阅读说明：本技术 一种抗菌抗病毒不锈钢及其制备方法 (Antibacterial and antiviral stainless steel and preparation method thereof ) 是由 薛烽 于红光 李梦婷 于 2020-06-30 设计创作，主要内容包括：本发明涉及一种抗菌抗病毒不锈钢及其制备方法,所述制备方法包括如下步骤：(1)将不锈钢进行阳极氧化,在所述不锈钢表面形成带有微孔的阳极氧化膜；(2)在溶胶A中浸泡和一次加热；(3)在溶胶B中浸泡和二次加热,得到抗菌抗病毒不锈钢；其中,所述溶胶A包括钛酸丁酯,所述溶胶B包括盐酸伐昔洛韦和阿昔洛韦。所述制备方法通过一次加热,将来自溶胶A中的钛酸丁酯主要分解成纳米二氧化钛,并且通过两次溶胶浸泡和加热处理,使得阳极氧化膜的微孔中和表面上均附着有纳米二氧化钛和盐酸伐昔洛韦、阿昔洛韦复合的抗菌抗病毒成分,使得不锈钢具有良好且持久的抗菌抗病毒性能；而且,所述制备方法操作简单,有利于大规模推广。(The invention relates to an antibacterial and antiviral stainless steel and a preparation method thereof, wherein the preparation method comprises the following steps: (1) anodizing the stainless steel to form an anodized film with micropores on the surface of the stainless steel; (2) soaking in the sol A and heating for the first time; (3) soaking in the sol B and heating for the second time to obtain the antibacterial and antiviral stainless steel; wherein the sol A comprises butyl titanate, and the sol B comprises valacyclovir hydrochloride and acyclovir. According to the preparation method, butyl titanate in the sol A is mainly decomposed into nano titanium dioxide through primary heating, and through two times of sol soaking and heating treatment, nano titanium dioxide, valaciclovir hydrochloride and acyclovir compound antibacterial and antiviral components are attached to micropores and the surface of an anodic oxidation film, so that the stainless steel has good and lasting antibacterial and antiviral properties; moreover, the preparation method is simple to operate and is beneficial to large-scale popularization.)

1. The preparation method of the antibacterial and antiviral stainless steel is characterized by comprising the following steps:

(1) anodizing the stainless steel to form an anodized film with micropores on the surface of the stainless steel;

(2) soaking the stainless steel obtained by the anodic oxidation in the step (1) in the sol A, and then taking out the soaked stainless steel for primary heating to obtain an antibacterial and antiviral stainless steel crude product;

(3) soaking the antibacterial and antiviral stainless steel crude product obtained in the step (2) in the sol B, taking out the soaked stainless steel, and heating for the second time to obtain antibacterial and antiviral stainless steel;

wherein the sol A comprises butyl titanate, and the sol B comprises valacyclovir hydrochloride and acyclovir.

2. The method according to claim 1, wherein the stainless steel is subjected to a pretreatment before the anodic oxidation in step (1);

preferably, the pretreatment sequentially comprises mechanical polishing, chemical degreasing and electrochemical polishing;

preferably, the mechanical polishing is surface grinding by using sand paper, and the grinding is carried out from 400 meshes to 3000 meshes;

preferably, the chemical oil removal is performed by using an oil removal liquid;

preferably, the degreasing fluid comprises 40-50 g/L of sodium hydroxide, 10-35 g/L of sodium carbonate and 5-15 g/L of sodium gluconate;

preferably, the temperature of the chemical oil removal is 65-85 ℃, and the time is 5-15 min;

preferably, the electrochemical polishing is performed in a polishing solution;

preferably, the polishing solution comprises 22-28 g/L of phosphoric acid, 10-16 g/L of sulfuric acid and 0.5-2 g/L of glycerol;

preferably, the electrochemical polishing temperature is 40-65 ℃, the time is 3-20 min, and the current density is 10-55A/dm²。

3. The production method according to claim 1 or 2, wherein the anodic oxidation of step (1) is carried out in an acidic oxidizing solution;

preferably, the composition of the acidic oxidizing solution comprises sulfuric acid, molybdenum salt and cerium salt;

preferably, the acidic oxidizing solution comprises 200-300 g/L of sulfuric acid, 20-35 g/L of molybdenum salt and 2-8 g/L of cerium salt;

preferably, the molybdenum salt comprises ammonium molybdate and/or sodium molybdate;

preferably, the cerium salt comprises cerium nitrate and/or cerium sulfate.

