CN102428213A - Method for treating the surface of a metal - Google Patents
Method for treating the surface of a metal Download PDFInfo
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- CN102428213A CN102428213A CN2010800190114A CN201080019011A CN102428213A CN 102428213 A CN102428213 A CN 102428213A CN 2010800190114 A CN2010800190114 A CN 2010800190114A CN 201080019011 A CN201080019011 A CN 201080019011A CN 102428213 A CN102428213 A CN 102428213A
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- surface treatment
- electrolytic solution
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 238000004381 surface treatment Methods 0.000 claims abstract description 48
- 239000008139 complexing agent Substances 0.000 claims abstract description 29
- 238000002848 electrochemical method Methods 0.000 claims abstract description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 70
- 230000008569 process Effects 0.000 claims description 42
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 22
- 238000005868 electrolysis reaction Methods 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 17
- 210000000981 epithelium Anatomy 0.000 claims description 15
- 150000003016 phosphoric acids Chemical class 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 150000004673 fluoride salts Chemical class 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical group OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 5
- 229940005740 hexametaphosphate Drugs 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 229910000737 Duralumin Inorganic materials 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical group [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical group [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 239000001226 triphosphate Substances 0.000 claims description 2
- 235000011178 triphosphate Nutrition 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 4
- 229910018125 Al-Si Inorganic materials 0.000 claims 1
- 229910018520 Al—Si Inorganic materials 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 238000004040 coloring Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 abstract 1
- 150000003681 vanadium Chemical class 0.000 abstract 1
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract 1
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 20
- 239000012528 membrane Substances 0.000 description 14
- 238000010586 diagram Methods 0.000 description 12
- 238000005286 illumination Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- -1 silicon metalloid Chemical class 0.000 description 5
- 208000035126 Facies Diseases 0.000 description 4
- 238000004512 die casting Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/14—Producing integrally coloured layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Inorganic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The present invention relates to a method for treating the surface of a metal, and more particularly, to an electrochemical method for treating the surface of a metal. The method for treating the surface of a metal according to the present invention comprises the steps of: preparing an electrolyte including vanadium salt and a complexing agent; immersing a metal in the electrolyte; and electrochemically treating the surface of the metal using the metal as a positive electrode. By using a surface treatment method of adding a vanadium oxide to an oxide film, the present invention obtains excellent effects of improving the corrosion resistance of the metal and a black coloring.
Description
Technical field
The present invention relates to the metallic surface treatment process, relate in particular to and utilize electrochemical method to carry out the method that metallic surface is handled.
Background technology
Generally speaking, metals such as aluminium and magnesium are good because of its ductility and snappiness, and proportion is little, and heat conduction and electroconductibility are big, and airborne erosion resistance number is used thereby be processed into various forms such as sheet material, thin material, bar, wire rod, tubing, section bar.Especially, be used for electronic product shell etc. recently, and, be used to form higher-grade and beautiful appearance.But metals such as pure aluminium and magnesium are low because of its intensity, gain in strength thereby need to add various elements.
In addition, under situation, for the flowability that satisfies metallic solution and intensity and add silicon as a kind of Al-Si alloy of duraluminum.But, if the Al-Si alloy is carried out surface treatment, then form the sull that constitutes by compound between the silicon metalloid and produce current mark (flow-mark) on the surface, thereby aspect surface treatment, have some problems.
Figure 18 is for carrying out the surface picture of surface-treated Al-Si alloy with the method for prior art.Can find out, produce current mark in the part that dots.In order to address these problems, utilize or the trial of various surface treatment methods such as plasma electrolysis oxidation process, but therefore reactive low because of the silicon that is formed at matrix, fail to deal with problems.
In addition, under the situation outside the Al-Si alloy, need develop surface treatment than the difficult metal and the surface treatment method of alloy.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art and a kind of good corrosion resistance is provided, and to the good metallic surface treatment process of coloring effect of black series.
In order to achieve the above object, metallic surface treatment process of the present invention comprises the steps: to prepare to comprise the electrolytic solution of vanadic salts and complexing agent; Impregnating metal in above-mentioned electrolytic solution; Reaching with above-mentioned metal is that anode carries out surface treatment through electrochemical method.
