Aluminum-silicon-copper-zinc coated steel plate with antibacterial property and manufacturing method of aluminum-silicon-copper-zinc coated steel plate

Abstract

The invention discloses an aluminum-silicon-copper-zinc coated steel plate with antibacterial performance and a manufacturing method thereof, and belongs to the field of hot dipping. The method comprises the following steps: (a) carrying out alkali washing, electrolytic degreasing, continuous annealing, hot dipping, air knife purging and cooling after plating on a cold-rolled substrate to form an aluminum-silicon coating steel plate; (b) depositing a copper film and a zinc film on the surface of the aluminum-silicon coated steel plate by using a magnetron sputtering coating technology to obtain an aluminum-silicon coated steel plate with the copper film and the zinc film; and (c) heating the aluminum-silicon coating steel plate with the copper film and the zinc film in a vacuum heating furnace, so that the coating and the surface film are fully diffused, and the aluminum-silicon-copper-zinc coating steel plate with the antibacterial property is prepared. According to the preparation method, a Cu system and a Zn system are jointly used as main antibacterial substances, and by means of a high-temperature diffusion mechanism, a deposition and diffusion two-step method is carried out on an aluminum-silicon coating steel plate, so that the composite coating is prepared.

Description

Technical Field

[0001] The invention relates to an aluminum-silicon-copper-zinc coated steel plate with antibacterial performance and a manufacturing method thereof, and belongs to the field of hot-dip coating. Background Art

[0002] Aluminum-silicon coating technology is a surface treatment process that improves the material's resistance to high-temperature oxidation and corrosion by hot-dip coating of aluminum-silicon alloy on the surface of steel. This technology originated in the mid-20th century and was initially used in high-temperature environment components such as automotive exhaust systems and industrial furnaces. Compared with traditional aluminum coatings, aluminum-silicon coatings significantly improve the fluidity of the coating due to the addition of silicon elements, reduce the brittleness of intermetallic compounds, and enable it to form a dense Al2O3 protective film at high temperatures of 600-900°C. In recent years, with the growing demand for lightweight and durability in new energy vehicles and photovoltaic equipment, this technology has further optimized the uniformity and bonding strength of the coating, becoming a key process for solving the oxidation problem of hot-formed steel, and has been widely used in automotive hot stamping parts, photovoltaic brackets and other fields.

[0003] In pursuit of health concepts, products with "antibacterial properties" are more popular among consumers. Therefore, it is necessary to prepare an aluminum-silicon-copper-zinc coated steel plate with antibacterial properties. Summary of the Invention

[0004] To address the challenges of the prior art, the present invention provides an aluminum-silicon-copper-zinc coated steel sheet with antibacterial properties and a method for manufacturing the same. The present invention utilizes Cu and Zn as the primary antibacterial substances and utilizes a high-temperature diffusion mechanism to produce the composite coating through a two-step "deposition + diffusion" process on the Al-Si coated steel sheet.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] A method for manufacturing an aluminum-silicon-copper-zinc coated steel plate with antibacterial properties, the manufacturing method comprising the following steps:

[0007] (a) A cold-rolled substrate is subjected to alkali washing and electrolytic degreasing treatment, continuous annealing, hot-dip plating, air knife purging, and post-plating cooling steps to form an aluminum-silicon (Al-Si) coated steel sheet;

[0008] (b) depositing a Cu thin film and a Zn thin film on the surface of an aluminum-silicon (Al-Si) coated steel plate using a magnetron sputtering coating technique, wherein the deposition order of the Cu thin film and the Zn thin film is not specifically required, thereby obtaining an aluminum-silicon (Al-Si) coated steel plate with Cu and Zn thin films;

[0009] (c) An aluminum-silicon (Al-Si) coated steel plate with Cu and Zn thin films is placed in a vacuum heating furnace for heating to allow sufficient diffusion of the coating and the surface film, thereby producing an aluminum-silicon-copper-zinc (Al-Si-Cu-Zn) coated steel plate with antibacterial properties.

