CN1796613A - Element of arc oxidation electrolyte of corrosion resistant magnesium alloy, and method of element of arc oxidation - Google Patents
Element of arc oxidation electrolyte of corrosion resistant magnesium alloy, and method of element of arc oxidation Download PDFInfo
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- CN1796613A CN1796613A CN 200410100410 CN200410100410A CN1796613A CN 1796613 A CN1796613 A CN 1796613A CN 200410100410 CN200410100410 CN 200410100410 CN 200410100410 A CN200410100410 A CN 200410100410A CN 1796613 A CN1796613 A CN 1796613A
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- arc oxidation
- ammonium salt
- magnesium alloy
- differential arc
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 30
- 238000005260 corrosion Methods 0.000 title claims abstract description 27
- 230000007797 corrosion Effects 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000003792 electrolyte Substances 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims description 62
- 230000003647 oxidation Effects 0.000 title claims description 56
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 32
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 24
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000467 phytic acid Substances 0.000 claims abstract description 24
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 24
- 229940068041 phytic acid Drugs 0.000 claims abstract description 24
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 19
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005238 degreasing Methods 0.000 claims abstract description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 9
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 9
- 238000005554 pickling Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- -1 alkali metal salt Chemical class 0.000 claims abstract description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 11
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 239000004115 Sodium Silicate Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 6
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 abstract description 5
- 235000010338 boric acid Nutrition 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000011780 sodium chloride Substances 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 229960002645 boric acid Drugs 0.000 abstract 2
- 238000012805 post-processing Methods 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 229960004011 methenamine Drugs 0.000 abstract 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 9
- 239000003595 mist Substances 0.000 description 9
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- 239000011777 magnesium Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000000280 densification Methods 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000004512 die casting Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
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Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
This invention relates to a corrosion resisting magnesium alloy micro-arc oxidation electrolyte and its micro-arc oxidation method. The electrolyte contains 5~25g/L phytic acid or its alkali metal salt, 5~40g/L hydrofluoric acid or its ammonium salt, 15~70g/L phosphoric acid or its ammonium salt, 5~60g/L boracic acid or its ammonium salt (and/or fluoboric acid or its ammonium salt). The process includes following steps: a) preprocessing, including grinding, degreasing and pickling. b) micro-arc oxidation. Hydrofluoric acid, phosphoric acid and boracic acid/fluoboric acid or their ammonium salts are added into phytic acid (or its alkali metal salt) solution, which is subsequently adjusted to a pH value of 6~10 with one or several species among ammonia, hexamethylene tetramine and diethylene triamine and then oxidized. c) Postprocessing. The micro-arc oxidation electrolyte adopted in this invention is free of Cr6+ and thus brings little pollution to the environment. The films obtained are smooth on the surface with only small-scale pores and have ceramic appearances. The oxidized samples without any postprocessing undergo a 5% NaCl neutral salt spray test and evaluated 8-class according to Criteria ASTM B537-70.
Description
Technical field
The present invention relates to magnesium alloy surface treatment, specifically a kind of corrosion resistance magnesium alloy differential arc oxidation electrolytic solution and differential arc oxidation method thereof.
Background technology
Magnesium alloy proportion is little, specific tenacity and specific rigidity height, heat-conductivity conducting is good, has good damping shock absorption and electro-magnetic screen function simultaneously, store content is abundant in addition, be easy to recycle, as electronic product, as mobile communication, the shell structure part of hand-held computer etc., can substitute the plastics that are widely used at present, satisfy light, thin, the miniaturization of electronic product and the requirement of Highgrade integration, be used widely just day by day.The extensive application of magnesium alloy on car body especially can realize car lightization.According to measuring and calculating, automotive dead weight alleviates 10%, and its fuel efficiency can improve 5.5%, because the lighting of automobile has reduced fuel consumption, has reduced the automobile greenhouse gas emissions simultaneously, has reduced pollution, has more important meaning in environment protection.Therefore, magnesium and magnesium alloy have become the preferred material in fields such as Hyundai Motor, electronics, communication and aerospace, are described as " the green engineering material of 21st century ".