Below, metallic surface treatment process of the present invention is elaborated.
At first, preparation need be carried out surface-treated metal and the electrolytic solution that comprises vanadic salts and complexing agent.
In the present invention, aluminum or aluminum alloy is arranged as the representational metal of surface treatment object, Al-Si alloy especially, and the preferable examples of object metal also has magnesium or magnesiumalloy.
Al-Si alloy in the duraluminum is because of can being made through die casting, thereby its utilization ratio is high, but also is to be difficult to carry out the representational metal of surface-treated, but can carry out surface treatment through surface treatment method of the present invention.
Metal being carried out surface treatment to form in the electrolytic solution of epithelium through electrochemical method, comprise vanadic salts and complexing agent on its surface according to the present invention.
In metallic surface treating processes of the present invention,, then can not form barium oxide, thereby be difficult to obtain desired result in whole metallic surface if use the simple electrolytic solution that adds vanadic salts.But, if utilization is carried out surface treatment according to the present invention to the object metal with the electrolytic solution that vanadic salts together adds complexing agent, then can be through reducing the formation that reduction current promotes barium oxide.Therefore, can evenly form barium oxide being formed on the whole sull of object metallic surface.Because of the phase black in color of the barium oxide in the sull that is formed at the object metallic surface, therefore, show picture black series in the metallic surface effect, and, improve rerum naturas such as erosion resistance.
In the present invention, the vanadic salts that is contained in electrolytic solution can use sodium metavanadate, vanadium tetrachloride, vanadylic chloride, ammonium vanadate etc., so long as vanadium is got final product with the material that ionic condition is present in the electrolytic solution.
Preferably, the concentration that is contained in the vanadic salts of above-mentioned electrolytic solution is 0.025～0.171M.
In the present invention, the complexing agent that is contained in electrolytic solution makes barium oxide be formed at whole object metallic surface through reducing the reduction current of vanadium, and, make black become more obvious, reduce surperficial illumination, thereby form slick surface.
Above-mentioned complexing agent can use Hydrocerol A, tartrate, YD 30 (EDTA), Padil etc., and preferably, uses EDTA.
Preferably, the concentration that makes an addition to the complexing agent of above-mentioned electrolytic solution is 0.003～0.07M.
In the present invention, comprise phosphoric acid salt in the above-mentioned electrolytic solution, learn the required various ions of surface treatment to carry supply rings, and phosphoric acid salt helps in electrolytic solution vanadium ion to be oxidizing to the object metallic surface.
Above-mentioned phosphoric acid salt can use trisodium phosphate, hexametaphosphate, second phosphoric acid salt, triphosphate etc., and preferably, uses hexametaphosphate.
Preferably, the phosphatic concentration that is contained in above-mentioned electrolytic solution is 0.005～0.05M.
The concentration of these electrolytic solution is extremely important.If the phosphoric acid salt in the electrolytic solution and the concentration of vanadic salts are lower than the Cmin of above-mentioned phosphoric acid salt and vanadic salts, then can not carry out surface treatment smoothly, and if be higher than Cmin, then the formation of sull will become inhomogeneous.
In the present invention, electrolytic solution as base soln, can mix use with acidic solution with mineral acids such as phosphoric acid, sulfuric acid and nitric acid and acetic acid, Hydrocerol A organic acids such as (citric acid) with zero(ppm) water.
In the present invention, in above-mentioned electrolytic solution, also can comprise oxyhydroxide, silicate, fluoride salt etc.
Can add oxyhydroxide to above-mentioned electrolytic solution, be the alkaline electrolyte more than 7.0 to be prepared into the pH condition.
In one embodiment of the present invention, above-mentioned oxyhydroxide can use Pottasium Hydroxide, sodium hydroxide etc., and preferably, the concentration of oxyhydroxide is 0.01～0.53M.
Above-mentioned silicate can use potassium silicate, water glass etc., and preferably, the concentration that is contained in the silicate of electrolytic solution is 0.008～0.3M.Surpass 0.3M if make an addition to the silicate of electrolytic solution, then hinder performance black because of generating Si oxide.