[0010] Furthermore, in step (a), the chemical composition of the cold-rolled substrate is calculated by mass percentage as follows: C: 0.003-1.2%, Si: 0.03-2.2%, Mn: 0.25-2.4%, S: ≤0.15%, P: ≤0.2%, Al: 0.004-0.25, B≤0.15%, Nb: ≤0.12%, V: ≤0.15%, Ti: ≤0.15%, Cr: ≤1.0%, Ni: ≤0.5%, Mo: ≤0.5%, and the balance (Bal.) is Fe and unavoidable impurities (referred to as Fe).

[0011] Furthermore, in step (a), the thickness of the cold-rolled substrate is 0.3-2.5 mm.

[0012] Furthermore, in step (a), during the alkaline washing and degreasing process, the alkaline solution used is a NaOH solution or a KOH solution, the mass concentration of the alkaline solution is 3-7%, and the temperature of the alkaline solution is 70-85°C.

[0013] Furthermore, in step (a), during the electrolytic degreasing process, the current value ranges from 1A to 15A.

[0014] Furthermore, in step (a), during the continuous annealing process, the annealing temperature is 650-860° C. and the strip speed is 30-155 m / min.

[0015] Furthermore, in step (a), during the hot-dip plating process, the plating solution used is an alloy plating solution prepared by melting Al-Si-Fe alloy ingots of a predetermined ratio.

[0016] Furthermore, the components of the alloy ingot with a predetermined ratio are calculated as follows by mass percentage: Si: 5-15 wt.%, Fe: 1-5 wt.%, and the balance is Al and unavoidable impurities (abbreviated as Al).

[0017] Furthermore, in step (a), during the hot dip coating process, the hot dip coating temperature is controlled to be 640-690°C, and the hot dip coating time is controlled to be 3-5s, wherein the temperature of the steel strip entering the pot is 5-10°C higher than the hot dip coating temperature.

[0018] Furthermore, in step (a), during the air knife blowing process, the air knife distance is controlled to be 10-30 mm, and the air knife pressure is controlled to be 100-200 mbar. By controlling the air knife blowing parameters, the thickness of the Al-Si coating after cooling is made to be 10-35 μm.

[0019] Furthermore, in step (a), the temperature is cooled to 15-35° C. during the cooling process after plating.

[0020] Furthermore, in step (b), the deposition order of the Cu film and the Zn film is: first depositing the Cu film and then depositing the Zn film; or first depositing the Zn film and then depositing the Cu film.

[0021] Furthermore, in step (b), during the magnetron sputtering process, the sputtering current is 0.2-0.9A, the temperature of the aluminum-silicon coated steel plate is 120-300°C, and the sputtering power is 40-200W.

[0022] Furthermore, in step (b), the thickness of the Cu film on the surface of the Al-Si coated steel plate is controlled to be 1-5 μm, and the thickness of the Zn film is controlled to be 1-5 μm.

[0023] Furthermore, in step (c), during the vacuum high-temperature diffusion process, the heating temperature is controlled at 450-600° C., the heating time is 1-5 minutes, and the coating is a mixture of Al, Si, Cu, and Zn.

[0024] The aluminum-silicon-copper-zinc coated steel plate with antibacterial properties manufactured by the above manufacturing method comprises a steel plate substrate and an aluminum-silicon-copper-zinc coating on the surface of the steel plate.

[0025] Beneficial effects of the present invention:

[0026] (1) The present invention provides an aluminum-silicon-copper-zinc coated steel plate with antibacterial properties and a method for manufacturing the same. A composite coating is prepared by a "two-step method" of prefabricating the coating and then performing diffusion annealing. The element distribution and organizational structure in the coating are regulated to provide the obtained steel plate with antibacterial properties.

[0027] (2) The present invention combines "antibacterial" with Al-Si coated steel plates, and uses a diffusion mechanism to make the Al-Si coated steel plates have both high temperature resistance and antibacterial properties.

