CN101285193A - Acidic solution for treating surface of magnesium alloy and processing method - Google Patents
Acidic solution for treating surface of magnesium alloy and processing method Download PDFInfo
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- CN101285193A CN101285193A CNA2007100905047A CN200710090504A CN101285193A CN 101285193 A CN101285193 A CN 101285193A CN A2007100905047 A CNA2007100905047 A CN A2007100905047A CN 200710090504 A CN200710090504 A CN 200710090504A CN 101285193 A CN101285193 A CN 101285193A
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Abstract
The invention relates to acid solution used for processing the magnesium alloy surface. The acid solution is water solution which contains acids, inhibitor and wetting agent, wherein, the acids are first acids or mixture of first acids and second acids; the first acids are selected from one type or a plurality of types among citric acids, oxalic acids, tartaric acids, methanoic acids, acetic acids, metacetonic acids, butyric acids, glutaric acids, phenylformic acids, benzene dicarboxylic acids, lactic acids, glycolic acids, glyoxylic acids and amino acids; and the second acids are hydrochloric acids and/or nitric acids. By adoption of the acid solution, the magnesium alloy surface can be fully activated; the membranous layer of a converting film which is formed on the magnesium alloy surface after chemical conversion process is compact, has erosion resistance and good binding force with a paint film. Moreover, the method is a environment-friendly method for processing the magnesium alloy surface.
Description
Technical field
The invention relates to a kind of acidic solution and treatment process that is used to handle Mg alloy surface.
Background technology
Light metal material commonly used has three kinds: titanium, aluminium, magnesium, and magnesium is wherein the lighter.The density of magnesium is 1.78 gram per centimeters
3, be 2/3 of aluminium, 2/5 of titanium.And that magnesium alloy has is heat-resisting, damping, intensity height, be easy to die cast, advantage such as can directly reclaim.Because in light weight, magnesium alloy is widely used in aerospace field.Recent years, magnesium alloy also was used to make notebook computer and some electronic product shell in a large number.In addition, magnesium alloy also is one of the most attractive structured material of automobile lightweight.Present many countries are all at development novel magnesium alloy die-casting technique.On the family expenses car, as having a wide range of applications on the parts such as wheel, seat frame, wheel box.But magnesium is as lively as a cricket metal, and standard potential is-2.36 volts, promptly form crisp and loose oxide film with oxygen in air, so the erosion resistance of magnesium alloy is very poor, has restricted the use of magnesium alloy.Therefore, the Structure of magnesium alloy material will carry out suitable surface treatment before use, and to improve its erosion resistance, this performance advantage to performance magnesium and magnesium alloy has great significance.
CN1837407A discloses the surface treatment method of a kind of magnesium or its alloy, this method comprises carries out oil removal treatment to workpiece surface earlier, then, immerse in the treatment solution magnesium or its alloy and stirred solution, soaking temperature is a room temperature, soak time is 0.5-10 minute, and above-mentioned treatment solution is that deionized water is formed by wetting agent and the surplus that mass percent is the oxalic acid of 0.5-10%, phosphoric acid that mass percent is 0.5-15%, mass percent is 1-10% ammonium bifluoride, inhibiter that mass percent is 1-3% and mass percent are 0.0005-0.001%.
The surface treatment method of this magnesium alloy comprises that elder generation carries out pre-treatment---oil removal treatment to magnesium alloy, contacts with acidic solution then, carries out pickling.This method is by being immersed in the above-mentioned pickling agent magnesium or its alloy with oxide film, oxide skin of removing magnesium or its alloy surface and the viscous deformation top layer skin of being with stress.Contain in the pickling agent that this method adopted and have toxic pharmaceutical chemicals ammonium bifluoride, meeting generation H after its hydrolysis
+And F
-, this pickling agent is equivalent to traditional hydrogen fluoride trealment liquid, and is harmful to human body and environment.In addition, the formed magnesium fluoride film of this method thin layer makes magnesium or its alloy surface activation deficiency, when further handling with chemical conversion solution, the conversion film of formation is inhomogeneous, and corrosion resistance nature is undesirable, and the surface resistivity height of conversion film, the surface resistivity of conversion film is too high can to limit Application of Magnesium, as before electrocoating paint is done on the conversion film surface, requires the conversion film of magnesium alloy to have strong electroconductibility, if the too high electroconductibility that can influence magnesium alloy of the surface resistivity of conversion film, and the bonding force of paint film is poor.
Can also further magnesium alloy be contacted with chemical conversion treatment solution after the pickling, it is in order to form the passive film that is formed by oxide compound or metal-salt at Mg alloy surface, to play the corrosion-resisting function to Mg alloy surface that magnesium alloy is contacted with chemical conversion treatment solution.Usually adopt chromium series elements solution that magnesium alloy is carried out chemical conversion in the prior art and handle, prevent that to form one deck dense film magnesium alloy is corroded.Though traditional chromate treating technology is respond well, wherein contains hexavalent chromium, toxicity is big, contaminate environment, and the cost of liquid waste disposal is higher.Simultaneously, with the chemical oxidation liquid that contains heavy metallic salt magnesium alloy is being carried out the occasion of chemical oxidation, when metal carried out recycling, heavy metal element can become impurity, influenced the composition of alloy.Therefore, adopting the Chrome-free chemical conversion treatment solution that magnesium alloy is carried out the surface-treated method more and more is subject to people's attention.
