阅读说明：本技术 一种锌铜钛合金板材的黑色阳极氧化膜制备方法 (Preparation method of black anodic oxide film of zinc-copper-titanium alloy plate ) 是由 彭明军 孔壮壮 段永华 起华荣 曹勇 孙勇 于 2020-12-02 设计创作，主要内容包括：本发明涉及一种锌铜钛合金板材的黑色阳极氧化膜制备方法,属于金属表面处理技术领域。本发明将锌铜钛合金板材依次进行碱洗、水洗、酸洗、水洗得到预处理锌铜钛合金板材；将预处理锌铜钛合金板材置于阳极氧化电解液中进行阳极氧化处理,洗涤并烘干即得锌铜钛合金板材的黑色阳极氧化膜。本发明的黑色阳极氧化膜具有颜色均匀,表面致密、耐蚀性良好的特点,并且其阳极氧化电解液的原料组成简单、成本低。(The invention relates to a preparation method of a black anodic oxide film of a zinc-copper-titanium alloy plate, belonging to the technical field of metal surface treatment. Sequentially carrying out alkali washing, water washing, acid washing and water washing on the zinc-copper-titanium alloy plate to obtain a pretreated zinc-copper-titanium alloy plate; and (3) placing the pretreated zinc-copper-titanium alloy plate in an anodic oxidation electrolyte for anodic oxidation treatment, washing and drying to obtain the black anodic oxide film of the zinc-copper-titanium alloy plate. The black anodic oxide film has the characteristics of uniform color, compact surface and good corrosion resistance, and the anodic oxide electrolyte has simple raw material composition and low cost.)

1. A preparation method of a black anodic oxide film of a zinc-copper-titanium alloy plate is characterized by comprising the following specific steps:

(1) sequentially carrying out alkali washing, water washing, acid washing and water washing on the zinc-copper-titanium alloy plate to obtain a pretreated zinc-copper-titanium alloy plate;

(2) and (2) placing the zinc-copper-titanium alloy plate pretreated in the step (1) in an anodic oxidation electrolyte for anodic oxidation treatment, washing and drying to obtain a black anodic oxide film of the zinc-copper-titanium alloy plate.

2. The method for preparing the black anodic oxide film of the zinc-copper-titanium alloy plate according to claim 1, wherein the method comprises the following steps: the temperature of the anodic oxidation treatment in the step (2) is 20-45 ℃, the time is 8-37 min, and the current density of the anode is 1-5A/dm²。

3. The method for preparing the black anodic oxide film of the zinc-copper-titanium alloy plate according to claim 1 or 2, wherein the method comprises the following steps: the anodic oxidation electrolyte in the step (2) comprises sodium hydroxide or potassium hydroxide, an oxidant, an accelerant, a stabilizer and deionized water.

4. The method for preparing the black anodic oxide film of the zinc-copper-titanium alloy plate according to claim 3, wherein the method comprises the following steps: the concentration of sodium hydroxide or potassium hydroxide in the anodic oxidation electrolyte is 5-40 g/L, the concentration of the oxidant is 2-20 g/L, the concentration of the accelerator is 2-90 g/L, and the concentration of the stabilizer is 0.1-4 g/L.

5. The method for preparing the black anodic oxide film of the zinc-copper-titanium alloy plate according to claim 3 or 4, wherein the method comprises the following steps: the oxidant is one or more of hydrogen peroxide, sodium chlorate, sodium nitrite, sodium perchlorate, potassium permanganate and potassium dichromate.

6. The method for preparing the black anodic oxide film of the zinc-copper-titanium alloy plate according to claim 3 or 4, wherein the method comprises the following steps: the accelerant is one or more of sodium borate, sodium silicate, sodium phosphate, sodium molybdate, sodium bicarbonate and sodium carbonate.

7. The method for preparing the black anodic oxide film of the zinc-copper-titanium alloy plate according to claim 3 or 4, wherein the method comprises the following steps: the stabilizer is one or more of potassium sodium tartrate, ammonium triacetate, glycerol, phenol and sodium benzoate.

