CN113638025A - Method suitable for coloring surface of aluminum alloy - Google Patents
Method suitable for coloring surface of aluminum alloy Download PDFInfo
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- CN113638025A CN113638025A CN202110802986.4A CN202110802986A CN113638025A CN 113638025 A CN113638025 A CN 113638025A CN 202110802986 A CN202110802986 A CN 202110802986A CN 113638025 A CN113638025 A CN 113638025A
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- aluminum alloy
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- 238000004040 coloring Methods 0.000 title claims abstract description 115
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 238000007789 sealing Methods 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 17
- 230000003213 activating effect Effects 0.000 claims abstract description 11
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims abstract description 11
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims abstract description 9
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims abstract description 7
- PAEYAKGINDQUCT-UHFFFAOYSA-N Ethyl 2-pyrrolecarboxylate Chemical compound CCOC(=O)C1=CC=CN1 PAEYAKGINDQUCT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 6
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 5
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940068041 phytic acid Drugs 0.000 claims abstract description 5
- 239000000467 phytic acid Substances 0.000 claims abstract description 5
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 5
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000004299 sodium benzoate Substances 0.000 claims abstract description 5
- 235000010234 sodium benzoate Nutrition 0.000 claims abstract description 5
- JCBPETKZIGVZRE-SCSAIBSYSA-N (2r)-2-aminobutan-1-ol Chemical compound CC[C@@H](N)CO JCBPETKZIGVZRE-SCSAIBSYSA-N 0.000 claims abstract description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 3
- 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 claims abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 238000001994 activation Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000007667 floating Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 241000872198 Serjania polyphylla Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- -1 black) Chemical compound 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 235000019993 champagne Nutrition 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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
- C25D11/12—Anodising more than once, e.g. in different baths
-
- 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
- C25D11/16—Pretreatment, e.g. desmutting
-
- 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
- C25D11/18—After-treatment, e.g. pore-sealing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention relates to a method suitable for coloring the surface of an aluminum alloy, which comprises the following steps: s1, performing alkali washing and acid washing on the aluminum alloy; s2, placing the aluminum alloy in an activating solution for electrolytic activation; s3, carrying out primary electrolytic coloring, namely putting the aluminum alloy into primary electrolytic coloring liquid for direct current electrolytic coloring, wherein the primary electrolytic coloring liquid comprises 35-50g/L nickel sulfate heptahydrate, 25-30g/L stannous sulfate, 1-2g/L metanilic acid, 2-3g/L disodium ethylene diamine tetraacetate, 5-7 g/L2-amino-1-butanol and 3-5g/L phytic acid; s4, secondary electrolytic coloring, namely, putting the aluminum alloy into secondary electrolytic coloring liquid for direct current electrolytic coloring, wherein the secondary electrolytic coloring liquid comprises 15-20g/L nickel sulfate heptahydrate, 10-20g/L stannous sulfate, 5-10g/L sodium benzoate, 4-6g/L polyethylene glycol, 1-2g/L ethyl 2-pyrrole carboxylate and 2-4g/L sodium trifluoromethanesulfonate; and S5, sealing the holes.
Description
Technical Field
The invention relates to the technical field of surface treatment, in particular to a method suitable for coloring the surface of an aluminum alloy.
Background
Aluminum alloys are lightweight, have high strength ratios, are easy to process, and have good corrosion resistance, and can be widely used in the fields of building materials, vehicle members, furniture, and the like due to these excellent properties of aluminum alloys. The aluminum alloy is anodized and electrolytically colored by forming a compact and thick oxide film on the surface of the aluminum alloy by an anodic oxidation method, so that the corrosion resistance, hardness, wear resistance and decorative performance of the aluminum alloy are further improved. The technical scheme of the existing aluminum alloy surface coloring is that after aluminum alloy is subjected to common sulfuric acid anodic oxidation, a colored oxide film is prepared in an electrolytic coloring tank containing metal salt, and light rays are scattered when the light rays irradiate the colored oxide film, so that the colored oxide film is colored. The metal salts currently used for coloring the surface of aluminum alloys include stannous sulfate (champagne, bronze, black), nickel sulfate (champagne, bronze, black), potassium permanganate (golden yellow), copper sulfate (red copper), selenium dioxide (kejin), etc.