But, further enlarge the application of magnesium alloy on automobile and 3C Product, must solve the corrosion and protection problem of magnesium alloy.Magnesium is the highest metallic substance of chemical activity in the existing structure material, and its standard potential is-2.37 volts.The oxide film that the surface forms naturally in atmosphere is loose porous, does not have provide protection substantially.Under various envrionment conditionss, when especially chlorion existed, the corrosion failure of magnesium and alloy thereof was very serious.
Magnesium alloy generally must carry out suitable surface treatment before use, and method has conversion film, anodic oxidation, plating, electroless plating and surface modification etc.Generally believe that anodic oxidation is to make magnesium and magnesium alloy obtain best corrosion proof method.The used power supply of anodic oxidation has direct current (DC), exchanges the branch of (AC) and pulse by waveform, has constant voltage and constant current other again by the control to output.Because OH
-Translational speed move soon than other negatively charged ion, the continuous current that therefore uses direct supply to carry out control current density certainly will cause near the positive column particularly OH of negatively charged ion
-Enrichment, cause unsettled Mg (OH)
2Film forms.Use the pulse power can effectively control near the suitable zwitterion ratio positive column, promote the better formation of anode oxide film such as wear resistance and solidity to corrosion, thus more superior than direct supply.Especially dipulse system more and more is subject to people's attention.This is because anodic oxidation generally relies on spark discharge to form oxide film, and spark discharge makes the anode surface local temperature very high, greater than 1000 ℃.After impressed voltage is greater than voltage breakdown, for the constant current oxidation, there is this moment spark to form on the sample always, the temperature of region of discharge raises rapidly, and melts forms when rapid solidification than gross blow hole; For the two pulse oxidation, when electric current was negative value, sample was a negative electrode, the H in the solution
+Move and separate out thereon to sample, this can take away the heat of specimen surface, oxide compound/electrolyte surface is cooled off better, thereby the porosity of film still less, and pattern is more even, and solidity to corrosion is improved.
Along with improving constantly of anodic oxidation operating voltage, someone is according to caused anodic oxidation phenomenon and gained film performance difference by the operating voltage difference, anodic oxidation voltage-current curve is divided into faraday district, three intervals in spark discharge district and arc discharge district, and will be called differential arc oxidation, plasma micro-arc oxidation or anode spark deposition corresponding to the anodic oxidation of voltage upper zone in the spark discharge district.It breaks through the restriction of conventional anodization technical work voltage, and high voltage discharge field is guided in the work area, has improved the compactness and the solidity to corrosion of anode oxide film greatly.Used electrolytic solution is generally acidity or basic solution at present, uses Cr in acidic solution
6+(as Dow17) has bigger harm to environment and health of human body; And use basic solution that its deficiency is also arranged, because voltage breakdown reduces along with the increase of pH value, and the relatively poor Mg (OH) of the high more easy more formation solidity to corrosion of pH value
2Or MgO film.In view of above consideration, develop a kind of Cr that do not contain
6+, operating voltage height, the pH value is low, solidity to corrosion is good electrolyte prescription and corresponding technology, become important research contents of magnesium anode oxidation technology.
Summary of the invention
In order to overcome above-mentioned deficiency, the object of the invention is to provide a kind of to be had than high anti-corrosion and used electrolytic solution corrosion resistance magnesium alloy differential arc oxidation electrolytic solution and the differential arc oxidation method thereof very little to environmental influence.
To achieve these goals, technical scheme of the present invention is:
1) pre-treatment: grind or degreasing pickling.Machine for workpiece adds and the die casting surface, can carry out degreasing and pickling successively; For workpiece with sand casting surface, should remove surperficial sand grains with mechanical means earlier, carry out oil removing and pickling then; And for smooth workpiece, only need in distilled water, to clean then with after the waterproof abrasive paper polishing successively from coarse to fine.
