CN110735171A - Method for preparing bicolor film layer by step method based on two-phase mixed solution - Google Patents
Method for preparing bicolor film layer by step method based on two-phase mixed solution Download PDFInfo
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- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims description 4
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- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical group C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
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- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical group [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
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- 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
- C25D11/26—Anodisation of refractory metals 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
- 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
-
- 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
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
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- Chemical & Material Sciences (AREA)
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- 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)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a -step method for preparing a bicolor film layer based on a biphase mixed solution, which comprises the following steps of (1) pickling a sample to be treated and rinsing, (2) determining a color area, immersing the sample in a mixed solution of oil-water biphase and biphase separation, wherein an oil phase is a conductive oil phase solution containing trace moisture of less than or equal to 1000ppm and having the conductivity of 10-200 mS/cm, and a water phase is a conductive water phase solution having the conductivity of more than 300mS/cm, (3) starting an anodic oxidation device, and obtaining bicolor film layers with different colors by times of anodic oxidation coloring, and (4) drying after rinsing to obtain a finished bicolor film layer.
Description
Technical Field
The invention belongs to the field of metal surface treatment, and particularly relates to methods for obtaining two different color film layers on a metal surface through times of coloring treatment.
Background
The prior art mainly comprises times of anodic coloring treatment, then local mask treatment is carried out for protection, then other areas to be colored are subjected to secondary corrosion or machining to expose a substrate, and then secondary anodic coloring is carried out to obtain two different color film layers.A patent publication No. CN: 101736383B discloses an "aluminum alloy anodic multicolor surface treatment method", which mainly comprises times of anodic coloring treatment to obtain color film layers of oxide films, then layers of transparent acid-resistant insulating plastic films are prepared on the anodized surfaces, then the oxide films are leaked out of the local outer surfaces for processing treatment, and then put into another electrolyte for secondary anodic coloring treatment to obtain more than color effects.
CN104711653A, a patent publication No. CN103320830B, which discloses " metal composite material and its preparation method", wherein after anodic oxidation, the aluminum oxide film is dyed at least twice by combining photosensitive glue and ultraviolet light curing protection, so that the aluminum oxide film has at least two colors, and the formation of different color film layers requires multiple glue applying and glue removing processes, and also has complicated processes.
Disclosure of Invention
Therefore, the invention provides methods for preparing a bicolor film layer by a -step method based on a biphasic mixed solution, which comprises the following steps:
(1) pickling and rinsing a sample to be treated;
(2) determining a color area, and immersing a sample in a mixed solution of oil-water biphase and biphase separation;
(3) starting the anodic oxidation device, and obtaining a bicolor film layer with different upper and lower colors by times of anodic oxidation coloring;
(4) and drying after rinsing to obtain a double-color film finished product.
, adopting a biphase separated mixed solution consisting of a conductive oil phase with the conductivity of 10-200 mS/cm and a conductive water phase solution with the conductivity of more than 300mS/cm, wherein the conductive oil phase contains trace moisture which is less than or equal to 1000 ppm.
, in the mixed solution in the step (2), the density of the oil phase is lower than that of the water phase, wherein the density of the oil phase is 0.78-0.98 g/L, and the density of the water phase is 1.01-1.20 g/L.
, the oil phase in step (2) contains water insoluble organic solvent, conductive polymer and additive, wherein the water insoluble organic solvent comprises one or more of butyl acetate, petroleum ether, ethyl acetate, chloroform, C2-C6 short chain fatty acid and liquid paraffin , and the conductive polymer comprises one or more of polyaniline, polyacetylene, polyphenylacetylene, polythiophene, polyparaphenylene, polyaniline, polypyrrole and polystyrenesulfonic acid .
, the conductive polymer in the oil phase in the step (2) comprises or more of polyaniline, polyacetylene, polyphenylacetylene, polythiophene, polyparaphenylene, polyaniline, polypyrrole and polystyrene sulfonic acid, the conductive polymer is polymerized by of solution polymerization, emulsion polymerization and microemulsion polymerization in a water phase, and the polymerization step comprises a water removal step for reducing the water content in the conductive polymer, wherein the water content is less than or equal to 1000 ppm.
, the additives in the oil phase in step (2) comprise an antioxidant, a complexing agent and a conductive aid, wherein the antioxidant, the complexing agent and the conductive aid comprise or more of phosphite ester, vitamin C, vitamin E, chitosan, carbon black and graphene.
the oil phase in the step (2) contains 10-30 wt% of solvent, 40-80 wt% of conductive polymer and 1-10 wt% of additive.