4. The preparation method according to any one of claims 1 to 3, wherein the anodic oxidation in the step (1) adopts direct current, the stainless steel is used as an anode, and graphite is used as a cathode;

preferably, the power supply voltage of the direct current is 5-20V;

preferably, the treatment time of the anodic oxidation in the step (1) is 20-35 min;

preferably, the treatment temperature of the anodic oxidation in the step (1) is 10-15 ℃.

5. The method according to any one of claims 1 to 4, wherein the sol A of step (2) further comprises silver nitrate and/or iodate;

preferably, the sol A in the step (2) comprises 0.8-1.5 mol/L of butyl titanate, 0.64-1.2 mol/L of silver nitrate, 20-35 g/L of iodate, 14.4-27 mol/L of absolute ethyl alcohol, 15-29 mol/L of deionized water and 0.75-1.64 mol/L of diethanolamine;

preferably, the iodate comprises any one or a combination of at least two of sodium iodate, potassium iodate, calcium iodate, or magnesium iodate.

6. The method according to any one of claims 1 to 5, wherein the temperature of the soaking in the step (2) is 15 to 25 ℃;

preferably, the soaking time in the step (2) is 20-45 min;

preferably, the temperature of the primary heating in the step (2) is 500-800 ℃;

preferably, the time of the primary heating in the step (2) is 8-25 min.

7. The production method according to any one of claims 1 to 6, wherein the sol B in the step (3) further comprises copper nitrate;

preferably, the sol B in the step (3) comprises 5-15 g/L valacyclovir hydrochloride, 4-20 g/L acyclovir, 3-18 g/L copper nitrate, 15-29 mol/L deionized water, 0.75-1.64 mol/L diethanolamine and 14.4-27 mol/L absolute ethyl alcohol.

8. The method according to any one of claims 1 to 7, wherein the temperature of the soaking in the step (3) is 15 to 25 ℃;

preferably, the soaking time in the step (3) is 8-19 min;

preferably, the temperature of the primary heating in the step (3) is 170-270 ℃;

preferably, the time of the primary heating in the step (3) is 11-38 min.

9. The method according to any one of claims 1 to 8, characterized by comprising the steps of:

(1) firstly, sequentially carrying out mechanical polishing, chemical degreasing and electrochemical polishing on stainless steel as pretreatment, and then carrying out anodic oxidation in an acidic oxidation solution to form an anodic oxidation film with micropores on the surface of the stainless steel;

wherein, the mechanical polishing is to polish the surface by using sand paper, and the surface is polished from 400 meshes to 3000 meshes; the chemical oil removal is carried out by adopting oil removal liquid, the oil removal liquid comprises 40-50 g/L of sodium hydroxide, 10-35 g/L of sodium carbonate and 5-15 g/L of sodium gluconate, the temperature of the chemical oil removal is 65-85 ℃, and the time is 5-15 min; the electrochemical polishing is carried out in a polishing solution, the polishing solution comprises 22-28 g/L of phosphoric acid, 10-16 g/L of sulfuric acid and 0.5-2 g/L of glycerol, the electrochemical polishing temperature is 40-65 ℃, the time is 3-20 min, and the current density is 10-55A/dm²；

The acidic oxidizing solution comprises 200-300 g/L of sulfuric acid, 20-35 g/L of molybdenum salt and 2-8 g/L of cerium salt; the anodic oxidation adopts direct current, the stainless steel is used as an anode, the graphite is used as a cathode, the power supply voltage of the direct current is 5-20V, the treatment time of the anodic oxidation is 20-35 min, and the treatment temperature of the anodic oxidation is 10-15 ℃;