Above-mentioned fluoride salt can use Potassium monofluoride, Sodium Fluoride, Neutral ammonium fluoride etc., and preferably, the concentration that is contained in the fluoride salt of electrolytic solution is 0.017～0.344M.
In one embodiment of the present invention; If carry out metallic surface treating processes of the present invention as the object metal with aluminum or aluminum alloy; Then be used for the electrolytic solution that metallic surface is handled; Add vanadic salts, phosphoric acid salt and complexing agent, and can also add oxyhydroxide, fluoride salt, silicate etc. as required.
If carry out surface treatment with aluminum or aluminum alloy as the object metal, then the pH value of above-mentioned electrolytic solution is 6～14.
In one embodiment of the present invention; If carry out metallic surface treating processes of the present invention as the object metal with magnesium or magnesiumalloy; Then be used for the electrolytic solution that metallic surface is handled; Add vanadic salts, phosphoric acid salt, oxyhydroxide, fluoride salt and complexing agent, and can also add silicate etc. as required.
If carry out surface treatment as the object metal with magnesium or magnesiumalloy, because of be lower than at 7.0 o'clock in the pH of electrolytic solution value corrosion reaction takes place then, therefore, the pH value of electrolytic solution need maintain more than 7.0, and, need guarantee certain electric conductivity simultaneously.In addition,, need under the pH of electrolytic solution value is higher than 7.0 solution condition, to guarantee to have sufficient activity, and problem such as deposition can not take place in order to realize black at Mg alloy surface.And more, the pH value of electrolytic solution is 12～14, and in above-mentioned scope, color representation was descended best.
The above-mentioned aluminum or aluminum alloy and magnesium or magnesiumalloy of utilizing carries out in the surface-treated process, is contained in vanadic salts, phosphoric acid salt, oxyhydroxide, fluoride salt, the silicate of electrolytic solution, the concrete kind and the concentration of complexing agent, and be identical with foregoing.
Then, in ready electrolytic solution, after the dipping object metal, be anode conducting electric current with impregnated metal, handle thereby carry out electrochemical surface.
If the metal to be impregnated in electrolytic solution is an anode, and is the electric current of negative electrode conducting interchange or pulse waveform with the stainless steel, electrochemical reaction then takes place in the metallic surface.Produce hydrogen on the stainless steel cathode surface, and,, the oxidizing reaction of metal takes place in the oxygenous while as the anodic metallic surface.In carrying out the electrochemical surface treating processes; If dielectric breakdown voltage (the Dielectric Breakdown Voltage that the voltage that applies through raising applies above can on anode oxide film, switch on; High-voltage more than 150～500V); Then, will form local arc (spark or plasma) because of the influence of the inner highfield that gas caused that is produced of sull.At this moment, with producing the high temperature instant melting of sull because of electric arc, but the phenomenon of solidifying immediately again because of the temperature of peripheral electrolytic solution.Become plasma electrolysis oxidation process through repeating the technology that above-mentioned phenomenon forms the skin membrane that is made up of composite oxides, and in the present invention, can in the electrochemical surface treating processes, utilize above-mentioned plasma electrolysis oxidation process.
Plasma electrolysis oxidation process of the present invention is through applying 2～200mA/cm
2The electric current of current density realize.If current density less than above-mentioned scope, then can't reach sufficient electrolytic oxidation, and, then reduce surface property (for example, spot corrosion (pit corrosion) taking place) because of the over-drastic electric current if be higher than above-mentioned scope.This will hinder the purpose that the present invention shows black.
In addition, preferably, the process time of plasma electricity price oxidation is 100～9000 seconds, if shorter than the above-mentioned time, then is difficult to accomplish plasma electrolysis oxidation, thereby is difficult to form the black skin membrane at the object metallic surface.In contrast, if longer than the above-mentioned time, then because of the over-drastic electric current reduces surface property, as spot corrosion etc. takes place.This will hinder the purpose that desire of the present invention improves black colorant property.
In the present invention, preferably,, not only have outstanding tint permanence through the object metallic surface is handled formed skin membrane, and, outstanding erosion resistance possessed simultaneously.For this reason, use vanadic salts in the present invention,, form the skin membrane that possesses erosion resistance with through when painted (black) is carried out in processing to the object metallic surface as water-soluble metal salt.
