CN103806069A - Method for improving binding force of magnesium alloy surface galvanized coating by improving acid activation process - Google Patents
Method for improving binding force of magnesium alloy surface galvanized coating by improving acid activation process Download PDFInfo
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Abstract
The invention relates to a method for improving binding force of a magnesium alloy surface galvanized coating by improving an acid activation process. The acid activation method is characterized by comprising the following steps: adjusting pH value to 1-5 by using ammonium water in 0.5g/L of thiourea, 10-40mL/L hydrogen nitrate (65%) and 0.5-1.5g/L oxalic acid, and soaking by an acid at room temperature for 10-50 seconds. By adopting the acid activation method, residual oxide skin and dirt can be effectively removed, and the surface is cleaner, has activity, and is good in binding force of coating and magnesium alloy, stronger in protective capability, and less in matrix loss in the treatment process.
Description
Technical field
The present invention relates to a kind of surface treatment method of metallic substance, particularly a kind of method that improves Mg alloy surface electrolytic coating bonding force by improving acid-wash activation technique.
Background technology
Magnesium alloy has the performances such as higher specific tenacity, specific rigidity and good casting, damping, machining, dimensional stability and good electromagnetic shielding.But Mg alloy surface tissue easily produces corrosion, usually needs its surface to process, to increase the barrier propterty of Mg alloy surface.Due to be about-2.37v of the electrochemical bit of MAGNESIUM METAL, just very easily oxidation in normal atmospheric environment, this layer of oxide film is loose, insecure, can not play the effect of protection base material, and has hindered the surface treatment of magnesium alloy, hinders magnesium alloy materials and applies.
At present, in magnesium alloy surface protective treatment process, mainly contain the methods such as application processing, chromate conversion coating processing, electroplating processes, electroless plating processing, anodizing, thermal spraying on surface.Wherein, bonderizing is simple to operate, with low cost, less pollution can be as the processing method that effectively improves organic coating layer bonding force and barrier propterty.When magnesium alloy is carried out to phosphatization, because magnesium is too active, several problems that are difficult to avoidance are run into.The one, magnesium alloy microcosmic anode in phosphating reaction process causes corrosion zanjon; The 2nd, very fast because reaction more acutely causes solution composition to change, the particularly consumption of hydrogen ion, zine ion and the accumulation of magnesium ion, can make batch machining difficulty like this, is unfavorable for industrialization promotion.
CN101643928A discloses a kind of method of electrodepositing phosphate/metal composite film on cathode of surface of magnesium alloy, there are following steps: 1) get magnesium alloy, clean the surface of described magnesium alloy according to mechanical scrubbing, alkali cleaning degreasing, acid-wash activation colour temperature order, then water Rapid Cleaning; 2) by the magnesium alloy energising after step 1 is cleaned, under 3-5V voltage, charged proceeding in phosphatizing liquid soaked rapidly, and magnesium alloy hangs over electric tank cathode, and zinc does anode, current density range 1A-10 ampere/square decimeter, energising 2-10 minute; 3) take out magnesium alloy, 50 ℃ of-90 ℃ of hot blast dryings, form phosphoric acid salt/metal composite film on the surface of magnesium alloy materials, complete the surface treatment of magnesium alloy materials.Should be at magnesium alloy materials surface coverage phosphoric acid salt/metal composite thin film, finer and close than common phosphatize phosphate coat structure, bonding force is good, and protective capacities is stronger; The loss for the treatment of processes matrix is few, and the composition range for the treatment of solution is wider, and solution is convenient to safeguard.
But the hydrofluoric acid of the conventional pickling activating process 11% that aforesaid method adopts embathes and can not effectively carry out acid-wash activation to Mg alloy surface, thereby affect bonding force and the phosphoric acid salt/metal composite film quality between galvanic deposit phosphoric acid salt/metal composite film and magnesium alloy thereafter.And in actual demand, bonding force higher between phosphoric acid salt/metal composite film and magnesium alloy and quality are had to widespread demand.