(2) soaking the stainless steel obtained by the anodic oxidation in the step (1) in the sol A for 20-45 min at the soaking temperature of 15-25 ℃, taking out the soaked stainless steel, and heating at 500-800 ℃ for 8-25 min for one time to obtain an antibacterial and antiviral stainless steel crude product;

wherein the sol A comprises 0.8-1.5 mol/L of butyl titanate, 0.64-1.2 mol/L of silver nitrate, 20-35 g/L of iodate, 14.4-27 mol/L of absolute ethyl alcohol, 15-29 mol/L of deionized water and 0.75-1.64 mol/L of diethanolamine; the iodate comprises any one or a combination of at least two of sodium iodate, potassium iodate, calcium iodate or magnesium iodate;

(3) soaking the antibacterial and antiviral stainless steel crude product obtained in the step (2) in the sol B for 8-19 min at the soaking temperature of 15-25 ℃, taking out the soaked stainless steel, and carrying out secondary heating at 170-270 ℃ for 11-38 min to obtain antibacterial and antiviral stainless steel;

the sol B comprises 5-15 g/L valacyclovir hydrochloride, 4-20 g/L acyclovir, 3-18 g/L copper nitrate, 15-29 mol/L deionized water, 0.75-1.64 mol/L diethanolamine and 14.4-27 mol/L absolute ethyl alcohol.

10. An antibacterial and antiviral stainless steel prepared by the preparation method of any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of metal material surface treatment, in particular to antibacterial and antiviral stainless steel and a preparation method thereof.

Background

The stainless steel is an alloy material with excellent corrosion resistance, wear resistance and toughness, has excellent mechanical property and good chemical stability, and has wide application in the building industry, furniture, kitchen equipment, automobile industry, office supplies and the like. Along with the improvement of living standard, people pay more and more attention to environment and self health, and stainless steel material can promote bacterial growth if contacting grease etc. in the use, brings adverse effect to people's health. Therefore, research and development of the antibacterial stainless steel become research hotspots of novel functional stainless steel in recent years, and the antibacterial stainless steel not only can maintain the mechanical property and the surface smoothness of a stainless steel matrix, but also has a certain antibacterial effect.

The antibacterial stainless steel can be roughly classified into alloy type antibacterial stainless steel added with antibacterial metal elements and surface coating type antibacterial stainless steel according to different preparation methods. The alloy type antibacterial stainless steel added with the antibacterial metal element refers to alloy type antibacterial stainless steel in which the antibacterial metal element is uniformly dispersed in the stainless steel by adding the antibacterial metal element in the preparation process of the stainless steel and then casting. For example, CN105543709A discloses a copper-containing antibacterial stainless steel, which is prepared from 60-90 parts of iron ore and 20-50 parts of copper ore, and the specific preparation method comprises: grinding the raw materials into powder, sieving with 1500-mesh sieve at 800-. Although the preparation method can enable the stainless steel to have a certain antibacterial effect, the use of a large amount of antibacterial element copper can increase the raw material cost, the preparation process is complicated, the energy consumption is high, and the preparation method is not suitable for large-scale popularization.

Compared with the alloy type antibacterial stainless steel added with antibacterial metal elements, the research on the surface coating type antibacterial stainless steel is more. For example, CN202619086U discloses a commercial photocatalyst antibacterial self-cleaning stainless steel workbench, wherein a titanium dioxide coating is disposed on the surface of the stainless steel workbench, so that the stainless steel workbench can efficiently kill bacteria and viruses on the outer surface under ultraviolet irradiation, and has an oil stain self-cleaning function, but the stainless steel workbench utilizes the photocatalytic property of titanium dioxide to kill viruses and bacteria, and can only exert a killing effect under illumination, thereby greatly limiting the service environment of the stainless steel workbench.