Technical Field

The invention relates to a preparation method of a black anodic oxide film of a zinc-copper-titanium alloy plate, belonging to the technical field of metal surface treatment.

Background

The zinc-copper-titanium alloy (also called titanium-zinc plate) is commonly used as a decorative material for the outer wall and the roof of a high-grade building, has extremely strong color expression and can keep good self-repairing property for more than 80-100 years. The zinc-copper-titanium alloy is prepared by adding high-purity titanium and copper ingots into pure zinc for smelting, and the addition of copper and titanium can increase the mechanical strength and creep resistance of the material, so that the zinc-copper-titanium alloy is more beneficial to practical application.

When the zinc-copper-titanium alloy plate is used as a building decoration material, a compact passivation protective layer can be formed on the surface of the zinc-copper-titanium alloy plate, because zinc has natural corrosion resistance, the zinc-copper-titanium alloy plate keeps an extremely slow corrosion rate, the corrosion rate is less than 1 micron/year, and the zinc-copper-titanium alloy plate with the thickness of 0.7 mm can be used for nearly 100 years. And the wound of the zinc-copper-titanium alloy can be automatically recovered, the wound surface can recover 0.001 micron one day, and the luster of metal can be kept in long-term use. However, the time for naturally forming the passive film of zinc is very long, and the time is different according to the natural meteorological conditions, but the time for naturally forming the compact protective layer is generally more than one year, and the naturally formed protective film is generally gray, has single color and is not beneficial to the application of the protective film as a decorative material, so the artificial rapid formation of the compact oxide film presenting other colors on the surface of the zinc-copper-titanium alloy plate material is very valuable for application.

At present, the literature of titanium zinc plates at home and abroad mainly focuses on the installation method, namely the installation method of using titanium zinc plates as roofing materials or curtain wall materials; the literature, "a titanium-zinc plate and a preparation method thereof" mainly relates to the technical field of metal smelting. For surface treatment, two modes of phosphorization and passivation are common in the existing zinc alloy surface treatment methods at home and abroad, the two surface treatment methods are developed for a long time, phosphorization is developed to a chromium-free process from a chromate passivation method, but the phosphorization and passivation treatment steps are multiple, the process is complicated, and the formed passivation film is generally gray and has the same color as a protective film naturally formed by the zinc alloy, is too single and cannot meet high-grade buildings with special requirements on color.

Disclosure of Invention

The invention provides a preparation method of a black anodic oxide film of a zinc-copper-titanium alloy plate, aiming at the problems of multiple treatment steps of phosphorization and passivation surface treatment of the zinc-copper-titanium alloy plate and too monotonous color of an unstable process protective film in the prior art.

A preparation method of a black anodic oxide film of a zinc-copper-titanium alloy plate comprises the following specific steps:

(1) sequentially carrying out alkali washing, water washing, acid washing and water washing on the zinc-copper-titanium alloy plate to obtain a pretreated zinc-copper-titanium alloy plate;

(2) placing the zinc-copper-titanium alloy plate pretreated in the step (1) in an anodic oxidation electrolyte for anodic oxidation treatment, washing and drying to obtain a black anodic oxide film of the zinc-copper-titanium alloy plate;

the temperature of the anodic oxidation treatment in the step (2) is 20-45 ℃, the time is 8-37 min, and the current density of the anode is 1-5A/dm²；

The anodic oxidation electrolyte in the step (2) comprises sodium hydroxide or potassium hydroxide, an oxidant, an accelerant, a stabilizer and deionized water;

the concentration of sodium hydroxide or potassium hydroxide in the anodic oxidation electrolyte is 5-40 g/L, the concentration of an oxidant is 2-20 g/L, the concentration of an accelerant is 2-90 g/L, and the concentration of a stabilizer is 0.1-4 g/L;

the oxidant is one or more of hydrogen peroxide, sodium chlorate, sodium nitrite, sodium perchlorate, potassium permanganate and potassium dichromate;

the accelerant is one or more of sodium borate, sodium silicate, sodium phosphate, sodium molybdate, sodium bicarbonate and sodium carbonate;

the stabilizer is one or more of potassium sodium tartrate, ammonium triacetate, glycerol, phenol and sodium benzoate.