Summary of the invention
Object of the present invention, is to provide a kind of method of electrodepositing phosphate/metal composite film on cathode of surface of magnesium alloy.The inventive method is at magnesium alloy materials surface coverage phosphoric acid salt/metal composite thin film, and finer and close than common phosphatize phosphate coat structure, bonding force is good, and protective capacities is stronger; The loss for the treatment of processes matrix is few.
For the deficiencies in the prior art, one of object of the present invention is to provide a kind of method that improves Mg alloy surface electrolytic coating bonding force by improving acid-wash activation technique.Described method is at magnesium alloy materials surface coverage phosphoric acid salt/metal composite thin film, and finer and close than common phosphatize phosphate coat structure, bonding force is better, and protective capacities is stronger; The loss for the treatment of processes matrix is few.
Realizing technical scheme of the present invention is:
A method that improves Mg alloy surface electrolytic coating bonding force by improving acid-wash activation technique, is characterized in that: acid-wash activation method is: thiocarbamide 0.5g/L, nitric acid (65%) 10～40mL/L, oxalic acid 0.5-1.5g/L, with ammoniacal liquor adjust pH to 1～5, room temperature, 10～50s, embathes.
A method that improves Mg alloy surface electrolytic coating bonding force by improving acid-wash activation technique, has following steps:
1) get magnesium alloy, clean the surface of described magnesium alloy according to mechanical scrubbing, alkali cleaning degreasing, acid-wash activation order, then by Rapid Cleaning in pure water or deionized water;
2) by the magnesium alloy energising after step 1 is cleaned, under 3-5V voltage, the charged phosphate solution that proceeds to soaks rapidly, and magnesium alloy hangs over electric tank cathode, and zinc does anode, and current setting is to 1-10A/D
2, 2-10 minute switches under normal temperature;
3) take out magnesium alloy, 50 ℃ of-90 ℃ of hot blast dryings, form phosphoric acid salt/metal composite film on the surface of magnesium alloy materials, complete the surface treatment of magnesium alloy materials.
Described step 1) in alkali cleaning degreasing method be: use 5g/l sodium hydroxide, 10g/l sodium phosphate, 10g/l sodium carbonate, 2g/l tensio-active agent mixing solutions washing, normal temperature agitation treatment 1min; Washing.
Described step 1) in acid-wash activation method be: thiocarbamide 0.4-0.6g/L, nitric acid (65%) 20-30mL/L, oxalic acid 0.5-1.5g/L, with ammoniacal liquor adjust pH to 1-5, room temperature, 10-50s, embathe, remove remaining oxide skin and dirt, make that surface is more clean an activity.
Described step 2) in the collocation method of etching solution be, first get zinc oxide zinc oxide 1-2 grams per liter water furnishing pasty state, after it being dissolved completely with phosphoric acid, add again following other reagent the thin up of adding, be made into phosphate solution: phosphoric acid 3-5 milliliter/liter, Sodium Fluoride 0.2-0.4 grams per liter, ammonium molybdate 0.2-1 grams per liter, sodium laurylsulfonate 0.1-0.2 grams per liter, tartrate 0.1-0.5 grams per liter.
Described step 2) in etching solution be: phosphoric acid 2-3 milliliter/liter, primary zinc phosphate 1-3 grams per liter, manganous carbonate 2-4 grams per liter, Sodium Fluoride 0.2-0.4 grams per liter, sodium laurylsulfonate 0.05-0.1 grams per liter, SODIUMNITRATE 0.1-0.2 grams per liter, Sodium Nitrite 0.2-0.4 grams per liter, citric acid 0.1-0.2 grams per liter.