Superficial Foreign Body is removed in described polishing or grinding (being mechanical pre-treatment), reduces surfaceness; Described degreasing is to adopt usually that alkaline solution is concentration 5～40g/l sodium hydroxide, 5～35g/l potassium hydroxide, 10～25g/l water glass, 10～30g/l yellow soda ash, 10～20g/l sodium phosphate is wherein a kind of or its compound, its wash temperature is controlled between 50～95 ℃, and the time is 5～15 minutes; Described pickling is that to adopt solution usually be the combination solution of a kind of acid or multiple acid in concentration 5～20g/l hydrofluoric acid, 5～15g/l nitric acid, 5～25g/l sulfuric acid, the 5～40g/l phosphoric acid, removes oxide on surface with its washing; Temperature is controlled at 20～60 ℃, and the time is 0.5～5 minute;
2) differential arc oxidation: in phytic acid or its an alkali metal salt, add hydrofluoric acid, phosphoric acid, boric acid and/or fluoroboric acid, it also can be their ammonium salt, one or more materials with ammoniacal liquor, hexamethylenetetramine, diethylenetriamine, the pH value of regulator solution, make it 6～10, use low value, then differential arc oxidation as far as possible.The consumption of phytic acid (or its an alkali metal salt) is 5g/L～25g/L, the consumption of hydrofluoric acid (or its ammonium salt) is 5g/L～40g/L, the consumption of phosphoric acid (or its ammonium salt) is 15g/L～70g/L, the consumption of boric acid (or its ammonium salt) is 15g/L～60g/L, and the consumption of fluoroboric acid (or its ammonium salt) is 5g/L～50g/L.Used power supply is the pulse power, and electrolyte temperature is controlled between 15～30 ℃, and the time is 2～40 minutes, and positive whole voltage is at least 350V;
The used power supply of the present invention preferably has the continuously adjustable pulse power of positive negative pulse stuffing, frequency and pulse duty factor, and current density can be 10mA/cm
2～80mA/cm
2, range of frequency is 100Hz～1000Hz, positive and negative pulse duty factor each 5～40%, positive whole voltage is 350～550V, negative whole voltage 50～300V.
Before the anodic oxidation, workpiece is with the poly fourfluoroplastics encapsulation of becoming attached to, and stainless steel is a negative electrode.Because during spark discharge, solution temperature can raise, thereby oxidation unit also comprises the stirring cooling apparatus.Stir electrolytic solution and low electrolyte temperature oxide compound/electrolyte surface is cooled off better, thereby the hole of film still less, and pattern is more even; Another effect that stirs is to suppress side reaction, especially gas to separate out on two electrodes.
In the used chemical reagent of the present invention, positively charged ion is controlled the cation concn of other valence state as far as possible except that alkalimetal ion and ammonium ion, generates precipitation to prevent they and reaction of phytic acid, reduces the concentration of phytic acid in the solution.
3) aftertreatment.In sodium silicate aqueous solution or nanometer Al
2O
3Sealing of hole in the colloidal sol is specially:
1) sealing of hole in the sodium silicate aqueous solution: in the sodium silicate aqueous solution of 50g/L,, place then in the air and cooled off 30 fens in 95 ℃ of heating 15 minutes.
2) at nanometer Al
2O
3Sealing of hole in the colloidal sol: at Al
2O
3In the colloidal sol, after the pulling film forming, heated 20～60 fens down, in air, cool off then at 150～200 ℃.
When magnesium alloy sample greasy dirt is serious, before the inventive method above-mentioned (alkali lye) degreasing, can adopt petroleum-type, aromatic species, hydro carbons or chloride kind solvent to carry out solvent treatment, to reach best degreasing effect; And all need wash after each operation steps of the present invention.
The used differential arc oxidation electrolytic solution of the present invention does not contain Cr
6+, environment is not had too big pollution.The rete of gained, smooth surface, pore diameter be little, have ceramic outward appearance.Without the oxidation sample of any aftertreatment,, be rated eight grades according to ASTM B537-70 standard through 5%NaCl neutral salt spray test 800 hours.
The present invention has following advantage:
1. adopt treatment process of the present invention, do not contain in the electrolytic solution human body and the very big Cr of environmental hazard
6+
2. differential arc oxidation electrolytic solution of the present invention, solution composition is simple, is easy to control, does not contain easy decomposition composition, process stabilizing.
3. the used phytic acid of the present invention is nontoxic.Phytic acid also claims phytic acid, extensively is present in oils and the seed corn.6 phosphates have only one to be in a position in the phytic acid molecular structure, and other 5 all on the e position.Wherein have 4 phosphates in the same plane, so phytic acid during with metal complex, easily forms the unit molecule protective membrane of one deck densification in the metallic surface in the metallic surface, can stop O effectively
2Deng entering the metallic surface, thereby slowed down corrosion of metal.In addition, because phytic acid is an organic substance, it is good with the paint bonding force, so the oxidation film layer of gained of the present invention is to paint bottom preferably.