The invention has the beneficial effects that:

(1) the black anodic oxide film of the copper-titanium alloy plate prepared by the anodic oxidation treatment method has the advantages of simple raw material composition, low cost, simple test steps, short consumed time, good corrosion resistance, reusability of anodic oxidation liquid and the like;

(2) the black anodic oxide film of the copper-titanium alloy plate has the advantages of uniform color, compact surface, good corrosion resistance, good application prospect and market competitiveness.

Drawings

FIG. 1 is a graph showing the appearance and appearance of a black anodized film formed on a zinc-copper-titanium alloy sheet according to example 1;

FIG. 2 is a microscopic morphology of a black anodic oxide film of the zinc-copper-titanium alloy plate of example 1;

FIG. 3 is a 7day salt spray test appearance of the black anodized film of the Zn-Cu-Ti alloy sheet of example 1;

FIG. 4 is a 7day salt spray post-test micrograph of a black anodized film of the zinc-copper-titanium alloy sheet of example 1;

FIG. 5 is a graph showing the appearance and appearance of a black anodized film formed on the zinc-copper-titanium alloy sheet according to example 2;

FIG. 6 is a microscopic morphology of a black anodic oxide film of the Zn-Cu-Ti alloy sheet according to example 2;

FIG. 7 is a graph showing the appearance and appearance of the black anodized film of the Zn-Cu-Ti alloy sheet of example 3

FIG. 8 is a micrograph of a black anodized film of the Zn-Cu-Ti alloy sheet of example 3.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.

Example 1: a preparation method of a black anodic oxide film of a zinc-copper-titanium alloy plate comprises the following specific steps:

(1) sequentially carrying out alkali washing oil removal, water washing, acid washing and deionized ultrasonic water washing on the zinc-copper-titanium alloy plate to obtain a pretreated zinc-copper-titanium alloy plate; the alkaline washing method comprises the following steps of putting the zinc-copper-titanium alloy plate into an alkaline washing solution to be ultrasonically washed for 2min at the temperature of 65 ℃; the pickling solution is hydrochloric acid with the mass concentration of 5%, and the pickling method is to place the zinc-copper-titanium alloy plate into the pickling solution for ultrasonic cleaning for 30 s;

(2) preparing an anodic oxidation electrolyte according to 8g/L of sodium hydroxide, 12g/L of sodium nitrite, 24g/L of sodium bicarbonate, 64g/L of sodium borate, 32g/L of sodium silicate and 0.4g/L of potassium sodium tartrate, wherein the preparation method comprises the steps of slowly adding the sodium hydroxide into deionized water at the temperature of 70 ℃, sequentially adding the sodium nitrite, the sodium bicarbonate, the sodium borate, the sodium silicate and the potassium sodium tartrate after the sodium hydroxide is completely dissolved, and fixing the volume after the sodium hydroxide is dissolved to obtain the anodic oxidation electrolyte;

(3) placing the zinc-copper-titanium alloy plate pretreated in the step (1) into the anodic oxidation electrolyte in the step (2), and controlling the current density to be 1A/dm at the temperature of 36 DEG C²Carrying out anodic oxidation treatment for 20min, washing and drying to obtain a black anodic oxide film of the zinc-copper-titanium alloy plate;

the appearance pattern of the black anodic oxide film of the zinc-copper-titanium alloy plate in the embodiment is shown in fig. 1, the microscopic pattern of the black anodic oxide film of the zinc-copper-titanium alloy plate is shown in fig. 2, and as can be seen from fig. 1 and 2, the black anodic oxide film of the zinc-copper-titanium alloy plate is uniform in color;