Described step 2) in etching solution be: primary zinc phosphate 1-3 grams per liter, nickelous nitrate 0.2-0.5 grams per liter, Sodium Fluoride 0.2-0.4 grams per liter, phosphate dihydrogen manganese 0.1-0.2 grams per liter, sodium laurylsulfonate 0.05-0.1 grams per liter, SODIUMNITRATE 0.1-0.2 grams per liter, Sodium Nitrite 0.2-0.4 grams per liter, citric acid 0.1-0.2 grams per liter.
The thickness of described phosphoric acid salt/metal composite film is 1-3 micron.
Described phosphoric acid salt/metal composite film is zinc phosphate/zinc composite membrane or zinc phosphate-manganous phosphate/zinc composite membrane or zinc phosphate-manganous phosphate/zinc-nickel composite membrane.
Adopt technical solution of the present invention, utilize additional power source, magnesium alloy is placed in to negative electrode, do anode with zinc metal sheet, in the surface treatment process of magnesium alloy materials, tank liquor consumption is mainly hydrogen ion and phosphate radical, be convenient to continuous processing, and can supplement by regularly directly adding phosphoric acid, and with in sodium hydroxide and excessive hydrogen ion, make the free acid 1-2.5 point of solution, total acidity 20-30 point, like this under certain galvanic action, negative electrode magnesium alloy micro anode in acid phosphatase salts solution will greatly dwindle, directly utilize general evolving hydrogen reaction to consume the hydrogen ion of near surface solution, break the dissociation equilibrium of water, promote three grades of dissociations of phosphate radical, thereby cause phosphatic deposition.
Adopt the inventive method, make the present invention in the time carrying out surface treatment, overpotential has exceeded the deposition potential of metal ion in this solution, therefore metal ion also can discharge and disperse be embedded in phosphate layer, these positions thicken and keep the reacting weight of liberation of hydrogen by continuing, phosphatic deposition can be proceeded.Therefore, adopt the inventive method to form the thickness of phosphoric acid salt/metal composite film on the surface of magnesium alloy materials, can pass through the size of electric current and the length control of time.Cathodic polarization effect will greatly reduce the dissolving of magnesium matrix, has avoided occurring larger positive polarity gap, reduces greatly dissolved ions and pollutes treatment soln, and extend the solution life-span; Due to electrocatalysis, the free acid concentration of solution can be lower, and the appearance of disperse metallographic phase has also avoided the uncontrollable concentrated liberation of hydrogen hole of common phosphatization to occur.Anode supplements the zine ion of cathode consumption with metallic zinc electrochemical dissolution, and auxiliary with insoluble anode, tank liquor consumption is mainly hydrogen ion and phosphate radical, can supplement by regularly directly adding phosphoric acid, and with in sodium hydroxide with excessive hydrogen ion.Electrolysis 2-10 minute, just can obtain complete composite membrane, and increasing electrolysis time thicknesses of layers increases, and after 10 minutes, roughness obviously increases, and in order to adapt to the needs of application transition layer, gauge control is advisable at 1-3 micron.
Adopt the inventive method, the formation phosphoric acid salt/metal composite thin film forming at Mg alloy surface, its film layer structure densification, bonding force is good.In the time carrying out Mg alloy surface processing, matrix loss reduces more than 1 times than chemical phosphatization, and solution is more easily safeguarded.This composite membrane has good physical and mechanical properties and barrier propterty, within 1 week, corrodes without obvious in indoor placement, can reach 1 grade with coating adhesion (cross-hatching), is applicable to short-term protection and the application transition layer of magnesium alloy.
Described reagent is commercially available, and wherein phosphorus acid content is 85%, and all the other are analytical reagent.
Formation phosphoric acid salt/metal composite thin film that Mg alloy surface forms, according to solution, main salt system adjustment obtains the composite membrane of heterogeneity, adjusts the speed of film deposition according to current density size, adjusts the thickness of film according to the treatment time.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment mono-
Treatment soln required for the present invention is pressed following preparation:
Get zinc oxide 1.5g water furnishing pasty state, after with phosphatase 24 ml, it being dissolved completely, then add successively following reagent: Sodium Fluoride 0.3g, molybdate 0.5g, sodium laurylsulfonate 0.1g, tartrate 0.3g, is diluted with water to 1 liter.
