CN112853420B - Fluoride-free super-hydrophobic self-cleaning antibacterial, mildewproof and antiviral stainless steel and preparation method thereof - Google Patents

Fluoride-free super-hydrophobic self-cleaning antibacterial, mildewproof and antiviral stainless steel and preparation method thereof Download PDF

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CN112853420B
CN112853420B CN202110050185.7A CN202110050185A CN112853420B CN 112853420 B CN112853420 B CN 112853420B CN 202110050185 A CN202110050185 A CN 202110050185A CN 112853420 B CN112853420 B CN 112853420B
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CN112853420A (en
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陈广川
于红光
王晶晶
王斐
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Anhui Tongxi Hi Tech New Material Co ltd
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Tongxi Group Co ltd
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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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Abstract

The invention provides fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and a preparation method thereof, wherein the preparation method comprises the following steps: (1) carrying out electrolytic activation treatment on the pretreated stainless steel to obtain surface activated stainless steel; (2) carrying out electrochemical deposition treatment on the surface activated stainless steel obtained in the step (1) to obtain stainless steel with a deposition layer; (3) and (3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel. The stainless steel surface film layer is uniform and compact, can effectively prevent pollutants from adhering, and has a self-cleaning function; the film layer has excellent, broad-spectrum and long-acting antibacterial, mildewproof and antiviral effects; the preparation method is efficient and environment-friendly, and can realize zero emission.

Description

Fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and preparation method thereof
Technical Field
The invention belongs to the technical field of stainless steel surface treatment, relates to stainless steel and a preparation method thereof, and particularly relates to fluorine-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and a preparation method thereof.
Background
In the prior art, hydrophobic stainless steel is usually obtained by modifying fluorine-containing substances, but the fluorine-containing substances not only seriously damage the environment, but also have biotoxicity and are one of the most easily degradable organic pollutants. In addition, the surface of the fluorine-containing hydrophobic stainless steel has the function of preventing bacterial adhesion in a short time, and does not have the performances of long-acting antibiosis, mildew prevention, virus resistance and the like.
CN111519112A discloses a preparation method of a multilayer antibacterial stainless steel material, which comprises a substrate steel material and a steel double-layer structure forming a surface antibacterial layer, wherein a double-layer composite material formed by metallurgically combining a substrate material and a surface layer material is formed by a double-layer composite casting method, a double-layer composite plate obtained by continuous casting is cut at a fixed length to obtain a double-layer plate blank with a fixed length, the double-layer plate blank is rolled to obtain the antibacterial stainless steel material, a semi-finished product is obtained by heat treatment, rolling and stamping, the semi-finished product is subjected to antibacterial heat treatment, coarse grinding, fine grinding, polishing, cleaning and other procedures, and then is dried and packaged to obtain a finished product. The invention has lower processing cost and larger thickness of the antibacterial layer. Although the stainless steel prepared by the method has certain antibacterial performance, the surface of the stainless steel does not have super-hydrophobic performance.
CN107815679A discloses a simple method for preparing a heat-resistant super-hydrophobic coating on a stainless steel surface, belongs to the field of metal surface treatment, and aims to improve the hydrophobic property of the stainless steel surface and avoid the problem that water vapor is condensed into water drops on the stainless steel surface. The preparation method of the heat-resistant super-hydrophobic coating comprises the following steps: 1. firstly, ultrasonically cleaning stainless steel by using acetone, then carrying out alkali cleaning by using NaOH solution, and finally ultrasonically cleaning by using deionized water; 2. carrying out acid washing and activating treatment on the cleaned stainless steel by using HF with the mass fraction of 10%; 3. soaking the stainless steel subjected to surface activation treatment into a rare earth metal salt or hafnium salt water solution for chemical conversion treatment; 4. and (3) placing the stainless steel with the metal oxide deposited on the surface in a vacuum environment with the pressure of <1Pa for treatment to finish the preparation of the heat-resistant super-hydrophobic coating on the surface of the stainless steel. The method provides a method for preparing the super-hydrophobic coating on the surface of the stainless steel, but the coating has no antibacterial property.
