CN101724880B - Electrolyte, anodization method and anodized silicon-aluminum alloy - Google Patents
Electrolyte, anodization method and anodized silicon-aluminum alloy Download PDFInfo
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- CN101724880B CN101724880B CN2008102169254A CN200810216925A CN101724880B CN 101724880 B CN101724880 B CN 101724880B CN 2008102169254 A CN2008102169254 A CN 2008102169254A CN 200810216925 A CN200810216925 A CN 200810216925A CN 101724880 B CN101724880 B CN 101724880B
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- electrolytic solution
- silumin
- ion
- equivalent
- metaphosphate
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003792 electrolyte Substances 0.000 title abstract description 18
- 229910000838 Al alloy Inorganic materials 0.000 title abstract 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 title abstract 3
- 238000002048 anodisation reaction Methods 0.000 title abstract 3
- -1 silicate ions Chemical class 0.000 claims abstract description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 86
- 229910000551 Silumin Inorganic materials 0.000 claims description 70
- 230000003647 oxidation Effects 0.000 claims description 68
- 238000007254 oxidation reaction Methods 0.000 claims description 68
- 239000003153 chemical reaction reagent Substances 0.000 claims description 22
- 239000000872 buffer Substances 0.000 claims description 17
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 150000005837 radical ions Chemical class 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 125000005341 metaphosphate group Chemical group 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract 2
- 239000011734 sodium Substances 0.000 description 30
- 238000012360 testing method Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000003628 erosive effect Effects 0.000 description 13
- 235000019353 potassium silicate Nutrition 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 11
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 description 11
- 241001460678 Napo <wasp> Species 0.000 description 10
- 229910021538 borax Inorganic materials 0.000 description 9
- 239000004328 sodium tetraborate Substances 0.000 description 9
- 235000010339 sodium tetraborate Nutrition 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000007743 anodising Methods 0.000 description 8
- 238000005238 degreasing Methods 0.000 description 8
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 description 7
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000413 hydrolysate Substances 0.000 description 5
- 238000002203 pretreatment Methods 0.000 description 5
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical class [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 150000003658 tungsten compounds Chemical class 0.000 description 3
- 229910000714 At alloy Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- OLGONLPBKFPQNS-UHFFFAOYSA-M sodium 2-(4-phenylphenyl)butanoate Chemical compound [Na+].CCC(C([O-])=O)c1ccc(cc1)-c1ccccc1 OLGONLPBKFPQNS-UHFFFAOYSA-M 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- 229910000737 Duralumin Inorganic materials 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229920001617 Vinyon Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 229940045916 polymetaphosphate Drugs 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides an electrolyte, an anodization method and an anodized silicon-aluminum alloy. The electrolyte contains equivalent silicate ions and equivalent metaphosphate ions, wherein the equivalent silicate ions refer to silicate ions converted from all ions and particles containing a silicon element based on equal silicon element content, and the quivalent metaphosphate ions refer to metaphosphate ions converted from all ions and particles containing a phosphor element based on equal phosphor element content; and the electrolyte refers to an alkaline hydrosol. By adopting the electrolyte, an anodization film with good hardness, wear resistance and corrosion resistance can be formed on the surface of the silicon-aluminum alloy.
Description
Technical field
The present invention relates to a kind of electrolytic solution, especially a kind of anodic oxidation electrolyte of silumin, and the anodised silumin that uses this electrolytic solution to obtain.
Background technology
The anodic oxidation of silumin, especially silumin (massfraction of Si element is not less than 1%) is difficulty, and reason is in the common anode oxidation process; Si in the alloy both had been insoluble to acid electrolyte, did not also react with electrolytic solution, residued in alloy surface after the anodic oxidation and formed " silicon ash "; Make the sull surface blackening and stain occur; Reduce homogeneity, compactness and the glossiness of sull, thereby make the performance of sull, reduce greatly like hardness, wear-resisting, corrosion-resistant etc.Silicone content is high more, and the anodic oxidation of alloy is more difficult, and the performance of the sull that obtains is poor more.
Summary of the invention
For solving the problem that silumin of the prior art is difficult to form hardness, wear-resisting, anode oxide film that erosion resistance is good; The present invention at first provides a kind of electrolytic solution; With this electrolytic solution silumin is carried out anodic oxidation, can form hardness, wear-resisting, sull that erosion resistance is good at alloy surface.
Two of the object of the invention provides the said electrolytic solution of a kind of use silumin is carried out anodised method.
Three of the object of the invention provides a kind of silumin anodic oxidation product that is obtained by above-mentioned anode oxidation method.