Getting the trade mark is AZ31 extrusion magnesium alloy, follows these steps to magnesium-alloy material to carry out surface treatment:
1. conventional mechanical scrubbing: with sandblast or sand papering, except deburring, oxide compound, additive, processing wet goods foreign matter extruding for, wash;
2. conventional alkali cleaning degreasing: use 5g/l sodium hydroxide, 10g/l sodium phosphate, 10g/l sodium carbonate, the washing of 2g/l tensio-active agent mixing solutions, normal temperature agitation treatment 1min; Washing;
3. acid-wash activation: thiocarbamide 0.4g/L, nitric acid (65%) 20mL/L, oxalic acid 0.5g/L, by ammoniacal liquor adjust pH to 1, room temperature, 10s, embathes;
4. galvanic deposit composite membrane: the magnesium alloy after activation is put into after pure water or deionized water Rapid Cleaning, be suspended on electric tank cathode, chargedly proceed to rapidly above-mentioned treatment soln immersion treatment, use 1A-2A/D
2current density electrolysis 2-10 minute, takes out the hot blast drying through 50 ℃-90 ℃, can make Mg alloy surface obtain zinc phosphate/zinc composite membrane.
Can process continuously workpiece, solution temperature can raise 10 ℃-20 ℃ by nature, but still can obtain this rete.
Embodiment 2
Treatment soln required for the present invention is pressed following preparation:
2.5 milliliters/liter of phosphoric acid, primary zinc phosphate 2 grams per liters, manganous carbonate 3 grams per liters, Sodium Fluoride 0.2 grams per liter, sodium laurylsulfonate 0.05 grams per liter, SODIUMNITRATE 0.1 grams per liter, Sodium Nitrite 0.4 grams per liter, citric acid 0.1 grams per liter.Directly agent dissolves is formed in water to required solution according to said sequence.
Getting the trade mark is AZ31 extrusion magnesium alloy, according to the following step, magnesium-alloy material is carried out to surface treatment:
1. conventional mechanical scrubbing: with sandblast or sand papering, except deburring, oxide compound, additive, processing wet goods foreign matter extruding for, wash;
2. conventional alkali cleaning degreasing: use 5g/L sodium hydroxide, 10g/L sodium phosphate, 10g/L sodium carbonate, the washing of 2g/L tensio-active agent mixing solutions, normal temperature agitation treatment 1min; Washing;
3. acid-wash activation: thiocarbamide 0.5g/L, nitric acid (65%) 25mL/L, oxalic acid 1g/L, by ammoniacal liquor adjust pH to 3, room temperature, 30s, embathes;
4. galvanic deposit composite membrane: the magnesium alloy after activation is put into after pure water or deionized water Rapid Cleaning, after energising, be suspended on electric tank cathode, chargedly proceed to rapidly above-mentioned treatment soln immersion treatment, use 1A-2A/D
2current density electrolysis 2-10 minute, takes out the hot blast drying through 50 ℃-90 ℃, makes Mg alloy surface obtain zinc phosphate-manganous phosphate/zinc composite membrane.
Can process continuously workpiece, solution temperature can raise 10 ℃-20 ℃ by nature, but still can obtain this rete.
Embodiment 3
Treatment soln required for the present invention is pressed following preparation:
2 grams of primary zinc phosphates, 0.3 gram of nickelous nitrate, 0.3 gram of Sodium Fluoride, 0.2 gram of phosphate dihydrogen manganese, 0.1 gram of sodium laurylsulfonate, 0.2 gram of SODIUMNITRATE, 0.3 gram of Sodium Nitrite, 0.1 gram of citric acid, is dissolved in 1 premium on currency.