CN1386902A discloses a kind of chemical conversion reagent, surface treatment method and Mg-alloy matrix that is used for magnesium alloy, and the chemical conversion reagent that this method adopts comprises phosphate anion and high manganese ion, and its pH value is 1.5-7.The source of described phosphate anion comprises phosphoric acid salt, as, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, Secondary ammonium phosphate, potassium primary phosphate, dipotassium hydrogen phosphate and ortho-phosphoric acid, the source of high manganese ion comprises the aqueous solution of potassium permanganate, sodium permanganate and ammonium permanganate.This treatment process comprises Mg-alloy matrix contacted with above-mentioned chemical conversion reagent, and this method can also be included in Mg-alloy matrix with before above-mentioned chemical conversion reagent contacts, and described Mg-alloy matrix carried out degreasing, acidleach and disacidify in advance wash mud and handle; The used acid of described acidleach comprises a kind of acid that is selected from sulfuric acid, nitric acid, phosphoric acid and the fluorochemicals at least; Be preferably silicofluoric acid and ortho-phosphoric acid mixed aqueous solution or sulfuric acid or aqueous nitric acid.Though this method can form conversion film on the Mg-alloy matrix surface,, the erosion resistance of this conversion film and paint film bonding force are all relatively poor, and not as the conversion film that is obtained by chromate process, and it is inhomogeneous to transform rete, is prone to the metal bright spot.
Summary of the invention
It is poor and have that toxicity can be detrimental to health and to the defective that environment pollutes, provide a kind of and be used to handle the acidic solution of Mg alloy surface and can make Mg alloy surface obtain the treatment method on surface of magnesium alloy of abundant activatory environmental protection to the activation performance of Mg alloy surface to the objective of the invention is to overcome the treatment soln that adopts in the existing surface treatment method of Mg alloy.
The present inventor finds, with the quality of the sour effect that magnesium alloy is cleaned, the key of subsequent disposal operation success or not often.For die casting, often use and contain chromic acid, hydrofluoric acid, nitric acid, phosphoric acid, one or more sour mixing solutionss in sulfuric acid and the silicofluoric acid clean, these acid tend to corrode magnesium alloy deep layer base material when cleaning magnesium alloy oxide film and metamorphic layer, Mg alloy surface is fully activated, and alloy surface can residually have grey film, the ash film remains in the atrament on the magnesium alloy substrate when being acid corrosion magnesium alloy oxide film and metamorphic layer, if can not remove the sticking power that totally can influence the passive film that forms in the subsequent chemistry treatment process, erosion resistance and paint film bonding force.And also contain objectionable impuritiess such as chromium, cyanogen, fluorine, manganese, boron in the above-mentioned acid, not only can be detrimental to health, also can pollute environment.
The invention provides a kind of acidic solution that is used to handle Mg alloy surface, this acidic solution is the aqueous solution that contains acid, inhibiter and wetting agent, wherein, described acid is first kind of acid, the perhaps mixture of first kind of acid and second kind of acid, described first kind of acid is selected from one or more in citric acid, oxalic acid, tartrate, formic acid, acetate, propionic acid, butyric acid, pentanedioic acid, phenylformic acid, phthalic acid, lactic acid, glycolic acid, glyoxylic acid and the amino acid, and described second kind of acid is hydrochloric acid and/or nitric acid.
The invention provides a kind of treatment method on surface of magnesium alloy, this method comprises magnesium alloy is contacted with acidic solution with degreasing fluid successively, described acidic solution is for containing acid, the aqueous solution of inhibiter and wetting agent, wherein, described acid is first kind of acid, the perhaps mixture of first kind of acid and second kind of acid, described first kind of acid is selected from citric acid, oxalic acid, tartrate, formic acid, acetate, propionic acid, butyric acid, pentanedioic acid, phenylformic acid, phthalic acid, lactic acid, glycolic acid, in glyoxylic acid and the amino acid one or more, described second kind of acid is hydrochloric acid and/or nitric acid.
Adopt acidic solution of the present invention oxide film, metamorphic layer, corrosion product and the metal segregation of Mg alloy surface thoroughly can be removed, can be at the residual grey film of alloy surface, and can not corrode magnesium alloy deep layer base material, Mg alloy surface is fully activated, the more important thing is, this method can provide even Mg alloy surface a kind of cleaning, highly active for subsequent chemistry conversion processing operation, can guarantee handling the conversion film rete densification that the back Mg alloy surface forms, erosion resistance and good through chemical conversion with the bonding force of paint film.And the thicknesses of layers homogeneous, resistance is low, and the electromagnetic wave shielding performance is good.In addition, the treatment solution that treatment process of the present invention adopts does not contain objectionable impuritiess such as chromium, cyanogen, fluorine, manganese, boron, therefore can not be detrimental to health, also can environment not polluted, and be a kind of environment amenable treatment process.