For achieving the above object; The present invention at first provides a kind of electrolytic solution; Comprise equivalent silicate ion, equivalent metaphosphate ion; All ions and the particulate that said equivalent silicate ion refers to contain in the electrolytic solution element silicon equates that by silicon content the silicate ion that is converted to, said equivalent metaphosphate ion refer to that all ions and the particulate of phosphorus element-containing in the electrolytic solution equate the metaphosphate ion that is converted to by phosphorus element content; Said electrolytic solution is alkaline water colloidal sol.
The present invention also provides a kind of silumin anodised method:
To pass through pretreated silumin and be immersed in according in the electrolytic solution of the present invention, the control maximum voltage is no more than 360V and carries out anodic oxidation.
The present invention and then a kind of anodised silumin is provided adopts preparation according to the method for the invention, its oxide thickness 10～20 μ m, and hardness >=HV400 is in the erosion resistance neutral salt spray continuously more than the 40h.
Beneficial effect of the present invention:
1. electrolytic solution raw material according to the present invention is easy to get, cheap, environmental friendliness.
2. anode oxidation method according to the present invention is simple to operate, need not special process.
3. all better according to hardness, wear resistance, erosion resistance, the sticking power of silumin anodic oxidation product sull of the present invention.
Embodiment
Silumin according to the present invention refers to that the massfraction of element silicon is not less than 1% silumin in the alloy.
Specify the present invention below.
Embodiment of the present invention provides a kind of electrolytic solution, comprises equivalent silicate ion, equivalent metaphosphate ion, and all ions and particulate that said equivalent silicate ion refers to contain in the electrolytic solution element silicon (Si) (are SiO
3 2-Hydrolysate) equate the silicate ion (SiO that is converted to by Si content
3 2-), said equivalent metaphosphate ion refers to that all ions of phosphorus element-containing in the electrolytic solution (P) and particulate (are PO
3 -Hydrolysate) equate the metaphosphate ion (PO that is converted to by P content
3 -), said electrolytic solution is alkaline water colloidal sol.
Electrolytic solution is made into the alkali solution colloidal sol that contains above-mentioned equivalent silicate ion, equivalent metaphosphate ion can realizes the present invention; Principle is the application of sol-gel processing in electrochemical filming, and essence is to form even, fine and close sull through following 2 factors at alloy surface: lyosol is to Al
3+, H
+, OH
-Absorption-desorption control Al
3+, H
+, OH
-Velocity of diffusion; The lyosol system also impels electric field distribution even.
Silicate ion SiO
3 2-Intense hydrolysis is alkalescence, forms the hydrolysate of multiple complicacies such as poly silicate ion, silicic acid, multi-silicate micelle, makes solution be colloidal sol or gel, so simple silicate ion SiO
3 2-In solution, exist hardly.So the present invention has introduced above-mentioned SiO
3 2-The notion of hydrolysate " the equivalent silicate ion " that equate by Si content to be converted to.If SiO
3 2-It is acid that the PH of solution is, and then silica gel can become white precipitate.If SiO
3 2-Concentration makes hydrolyzed solution be gel too greatly, and the anode oxide film that then generates is inhomogeneous, and poor-performing can not be realized the present invention.So should control electrolytic solution is alkaline water colloidal sol.Alkalescence, two controlling factors of the water-sol can be controlled the concentration of equivalent silicate ion to realize the present invention.
Metaphosphoric acid radical PO
3 -A little less than the hydrolysis, its hydrolysis can form multiple complicated hydrolysates such as polymetaphosphate radical ion, polyphosphoric acid radical ion, and hydrolyzed solution is slightly acidic or neutrality.(the pH value 6～9 of the Trisodium trimetaphosphate aqueous solution of massfraction 1% (0.03mol/L) under the room temperature.) simple metaphosphoric acid radical PO
3 -In solution, exist hardly, so the present invention has introduced above-mentioned PO
3 -The notion of " equivalent metaphosphate ion " that hydrolysate equates by P content to be converted to.PO
3 -(form with equivalent metaphosphate ion in solution exists) is a kind of buffer reagent commonly used, and effect in the present invention also is a buffer reagent.The contriver finds that equivalent metaphosphate ion is to realizing that the present invention is necessary.The content of equivalence metaphosphate ion is to guarantee that electrolytic solution is that the alkaline water colloidal sol that contains equivalent silicate ion and equivalent metaphosphate ion exceeds.That is to say, electrolytic solution is made into the alkaline water colloidal sol that comprises said equivalent silicate ion and said equivalent metaphosphate ion, promptly define the concentration of equivalent metaphosphate ion.