Getting the trade mark is AZ31 extrusion magnesium alloy, and peace the following step carries out surface treatment to magnesium-alloy material:
1. conventional mechanical scrubbing: with sandblast or sand papering, except deburring, oxide compound, additive, processing wet goods foreign matter extruding for, wash;
2. conventional alkali cleaning degreasing: use 5g/L sodium hydroxide, 10g/L sodium phosphate, 10g/L sodium carbonate, the washing of 2g/L tensio-active agent mixing solutions, normal temperature agitation treatment 1min; Washing;
3. acid-wash activation: thiocarbamide 0.6g/L, nitric acid (65%) 30mL/L, oxalic acid 1.5g/L, by ammoniacal liquor adjust pH to 5, room temperature, 50s, embathes;
4. galvanic deposit composite membrane: the magnesium alloy after activation is put into after pure water or deionized water Rapid Cleaning, after energising, be suspended on electric tank cathode, chargedly proceed to rapidly above-mentioned treatment soln immersion treatment, use 1A-2A/D
2(ampere/square decimeter) current density electrolysis 2-10 minute, takes out the hot blast drying through 50 ℃-90 ℃, makes Mg alloy surface obtain zinc phosphate-manganous phosphate/zinc-nickel composite membrane.
Can process continuously workpiece, solution temperature can raise 10 ℃-20 ℃ by nature, but still can obtain this rete.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (8)
1. one kind is improved the method for Mg alloy surface electrolytic coating bonding force by improving acid-wash activation technique, it is characterized in that: acid-wash activation method is: thiocarbamide 0.5g/L, nitric acid (65%) 10～40mL/L, oxalic acid 0.5-1.5g/L, with ammoniacal liquor adjust pH to 1～5, room temperature, 10～50s, embathes.
2. a method that improves Mg alloy surface electrolytic coating bonding force by improving acid-wash activation technique, is characterized in that there are following steps:
1) get magnesium alloy, clean the surface of described magnesium alloy according to mechanical scrubbing, alkali cleaning degreasing, acid-wash activation order, then by pure water or deionized water Rapid Cleaning;
2) by the magnesium alloy energising after step 1 is cleaned, under 3-5V voltage, the charged phosphate solution that proceeds to soaks rapidly, and magnesium alloy hangs over electric tank cathode, and zinc does anode, and current setting is to 1-10A/dm
22-10 minute switches under normal temperature, the collocation method of phosphate solution is first to get zinc oxide 1-2 grams per liter water furnishing pasty state, after it being dissolved completely with phosphoric acid, add again following other reagent thin up, be made into phosphate solution: phosphoric acid 3-5 milliliter/liter, Sodium Fluoride 0.2-0.4 grams per liter, ammonium molybdate 0.2-1 grams per liter, sodium laurylsulfonate 0.1-0.2 grams per liter, tartrate 0.1-0.5 grams per liter;
3) take out magnesium alloy, 50 ℃ of-90 ℃ of hot blast dryings, form zinc phosphate/zinc composite membrane on the surface of magnesium alloy materials, complete the surface treatment of magnesium alloy materials;
Described acid-wash activation method is: thiocarbamide 0.5g/L, and nitric acid (65%) 10～40mL/L, oxalic acid 0.5-1.5g/L, by ammoniacal liquor adjust pH to 1～5, room temperature, 10～50s, embathes.
3. method according to claim 2, is characterized in that: the thickness of described zinc phosphate/zinc composite membrane is 1-3 micron.
