CN114703527A - Anodic oxidation dyeing process - Google Patents
Anodic oxidation dyeing process Download PDFInfo
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- CN114703527A CN114703527A CN202210242466.7A CN202210242466A CN114703527A CN 114703527 A CN114703527 A CN 114703527A CN 202210242466 A CN202210242466 A CN 202210242466A CN 114703527 A CN114703527 A CN 114703527A
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- 238000004043 dyeing Methods 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000003647 oxidation Effects 0.000 title claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 33
- 239000000975 dye Substances 0.000 claims abstract description 45
- 238000007789 sealing Methods 0.000 claims abstract description 36
- 238000005562 fading Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000002791 soaking Methods 0.000 claims abstract description 22
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 20
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 239000000980 acid dye Substances 0.000 claims abstract description 7
- JAOZKJMVYIWLKU-UHFFFAOYSA-N sodium 7-hydroxy-8-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalene-1,3-disulfonic acid Chemical compound C1=CC=C2C(=C1)C(=CC=C2S(=O)(=O)O)N=NC3=C(C=CC4=CC(=CC(=C43)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] JAOZKJMVYIWLKU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010407 anodic oxide Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 8
- 230000004075 alteration Effects 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 5
- 238000013461 design Methods 0.000 abstract description 19
- 239000000243 solution Substances 0.000 description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- -1 organic acid sodium salt Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000005237 degreasing agent Methods 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000003086 colorant 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
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical group [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229910001845 yogo sapphire 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
- C25D11/14—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
-
- 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
- C25D11/24—Chemical after-treatment
-
- 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
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
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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)
- General Chemical & Material Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention provides an anodic oxidation dyeing process, which comprises the steps of dyeing and fading: and (3) dyeing: and dyeing the surface of a workpiece to be dyed by using an acid dye, wherein the surface of the workpiece to be dyed is an anodic oxide film layer. A fading step: soaking the dyed workpiece in a first solution, and setting the soaking time according to the requirement; the first solution is a sodium sulfate solution. The acid dye comprises a gray dye, an additive and a second solution; the gray dyes include black 420 dye, black 411 dye, and red 102 dye; the additive comprises a nickel-free hole sealing liquid; the second solution is a sodium sulfate solution. The concentration of the first solution is 0.2g/L +/-0.01 g/L. The anodic oxidation dyeing process disclosed by the invention is simple in steps, can meet the design requirements, and simultaneously ensures the stability of the process.
Description
Technical Field
The invention relates to the technical field of metal manufacturing and processing, in particular to an anodic oxidation dyeing process.
Background
Metal products, such as aluminum alloy, magnesium alloy or titanium alloy, are generally anodized to form an anodized film having good wear resistance on the surface thereof. In order to diversify the surface color of the product, the product is subjected to dyeing treatment or spraying treatment after anodic oxidation.
Dyeing is the most critical step in the anodic process, and is also the most unstable and difficult-to-control station, and the dependence on the process stability of each oxidation section is very high. At present, a project design has a small control range of color difference after dyeing, and the design requirements on a value, a value and an L value are very high, so that the color depth is required not to be too deep, and the color is required not to be too light. If the traditional dyeing method is adopted for color fading finishing, the L value and the a and b values are often greatly changed at the same time, the traditional dyeing method can hardly meet the design requirement, and the dyeing method which can reduce the L value range representing the depth and does not greatly influence the a and b values is required according to the design requirement at present.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an anodic oxidation dyeing process to meet the design requirements and ensure the stability of the process.
In order to achieve the purpose, the invention adopts the technical scheme that:
an anodic oxidation dyeing process, comprising a dyeing step and a fading step:
and (3) dyeing: carrying out dyeing treatment on the surface of a workpiece to be dyed by using an acid dye, wherein the surface of the workpiece to be dyed is an anodic oxide film layer;
a fading step: soaking the dyed workpiece in a first solution, and setting the soaking time according to the requirement; the first solution is a sodium sulfate solution.