Disclosure of Invention
In order to solve the technical problems, the invention provides the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and the preparation method thereof, wherein the surface film layer of the stainless steel is uniform and compact, can effectively prevent pollutants from adhering, and has a self-cleaning function; the film layer has excellent, broad-spectrum and long-acting antibacterial, mildewproof and antiviral effects; the preparation method is efficient and environment-friendly, and can realize zero emission.
In order to achieve the technical effects, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a preparation method of fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which comprises the following steps:
(1) carrying out electrolytic activation treatment on the pretreated stainless steel to obtain surface activated stainless steel;
(2) carrying out electrochemical deposition treatment on the surface activated stainless steel obtained in the step (1) to obtain stainless steel with a deposition layer;
(3) and (3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel.
According to the invention, firstly, pretreatment is carried out, then electrolytic activation is carried out to remove a passivation film, meanwhile, antibacterial components are loaded, then, electrochemical deposition and heating oxidation are carried out to prepare a micro-nano structure on the surface of stainless steel, and finally, low-surface-energy substance modification treatment is carried out.
As a preferable technical scheme of the invention, the pretreatment in the step (1) comprises alkali washing oil removal and water washing.
As a preferable embodiment of the present invention, the composition of the electrolytic activation solution used in the electrolytic activation treatment in the step (1) includes, in terms of mass percentage:
Figure BDA0002898900600000031
the mass% of the antibacterial agent may be 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, or 0.45%, the mass% of the activator may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, the mass% of the accelerator may be 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, or 14%, and the mass% of the activator may be 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, or 0.45%, but is not limited to the values listed, and other values not listed in the above numerical ranges are also applicable.
In the invention, the antibacterial agent is added into the electrolytic activation solution, and the effective antibacterial component is loaded on the surface while the passivation film is removed and the metal crystalline structure is exposed to provide a good surface state for the subsequent process, so that the film layer has the functions of antibiosis, mildew prevention, antivirus and the like.
Preferably, the antimicrobial agent comprises any one of silver nitrate, silver sulfate or cerium nitrate, or a combination of at least two of these, typical but non-limiting examples being: a combination of silver nitrate and silver sulfate, a combination of silver sulfate and cerium nitrate, a combination of cerium nitrate and silver nitrate, or a combination of silver nitrate, silver sulfate and cerium nitrate, and the like.
Preferably, the activator comprises any one of, or a combination of at least two of, sulfuric acid, phosphoric acid, boric acid, citric acid or oxalic acid, typical but non-limiting examples of which are: a combination of sulfuric acid and phosphoric acid, a combination of phosphoric acid and boric acid, a combination of boric acid and citric acid, a combination of oxalic acid and sulfuric acid, or a combination of sulfuric acid, phosphoric acid, and boric acid, and the like.
Preferably, the accelerator comprises any one of, or a combination of at least two of, ammonium sulfate, disodium hydrogen phosphate, dipotassium hydrogen phosphate or disodium ethylenediaminetetraacetate, typical but non-limiting examples of which are: a combination of ammonium sulfate and disodium hydrogen phosphate, a combination of disodium hydrogen phosphate and dipotassium hydrogen phosphate, a combination of dipotassium hydrogen phosphate and disodium ethylenediaminetetraacetate, a combination of ammonium sulfate and disodium ethylenediaminetetraacetate, or a combination of ammonium sulfate, disodium hydrogen phosphate and dipotassium hydrogen phosphate, and the like.
Preferably, the active agent comprises sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.
As a preferable technical scheme of the invention, the current density of the electrolytic activation in the step (1) is 0.1-10A/dm2E.g. 0.2A/dm2、0.5A/dm2、1A/dm2、2A/dm2、3A/dm2、4A/dm2、5A/dm2、6A/dm2、7A/dm2、8A/dm2Or 9A/dm2And the like, but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
Preferably, the voltage for the electrolytic activation in step (1) is 0.1-5V, such as 0.2V, 0.5V, 1V, 1.5V, 2V, 2.5V, 3V, 3.5V, 4V or 4.5V, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature for the electrolytic activation in step (1) is 15 to 35 ℃, such as 16 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃ or 34 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time for electrolytic activation in step (1) is 1-10 min, such as 2min, 3min, 4min, 5min, 6min, 7min, 8min or 9min, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferable technical scheme of the invention, the deposition solution for electrochemical deposition in the step (2) comprises the following components in percentage by mass:
1-3% of soluble metal salt;
5-15% of a complexing agent;
3-10% of alkali;
the balance being water.