, the conductive water phase in step (2) is a non-neutral system comprising or more of sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid, sodium hydroxide, sodium carbonate and sodium oxalate, wherein the percentage of the single solute is 1% -5%, and the balance is water.
, the sample is made of aluminum and its alloy, titanium and its alloy, magnesium alloy, stainless steel.
Compared with the prior art, the method has the advantages that multiple coloring treatments such as mask/mask removing treatment or machining film removing required by the traditional process are reduced, a non-traditional single -phase solution system is adopted, a specific double-phase separated double-phase mixed solution system with larger property difference is used for carrying out anodic oxidation reaction, and a -step method can obtain the double-color film layer through times of anodic oxidation coloring treatment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic view of the step process for preparing a two-color film.
FIG. 2A sample object picture of a two-color film layer obtained after treatment in example 1.
FIG. 3 scanning electron micrographs of sample interfaces of two-color film layers obtained after treatment in example 1.
Figure 4 a composition profile of a colour film layer 1 after treatment of example 1 to obtain a two-colour film layer is illustrated.
Figure 5 a composition profile of a colour film layer 2 after treatment of example 1 to obtain a two-colour film layer is illustrated.
Detailed Description
The technical solutions in the embodiments of the present invention will be fully described below with reference to the implementation manners of the present invention, and the described embodiments are only some examples of the present invention. All embodiments that can be made by a person skilled in the art without inventive efforts based on the embodiments of the present invention shall fall within the scope of protection of the present invention.
Example 1
The invention provides methods for preparing a bicolor film layer by steps based on a biphasic mixed solution, which comprises the following steps:
(1) pickling a Ti6Al4V titanium alloy sample in a solution containing 3% hydrofluoric acid at room temperature for 30s, and rinsing with water;
(2) determining a corresponding color area, immersing the titanium alloy in an oil-water two-phase mixed solution according to the requirements of the color area, wherein an oil phase in the two-phase solution adopts an organic solvent containing 5% of butyl acetate, 6% of ethyl acetate and 5% of paraffin to dissolve a 80% polyaniline conductive polymer mixed solution which is subjected to solution polymerization and water removal treatment, and then adding 1% of vitamin C, 1% of vitamin E and 2% of graphene to form the oil phase with the density of 0.78g/L, the water content of 628ppm and the conductivity of 10 mS/cm; the water phase in the two-phase solution is mixed acid liquid prepared by 5 percent sulfuric acid and 1 percent hydrochloric acid, and the balance is water, the conductivity of the mixed acid liquid is 350.2mS/cm, the density of the mixed acid liquid is 1.20g/L, and the solution and an oil-water two-phase interface are kept still;
(3) after the sample is immersed, connecting the sample as an anode with a direct-current stabilized voltage supply, connecting a cathode with 316L stainless steel as a cathode plate, adjusting the voltage to 82V direct-current voltage, starting an anode coloring device, oxidizing and coloring for 30s at room temperature, and obtaining bicolor films with different upper and lower colors through times of anodic coloring and oxidation;
(4) and (3) drying after rinsing to obtain a double-color film finished product, wherein the oil phase area sample is purple red, and the water phase area sample is green.
FIG. 1 is a schematic diagram of steps of processing a bicolor film, FIG. 2 is a sample object diagram of the bicolor film obtained after processing in example 1, FIG. 3 is a scanning electron microscope image of a sample interface of the bicolor film obtained after processing in example 1, and FIGS. 4 and 5 are diagrams respectively illustrating component spectra of the color film 1 and the color film 2 of the bicolor film obtained after processing in example 1.
Example 2
The invention provides methods for preparing a bicolor film layer by steps based on a biphasic mixed solution, which comprises the following steps:
(1) in a solution containing 10% nitric acid and 3% hydrofluoric acid, TA4 pure titanium samples are pickled at room temperature for 90s, and water rinsing is carried out;
(2) determining a corresponding color area, immersing a pure titanium sample in an oil-water two-phase mixed solution according to the requirements of the color area, wherein an oil phase in the two-phase solution adopts an organic solvent containing 30% short-chain fatty acid isobutyric acid to dissolve a conductive polymer mixed solution of 30% polyphenylacetylene and 34% polypyrrole which is subjected to solution polymerization and water removal treatment, and then adding 5% of graphene and 1% of phosphite ester to form the oil phase with the density of 0.86g/L, the water content of 812ppm and the conductivity of 12.7 mS/cm; the water phase in the two-phase solution is mixed acid solution prepared by 5 percent of oxalic acid and 5 percent of citric acid, and the balance of water, the conductivity of the mixed acid solution is 560mS/cm, the density of the mixed acid solution is 1.10g/L, and the interface of the solution and the oil-water two-phase solution is kept still;
(3) after the sample is immersed, connecting the sample as an anode with a direct-current stabilized voltage supply, connecting a cathode with 316L stainless steel as a cathode plate, adjusting the voltage to be 32V direct-current voltage, starting an anode coloring device, oxidizing and coloring for 60s at room temperature, and obtaining bicolor films with different upper and lower colors through times of anode coloring and oxidation;
(4) and (3) drying after rinsing to obtain a double-color film finished product, wherein the oil phase area sample is brown blue, and the water phase area sample is light blue.