Embodiment
According to the acidic solution that is used to handle Mg alloy surface provided by the invention, described first kind of acid is selected from one or more in citric acid, oxalic acid, tartrate, formic acid, acetate, propionic acid, butyric acid, pentanedioic acid, phenylformic acid, phthalic acid, lactic acid, glycolic acid, glyoxylic acid and the amino acid; Described amino acid can be existing any amino acid, usually can be in common 20 kinds of primary amino acids one or more, as L-Ala, arginine, aspartic acid, halfcystine, glutamine, L-glutamic acid, glycine, Histidine, Isoleucine, leucine, Methionin, methionine(Met), phenylalanine, proline(Pro), Serine, Threonine, tryptophane, tyrosine and Xie Ansuan; Be preferably in glyoxylic acid, formic acid, acetate, oxalic acid and the tartrate one or more; Described second kind of acid is to the inactive acid of magnesium alloy, is preferably hydrochloric acid and/or nitric acid.In described acidic solution, the weight ratio of described second kind of acid and first kind of acid is 0-0.2: 1, be preferably 0.1-0.15: 1.
Acid in the acidic solution of the present invention not can with the Mg in the magnesium alloy
2+Generate the throw out layer, adopt acidic solution of the present invention oxide film, metamorphic layer, corrosion product and the metal segregation of Mg alloy surface thoroughly can be removed, can be at the residual grey film of alloy surface, and can not corrode magnesium alloy deep layer base material, Mg alloy surface is fully activated, the more important thing is that this method can be handled for follow-up chemical conversion a kind of cleaning, highly active even Mg alloy surface are provided.
Inhibiter in the acidic solution of the present invention can be the various inhibiter of this area routine, as in triethanolamine oleate, oleic acid diethanolamine, trolamine, hexamethylenetetramine, thiocarbamide, benzotriazole, Sunmorl N 60S, Sodium Benzoate, water glass, SODIUMNITRATE, kelene yl pyridines ammonium salt, tetrahydroglyoxaline based compound and the oleoyl sarcosinates one or more, be preferably the mixture of hexamethylenetetramine and Sunmorl N 60S.Described inhibiter can form one deck isolated substance between Mg alloy surface and acid etch liquid, thereby has stoped the continuous dissolving of magnesium alloy, plays corrosion inhibition, also can prevent to separate out because of hydrogen simultaneously the generation of " hydrogen embrittlement " phenomenon that produces.When " hydrogen embrittlement " phenomenon took place Mg alloy surface, a lot of spileholes can appear in its surface, had a strong impact on the cleaning quality of magnesium alloy, caused the performances such as sticking power, erosion resistance and paint film bonding force of the conversion film that obtains through the subsequent chemistry conversion processing not good.
The kind of the wetting agent in the acidic solution of the present invention is conventionally known to one of skill in the art, as being in nonionogenic tenside or the sulfonate type anion surfactant one or more, as: OP emulsifying agent, tween emulsifier, as in Tween80 and the fatty alcohol-polyoxyethylene ether one or more, be preferably fatty alcohol-polyoxyethylene ether.Described wetting agent can repel the adsorbed gas of Mg alloy surface, helps contacting of acidic solution and Mg alloy surface.
According to the present invention, the weight ratio of the acid in the described acidic solution, inhibiter and wetting agent is 1: 0.1-0.8: 0.01-0.08 is preferably 1: 0.15-0.5: 0.01-0.05.
Can also contain stablizer in the acidic solution of the present invention, described stablizer can be selected from one or more in citric acid, oxyacetic acid, ethylenediamine tetraacetic acid (EDTA) and their salt; Wherein, described citric acid can also be as stablizer and magnesium ion complexing, the aforementioned stable agent all very easily with the magnesium ion complexing, and the complex compound that is generated can not form precipitation in the aqueous solution, can significantly improve the work-ing life of acidic solution.The weight ratio of acid is 0.1-0.2 in described stablizer and the acidic solution: 1, be preferably 0.1-0.15: 1.
According to treatment process provided by the invention, the temperature that contacts with acidic solution can be that room temperature is to the boiling point that is not higher than acid in the described acidic solution, in order to protect Working environment and to avoid corroding or excessive dirt forms the infringement that thing causes owing to over-drastic, the temperature that contacts with acidic solution is preferably 20-70 ℃, more preferably 25-65 ℃; The time that contacts with acidic solution is 10 second-5 minute, is preferably 10 second-2 minute; The pH value of described acidic solution is generally 1-5.
Magnesium alloy is used as the oil in water emulsion severe contamination of releasing agent often in pouring operation, and according to the casting condition of alloy, isolated chromatography layer can occur at alloy surface.In the case, for the carrying out that guarantees that pickling and the chemical conversion that preferably includes are subsequently handled, need with magnesium alloy with contact with degreasing fluid before acidic solution contacts.
Magnesium alloy is contacted with degreasing fluid, the releasing agent and the cutting fluid of infiltrating magnesium alloy in the grease of Mg alloy surface and the oxide compound and the course of processing can be removed, described degreasing fluid is to contain the aqueous solution that is selected from one or more sodium salts in tertiary sodium phosphate, yellow soda ash and the water glass.Can also contain tensio-active agent in the described degreasing fluid, described tensio-active agent can be selected from Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyoxyethylene alkylphenol ether and contain the tensio-active agent of polyoxyethylene alkylphenol ether, as among the OP-10 one or more.
In every liter of degreasing fluid, the content of described sodium salt is the 10-40 gram, is preferably the 15-30 gram; The content of described tensio-active agent is the 0-5 gram, is preferably the 0.5-3 gram.
