CN111763978A

CN111763978A - Antibacterial and antiviral aluminum alloy and preparation method thereof

Info

Publication number: CN111763978A
Application number: CN202010624237.2A
Authority: CN
Inventors: 薛烽; 于红光; 李梦婷
Original assignee: Nanjing Tongxi Tongkang Antibacterial Material Technology Co ltd
Current assignee: Anhui Tongxi Hi Tech New Material Co ltd
Priority date: 2020-06-30
Filing date: 2020-06-30
Publication date: 2020-10-13
Anticipated expiration: 2040-06-30
Also published as: CN111763978B

Abstract

The invention relates to an antibacterial and antiviral aluminum alloy and a preparation method thereof, wherein the preparation method comprises the following steps: (1) carrying out anodic oxidation on an aluminum alloy to form an anodic oxidation film with micropores on the surface of the aluminum alloy; (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 aluminum alloy; wherein the sol A comprises butyl titanate, and the sol B comprises ribavirin and acyclovir. According to the preparation method, butyl titanate in the sol A is mainly decomposed into nano titanium dioxide through one-time heating, and through two-time sol soaking and heating treatment, nano titanium dioxide, ribavirin and acyclovir composite antibacterial and antiviral components are attached to micropores and the surface of an anodic oxide film, so that the aluminum alloy has good and lasting antibacterial and antiviral properties; moreover, the preparation method is simple to operate and is beneficial to large-scale popularization.

Description

Antibacterial and antiviral aluminum alloy and preparation method thereof

Technical Field

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

Background

Aluminum alloy is a non-ferrous metal material which is most widely applied in industry, widely applied to aviation, automobiles, ships, mechanical manufacturing, chemical industry and the like, and is a non-ferrous metal material which can be frequently contacted in daily life of people. Along with the rapid development of industrial economy, the demand of aluminum alloy is increasing day by day, but the aluminum alloy is easy to breed bacteria in humid air to generate corrosion phenomenon, originally, small spot corrosion can spread into large scale corrosion along with the continuous increase of corrosion degree, and the use and decoration effect of the aluminum alloy are seriously influenced. Therefore, research and development of antibacterial aluminum alloy become a research hotspot of novel functional aluminum alloy in recent years, and the antibacterial aluminum alloy not only can maintain the mechanical property and the surface smoothness of an aluminum alloy matrix, but also has a certain antibacterial effect.

The antibacterial aluminum alloys can be roughly classified into alloy type antibacterial aluminum alloys to which antibacterial metal elements are added and surface coating type antibacterial aluminum alloys according to different preparation methods. The alloy type antibacterial aluminum alloy added with the antibacterial metal elements refers to the alloy type antibacterial aluminum alloy which is formed by adding the antibacterial metal elements in the preparation process of the aluminum alloy and further casting the alloy type antibacterial aluminum alloy with the antibacterial metal elements uniformly dispersed in the aluminum alloy. For example, CN107267814A discloses an antibacterial aluminum alloy and a preparation method thereof, which comprises adding a proper amount of one or two of Cu and Ag into aluminum, and performing antibacterial treatment to disperse and separate out a nano-copper-rich phase or a silver-rich phase, wherein the nano-copper-rich phase or the silver-rich phase is uniformly distributed in an aluminum alloy matrix, so as to endow the aluminum alloy with good antibacterial performance. Although the antibacterial aluminum alloy has certain antibacterial performance, the use of a large amount of antibacterial metal elements can increase the raw material cost, the preparation process is complicated, the energy consumption is high, and the antibacterial aluminum alloy is not suitable for large-scale popularization.

Compared with the alloy type antibacterial aluminum alloy added with the antibacterial metal elements, the research on the surface coating type antibacterial aluminum alloy is more. For example, CN109161885A discloses an antibacterial functional modification method for aluminum alloy surface, which uses aluminum alloy as a substrate, and firstly hydroxylates the aluminum alloy surface by a simple and environment-friendly water treatment method to make the surface have reaction activity; then, the chemical activity of the antibacterial quaternary ammonium salt which can perform coupling reaction with hydroxyl is utilized to perform dehydration coupling reaction with the hydroxyl on the surface of the activated aluminum alloy, and the antibacterial quaternary ammonium salt is grafted to the surface of the aluminum alloy, so that the surface of the aluminum alloy obtains an antibacterial function. Although the method can endow the aluminum alloy with certain antibacterial performance, the antibacterial components are only limited to the antibacterial quaternary ammonium salt, cannot meet the multielement and complex antibacterial requirements, and is not suitable for large-scale popularization.