The mass percentage of the soluble metal salt may be 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, or 2.8%, the mass percentage of the complexing agent may be 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, or 14%, and the mass percentage of the base may be 4%, 5%, 6%, 7%, 8%, or 9%, but is not limited to the values listed, and other values not listed in the above numerical ranges are also applicable.
According to the invention, the electrolyte in the bath solution can be dispersed and distributed under the action of constant-temperature magnetic stirring, the film is more uniform, and then the electrolyte is heated and oxidized to generate oxide particles on the surface, so that a micro-nano structure is obtained, the surface free energy is reduced, and the surface hydrophobicity is improved.
Preferably, the soluble metal salt comprises any one of copper sulphate, zinc sulphate or nickel sulphate, or a combination of at least two of these, typical but non-limiting examples being: combinations of copper sulfate and zinc sulfate, zinc sulfate and nickel sulfate, nickel sulfate and copper sulfate, or copper sulfate, zinc sulfate and nickel sulfate, and the like.
Preferably, the complexing agent comprises any one of, or a combination of at least two of, potassium sodium tartrate, sodium pyrophosphate, potassium pyrophosphate or sodium citrate, typical but non-limiting examples of which are: sodium potassium tartrate and sodium pyrophosphate, sodium pyrophosphate and potassium pyrophosphate, potassium pyrophosphate and sodium citrate, sodium citrate and sodium potassium tartrate, or potassium sodium tartrate, sodium pyrophosphate and potassium pyrophosphate, and the like.
Preferably, the base comprises sodium hydroxide.
As a preferable technical scheme of the invention, the current density of the electrochemical deposition in the step (2) is 1-100 mA/dm2E.g. 2mA/dm2、5mA/dm2、10mA/dm2、20mA/dm2、30mA/dm2、40mA/dm2、50mA/dm2、60mA/dm2、70mA/dm2、80mA/dm2Or 90mA/dm2And the like, but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
Preferably, the voltage of the electrochemical deposition in step (2) is 0.1-2V, such as 0.2V, 0.5V, 0.8V, 1V, 1.2V, 1.5V or 1.8V, but is not limited to the recited values, and other unrecited values in the range of values are also applicable.
Preferably, the temperature of the electrochemical deposition in step (2) is 25-75 ℃, such as 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time of the electrochemical deposition in step (2) is 40-60 min, such as 42min, 45min, 48min, 50min, 52min, 55min or 58min, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the electrochemical deposition in step (2) is performed under stirring at a rate of 60 to 150rpm, such as 70rpm, 80rpm, 90rpm, 100rpm, 110rpm, 120rpm, 130rpm, 140rpm, and the like, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferable technical scheme of the invention, the soaking solution used for soaking modification in the step (3) comprises the following components in percentage by mass:
0.1-1% of a low surface energy compound;
0.05-15% of a coupling agent;
the balance being solvent.
The mass percentage of the low surface energy compound may be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, or 0.9%, and the mass percentage of the coupling agent may be 0.1%, 0.2%, 0.5%, 1%, 2%, 5%, 8%, 10%, 12%, or 14%, but is not limited to the values listed, and other values not listed in the above numerical ranges are also applicable.
According to the invention, stainless steel is placed in low surface energy fluorine-free modification liquid added with a coupling agent for modification treatment and then is dried and cured to obtain the super-hydrophobic self-cleaning surface, and the addition of the coupling agent can improve the binding force between a modified substance and a metal matrix, improve the compactness of a film layer and enhance the durability of the film layer.
Preferably, the low surface energy compound comprises any one of stearic acid, myristic acid, oleic acid or hydrogen-containing silicone oil, or a combination of at least two of these, typical but non-limiting examples being: combinations of stearic acid and myristic acid, myristic acid and oleic acid, oleic acid and hydrogen-containing silicone oil, hydrogen-containing silicone oil and stearic acid, or stearic acid, myristic acid and oleic acid, and the like.