Example 3
The invention provides methods for preparing a bicolor film layer by steps based on a biphasic mixed solution, which comprises the following steps:
(1) pickling a 6061 aluminum alloy sample in a solution containing 6% nitric acid and 3% hydrofluoric acid at room temperature for 30s, and rinsing with water;
(2) determining a corresponding color area, and immersing the aluminum alloy in an oil-water two-phase mixed solution according to the requirements of the color area, wherein an oil phase in the two-phase solution adopts an organic solvent containing 5% of petroleum ether, 4% of butyl acetate and 1% of trichloromethane to dissolve a 40% polystyrene sulfonic acid and 40% polythiophene conductive polymer mixed solution which is subjected to solution polymerization and water removal treatment, and then adding 1% of vitamin C and 9% of carbon black to form an oil phase with the density of 0.98g/L, the water content of 708ppm and the conductivity of 105 mS/cm; the water phase in the two-phase solution is mixed acid liquid prepared by 5 percent sulfuric acid and 1 percent hydrochloric acid, and the balance is water, the conductivity of the mixed acid liquid is 350.2mS/cm, the density of the mixed acid liquid is 1.20g/L, and the solution and an oil-water two-phase interface are kept still;
(3) after a sample is immersed, connecting the sample as an anode with a direct-current stabilized power supply, connecting a cathode with 316L stainless steel as a cathode plate, adjusting the voltage to be 10V of direct current, starting an anodic oxidation device, anodizing for 600s at room temperature, placing the sample in a light blue coloring agent for dyeing after anodizing, and obtaining a bicolor film layer with different upper and lower colors by anodizing and coloring for times;
(4) and (3) drying after rinsing to obtain a double-color film finished product, wherein the oil phase area sample is light brown, and the water phase area sample is light blue.
Example 4
The invention provides methods for preparing a bicolor film layer by steps based on a biphasic mixed solution, which comprises the following steps:
(1) the TC20 titanium alloy sample is pickled in a solution containing 5% hydrofluoric acid at room temperature for 60s, and is rinsed by water;
(2) determining a corresponding color area, and immersing the titanium alloy in an oil-water two-phase mixed solution according to the requirements of the color area, wherein an oil phase in the two-phase solution adopts an organic solvent containing 5% butyl acetate and 10% petroleum ether to dissolve a 76% polypyrrole and 2% polyparaphenylene mixed solution subjected to solution polymerization and water removal treatment, and then adding 2% phosphite and 5% graphene to form the oil phase with the density of 0.82g/L, the water content of 860ppm and the conductivity of 18.2 mS/cm; the water phase in the two-phase solution is a mixed acid solution prepared by oxalic acid with the content of 5 percent and nitric acid with the content of 2 percent, and the balance is water, the conductivity of the mixed acid solution is 502.3mS/cm, the density of the mixed acid solution is 1.19g/L, and the solution and an oil-water two-phase interface are kept still;
(3) after the sample is immersed, connecting the sample as an anode with a direct-current stabilized voltage supply, connecting a cathode with 316L stainless steel as a cathode plate, adjusting the voltage to be 50V of direct current, starting an anode coloring device, oxidizing and coloring for 60s at room temperature, and obtaining bicolor films with different upper and lower colors through times of anodic coloring and oxidation;
(4) and (3) drying after rinsing to obtain a double-color film finished product, wherein the oil phase area sample is silver, and the water phase area sample is golden yellow.