In addition, the present invention provides according to the present invention and carries out surface treatment to form the metal of the epithelium that comprises barium oxide in the object metallic surface.
Above-mentioned object metal can use aluminium, duraluminum, magnesium or magnesiumalloy.
If according to the present invention above-mentioned object metal is carried out surface treatment, then formation comprises the epithelium of MOX and barium oxide in the object metallic surface, thereby when showing the black colorant effect, possesses outstanding erosion resistance.
The present invention improves the erosion resistance of metal through being utilized in the surface treatment method that comprises barium oxide in the sull, and obtains the outstanding coloring effect of black series.
Description of drawings
Fig. 1 is the section electron micrograph of the Al-Si alloy of the embodiment of the invention 1;
Fig. 2 is the surface electronic microphotograph of the Al-Si alloy of the embodiment of the invention 1;
Fig. 3 is the EDS analytical results synoptic diagram of the Al-Si alloy surface sull of the embodiment of the invention 1;
Fig. 4 is the surface optical microphotograph of Al-Si alloy test piece;
Fig. 5 and Fig. 6 are to the facies analysis of the Al-Si alloy surface sull of the embodiment of the invention 1 synoptic diagram as a result;
Fig. 7 is the section electron micrograph of the magnesiumalloy of the embodiment of the invention 2;
Fig. 8 is the surface electronic microphotograph of the magnesiumalloy of the embodiment of the invention 2;
Fig. 9 is the EDS analytical results synoptic diagram of the Mg alloy surface sull of the embodiment of the invention 2;
Figure 10 to Figure 12 is to the facies analysis of the Mg alloy surface sull of the embodiment of the invention 2 synoptic diagram as a result;
Figure 13 carries out nano impress result of experiment synoptic diagram for the Mg alloy surface sull to embodiments of the invention 2 and comparative example 1;
Figure 14 is the Mg alloy surface change in color synoptic diagram of expression embodiments of the invention 2 and comparative example 1;
Figure 15 is the synoptic diagram as a result of the Mg alloy surface illumination of the measurement embodiment of the invention 2;
Figure 16 is for passing through the result curve figure of the surperficial illumination of AFM analysis to measure magnesiumalloy under the state that in electrolytic solution, does not add complexing agent in one embodiment of this invention;
Figure 17 is the result curve figure that in electrolytic solution, passes through the surperficial illumination of AFM analysis to measure magnesiumalloy in one embodiment of this invention under the state of interpolation complexing agent;
Figure 18 is for carrying out the surface picture of surface-treated Al-Si alloy with the method for prior art.
Embodiment
Below, the present invention will be described through preferred embodiment.But following embodiment etc. are to example of the present invention and unrestricted the present invention.
< embodiment 1 >
The preparation of test piece
(the ADC12 kind: silicon 12 weight %) specimen preparation becomes the sheet material of wide 15mm, high 20mm, thick 1mm to the Al-Si alloy that die casting is formed, and utilizes after the even grinding of SiC sand paper (#1000), utilizes alcohol to clean and carries out drying afterwards.
Fig. 4 is the microphotograph of the surface light of the ready test piece of expression.As shown in the figure, the Al-Si alloy that die casting forms exists with silicon compound with α-Al mutually mutually.
Electrolytical preparation
In the zero(ppm) water of 4L, dissolve ammonium vanadate (NH
4VO
3) 0.025M, hexametaphosphate 0.005M and prepare electrolytic solution as the EDTA0.003M of complexing agent.
Implement plasma electrolysis oxidation process
Fill ready electrolytic solution and make test piece be positioned at anode to the device of the output voltage with 20kW, whipping appts and refrigerating unit, and make stainless steel be positioned at negative electrode.
Keeping under 20 ℃ the state of temperature of electrolytic solution, at 100mA/cm
2Current density, use AC power to implement the plasma electrolysis oxidation process in 900 seconds.
Fig. 1 and Fig. 2 are the section and the surface electronic microphotograph of the Al-Si alloy of embodiment 1.Shown in the cross sectional photograph of Fig. 1, go up mutually with silicon compound mutually at the α-Al that constitutes the Al-Si alloy that die casting forms, integral body is formed uniformly a kind of sull.Like the surface picture of Fig. 2, the fine and close sull that forms on whole Al-Si alloy.