The pH value of described degreasing fluid is 8-14, and the temperature that contacts with described degreasing fluid can be 30-80 ℃, is preferably 40-70 ℃; The time that contacts with degreasing fluid can be 1-40 minute, is preferably 3-30 minute.
According to method of the present invention, after described magnesium alloy is carried out degreasing and acid treatment, thereby oxide film, metamorphic layer, corrosion product and the metal segregation etc. of having removed Mg alloy surface activate alloy surface, under the preferable case, in order to make Mg alloy surface obtain conversion film with splendid erosion resistance, high paint film bonding force and low surface resistivity performance, this method also comprise this with magnesium alloy successively with degreasing fluid with after acidic solution contacts, contact with chemical conversion treatment solution, to promote the generation of Mg alloy surface oxide film, increase the compactness and the glossiness of film.
The kind of described chemical conversion treatment solution, composition and the method that contacts with chemical conversion treatment solution and condition are conventionally known to one of skill in the art, the chemical conversion treatment solution that the present invention preferably adopts is the aqueous solution that contains water-soluble phosphate, phosphoric acid and film coalescence aid, described water-soluble phosphate can form the conversion film of one deck densification at Mg alloy surface as membrane-forming agent, and described water-soluble phosphate can be selected from one or more in monocalcium phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate and the primary magnesium phosphate; Described film coalescence aid helps the film forming of dihydrogen phosphate at Mg alloy surface, and described film coalescence aid can be in sodium metavanadate, ammonium meta-vanadate, potassium metavanadate, magnesium nitrate and the SODIUMNITRATE one or more.The phosphoric acid that contains in the described chemical conversion treatment solution can also provide phosphate anion in that the hydrionic while is provided, and helps to make with the film coalescence aid effect conversion film refinement, the densification of formation.
The weight ratio of the water-soluble phosphate in the described chemical conversion treatment solution, phosphoric acid and film coalescence aid is 5-50: 1-17: 1, be preferably 5-20: 1-10: 1.
In the process of magnesium alloy being carried out the chemical conversion processing, preferred pH value of regulating described treatment solution is 1-6, the method of described adjusting treatment solution pH value can adopt conventional method, as adopt acid-base modifier to regulate, as, aqueous sodium hydroxide solution, ammoniacal liquor or phosphate aqueous solution wait to be regulated.
In chemical conversion processing process, the temperature that contacts with described chemical conversion treatment solution is 15-60 ℃, is preferably 20-55 ℃; The time that contacts with chemical conversion treatment solution is 10 second-10 minute, is preferably 30 second-3 minute.
According to the present invention, magnesium alloy is contacted with acidic solution carry out pickling after, Mg alloy surface also can what remainingly have a small amount of acidic solution and residual film of segregation intermetallic compound and a residual film of oxide compound, in order to make the more smooth cleaning of Mg alloy surface, and more help contacting the back and form more even, fine and close conversion film with chemical conversion treatment solution, more preferably under the situation, this method also comprises, with magnesium alloy successively with degreasing fluid with after acidic solution contacts, with before chemical conversion solution contacts, contact with basic solution.
With magnesium alloy successively with degreasing fluid with after acidic solution contacts, with before chemical conversion solution contacts, contact with basic solution, to remove residual a small amount of acidic solution of Mg alloy surface and the residual film of segregation intermetallic compound and the residual film of oxide compound, the kind of described basic solution, method and the condition forming and contact with alkali solution are conventionally known to one of skill in the art, the basic solution that the present invention preferably adopts is the aqueous solution of alkali metal compound, and described alkali-metal compound can be selected from sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium phosphate, potassiumphosphate, trisodium phosphate, potassium pyrophosphate, in sodium-metaphosphate and the potassium metaphosphate one or more.
With process that basic solution contacts in, the concentration of described basic solution is not particularly limited, under the preferable case, the pH value of described basic solution is 8-14, the temperature that contacts with basic solution is 30-80 ℃, is preferably 50-80 ℃; The time that contacts with basic solution is 10 second-5 minute, is preferably 1-3 minute.
According to method provided by the invention, this method also is included in the washing step between each treatment process, and the method for washing can adopt various method for washing known in the art, as artificial washing or ultrasonic wave washing.Washing times between described each treatment process and washing condition are not particularly limited, as long as the treatment solution of Mg alloy surface is fully removed clean.The temperature of described washing is preferably 10-60 ℃.Under the preferable case, the washing times after described skimming treatment is 1-3 time; Washing times after described acid treatment is 2-4 time; Washing times after described basic solution is handled is 2-4 time; The washing times of handling laggard row in described chemical conversion is 1-3 time.The used water of washing step is various water of the prior art, as municipal tap water, deionized water, distilled water, pure water or their mixture.
The described method that magnesium alloy is contacted with treatment solution in each treatment process successively is preferably magnesium alloy is immersed in the treatment solution, perhaps use treatment solution drip washing magnesium alloy, preferably magnesium alloy can also be soaked in ultrasonic wave, to guarantee fully contacting of treatment solution that magnesium alloy and each treatment step are adopted.
The described method that Mg alloy surface is handled also is included in the drying treatment after last washing is handled, and described exsiccant method can adopt the method for well known to a person skilled in the art, as vacuum in dry, seasoning and forced air drying etc.Described exsiccant temperature is a room temperature to 150 ℃, is preferably 80-130 ℃; The exsiccant time is 10-60 minute, is preferably 20-40 minute.