Said equivalent silicate ion is by soluble silicate, silicic acid (H
2SiO
3), silicon hydroxide (H
4SiO
4), silicon-dioxide (SiO
2) at least a providing, said equivalent metaphosphate ion is by at least a the providing in metaphosphoric acid, the solubility metaphosphate.If select soluble silicate for use, like water glass (Na
2SiO
3), potassium silicate (K
2SiO
3), get then that it is water-soluble in right amount, add at least a in metaphosphoric acid, the solubility metaphosphate then, be made into the alkaline water-sol and get final product; If select silicic acid (H for use
2SiO
3), silicon hydroxide (H
4SiO
4) or silicon-dioxide (SiO
2), then should it be dissolved in the aqueous solution of alkali earlier, like sodium hydroxide (NaOH), Pottasium Hydroxide (KOH), ammoniacal liquor (NH
3H
2O) the aqueous solution makes silicic acid (H
2SiO
3), silicon hydroxide (H
4SiO
4) or silicon-dioxide (SiO
2) generate corresponding soluble silicate with alkali reaction, add at least a in metaphosphoric acid, the solubility metaphosphate (like Trisodium trimetaphosphate, Sodium hexametaphosphate 99) then, obtain alkaline water colloidal sol.
The concentration of said alkaline water colloidal sol intermediate ion is preferably descended train value:
Equivalence silicate ion concentration 0.04～0.2mol/L,
Equivalence metaphosphate ion concentration 0.02～0.2mol/L.
The hardness of the silumin anode oxide film that obtains like this, wear resistance, erosion resistance, sticking power are all better.
Said electrolytic solution can also contain alkaline buffer reagent, adds hardness and wear resistance that alkaline buffer reagent can improve the silumin anode oxide film.The alkalescence buffer reagent refers to that water-soluble back PH is the buffer reagent of alkalescence.Said alkaline buffer reagent preferred boric acid salt buffer reagent.Can be through in said electrolytic solution, adding the solubility borate, like borax (Na
2B
4O
710H
2O), or the borate buffer solution for preparing, make like the method for tetraborate buffered soln and contain the borate buffer reagent in the electrolytic solution.Preferred 0.005～the 0.03mol/L of the concentration of said borate buffer reagent in said electrolytic solution (, referring to that then solute in the tetraborate buffered soln is to the concentration of said electrolytic solution) if add the tetraborate buffered soln prepare.The contriver discovers, contains hardness and wear resistance that the borate buffer reagent can improve the silumin anode oxide film in the said electrolytic solution.But the collocation method of reference standard borate buffer solution, according to the concentration of above-mentioned preferred borate buffer reagent, the configuration borate buffer solution.The collocation method of standard borate buffer solution: take by weighing borax (Na
2B
4O
710H
2O) (3.80 ± 0.01) g (noting: can not dry by the fire) is dissolved in and boiled in advance in 15～30min and the rapid refrigerative zero(ppm) water, and is diluted to 1000ml.Put airtight preservation in the vinyon bottle.To prevent airborne CO when depositing
2Entering.
The pH value of said electrolytic solution can pass through exogenously added alkali according to circumstances, like NaOH, KOH, NH
3H
2O controls.The pH value of said electrolytic solution is 10～11 o'clock, and the slickness of gained sull is best, so preferred PH=10～11.
Said anodic oxidation electrolyte can also contain additive, and said additive is selected from least a in transistion metal compound that transition metal oxygen acid radical ion can be provided after water-soluble, solubility polyoxometallate, the solubility heteropoly compound.Saidly can provide the transistion metal compound of transition metal oxygen acid root to comprise transition metal oxide, transition metal complex, transition metal oxygen acid, transition metal oxysalt after water-soluble.The effect of said additive comprises: the performance such as wear resistance, hardness, erosion resistance, electrical insulating property of improving the silumin anode oxide film; Make the silumin anode oxide film have distinct colors.The example of said additive such as soluble tungstate salt, molybdate, vannadate, V
2O
5, MoO
3, WO
3, MnO
2, CrO
3The contriver studies proof: add tungsten compound, molybdenum compound or vanadium compound that one or more can provide the oxygen acid radical ion of tungsten, molybdenum or vanadium after water-soluble; Like soluble tungstate salt, soluble molybdenum hydrochlorate or soluble vanadium hydrochlorate, can improve the wear resistance of sull.The addition of said additive is not more than 20g/ and rises electrolytic solution.In addition, the contriver finds, in electrolytic solution, adds the tungsten compound that the oxygen acid radical ion of tungsten can be provided after water-soluble, like soluble tungstate salt, can improve the slickness of sull.