The technical problems of the existing aluminum alloy surface coloring technical scheme are as follows: 1. uneven coloring is easy to occur in the anodic oxidation coloring process of the aluminum alloy surface; 2. to improve the decorative effect of anodic oxidation coloration of aluminum alloys, it is often necessary to add toxic nickel-based metals to the coloration bath and to consume large amounts of metal salt solutions.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a method suitable for coloring the surface of an aluminum alloy, which can make the surface of the aluminum alloy more uniformly colored and can make the surface of the aluminum alloy present a black colored layer with good texture.
The technical effect to be achieved by the invention is realized by the following scheme:
the invention provides a method suitable for coloring the surface of an aluminum alloy, which comprises the following steps:
s1, performing pretreatment, wherein the pretreatment comprises alkali washing and acid washing to obtain the aluminum alloy with a smooth and clean surface and active chemical property;
s2, activating, namely putting the aluminum alloy into an activating solution for electrolytic activation, wherein the activating solution comprises 10-20g/L sulfuric acid, 30-40g/L sodium dihydrogen phosphate and 0.2-0.3g/L sodium acetate, the activating temperature is 75-80 ℃, the electrolysis time is 45-60S, and the current density is 0.1-0.15A/dm2；
S3, primary electrolytic coloring, namely, putting the aluminum alloy into primary electrolytic coloring liquid for direct current electrolytic coloring, wherein the primary electrolytic coloring liquid comprises 35-50g/L nickel sulfate heptahydrate, 25-30g/L stannous sulfate, 1-2g/L metanilic acid, 2Disodium ethylene diamine tetraacetate of 3g/L, 2-amino-1-butanol of 5-7g/L and phytic acid of 3-5g/L, the pH value of said primary electrolytic colouring liquor is regulated in the range of 4.8-5.0 by using dilute sulfuric acid and ammonia water, colouring temperature is 40-60 deg.C, and coloured constant current density is 0.6-0.8A/dm2Coloring for 1-3min, and applying graphite electrode as counter electrode;
s4, secondary electrolytic coloring, namely placing the aluminum alloy in a secondary electrolytic coloring liquid for direct current electrolytic coloring, wherein the secondary electrolytic coloring liquid comprises 15-20g/L nickel sulfate heptahydrate, 10-20g/L stannous sulfate, 5-10g/L sodium benzoate, 4-6g/L polyethylene glycol, 1-2g/L ethyl 2-pyrrole carboxylate and 2-4g/L sodium trifluoromethylsulfonate, the secondary electrolytic coloring liquid utilizes dilute sulfuric acid and ammonia water to adjust the pH value to be 4.0-4.5, the coloring temperature is 40-60 ℃, and the constant current density of coloring is 0.3-0.6A/dm2Coloring for 5-10min, and applying graphite electrode as counter electrode;
s5, sealing holes, namely, spraying and washing the electrolytically colored aluminum alloy surface, and then soaking the aluminum alloy surface into a hole sealing liquid for sealing holes, wherein the hole sealing liquid comprises 5-10g/L of vinyl trimethoxy silane, 5-8g/L of triethanolamine, 4-8g/L of sodium silicate and 7-7.5g/L of N, N-dimethyl formamide, the pH value of the hole sealing liquid is adjusted to be 6-6.5 by using dilute sulfuric acid and ammonia water, the hole sealing temperature is 80-90 ℃, and the hole sealing duration is 5-10 min.
And a water washing procedure is also included between the adjacent steps, for example, the surface of the aluminum alloy is washed by flowing deionized water.
In one embodiment, the pre-processing specifically comprises: soaking the aluminum alloy in alkaline washing solution at 50-70 deg.C for 2-3min, washing the aluminum alloy with deionized water, and soaking in acid washing solution for 4-5 min. The alkaline washing solution comprises 30-40g/L of sodium hydroxide, 0.2-0.5g/L of sodium dodecyl sulfate and 1-2g/L of sodium gluconate, and the pickling solution is a mixed solution of sulfuric acid and nitric acid.
The surface of the aluminum alloy is covered with an oxide film, the main component of the oxide film is aluminum oxide, in the electrolytic coloring process, metal ions in the primary electrolytic coloring liquid/the secondary electrolytic coloring liquid are subjected to electrolytic precipitation in oxide film holes, electrons must move to the surface of the oxide film, and the metal ions are deposited and colored in gaps of the oxide film.