Preferably, the coupling agent comprises any one of KH550, KH602, KH792 or KH570, or a combination of at least two of these, typical but non-limiting examples being: a combination of KH550 and KH602, a combination of KH602 and KH792, a combination of KH792 and KH570, a combination of KH570 and KH550, a combination of KH550, KH602 and KH792, or the like.
Preferably, the solvent comprises any one of ethanol, methanol or ethylene glycol or a combination of at least two of the following typical but non-limiting examples: a combination of ethanol and methanol, a combination of methanol and ethylene glycol, a combination of ethylene glycol and ethanol, or a combination of ethanol, methanol, and ethylene glycol, and the like.
In a preferred embodiment of the present invention, the temperature of the thermal oxidation in the step (3) is 100 to 200 ℃, for example, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ or 190 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the time for the thermal oxidation in step (3) is 1 to 2 hours, such as 1.1 hour, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature for the soaking modification in step (3) is 40-60 ℃, such as 42 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃ or 58 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the soaking modification time in the step (3) is 12-36 h, such as 13h, 15h, 18h, 21h, 24h, 27h, 30h, 33h or 35h, but not limited to the recited values, and other values in the range of the recited values are also applicable.
Preferably, the temperature of the drying treatment in step (3) is 60 to 80 ℃, such as 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃ or 78 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying time in step (3) is 30-90 min, such as 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min or 85min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the preparation method of the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel comprises the following steps:
(1) electrolyzing and activating the pretreated stainless steelChemical treatment, wherein the current density of the electrolytic activation is 0.1-10A/dm2The voltage is 0.1-5V, the temperature is 15-35 ℃, and the time is 1-10 min, so as to obtain the surface activated stainless steel;
(2) carrying out electrochemical deposition treatment on the surface activated stainless steel obtained in the step (1) under stirring, wherein the current density of the electrochemical deposition is 1-100 mA/dm2The voltage is 0.1-2V, the temperature is 25-75 ℃, the time is 40-60 min, and the stirring speed is 60-150 rpm, so that the stainless steel with the deposited layer is obtained;
(3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel;
wherein the temperature of the heating oxidation is 100-200 ℃, and the time is 1-2 h; the temperature of the soaking modification is 40-60 ℃, and the time is 12-36 h; the drying temperature is 60-80 ℃, and the drying time is 30-90 min.
The invention also aims to provide the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which is prepared by any one of the preparation methods of the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention provides a fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and a preparation method thereof, wherein the static contact angle of the super-hydrophobic surface of the stainless steel can reach more than 150 degrees, the rolling angle is less than 8 degrees, the surface film layer is uniform and compact, the adhesion of pollutants can be effectively prevented, and the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel has a self-cleaning function;
(2) the invention provides a fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and a preparation method thereof, wherein a film layer of the stainless steel has excellent, broad-spectrum and long-acting antibacterial mildew-proof antiviral effects; (3) the invention provides fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and a preparation method thereof.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of fluorine-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which comprises the following steps:
(1) performing electrolytic activation treatment on the pretreated stainless steel, wherein the current density of the electrolytic activation is 0.1A/dm2The voltage is 0.1V, the temperature is 15 ℃, and the time is 10min, so as to obtain the surface activated stainless steel;
(2) subjecting the surface activated stainless steel of the step (1) to electrochemical deposition treatment under stirring, wherein the current density of the electrochemical deposition is 1mA/dm2The voltage is 0.1V, the temperature is 25 ℃, the time is 60min, and the stirring speed is 60rpm, so that the stainless steel with the deposition layer is obtained;
(3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel;
wherein the temperature of the heating oxidation is 100 ℃, and the time is 2 h; the temperature of the soaking modification is 40 ℃, and the time is 36 h; the drying temperature is 60 ℃ and the drying time is 90 min.
The composition of the electrolytic activation solution used in the electrolytic activation treatment in the step (1) comprises the following components in percentage by mass:
Figure BDA0002898900600000091
Figure BDA0002898900600000101
the deposition solution obtained by the electrochemical deposition in the step (2) comprises the following components in percentage by mass:
1% of copper sulfate;
5% of potassium sodium tartrate;
3% of sodium hydroxide;
the balance being water.