the corrosion resistance of the zinc-copper-titanium alloy plate coated with the black anodic oxide film is tested by performing a salt spray test on the untreated zinc-copper-titanium alloy plate and the zinc-copper-titanium alloy plate coated with the black anodic oxide film, the time of the zinc-copper-titanium alloy plate coated with the black anodic oxide film is 34 hours later than the time of the untreated zinc-copper-titanium alloy plate with white rust, and the weight loss of the zinc-copper-titanium alloy plate coated with the black anodic oxide film is 78.4g/m after 7day of salt spray test on average²The weight loss of the untreated zinc-copper-titanium alloy plate is 127.6g/m on average²On the left and right, only 61.4% of the weight loss of the untreated zinc-copper-titanium alloy shows that the zinc-copper-titanium alloy plate coated with the black anodic oxide film has better corrosion resistance;

the appearance of the zinc-copper-titanium alloy plate after the 7day anodic oxide film salt spray test is shown in FIG. 3, the microscopic appearance is shown in FIG. 4, and the appearance after corrosion is mainly pitting corrosion;

the zinc-copper-titanium alloy plate coated with the black anodic oxide film is folded in half without cracks and stripping, is flattened after being folded without cracks, is subjected to thermal shock for three times at the temperature of-50-100 ℃, has no cracks and stripping, and has good performance through a cupping test, a scratch test and the like.

Example 2: a preparation method of a black anodic oxide film of a zinc-copper-titanium alloy plate comprises the following specific steps:

(1) sequentially carrying out alkali washing oil removal, water washing, acid washing and deionized ultrasonic water washing on the zinc-copper-titanium alloy plate to obtain a pretreated zinc-copper-titanium alloy plate; the alkaline washing method comprises the following steps of putting the zinc-copper-titanium alloy plate into an alkaline washing solution to be ultrasonically washed for 2min at the temperature of 65 ℃; the pickling solution is hydrochloric acid with the mass concentration of 5%, and the pickling method is to place the zinc-copper-titanium alloy plate into the pickling solution for ultrasonic cleaning for 30 s;

(2) preparing an anodic oxidation electrolyte according to 16g/L of sodium hydroxide, 8g/L of sodium nitrite, 24g/L of sodium bicarbonate, 23g/L of sodium phosphate, 39g/L of sodium molybdate and 0.1g/L of potassium sodium tartrate, wherein the preparation method comprises the steps of slowly adding the sodium hydroxide into deionized water at the temperature of 70 ℃, after the sodium hydroxide is completely dissolved, sequentially adding the sodium nitrite, the sodium bicarbonate, the sodium phosphate, the sodium molybdate and the potassium sodium tartrate, and after the sodium hydroxide is dissolved, fixing the volume to obtain the anodic oxidation electrolyte;

(3) placing the zinc-copper-titanium alloy plate pretreated in the step (1) into the anodic oxidation electrolyte in the step (2), and controlling the current density to be 5A/dm at the temperature of 40 DEG C²Carrying out anodic oxidation treatment for 16min, washing and drying to obtain a black anodic oxide film of the zinc-copper-titanium alloy plate;

the appearance pattern of the black anodic oxide film of the zinc-copper-titanium alloy plate in the embodiment is shown in fig. 5, the microscopic pattern of the black anodic oxide film of the zinc-copper-titanium alloy plate is shown in fig. 6, and it can be seen from fig. 5 and 6 that the black anodic oxide film of the zinc-copper-titanium alloy plate is uniform in color;

the corrosion resistance of the zinc-copper-titanium alloy plate coated with the black anodic oxide film is tested by performing a salt spray test on the untreated zinc-copper-titanium alloy plate and the zinc-copper-titanium alloy plate coated with the black anodic oxide film, the time of the zinc-copper-titanium alloy plate coated with the black anodic oxide film is 38 hours later than the time of the untreated zinc-copper-titanium alloy plate with white rust, and the weight loss of the zinc-copper-titanium alloy plate coated with the black anodic oxide film is 79.7g/m after 7day of salt spray test on average²The weight loss of the untreated zinc-copper-titanium alloy plate is 127.6g/m on average²On the left and right, only 62.5% of the weight loss of the untreated zinc-copper-titanium alloy is shown, which indicates that the zinc-copper-titanium alloy plate coated with the black anodic oxide film has better corrosion resistance;