The method for coloring the surface of the aluminum alloy provided by the invention has the advantages that the original oxide film on the surface of the aluminum alloy is removed in the pretreatment step, the activation points are formed on the surface of the aluminum alloy by the electrolytic activation in the activation step, and meanwhile, the oxide film newly generated on the surface of the aluminum alloy is more smooth and uniform, so that the uniformity of the subsequent electrolytic coloring is favorably improved. During the activation step, the activation process of the aluminum alloy is carried out in an ultrasonic environment, and the ultrasonic frequency is 80-120KHz, so that the aluminum alloy oxide layer is prevented from being uneven due to bubbles generated on the surface of the aluminum alloy in the activation process.
The invention provides a method for coloring the surface of aluminum alloy, which comprises two times of electrolytic coloring, wherein a colored film layer is formed on the surface of an aluminum alloy oxide film by one time of electrolytic coloring, a more firm and tough colored layer is attached to the colored film layer by the second time of electrolytic coloring, and the colored layer is black in color. Both the colored film layer and the colored layer can be regarded as an anodic oxide layer.
In the primary electrolytic coloring liquid, nickel sulfate heptahydrate and stannous sulfate provide metal ions, ethylene diamine tetraacetic acid is used as a complexing agent, phytic acid is used as a pH stabilizer, metanilic acid is used as a blackening agent, and 2-amino-1-butanol is used as a penetrating agent.
In the secondary electrolytic coloring liquid, nickel sulfate heptahydrate and stannous sulfate provide metal ions, sodium benzoate is used as a pH stabilizer, polyethylene glycol is used as a penetrating agent, and 2-pyrrole ethyl carboxylate and sodium trifluoromethyl sulfonate are used as blackening agents.
When secondary electrolytic coloring is carried out, the colored film layer generated in the primary electrolytic coloring process is converted into an alternating current oxide film by virtue of the acid environment in the secondary main color liquid, the structure of the colored film layer cannot be changed, and macroscopically, the colored layer on the surface of the aluminum alloy is more uniform and deep in coloring without 'floating color'.
Compared with the prior art, the technical scheme provided by the invention has at least the following beneficial effects:
1. the invention provides a method suitable for coloring the surface of an aluminum alloy, which utilizes two times of electrolytic coloring and hole sealing to ensure that a coloring layer on the surface of the aluminum alloy is more uniform and stable and has higher hardness, and the coloring layer of the aluminum alloy finally presents a black coloring layer with good texture and is suitable for coloring a high-end aluminum alloy piece;
2. the hole sealing liquid adopted by the invention does not contain heavy metals, is nontoxic and harmless to people and environment, and the color of the surface of the aluminum alloy after hole sealing treatment is uniform and stable, and the corrosion resistance is improved;
3. the penetrating agent and the blackening agent adopted by the invention can effectively improve the utilization efficiency of metal ions, and the use of the blackening agent can replace toxic nickel metal, thereby avoiding adding toxic nickel metal into the primary electrolytic coloring liquid/the secondary electrolytic coloring liquid and reducing the consumption of a metal salt solution in the primary electrolytic coloring liquid/the secondary electrolytic coloring liquid;
4. the synergistic effect of the m-aminobenzene sulfonic acid and the 2-amino-1-butanol can enable a colored film layer with good leveling performance and uniformity to be formed on the surface of the aluminum alloy oxide film after the primary electrolytic coloring, and the synergistic effect of the polyethylene glycol, the 2-pyrrole ethyl carboxylate and the sodium trifluoromethanesulfonate enables the colored film layer to be good in coloring uniformity and wider in coloring range in the primary electrolytic coloring process.
Detailed Description
The present invention will be described in detail with reference to examples.
The aluminum alloy adopted in the embodiment of the invention is 20 x 5cm3The seventh series aluminum alloy sheet.
