CN117587482A - Titanium and titanium alloy anodic oxidation multicolor pattern coloring process - Google Patents

Titanium and titanium alloy anodic oxidation multicolor pattern coloring process Download PDF

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Publication number
CN117587482A
CN117587482A CN202311555247.5A CN202311555247A CN117587482A CN 117587482 A CN117587482 A CN 117587482A CN 202311555247 A CN202311555247 A CN 202311555247A CN 117587482 A CN117587482 A CN 117587482A
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Prior art keywords
oxidation
product
titanium alloy
titanium
anodic oxidation
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CN202311555247.5A
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王镔
姜国华
孙晓东
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Changzhou Tianda Aluminum Industry Co ltd
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Changzhou Tianda Aluminum Industry Co ltd
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Priority to CN202311555247.5A priority Critical patent/CN117587482A/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/26Anodisation of refractory metals or alloys based thereon

Abstract

The invention discloses a titanium and titanium alloy anodic oxidation multicolor pattern coloring process, which comprises the following steps: s1: activating a product; s2, anodic oxidation; s3, local oxidation; s4, cleaning; s5, coating; the novel application of the improved electroplating brush pen can realize the combination of any color of more complex patterns on the surface of titanium alloy, can realize the combination of patterns with more colors, is simpler in process, can firstly mask the patterns to be colored, and can realize the oxidation coloring of patterns with various colors at one time by utilizing the improved electroplating brush pen to perform local oxidation outside an oxidation tank after the oxidation tank is oxidized, so that the mass production is more feasible, and meanwhile, the anti-fingerprint coating is applied after the oxidation coloring, thereby ensuring the pollution resistance of the colors and the brightness of the colors, and simultaneously improving the wear resistance of an oxidation film.

Description

Titanium and titanium alloy anodic oxidation multicolor pattern coloring process
Technical Field
The invention relates to the technical field of titanium metal oxidation coloring, in particular to a titanium and titanium alloy anodic oxidation multicolor pattern coloring process.
Background
Titanium and its alloys rapidly form dense oxide films and chemical stability at room temperature due to their excellent thermal stability, high specific strength, low density, excellent biocompatibility. Although titanium and its alloys are silver gray in nature, they can be subjected to various oxidation and coloring treatments to form an oxide film on their surfaces, which gives them a rich color.
However, the existing coloring technology of titanium and titanium alloy is as follows: in CN 101096772B, the method for preparing the anodic oxidation colorful pattern of the titanium alloy, a, firstly, coloring the titanium alloy with one color; b. etching to remove the part of the required pattern; c. electrolyzing the other color with a lower voltage than step a; d. the steps a, b and c are repeated, but the voltage used in the later step is lower than the voltage used in the previous step, so that various color patterns are realized, and the problem of single anodic oxidation coloring of the titanium alloy is solved. Although the method described in CN 101096772B, "preparation method of titanium alloy anodic oxidation colorful pattern" is a pattern that can realize multiple colors, the method is relatively inefficient. The pattern of the next color needs to be etched and removed every time, because the surface of the pattern is formed with a compact oxide film, the etching speed is slower, the brightness of the etched surface is reduced, the hanger is needed to be put on again after each etching, and the pattern is completely immersed in an oxidizing solution for integral oxidation, and the oxidation efficiency is lower; finally, the first oxidation color is highest by the method described in the patent, then the voltage is reduced in sequence, and any combination of colors between the base surface and the pattern surface cannot be realized. Meanwhile, the anodic oxidation coloring oxide film of the titanium alloy generates various colors through light interference, and the oxide film is thinner, is not resistant to fingerprints, is easy to pollute and change color and is easy to wear, so that a plurality of challenges are presented to the popularization of the technology.