CN108950498A discloses a preparation method of an antibacterial stainless steel plate, which comprises grinding and polishing, acid washing and alkali washing, molybdenum treatment by plasma permeation, hot rolling and densification, passivation and antibacterial layer preparation, wherein the preparation method improves the wear resistance and corrosion resistance of the stainless steel surface layer through double protection of a molybdenum layer and a passivation layer, and improves the antibacterial performance of the stainless steel through a surface antibacterial layer, but the antibacterial layer is formed by soaking and calcining of antibacterial liquid, so that the problem of uneven distribution of the antibacterial layer is solved, and the antibacterial performance is easily peeled off to be greatly reduced.

CN108950575A discloses a preparation process of an antibacterial stainless steel, which comprises cleaning, polishing, acid cleaning, passivation, alkaline water washing, neutralization, vacuum coating, hot-pressing sintering, diffusion plating, sintering and annealing treatment, wherein antibacterial components in an antibacterial solution can be permeated and fixed on the surface layer of the stainless steel only through the vacuum coating, hot-pressing sintering, diffusion plating, sintering and annealing treatment, so that the preparation process is complex in operation, consumes a large amount of energy and is not suitable for large-scale popularization.

CN109930191A discloses an antibacterial stainless steel and a preparation method thereof, which comprises the steps of pretreating the stainless steel, placing the pretreated stainless steel in an acid solution, carrying out oxidation and coloring treatment by adopting alternating current, and then carrying out hole sealing treatment to obtain the antibacterial stainless steel. The preparation method adopts electrodeposition to attach the antibacterial ingredients to the surface of the stainless steel, so that the cost is high, the operation is complicated, and the rapid production is not facilitated.

However, since the safety of people's lives and properties has been seriously threatened by various viruses in recent years, especially viruses such as SARS virus, H1N1 influenza virus, dengue virus, Ebola virus and novel coronavirus cause millions of human infections and deaths worldwide. Currently, some viruses are still abundantly spread in certain regions and countries. Among various methods for coping with viral infection, although antiviral vaccines are the most effective, since vaccines have specificity and only prevent infection by specific viruses, development of antiviral materials, particularly antiviral stainless steel, which can effectively kill various viruses is required.

In summary, there is a need to develop an antibacterial and antiviral stainless steel and a preparation method thereof, so that the stainless steel has antibacterial and antiviral properties, meets the diversified and complex antibacterial and antiviral requirements of people, and can be popularized on a large scale.

Disclosure of Invention

In view of the problems in the prior art, the invention provides an antibacterial and antiviral stainless steel and a preparation method thereof, wherein the preparation method comprises the steps of anodizing the stainless steel, forming an anodic oxidation film with micropores on the surface of the stainless steel, and attaching antibacterial and antiviral components derived from two sols to the micropores and the surface of the anodic oxidation film through twice sol soaking and heating treatment, so that the stainless steel has good and lasting antibacterial and antiviral properties; moreover, the preparation method is simple to operate and is beneficial to large-scale popularization.

In order to achieve the purpose, the invention adopts the following technical scheme:

one of the purposes of the invention is to provide a preparation method of an antibacterial and antiviral stainless steel, which comprises the following steps:

(1) anodizing the stainless steel to form an anodized film with micropores on the surface of the stainless steel;

(2) soaking the stainless steel obtained by the anodic oxidation in the step (1) in the sol A, and then taking out the soaked stainless steel for primary heating to obtain an antibacterial and antiviral stainless steel crude product;

(3) soaking the antibacterial and antiviral stainless steel crude product obtained in the step (2) in the sol B, taking out the soaked stainless steel, and heating for the second time to obtain antibacterial and antiviral stainless steel;

wherein the sol A comprises butyl titanate, and the sol B comprises valacyclovir hydrochloride and acyclovir.

According to the preparation method, an anodic oxidation film with micropores is formed on the surface of the stainless steel through anodic oxidation, the butyl titanate in the sol A is mainly decomposed into nano titanium dioxide through one-time heating, and the nano titanium dioxide serving as an antibacterial and antiviral inorganic compound and the valaciclovir hydrochloride and the acyclovir serving as an antibacterial and antiviral organic compound are compounded through two-time sol soaking and heating treatment, so that the nano titanium dioxide is filled in the micropores of the anodic oxidation film and is attached to the surface of the anodic oxidation film, the stainless steel has good and lasting antibacterial and antiviral performances, the antibacterial rate is greater than or equal to 99%, and the antiviral rate is greater than or equal to 99%; moreover, the preparation method is simple to operate and is beneficial to large-scale popularization.

