CN113430617A - Titanium alloy anodic oxidation liquid and titanium alloy color surface treatment process - Google Patents
Titanium alloy anodic oxidation liquid and titanium alloy color surface treatment process Download PDFInfo
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- CN113430617A CN113430617A CN202110677718.4A CN202110677718A CN113430617A CN 113430617 A CN113430617 A CN 113430617A CN 202110677718 A CN202110677718 A CN 202110677718A CN 113430617 A CN113430617 A CN 113430617A
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- 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
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Abstract
The invention discloses a titanium alloy anodic oxidation liquid and a titanium alloy color surface treatment process, wherein the titanium alloy anodic oxidation liquid comprises the following components: 60-120 mL/L of phosphoric acid, 5-15 g/L of oxalic acid, 2-5 g/L of additive A, 1-3 g/L of additive B and 0.2-1 g/L of rare earth oxide; the additive A is a benzenesulfonic acid derivative; the additive B is salicylic acid derivatives. The anodic oxidation liquid provided by the invention can form an oxide film layer uniformly covered on the surface of the titanium alloy, the oxide film layer has uniform and bright color, is smooth and fine, and shows different colors under different voltage conditions, and meanwhile, the oxide film layer can obviously improve the hardness of the surface of the titanium alloy, thereby improving the anti-friction performance of the surface of the titanium alloy.
Description
Technical Field
The invention relates to the field of titanium alloy surface treatment, in particular to titanium alloy anodic oxidation liquid and a titanium alloy surface treatment process.
Background
The titanium alloy (TC4) has excellent performances such as excellent corrosion resistance and biocompatibility and is widely applied to the technical fields of aerospace, electronic equipment, biology, chemical engineering and the like, but the defects of poor wear resistance, low hardness and the like of the titanium alloy limit the application and development of the titanium alloy, and the titanium alloy needs to be subjected to surface treatment in practical application to improve the mechanical property of the titanium alloy; with the improvement of living standard and the pursuit of beauty, the product is often required to be endowed with more beautiful appearance, so that the mechanical property of the titanium alloy is improved, and the surface of the titanium alloy is required to be colored so as to meet the market demand.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the invention provides a titanium alloy anodizing solution, which can be used for adhering a uniform oxide film on the surface of a titanium alloy under anodizing condition treatment, so as to improve the hardness of the titanium alloy and color the surface of the titanium alloy.
The invention also aims to provide a titanium alloy color surface treatment process.
The purpose of the invention is realized by the following technical scheme:
a titanium alloy anodic oxidation liquid comprises the following components: 60-120 mL/L of phosphoric acid, 5-15 g/L of oxalic acid, 2-4 g/L of additive A, 1-3 g/L of additive B and 0.2-1 g/L of rare earth oxide;
the additive A is a benzenesulfonic acid derivative;
the additive B is salicylic acid derivatives.
In one embodiment, the titanium alloy is a TC4 titanium alloy.
In one embodiment, the benzene sulfonic acid derivative is at least one of 3-aminobenzene sulfonic acid and sodium dodecyl benzene sulfonate.
In one embodiment, the additive A is a compound of 3-aminobenzene sulfonic acid and sodium dodecyl benzene sulfonate, and the mass ratio of the 3-aminobenzene sulfonic acid to the sodium dodecyl benzene sulfonate is 1: 1.
in one embodiment, the additive B is sulfosalicylic acid.
In one embodiment, the rare earth oxide is La2O3And Y2O3The mixed oxide of La2O3And Y2O3The dosage ratio of 1: 3.
further, the invention also provides a titanium alloy color surface treatment process, which comprises the following steps: sequentially carrying out oil removal, acid washing, anodic oxidation, sealing and drying treatment on the titanium alloy;
the anodic oxidation treatment is to put the titanium alloy after acid washing into the titanium alloy anodic oxidation solution provided by the invention, and the temperature is 15 toThe current density is 5-10A/dm at 35 DEG C2And carrying out anodic oxidation for 20-30 min under the condition of 20-80V of voltage.
In one embodiment, the oil removal step is to wash the titanium alloy with hot water, then place the washed titanium alloy in ethanol solution for ultrasonic treatment for 20-30 min, and then wash the titanium alloy with water.
In one embodiment, the pickling is to immerse the titanium alloy after oil removal in a pickling solution for 30s to 1min, wherein the pickling solution is prepared by mixing hydrofluoric acid, dilute nitric acid and water in a volume ratio of 1: 5: 30 proportion, and washing with water after the pickling solution is soaked.
In one embodiment, the sealing is to seal the titanium alloy after acid washing in deionized water at 90 ℃ for 30-40 min.
In one embodiment, the drying is to dry the sealed titanium alloy for 1-3 hours at 80-120 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention provides a titanium alloy anodic oxidation liquid, by using the anodic oxidation liquid provided by the invention, an oxide film layer which is uniformly covered can be formed on the surface of a titanium alloy, the color of the oxide film layer is uniform, bright, smooth and fine, the oxide film layer shows different colors under different voltage conditions, and meanwhile, the oxide film layer can obviously improve the hardness of the surface of the titanium alloy and improve the anti-friction performance of the surface of the titanium alloy.