Therefore, providing a new anodic oxidation multicolor pattern coloring process for titanium and titanium alloy to solve the defects existing in the prior art is a problem to be solved at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a titanium and titanium alloy anodic oxidation multicolor pattern coloring process, the invention innovatively uses an improved electroplating brush pen to apply, can realize any color combination of more complex patterns on the surface of titanium alloy, can realize more color pattern combination, is simpler in process, can firstly mask the patterns to be colored, and can realize the oxidation coloring of multiple color patterns at one time by utilizing the improved electroplating brush pen to perform local oxidation outside an oxidation tank after the oxidation tank is oxidized, thereby enabling mass production to be more feasible, and simultaneously performing the application of an anti-fingerprint coating after the oxidation coloring, thereby ensuring the color pollution resistance and the color brightness, and simultaneously improving the wear resistance of an oxidation film.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a titanium and titanium alloy anodic oxidation multicolor pattern coloring process comprises the following steps:
s1, activating a product: activating the whole titanium alloy product, drying the activated product by using an oven after the activation, masking the activated product at the position needing multicolor pattern treatment by using a prepared pattern film, and fixing the masked titanium alloy product by using a hanger;
s2, anodic oxidation: immersing the whole titanium alloy product subjected to the fixing in an oxidation tank with an oxidation solution for anodic oxidation coloring;
s3, cleaning: cleaning the product after anodic oxidation coloring in the step S2, removing a shielding film after cleaning, and drying the whole anodic oxidized titanium alloy product by using an oven;
s4, local oxidation: dipping an oxidation solution by using an improved electroplating brush pen to locally oxidize the previous shielding position on the oxidized titanium alloy product according to the color setting appointed color oxidation voltage of each pattern;
s5, coating: and (3) degreasing, cleaning and drying the product subjected to the partial oxidation by using a cleaning agent, soaking or spraying the product by using an anti-fingerprint coating solution, and placing the product in an oven for baking at 150-170 ℃ for 40 minutes after the anti-fingerprint coating uniformly coats the surface of the product.
A titanium and titanium alloy anodic oxidation multicolor pattern coloring process comprises the following steps:
s1, activating a product: activating the whole titanium alloy product, and washing and fixing the titanium alloy product by using a hanger after the activation;
s2, anodic oxidation: immersing the whole fixed product into an oxidizing solution for anodic coloring treatment, cleaning the product after coloring, and drying the whole titanium alloy product by using an oven after cleaning;
s3, local oxidation: pasting a hollowed-out shielding film at a preset position, and then locally oxidizing and coloring the patterns at the hollowed-out part according to a specified color by utilizing an improved electroplating brush pen nib wetting and oxidizing solution;
s4, cleaning: the local oxidation coloring is completed, the shielding glue is removed, and the whole product is cleaned and then dried by an oven;
s5, coating: and (3) degreasing, cleaning and drying the product subjected to cleaning by using a cleaning agent, soaking or spraying the product by using an anti-fingerprint coating solution, and placing the product in an oven for baking at 150-170 ℃ for 40 minutes after the anti-fingerprint coating uniformly coats the surface of the product.
Preferably, different coloring processes are adopted according to different oxidation voltages adopted by different colorful oxidation colors.
Preferably, in step S1, the activating treatment specifically includes: immersing the titanium alloy product into an activating solution for soaking and activating treatment, wherein the working parameters of the activating solution are as follows: the working temperature is 25-40 ℃ and the soaking time is 3-10 min.
Preferably, the activating solution is one or more of 50-500 mL/L of 67% nitric acid, 30-100mL/L of ammonium bifluoride, 20-100mL/L of 40% hydrofluoric acid and 45-60g/L of sodium fluoride.
Preferably, in step S2, the range of the oxidation voltage is specifically defined as 10-100V, and the oxidation time is defined as 0.5-10 min.
Preferably, the oxidizing solution consists of: 10-250g/L of tartaric acid, 5-50mL/L of lactic acid, 10-200g/L of oxalic acid, 10-200g/L of citric acid, 10-100mL/L of hydrogen peroxide and 5-50mL/L of glycerol.
Preferably, in step S3, the method for improving the electroplating brush pen is specifically to replace the brush head of the traditional electroplating brush pen with one of a planar brush head or a brush pen-shaped brush head.
Preferably, in step S5, the cleaning agent is selected from micro-90 cleaning agents.
Preferably, in step S5, the anti-fingerprint coating solution is an RA series anti-fingerprint coating solution.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention innovatively uses the improved electroplating brush pen to carry out local anodic oxidation treatment outside the oxidation tank solution, and can treat a plurality of patterns with different colors at one time, so that the preparation method is greatly simplified, and batch production is possible.