The technical scheme is further improved as follows:
the acid dye comprises a gray dye, an additive and a second solution; the gray dyes include black 420 dye, black 411 dye, and red 102 dye; the additive comprises a nickel-free hole sealing liquid; the second solution is a sodium sulfate solution.
The concentration of the black 420 dye is 1.6g/L +/-0.1 g/L; the concentration of the black 411 dye is 0.8g/L +/-0.1 g/L; the concentration of the red 102 dye is 0.14g/L +/-0.01 g/L; the concentration of the nickel-free hole sealing liquid is 1.8g/L +/-0.1 g/L; the concentration of the second solution is 0.4g/L +/-0.01 g/L.
The concentration of the first solution is 0.2g/L +/-0.01 g/L.
The dyeing method further comprises a water washing step before the dyeing step, wherein the water washing step comprises 1-4 water washing procedures, the water washing procedures are completed in a normal-temperature pure water tank, and the time of each water washing procedure is 30 +/-10 seconds.
The dyeing step is finished in a dyeing tank, the temperature of the dyeing tank is controlled to be 20 +/-2 ℃, and the dyeing time is controlled to be 480 +/-120 seconds; the pH value in the staining tank is controlled to be 5.7 +/-0.2.
And the dyeing step is followed by a step of measuring chromatic aberration, wherein a spectrocolorimeter is adopted to measure the chromatic aberration of the dyed workpiece, and the soaking time of the fading step is set according to the measurement result.
And a hole sealing step is further included after the color fading step, the temperature range during hole sealing is 95 +/-2 ℃, the hole sealing liquid is nickel-free hole sealing liquid, and the hole sealing time is 55 +/-5 minutes.
And a drying step is also included after the hole sealing step.
The anodic oxide film layer is of a porous unit cell structure.
According to the technical scheme, the anodic oxidation dyeing process is very simple in process method, and the dyed workpiece meeting the design requirement can be obtained only by dyeing the workpiece and then soaking the workpiece in a sodium sulfate solution. The color fading is carried out by using the sodium sulfate solution, the process of the sodium sulfate solution is neutral, the corrosion of an acid-base reagent to a workpiece is avoided, the reduction of the L value representing the color depth can be ensured, the influence on the a value and the b value is small, the L value and the a value and the b value in the design can be simultaneously met, and the test of the workpiece performance is not influenced.
Drawings
FIG. 1 is a schematic flow chart of an anodic oxidation dyeing process according to an embodiment of the present invention.
FIG. 2 is a schematic diagram of the fading of an oxide film according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Fig. 1 is a schematic flow chart of an anodic oxidation dyeing process according to an embodiment of the present invention.
Dyeing is the most critical, most unstable and most difficult to control station in the anode process, and has very high dependence on the process stability of each oxidation section, and even if the washing time is slightly different, the shade and color system can be influenced.
In this embodiment, the control range of the color is relatively small, and the control range after the final dyeing is as follows:
L:0—1.0;a:-0.25—0.55;b:0.5-1.0。
example 1: the anodic oxidation dyeing process of the embodiment comprises the following steps:
s1, anodizing:
s1.1, hanging a workpiece: putting a workpiece to be dyed in the jig, and hanging the jig in a hanging machine, wherein the workpiece is an aluminum product. Firstly, a workpiece is soaked in an oil removal groove loaded with an oil removal agent at normal temperature, and is soaked in the oil removal agent for 180 seconds at the temperature of 50 ℃. The degreasing agent comprises, by mass, 35% of an organic acid sodium salt, 9% of a corrosion inhibitor and 12% of a complexing agent, wherein the organic acid sodium salt is sodium citrate, the corrosion inhibitor is ethylene glycol, and the complexing agent is sodium pyrophosphate.