(2) The titanium alloy color surface treatment process provided by the invention has the characteristics of simple process, strong operability, simplicity, convenience and high efficiency.
(3) The compound of the 3-aminobenzene sulfonic acid and the sodium dodecyl benzene sulfonate is adopted as the slow release additive, and the compound of the 3-aminobenzene sulfonic acid and the sodium dodecyl benzene sulfonate is compounded and cooperated, so that the use amount of the corrosion inhibitor can be reduced, an oxide film is kept compact and smooth, meanwhile, the 3-aminobenzene sulfonic acid has low toxicity, the sodium dodecyl benzene sulfonate is compounded and used, the biological toxicity of the corrosion inhibitor can be reduced, and the environment protection is facilitated.
(4) The titanium alloy anode oxidizing solution provided by the invention is added with rare earth oxide, and specifically adopts La2O3And Y2O3The mixed oxide forms a Ti-La-Y oxide film on the surface of the titanium alloy in the anodic oxidation process, and La2O3And Y2O3Can produce a catalytic effect on anodic oxidation, thereby accelerating the generation speed of the oxide film and improving the thickness and hardness of the oxide film.
(5) The invention adopts sulfosalicylic acid as a metal complexing agent, wherein stable complex compounds can be formed with Ti ions, La ions and Y ions in the anodic oxidation process and are attached to the surface of the titanium alloy, so that the stability of an oxide film is improved, and the corrosion resistance of the oxide film is improved.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto. All the raw materials and reagents in the present invention are commercially available conventional raw materials and reagents unless otherwise specified.
The embodiment of the invention adopts TC4 titanium alloy, and the mass percentage of the main components is as follows:
iron (Fe): ≦ 0.3, carbon (C): 0.1 ≦ nitrogen (N): ≦ 0.05, hydrogen (H): ≦ 0.015, oxygen (O): ≦ 0.2, aluminum (Al): 5.5-6.8, vanadium (V): 3.5 to 4.5, and the balance being titanium (Ti).
Carrying out color surface treatment on the TC4 titanium alloy according to the following steps:
oil removal: washing a TC4 titanium alloy with hot water, then putting the washed titanium alloy into ethanol solution, carrying out ultrasonic treatment for 20-30 min, and then washing with water;
acid washing: soaking the degreased titanium alloy in a pickling solution for 30 s-1 min, wherein the pickling solution is prepared by mixing hydrofluoric acid, dilute nitric acid and water by volume in a proportion of 1: 5: 30 proportion, and washing with water after the pickling solution is soaked;
anodic oxidation: the anodic oxidation treatment is to put the titanium alloy after acid washing into the titanium alloy anodic oxidation solution provided by the invention, and the current density is 5-10A/dm at 15-35 DEG C2Anodizing for 20-30 min under the condition of 20-80V voltage;
and (3) sealing: sealing the titanium alloy subjected to acid washing in deionized water at 90 ℃ for 30-40 min;
drying: and drying the sealed titanium alloy for 1-3 h at the temperature of 80-120 ℃.
The formulations of the anodizing solutions of examples 1-6 and comparative examples 1-3 are shown in Table 1, and the specific parameters of the anodizing process are shown in Table 2.
TABLE 1 formulation ratio of anodizing solutions of different examples
TABLE 2 anodizing Process parameters for various examples
| Item | Temperature of | Current density A/dm2 | Voltage V | Anodic oxidation time min |
| Example 1 | 15 | 5 | 20 | 25 |
| Example 2 | 20 | 6 | 30 | 20 |
| Example 3 | 25 | 7 | 40 | 25 |
| Example 4 | 30 | 8 | 60 | 20 |
| Example 5 | 25 | 9 | 70 | 30 |
| Example 6 | 35 | 10 | 80 | 30 |
| Comparative example 1 | 15 | 5 | 20 | 25 |
| Comparative example 2 | 15 | 5 | 20 | 25 |
| Comparative example3 | 15 | 5 | 20 | 10 |
Further, after the surface treatment was performed on each of the examples and comparative examples according to the parameters in tables 1 and 2, the appearance evaluation and the performance test were performed on the oxide film layer formed on each of the titanium alloy samples, and the specific results are shown in table 3.
Wherein the appearance color is judged to be obtained by visual observation under sunlight; the surface roughness is measured by a handheld surface roughness measuring instrument of Sanfeng Japan; the thickness of the oxide film is detected by a metallographic microscope to detect the cross section of the titanium alloy; the oxide film hardness was measured using a silver micro Vickers hardness tester HVS-1000A.