Example 1
The embodiment provides a method suitable for coloring the surface of an aluminum alloy, which comprises the following steps:
s1, pretreating, namely soaking the aluminum alloy in an alkaline washing solution at the temperature of 60 ℃ for 3min, washing the aluminum alloy after alkaline washing with deionized water, and then soaking in an acid washing solution for 5min to obtain the aluminum alloy with a smooth and clean surface and active chemical properties;
s2, activating, namely putting the aluminum alloy into an activating solution for electrolytic activation, wherein the activating solution comprises 15g/L sulfuric acid and 35g/L of sodium dihydrogen phosphate and 0.25g/L of sodium acetate, the activation temperature is 78 ℃, the electrolysis time is 50s, and the current density is 0.12A/dm2The electrolytic activation process is carried out in an ultrasonic environment, and the ultrasonic frequency is 100 KHz;
s3, primary electrolytic coloring, namely, placing the aluminum alloy into primary electrolytic coloring liquid for direct current electrolytic coloring, wherein the primary electrolytic coloring liquid comprises 40g/L nickel sulfate heptahydrate, 28g/L stannous sulfate, 1.5g/L m-aminobenzene sulfonic acid, 2.5g/L disodium ethylene diamine tetraacetate, 6 g/L2-amino-1-butanol and 4g/L phytic acid, the pH value of the primary electrolytic coloring liquid is adjusted to be 4.9 by dilute sulfuric acid and ammonia water, the coloring temperature is 50 ℃, and the coloring constant current density is 0.7A/dm2The coloring time is 2min, and a graphite electrode is adopted as a counter electrode;
s4, secondary electrolytic coloring, namely, putting the aluminum alloy into secondary electrolytic coloring liquid for direct current electrolytic coloring, wherein the secondary electrolytic coloring liquid comprises 18g/L nickel sulfate heptahydrate, 15g/L stannous sulfate, 7g/L sodium benzoate, 5g/L polyethylene glycol, 1.5g/L ethyl 2-pyrrole carboxylate and 3g/L sodium trifluoromethanesulfonate, the secondary electrolytic coloring liquid utilizes dilute sulfuric acid and ammonia water to adjust the pH to 4.4, the coloring temperature is 50 ℃, and the constant current density of coloring is 0.5A/dm2The coloring time is 8min, and a graphite electrode is adopted as a counter electrode;
s5, sealing holes, namely, spraying and washing the electrolytically colored aluminum alloy surface, and then soaking the aluminum alloy surface into a hole sealing liquid for sealing holes, wherein the hole sealing liquid comprises 6g/L vinyl trimethoxy silane, 7g/L triethanolamine, 5g/L sodium silicate and 7.2g/L N, N-dimethyl formamide, the pH value of the hole sealing liquid is adjusted to 6.3 by using dilute sulfuric acid and ammonia water, the hole sealing temperature is 85 ℃, and the hole sealing duration is 9 min.
Example 2
The present embodiment provides a method suitable for coloring an aluminum alloy surface, and the method provided in the present embodiment is different from the method provided in embodiment 1 only in that: the method provided by the embodiment adopts the method that the primary electrolytic coloring does not contain 2-amino-1-butanol.
Example 3
The present embodiment provides a method suitable for coloring an aluminum alloy surface, and the method provided in the present embodiment is different from the method provided in embodiment 1 only in that: the primary electrolytic coloring adopted in the method provided by the implementation does not contain m-aminobenzene sulfonic acid.
Example 4
The present embodiment provides a method suitable for coloring an aluminum alloy surface, and the method provided in the present embodiment is different from the method provided in embodiment 1 only in that: the secondary electrolytic coloring employed in the method provided by this embodiment does not contain polyethylene glycol.
Example 5
The present embodiment provides a method suitable for coloring an aluminum alloy surface, and the method provided in the present embodiment is different from the method provided in embodiment 1 only in that: the secondary electrolytic coloring employed in the method provided by this embodiment does not contain ethyl 2-pyrrolecarboxylate.
Example 6
The present embodiment provides a method suitable for coloring an aluminum alloy surface, and the method provided in the present embodiment is different from the method provided in embodiment 1 only in that: the secondary electrolytic coloring employed in the method provided by this embodiment does not contain trifluoromethanesulfonic acid.
The blackness and color uniformity of the colored aluminum alloys of examples 1-6 were recorded, and the results are shown in Table 1 below.
The colored layers prepared in examples 3 and 5 to 6 had many pits on the surface, had rough surfaces, and had "floating ash", and the uniformity of the colored layers prepared in examples 2 and 4 was poor; the colored layer prepared in example 1 has fewer pits, a smooth surface, no floating ash, good uniformity and a black colored layer with good texture, which indicates that metal ions are uniformly deposited in the colored film layer of the aluminum alloy and the pore structure of the colored layer. Therefore, the synergistic effect of the m-aminobenzene sulfonic acid and the 2-amino-1-butanol and the synergistic effect of the polyethylene glycol, the ethyl 2-pyrrole carboxylate and the sodium trifluoromethyl sulfonate have important influence on the construction of the microcosmic junction surface structure of the coloring layer and the uniformity of the coloring layer.