[0028] (3) The present invention is based on the inorganic antibacterial mechanism and selects Cu and Zn metal ions that are both safe and antibacterial as the main antibacterial components. This type of inorganic antibacterial material exerts its bactericidal effect by releasing heavy metal cations (such as Cu2+ and Zn2+): on the one hand, the metal ions can directly destroy the cell membrane structure of bacteria; on the other hand, they can penetrate into the interior of the bacteria, bind to key enzymes in the cells, inactivate them, and thus inhibit the metabolism and reproduction of bacteria. Compared with other heavy metal antibacterial agents, Cu and Zn have lower toxicity and are relatively safe for the human body. At the same time, they can still provide efficient broad-spectrum antibacterial properties and can be widely used in various materials and products that require sanitary protection.

[0029] (4) The antibacterial (Staphylococcus aureus, Escherichia coli) rate of the aluminum-silicon-copper-zinc coated steel plate prepared by the present invention can reach 85-95%. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a mechanism diagram of the preparation process of the aluminum-silicon-copper-zinc coated steel plate of the present invention. DETAILED DESCRIPTION

[0031] The following non-limiting examples may enable those skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way.

[0032] Examples 1-5

[0033] A method for manufacturing an aluminum-silicon-copper-zinc coated steel plate with antibacterial properties, comprising the following steps:

[0034] (a) melting an Al-Si-Fe alloy ingot of a predetermined ratio to prepare an alloy plating solution; wherein the composition of each element in the alloy plating solution is shown in Table 1;

[0035] (b) The cold-rolled substrate was subjected to alkali washing and electrolytic degreasing, continuous annealing, hot-dip plating, air knife purging, and post-plating cooling to form an Al-Si coated steel sheet; wherein, the alkali solution used in the alkali washing and degreasing process was a NaOH solution; the composition of the cold-rolled substrate is shown in Table 2, and the thickness is shown in Table 5; the preparation process parameters of the Al-Si coated steel sheet are shown in Table 3, and the steel sheet was cooled to room temperature after plating; the thickness of the Al-Si coating is shown in Table 5;

[0036] (c) Using magnetron sputtering technology, a Cu thin film and a Zn thin film are sequentially deposited on the surface of the Al-Si coated steel plate to obtain an Al-Si coated steel plate with Cu and Zn thin films; wherein the process parameters of the magnetron sputtering process are shown in Table 4, and the thickness of the Zn film is shown in Table 5;

[0037] (d) The Al-Si coated steel plate with Cu and Zn thin films was placed in a vacuum heating furnace for heating to allow sufficient diffusion between the coating and the surface film, thereby producing an Al-Si-Cu-Zn coated steel plate with antibacterial properties; the parameters controlled during the vacuum high-temperature diffusion process are shown in Table 6.

[0038] Table 1 Proportion of each element in the alloy plating solution (mass ratio wt.%)

[0039] Si Fe Al Example 1 9.3 3.6 margin Example 2 8.7 2.8 margin Example 3 10.6 1.9 margin Example 4 11.2 4.0 margin Example 5 9.7 2.2 margin

[0040] Table 2 Chemical composition of cold-rolled substrate (wt.%)

[0041] C Si Mn S P Al B Nb V Ti Cr Ni Mo Fe. Example 1 0.17 1.29 1.1 0.05 0.06 0.13 0.04 - - 0.06 - - 0.06 Bal. Example 2 0.25 0.24 1.4 0.02 0.02 0.03 0.02 - 0.05 - 0.06 - - Bal. Example 3 0.46 1.3 2.2 0.01 0.07 0.15 - - 0.02 - 0.03 - Bal. Example 4 0.36 0.4 1.4 0.03 0.05 0.06 0.06 - - 0.01 - 0.3 0.02 Bal. Example 5 0.13 0.85 1.3 0.04 0.07 0.08 0.07 0.04 - 0.06 - 0.2 - Bal.