Example 5
The invention provides methods for preparing a bicolor film layer by steps based on a biphasic mixed solution, which comprises the following steps:
(1) pickling pure titanium samples in a solution containing 3% hydrofluoric acid at room temperature for 120s, and rinsing with water;
(2) determining a corresponding color area, immersing the titanium alloy in an oil-water two-phase mixed solution according to the requirements of the color area, wherein an oil phase in the two-phase solution adopts an organic solvent containing 10% of ethyl acetate and 5% of paraffin wax to dissolve a conductive polymer mixed solution of 47% of polyacetylene and 30% of polyphenylacetylene which are subjected to solution polymerization and water removal treatment, and then adding 5% of vitamin E, 1% of chitosan and 2% of carbon black to form the oil phase with the density of 0.90g/L, the water content of 450ppm and the conductivity of 185.5 mS/cm; the water phase in the two-phase solution is mixed acid liquor prepared by adopting 5 percent of sodium hydroxide, 1 percent of sodium oxalate and 1 percent of sodium carbonate and the balance of water, the conductivity of the mixed acid liquor is 620.2mS/cm, the density of the mixed acid liquor is 1.08g/L, and the interface of the solution and the oil-water two-phase is kept still;
(3) after the sample is immersed, connecting the sample as an anode with a direct-current stabilized voltage supply, connecting a cathode with 316L stainless steel as a cathode plate, adjusting the voltage to be 22V direct-current voltage, starting an anode coloring device, oxidizing and coloring for 60s at room temperature, and obtaining bicolor films with different upper and lower colors through times of anode coloring and oxidation;
(4) and (3) drying after rinsing to obtain a double-color film finished product, wherein the oil phase area sample is light blue, and the water phase area sample is dark blue.
The above-mentioned embodiments are only specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can make several improvements and modifications within the technical scope of the present invention, and these improvements and modifications are considered to be within the scope of the present invention.
Claims (9)
1. A method for preparing a bicolor film layer by an step method based on a two-phase mixed solution is characterized by comprising the following steps:
(1) pickling and rinsing a sample to be treated;
(2) determining a color area, and immersing a sample in a mixed solution of oil-water biphase and biphase separation;
(3) starting the anodic oxidation device, and obtaining a bicolor film layer with different upper and lower colors by times of anodic oxidation coloring;
(4) and drying after rinsing to obtain a double-color film finished product.
2. The method for preparing the bicolor film layer by the step method based on the two-phase mixed solution according to claim 1, wherein the two-phase mixed solution of oil and water is a two-phase separated mixed solution consisting of a conductive oil phase with the conductivity of 10-200 mS/cm and a conductive aqueous phase solution with the conductivity of more than 300mS/cm, and the conductive oil phase contains trace moisture with the concentration of 1000ppm or less.
3. The -step method for preparing two-color film layer based on two-phase mixture solution according to claim 2, wherein the oil phase and the water phase are separated to obtain a mixture solution, the density of the oil phase is lower than that of the water phase, the density of the oil phase is 0.78-0.98 g/L, and the density of the water phase is 1.01-1.20 g/L.
4. The method for -step preparation of a two-phase mixed solution based on two-phase mixed solution as claimed in claim 3, wherein the oil phase comprises a water-insoluble organic solvent, a conductive polymer and an additive, wherein the water-insoluble organic solvent comprises one or more of butyl acetate, petroleum ether, ethyl acetate, chloroform, C2-C6 short chain fatty acids, and liquid paraffin.
5. The method for preparing a bicolor film layer by steps based on a biphasic mixture solution according to claim 4, wherein the conductive polymer comprises or more of polyaniline, polyacetylene, polyphenylacetylene, polythiophene, polyparaphenylene, polyaniline, polypyrrole and polystyrene sulfonic acid, the conductive polymer is polymerized by of solution polymerization, emulsion polymerization and microemulsion polymerization in an aqueous phase, and the polymerization step comprises a water removal step for reducing the water content in the conductive polymer, wherein the water content is less than or equal to 1000 ppm.
6. The additive in the oil phase according to claim 4, comprising an antioxidant, a complexing agent, a conductive aid, wherein the antioxidant, complexing agent, conductive aid comprise or more of phosphite, vitamin C, vitamin E, chitosan, carbon black, graphene.
7. The oil phase according to claim 4, 5 or 6, wherein the weight percentage of the solvent in the oil phase is 10-30%, the weight percentage of the conductive polymer is 40-80%, and the weight percentage of the additive is 1-10%.
8. The method for preparing the bicolor film layer by the step method based on the two-phase mixed solution according to claim 1 or 2, wherein the conductive water phase is a non-neutral system and comprises or more of sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid, sodium hydroxide, sodium carbonate and sodium oxalate, wherein the percentage of the single solute is 1% -5%, and the balance is water.
9. The -step method for preparing a bi-color film according to claim 1, wherein the material is selected from the group consisting of aluminum and its alloys, titanium and its alloys, magnesium alloys, and stainless steel.
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