.PIN-4 additive
Take by weighing gelatin 40 gram, place 50-60 hot water, be stirred to moltenly, boil, obtain 4 times of concentrated solutions of PIN-4 additive.
3. the preparation of neutralizing treatment liquid:
Take by weighing potassium pyrophosphate 80g and be dissolved in the 200ml pure water, after the stirring and dissolving, add 4 times of each 250ml of concentrated solution of PIN-3 additive and PIN-4 additive respectively, mend pure water, obtain neutralizing treatment liquid B-1 to 1000ml.
The preparation of preparation Embodiment C pre-chemical plating nickel liquid
1. pre-chemical plating nickel liquid SAU-1 additive
| SAU-1 forms | Buffer reagent | Buffer reagent | Complexing agent | Wetting agent |
| Composition | Sodium acetate | Natrium hydrocitricum | Lactic acid | Dodecyl sulfate |
| Weight g/L | 40 | 60 | 40ml/L | 20 |
Take by weighing above gram number and volume, be dissolved in 4 times of concentrated solutions that obtain the SAU-1 additive in 1 liter of pure water.
2. pre-chemical plating nickel liquid SAU-2 additive
| SAU-2 forms | Catalyzer | Catalyzer |
| Composition | Sodium Glutamate | Neodymium |
| Weight g/L | 12 | 1 |
Take by weighing above gram number, be dissolved in 10 times of concentrated solutions that obtain the SAU-2 additive in 1 liter of pure water.
2. pre-chemical plating nickel liquid SAU-3 additive
| SAU-3 forms | Stablizer |
| Composition | Potassium Iodate |
| Weight g/L | 0.1 |
Take by weighing above gram number, be dissolved in 10 times of concentrated solutions that obtain the SAU-3 additive in 1 liter of pure water.
3. the preparation of pre-chemical plating nickel liquid
Single nickel salt 15g, ortho phosphorous acid nickel 10g, ammonium bifluoride 10g, inferior sodium phosphate 10g are dissolved in the pure water of 500ml, add the concentrated solution of 250ml SAU-1 additive, and transferring its pH value with ammoniacal liquor is 7, and the benefit pure water obtains pre-chemical plating nickel liquid C-1 to 1000ml.
SAU-2 additive or inferior sodium phosphate strong solution are the reaction accelerator activator, can be optionally cross in the chemical nickel plating speed of response and can add when slow.
The SAU-3 additive is a stablizer, can optionally add when the chemical nickel plating speed of response is too fast.
The preparation of preparation embodiment D chemical nickel-plating liquid
1. chemical nickel-plating liquid SAU-4 additive
| SAU-4 forms | Buffer reagent | Buffer reagent | Complexing agent | Brightening agent | Wetting agent |
| Composition | Sodium acetate | Natrium hydrocitricum | Lactic acid | Cadmium Sulphate | Dodecyl sulfate |
| Weight g/L | 40 | 30 | 60ml/L | 0.004 | 20 |
Take by weighing above gram number and volume, be dissolved in 4 times of concentrated solutions that obtain the SAU-4 additive in 1 liter of pure water.
2. the preparation of chemical nickel-plating liquid:
Single nickel salt 15g, ortho phosphorous acid nickel 10g, ammonium bifluoride 10g, inferior sodium phosphate 10g are dissolved in the hot pure water of 500ml, add the concentrated solution of 250ml SAU-4 additive, and transferring its pH value with ammoniacal liquor is 5, mend pure water to 1000ml chemical nickel-plating liquid D-1.
Catalysis is with SAU-2 additive and the stable SAU-3 additive of using, and is identical in purposes and the pre-chemical plating nickel liquid.
Above-mentioned prescription is applicable to magnesium alloy AZ91D, AM60 etc.
Test 1 neutral salt spray test
Neutral salt spray test carries out with SST-7NL type spray testing machine.Adopt 5% the NaCl aqueous solution, 35 ± 5 ℃, pH6.5-7.2.Solution spraying continuously stopped in 24 hours.Measuring point corroded area (%).
Embodiment 1
Sample is a MP3 player shell.