The soaking solution used for soaking modification in the step (3) comprises the following components in percentage by mass:
0.1 percent of stearic acid;
KH550 0.05％；
the balance of ethanol.
Example 2
The embodiment provides a preparation method of fluorine-free super-hydrophobic self-cleaning antibacterial, mildewproof and antiviral stainless steel, which comprises the following steps:
(1) performing electrolytic activation treatment on the pretreated stainless steel, wherein the current density of the electrolytic activation is 10A/dm2The voltage is 5V, the temperature is 35 ℃, and the time is 1min, so as to obtain the surface activated stainless steel;
(2) subjecting the surface-activated stainless steel of step (1) to an electrochemical deposition treatment with stirring, the electrochemical deposition having a current density of 100mA/dm2The voltage is 2V, the temperature is 75 ℃, the time is 40min, the stirring speed is 150rpm, and the stainless steel with a deposition layer is obtained;
(3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel;
wherein the temperature of the heating oxidation is 200 ℃, and the time is 1 h; the temperature of the soaking modification is 60 ℃, and the time is 12 hours; the drying temperature is 80 deg.C, and the drying time is 30 min.
The composition of the electrolytic activation solution used in the electrolytic activation treatment in the step (1) comprises the following components in percentage by mass:
Figure BDA0002898900600000111
the deposition solution obtained by the electrochemical deposition in the step (2) comprises the following components in percentage by mass:
3 percent of zinc sulfate;
15% of sodium pyrophosphate;
10% of sodium hydroxide;
the balance being water.
The soaking solution used for soaking modification in the step (3) comprises the following components in percentage by mass:
1% of myristic acid;
KH602 15％；
the balance being methanol.
Example 3
The embodiment provides a preparation method of fluorine-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which comprises the following steps:
(1) performing electrolytic activation treatment on the pretreated stainless steel, wherein the current density of the electrolytic activation is 1A/dm2The voltage is 1V, the temperature is 20 ℃, and the time is 8min, so as to obtain the surface activated stainless steel;
(2) subjecting the surface-activated stainless steel of step (1) to an electrochemical deposition treatment with stirring, wherein the current density of the electrochemical deposition is 10mA/dm2The voltage is 0.5V, the temperature is 35 ℃, the time is 55min, and the stirring speed is 80rpm, so that the stainless steel with the deposition layer is obtained;
(3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel;
wherein the temperature of the heating oxidation is 120 ℃, and the time is 1.8 h; the temperature of the soaking modification is 45 ℃, and the time is 30 hours; the drying temperature is 65 ℃ and the drying time is 75 min.
The composition of the electrolytic activation solution used in the electrolytic activation treatment in the step (1) comprises the following components in percentage by mass:
Figure BDA0002898900600000121
the deposition solution obtained by the electrochemical deposition in the step (2) comprises the following components in percentage by mass:
1.5 percent of nickel sulfate;
8% of potassium pyrophosphate;
5% of sodium hydroxide;
the balance being water.
The soaking solution used for soaking modification in the step (3) comprises the following components in percentage by mass:
0.5 percent of oleic acid;
KH792 1.5％；
the balance being ethylene glycol.
Example 4
The embodiment provides a preparation method of fluorine-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which comprises the following steps:
the embodiment provides a preparation method of fluorine-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which comprises the following steps:
(1) performing electrolytic activation treatment on the pretreated stainless steel, wherein the current density of the electrolytic activation is 8A/dm2The voltage is 4V, the temperature is 30 ℃, and the time is 8min, so as to obtain the surface activated stainless steel;
(2) subjecting the surface activated stainless steel of step (1) to electrochemical deposition treatment under stirring, wherein the current density of the electrochemical deposition is 80mA/dm2The voltage is 1V, and the temperature is 60 DEG CThe time is 45min, and the stirring speed is 120rpm, so that the stainless steel with the deposition layer is obtained;
(3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel;
wherein the temperature of the heating oxidation is 180 ℃, and the time is 1.2 h; the temperature of the soaking modification is 55 ℃, and the time is 18 h; the drying temperature is 75 ℃ and the drying time is 40 min.