4. the oxidation film layer that adopts the present invention to make, thickness is even, fine and close, and is strong with basal body binding force, and solidity to corrosion is good.
5. raw material of the present invention is easy to get, and is suitable for suitability for industrialized production.
Below in conjunction with embodiment in detail the present invention is described in detail.
Embodiment 1
Sample is extruding attitude AZ91D magnesium alloy, and size is 60 * 60 * 10mm
3, its concrete operations step is:
1. mechanical pretreatment: grind with sandblast or sand paper, remove deburring, firm oxide compound, extruding with lubricator, releasing agent, casting model powder, cutting wet goods foreign matter, reduce surfaceness; Washing;
2. degreasing:, remove lubricant that general dirt, sintering adhere to, cutting agent etc. with 10g/l sodium hydroxide, 15g/l sodium phosphate, the washing of 15g/l yellow soda ash combination solution; Temperature is controlled at 70 ℃, and the time is 5 minutes; Washing;
3. pickling: with the composite acid solution washing in 1: 1 by volume of dense hydrofluoric acid, phosphoric acid, wherein the mass percent concentration of HF is no less than 40% in the hydrofluoric acid, H in the phosphoric acid
3PO
4Mass percent concentration be no less than 85%, remove lubricant, the lubricant of bringing into, steel grit, casting model powder and other dirts that oxide skin, corrosion product, the sintering do not removed in the degreasing adhere to; Temperature is 30 ℃, and the time is 1 minute; Washing;
4. activation or arrangement: normal temperature, adopting mass percent concentration is 5% hydrofluoric acid solution, removes metallic surface oxide film as thin as a wafer, removes the pickling ash, the time is 1 minute; Washing;
5. differential arc oxidation
To immerse through the magnesium alloy sample of pre-treatment in the described anodic oxidation electrolyte, solution is formed (phytic acid 10g/L, hydrofluoric acid 20g/L, phosphatase 24 8g/L, fluoroboric acid 10g/L) by phytic acid, hydrofluoric acid, phosphoric acid, fluoroboric acid.Add ammoniacal liquor or diethylenetriamine, the pH value that makes solution is 8～10.Adopt and stir and refrigerating unit, the control solution temperature is 16 ℃.Use the positive pulse electric current, frequency 600Hz, current density 40mA/cm
2, dutycycle 15%, oxidization time 2 minutes, whole voltage 350V.Oxidation film layer thickness is 5 μ m, and the oxide film color is a silver gray, the smooth surface densification.
6. the sample of oxidation without any aftertreatment, adopts salt mist experiment to estimate its solidity to corrosion.
Salt mist experiment is undertaken by ASTMB117 and ASTMB398 standard.Experimental temperature is 35.5 ± 0.5 ℃, and used corrosive medium is the 5%NaCl solution of pH=7, and the sample testing face is 20 ℃ with angle that vertical direction becomes, and except that test surfaces, other each face of sample is all protected with silica gel sealing.Behind the salt fog 800h, grade, can reach eight grades according to ASTM B537-70 standard.
Embodiment 2
Adopt die casting AZ91HP magnesium alloy.
Sample line cuts into 50 * 50 * 10mm
3Rectangular parallelepiped with the polishing successively from coarse to fine of the waterproof abrasive paper of 180～1000#, cleans in distilled water then, cleans with acetone at last and inserts in the moisture eliminator stand-by behind air drying.
Difference from Example 1 is:
1. differential arc oxidation: will put into described anodic oxidation electrolyte through the magnesium alloy sample of pre-treatment, solution is formed (phytic acid 5g/L, hydrofluoric acid 28g/L, phosphatase 24 0g/L by phytic acid, hydrofluoric acid, phosphoric acid, boric acid, fluoroboric acid and hexamethylenetetramine, boric acid 35g/L, HBF
410g/L, hexamethylenetetramine 300g/L).With the ammoniacal liquor adjust pH is 7.5.Adopt and stir and refrigerating unit, the control solution temperature is 16 ℃, uses dual-pulse power supply, 600 hertz of frequencies, positive current density 40mA/cm
2, positive dutycycle 15%, negative current density 20mA/cm
2, negative dutycycle 25%, oxidization time 4 minutes, positive whole voltage 400V, negative whole voltage 120V.Oxidation film layer thickness is 8 μ m, and the oxide film color is a white, the smooth surface densification.