Method provided by the invention can be carried out surface treatment to the magnesium alloy of arbitrary form, adopts the AZ91D die cast product as the surface-treated sample in specific embodiments of the invention.
To the present invention be described in more detail by embodiment below.
Embodiment 1
This embodiment illustrates treatment method on surface of magnesium alloy provided by the invention.
(1) skimming treatment:
29 gram tertiary sodium phosphates and 1 gram tensio-active agent Sodium dodecylbenzene sulfonate are dissolved in the 1000 gram water, stir, obtain degreasing fluid.
Under 60 ℃, AZ91D (Nanjing Yunhai Special Metal Co., Ltd) diecast magnesium alloy goods ultrasonic wave in above-mentioned tertiary sodium phosphate degreasing fluid that will be of a size of 80 * 50 * 2 millimeters was soaked 10 minutes, take out, be cooled to room temperature, again magnesium alloy is washed 2 times at the deionized water for ultrasonic ripple, each 2 minutes, fully degreasing fluid is cleaned up.
(2) acid treatment:
20 milliliters of glyoxylic acids, 3 gram hexamethylenetetramines, 3 gram Sunmorl N 60Ss and 1 gram fatty alcohol-polyoxyethylene ether and 1000 are restrained water mix, obtain the pH value and be 2.5 acidic aqueous solution.
Under 50 ℃, the magnesium alloy after will handling through step (1) soaks 1 fen half in above-mentioned acidic aqueous solution, take out, and is cooled to room temperature, magnesium alloy is manually shaken washing 2 times in deionized water again, and each 3 minutes fully to clean up acidic solution.
Magnesium alloy after will handling through above-mentioned steps descended dry 30 minutes at 130 ℃, obtained through the magnesium alloy after the surface treatment.
Embodiment 2
This embodiment illustrates treatment method on surface of magnesium alloy provided by the invention
Method according to embodiment 1 is carried out skimming treatment and acid treatment to magnesium alloy, different is, to mix the pH value that obtains be 2.5 acidic aqueous solution to the acidic solution in the described acid treatment step in order 20 milliliters of glyoxylic acids, 1 gram fatty alcohol-polyoxyethylene ether, 4 gram citric acids, 3 gram hexamethylenetetramines and 3 gram Sunmorl N 60Ss and 1000 are restrained water.
Embodiment 3
This embodiment illustrates treatment method on surface of magnesium alloy provided by the invention
Method according to embodiment 1 is carried out skimming treatment and acid treatment to magnesium alloy, different is, the acidic solution in the described acid treatment step is 1.5 acidic aqueous solution for the pH value that 20 milliliters of glyoxylic acids, 2 milliliters of nitric acid, 1 gram fatty alcohol-polyoxyethylene ether, 3 gram hexamethylenetetramines, 3 gram Sunmorl N 60Ss and 1000 is restrained water and mix to obtain.
Embodiment 4
This embodiment illustrates treatment method on surface of magnesium alloy provided by the invention
Method according to embodiment 1 is carried out skimming treatment and acid treatment to magnesium alloy, different is, the acidic solution in the described acid treatment step is 1.5 acidic aqueous solution for the pH value that 20 milliliters of glyoxylic acids, 2 milliliters of nitric acid, 1 gram fatty alcohol-polyoxyethylene ether, 4 gram ethylenediamine tetraacetic acid (EDTA)s, 3 gram hexamethylenetetramines, 3 gram Sunmorl N 60Ss and 1000 is restrained water and mix to obtain.
Embodiment 5
This embodiment illustrates treatment method on surface of magnesium alloy provided by the invention
Method according to embodiment 1 is carried out skimming treatment and acid treatment to magnesium alloy, and different is after acid treatment, magnesium alloy to be continued to contact with chemical conversion treatment solution.
Described chemical conversion treatment solution is: 20 gram monocalcium phosphates, 6 gram phosphoric acid, the inclined to one side sodium vanadate of 1 gram are dissolved in the 1000 gram water, and mixing and stirring obtains the pH value and is 2.5 chemical conversion treatment solution.
Under 45 ℃, will in above-mentioned treatment solution, soak 45 seconds through the magnesium alloy after the overpickling, take out, be cooled to room temperature, again magnesium alloy is manually shaken washing 2 times in deionized water, washed 2 minutes, fully chemical conversion treatment solution is cleaned up at every turn.
Magnesium alloy after will handling through above-mentioned steps descended dry 30 minutes at 130 ℃, obtained through the magnesium alloy after the surface treatment.
Embodiment 6
This embodiment illustrates treatment method on surface of magnesium alloy provided by the invention
Magnesium alloy is carried out skimming treatment, acid treatment and contact with chemical conversion treatment solution according to the method for embodiment 5, different is, after acid treatment, and with magnesium alloy with before chemical conversion treatment solution contacts, magnesium alloy is contacted with basic solution.
Described basic solution is: 35 gram sodium hydroxide are dissolved in the 1000 gram water, mix, obtain the pH value and be 14 alkaline aqueous solution.