The composition of the electrolytic activation solution used in the electrolytic activation treatment in the step (1) comprises the following components in percentage by mass:
Figure BDA0002898900600000131
the deposition solution obtained by the electrochemical deposition in the step (2) comprises the following components in percentage by mass:
2 percent of copper sulfate;
10% of sodium citrate;
7% of sodium hydroxide;
the balance being water.
The soaking solution used for soaking modification in the step (3) comprises the following components in percentage by mass:
0.5 percent of hydrogen-containing silicone oil;
KH570 10％；
the balance of ethanol.
Comparative example 1
This comparative example was carried out under the same conditions as in example 4 except that the electrolytic activation treatment of step (1) was not carried out.
Comparative example 2
In this comparative example, the same conditions as in example 4 were used except that silver nitrate was not added to the electrolytic activation solution in step (1) and that an equivalent amount of silver nitrate was added to the immersion solution.
Comparative example 3
This comparative example was conducted under the same conditions as in example 4 except that the heat oxidation treatment was not conducted in step (3).
The static contact angle and the rolling angle of the surfaces of the stainless steels prepared in examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in table 1.
Static contact angle and rolling angle were measured using a video contact angle measuring instrument model OCA 15Pro from Datapysics.
TABLE 1
Figure BDA0002898900600000141
Figure BDA0002898900600000151
The stainless steels prepared in examples 1 to 4 and comparative examples 1 to 3 were tested for their antibacterial, antifungal and antiviral properties, and the results are shown in table 2.
And (3) testing antibacterial performance: the antibacterial rate of Escherichia coli and Staphylococcus aureus is tested according to GB/T21510-.
And (3) testing the mildew resistance: refer to GB/T24346-2009 evaluation of mildew resistance of textiles.
And (3) testing antiviral performance: the anti-H1N 1 and H3N2 influenza virus rates are detected by referring to ISO18184:2014(E) textile anti-virus performance test method.
TABLE 2
Figure BDA0002898900600000152
Figure BDA0002898900600000161
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (19)

1. A preparation method of fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel is characterized by comprising the following steps:
(1) carrying out electrolytic activation treatment on the pretreated stainless steel to obtain surface activated stainless steel;
the composition of the electrolytic activation solution used in the electrolytic activation treatment in the step (1) comprises the following components in percentage by mass:
Figure FDA0003516815500000011
the antibacterial agent comprises any one or the combination of at least two of silver nitrate, silver sulfate or cerium nitrate;
the activating agent comprises any one or the combination of at least two of sulfuric acid, phosphoric acid, boric acid, citric acid or oxalic acid;
the accelerator comprises any one or the combination of at least two of ammonium sulfate, disodium hydrogen phosphate, dipotassium hydrogen phosphate or disodium ethylene diamine tetraacetate;
the active agent comprises sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate;
(2) carrying out electrochemical deposition treatment on the surface activated stainless steel obtained in the step (1) to obtain stainless steel with a deposition layer;
the deposition solution obtained by the electrochemical deposition in the step (2) comprises the following components in percentage by mass:
1-3% of soluble metal salt;
5-15% of a complexing agent;
3-10% of alkali;
the balance of water;
the soluble metal salt comprises any one or the combination of at least two of copper sulfate, zinc sulfate or nickel sulfate;
the complexing agent comprises any one or the combination of at least two of potassium sodium tartrate, sodium pyrophosphate, potassium pyrophosphate and sodium citrate;
(3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel;
the soaking solution used for soaking modification in the step (3) comprises the following components in percentage by mass:
0.1-1% of a low surface energy compound;
0.05-15% of a coupling agent;
the balance being solvent;
the low surface energy compound comprises any one or combination of at least two of stearic acid, myristic acid, oleic acid or hydrogen-containing silicone oil;
the coupling agent comprises any one of KH550, KH602, KH792 or KH570 or the combination of at least two of the same;
the temperature of the heating oxidation in the step (3) is 100-200 ℃;
and (4) the time of heating and oxidizing in the step (3) is 1-2 h.
2. The method according to claim 1, wherein the pretreatment of step (1) comprises alkali washing to remove oil and water washing.