the zinc-copper-titanium alloy plate coated with the black anodic oxide film is folded in half without cracks and stripping, is flattened after being folded without cracks, is subjected to thermal shock for three times at the temperature of-50-100 ℃, has no cracks and stripping, and has good performance through a cupping test, a scratch test and the like.

Example 3: a preparation method of a black anodic oxide film of a zinc-copper-titanium alloy plate comprises the following specific steps:

(1) sequentially carrying out alkali washing oil removal, water washing, acid washing and deionized ultrasonic water washing on the zinc-copper-titanium alloy plate to obtain a pretreated zinc-copper-titanium alloy plate; the alkaline washing method comprises the following steps of putting the zinc-copper-titanium alloy plate into an alkaline washing solution to be ultrasonically washed for 2min at the temperature of 65 ℃; the pickling solution is hydrochloric acid with the mass concentration of 5%, and the pickling method is to place the zinc-copper-titanium alloy plate into the pickling solution for ultrasonic cleaning for 30 s;

(2) preparing an anodic oxidation electrolyte according to 18g/L of sodium hydroxide, 4g/L of sodium nitrite, 24g/L of sodium bicarbonate, 12g/L of sodium phosphate, 24g/L of sodium molybdate and 0.1g/L of potassium sodium tartrate, wherein the preparation method comprises the steps of slowly adding the sodium hydroxide into deionized water at the temperature of 70 ℃, after the sodium hydroxide is completely dissolved, sequentially adding the sodium nitrite, the sodium bicarbonate, the sodium phosphate, the sodium molybdate and the potassium sodium tartrate, and after the sodium hydroxide is dissolved, fixing the volume to obtain the anodic oxidation electrolyte;

(3) placing the zinc-copper-titanium alloy plate pretreated in the step (1) into the anodic oxidation electrolyte in the step (2), and controlling the current density to be 3A/dm at the temperature of 35 DEG C²Carrying out anodic oxidation treatment for 30min, washing and drying to obtain a black anodic oxide film of the zinc-copper-titanium alloy plate;

the appearance pattern of the black anodic oxide film of the zinc-copper-titanium alloy plate in the embodiment is shown in fig. 7, the microscopic pattern of the black anodic oxide film of the zinc-copper-titanium alloy plate is shown in fig. 8, and it can be seen from fig. 7 and 8 that the black anodic oxide film of the zinc-copper-titanium alloy plate is uniform in color;

the untreated zinc-copper-titanium alloy and the zinc-copper-titanium alloy plate coated with the black anodic oxide film are subjected to a salt spray test to test the corrosion resistance of the zinc-copper-titanium alloy plate, and the zinc-copper-titanium alloy plate coated with the black anodic oxide filmThe gold plate is 32 hours later than the untreated zinc-copper-titanium alloy plate, and the weight loss of the zinc-copper-titanium alloy plate coated with the black anodic oxide film is 82.3g/m after the salt spray test of 7day²The weight loss of the untreated zinc-copper-titanium alloy plate is 127.6g/m on average²About, only 64.5% of the weight loss of the untreated zinc-copper-titanium alloy indicates that the zinc-copper-titanium alloy plate coated with the black anodic oxide film has better corrosion resistance;

the zinc-copper-titanium alloy plate coated with the black anodic oxide film is folded in half without cracks and stripping, is flattened after being folded without cracks, is subjected to thermal shock for three times at the temperature of-50-100 ℃, has no cracks and stripping, and has good performance through a cupping test, a scratch test and the like.

While the present invention has been described in detail with reference to the specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.