Said anodic oxidation electrolyte can also contain AS and/or amphoterics.Said influence of surfactant comprises the aperture that reduces anode oxide film, improves the homogeneity of film.Preferred 1～the 5g/ of the addition of said tensio-active agent rises electrolytic solution.The example of said tensio-active agent such as X 2073, sodium lauryl sulphate, EDTA Disodium.
A kind of silumin anode oxidation method:
To pass through pretreated silumin and be immersed in according in the electrolytic solution of the present invention, the control maximum voltage is no more than 360V, and preferred maximum voltage is no more than 320V and carries out anodic oxidation.The preferred constant current oxidation of said anodic oxidation, more preferably pulse constant current oxidation.Also the may command maximum voltage is no more than 360V, and preferred maximum voltage is no more than 320V, adopts alternating-current to carry out anodic oxidation.When using alternating-current, the color of the sull that obtains meeting difference and direct current, other performances of sull such as hardness, wear resistance, erosion resistance etc. can be poorer slightly than pulse direct current, but still can realize the present invention.
According to general knowledge known in this field, the difference of hard anodizing technology and common anode oxidizing process is: hard anodizing need be controlled lower electrolyte temperature (generally being no more than 20 ℃).So adopt the anodised processing parameter of silumin according to the present invention, the control electrolyte temperature can carry out hard anodizing to silumin below 20 ℃.Dying not only to be used for the common anode oxidation process of silumin according to electrolytic solution of the present invention, also can be used for the hard anodizing technology of silumin.
Can be not less than 1% the well behaved sull of silumin surface formation at the massfraction of Si according to electrolytic solution of the present invention and anode oxidation method thereof; Certainly also can be used for the common anode oxidation of the ordinary silicon duraluminum of Si massfraction lower (being not more than 1%), and hard anodizing technology.
A kind of anodised silumin, preparation is characterized in that oxide thickness 10～20 μ m according to the method for the invention, hardness >=HV400 is in the erosion resistance neutral salt spray continuously more than the 40h.
In the silumin (Al-Si alloy), Si is main alloy element, and Si improves the flowability of alloy, reduces the thermo-cracking tendency, reduces and loosens, and improves resistance to air loss.This type alloy has good erosion resistance, medium intensity, hardness and medium machining property.Press Si content difference in the alloy, can be divided into different models, its performance is also different with purposes.Silumin has higher high temperature strength, good thermostability and wear resistance, is widely used in fields such as automobile, electronics, like parts such as the piston of motor car engine, cylinder sleeve, body, brake shoes, belt wheel, phone housing and inner member etc.Castability, mechanical behavior under high temperature, wear resisting property like the ZL108 type alloy of Si content 10～13% are all better, can be used to make internal combustion engine.The massfraction of Si generally surpasses 15% in the hypereutectic silumin.This type alloy is with the increase of Si content, and density reduces, and thermal expansivity reduces, and hardness, wear resistance and system stability improve, mainly as piston material.
Embodiment 1
At first AC1A silumin (Si element massfraction 1.2%) is carried out surface preparation, its step comprises degreasing, washing.Concrete technology is following:
Degreasing: with carrying out skimming treatment in the following washing lotion of forming (solvent is a water) of AD1A silumin immersion:
Yellow soda ash 25g/L
Sodium phosphate 20g/L
Tripoly phosphate sodium STPP 5g/L
Sodium hydroxide 0.5g/L
Washing: with the surface of the AD1A silumin after deionized water rinsing skimming treatment 2min.
By the electrolytic solution under the following formulated room temperature, solvent is 1 premium on currency then:
Water glass (Na
2SiO
3) 0.12mol/L (15g/L)
Trisodium trimetaphosphate (NaPO
3)
30.013mol/L (4g/L)
Borax (Na
2B
4O
710H
2O) 0.013mol/L (5g/L)
Sodium wolframate (Na
2WO
42H
2O) 5g/ rises electrolytic solution
EDTA Disodium (EDTA-2Na) 3g/ rises electrolytic solution
Water glass (Na
2SiO
3) the equivalent silicate ion in the electrolytic solution, Trisodium trimetaphosphate (NaPO be provided
3)
3Equivalent metaphosphate ion in the electrolytic solution is provided.15g water glass (Na
2SiO
3) (0.12mol) be dissolved in 1L water after, the amount of substance of the equivalent silicate ion in the solution (mol) equals Na
2SiO
3Middle SiO
3 2-Amount of substance, be 0.12mol.4g Trisodium trimetaphosphate (NaPO
3)
3(0.013mol) be dissolved in 1L water after, the amount of substance of the equivalent metaphosphate ion in the solution (mol) equals (NaPO
3)
3Middle PO
3 -Amount of substance, be 0.039mol.