Fig. 3 is the EDS analytical results of the Al-Si alloy surface sull of embodiment 1, and sull is made up of compositions such as aluminium, oxygen, vanadium, phosphorus.
Fig. 5 and Fig. 6 are to the facies analysis of the Al-Si alloy surface sull of embodiment 1 synoptic diagram as a result.In Fig. 5, can confirm to exist in the sull Al
2O
3Phase, and in Fig. 6, can confirm to exist in the sull V
2The O phase.The major part of sull is with Al
2O
3Exist mutually, and estimate because of V
2O
3The painted of black series accomplished in the existence of phase.
Table 1 is for analyzing the result that the sample that under the electrolytic solution condition of Al-Si alloy that does not add embodiment 1 and complexing agent, carries out the epithelium processing is experimentized through AFM.It is lower in electrolytic solution, to add the surperficial illumination numerical value that carries out the sample that epithelium handles under the condition of complexing agent, and than carrying out the sample that epithelium is handled under the electrolytic solution condition of complexing agent not adding, its surface is quite smooth.
[table 1]
< embodiment 2 >
The preparation of test piece
Under 350 ℃ temperature condition; Test piece is carried out specimen preparation being become the sheet material of wide 30mm, high 40mm, thick 2mm after 12 hours the homogenizing thermal treatment and cooling to AZ91 magnesiumalloy (aluminium 8.29 weight %, zinc 0.83 weight %, manganese 0.31 weight %, all the other be Mg).Utilize SiC sand paper (#1000) evenly to grind after the test piece surface, with alcohol washing and carry out drying.
Electrolytical preparation
Dissolved hydrogen potassium oxide 0.5M, Calcium Fluoride (Fluorspan) 0.086M, ammonium vanadate (NH in the zero(ppm) water of 4L
4VO
3) 0.111M, hexametaphosphate 0.04M and prepare electrolytic solution as the EDTA0.058M of complexing agent.
Implement plasma electrolysis oxidation process
Fill ready electrolytic solution and make test piece be positioned at anode to the device of the output voltage with 20kW, whipping appts and refrigerating unit, and make stainless steel be positioned at negative electrode.
Utilize AC power at 100mA/cm
2Current density under carry out 10 minutes plasma electrolysis oxidation process.
< comparative example 1 >
Through except that not comprising the ammonium vanadate, the method identical with the electrolytic solution set-up procedure of embodiment 2 prepares electrolytic solution.In addition, the preparation of test piece and plasma electrolysis oxidation process are to implement with embodiment 2 identical methods.
Fig. 7 and Fig. 8 are the section and the surface electronic microphotograph of the magnesiumalloy of embodiment 2.Like the cross sectional photograph of Fig. 7, skin membrane compared to prior art forms the quite skin membrane of the structure of densification.At this moment, when carrying out the epithelium processing in about 100 seconds, the thickness of skin membrane becomes the level of about 5 μ m.Like the surface picture of Fig. 8, be the typical surface picture that occurs in the plasma electrolysis oxidation, form pore on its surface.
Fig. 9 is the EDS analytical results of the Mg alloy surface sull of embodiment 2, and sull is made up of compositions such as magnesium, oxygen, vanadium, phosphorus.
Figure 10 to Figure 12 is to the facies analysis of the Mg alloy surface sull of embodiment 2 synoptic diagram as a result.In Figure 10, can confirm in sull, to have the MgO phase, in Figure 11, can confirm in sull, to exist KH
2PO
4Phase, and in Figure 12, can confirm in sull, to exist V
2O
3Phase.The major part of sull exists with MgO.The VO that exists in solution
3 -Ion, the electric field of the electric arc that produces during through plasma electrolysis oxidation move to anode one side.Therefore, the VO of anode one side
3 -Ionic concn is higher than negative electrode one side.