3. The method according to claim 1, wherein the current density of the electrolytic activation in the step (1) is 0.1 to 10A/dm2。
4. The method according to claim 1, wherein the voltage for the electrolytic activation in step (1) is 0.1 to 5V.
5. The method according to claim 1, wherein the temperature of the electrolytic activation in the step (1) is 15 to 35 ℃.
6. The method according to claim 1, wherein the time for the electrolytic activation in step (1) is 1 to 10 min.
7. The method of claim 1, wherein the base comprises sodium hydroxide.
8. The method according to claim 1, wherein the electrochemical deposition in step (2) has a current density of 1 to 100mA/dm2。
9. The method according to claim 1, wherein the voltage of the electrochemical deposition in step (2) is 0.1-2V.
10. The method according to claim 1, wherein the temperature of the electrochemical deposition in the step (2) is 25 to 75 ℃.
11. The method according to claim 1, wherein the time of the electrochemical deposition in step (2) is 40-60 min.
12. The method according to claim 1, wherein the electrochemical deposition in step (2) is performed under stirring at a rate of 60 to 150 rpm.
13. The method of claim 1, wherein the solvent comprises any one of ethanol, methanol, or ethylene glycol, or a combination of at least two thereof.
14. The preparation method according to claim 1, wherein the temperature for the soaking modification in the step (3) is 40-60 ℃.
15. The preparation method according to claim 1, wherein the soaking modification time in the step (3) is 12-36 h.
16. The method according to claim 1, wherein the temperature of the drying treatment in the step (3) is 60 to 80 ℃.
17. The preparation method according to claim 1, wherein the drying time in the step (3) is 30-90 min.
18. The method of claim 1, comprising the steps of:
(1) carrying out electrolytic activation treatment on the pretreated stainless steel, wherein the current density of the electrolytic activation is 0.1-10A/dm2The voltage is 0.1-5V, the temperature is 15-35 ℃, and the time is 1-10 min, so as to obtain the surface activated stainless steel;
the composition of the electrolytic activation solution used in the electrolytic activation treatment in the step (1) comprises the following components in percentage by mass:
Figure FDA0003516815500000041
the antibacterial agent comprises any one or the combination of at least two of silver nitrate, silver sulfate or cerium nitrate;
the activating agent comprises any one or the combination of at least two of sulfuric acid, phosphoric acid, boric acid, citric acid or oxalic acid;
the accelerator comprises any one or the combination of at least two of ammonium sulfate, disodium hydrogen phosphate, dipotassium hydrogen phosphate or disodium ethylene diamine tetraacetate;
the active agent comprises sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate;
(2) carrying out electrochemical deposition treatment on the surface activated stainless steel obtained in the step (1) under stirring, wherein the current density of the electrochemical deposition is 1-100 mA/dm2The voltage is 0.1-2V, the temperature is 25-75 ℃, the time is 40-60 min, and the stirring speed is 60-150 rpm, so that the stainless steel with the deposited layer is obtained;
the deposition solution for electrochemical deposition in the step (2) comprises the following components in percentage by mass:
1-3% of soluble metal salt;
5-15% of a complexing agent;
3-10% of alkali;
the balance of water;
the soluble metal salt comprises any one or the combination of at least two of copper sulfate, zinc sulfate or nickel sulfate;
the complexing agent comprises any one or the combination of at least two of potassium sodium tartrate, sodium pyrophosphate, potassium pyrophosphate and sodium citrate;
the base comprises sodium hydroxide;
(3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel;
the soaking solution used for soaking modification in the step (3) comprises the following components in percentage by mass:
0.1-1% of a low surface energy compound;
0.05-15% of a coupling agent;
the balance being solvent;
the low surface energy compound comprises any one or combination of at least two of stearic acid, myristic acid, oleic acid or hydrogen-containing silicone oil;
the coupling agent comprises any one of KH550, KH602, KH792 or KH570 or the combination of at least two of the same;
the solvent comprises any one or the combination of at least two of ethanol, methanol or glycol;
wherein the temperature of the heating oxidation is 100-200 ℃, and the time is 1-2 h; the temperature of the soaking modification is 40-60 ℃, and the time is 12-36 h; the drying temperature is 60-80 ℃, and the drying time is 30-90 min.
19. A fluorine-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which is prepared by the preparation method of any one of claims 1 to 18.
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