(auspicious precious metal company limited makes with the rectangular ingot of AZ91D magnesium alloy; Contain 89.5wt% magnesium, 9.1wt% aluminium, 0.8wt% zinc, 0.2wt% manganese) be shaped to the outer shell workpiece of slice-type with Japanese hot chamber machine.Artificial selection does not have the blank of surface imperfection, folder sand, pore and material segregation.
Blank is under 60 ℃ in temperature after grinding with fine sand paper, uses aqueous sodium carbonate (pH=10) to blank oil wax removal 3 minutes.
Activation treatment liquid A-1 with the preparation of preparation embodiment A under 30 ℃ temperature activates 10 minutes to the workpiece through oil removal treatment, shakes simultaneously.In the reactivation process, adopt AC transformer to do pulse electrolysis, voltage of alternating current 3-5V, 3 minutes time is to add strong activating effect.
In under 70 ℃ temperature, carrying out and operation 2 minutes, shake simultaneously with the neutralizing treatment liquid B-1 of preparation Embodiment B preparation.
Activation treatment liquid A-2 with the preparation of preparation embodiment A under 30 ℃ temperature carried out re-activation 5 minutes, shook simultaneously.
Pre-chemical plating nickel liquid C-1 with the preparation of preparation Embodiment C carries out preplating chemical nickel operation.Because the reaction toggle speed is slower, excite 10 minutes to start reaction with the energising of tinsel negative electrode contact magnesium workpiece down at 70 ℃, shake simultaneously.
Chemical nickel-plating liquid D-1 with preparation embodiment D preparation carries out the chemical nickel plating operation.70 ℃ of chemical nickel plating temperature, are shaken simultaneously at 30 minutes time.
150 ℃ of thermal treatments, 40 minutes.Carrying out routine subsequently electroplates.
Electroplate liquid adopts conventional decorative electroplating liquid to carry out.Electroplate burnt copper, chargedly go into groove, 20 minutes; The sour copper strips electricity of light is gone into groove, 20 minutes; Half light nickel 10 minutes; Bright nickel 10 minutes; Chromium 2 minutes.
Neutral salt spray test for evaluating is less than 1%, reaches the finished product requirement.
Embodiment 2
The small-sized accessory of sample car movable axis.
Mg-based material is that the rectangular ingot of AZ91D magnesium alloy (sea of clouds Metaux Speciaux S. A. contains 89wt% magnesium, aluminium 9wt%, zinc 0.8wt%, manganese 0.2wt%) is shaped to little axle with holes with German hot chamber machine.The shape more complicated.There are a small amount of nonmetal husky hole, pore in the surface.
After the mechanical grinding polishing, be under 60 ℃, use aqueous sodium carbonate (pH=10) blank oil wax removal 3 minutes in temperature.
Activation treatment liquid A-1 with the preparation of preparation embodiment A under 30 ℃ temperature activates 10 minutes to the workpiece through oil removal treatment, shakes simultaneously.In the reactivation process, adopt AC transformer to do pulse electrolysis, voltage of alternating current 3-5V, 3 minutes time is to add strong activating effect.
In under 70 ℃ temperature, carrying out and operation 2 minutes, shake simultaneously with the neutralizing treatment liquid B-1 of preparation Embodiment B preparation.
Activation treatment liquid A-2 with the preparation of preparation embodiment A under 30 ℃ temperature carried out re-activation 5 minutes, shook simultaneously.
Pre-chemical plating nickel liquid C-1 with the preparation of preparation Embodiment C carries out preplating chemical nickel operation.Because the reaction toggle speed is slower, excite 10 minutes to start reaction with the energising of tinsel negative electrode contact magnesium workpiece down at 70 ℃, shake simultaneously.
Chemical nickel-plating liquid D-1 with preparation embodiment D preparation carries out the chemical nickel plating operation.70 ℃ of chemical nickel plating temperature, are shaken simultaneously at 50 minutes time.
150 ℃ of thermal treatments, 40 minutes.Carrying out routine subsequently electroplates.