The VO that is present in anode one side
3Form skin membrane around the-ion, the discharge channel of the electric arc that when plasma electrolysis oxidation, produces.Because of the be as the criterion active condition of surface of safe phase of formed skin membrane, surface energy is high, thereby can play the effect that absorbs external agency.As a result, in order to reduce the surface energy of established skin membrane, be present in the VO between the surface of electrolytic solution and sample
3 -Ion will absorb to skin membrane.That is VO,
3-ion is with barium oxide (V
2O
3) form get in the skin membrane, thereby form the skin membrane of black.
Figure 13 carries out nano impress result of experiment synoptic diagram for the Mg alloy surface sull to embodiments of the invention 2.Thereby measurement is carried out the result of hardness of magnesiumalloy that the plasma electrolysis oxidation in 100 seconds has the skin membrane about about 5 μ m for 180mN in embodiment 2.In comprising the electrolytic solution of vanadium, under the situation of the comparative example 1 of electrolytic oxidation, only do not reach the level of about 115mN.Utilize the Oliver-Pharr method with the result that it is scaled hardness value to do, the hardness value of embodiment 2 and comparative example 1 respectively is 7.4GPa and 5.9GPa.
Figure 14 is the Mg alloy surface change in color synoptic diagram of expression embodiment 2.In not comprising the electrolytic solution of vanadium, carry out the surface of the magnesiumalloy of plasma electrolysis oxidation processing in the surface treatment liquid of the comparative example 1 of electrolytic oxidation, all be white in color with the variation of coating voltage is irrelevant.But in the electrolytic solution of embodiment 2, carry out the surface of the magnesiumalloy that plasma electrolysis oxidation handles,, be brown, and more than 210V, apply voltage, form the sull of black in initial low voltage with the increase that applies voltage.This be because, the addition that is contained in the vanadium of sull along with the increase of oxide thickness increases gradually, therefore, the barium oxide that is present in the sull increases gradually.
Figure 15 is the synoptic diagram as a result of the Mg alloy surface illumination of measurement embodiment 2.Observations shows, occurs slick surface till the 210V, and it is quite coarse to carry out the surperficial illumination of the sample that epithelium handles under the voltage applying more than the 250V.
In addition, table 2 is for passing through the AFM analysis to measure under the condition of embodiment 2, and the magnesiumalloy that in electrolytic solution, adds complexing agent reaches the result of the surperficial illumination of the sample that carries out the epithelium processing under the electrolytic solution condition of not adding complexing agent.In addition; Figure 16 is the result curve figure of the surperficial illumination through AFM analysis to measure magnesiumalloy down for the state that in electrolytic solution, do not add complexing agent in one embodiment of this invention, and Figure 17 be the result curve figure that in electrolytic solution, passes through the surperficial illumination of AFM analysis to measure magnesiumalloy in one embodiment of this invention under the state of interpolation complexing agent.
As shown in table 2, along with in electrolytic solution, adding complexing agent, the surperficial illumination step-down of the sample of handling through epithelium, and than carrying out the sample that epithelium is handled under the electrolytic solution condition of complexing agent not adding, its surface is quite smooth.That is, through adding complexing agent, Ra, Ry, Rq reduce nearly 20%.Shown in figure 16, than the alloy of embodiments of the invention 2, the pore that the alloy surface of handling with the electrolytic solution that does not add complexing agent forms becomes big, thereby has the difference of mountain and ditch.
[table 2]
The foregoing description is only unrestricted in order to explanation the present invention; Those of ordinary skill in the art is to be understood that; Can make amendment, be out of shape the present invention or be equal to replacement, and not break away from the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (24)
1. a surface treated metal is characterized in that, comprising:
The metal mother metal; And
Epithelium is formed on the above-mentioned metal mother metal and comprises barium oxide.
2. surface treated metal according to claim 1 is characterized in that: above-mentioned metal mother metal is the mother metal that comprises aluminum or aluminum alloy, and in above-mentioned epithelium, also comprises al oxide.
3. surface treated metal according to claim 1 is characterized in that: above-mentioned metal mother metal is the mother metal that comprises magnesium or magnesiumalloy, and in above-mentioned epithelium, also comprises magnesium oxide.
4. surface treated metal according to claim 1 is characterized in that: above-mentioned epithelium black in color.