2. the sample of oxidation without any aftertreatment, adopts salt mist experiment to estimate its solidity to corrosion.
The salt mist experiment method, is graded according to ASTM B537-70 standard behind the salt mist experiment 800h with example 1, can reach nine grades.
Embodiment 3
Adopt die casting AM60 magnesium alloy.
Sample line cuts into 50 * 50 * 10mm
3Rectangular parallelepiped with the polishing successively from coarse to fine of the waterproof abrasive paper of 180～1000#, cleans in distilled water then, cleans with acetone at last and inserts in the moisture eliminator stand-by behind air drying.
Difference from Example 1 is:
1. differential arc oxidation: will put into described anodic oxidation electrolyte through the magnesium alloy sample of pre-treatment, solution is formed (phytic acid 20g/L, hydrofluoric acid 20g/L, phosphoric acid 68g/L by phytic acid, hydrofluoric acid, phosphoric acid, fluoroboric acid and hexamethylenetetramine, fluoroboric acid 20g/L, hexamethylenetetramine 200g/L).With the ammoniacal liquor adjust pH is 7.5.Adopt and stir and refrigerating unit, the control solution temperature is 16 ℃, uses the positive pulse electric current, 800 hertz of frequencies, positive current density 40mA/cm
2, positive dutycycle 25%, oxidization time 5 minutes, positive whole voltage 450V.Oxidation film layer thickness is 20 μ m, and the oxide film color is a black, the smooth surface densification.
2. sealing of hole in sodium silicate aqueous solution is specially:
In the sodium silicate aqueous solution of 50g/L,, place then in the air and cooled off 30 fens in 95 ℃ of heating 15 minutes.
The salt mist experiment method, is graded according to ASTM B537-70 standard behind the salt mist experiment 800h with example 1, can reach nine grades.
Embodiment 4
Adopt die casting AZ91HP magnesium alloy.
Sample line cuts into 50 * 50 * 10mm
3Rectangular parallelepiped with the polishing successively from coarse to fine of the waterproof abrasive paper of 180～1000#, cleans in distilled water then, cleans with acetone at last and inserts in the moisture eliminator stand-by behind air drying.
Difference from Example 1 is:
1. differential arc oxidation: will put into described anodic oxidation electrolyte through the magnesium alloy sample of pre-treatment, solution is formed (phytic acid 5g/L, ammonium bifluoride 28g/L, ammonium phosphate 50g/L by phytic acid, ammonium bifluoride, ammonium phosphate, boric acid and hexamethylenetetramine, boric acid 35g/L, hexamethylenetetramine 300g/L).With the diethylenetriamine adjust pH is 7.5.Adopt and stir and refrigerating unit, the control solution temperature is 16 ℃, uses the positive pulse electric current, 800 hertz of frequencies, current density 40mA/cm
2, dutycycle 15%, oxidization time 4 minutes, whole voltage 400V.Oxidation film layer thickness is 15 μ m, and the oxide film color is a silver gray.
2. at nanometer Al
2O
3Sealing of hole in the colloidal sol: at Al
2O
3In the colloidal sol, after the pulling film forming, heat half an hour down, in air, cool off then at 180 ℃.
The salt mist experiment method, is graded according to ASTM B537-70 standard behind the salt mist experiment 800h with example 1, can reach nine grades.
Embodiment 5
Difference from Example 2 is:
Adopt and stir and refrigerating unit, the control solution temperature is 20 ℃, uses the two pulse electric current, 1000 hertz of frequencies, positive current density 80mA/cm
2, positive dutycycle 5%, negative current density 30mA/cm
2, negative dutycycle 20%, oxidization time 20 minutes, positive whole voltage 500V, negative whole voltage 200V.Oxidation film layer thickness is 30 μ m, and the oxide film color is a silver gray, the smooth surface densification.