Then carry out anodic oxidation: the AD1A silumin that will pass through degreasing, washing is put into anodizing tank, adopts the direct impulse pattern to carry out anodic oxidation.The negative electrode of oxidation trough is a stainless steel plate, and anode is the AD1A silumin, and conducting medium is above-mentioned electrolytic solution, 25 ℃ of tank liquor temperatures.Anodised other processing parameters are following:
Frequency 500HZ
Dutycycle 20%
Current density 5A/dm
2,
Pulse direct current constant current oxidation, voltage stop oxidation after being raised to 300V from 0, obtain even, fine and close, ganoid taupe sull.
Embodiment 2
Carry out the pre-treatment of surperficial degreasing, washing with reference to 1 pair of ADC7 silumin of embodiment (Si element massfraction 4.5～9.5%).
By the silumin anodic oxidation electrolyte under the following formulated room temperature, solvent is 1 premium on currency then:
Water glass (Na
2SiO
3) 0.12mol/L (15g/L)
Trisodium trimetaphosphate (NaPO
3)
30.033mol/L (10g/L)
Borax (Na
2B
4O
710H
2O) 0.010mol/L (4g/L)
Sodium orthomolybdate (Na
2MoO
42H
2O) 8g/ rises electrolytic solution
EDTA Disodium (EDTA-2Na) 2g/ rises electrolytic solution
Carry out anodic oxidation with reference to 1 pair of ADC7 silumin of embodiment then, different is the prescription and the anode oxidation process parameter of electrolytic solution.The prescription of electrolytic solution as above, the anode oxidation process parameter different with embodiment 1 is following:
Frequency 300HZ
Dutycycle 25%
Current density 10A/dm
2,
Pulse direct current constant current oxidation, voltage stop oxidation after being raised to 320V from 0, obtain even, fine and close, ganoid brown sull.
Embodiment 3
Carry out the pre-treatment of surperficial degreasing, washing with reference to 1 pair of ADC12 silumin of embodiment (Si element massfraction 9.6～12%).
By the silumin anodic oxidation electrolyte under the following formulated room temperature, solvent is 1 premium on currency then:
Water glass (Na
2SiO
3) 0.082mol/L (10g/L)
Trisodium trimetaphosphate (NaPO
3)
30.020mol/L (6g/L)
Borax (Na
2B
4O
710H
2O) 0.026mol/L (10g/L)
Sodium wolframate (Na
2WO
42H
2O) 5g/ rises electrolytic solution
Sodium orthomolybdate (Na
2MoO
42H
2O) 10g/ rises electrolytic solution
EDTA Disodium (EDTA-2Na) 1g/ rises electrolytic solution
Carry out anodic oxidation with reference to 1 pair of ADC12 silumin of embodiment then, different is the prescription and the anode oxidation process parameter of electrolytic solution.The prescription of electrolytic solution as above, the anode oxidation process parameter different with embodiment 1 is following:
Frequency 1000HZ
Dutycycle 35%
Current density 15A/dm
2,
Pulse direct current constant current oxidation, voltage stop oxidation after being raised to 280V from 0, obtain even, fine and close, ganoid taupe sull.
Embodiment 4
Carry out the pre-treatment of surperficial degreasing, washing with reference to 1 pair of AC8A silumin of embodiment (Si element massfraction 11～13%).
By the silumin anodic oxidation electrolyte under the following formulated room temperature, solvent is 1 premium on currency then:
Water glass (Na
2SiO
3) 0.16mol/L (20g/L)
Trisodium trimetaphosphate (NaPO
3)
30.039mol/L (12g/L)
Borax (Na
2B
4O
710H
2O) 0.013mol/L (5g/L)
Ammonium meta-vanadate (NH
4VO
3) 2g/ rises electrolytic solution
Sodium orthomolybdate (Na
2MoO
42H
2O) 5g/ rises electrolytic solution
EDTA Disodium (EDTA-2Na) 4g/ rises electrolytic solution
Carry out anodic oxidation with reference to 1 pair of AC8A silumin of embodiment then, different is the prescription and the anode oxidation process parameter of electrolytic solution.The prescription of electrolytic solution as above, the anode oxidation process parameter different with embodiment 1 is following:
Frequency 800HZ
Dutycycle 15%
Current density 8A/dm
2,
Pulse direct current constant current oxidation, voltage stop oxidation after being raised to 250V from 0, obtain even, fine and close, ganoid taupe sull.