The following technical solutions are preferred but not limited to the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and realized by the following technical solutions.

As a preferable embodiment of the present invention, the stainless steel is pretreated before the anodic oxidation in the step (1).

Preferably, the pretreatment sequentially comprises mechanical polishing, chemical degreasing and electrochemical polishing.

Preferably, the mechanical polishing is surface grinding by using sand paper, and the grinding is carried out from 400 meshes to 3000 meshes.

Preferably, the chemical degreasing is performed using a degreasing liquid.

Preferably, the degreasing fluid comprises 40-50 g/L of sodium hydroxide, such as 40g/L, 42g/L, 44g/L, 45g/L, 46g/L, 48g/L or 50g/L, etc., 10-35 g/L of sodium carbonate, such as 10g/L, 15g/L, 20g/L, 25g/L, 30g/L or 35g/L, etc., 5-15 g/L of sodium gluconate, such as 5g/L, 8g/L, 10g/L, 11g/L, 14g/L or 15g/L, etc., but not limited to the recited values, and other values not recited in the respective value ranges are also applicable.

Preferably, the chemical degreasing temperature is 65-85 ℃, such as 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 85 ℃, and the time is 5-15 min, such as 5min, 8min, 11min, 14min or 15min, but the chemical degreasing temperature is not limited to the recited values, and other non-recited values in the respective value ranges are also applicable.

Preferably, the electrochemical polishing is performed in a polishing liquid.

Preferably, the polishing slurry has a composition comprising 22 to 28g/L of phosphoric acid, such as 22g/L, 24g/L, 26g/L, or 28g/L, etc., 10 to 16g/L of sulfuric acid, such as 10g/L, 12g/L, 14g/L, or 16g/L, etc., and 0.5 to 2g/L of glycerol, such as 0.5g/L, 1g/L, 1.5g/L, or 2g/L, etc., but not limited to the recited values, and other values not recited within the respective ranges of values are equally applicable.

Preferably, the electrochemical polishing temperature is 40-65 deg.C, such as 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C or 65 deg.C, time is 3-20 min, such as 3min, 8min, 13min, 18min or 20min, and current density is 10-55A/dm²E.g. 10A/dm²、20A/dm²、30A/dm²、40A/dm²、50A/dm²Or 55A/dm²And the like, but are not limited to the recited numerical values, and other numerical values not recited in the respective numerical ranges are also applicable.

After the mechanical polishing, the chemical degreasing and the electrochemical polishing, the stainless steel is washed by water to remove residual solution, so that the influence on subsequent treatment is avoided; in addition, through mechanical polishing, chemical degreasing and electrochemical polishing, oil stains, impurities, dust and the like on the surface of the stainless steel can be effectively removed, and the subsequent two sol soaking and heating treatments are facilitated.

In a preferred embodiment of the present invention, the anodic oxidation in the step (1) is performed in an acidic oxidizing solution.

Preferably, the composition of the acidic oxidizing solution comprises sulfuric acid, molybdenum salt and cerium salt.

Preferably, the acidic oxidizing solution has a composition comprising 200 to 300g/L sulfuric acid, such as 200g/L, 220g/L, 240g/L, 250g/L, 270g/L, 280g/L or 300g/L, molybdenum salt 20 to 35g/L, such as 20g/L, 25g/L, 30g/L or 35g/L, cerium salt 2 to 8g/L, such as 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L or 8g/L, but not limited to the recited values, and other values not recited in the respective ranges of values are also applicable.

Preferably, the molybdenum salt comprises ammonium molybdate and/or sodium molybdate.

Preferably, the cerium salt comprises cerium nitrate and/or cerium sulfate.

In a preferred embodiment of the present invention, the anodic oxidation in step (1) is performed by using a direct current, the stainless steel as an anode, and graphite as a cathode.