Conventional electroplate burnt copper, chargedly went into groove 30 minutes; Bright copper was chargedly gone into groove 20 minutes; Half light nickel 20 minutes; Bright nickel 10 minutes; Pearl nickel; Light chromium.
Neutral salt spray test for evaluating is less than 1%, reaches the finished product requirement.
Can find that from the result of above embodiment the inventive method goes for difform sample, obtain the even and fine and close chemical plating of high-bond, have excellent anti-corrosion effect.Simultaneously, the inventive method can be electroplated with routine and is connected, and obtains having the product of excellent appearance.
The above-mentioned all embodiment that exemplify are just to the further specifying of the present invention program, helping to understand better and realize the present invention, rather than to any restriction of the application's scope.
Claims (10)
1. the chemical plating method of mg-based material comprises subordinate's step:
(a) mg-based material is carried out alkaline paraffin removal;
(b) with comprising the acidic solution activation that the contains villiaumite mg-based material through paraffin removal, this acidic solution is chloride ion-containing not, and pH is 2.0 to 5.0; With comprising alkali metal pyrophosphate salts, the alkaline neutralizer that contains villiaumite and hypophosphite is handled activated mg-based material subsequently, and the pH of this neutralizer is 8.0 to 12.0;
(c) pre-chemical plating nickel, wherein pre-chemical plating nickel liquid comprises the nickel salt of 10-80g/L, the hypophosphite that contains villiaumite and 20-100g/L of 5-50g/L, no chlorion, pH are 5.0-9.0;
(d) chemical nickel plating, wherein chemical nickel-plating liquid comprises the nickel salt of 10-100g/L, the hypophosphite of 10-80g/L, no chlorion, pH are 3-7; With
(e) Ren Xuan thermal treatment.
2. the process of claim 1 wherein that described mg-based material is a magnesium alloy.
3. the process of claim 1 wherein that the described villiaumite that contains is selected from Neutral ammonium fluoride, Sodium Fluoride, hydrofluoric acid and ammonium bifluoride.
4. the method for claim 3, the wherein said villiaumite that contains is an ammonium bifluoride.
5. the process of claim 1 wherein switches in the step (c) excites and/or applies laser, ultraviolet ray.
6. the process of claim 1 wherein and also comprise the additive that is selected from buffer reagent, complexing agent, wetting agent, stablizer, catalyzer in the chemical nickel-plating liquid of the pre-chemical plating nickel liquid of step (c) and/or step (d).
7. the method for claim 6, wherein buffer reagent comprises acetate/sodium acetate, Succinic Acid/borax, sodium bisuccinate/Soduxin, natrium hydrocitricum/sodium hydroxide, propanedioic acid hydrogen sodium/sodium hydroxide, potassium primary phosphate/borax, borax/boric acid, ammonia chloride/ammoniacal liquor, or its combination; Complexing agent comprises acetic acid, lactic acid, succsinic acid, oxyacetic acid, oxysuccinic acid, citric acid, glycine, L-Ala, or its combination; Wetting agent comprises dodecyl sulfate, dodecane sulfonate, n-octyl sodium sulfate; Stablizer comprises thiocarbamide, Potassium Iodate, toxilic acid, Sulfothiorine; Catalyzer comprises propanedioic acid, Succinic Acid, Padil, propionic acid, Sodium Fluoride, Sodium Glutamate, rare-earth elements of lanthanum La, neodymium Nd.
8. the process of claim 1 wherein that described nickel salt comprises single nickel salt, nickelous carbonate, nickel acetate, ortho phosphorous acid nickel, nickel sulfamic acid, methylsulphonic acid nickel or its combination.
9. the method for claim 8, wherein said nickel salt is a single nickel salt.
10. the method for claim 1 also comprises the plating of step (f) water law.
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| CNB2005100991043A CN100462479C (en) | 2005-09-05 | 2005-09-05 | Chemical plating method for Mg and its alloy |
| HK07105648.8A HK1099793A1 (en) | 2005-09-05 | 2007-05-29 | Method of electroless plating on magnesium and alloy thereof |
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| CN100462479C (en) | 2009-02-18 |
| HK1099793A1 (en) | 2007-08-24 |
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