Embodiment 5
Carry out the pre-treatment of surperficial degreasing, washing with reference to 1 pair of AC8A silumin of embodiment.
By the silumin anodic oxidation electrolyte under the following formulated room temperature, solvent is 1 premium on currency then:
Water glass (Na
2SiO
3) 0.123mol/L (15g/L)
Trisodium trimetaphosphate (NaPO
3)
30.026mol/L (8g/L)
Borax (Na
2B
4O
710H
2O) 0.010mol/L (4g/L)
Ammonium meta-vanadate (NH
4VO
3) 15g/ rises electrolytic solution
Sodium wolframate (Na
2WO
42H
2O) 8g/ rises electrolytic solution
EDTA Disodium (EDTA-2Na) 4g/ rises electrolytic solution
Carry out anodic oxidation with reference to 1 pair of AC8A silumin of embodiment then, different is the prescription and the anode oxidation process parameter of electrolytic solution.The prescription of electrolytic solution as above, the anode oxidation process parameter different with embodiment 1 is following:
Frequency 1500HZ
Dutycycle 30%
Current density 25A/dm
2,
Pulse direct current constant current oxidation, voltage stop oxidation after being raised to 300V from 0, obtain even, fine and close, ganoid black oxide film.
Embodiment 6
Carry out the pre-treatment of surperficial degreasing, washing with reference to 1 pair of AC1A silumin of embodiment.
By the silumin anodic oxidation electrolyte under the following formulated room temperature, solvent is 1 premium on currency then:
Water glass (Na
2SiO
3) 0.082mol/L (10g/L)
Trisodium trimetaphosphate (NaPO
3)
30.026mol/L (8g/L)
Carry out anodic oxidation with reference to 1 pair of AC8A silumin of embodiment then, different is the prescription and the anode oxidation process parameter of electrolytic solution.The prescription of electrolytic solution as above, the anode oxidation process parameter different with embodiment 1 is following:
Frequency 1500HZ
Dutycycle 30%,
Current density 20A/dm
2,
Setting pulse direct current constant current oxidation, voltage stop oxidation after being raised to 300V from 0.
Embodiment 7
With reference to the method for embodiment 6, difference is: water glass (Na
2SiO
3) 0.041mol/L (5g/L), contain the borax (Na of 0.013mol/L (5g/L) in the electrolytic solution
2B
4O
710H
2O), direct current density 20A/dm
2The constant current anodic oxidation.
Comparative Examples
The AC8A silumin does not carry out anodize, directly tests correlated performance.
Each embodiment and Comparative Examples are carried out performance test.The reagent of using in the embodiment of the invention, raw material, testing method and standard, testing tool, test result are shown in following table 1～4.
Performance test:
1. corrosion resistance nature test
Silumin by GB GB6458-86 or the oxidation of ISO3768-1976 antianode carries out the erosion resistance test.
Test result: black splotch do not occur through the same silumin about 2min alloy surface after spraying salts solution of any surface-treated; And the silumin that the method that adopts the embodiment of the invention obtains sprayed salts solution after 48 hours, in humidity cabinet, observed high silicon die casting aluminium sample surfaces and had no variation.
2. sticking power test
To carry out the test of anode oxide film sticking power according to the method for GB ASTM-D3359 according to the silumin of the embodiment of the invention.The sticking power grade standard is as shown in table 3.
3. hardness test
To and not pass through the same silumin of any surface-treated according to the silumin of the embodiment of the invention according to the GB/T4340.1-1999 standard; (the prosperous great test set of Dongguan City ltd produces on the Vickers' hardness experimental machine; Model 401MVA) test, pressure head 200 grams, 15 seconds loading times; Test three points respectively, and calculate its arithmetical av.The result sees table 4.
4. wearability test
To on RCA paper tape wear resistant instrument (the global detecting instrument in Dongguan ltd produces, model F350008), carry out wearability test according to the silumin of the embodiment of the invention.Load 175 grams, testing standard are the no sharp traces of 2000 circles.The result is as shown in table 4.