S1.2, primary water washing: soaking the deoiled workpiece in a rinsing tank filled with water for 20 seconds at normal temperature, and then soaking the workpiece in a neutralizing tank filled with a mixed solution of nitric acid and a film removing agent for 60 seconds at normal temperature. Wherein the concentration of the nitric acid in the mixed solution of the nitric acid and the film removing agent is 240g/L, and the concentration of the film removing agent is 120 g/L.
S1.3, chemical polishing: at normal temperature, the workpiece is soaked in a water washing tank filled with water for 20 seconds, then the hanging machine is moved, the workpiece enters a chemical polishing pool, and the workpiece is soaked in a chemical polishing tank filled with chemical polishing liquid for 110 seconds at 85 ℃ for chemical polishing. The chemical polishing solution comprises phosphoric acid, an additive and sulfuric acid, wherein the mass ratio of the phosphoric acid to the additive to the sulfuric acid in the chemical polishing solution is 7:2:1, and the additive contains 5% of copper sulfate, 15% of polyethylene glycol, 20% of sulfuric acid and 40% of phosphoric acid in percentage by mass.
S1.4, secondary water washing: and moving the hanging machine to enable the workpiece to enter a rinsing bath to be soaked for 20 seconds, wherein the rinsing bath is filled with clear water and provided with an ultrasonic machine, after the workpiece is rinsed, soaking the workpiece in a neutralization tank filled with a mixed solution of nitric acid and a film removing agent for 60 seconds at normal temperature, then moving the workpiece into another rinsing bath to be soaked for 20 seconds at normal temperature, and then rinsing the surface of the workpiece by spraying clean water until no residual reagent is left on the surface. Wherein the concentration of the nitric acid is 240g/L, and the concentration of the film remover is 120 g/L.
S1.5, anodic oxidation: the hanging machine moves to enable the workpiece to enter an oxidation tank, oxidation liquid is contained in the oxidation tank, and a thin anodic oxidation film layer is formed on the surface of the workpiece by adopting an anodic oxidation method at normal temperature. In this application, the temperature of the anodic oxidation was 19 ℃, the voltage was 15V, and the oxidation time was 2400 seconds. Wherein the anodic oxidation liquid comprises sulfuric acid and aluminum ions, and the concentration of the aluminum ions in the anodic oxidation liquid is 6 g/L. Wherein the concentration of the sulfuric acid in the anodic oxidation solution is 180 g/L.
The anodic oxide film consists of a large number of hexagonal unit cells vertical to the metal surface, the center of each unit cell is provided with a film hole and has strong adsorption force, when an oxidized aluminum product is soaked in a dye solution, dye molecules enter the film holes of the porous layer through diffusion, and simultaneously form covalent bonds and ionic bonds which are difficult to separate with the oxide film, the ionic bonding is reversible, desorption can occur under certain conditions, therefore, hole sealing treatment must be carried out after dyeing, the dye is solidified in the film holes, and the corrosion resistance, wear resistance and other characteristics of the oxide film are improved.
S1.6, washing for three times: and (4) moving the hanging machine to enable the workpiece to enter a washing tank, wherein the temperature of the washing tank is normal temperature, and the time of a washing program is 30 +/-10 seconds. And then, carrying out ultrasonic treatment on the metal piece with the oxide film in an activating agent for 180 seconds at the temperature of 50 ℃ so as to activate the oxide film. The activating agent comprises water and a solute, wherein the solute comprises 75% of sodium citrate and 25% of sodium acetate in percentage by mass.
S2, dyeing:
s2.1: dyeing: the hanging machine moves again to move the workpiece into a dyeing tank, the dyeing tank is filled with weak acidic dyeing liquid, the pH value of the dyeing tank is controlled to be 5.7 +/-0.2, the temperature of the dyeing tank is controlled to be 20 +/-2 ℃, and the dyeing time is controlled to be 480 +/-120 seconds.
The acid dye comprises a gray dye, an additive and a second solution; the gray dyes include black 420 dye, black 411 dye, and red 102 dye; the additive comprises a nickel-free hole sealing liquid; the second solution is a sodium sulfate solution.