CN109881235A discloses an antibacterial treatment method for the surface of an aluminum alloy, the method comprises the steps of cleaning the surface of the aluminum alloy, polishing, degreasing the surface of the aluminum alloy through a sodium carbonate solution, anodizing to obtain the aluminum alloy with an oxide film, placing the aluminum alloy in a colorless nano silver solution, performing ultrasonic treatment, taking out, baking, repeating the ultrasonic treatment and baking operations for 4-5 times, and naturally cooling to obtain the antibacterial treated aluminum alloy. Although the method can endow the aluminum alloy with certain antibacterial performance, the antibacterial component is only limited to nano silver, and the method can not meet the multielement and complex antibacterial requirement, has the defect of high price and is not suitable for large-scale popularization.

CN107130276A discloses an antibacterial aluminum and its manufacturing method, which comprises preparing a porous alumina membrane layer by anodic oxidation, depositing an antibacterial metal in the pores of the porous alumina membrane layer by electrolytic deposition, and finally sealing the pores by boiling water sealing treatment. Although the manufacturing method can ensure that the antibacterial metal is deposited uniformly, firmly and stably to achieve a certain antibacterial effect, the manufacturing method has the advantages of higher cost and complex operation, and is not beneficial to rapid production.

CN110055572A discloses a method for surface treatment of aluminum alloy, which comprises the steps of carrying out pretreatment such as sand blasting, alkali washing and acid washing on the aluminum alloy, placing the aluminum alloy in an acidic oxidizing solution, alternately carrying out oxidation and deposition under the condition of alternating current, then reducing voltage, and carrying out hole sealing treatment in the same solution to obtain the antibacterial aluminum alloy. Although the manufacturing method can ensure that the antibacterial metal is deposited uniformly, firmly and stably to achieve a certain antibacterial effect, the manufacturing method has the advantages of higher cost and complex operation, and is not beneficial to rapid production.

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 aluminum alloys, which can effectively kill various viruses is required. For example, CN103781945A discloses an antiviral aluminum component and a manufacturing method thereof, the manufacturing method includes the following steps: anodizing an aluminum material composed of aluminum or an aluminum alloy to form a surface film having micropores on the surface of the aluminum material; and depositing an antiviral inorganic compound in the micropores of the aluminum material surface film by electrochemical treatment. Although the antiviral aluminum component has certain antiviral performance, the manufacturing method needs to perform not only electrodeposition but also soaking treatment after anodic oxidation, and the operation is relatively complicated, which is not favorable for rapid production.

In summary, there is a need to develop an antibacterial and antiviral aluminum alloy and a preparation method thereof, so that the aluminum alloy 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 aluminum alloy and a preparation method thereof, wherein the preparation method comprises the steps of carrying out anodic oxidation on the aluminum alloy, forming an anodic oxidation film with micropores on the surface of the aluminum alloy, and then carrying out sol soaking and heating treatment twice to attach antibacterial and antiviral components derived from two kinds of sol into the micropores of the anodic oxidation film and onto the surface of the anodic oxidation film, so that the aluminum alloy 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 aluminum alloy, which comprises the following steps:

(1) carrying out anodic oxidation on an aluminum alloy to form an anodic oxidation film with micropores on the surface of the aluminum alloy;

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

(3) soaking the antibacterial and antiviral aluminum alloy crude product obtained in the step (2) in the sol B, and then taking out the soaked aluminum alloy for secondary heating to obtain an antibacterial and antiviral aluminum alloy;

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

According to the preparation method, an anodic oxidation film with micropores is formed on the surface of the aluminum alloy 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 ribavirin and 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 attached to the surface of the anodic oxidation film, the aluminum alloy 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 aluminum alloy is pretreated before the anodic oxidation in the step (1).

Preferably, the pretreatment comprises sand blasting, alkali washing and acid washing in sequence.