Preferably, the supply voltage of the dc current is 5 to 20V, for example, 5V, 10V, 15V, or 20V, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.

Preferably, the anodizing treatment time in step (1) is 20-35 min, such as 20min, 25min, 30min or 35min, but not limited to the recited values, and other values in the range are also applicable.

Preferably, the treatment temperature of the anodic oxidation in the step (1) is 10 to 15 ℃, for example, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃ or 15 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

As a preferable technical scheme of the invention, the sol A in the step (2) further comprises silver nitrate and/or iodate.

Preferably, the composition of the sol A in the step (2) comprises 0.8-1.5 mol/L of butyl titanate, such as 0.8mol/L, 1.0mol/L, 1.2mol/L, 1.4mol/L or 1.5 mol/L; 0.64-1.2 mol/L of silver nitrate, such as 0.64mol/L, 0.74mol/L, 0.84mol/L, 0.9mol/L, 1.04mol/L, 1.1mol/L or 1.2 mol/L; 20-35 g/L iodate, such as 20g/L, 22g/L, 25g/L, 28g/L, 30g/L, 32g/L or 35g/L and the like; 14.4-27 mol/L of absolute ethyl alcohol, such as 14.4mol/L, 15mol/L, 18mol/L, 20mol/L, 22mol/L, 25mol/L, 26mol/L or 27 mol/L; 15-29 mol/L deionized water, such as 15mol/L, 18mol/L, 20mol/L, 22mol/L, 24mol/L, 27mol/L or 29mol/L and the like; diethanolamine 0.75-1.64 mol/L, such as 0.75mol/L, 0.9mol/L, 1.1mol/L, 1.3mol/L, 1.5mol/L or 1.64 mol/L; however, the numerical values are not limited to the specific ones, and other numerical values not specified in the respective numerical ranges are also applicable.

Preferably, the iodate comprises any one or a combination of at least two of sodium iodate, potassium iodate, calcium iodate, or magnesium iodate, with typical but non-limiting examples being: combinations of sodium iodate and potassium iodate, potassium iodate and calcium iodate, calcium iodate and magnesium iodate, or sodium iodate and magnesium iodate, and the like.

The sol A comprises butyl titanate, silver nitrate and iodate, after the sol A is heated for the next time, the butyl titanate is mainly decomposed into nano titanium dioxide, the silver nitrate is mainly decomposed into nano silver oxide, the iodate is mainly decomposed into a nano iodine simple substance, and an antibacterial and antiviral inorganic compound formed by compounding three nano materials has synergistic effect, so that the antibacterial and antiviral performance can be better exerted; in addition, the sol A is prepared according to a specific proportion, so that the sol A has good viscosity, is more easily combined with an anodic oxide film of stainless steel, and is not easy to flow in the subsequent heating process, thereby avoiding the problem of uneven adhesion of the sol.

In a preferred embodiment of the present invention, the temperature of the soaking in the step (2) is 15 to 25 ℃, for example, 15 ℃, 17 ℃, 19 ℃, 20 ℃, 22 ℃ or 25 ℃, but the temperature is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.

Preferably, the soaking time in step (2) is 20-45 min, such as 20min, 25min, 30min, 35min, 40min or 45min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the temperature of the first heating in step (2) is 500 to 800 ℃, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the time for one heating in step (2) is 8-25 min, such as 8min, 10min, 13min, 15min, 18min, 20min, 22min or 25min, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.

According to the invention, the temperature is controlled to be 500-800 ℃ in one-time heating, the time is 8-25 min, so that the butyl titanate in the sol A can be mainly decomposed into nano titanium dioxide, the silver nitrate is mainly decomposed into nano silver oxide, the iodate is mainly decomposed into a nano iodine simple substance, and the absolute ethyl alcohol, the deionized water and the diethanol amine can be sufficiently evaporated, so that the antibacterial and antiviral inorganic compound compounded by three nano materials can be uniformly attached to the micropores and the surface of the anodic oxide film.

As a preferable technical solution of the present invention, the sol B in the step (3) further includes copper nitrate.