The concentration of the black 420 dye is 1.6g/L +/-0.1 g/L; the concentration of the black 411 dye is 0.8g/L +/-0.1 g/L; the concentration of the red 102 dye is 0.14g/L +/-0.01 g/L; the concentration of the nickel-free hole sealing liquid is 1.8g/L +/-0.1 g/L; the concentration of the second solution is 0.4g/L +/-0.01 g/L.
Specifically, the BLACK 420 dye of Oretac BLACK _ GRLH used in the present example, at a concentration of 1.6 g/L; the BLACK 411 dye of Orye TAC BLACK _ BLH, the concentration is 0.8 g/L; oretac RED _ BLD 102 dye at a concentration of 0.14 g/L. The additive is an Orye nickel-free hole sealing liquid E _110 with the concentration of 1.8 g/L; the second solution is sodium sulfate pure water solution, and the concentration is 0.4 g/L.
The addition of proper amount of additive to the dye can make the color of the large surface (p1, p2 point) and the color of the side surface (p3, p4 point) of the workpiece consistent in the value of a (red green) and the value of b (yellow blue). The sodium sulfate of the second solution is used as a retarding agent in the dyeing agent, and the sodium sulfate is added into the dye, so that the surface color of the dyed workpiece is more uniform, and the problems of inconsistent colors of the periphery of the surface of the product and the middle color of the surface of the product are not easy to occur.
S2.2: and (4) washing for four times: and (4) moving the hanging machine to enable the workpiece to enter a washing tank, wherein the temperature of the washing tank is normal temperature, and the time of a washing program is 30 +/-10 seconds.
The anodic oxide film is composed of a large number of hexagonal unit cells vertical to the metal surface, the center of each unit cell is provided with a film hole and has strong adsorption force, when the oxidized aluminum product is soaked in a dye solution, dye molecules enter the film holes of the porous layer through diffusion, and simultaneously form covalent bonds and ionic bonds which are difficult to separate with the oxide film, the ionic bonding is reversible, desorption can occur under certain conditions, therefore, hole sealing treatment must be carried out after dyeing, the dye is solidified in the film holes, and the corrosion resistance, wear resistance and other characteristics of the oxide film are improved.
S3, measuring chromatic aberration: a spectrocolorimeter is used for measuring color difference (generally measured with water), and if the measurement result is deep, fading treatment is required.
S4, fading step: soaking the dyed workpiece in a first solution, and setting the soaking time according to the requirement; the first solution is sodium sulfate pure water solution. The concentration of the first solution is 0.2g/L +/-0.01 g/L, and the soaking time of the fading step is set according to the result of measuring the color difference. For example, when the mixture is soaked in a 0.2g/L pure water solution of sodium sulfate for one minute, the average L value is 0.74; when the tea is soaked for three minutes, the average L value is shallow 1.32; after five minutes of soaking, the average L value was 1.84. The concentration of the sodium sulfate solution and the fading soaking time can be selected according to the actual design requirements. The change of the a value and the b value is within 0.1 in the fading soaking process of one minute, three minutes and five minutes. That is, after the workpiece is soaked in the sodium sulfate solution, the change of the L value is obvious, the change of the a value and the b value is not large, the gray level of the surface of the workpiece is light, but the color is not greatly changed, which is the research object of the present invention.
As shown in table 1, the variation values of L, a and b obtained after the workpiece was immersed in a sodium sulfate solution having a concentration of 0.2g/L for one minute, three minutes and five minutes, respectively, were included in each set of 10 test data. Wherein the Lab value trend is as follows: the longer the soaking time is, the more forward the L value is, the lighter the color is; the value of a goes forward, which indicates that the color is redder; the more the b value goes forward, the more yellow the color is. As can be seen from the data in the following table, in 30 groups of data, the change of the a value and the b value is not large, and within 0.1, the design requirement can be met.