Under 75 ℃, will in above-mentioned alkaline processing liquid, soak 3 minutes through the magnesium alloy after the overpickling, take out, be cooled to room temperature, again magnesium alloy is manually shaken washing 2 times in deionized water, washed 2 minutes, fully basic solution is cleaned up at every turn.Contact with chemical conversion treatment solution then also and obtain through the magnesium alloy after the surface treatment after the drying.
Embodiment 7
This embodiment illustrates the method that Mg alloy surface is handled provided by the invention
Method according to embodiment 5 is carried out surface treatment to AZ91D diecast magnesium alloy goods, different is, described acidic aqueous solution is the acidic solution described in the embodiment 3, and the temperature that contacts with described acidic solution is 50 ℃, and the time that contacts with described acidic solution was 50 seconds.
Embodiment 8
This embodiment illustrates the method that Mg alloy surface is handled provided by the invention
Method according to embodiment 6 is carried out surface treatment to AZ91D diecast magnesium alloy goods, different is, described acidic aqueous solution is the acidic solution described in the embodiment 3, and the temperature that contacts with described acidic solution is 50 ℃, and the time that contacts with described acidic solution is 90 seconds.
Embodiment 9
This embodiment illustrates the method that Mg alloy surface is handled provided by the invention
According to embodiment 6 described methods AZ91D diecast magnesium alloy goods are carried out surface treatment, different is, described acidic aqueous solution is the acidic solution described in the embodiment 4, and the temperature that contacts with described acidic solution is 55 ℃, and the time that contacts with acidic solution is 1 minute.
Embodiment 10
This embodiment illustrates the method that Mg alloy surface is handled provided by the invention
According to embodiment 6 described methods AZ91D diecast magnesium alloy goods are carried out surface treatment, different is, described acidic solution mixes for 2 milliliters of hydrochloric acid, 1.5 milliliters of nitric acid, 20 milliliters of glyoxylic acids, 5 milliliters of tartrate, 4 gram citric acids, 4 gram Sunmorl N 60Ss, 2 gram trolamines, 0.5 gram Tween80,4 gram ethylenediamine tetraacetic acid (EDTA)s and 1000 being restrained water that to obtain the pH value be 3 acidic aqueous solution, the temperature that contacts with described acidic solution is 58 ℃, and the time that contacts with described acidic solution is 90 seconds.
Embodiment 11
This embodiment illustrates the method that Mg alloy surface is handled provided by the invention
Method according to embodiment 6 is carried out surface treatment to AZ91D diecast magnesium alloy goods, different is, described acidic solution mixes for 2.5 milliliters of hydrochloric acid, 10 milliliters of glyoxylic acids, 5 milliliters of formic acid, 5 milliliters of acetate, 5 milliliters of tartrate, 2 gram oleic acid diethanolamine, 2 gram trolamines, 0.5 gram Tween80,3 gram oxyacetic acids and 1000 being restrained water that to obtain the pH value be 3 acidic aqueous solution.To obtain the pH value in the water be 13 alkaline aqueous solution to described alkaline aqueous solution in order 20 gram potassium hydroxide and 10 gram yellow soda ash are dissolved in 1000 grams, and the temperature that contacts with described alkaline aqueous solution is 75 ℃, and the time that contacts with described alkaline aqueous solution is 30 seconds.To obtain the pH value after the 1000 gram water mixing and stirring be 3 chemical conversion treatment solution to described chemical conversion treatment solution in order 40 gram monocalcium phosphates, 10 gram phosphoric acid and the inclined to one side alum of 2.5 grams acid ammonium are dissolved in.The temperature that contacts with described chemical conversion treatment solution is 45 ℃, and the time that contacts with described chemical conversion treatment solution is 50 seconds.
Embodiment 12
This embodiment illustrates the method that Mg alloy surface is handled provided by the invention
Method according to embodiment 6 is carried out surface treatment to AZ91D diecast magnesium alloy goods, and different is that described acidic solution is embodiment 4 described acidic aqueous solutions.To obtain the pH value in the water be 13 alkaline aqueous solution to described alkaline aqueous solution in order 20 gram potassium hydroxide and 10 gram yellow soda ash are dissolved in 1000 grams, and the temperature that contacts with described alkaline aqueous solution is 75 ℃, and the time that contacts with described alkaline aqueous solution is 30 seconds.To obtain the pH value after the 1000 gram water mixing and stirring be 3 chemical conversion treatment solution to described chemical conversion treatment solution in order 40 gram monocalcium phosphates, 10 gram phosphoric acid and the inclined to one side alum of 2.5 grams acid ammonium are dissolved in.The temperature that contacts with described chemical conversion treatment solution is 40 ℃, and the time that contacts with described chemical conversion treatment solution is 1 minute.
Comparative Examples 1
The treatment method on surface of magnesium alloy of this Comparative Examples explanation prior art
Method according to the disclosed embodiment 1 of CN1837407A is carried out surface treatment to AZ91D diecast magnesium alloy goods.And above-mentioned treated magnesium alloy is contacted with chemical conversion treatment solution with basic solution successively according to the method for embodiment 6.
Comparative Examples 2
The treatment method on surface of magnesium alloy of this Comparative Examples explanation prior art
Method according to the disclosed embodiment 1 of CN1386902A is carried out surface treatment to AZ91D diecast magnesium alloy goods.