Preferably, the composition of the sol B in the step (3) comprises 5-15 g/L of valacyclovir hydrochloride, such as 5g/L, 8g/L, 10g/L, 11g/L, 14g/L or 15 g/L; 4-20 g/L of acyclovir, such as 4g/L, 8g/L, 10g/L, 12g/L, 15g/L, 18g/L or 20g/L and the like; 3-18 g/L of copper nitrate, such as 3g/L, 5g/L, 8g/L, 10g/L, 12g/L, 15g/L, 16g/L or 18 g/L; 15-29 mol/L deionized water, such as 15mol/L, 18mol/L, 20mol/L, 22mol/L, 24mol/L, 27mol/L or 29mol/L and the like; diethanolamine 0.75-1.64 mol/L, such as 0.75mol/L, 0.9mol/L, 1.1mol/L, 1.3mol/L, 1.5mol/L or 1.64 mol/L; 14.4-27 mol/L of absolute ethyl alcohol, such as 14.4mol/L, 15mol/L, 18mol/L, 20mol/L, 22mol/L, 25mol/L, 26mol/L or 27 mol/L; however, the numerical values are not limited to the specific ones, and other numerical values not specified in the respective numerical ranges are also applicable.

The sol B comprises valacyclovir hydrochloride, acyclovir and copper nitrate, and after subsequent secondary heating, the copper nitrate can be guaranteed to be mainly decomposed into nano copper oxide and nano cuprous oxide, and the valacyclovir hydrochloride and the acyclovir are not decomposed by heating, so that a compound antibacterial and antiviral material is formed by the synergistic effect of the valacyclovir hydrochloride, the nano cuprous oxide and the nano copper oxide, and the antibacterial and antiviral performance is further exerted; in addition, the sol B is prepared according to a specific proportion, so that the sol B has good viscosity, is more easily combined with an anodic oxide film of stainless steel, and is not easy to flow in the subsequent secondary heating process, thereby avoiding the problem of uneven adhesion of the sol.

In a preferred embodiment of the present invention, the temperature of the soaking in the step (3) is 15 to 25 ℃, for example, 15 ℃, 17 ℃, 19 ℃, 20 ℃, 22 ℃ or 25 ℃, but the temperature is not limited to the above-mentioned values, and other values not shown in the above-mentioned range of values are also applicable.

Preferably, the soaking time in step (3) is 8-19 min, such as 8min, 10min, 12min, 15min, 17min or 19min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the temperature of the primary heating in step (3) is 170 to 270 ℃, for example 170 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃ or 270 ℃, 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 one heating in step (3) is 11-38 min, such as 11min, 15min, 19min, 23min, 27min, 31min, 35min or 38min, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.

According to the invention, the secondary heating is carried out at the temperature of 170-270 ℃ for 11-38 min, so that the copper nitrate in the sol B is mainly decomposed into nano copper oxide and nano cuprous oxide, valaciclovir hydrochloride and acyclovir are not decomposed by heating, and absolute ethyl alcohol, deionized water and diethanol amine can be sufficiently evaporated, so that a compound antibacterial and antiviral material is formed under the synergistic action of the three components and is uniformly attached to micropores and the surface of an anodic oxide film.

As a preferred technical scheme of the invention, the preparation method comprises the following steps:

(1) firstly, sequentially carrying out mechanical polishing, chemical degreasing and electrochemical polishing on stainless steel as pretreatment, and then carrying out anodic oxidation in an acidic oxidation solution to form an anodic oxidation film with micropores on the surface of the stainless steel;

wherein, the mechanical polishing is to polish the surface by using sand paper, and the surface is polished from 400 meshes to 3000 meshes; the chemical oil removal is carried out by adopting oil removal liquid, the oil removal liquid comprises 40-50 g/L of sodium hydroxide, 10-35 g/L of sodium carbonate and 5-15 g/L of sodium gluconate, the temperature of the chemical oil removal is 65-85 ℃, and the time is 5-15 min; the electrochemical polishing is carried out in a polishing solution, the polishing solution comprises 22-28 g/L of phosphoric acid, 10-16 g/L of sulfuric acid and 0.5-2 g/L of glycerol, the electrochemical polishing temperature is 40-65 ℃, the time is 3-20 min, and the current density is 10-55A/dm²；