4. a method for electrodepositing phosphate/metal composite film on cathode of surface of magnesium alloy, is characterized in that, has following steps:
1) get magnesium alloy, clean the surface of described magnesium alloy according to mechanical scrubbing, alkali cleaning degreasing, acid-wash activation order, then by pure water or deionized water Rapid Cleaning;
2) by the magnesium alloy energising after step 1 is cleaned, under 3-5V voltage, the charged phosphate solution that proceeds to soaks rapidly, and magnesium alloy hangs over electric tank cathode, and zinc does anode, and current setting is to 1-10A/dm
22-10 minute switches under normal temperature, phosphate solution is: phosphoric acid 2-3 milliliter/liter, primary zinc phosphate 1-3 grams per liter, manganous carbonate 2-4 grams per liter, Sodium Fluoride 0.2-0.4 grams per liter, sodium laurylsulfonate 0.05-0.1 grams per liter, SODIUMNITRATE 0.1-0.2 grams per liter, Sodium Nitrite 0.2-0.4 grams per liter, citric acid 0.1-0.2 grams per liter;
3) take out magnesium alloy, 50 ℃ of-90 ℃ of hot blast dryings, form zinc phosphate-manganous phosphate/zinc composite membrane on the surface of magnesium alloy materials, complete the surface treatment of magnesium alloy materials;
Described acid-wash activation method is: thiocarbamide 0.5g/L, and nitric acid (65%) 10～40mL/L, oxalic acid 0.5-1.5g/L, by ammoniacal liquor adjust pH to 1～5, room temperature, 10～50s, embathes.
5. method according to claim 4, is characterized in that: the thickness of described zinc phosphate-manganous phosphate/zinc composite membrane is 1-3 micron.
6. a method for electrodepositing phosphate/metal composite film on cathode of surface of magnesium alloy, is characterized in that, has following steps:
1) get magnesium alloy, clean the surface of described magnesium alloy according to mechanical scrubbing, alkali cleaning degreasing, acid-wash activation order, then by pure water or deionized water Rapid Cleaning;
2) by the magnesium alloy energising after step 1 is cleaned, under 3-5V voltage, the charged phosphate solution that proceeds to soaks rapidly, and magnesium alloy hangs over electric tank cathode, and zinc does anode, and current setting is to 1-10A/dm
22-10 minute switches under normal temperature, phosphate solution is: primary zinc phosphate 1-3 grams per liter, nickelous nitrate 0.2-0.5 grams per liter, Sodium Fluoride 0.2-0.4 grams per liter, phosphate dihydrogen manganese 0.1-0.2 grams per liter, sodium laurylsulfonate 0.05-0.1 grams per liter, SODIUMNITRATE 0.1-0.2 grams per liter, Sodium Nitrite 0.2-0.4 grams per liter, citric acid 0.1-0.2 grams per liter;
3) take out magnesium alloy, 50 ℃ of-90 ℃ of hot blast dryings, form zinc phosphate-manganous phosphate/zinc-nickel composite membrane on the surface of magnesium alloy materials, complete the surface treatment of magnesium alloy materials;
Described acid-wash activation method is: thiocarbamide 0.5g/L, and nitric acid (65%) 10～40mL/L, oxalic acid 0.5-1.5g/L, by ammoniacal liquor adjust pH to 1～5, room temperature, 10～50s, embathes.
7. method according to claim 6, is characterized in that: the thickness of described zinc phosphate-manganous phosphate/zinc-nickel composite membrane is 1-3 micron.
8. the surface treatment method of magnesium alloy materials according to claim 6, it is characterized in that: described step 1) in alkali cleaning degreasing method be: use 5g/l sodium hydroxide, 10g/l sodium phosphate, 10g/l sodium carbonate, the washing of 2g/l tensio-active agent mixing solutions, normal temperature agitation treatment 1min; Washing.
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| CN201210451668.9A CN103806069A (en) | 2012-11-12 | 2012-11-12 | Method for improving binding force of magnesium alloy surface galvanized coating by improving acid activation process |
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| CN201210451668.9A CN103806069A (en) | 2012-11-12 | 2012-11-12 | Method for improving binding force of magnesium alloy surface galvanized coating by improving acid activation process |
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Application publication date: 20140521 |