Embodiment 13-20
This embodiment carries out the test of erosion resistance, paint film bonding force and lacquer-film surface resistivity to the magnesium alloy through after surperficial processing that embodiment 5-12 obtains respectively.
The erosion resistance test:
According to JIS Z-2371 standard, be that 5% sodium chloride brine is sprayed at the Mg alloy surface after surface treatment with concentration, after 8 hours, observe and the corrosion rate of measuring and calculating magnesium alloy.
Corrosion rate=(surface-area of the region area/magnesium alloy that is corroded) * 100%
The result is as shown in table 1.
The assessment of paint film bonding force (test of hundred lattice):
To apply with epoxypaint through the magnesium alloy sample that obtains after the chemical conversion treatment process and (apply altogether 3 times, toast after each the coating, total coating thickness is 50 microns), in 80 ℃ of dryings 30 minutes, then the magnesium alloy sample is carried out the performance test of paint film bonding force at last.
Testing method: mark 100 of the lattice numbers (scratch depth is controlled at and guarantees film lower substrate metal exposed) that are spaced apart 1 millimeter of uniform size with sharp blade at Mg alloy surface, the lattice that the statistics film comes off is counted N1, to stick width be 24 millimeters scotch tape in the lattice zone of drawing on film, and guarantee to combine between adhesive tape and the film that grid is arranged tight.After 5 minutes, adhesive tape is uncovered, and added up the lattice that film comes off once more and count N2 with the power of a vertical face.Appraisal procedure is as follows: adopt centesimal system, lacquer-binding force of membrane mark Z (%)=100-(N1+N2) * 100%.
The result is as shown in table 1.
The assessment of conversion film surface resistivity:
Measure the surface resistivity of magnesium alloy conversion film in surface resistivity (Loresta MP, Mitsubishi Chemical Corp, model CP-T350, two-point probe MCP-TP01).
Comparative Examples 3-4
This Comparative Examples is carried out the test of erosion resistance and paint film bonding force and lacquer-film surface resistivity to the reference magnesium alloy through after surperficial processing that Comparative Examples 1-2 obtains respectively.
According to the method for embodiment 13-20 the magnesium alloy after handling through the surface is carried out the test of corrosion resistance nature and lacquer-film sticking power, different is described magnesium alloy is the magnesium alloy of the reference method that adopts Comparative Examples 1-2 after handling.
The result is as shown in table 1.
Table 1
| The embodiment numbering | Surface resistivity (ohm) | The regional percentage that is corroded S (%) | Lacquer-binding force of membrane mark (%) |
| Embodiment 13 | 1.0 | S＜5 | 95 |
| Embodiment 14 | 0.05 | S＜5 | 100 |
| Embodiment 15 | 0.80 | S＜5 | 97 |
| Embodiment 16 | 0.03 | S＜5 | 100 |
| Embodiment 17 | 0.03 | S＜2 | 100 |
| Embodiment 18 | 0.04 | S＜2 | 100 |
| Embodiment 19 | 0.05 | S＜4 | 100 |
| Embodiment 20 | 0.04 | S＜2 | 100 |
| Comparative Examples 3 | 1.70 | 8＜S＜15 | 86 |
| Comparative Examples 4 | 2.25 | 10＜S＜20 | 85 |
Data from table 1 as can be seen, after adopting method of the present invention that Mg alloy surface is handled, the regional ratio that is corroded that transforms rete is all less than 5%, lacquer-binding force of membrane mark is more than 95%, illustrate adopt acidic solution of the present invention to carry out after the acid treatment and carry out the chemical conversion treatment reason Mg alloy surface after, in the conversion film rete densification that Mg alloy surface forms, erosion resistance and good with the bonding force of paint film, and surface resistivity is also lower, illustrates the electromagnetic wave shielding performance good.The result of comparing embodiment 14 and Comparative Examples 3 as can be seen, though the method for the foregoing description 14 and Comparative Examples 3 all adopts identical chemical conversion processing method after acid treatment, but adopt the erosion resistance of conversion film of the Mg alloy surface that method of the present invention obtains and the method that the paint film bonding force obviously is better than Comparative Examples, the activity performance that employing acidic solution of the present invention is described is good, can be with the oxide film of Mg alloy surface, metamorphic layer, corrosion product and metal segregation are thoroughly removed, can be at the residual grey film of alloy surface, and can not corrode magnesium alloy deep layer base material, Mg alloy surface is fully activated, for subsequent chemistry conversion processing operation provides a kind of cleaning, highly active even Mg alloy surface, therefore, after carrying out the chemical conversion processing, in the conversion film rete densification that Mg alloy surface forms, erosion resistance and good with the bonding force of paint film.In addition, all do not contain objectionable impuritiess such as chromium, cyanogen, fluorine, manganese and boron in pickling agent that adopts in the treatment process provided by the invention and the chemical conversion treatment solution, therefore can not be detrimental to health, also can not pollute environment, be a kind of environment amenable treatment process.
Claims (18)
1, a kind of acidic solution that is used to handle Mg alloy surface, this acidic solution is the aqueous solution that contains acid, inhibiter and wetting agent, it is characterized in that, described acid is first kind of acid, the perhaps mixture of first kind of acid and second kind of acid, described first kind of acid is selected from one or more in citric acid, oxalic acid, tartrate, formic acid, acetate, propionic acid, butyric acid, pentanedioic acid, phenylformic acid, phthalic acid, lactic acid, glycolic acid, glyoxylic acid and the amino acid, and described second kind of acid is hydrochloric acid and/or nitric acid.