Preferably, the sand used for sand blasting has a particle size of 50 to 150 mesh, for example, 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh, 100 mesh, 110 mesh, 120 mesh, 130 mesh, 140 mesh or 150 mesh, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

The sand blasting is carried out on the surface of the aluminum alloy uniformly by adopting a sand blasting machine, so that impurities and scratches on the surface of the aluminum alloy can be removed. After the sand blasting treatment is finished, the ethanol is adopted for ultrasonic cleaning and water washing in sequence, so that the adverse effect on the next alkali washing can be effectively reduced.

Preferably, the alkaline cleaning is performed by using 40-50 g/L sodium hydroxide solution, such as 40g/L, 41g/L, 42g/L, 43g/L, 44g/L, 45g/L, 46g/L, 47g/L, 48g/L, 49g/L or 50g/L, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.

Preferably, the temperature of the alkaline washing is 40 to 65 ℃, for example 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ or 65 ℃, 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 of the alkaline washing is 5-9 min, such as 5min, 6min, 7min, 8min or 9min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the acid washing is performed with 100-150 g/L nitric acid solution, such as 100g/L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L, etc., 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 acid washing is 20 to 30 ℃, for example, 20 ℃, 22 ℃, 24 ℃, 25 ℃, 26 ℃, 28 ℃ or 30 ℃, 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 the acid washing is 0.5 to 2min, such as 0.5min, 1min, 1.5min or 2min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.

After the alkali washing and the acid washing, the aluminum alloy is washed by water to remove residual alkali or acid, so that the influence on subsequent treatment is avoided; in addition, through alkali washing and acid washing, oil stains, impurities, dust and the like on the surface of the aluminum alloy can be effectively removed, and the subsequent two sol soaking and heating treatment can be more favorably carried out.

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

Preferably, the acidic oxidizing solution is a sulfuric acid solution of 150-210 g/L, such as 150g/L, 160g/L, 170g/L, 180g/L, 190g/L, 200g/L, or 210g/L, but not limited to the recited values, and other values not recited in the range of values are also applicable.

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

Preferably, the current density of the direct current is 2.5-10A/dm²For example 2.5A/dm²、3A/dm²、4A/dm²、5.5A/dm²、6A/dm²、7A/dm²、8A/dm²、9A/dm²Or 10A/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 supply voltage of the dc current is 18 to 35V, for example 18V, 20V, 22V, 26V, 30V, 34V or 35V, but is not limited to the values listed, and other values not listed in the range of 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; the above concentrations are not limited to the recited values, and other values not recited within the respective 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 tetrabutyl titanate, silver nitrate and iodate, wherein after the tetrabutyl titanate is heated for the next time, the tetrabutyl titanate is mainly decomposed into nano titanium dioxide, the silver nitrate is mainly decomposed into nano silver oxide and a silver simple substance, the iodate is mainly decomposed into a nano iodine simple substance and an iodine compound, 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 easy to combine with an anodic oxide film of an aluminum alloy, is not easy to flow in the subsequent heating process, and further avoids 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 ribavirin, 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; the above concentrations are not limited to the recited values, and other values not recited within the respective ranges are also applicable.

The sol B comprises ribavirin, acyclovir and copper nitrate, and after subsequent secondary heating, the sol B not only can ensure that the copper nitrate is mainly decomposed into nano copper oxide and nano cuprous oxide, but also can not ensure that the ribavirin and the acyclovir are decomposed by heating, and the ribavirin, the acyclovir, the nano cuprous oxide, the nano copper oxide and the nano cuprous oxide synergistically act to form a compound antibacterial and antiviral material, so that the antibacterial and antiviral properties are 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 an aluminum alloy, is not easy to flow in the subsequent secondary heating process, and further avoids 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, the ribavirin and the acyclovir are not decomposed by heating, and the absolute ethyl alcohol, the deionized water and the diethanol amine can be sufficiently evaporated, so that the three materials are synergistic to form a compound antibacterial and antiviral material and are uniformly attached to micropores and the surface of the anodic oxide film.