TABLE 1
After the fading step, if the Lab value still can not meet the design requirement and the color is still deep, the fading step operation is repeated until the measured color difference result can meet the design requirement.
S5, hole sealing step: and soaking the faded workpiece in a washing tank filled with clear water for 20 seconds at normal temperature, and then soaking the workpiece in a hole sealing tank filled with hole sealing liquid for 55 +/-5 minutes at the temperature of 95 +/-2 ℃ to perform hole sealing treatment. The hole sealing liquid is nickel-free hole sealing liquid, in this embodiment, specifically OreodX-500 hole sealing liquid, and the concentration of the hole sealing liquid is 10-15 g/L.
The hole sealing treatment is to keep the oxide film of the anhydrous substance with crystal water through water and reaction, and the hole is closed after the volume expansion. Hydration of an anodized film after aluminum anodization is performed in order to reduce the porosity and adsorption capacity of the anodized film. The surface of the aluminum anodized film immersed in high-temperature water and the inner surfaces of the micropores thereof produce boehmite alumina by hydration reaction. Thus, the pollution resistance and the corrosion resistance of the sealing agent can be ensured, and the aim of sealing treatment is fulfilled. The chemical reaction formula is as follows:
Al2O3+H2o → 2AlO (OH) → Al2O3-H2O boehmite
S6, drying: washing the workpiece in a water washing tank containing water at normal temperature for 20 seconds, carrying out ultrasonic treatment in water at 70 ℃ for 30 seconds, washing in water at 70 ℃ for 30 seconds, and finally drying at 70 ℃ for 1200 seconds to obtain the dyed workpiece.
The commonly used instrument for measuring chromatic aberration is a spectrocolorimeter model CM-700D of Konika Meinenda, wherein the L value in the spectrocolorimeter represents the depth, 0 represents the central color plate value, and the positive direction is light and the negative direction is deep; the value a represents the red and green directions, the same value 0 represents the central color plate value, the positive direction is more yellow than the central plate, and the negative direction is more blue than the central plate; the b value represents the yellow-blue direction, and likewise 0 represents the center panel value, with the positive direction being more yellow than the center panel and the negative direction being more blue than the center panel. After dyeing, the water is taken for measurement, and the color difference can be changed after sealing, so that the measured value before sealing and the measured value after drying have certain difference.
As shown in table 2, the L value in the negative direction after dyeing represents an average depth of 1.52 to the color plate, an average green value of 0.47 to the a value, an average yellow value of 0.7 to the b value, an average depth of 0.11 to the L value after 3 minutes of sodium sulfate soaking, an average green value of 0.42 to the a value, and an average yellow value of 0.77 to the b value, which are measured values after drying. It is to be noted here that only large areas can be measured after dyeing. After drying, P1 and P2 represent two points on the large face, and P3 and P4 represent 2 points on the side face. For example, in the present embodiment, the design value range is as follows: the range of the L value after drying is +2.6- +2.4, the side edge is +1.7- +1.2, the range of the a value is +/-0.25, the range of the b value is +0.45- +0.6, and the final result can meet the design requirement as shown in Table 2.
TABLE 2
The workpiece is also subjected to performance tests after dyeing, including salt spray tests and UV tests. When acid and alkaline solutions of the traditional method are used for fading, the pores of the oxide film are enlarged, the dye is easy to overflow, even the color is faded, the trend of the value a (red, green) and the value b (yellow and blue) is influenced, the deviation of the color system is too large, and the color difference measurement result cannot meet the design requirement. Meanwhile, the acid and alkaline solutions are used for fading, so that the performance test of subsequent workpieces is greatly influenced, and the performance test result is prone to be deviated.