TABLE 3 results of the anodizing process treatment of various examples
According to the detection results of the embodiments 1 to 6, with the gradual increase of the temperature, the current density and the voltage value in the anodic oxidation process parameters, the color of the oxide film of the titanium alloy after anodic oxidation is different, and the thickness and the hardness of the oxide film are gradually increased, wherein the thickness is 13 to 30um, and the hardness is greater than 450 HV; among them, comparative example 1 is different from example 1 in that rare earth oxide, which is absent in the anodizing solution, causes significant reduction in thickness and hardness of the oxide film, and it was verified that La2O3And Y2O3The addition of the catalyst can generate catalytic effect on anodic oxidation, thereby accelerating the generation speed of the oxide film and improving the thickness and the hardness of the oxide film; the difference between the comparative example 2 and the example 1 is that the simple 3-aminobenzenesulfonic acid is adopted as the corrosion inhibitor in the anodic oxidation liquid, and although the usage amount of the 3-aminobenzenesulfonic acid in the comparative example 2 is consistent with the usage amount of the compound corrosion inhibitor in the example 1, the finally formed oxide film hasThe surface roughness is obviously improved, which shows that the slow release effect of the compound preparation of the 3-aminobenzene sulfonic acid and the sodium dodecyl benzene sulfonate can be improved, and the sodium dodecyl benzene sulfonate can play a role in emulsifying and dispersing and improve the generation uniformity of an oxide film as an anionic surfactant; comparative example 3 differs from example 1 in that the anodic oxidation time is less than the limit value of the present invention, and finally the thickness and hardness of the oxide film formed on the surface of the titanium alloy are significantly lower than those of example 1.
The above embodiments are the best mode for carrying out the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent substitutions and are included in the scope of the present invention.
Claims (10)
1. The titanium alloy anodic oxidation liquid is characterized by comprising the following components: 60-120 mL/L of phosphoric acid, 5-15 g/L of oxalic acid, 1-3 g/L of additive A, 1-3 g/L of additive B and 0.2-1 g/L of rare earth oxide;
the additive A is a benzenesulfonic acid derivative;
the additive B is salicylic acid derivatives.
2. The titanium alloy anodizing solution according to claim 1, wherein: the additive A is a compound of 3-aminobenzene sulfonic acid and sodium dodecyl benzene sulfonate.
3. The titanium alloy anodizing solution according to claim 2, wherein: the mass ratio of the 3-aminobenzenesulfonic acid to the sodium dodecyl benzene sulfonate is 1: 1.
4. the titanium alloy anodizing solution according to claim 1, wherein: the additive B is sulfosalicylic acid.
5. The titanium alloy anodizing solution according to claim 1, whereinThe method comprises the following steps: the rare earth oxide is La2O3And Y2O3Mixed oxides of (4).
6. A titanium alloy color surface treatment process is characterized in that: sequentially carrying out oil removal, acid washing, anodic oxidation, sealing and drying treatment on the titanium alloy;
the anodic oxidation treatment is to put the titanium alloy after acid washing into the titanium alloy anodic oxidation solution of any one of claims 1 to 5, and the current density is 5 to 10A/dm at 15 to 35 DEG C2And carrying out anodic oxidation for 25-30 min under the condition of 20-80V of voltage.
7. The titanium alloy color surface treatment process according to claim 6, characterized in that: the oil removal step is to wash the titanium alloy with hot water, then place the titanium alloy in ethanol solution for ultrasonic treatment for 20-30 min, and then wash the titanium alloy with water.
8. The titanium alloy color surface treatment process according to claim 6, characterized in that: the pickling is to immerse the titanium alloy after oil removal into a pickling solution for 30 s-1 min, wherein the pickling solution is prepared by mixing hydrofluoric acid, dilute nitric acid and water by volume in a proportion of 1: 5: 30 proportion, and washing with water after the pickling solution is soaked.
9. The titanium alloy color surface treatment process according to claim 6, characterized in that: and the sealing is to seal the titanium alloy after acid washing in deionized water at 90 ℃ for 30-40 min.
10. The titanium alloy color surface treatment process according to claim 6, characterized in that: and the drying is to dry the sealed titanium alloy for 1-3 hours at the temperature of 80-120 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114164475A (en) * | 2021-11-25 | 2022-03-11 | 攀枝花学院 | Method for electrochemically treating magnesium or magnesium alloy surface |
| CN117552068A (en) * | 2024-01-11 | 2024-02-13 | 沈阳欧施盾新材料科技有限公司 | Technological method for protecting oxidation defect of inner wall of titanium alloy gas cylinder in hot working process and application thereof |
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| CN114164475A (en) * | 2021-11-25 | 2022-03-11 | 攀枝花学院 | Method for electrochemically treating magnesium or magnesium alloy surface |
| CN114164475B (en) * | 2021-11-25 | 2024-03-15 | 攀枝花学院 | Electrochemical treatment method for magnesium or magnesium alloy surface |
| CN117552068A (en) * | 2024-01-11 | 2024-02-13 | 沈阳欧施盾新材料科技有限公司 | Technological method for protecting oxidation defect of inner wall of titanium alloy gas cylinder in hot working process and application thereof |
| CN117552068B (en) * | 2024-01-11 | 2024-04-02 | 沈阳欧施盾新材料科技有限公司 | Technological method for protecting oxidation defect of inner wall of titanium alloy gas cylinder in hot working process and application thereof |
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