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

(1) firstly, sequentially carrying out sand blasting, alkali washing and acid washing on the aluminum alloy 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 aluminum alloy;

wherein the sand used for sand blasting has a particle size of 50-150 meshes; the alkaline washing adopts 40-50 g/L sodium hydroxide solution, the temperature of the alkaline washing is 40-65 ℃, and the time is 5-9 min; the pickling is carried out by adopting 100-150 g/L nitric acid solution, the pickling temperature is 20-30 ℃, and the pickling time is 0.5-2 min;

the anodic oxidation is carried out in a sulfuric acid solution of 150-210 g/L, the anodic oxidation adopts direct current, the aluminum alloy is used as an anode, graphite is used as a cathode, and the anodic oxidation is carried out in the presence of a sulfuric acid solution of 150-210 g/LThe current density of the direct current is 2.5-10A/dm²The power supply voltage of the direct current is 18-35V, 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 aluminum alloy 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 aluminum alloy, and heating at 500-800 ℃ for 8-25 min for one time to obtain an antibacterial and antiviral aluminum alloy 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 aluminum alloy 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 aluminum alloy, and carrying out secondary heating at 170-270 ℃ for 11-38 min to obtain an antibacterial and antiviral aluminum alloy;

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

The second purpose of the invention is to provide the antibacterial and antiviral aluminum alloy 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 aluminum alloy through anodic oxidation, and then the antibacterial and antiviral inorganic compounds such as nano titanium dioxide and the like and the ribavirin and the acyclovir which are antibacterial and antiviral organic compounds are compounded together through sol soaking and heating for two times, 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 aluminum alloy 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 scanning electron microscope image of the surface of the antibacterial and antiviral aluminum alloy according to example 1 of the present invention, wherein the dark color region is an anodic oxide film, and the light color region is a composite antibacterial and antiviral component;

FIG. 2 is a schematic cross-sectional view of an antibacterial and antiviral aluminum alloy according to example 1 of the present invention;

in the figure: 1-an aluminum alloy; 2-anodic oxide film; 3-micropores; 4-composite antibacterial and antiviral component; 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 aluminum alloy comprises the following steps:

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

example 1

The embodiment provides a preparation method of an antibacterial and antiviral aluminum alloy, which comprises the following steps:

(1) firstly, sequentially carrying out sand blasting, alkali washing and acid washing on the aluminum alloy as pretreatment, wherein the grain diameter of sand used for sand blasting is 120 meshes, the alkali washing adopts 45g/L sodium hydroxide solution, the alkali washing is carried out for 7min at 55 ℃, the acid washing is carried out after the washing with water, the acid washing adopts 130g/L nitric acid solution, the acid washing is carried out for 1.5min at 25 ℃, and the drying is carried out after the washing with water; then carrying out anodic oxidation in 200g/L sulfuric acid solution, adopting direct current with the current density of 9A/dm and the aluminum alloy as an anode and graphite as a cathode²Forming an anodic oxide film with micropores on the surface of the aluminum alloy by performing anodic oxidation treatment at 15 ℃ for 30min under the condition that the power supply voltage is 30V;

(2) soaking the aluminum alloy obtained by the anodic oxidation in the step (1) in the sol A for 35min at the temperature of 20 ℃, taking out the soaked aluminum alloy, and heating at 600 ℃ for 13min for one time to obtain an antibacterial and antiviral aluminum alloy crude product;

wherein the composition of the sol A is 1.2mol/L of butyl titanate, 0.9mol/L of silver nitrate, 27g/L of sodium iodate, 18mol/L of absolute ethyl alcohol, 20mol/L of deionized water and 1.15mol/L of diethanolamine;

(3) soaking the antibacterial and antiviral aluminum alloy crude product obtained in the step (2) in the sol B for 15min at the temperature of 25 ℃, taking out the soaked aluminum alloy, and carrying out secondary heating at the temperature of 230 ℃ for 23min to obtain an antibacterial and antiviral aluminum alloy;

the sol B comprises 13g/L of ribavirin, 15g/L of acyclovir, 9g/L of copper nitrate, 19mol/L of deionized water, 1.16mol/L of diethanolamine and 20mol/L of absolute ethyl alcohol.