The fading principle of this example is as follows: as shown in figure 2, because the oxide film forms covalent bonds and ionic bonds which are difficult to separate, but the ionic bonding is reversible, desorption can occur under certain conditions, the bonding of the covalent bonds and the ionic bonds can be destroyed after certain inorganic salt solution enters the oxide film, and the adsorbed dye can overflow because inorganic salt substances can enter pores to degrade the oxide film and the adsorbed dye can overflow under the condition that the product is not subjected to hole sealing treatment after dyeing. The pH of the sodium sulfate inorganic salt is neutral, and the dye can enter an oxidation film to be limited and can uniformly overflow.
The dyeing process provided by the invention can ensure that the value a and the value b are basically kept unchanged while the value L is reduced, so that the color difference of the surface of the workpiece is adjusted to meet the design requirement. And the process steps are simple, and the process stability is strong.
After a gray product is dyed, the gray product is soaked in acid-biased and alkaline solutions such as traditional sulfuric acid, acetic acid, ammonia water, 161 degreasing agent and the like for fading, all three color values are easy to fade, so that the deviation between the a value and the b value after dyeing and a design value is too large, the design requirement cannot be met, and the three values of L, a and b cannot meet the design requirement no matter by controlling time, controlling reagent concentration or controlling process temperature.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only express preferred 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 (10)
1. An anodic oxidation dyeing process, characterized in that it comprises a dyeing step and a fading step:
and (3) dyeing: carrying out dyeing treatment on the surface of a workpiece to be dyed by using an acid dye, wherein the surface of the workpiece to be dyed is an anodic oxide film layer;
a fading step: soaking the dyed workpiece in a first solution, and setting the soaking time according to the requirement; the first solution is a sodium sulfate solution.
2. The anodic oxidation dyeing process according to claim 1, characterized in that: the acid dye comprises a gray dye, an additive and a second solution; the gray dyes include black 420 dye, black 411 dye, and red 102 dye; the additive comprises a nickel-free hole sealing liquid; the second solution is a sodium sulfate solution.
3. The anodic oxidation dyeing process according to claim 2, characterized in that: the concentration of the black 420 dye is 1.6g/L +/-0.1 g/L; the concentration of the black 411 dye is 0.8g/L +/-0.1 g/L; the concentration of the red 102 dye is 0.14g/L +/-0.01 g/L; the concentration of the nickel-free hole sealing liquid is 1.8g/L +/-0.1 g/L; the concentration of the second solution is 0.4g/L +/-0.01 g/L.
4. The anodic oxidation dyeing process according to claim 1, characterized in that: the concentration of the first solution is 0.2g/L +/-0.01 g/L.
5. The anodic oxidation dyeing process according to claim 1, characterized in that: the dyeing method further comprises a water washing step before the dyeing step, wherein the water washing step comprises 1-4 water washing procedures, the water washing procedures are completed in a normal-temperature pure water tank, and the time of each water washing procedure is 30 +/-10 seconds.
6. The anodic oxidation dyeing process according to claim 1, characterized in that: the dyeing step is finished in a dyeing tank, the temperature of the dyeing tank is controlled to be 20 +/-2 ℃, and the dyeing time is controlled to be 480 +/-120 seconds; the pH value in the dyeing tank is controlled to be 5.7 +/-0.2.
7. The anodic oxidation dyeing process according to claim 1, characterized in that: and the dyeing step is followed by a step of measuring chromatic aberration, wherein a spectrocolorimeter is adopted to measure the chromatic aberration of the dyed workpiece, and the soaking time of the fading step is set according to the measurement result.
8. The anodic oxidation dyeing process according to claim 1, characterized in that: and a hole sealing step is further included after the color fading step, the temperature range during hole sealing is 95 +/-2 ℃, the hole sealing liquid is nickel-free hole sealing liquid, and the hole sealing time is 55 +/-5 minutes.
9. The anodic oxidation dyeing process according to claim 8, characterized in that: and a drying step is also included after the hole sealing step.
10. The anodic oxidation dyeing process according to claim 1, characterized in that: the anodic oxidation film layer is of a porous unit cell structure.
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