Table 1: embodiment of the invention agents useful for same and raw material
| Chemical reagent/raw material | Purity | The source |
| Water glass (Na 2SiO 3) | Analytical pure | Guangdong brilliance chemistry ltd |
| Trisodium trimetaphosphate (NaPO 3) 3 | Analytical pure | Guangdong brilliance chemistry ltd |
| Borax (Na 2B 4O 7·10H 2O) | Analytical pure | Guangdong brilliance chemistry ltd |
| Sodium orthomolybdate (Na 2MoO 4·2H 2O) | Analytical pure | Guangdong chemical reagent factory |
| Sodium hydroxide (NaOH) | Analytical pure | Guangdong brilliance chemistry ltd |
[0137]
| Ammonium meta-vanadate (NH 4VO 3) | Analytical pure | Guangdong chemical reagent factory |
| Sodium wolframate (Na 2WO 42H 2O) | Analytical pure | Shanghai experiment reagent ltd |
| EDTA Disodium (EDTA-2Na) | Analytical pure | Guangdong brilliance chemistry ltd |
Table 2: used various testing method of the embodiment of the invention and instrument
| The instrument title | The place of production, model |
| The Vickers' hardness experimental machine | The prosperous great test set of Dongguan City ltd, the 401MVA type |
| RCA paper tape wear resistant instrument | Dongguan global detecting instrument ltd, the F350008 type |
| Salt-mist corrosion tester | Southern Jiangsu, Wuxi testing installation ltd, the YWX/Q-250 type |
Table 3 sticking power standard
| Grade | Implication |
| 5B | Scribing edge is smooth, does not all have coating at edge and the point of crossing place of line and comes off |
| 4B | There is the peeling paint of small pieces at place, point of crossing in line, and the total area that comes off is less than 5% |
| 3B | Edge and place, point of crossing in line have the coating of small pieces to come off, and come off the total area between 5～15% |
| 2B | Edge and place, point of crossing in line have coating in blocks to come off, and come off the total area between 15～35% |
| 1B | Edge and place, point of crossing in line have coating in blocks to come off, and come off the total area between 35～65% |
| 0B | Edge and place, point of crossing in line have coating in blocks to come off, and the total area that comes off is greater than 65% |
Table 4 anode oxide film The performance test results
| Embodiment/Comparative Examples | Film thickness | Erosion resistance | Sticking power | Wear resistance (number of turns that cut occurs) | Hardness |
| Instance 1 | 14μm | 48h | 5B | 2750 | HV492 |
[0144]
| Instance 2 | 16 μ m | 48h | 5B | 2865 | HV486 |
| Instance 3 | 15 μ m | 48h | 5B | 2806 | HV493 |
| Instance 4 | 13 μ m | 48h | 5B | 2706 | HV490 |
| Instance 5 | 15 μ m | 48h | 5B | 2930 | HV500 |
| Instance 6 | 13 μ m | 48h | 5B | 2200 | HV428 |
| Instance 7 | 16 μ m | 48h | 5B | 2688 | HV475 |
| Comparative Examples | - | 2min | - | Obvious cut promptly appears in 46 circles | HV225 |
Can find out from last table 4:
1. all better to erosion resistance, hardness, wear resistance that silumin carries out the sull that anodic oxidation obtains with the electrolytic solution (embodiment 6) that only contains equivalent silicate ion and equivalent metaphosphate ion.Electrolyte prescription, operating procedure are all simple.(evaluation of wear resistance: adopt the abrasion resistance test method of the embodiment of the invention, can think to reach 2000 circles, the sull wear resistance is better.)
2. comparing embodiment 1～5,7 and embodiment 6 can find out: with the electrolytic solution that contains equivalent silicate ion, equivalent metaphosphate ion and borate buffer reagent wear resistance and the hardness that silumin carries out the sull that anodic oxidation obtains is improved a lot.Wherein, The hardness of the product of embodiment 1～5,7 is carried out hard anodizing far above the silumin that adopts sulfuric acid electrolyte to element silicon massfraction 10～13% and is handled available 300～400HV hardness; Both avoided hard anodizing to use sulfuric acid as of the pollution of electrolytic solution staple to environment; Also need not to control low temperature in the anode oxidation process process, simplified technology.
3. comparing embodiment 1～5 can be found out with the wear resistance of the sull of embodiment 7: tungsten compound, molybdenum compound or vanadium compound that the oxygen acid radical ion of tungsten, molybdenum or vanadium can be provided after the electrolytic solution interpolation that contains equivalent silicate ion, equivalent metaphosphate ion and borate buffer reagent is water-soluble; Like soluble tungstate salt, soluble molybdenum hydrochlorate or soluble vanadium hydrochlorate, can improve the wear resistance of sull.