Fig. 1 is a scanning electron microscope image of the surface of the antibacterial and antiviral aluminum alloy prepared in the embodiment, wherein a dark color region is an anodic oxide film 2, and a light color region is a composite antibacterial and antiviral component 4;

fig. 2 is a schematic cross-sectional view of the antibacterial and antiviral aluminum alloy prepared in this embodiment, and as can be seen from fig. 2, by using the method for preparing an antibacterial and antiviral aluminum alloy according to the present invention, an anodic oxide film 2 with micropores 3 is formed on the surface of an aluminum alloy 1, and after two sol soaking and heating treatments, composite antibacterial and antiviral components 42 in the micropores are attached to the micropores 3, and composite antibacterial and antiviral components 41 on the surface of the film layer are attached to the surface of the anodic oxide film 2.

Example 2

This example provides a method for preparing an antibacterial and antiviral aluminum alloy, except that silver nitrate in the sol a in step (2) is omitted, that is, the composition of the sol a is 1.2mol/L of butyl titanate, 27g/L of sodium iodate, 18mol/L of absolute ethanol, 20mol/L of deionized water, and 1.15mol/L of diethanolamine, and other conditions are the same as those in example 1.

Example 3

This example provides a method for preparing an antibacterial and antiviral aluminum alloy, except that sodium iodate in the sol a in step (2) is omitted, that is, the composition of the sol a is 1.2mol/L butyl titanate, 0.9mol/L silver nitrate, 18mol/L absolute ethyl alcohol, 20mol/L deionized water, and 1.15mol/L diethanolamine, and the other conditions are the same as those in example 1.

Example 4

This example provides a method for preparing an antibacterial and antiviral aluminum alloy, except that the copper nitrate in the sol B in step (3) is omitted, that is, the composition of the sol B is ribavirin 13g/L, acyclovir 15g/L, copper nitrate 9g/L, deionized water 19mol/L, diethanolamine 1.16mol/L, and absolute ethanol 20mol/L, and the other conditions are the same as those in example 1.

Example 5

(1) firstly, sequentially carrying out sand blasting, alkali washing and acid washing on the aluminum alloy as pretreatment, wherein the grain diameter of sand used for sand blasting is 50 meshes, the alkali washing adopts 40g/L sodium hydroxide solution, the alkali washing is carried out for 5min at 65 ℃, the acid washing is carried out after the washing with water, the acid washing adopts 100g/L nitric acid solution, the acid washing is carried out for 0.5min at 30 ℃, and the drying is carried out after the washing with water; then carrying out anodic oxidation in a sulfuric acid solution of 150g/L by adopting direct currentThe aluminum alloy is used as an anode, graphite is used as a cathode, and the current density of the direct current is 2.5A/dm²Forming an anodic oxide film with micropores on the surface of the aluminum alloy by performing anodic oxidation treatment at 15 ℃ for 20min under the condition that the power supply voltage is 18V;

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

wherein the composition of the sol A is 0.8mol/L of butyl titanate, 0.64mol/L of silver nitrate, 20g/L of sodium iodate, 14.4mol/L of absolute ethyl alcohol, 15mol/L of deionized water and 0.75mol/L of diethanolamine;

(3) soaking the antibacterial and antiviral aluminum alloy crude product obtained in the step (2) in the sol B for 19min at the temperature of 15 ℃, taking out the soaked aluminum alloy, and carrying out secondary heating at the temperature of 170 ℃ for 38min to obtain an antibacterial and antiviral aluminum alloy;

the sol B comprises 5g/L of ribavirin, 4g/L of acyclovir, 3g/L of copper nitrate, 15mol/L of deionized water, 0.75mol/L of diethanolamine and 14.4mol/L of absolute ethyl alcohol.

Example 6

(1) firstly, sequentially carrying out sand blasting, alkali washing and acid washing on the aluminum alloy as pretreatment, wherein the grain diameter of sand used for sand blasting is 150 meshes, the alkali washing adopts 50g/L sodium hydroxide solution, the alkali washing is carried out for 9min at 40 ℃, the acid washing is carried out after the washing with water, the acid washing adopts 150g/L nitric acid solution, the acid washing is carried out for 2min at 20 ℃, and the acid washing is carried out for blow-drying after the washing with water; then carrying out anodic oxidation in an acidic oxidizing solution, wherein the composition of the acidic oxidizing solution is 210g/L sulfuric acid, the direct current is adopted, the aluminum alloy is used as an anode, graphite is used as a cathode, and the current density of the direct current is 10A/dm²Forming an anodic oxide film with micropores on the surface of the aluminum alloy by performing anodic oxidation treatment at 10 ℃ for 35min under the condition that the power supply voltage is 35V;