2. The invention can carry out colorful artistic word writing and direct drawing of patterns by innovatively using the thin hard brush pen, and lays a foundation for the possibility of customizing titanium alloy.
3. According to the invention, the anti-fingerprint coating is used for treatment after oxidation coloring, so that the fingerprint resistance and wear resistance of the product are improved, and the application scene is wider.
Drawings
FIG. 1 is a flow chart of a process for coloring a titanium and titanium alloy anodic oxidation multicolor pattern according to the invention;
FIG. 2 is a schematic representation of the anodic oxidation of titanium and titanium alloy according to example 1.
Detailed Description
The present invention now will be described more fully hereinafter with reference to the accompanying drawings, in which it is shown, however, to illustrate some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1-2, the present invention provides a technical solution:
example 1
S101, activating a product: soaking the whole titanium alloy product in 67% nitric acid with the concentration of 50mL/L at the temperature of 25 ℃ for 3min, drying the titanium alloy product in an oven after the treatment is finished, and shielding the activated product at the position needing multicolor pattern treatment by using a prepared pattern film, wherein the shielded titanium alloy product is fixed by using a hanger;
s102, anodic oxidation: fixing the shielded titanium alloy product by using a hanger, integrally immersing the titanium alloy product into an oxidizing solution, and performing anodic oxidation coloring for 2.5min at an oxidation voltage of 51V;
s103, cleaning: cleaning the product after anodic oxidation coloring in the step S3, removing a shielding film after cleaning, and drying the whole anodic oxidized titanium alloy product by using an oven;
s104, local oxidation: dipping an oxidation solution by using the improved electroplating brush pen to perform local oxidation on the previous shielding at the voltage of 69V;
s105, coating: and (3) degreasing and cleaning the cleaned and dried product by micro-90, drying the cleaned product by a baking oven, soaking or spraying the product by RA series anti-fingerprint coating solution, and placing the product in the baking oven for baking at 150 ℃ for 40 minutes after the anti-fingerprint coating uniformly coats the surface of the product.
The oxidizing solution comprises the following components:
reagent(s) Concentration of
Tartaric acid 10g/L
Lactic acid 5mL/L
Oxalic acid 10g/L
Citric acid 10g/L
Hydrogen peroxide 10mL/L
Glycerol 5mL/L
Example 2
S201, activating a product: soaking the whole titanium alloy product in 60g/L ammonium bifluoride at 30 ℃ for 5min, drying the titanium alloy product in an oven after the treatment, and shielding the activated product at the position needing multicolor pattern treatment by using a prepared pattern film, wherein the shielded titanium alloy product is fixed by using a hanger;
s202, anodic oxidation: fixing the shielded titanium alloy product by using a hanger, integrally immersing the titanium alloy product into an oxidizing solution, and performing anodic oxidation coloring for 0.9min at an oxidation voltage of 26V;
s203, cleaning: cleaning the product after anodic oxidation coloring in the step S3, removing a shielding film after cleaning, and drying the whole anodic oxidized titanium alloy product by using an oven;
s204, local oxidation: dipping an oxidation solution by using the improved electroplating brush pen to perform local oxidation on the previous shielding at the voltage of 80V;
s205, coating: and (3) degreasing and cleaning the cleaned and dried product by micro-90, drying the cleaned product by a baking oven, soaking or spraying the product by RA series anti-fingerprint coating solution, and baking the product in the baking oven at 155 ℃ for 40 minutes after the anti-fingerprint coating uniformly coats the surface of the product.
Example 3
S301, activating a product: soaking the whole titanium alloy product in 70 ml/L40% hydrofluoric acid at 35 ℃ for 7min, drying the product after the treatment, and shielding the activated product at the position needing multicolor pattern treatment by using a prepared pattern film, wherein the shielded titanium alloy product is fixed by using a hanger;
s302, anodic oxidation: fixing the shielded titanium alloy product by using a hanger, integrally immersing the titanium alloy product into an oxidizing solution, and performing anodic oxidation coloring for 2.15min at an oxidation voltage of 92V;
s303, cleaning: cleaning the product after anodic oxidation coloring in the step S3, removing a shielding film after cleaning, and drying the whole anodic oxidized titanium alloy product by using an oven;
s304, local oxidation: dipping the oxidation solution by using the improved electroplating brush pen to perform local oxidation under the voltage of 26V;
s305, coating: and (3) degreasing and cleaning the cleaned and dried product by micro-90, drying the cleaned product by a baking oven, soaking or spraying the product by RA series anti-fingerprint coating solution, and baking the product in the baking oven at 160 ℃ for 40 minutes after the anti-fingerprint coating uniformly coats the surface of the product.