[0042] Table 3 Preparation process parameters of Al-Si coated steel plates

[0043]

[0044] Table 4 Magnetron sputtering process parameters

[0045]

[0046] Table 5 Thickness of cold-rolled substrate, Al-Si coating, Cu film, and Zn film

[0047] Cold rolled substrate / mm Al-Si coating / μm Cu film / μm Zn thin film / μm Example 1 1.3 21 4 5 Example 2 0.5 13 1 2 Example 3 2.0 32 5 4 Example 4 1.4 24 3 3 Example 5 1.8 15 2 1

[0048] Table 6 Parameter control of vacuum high temperature diffusion process

[0049]

[0050]

Claims

1. A method for manufacturing an aluminum-silicon-copper-zinc coated steel plate with antibacterial properties, characterized in that: The following steps are involved: (a) a cold-rolled substrate is subjected to alkali washing and electrolytic degreasing, continuous annealing, hot-dip plating, air knife purging, and post-plating cooling to form an aluminum-silicon coated steel sheet; (b) depositing a copper film and a zinc film on the surface of the aluminum-silicon coated steel plate using a magnetron sputtering coating technique to obtain an aluminum-silicon coated steel plate with copper and zinc films; (c) placing the aluminum-silicon coated steel plate with copper and zinc films in a vacuum heating furnace for heating to allow the coating and the surface film to fully diffuse, thereby obtaining an aluminum-silicon-copper-zinc coated steel plate with antibacterial properties.

2. The manufacturing method according to claim 1, characterized in that In step (a), the chemical composition of the cold-rolled substrate is as follows by mass percentage: C: 0.003-1.2%, Si: 0.03-2.2%, Mn: 0.25-2.4%, S: ≤0.15%, P: ≤0.2%, Al: 0.004-0.25, B ≤0.15%, Nb: ≤0.12%, V: ≤0.15%, Ti: ≤0.15%, Cr: ≤1.0%, Ni: ≤0.5%, Mo: ≤0.5%, and the balance is Fe and unavoidable impurities; the thickness of the cold-rolled substrate is 0.3-2.5 mm.

3. The manufacturing method according to claim 1, characterized in that In step (a), during the alkaline degreasing process, the alkaline solution used is a NaOH solution or a KOH solution, the mass concentration of the alkaline solution is 3-7%, and the temperature of the alkaline solution is 70-85° C.; during the electrolytic degreasing process, the current value is 1A-15A.

4. The manufacturing method according to claim 1, characterized in that In step (a), during the continuous annealing process, the annealing temperature is 650-860° C. and the strip speed is 30-155 m / min; During the hot-dip plating process, the plating solution used is an alloy plating solution prepared by melting an Al-Si-Fe alloy ingot; wherein the composition of the alloy ingot is as follows by mass percentage: Si: 5-15%, Fe: 1-5%, and the balance is Al and inevitable impurities.

5. The manufacturing method according to claim 1, characterized in that In step (a), during the hot dip coating process, the hot dip coating temperature is controlled to be 640-690° C., the hot dip coating time is 3-5 seconds, and the temperature of the steel strip entering the pot is 5-10° C. higher than the hot dip coating temperature; During the air knife blowing process, the air knife distance is 10-30mm and the air knife pressure is 100-200mbar. By controlling the air knife blowing parameters, the thickness of the aluminum silicon coating after cooling is 10-35μm. Cool to 15-35℃ during the post-plating cooling process.

6. The manufacturing method according to claim 1, characterized in that In step (b), the deposition order of the copper film and the zinc film is: first depositing the copper film and then depositing the zinc film; or first depositing the zinc film and then depositing the copper film.

7. The manufacturing method according to claim 1, characterized in that In step (b), during the magnetron sputtering process, the sputtering current is 0.2-0.9A, the temperature of the aluminum-silicon coated steel plate is 120-300°C, and the sputtering power is 40-200W.

8. The manufacturing method according to claim 1, characterized in that In step (b), the thickness of the copper film on the surface of the aluminum-silicon coated steel plate is controlled to be 1-5 μm, and the thickness of the zinc film is controlled to be 1-5 μm.

9. The manufacturing method according to claim 1, characterized in that In step (c), the heating temperature is controlled at 450-600° C. and the heating time is controlled at 1-5 minutes.

10. The aluminum-silicon-copper-zinc coated steel sheet with antibacterial properties manufactured by the manufacturing method according to any one of claims 1 to 9, characterized in that: The aluminum-silicon-copper-zinc coated steel plate comprises a steel plate substrate and an aluminum-silicon-copper-zinc coating on the surface of the steel plate substrate.

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