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

wherein the composition of the sol A is 1.5mol/L of butyl titanate, 1.2mol/L of silver nitrate, 35g/L of sodium iodate, 27mol/L of absolute ethyl alcohol, 29mol/L of deionized water and 1.64mol/L of diethanolamine;

(3) soaking the antibacterial and antiviral aluminum alloy crude product obtained in the step (2) in the sol B for 8min at the temperature of 25 ℃, taking out the soaked aluminum alloy, and carrying out secondary heating at the temperature of 270 ℃ for 11min to obtain an antibacterial and antiviral aluminum alloy;

the sol B comprises 15g/L of ribavirin, 20g/L of acyclovir, 18g/L of copper nitrate, 29mol/L of deionized water, 1.64mol/L of diethanolamine and 27mol/L of absolute ethyl alcohol.

Comparative example 1

The comparative example provides a preparation method of an antibacterial and antiviral aluminum alloy, except that the butyl titanate in the sol A in the step (2) is omitted, namely the sol A comprises 0.9mol/L silver nitrate, 27g/L sodium iodate, 18mol/L absolute ethyl alcohol, 20mol/L deionized water and 1.15mol/L diethanolamine, and other conditions are completely the same as those in the example 1.

Comparative example 2

The comparative example provides a preparation method of an antibacterial and antiviral aluminum alloy, except that ribavirin in the sol B in the step (3) is omitted, namely the composition of the sol B is 15g/L of acyclovir, 9g/L of copper nitrate, 19mol/L of deionized water, 1.16mol/L of diethanolamine and 20mol/L of absolute ethyl alcohol, and other conditions are completely the same as those in example 1.

Comparative example 3

The comparative example provides a preparation method of an antibacterial and antiviral aluminum alloy, except that acyclovir in the sol B obtained in the step (3) is omitted, namely the sol B comprises 13g/L of ribavirin, 9g/L of copper nitrate, 19mol/L of deionized water, 1.16mol/L of diethanolamine and 20mol/L of absolute ethyl alcohol, and other conditions are completely the same as those in the example 1.

Comparative example 4

The comparative example provides a preparation method of an antibacterial and antiviral aluminum alloy, except that the ribavirin and acyclovir in the sol B obtained in the step (3) are omitted, namely the sol B comprises 9g/L of copper nitrate, 19mol/L of deionized water, 1.16mol/L of diethanolamine and 20mol/L of absolute ethyl alcohol, and other conditions are completely the same as those in the example 1.

Comparative example 5

This comparative example provides a method for producing an antibacterial and antiviral aluminum alloy, except that the primary heating in step (2) and the secondary heating in step (3) were replaced with air-drying at room temperature for 24 hours, and the other conditions were exactly the same as in example 1.

Comparative example 6

This comparative example provides an aluminum alloy without any treatment.

The antibacterial and antiviral aluminum alloys prepared in the above examples 1 to 6 and comparative examples 1 to 5, and the aluminum alloy which is not subjected to any treatment in the comparative example 6 were subjected to antibacterial performance test and antiviral performance test, specifically as follows:

and (3) testing antibacterial performance: according to the national standard GB/T24170.1-2009 part 1 of surface antibacterial stainless steel: the method disclosed in electrochemical method uses Escherichia coli and Staphylococcus aureus as test strains;

antiviral Performance test Using influenza A virus (H3N2) and feline calicivirus (F9) as test viruses purchased from the center for microbiological analysis and detection in Guangdong province, 4cm × 4cm aluminum alloy specimens were placed in plastic petri dishes and 0.1mL of a virus solution having a concentration of 100TCID 50/50. mu.L was added dropwise to the specimens and allowed to act at room temperature for 30min, at which time a PET film (4cm × 4cm) was coated on the specimen surface to keep the contact area between the virus solution and the specimens constant, 1900. mu.L of SCDLP culture solution was added after allowing the virus solution to act for 30min and virus was washed out by air-blowing, and then each reaction specimen was diluted to 10 ℃ with MEM culture solution^-2～10^-5(10-fold serial dilution), 100. mu.L of the sample solution was inoculated onto MDCK cells or CRFK cells cultured in a petri dish. Standing the culture for 60min until the virus is adsorbed by the cellsThe cultures in the petri dishes were overlaid with 0.7% agar medium. At 34 ℃ in 5% CO₂After 48h incubation in an incubator, the cultures were fixed in formalin. The number of plaques formed by methylene blue staining was counted and the antiviral rate was calculated.