Reagent(s) Concentration of
Tartaric acid 80g/L
Lactic acid 25mL/L
Oxalic acid 80g/L
Citric acid 70g/L
Hydrogen peroxide 50mL/L
Glycerol 25mL/L
Example 4
S401, activating a product: soaking the whole titanium alloy product in 45g/L sodium fluoride at 35 ℃ for 9min, drying the titanium alloy product in an oven after the treatment, and shielding the activated product at the position needing multicolor pattern treatment by using a prepared pattern film, wherein the shielded titanium alloy product is fixed by using a hanger;
s402, anodic oxidation: fixing the shielded titanium alloy product by using a hanger, integrally immersing the titanium alloy product into an oxidizing solution, and performing anodic oxidation coloring for 1.45min at an oxidation voltage of 80V;
s403, cleaning: cleaning the product after anodic oxidation coloring in the step S3, removing a shielding film after cleaning, and drying the whole anodic oxidized titanium alloy product by using an oven;
s404, local oxidation: dipping the oxidation solution by using the improved electroplating brush pen to locally oxidize the previous shielding position at 51V;
s405, coating: and (3) degreasing and cleaning the cleaned and dried product by micro-90, drying the cleaned product by a baking oven, soaking or spraying the product by RA series anti-fingerprint coating solution, and baking the product in the baking oven at 165 ℃ for 40 minutes after the anti-fingerprint coating uniformly coats the surface of the product.
Example 5
S501, product activation: soaking the whole titanium alloy product in 67% nitric acid with the concentration of 500mL/L at the temperature of 40 ℃ for 10min, drying the titanium alloy product in an oven after the treatment is finished, and shielding the activated product at the position needing multicolor pattern treatment by using a prepared pattern film, wherein the shielded titanium alloy product is fixed by using a hanger;
s502, anodic oxidation: fixing the shielded titanium alloy product by using a hanger, integrally immersing the titanium alloy product into an oxidizing solution, and performing anodic oxidation coloring for 10min at an oxidation voltage of 51V;
s503, cleaning: cleaning the product after anodic oxidation coloring in the step S3, removing a shielding film after cleaning, and drying the whole anodic oxidized titanium alloy product by using an oven;
s504, local oxidation: dipping an oxidation solution by using the improved electroplating brush pen to perform local oxidation on the condition that the previous shielding is at 92V;
s505, coating: and (3) degreasing and cleaning the cleaned and dried product by micro-90, drying the cleaned product by a baking oven, soaking or spraying the product by RA series anti-fingerprint coating solution, and placing the product in the baking oven for baking for 40 minutes at 150-170 ℃ after the anti-fingerprint coating uniformly coats the surface of the product.
Reagent(s) Concentration of
Tartaric acid 250g/L
Lactic acid 50mL/L
Oxalic acid 200g/L
Citric acid 200g/L
Hydrogen peroxide 100mL/L
Glycerol 50mL/L
Comparative example
Comparative example 1: comparative example 1 is different from example 1 in that only the step S5 originally existing in example 1 was omitted in comparative example 1, so that the step of "immersing the dried product in RA-series anti-fingerprint coating solution, taking out the product after the coating was uniform, and baking at 150 ℃ for 40 minutes" was omitted, and the remaining steps were exactly the same as in example 1 in comparative example 1.
The anti-fingerprint property and the abrasion resistance of examples 1 to 5 and comparative example 1 were measured, and the test results are shown in Table 1:
TABLE 1
The color properties of examples 1-5 were tested and the test results are shown in Table 2:
TABLE 2
The test results in table 2 show that the titanium and titanium alloy anodic oxidation multicolor pattern coloring process provided by the invention innovatively uses the improved electroplating brush pen application, so that any combination of more complex patterns with any colors and more pattern combinations are displayed on the surface of the titanium alloy, and artificial artistic signature and pattern drawing can be realized by the improved electroplating brush pen.