2, acidic solution according to claim 1, wherein, the weight ratio of described second kind of acid and first kind of acid is 0-0.2: 1.
3, acidic solution according to claim 2, wherein, the weight ratio of described second kind of acid and first kind of acid is 0.1-0.15: 1.
4, acidic solution according to claim 1, wherein, in the described acidic solution, the weight ratio of acid, inhibiter and wetting agent is 1: 0.1-0.8: 0.01-0.08.
5, according to claim 1 or 4 described acidic solutions, wherein, described inhibiter is selected from one or more in triethanolamine oleate, oleic acid diethanolamine, trolamine, hexamethylenetetramine, thiocarbamide, benzotriazole, Sunmorl N 60S, Sodium Benzoate, water glass, SODIUMNITRATE, kelene yl pyridines ammonium salt, tetrahydroglyoxaline based compound and the oleoyl sarcosinates; Described wetting agent is selected from one or more in OP emulsifying agent, tween emulsifier and the fatty alcohol-polyoxyethylene ether.
6, acidic solution according to claim 1 wherein, also contains stablizer in the described acidic solution, described stablizer is selected from one or more in citric acid, oxyacetic acid, ethylenediamine tetraacetic acid (EDTA) and their salt; Described stablizer is 0.1-0.2 with the weight ratio of acid: 1.
7, a kind of treatment method on surface of magnesium alloy, this method comprises magnesium alloy is contacted with acidic solution with degreasing fluid successively, described acidic solution is the aqueous solution that contains acid, inhibiter and wetting agent, it is characterized in that, described acid is first kind of acid, the perhaps mixture of first kind of acid and second kind of acid, described first kind of acid is selected from one or more in citric acid, oxalic acid, tartrate, formic acid, acetate, propionic acid, butyric acid, pentanedioic acid, phenylformic acid, phthalic acid, lactic acid, glycolic acid, glyoxylic acid and the amino acid, and described second kind of acid is hydrochloric acid and/or nitric acid.
8, method according to claim 7, wherein, the weight ratio of described second kind of acid and first kind of acid is 0-0.2: 1.
9, method according to claim 8, wherein, the weight ratio of described second kind of acid and first kind of acid is 0.1-0.15: 1.
10, method according to claim 7, wherein, in the described acidic solution, the weight ratio of acid, inhibiter and wetting agent is 1: 0.1-0.8: 0.01-0.08.
11, method according to claim 7, wherein, the pH value of described acidic solution is 1-5, and the temperature that contacts with acidic solution is 20-70 ℃, and the time that contacts with acidic solution is 10 second-5 minute.
12, method according to claim 7, wherein, this method also be included in magnesium alloy successively with degreasing fluid with after acidic solution contacts, contact with chemical conversion treatment solution.
13, method according to claim 12, wherein, this method also be included in magnesium alloy successively with degreasing fluid with after acidic solution contacts, with before chemical conversion solution contacts, contact with basic solution.
14, method according to claim 13, wherein, described basic solution is the aqueous solution of alkali metal compound, and described alkali metal compound is selected from one or more in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium phosphate, potassiumphosphate, trisodium phosphate, potassium pyrophosphate, sodium-metaphosphate and the potassium metaphosphate; The pH value of described basic solution is 10-14, and the temperature that contacts with basic solution is 50-80 ℃, and the time that contacts with basic solution is 1-3 minute.
15, according to claim 12 or 13 described methods, wherein, described chemical conversion treatment solution is the aqueous solution that contains water-soluble phosphate, phosphoric acid and film coalescence aid, and described water-soluble phosphate is selected from one or more in monocalcium phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate and the primary magnesium phosphate; Described film coalescence aid is one or more in sodium metavanadate, ammonium meta-vanadate, potassium metavanadate, magnesium nitrate and the SODIUMNITRATE; The weight ratio of water-soluble phosphate, phosphoric acid and film coalescence aid is 5-50: 1-17 in the described chemical conversion treatment solution: 1; The pH value of described chemical conversion treatment solution is 1-6; The temperature that contacts with chemical conversion treatment solution is 20-55 ℃, and the time that contacts with chemical conversion treatment solution is 30 second-3 minute.
16, according to claim 7,12 or 13 described methods, wherein, described degreasing fluid is to contain the aqueous solution that is selected from one or more sodium salts in tertiary sodium phosphate, yellow soda ash and the water glass; In every liter of degreasing fluid, the content of described sodium salt is the 10-40 gram; The pH value of described degreasing fluid is 8-14, and the temperature that contacts with degreasing fluid is 30-80 ℃, and the time that contacts with degreasing fluid is 1-40 minute.
17, method according to claim 16, wherein, also contain tensio-active agent in the described degreasing fluid, described tensio-active agent is selected from Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyoxyethylene alkylphenol ether and contains in the tensio-active agent of polyoxyethylene alkylphenol ether one or more, is the 0-5 gram at the content of tensio-active agent described in every liter of degreasing fluid.
18, according to claim 7,12 or 13 described methods, wherein, this method also is included in the water-washing step after each treatment process.
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