In addition, the contriver finds, and is better to the slickness that silumin carries out the sull that anodic oxidation obtains with the electrolytic solution that adds soluble tungstate salt.
Hardness, wear resistance, erosion resistance, sticking power according to silumin anode oxide film of the present invention are all better; Can be used for the above-mentioned performance requriements of silumin higher; Especially hardness and the wear resistance product of having relatively high expectations; Like mobile phone component (like shell, inner member, antenna etc.), automobile component, like piston of engine, cylinder sleeve, body, brake shoes etc.
Claims (12)
1. electrolytic solution; Comprise equivalent silicate ion, equivalent metaphosphate ion; All ions and the particulate that said equivalent silicate ion refers to contain in the electrolytic solution element silicon equates the silicate ion that is converted to by silicon content; Said equivalent silicate ion is by at least a the providing in soluble silicate, silicic acid, silicon hydroxide, the silicon-dioxide, and said equivalent silicate ion hydrolysis makes solution be the colloidal sol shape; All ions and the particulate that said equivalent metaphosphate ion refers to phosphorus element-containing in the electrolytic solution equates the metaphosphate ion that is converted to by phosphorus element content, and said equivalent metaphosphate ion is by at least a the providing in metaphosphoric acid, the solubility metaphosphate; Said electrolytic solution is alkaline water colloidal sol.
2. according to the electrolytic solution of claim 1, said ionic concentration is following:
Equivalence silicate ion concentration 0.04～0.2mol/L,
Equivalence metaphosphate ion concentration 0.02～0.2mol/L.
3. according to the electrolytic solution of claim 1, also contain alkaline buffer reagent.
4. according to the electrolytic solution of claim 1, also contain the borate buffer reagent.
5. according to the electrolytic solution of claim 4, the concentration of the said electrolytic solution of said borate buffer reagent mesoboric acid salt pair is 0.005～0.03mol/L.
6. according to the electrolytic solution of claim 1, pH=10～11.
7. according to the electrolytic solution of claim 1, also contain additive, said additive is selected from least a in transistion metal compound that transition metal oxygen acid radical ion can be provided after water-soluble, solubility polyoxometallate, the solubility heteropoly compound.
8. according to the electrolytic solution of claim 7, the addition of said additive is not more than 20g/ and rises electrolytic solution.
9. according to the electrolytic solution of claim 1, also contain AS and/or amphoterics.
10. according to the electrolytic solution of claim 9, the addition of said tensio-active agent is that 1～5g/ rises electrolytic solution.
11. silumin anode oxidation method:
To pass through pretreated silumin and be immersed in any one electrolytic solution of claim 1～9, the control maximum voltage is no more than 360V and carries out anodic oxidation.
12. silumin anode oxidation method:
To pass through pretreated silumin and be immersed in any one electrolytic solution of claim 1～9, the control maximum voltage is no more than 320V and carries out anodic oxidation, and the massfraction of Si element is not less than 1% in the said silumin.
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| CN109518250A (en) * | 2017-09-18 | 2019-03-26 | 东莞东阳光科研发有限公司 | A kind of anodic oxidation device and method using device aluminium powder anodic oxidation under alkaline condition |
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| CN110257876A (en) * | 2018-03-12 | 2019-09-20 | 深圳市裕展精密科技有限公司 | The production method of anode oxide film |
| CN108823626B (en) * | 2018-05-27 | 2020-11-03 | 中南大学 | Al (aluminum)2O3Al/Mg layered density gradient material and preparation method and application thereof |
| EP3696299A1 (en) * | 2019-02-15 | 2020-08-19 | Coventya GmbH | Method for producing a corrosion-resistant aluminum-silicon alloy casting, corresponding corrosion-resistant aluminum-silicon alloy casting and its use |
| CN109913923B (en) * | 2019-04-29 | 2020-09-22 | 东莞市慧泽凌化工科技有限公司 | Surface treatment liquid and method for surface treatment of magnesium alloy aluminum alloy composite part |
| CN110219031B (en) * | 2019-06-06 | 2020-12-08 | 北京航空航天大学 | Anodic oxidation electrolyte and method, and aluminum or aluminum alloy with anodic oxidation film |
| CN111363960A (en) * | 2020-04-28 | 2020-07-03 | 华南理工大学 | Anodized thin-wall die-casting aluminum alloy material, preparation method thereof and thin-wall appearance part |
| CN111893540B (en) * | 2020-07-15 | 2021-08-10 | 东莞理工学院 | Preparation method of aluminum-silicon alloy micro-arc oxidation film layer |
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