The results of the specific tests on antibacterial and antiviral properties are shown in Table 1.

TABLE 1

From table 1, the following points can be seen:

(1) according to the preparation method, an anodic oxidation film with micropores is formed on the surface of the aluminum alloy through anodic oxidation, and then the antibacterial and antiviral inorganic compounds such as nano titanium dioxide and the like and the ribavirin and the acyclovir which are antibacterial and antiviral organic compounds are compounded together through sol soaking and heating for two times, 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 aluminum alloy 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%; moreover, the preparation method has short flow and simple operation, and is beneficial to large-scale popularization;

(2) comparing example 1 with examples 2 to 4, it can be seen that, although the antibacterial rate and the antiviral rate of the aluminum alloy are both greater than or equal to 99%, the antibacterial rate and the antiviral rate are both slightly reduced, regardless of omitting the silver nitrate or the sodium iodate in the sol A or omitting the copper nitrate in the sol B;

(3) comparing example 1 with comparative example 1, it can be seen that the omission of butyl titanate from sol A reduces the antibacterial rate of aluminum alloy against Staphylococcus aureus to 97% and the antiviral rate against feline calicivirus (F9) to 90%;

(4) comparing example 1 with comparative examples 2-4, it can be seen that, when ribavirin and/or acyclovir in the sol B are omitted, although the antibacterial rate of the aluminum alloy is only slightly reduced, the lowest value is still 94%, the antiviral rate of the aluminum alloy is obviously reduced, and when ribavirin and acyclovir are omitted, the antiviral rate of the aluminum alloy to feline calicivirus (F9) is only 58%;

(5) it can be seen from the comparison of example 1 and comparative example 5 that, the primary heating and the secondary heating are replaced by air drying at room temperature for 24 hours, which not only fails to provide the temperature required for thermal decomposition of butyl titanate, silver nitrate, sodium iodate and copper nitrate, but also causes incomplete volatilization of diethanolamine, ethanol and deionized water, and wraps butyl titanate, and the like, thereby preventing the butyl titanate and the like from being decomposed into effective components and preventing the antibacterial performance and the antiviral performance from being exerted.

The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

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

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

preferably, the pretreatment sequentially comprises sand blasting, alkali washing and acid washing;

preferably, the sand used for sand blasting has a particle size of 50-150 meshes;

preferably, the alkali washing adopts 40-50 g/L sodium hydroxide solution;

preferably, the temperature of the alkaline washing is 40-65 ℃, and the time is 5-9 min;

preferably, the acid washing adopts 100-150 g/L nitric acid solution;

preferably, the pickling temperature is 20-30 ℃, and the pickling time is 0.5-2 min.

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 acidic oxidizing solution is a sulfuric acid solution with the concentration of 150-210 g/L.

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 aluminum alloy is used as an anode, and graphite is used as a cathode;

preferably, the current density of the direct current is 2.5-10A/dm²；

Preferably, the power supply voltage of the direct current is 18-35V;

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 composition of the sol B in the step (3) comprises 5-15 g/L of ribavirin, 4-20 g/L of acyclovir, 3-18 g/L of copper nitrate, 15-29 mol/L of deionized water, 0.75-1.64 mol/L of diethanolamine and 14.4-27 mol/L of 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:

the anodic oxidation is carried out in a sulfuric acid solution of 150-210 g/L, the anodic oxidation adopts direct current, the aluminum alloy is used as an anode, graphite is used as a cathode, and the current density of the direct current is 2.5-10A/dm²The power supply voltage of the direct current is 18-35V, the treatment time of the anodic oxidation is 20-35 min, and the treatment temperature of the anodic oxidation is 10-15 ℃;

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