Embodiment 6
Difference from Example 2 is:
Adopt and stir and refrigerating unit, the control solution temperature is 30 ℃, uses the two pulse electric current, 100 hertz of frequencies, positive current density 60mA/cm
2, positive dutycycle 15%, negative current density 10mA/cm
2, negative dutycycle 38%, oxidization time 8 minutes, positive whole voltage 350V, negative whole voltage 80V.Oxidation film layer thickness is 6 μ m, and the oxide film color is a white, the smooth surface densification.
Claims (8)
1, a kind of corrosion resistance magnesium alloy differential arc oxidation electrolytic solution, it is characterized in that comprising phytic acid or its an alkali metal salt, hydrofluoric acid or its ammonium salt, phosphoric acid or its ammonium salt, and one or both of boric acid or its ammonium salt, fluoroboric acid or its ammonium salt, wherein: phytic acid or its an alkali metal salt 5g/L～25g/L, hydrofluoric acid or its ammonium salt 5g/L～40g/L, phosphoric acid or its ammonium salt 15g/L～70g/L, boric acid or its ammonium salt 5g/L～60g/L, fluoroboric acid or its ammonium salt 5g/L～50g/L.
2, a kind of corrosion resistance magnesium alloy differential arc oxidation method is characterized in that, as follows operation:
1) pre-treatment: workpiece is ground or degreasing pickling;
2) differential arc oxidation: in phytic acid or its an alkali metal salt, add hydrofluoric acid, phosphoric acid, boric acid and/or fluoroboric acid, or their ammonium salt, one or more materials with ammoniacal liquor, hexamethylenetetramine, diethylenetriamine, the pH value of regulator solution makes it 6～10, then differential arc oxidation; Used power supply is the pulse power, and electrolyte temperature is controlled between 15～30 ℃, and the time is 2～40 minutes, and whole voltage is at least 350V;
3) aftertreatment: in sodium silicate aqueous solution or nanometer Al
2O
3Sealing of hole in the colloidal sol.
3, according to the described corrosion resistance magnesium alloy differential arc oxidation method of claim 2, it is characterized in that: it is concentration 5～40g/l sodium hydroxide, 5～35g/l potassium hydroxide, 10～25g/l water glass, 10～30g/l yellow soda ash that alkaline solution is adopted in described degreasing, 10～20g/l sodium phosphate is wherein a kind of or its compound, its wash temperature is controlled between 50～95 ℃, and the time is 5～15 minutes; It is the combination solution of a kind of acid or multiple acid in concentration 5～20g/l hydrofluoric acid, 5～15g/l nitric acid, 5～25g/l sulfuric acid, the 5～40g/l phosphoric acid that solution is adopted in described pickling, and its wash temperature is controlled at 20～60 ℃, and the time is 0.5～5 minute.
4, according to the described corrosion resistance magnesium alloy differential arc oxidation method of claim 2, it is characterized in that: used power supply is the pulse power, and it has the continuously adjustable characteristics of positive negative pulse stuffing, frequency and pulse duty factor, and current density is 10mA/cm
2～80mA/cm
2, range of frequency is 100Hz～1000Hz, positive and negative pulse duty factor each 5～40%, positive whole voltage is 350～550V, negative whole voltage 50～300V.
5, according to the described corrosion resistance magnesium alloy differential arc oxidation method of claim 2, it is characterized in that: described aftertreatment is included in the sodium silicate aqueous solution or at Al
2O
3Sealing of hole in the Nano sol.
6, according to the described corrosion resistance magnesium alloy differential arc oxidation method of claim 5, it is characterized in that: described in sodium silicate aqueous solution sealing of hole: in the sodium silicate aqueous solution of 50g/L, handled 15 minutes in 95 ℃, placed in the air cooling then 30 minutes; Described at Al
2O
3Sealing of hole in the Nano sol: at Al
2O
3In the colloidal sol, after the pulling film forming, heated 10～60 fens down, in air, cool off then at 150～200 ℃.
7, according to the described corrosion resistance magnesium alloy differential arc oxidation method of claim 2, it is characterized in that: gained oxidation film layer thickness is 5～40 μ m, and the color of oxide film is white, silver gray or black by the content decision of phytic acid and phosphoric acid.
8, according to claim 3, one of 4 described corrosion resistance magnesium alloy differential arc oxidation methods, it is characterized in that: all need wash after described each operation steps.
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