Meanwhile, the test results in table 1 show that the application of the anti-fingerprint coating after oxidation coloring not only ensures the anti-contamination property of the color and the brightness of the color, but also improves the abrasion resistance of the oxide film, and the film layer is not abraded after 1000 times of abrasion compared with comparative example 1, thereby greatly prolonging the service life of the product and producing economic benefits.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. The anodic oxidation multicolor pattern coloring process for titanium and titanium alloy is characterized by comprising the following steps of:
s1, activating a product: activating the whole titanium alloy product, drying the titanium alloy product by using an oven after the activation, masking the activated product by using a prepared pattern film at a position needing multicolor pattern treatment, and fixing the masked titanium alloy product by using a hanger;
s2, anodic oxidation: immersing the whole titanium alloy product subjected to S1 fixation into an oxidation tank with an oxidation solution for anodic oxidation coloring;
s3, cleaning: cleaning the product after anodic oxidation coloring in the step S2, removing a shielding film after cleaning, and drying the whole anodic oxidized titanium alloy product by using an oven;
s4, local oxidation: dipping an oxidation solution by using an improved electroplating brush pen to locally oxidize the previous shielding position on the oxidized titanium alloy product according to the color setting appointed color oxidation voltage of each pattern;
s5, coating: and (3) degreasing, cleaning and drying the product after the partial oxidation is finished by using a cleaning agent, soaking or spraying the product by using an anti-fingerprint coating solution, and placing the product in an oven for baking at 150-170 ℃ for 40 minutes after the anti-fingerprint coating is uniformly coated on the surface of the product.
2. The process for anodizing multiple color patterns of titanium and titanium alloy according to claim 1, wherein if the oxidation voltage of the multiple color patterns is higher than the oxidation voltage of the substrate, the masking process of the pattern film is not needed in S1, and the masking process of the hollowed masking film is also performed on the anodized and colored product in S3.
3. The process of claim 1, wherein the pattern is one or more of a hand-drawn pattern and an artistic signature.
4. The process for anodic oxidation of a titanium or titanium alloy according to claim 1, wherein in step S1, the activation treatment is specifically: immersing the titanium alloy product into an activating solution for soaking and activating treatment, wherein the working parameters of the activating solution are as follows: the working temperature is 25-40 ℃ and the soaking time is 3-10 min.
5. The anodic oxidation multicolor pattern coloring process for titanium and titanium alloy according to claim 4, wherein the activating solution is one or more of 67% nitric acid of 50-500 mL/L, ammonium bifluoride of 30-100mL/L, 40% hydrofluoric acid of 20-100mL/L, sodium fluoride of 45-60 g/L.
6. The process for coloring a titanium and titanium alloy anodized multi-color pattern according to claim 1, wherein in step S2, the anodic oxidation is specifically defined by a voltage range of 10-100V and an oxidation time of 0.5-10 min.
7. The process for anodic oxidation of multicolor patterns of titanium and titanium alloys according to claim 1, wherein the oxidizing solution is composed of the following components: 10-250g/L of tartaric acid, 5-50mL/L of lactic acid, 10-200g/L of oxalic acid, 10-200g/L of citric acid, 10-100mL/L of hydrogen peroxide and 5-50mL/L of glycerol.
8. The process according to claim 1, wherein in step S3, the method for improving the electroplating brush is to replace the brush head of the conventional electroplating brush with one of a planar brush head and a brush-pen-shaped brush head.
9. The process for anodic oxidation of titanium and titanium alloys according to claim 1, wherein in step S5, the cleaning agent is selected from micro-90 cleaning agents.
10. The anodic oxidation multicolor pattern coloring process for titanium and titanium alloy according to claim 1, wherein in step S5, the anti-fingerprint coating solution is RA series anti-fingerprint coating solution.
CN202311555247.5A 2023-11-21 2023-11-21 Titanium and titanium alloy anodic oxidation multicolor pattern coloring process Pending CN117587482A (en)

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