5. a metallic surface treatment process is characterized in that, comprises the steps:
Preparation comprises the electrolytic solution of vanadic salts and complexing agent;
Impregnating metal in above-mentioned electrolytic solution; And
With above-mentioned metal is that anode carries out surface treatment through electrochemical method.
6. metallic surface treatment process according to claim 5 is characterized in that: vanadic salts is selected from sodium metavanadate, vanadium tetrachloride, vanadylic chloride, ammonium vanadate.
7. metallic surface treatment process according to claim 5 is characterized in that: in above-mentioned electrolytic solution, the concentration of vanadic salts is 0.025～0.171M.
8. metallic surface treatment process according to claim 5 is characterized in that: above-mentioned complexing agent is selected from Hydrocerol A, tartrate, YD 30 (EDTA), Padil.
9. metallic surface treatment process according to claim 5 is characterized in that: in above-mentioned electrolytic solution, the concentration of complexing agent is 0.003～0.07M.
10. metallic surface treatment process according to claim 5 is characterized in that: above-mentioned metal uses aluminum or aluminum alloy, and in above-mentioned electrolytic solution, also comprises phosphoric acid salt.
11. metallic surface treatment process according to claim 10 is characterized in that: above-mentioned duraluminum uses Al-Si.
12. metallic surface treatment process according to claim 10 is characterized in that: also comprise from oxyhydroxide, fluoride salt and silicate in the above-mentioned electrolytic solution and select more than one.
13. metallic surface treatment process according to claim 10 is characterized in that: the pH value of above-mentioned electrolytic solution is 6～14.
14. metallic surface treatment process according to claim 5 is characterized in that: above-mentioned metal uses magnesium or magnesiumalloy, and in above-mentioned electrolytic solution, also comprises phosphoric acid salt, oxyhydroxide and fluoride salt.
15. metallic surface treatment process according to claim 14 is characterized in that: in above-mentioned electrolytic solution, also comprise silicate.
16. metallic surface treatment process according to claim 14 is characterized in that: the pH value of above-mentioned electrolytic solution is 12～14.
17. according to claim 10 or 14 described metallic surface treatment processs; It is characterized in that: above-mentioned phosphoric acid salt is selected from trisodium phosphate, hexametaphosphate, second phosphoric acid salt, triphosphate, and the phosphatic concentration in electrolytic solution is 0.005～0.05M.
18. according to claim 12 or 14 described metallic surface treatment processs, it is characterized in that: above-mentioned oxyhydroxide is Pottasium Hydroxide or sodium hydroxide, and the concentration of the oxyhydroxide in electrolytic solution is 0.01～0.53M.
19. according to claim 12 or 15 described metallic surface treatment processs, it is characterized in that: above-mentioned silicate is potassium silicate or water glass, and the concentration of the silicate in electrolytic solution is 0.008～0.3M.
20. according to claim 12 or 15 described metallic surface treatment processs, it is characterized in that: above-mentioned fluoride salt is Potassium monofluoride, Sodium Fluoride or Neutral ammonium fluoride, and the concentration of the fluoride salt in electrolytic solution is 0.017～0.344M.
21. metallic surface treatment process according to claim 5 is characterized in that: above-mentioned electrochemical surface treatment process is a plasma electrolysis oxidation.
22. metallic surface treatment process according to claim 21 is characterized in that: above-mentioned plasma electrolysis oxidation is accomplished through the voltage that applies 150～500V.
23. metallic surface treatment process according to claim 21 is characterized in that: with surface treatment object metal is anode, and stainless steel is that negative electrode is accomplished above-mentioned plasma electrolysis oxidation.
24. metallic surface treatment process according to claim 21 is characterized in that: above-mentioned plasma electrolysis oxidation carried out for 100～9000 seconds.
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| KR1020100036848A KR101195458B1 (en) | 2009-04-22 | 2010-04-21 | Method for treating the surface of metal |
| PCT/KR2010/002519 WO2010123289A2 (en) | 2009-04-22 | 2010-04-22 | Method for treating the surface of a metal |
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| CN102428213B (en) | 2015-04-01 |
| KR20100116546A (en) | 2010-11-01 |
| KR101195458B1 (en) | 2012-10-30 |
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