TABLE 1
| Apparent color | Color uniformity | Degree of blackness | |
| Example 1 | Pure black color | The surface color is uniform | Darkest black |
| Example 2 | Black and white | Uneven surface color | Black colour |
| Example 3 | Red and black | With floating ash on the surface | Black color not |
| Example 4 | Black and white | Uneven surface color | Black colour |
| Example 5 | Red and black | With floating ash on the surface | Black color not |
| Example 6 | Red and black | With floating ash on the surface | Black color not |
It can be seen from the above embodiments that the present invention provides a method for coloring an aluminum alloy surface, which utilizes two times of electrolytic coloring and sealing to make a colored layer more uniform and stable, and has higher hardness, and the colored layer of the aluminum alloy finally presents a black colored layer with good texture.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (6)
1. A method for coloring an aluminum alloy surface, comprising the steps of:
s1, performing alkali washing and acid washing on the aluminum alloy;
s2, placing the aluminum alloy in an activating solution for electrolytic activation;
s3, carrying out primary electrolytic coloring, namely putting the aluminum alloy into primary electrolytic coloring liquid for direct current electrolytic coloring, wherein the primary electrolytic coloring liquid comprises 35-50g/L nickel sulfate heptahydrate, 25-30g/L stannous sulfate, 1-2g/L metanilic acid, 2-3g/L disodium ethylene diamine tetraacetate, 5-7 g/L2-amino-1-butanol and 3-5g/L phytic acid;
s4, secondary electrolytic coloring, namely placing the aluminum alloy in a secondary electrolytic coloring liquid for direct current electrolytic coloring, wherein the secondary electrolytic coloring liquid comprises 15-20g/L nickel sulfate heptahydrate, 10-20g/L stannous sulfate, 5-10g/L sodium benzoate, 4-6g/L polyethylene glycol, 1-2g/L ethyl 2-pyrrole carboxylate and 2-4g/L sodium trifluoromethanesulfonate;
s5, sealing holes, namely soaking the aluminum alloy into sealing liquid for sealing holes.
2. The method of claim 1, wherein the activating solution comprises 10-20g/L sulfuric acid, 30-40g/L sodium dihydrogen phosphate, and 0.2-0.3g/L sodium acetate, the activating temperature is 75-80 ℃, the electrolysis time is 45-60s, and the current density is 0.1-0.15A/dm2。
3. The method according to claim 1, wherein the pH of the primary electrolytic coloring liquid is adjusted to be in the range of 4.8 to 5.0 by using dilute sulfuric acid and ammonia water, the coloring temperature of the primary electrolytic coloring is 40 to 60 ℃, and the constant current density of the primary electrolytic coloring is 0.6 to 0.8A/dm2And the time length of the one-time electrolytic coloring is 1-3 min.
4. The method according to claim 1, wherein the secondary electrolytic coloring liquid is adjusted to have a pH value in the range of 4.0 to 4.5 by using dilute sulfuric acid and aqueous ammonia, the coloring temperature of the secondary electrolytic coloring is 40 to 60 ℃, and the constant current density of the secondary electrolytic coloring is 0.3 to 0.6A/dm2And the time length of the secondary electrolytic coloring is 5-10 min.
5. The method of claim 1, wherein: and the counter electrodes used for the primary electrolytic coloring and the secondary electrolytic coloring are graphite electrodes.
6. The method according to claim 1, wherein the components of the sealing liquid comprise 5-10g/L of vinyltrimethoxysilane, 5-8g/L of triethanolamine, 4-8g/L of sodium silicate and 7-7.5g/L of N, N-dimethylformamide, the pH value of the sealing liquid is adjusted to be in the range of 6-6.5 by using dilute sulfuric acid and ammonia water, the sealing temperature is 80-90 ℃, and the sealing time is 5-10 min.
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| CN115449878A (en) * | 2022-08-24 | 2022-12-09 | 四会市建鑫装饰材料有限公司 | Black coloring process for aluminum profile |
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