The acidic oxidizing solution comprises 200-300 g/L of sulfuric acid, 20-35 g/L of molybdenum salt and 2-8 g/L of cerium salt; the anodic oxidation adopts direct current, the stainless steel is used as an anode, the graphite is used as a cathode, the power supply voltage of the direct current is 5-20V, the treatment time of the anodic oxidation is 20-35 min, and the treatment temperature of the anodic oxidation is 10-15 ℃;

(2) soaking the stainless steel obtained by the anodic oxidation in the step (1) in the sol A for 20-45 min at the soaking temperature of 15-25 ℃, taking out the soaked stainless steel, and heating at 500-800 ℃ for 8-25 min for one time to obtain an antibacterial and antiviral stainless steel crude product;

wherein the sol A comprises 0.8-1.5 mol/L of butyl titanate, 0.64-1.2 mol/L of silver nitrate, 20-35 g/L of iodate, 14.4-27 mol/L of absolute ethyl alcohol, 15-29 mol/L of deionized water and 0.75-1.64 mol/L of diethanolamine; the iodate comprises any one or a combination of at least two of sodium iodate, potassium iodate, calcium iodate or magnesium iodate;

(3) soaking the antibacterial and antiviral stainless steel crude product obtained in the step (2) in the sol B for 8-19 min at the soaking temperature of 15-25 ℃, taking out the soaked stainless steel, and carrying out secondary heating at 170-270 ℃ for 11-38 min to obtain antibacterial and antiviral stainless steel;

the sol B comprises 5-15 g/L valacyclovir hydrochloride, 4-20 g/L acyclovir, 3-18 g/L copper nitrate, 15-29 mol/L deionized water, 0.75-1.64 mol/L diethanolamine and 14.4-27 mol/L absolute ethyl alcohol.

The second purpose of the invention is to provide the antibacterial and antiviral stainless steel prepared by the preparation method of the first purpose.

Compared with the prior art, the invention at least has the following beneficial effects:

(1) according to the preparation method, an anodic oxidation film with micropores is formed on the surface of the stainless steel through anodic oxidation, and then through sol soaking and heating treatment for two times, antibacterial and antiviral inorganic compounds such as nano titanium dioxide and valaciclovir hydrochloride and acyclovir which are used as antibacterial and antiviral organic compounds are compounded together, so that the antibacterial and antiviral inorganic compounds are filled in the micropores of the anodic oxidation film and attached to the surface of the anodic oxidation film, the stainless steel has good and lasting antibacterial and antiviral properties, the antibacterial rate is more than or equal to 99%, and the antiviral rate is more than or equal to 99%;

(2) the preparation method disclosed by the invention is short in process, simple to operate and beneficial to large-scale popularization.

Drawings

FIG. 1 is a schematic cross-sectional view of an antibacterial and antiviral stainless steel according to example 1 of the present invention;

in the figure: 1-stainless steel; 2-anodic oxide film; 3-micropores; 41-composite antibacterial and antiviral components on the surface of the film layer; 42-composite antibacterial and antiviral component in micropores.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. 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.

The preparation method of the antibacterial and antiviral stainless steel comprises the following steps:

(1) anodizing the stainless steel to form an anodized film with micropores on the surface of the stainless steel;

(2) soaking the stainless steel obtained by the anodic oxidation in the step (1) in the sol A, and then taking out the soaked stainless steel for primary heating to obtain an antibacterial and antiviral stainless steel crude product;

(3) soaking the antibacterial and antiviral stainless steel crude product obtained in the step (2) in the sol B, taking out the soaked stainless steel, and heating for the second time to obtain antibacterial and antiviral stainless steel;

wherein the sol A comprises butyl titanate, and the sol B comprises valacyclovir hydrochloride and acyclovir.

Typical but non-limiting examples of the invention are as follows: