Antibacterial metal product, composition and preparation method thereof

Abstract

The invention discloses an antibacterial metal product, which belongs to the field of antibacterial metal, and specifically comprises a metal matrix, a micro-arc oxidation ceramic layer and an antibacterial layer, the micro-arc oxidation ceramic layer is arranged on at least part of the surface of the metal matrix, the antibacterial layer is arranged on the surface of the metal matrix or the surface of the micro-arc oxidation ceramic layer, and the main component of the antibacterial layer is an antibacterial composition. The micro-arc oxidation ceramic layer is arranged on the metal matrix, the surface of the metal matrix has excellent mechanical performance, meanwhile, the antibacterial layer is arranged outside the micro-arc oxidation ceramic layer, hole sealing can be well conducted on the micro-arc oxidation ceramic layer, the antibacterial stability is improved through tight combination of the antibacterial layer and the micro-arc oxidation ceramic layer, and the service life of the metal matrix is prolonged. And the sterilizing agent is not easy to fall off and has better sterilizing effect persistence.

Description

Technical Field

[0001] The invention belongs to the technical field of antibacterial metals, and in particular relates to an antibacterial metal product, a composition and a preparation method thereof. Background Art

[0002] In recent years, with the development and progress of society and science and technology, people have a better understanding of bacteria and other microorganisms in the living environment. Some bacteria that can cause harm to people's health are commonly found in various objects that people come into contact with, especially through food or drinks, etc., entering the body from the mouth, which has an adverse effect on the body. In response to this phenomenon, antibacterial technology has attracted more and more attention.

[0003] Metal products have good electrical and thermal conductivity, great plasticity, high strength and toughness, and are therefore widely used in aerospace, machinery, navigation, and transportation. However, metal products that have not been treated with antibacterial agents generally do not have antibacterial properties and cannot be used reasonably in many situations. In view of this situation, people have begun to do some research; for example, in China invention patent CN104827727A, the patent name is "antibacterial metal plate", the publication date: August 12, 2015, discloses an antibacterial metal plate, including a metal substrate, the metal substrate is coated with an antibacterial topcoat, the antibacterial topcoat includes the following components in thousandths by mass: polyester resin 350-470‰; cross-linking agent 50-85‰; catalyst 1.5-2.5‰; antibacterial agent 15-40‰; pigment 280-360‰; other additives 10-25‰; solvent 80-170‰; including the following preparation method: batching, and compounding and stirring evenly; then grinding and dispersing to a qualified fineness; then adding a cross-linking agent, a catalyst, other additives and an antibacterial agent, stirring evenly to form an antibacterial topcoat for an antibacterial metal plate; and finally making an antibacterial metal plate. This technology makes the metal surface have antibacterial properties by coating the metal substrate with antibacterial topcoat, but this technology has many disadvantages such as not resistant to water washing, slow bactericidal effect, and easy to fall off.

[0004] In the Chinese invention patent CN105941476A, the patent name is "Antimicrobial metal ion particles, preparation method thereof and antimicrobial metal ion liquid using antimicrobial metal ions", and the publication date is September 21, 2016. A preparation method of antimicrobial metal ion particles is disclosed, which includes the following steps: (1) adding water to silver salt and zinc salt to prepare a replacement liquid; (2) adding a modified ore powder composition to the replacement liquid, stirring, removing the supernatant, and drying the particles to obtain antimicrobial metal ion particles, wherein the modified ore powder composition is a composition obtained by modifying a mixture of zeolite and sepiolite with a mixture of a starch-type impregnating agent and amphoteric imidazoline as a modifier. The invention is to prepare a replacement liquid by adding water to silver salt and zinc salt, and then adding modified ore powder to mix, removing the supernatant and drying to form antimicrobial metal ion particles, and the antimicrobial property is mainly achieved through the antimicrobial properties of metallic silver and zinc; however, the antimicrobial metal ions prepared by this method have many disadvantages such as poor binding force with the product, slow bactericidal effect, high cost, and complicated steps. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide an antibacterial metal product, which has the advantages of stable bactericidal performance, simple structure, not easy to fall off, and long-lasting bactericidal effect. In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions: an antibacterial metal product, including a metal substrate, a micro-arc oxidation ceramic layer and an antibacterial layer; the micro-arc oxidation ceramic layer is arranged on at least part of the surface of the metal substrate, the antibacterial layer is arranged on the surface of the metal substrate or the surface of the micro-arc oxidation ceramic layer, and the main component of the antibacterial layer is an antibacterial composition. In this solution, by arranging a micro-arc oxidation ceramic layer on the metal substrate, the surface of the metal substrate has excellent mechanical properties. At the same time, an antibacterial layer is arranged outside the micro-arc oxidation ceramic layer, which can well seal the micro-arc oxidation ceramic layer. Through the close combination of the antibacterial layer and the micro-arc oxidation ceramic layer, the antibacterial stability is increased, it is not easy to fall off, and the bactericidal effect is more sustainable.

[0006] The antibacterial layer includes any one or more of silver nitrate, silver acetate or silver halide, and the antibacterial layer also includes any one or more of calcium oxide, iron oxide and zinc oxide; the antibacterial layer also includes phosphorus pentoxide, calcium phosphate and sodium oxide; the metal substrate is also provided with a hydrophobic antibacterial layer, and the hydrophobic antibacterial layer includes at least one of dimethylsiloxane polyurethane, polypropylene and polyethylene. This scheme inactivates the surface proteins of bacteria and viruses through the antibacterial property of silver ions, and further extinguishes bacteria and viruses through the antibacterial property of calcium, iron and zinc to achieve the effect of sterilization; phosphorus pentoxide, calcium phosphate and sodium oxide are added to the antibacterial material, so that the antibacterial material can be combined to form phosphate, which has a unique network structure of phosphorus oxygen tetrahedron, so that the phosphate obtains a slow release performance, and the antibacterial ions are loaded through the network structure of the phosphate, so that the antibacterial material obtains a slow release effect, effectively prolonging the antibacterial durability. By setting a hydrophobic antibacterial layer, the hydrophobicity of the surface of the metal substrate can be improved, impurities are not easily loaded, and it is easy to clean.

[0007] Preferably, the step of providing the micro-arc oxidation ceramic layer on the metal substrate is:

[0008] (1) cleaning the surface of the metal substrate;

[0009] (2) preparing a micro-arc oxidation electrolyte for standby use, using at least one of aluminate, sodium hydroxide and metaaluminate to prepare the micro-arc oxidation electrolyte, wherein the concentration of the aluminate and the metaaluminate is 11-28 g / L, and the concentration of the sodium hydroxide is 3-10 g / L; adding additives to the micro-arc oxidation electrolyte, wherein the concentrations of the additives are: sodium tungstate 2-12 g / L, sodium molybdate 0.5-2.5 g / L, sodium citrate 2-6 g / L, and disodium ethylenediaminetetraacetic acid 4-12 g / L;

[0010] (3) placing the metal substrate into a prepared micro-arc oxidation electrolyte and treating it at room temperature for 30-60 minutes, so that the metal substrate obtains a micro-arc oxidation ceramic layer.

[0011] This solution covers the surface of the metal substrate with a micro-arc oxidation ceramic layer by electrolysis. The method is low-cost, can be carried out at room temperature, saves energy, is simple to operate, and can be generally applied to most metal products.

[0012] Furthermore, the present invention also provides an antibacterial composition, which mainly comprises the following components in parts by weight: 12-20 parts of any one or more of a silver compound, a zinc compound or a copper compound, 2-3 parts of citric acid, 1-3 parts of glycerol, 2-3 parts of a collagen-like substance, 3-6 parts of a stabilizer, and 5-10 parts of colloidal silicon dioxide, wherein the stabilizer is glycerol.

[0013] Further, the present invention also provides an antibacterial composition, mainly comprising the following components: a biguanide antibacterial agent, a quaternary ammonium salt, and ethanol, wherein the weight ratio of the biguanide antibacterial agent, the quaternary ammonium salt, and the ethanol is 5-16:12-23:20-30, and the quaternary ammonium salt is selected from any one of chlorhexidine, benzalkonium bromide, a chloride-type quaternary ammonium salt, a bromide-type quaternary ammonium salt, and an organosilicon quaternary ammonium salt. The antibacterial composition provided by this scheme has the advantages of no irritation to the skin and mucous membranes, good stability, no damage to the disinfected articles, and environmental friendliness, and the disinfection ability is a medium-to-low level disinfectant, and can be adsorbed by macroporous substances.

[0014] Furthermore, the present invention also provides a method for preparing an antibacterial metal product, comprising the following steps:

[0015] (a) Pretreatment: removing the oxidation layer of the antibacterial metal substrate under vacuum;

[0016] (b) crushing the antibacterial metal or antibacterial ion-containing compound under vacuum, putting it into a nano fine grinder for full grinding for 1-2 hours, stably controlling the temperature at 10-25 degrees, opening and taking out the ground particles every 10 minutes, and detecting the particle size and shape of the particles by a particle size and shape measuring instrument;

[0017] (c) dissolving the fine powder obtained by grinding in 0.5-1.2% acetic acid solution, placing the fine powder in a mixer and stirring the mixture for 10-20 minutes, monitoring the temperature in real time, and maintaining the temperature at 10-25° C. during mixing to form an antibacterial suspension for use;

[0018] (d) applying the antibacterial suspension evenly on the surface of the metal product, and repeatedly rubbing and / or increasing the pressure on the surface of the metal product during the application process to accelerate the penetration of the antibacterial suspension into the surface of the metal product.

[0019] This solution can effectively prevent the metal substrate from being oxidized by removing the oxide layer and crushing and grinding the metal substrate under vacuum, thereby improving the overall antibacterial performance. Grinding the metal substrate with a nano-fine grinder provides convenience for the subsequent preparation of antibacterial suspension. The antibacterial metal product obtained by applying the antibacterial suspension to the surface of the metal product has a long-lasting antibacterial effect and good antibacterial effect. The method is simple and easy to operate.

[0020] Furthermore, the present invention also provides a method for preparing an antibacterial metal product, comprising the following steps:

[0021] (1) placing a metal substrate in a micro-arc oxidation electrolyte, adding an additive for micro-arc oxidation, and treating at room temperature for 30 to 60 minutes to obtain a micro-arc oxidation ceramic layer;

[0022] (2) cleaning, drying, sensitization and activation pretreatment;

[0023] (3) The treated metal substrate is placed in the cathode of the prepared electrolytic cell to allow the antibacterial ions of the cathode to enter the surface of the ceramic layer and treated for 30 to 60 minutes to obtain an antibacterial metal product with high antibacterial properties.

[0024] The micro-arc oxidation electrolyte described in step (1) is one or more of silicate, borate and phosphate, and the concentration used is: the concentration of silicate and phosphate is 1-35g / L, and the concentration of borate is 1-8g / L. The additives and their concentrations in the micro-arc oxidation electrolyte are: sodium tungstate 4-18g / L, sodium silicate 3-10g / L, sodium hydroxide 1-3g / L, sodium ethylenediaminetetraacetate 1-4g / L, potassium sodium tartrate 0.2-6g / L, boric acid 0.4-1g / L, cerium nitrate 0.1-0.4g / L, and the pH value of the micro-arc oxidation electrolyte is 9.

[0025] Furthermore, the present invention also provides a method for preparing an antibacterial metal product, comprising the following steps:

[0026] (1) providing an electrolytic cell, wherein an electrolyte is provided in the electrolytic cell, wherein the main component of the electrolyte is a salt solution containing antibacterial ions;

[0027] (2) applying a preset voltage to the electrolytic cell so that the antibacterial ions are gathered at the negative electrode of the electrolytic cell under the action of the voltage, wherein the preset voltage ranges from 20 V to 700 V;

[0028] (3) providing a metal product and placing it at the negative electrode of the electrolytic cell; antibacterial ions enter the surface of the metal product;

[0029] (4) After a period of time, the metal product is taken out, cleaned, and dried to obtain an antibacterial metal product.

[0030] Through this method, the antibacterial ions completely cover the surface of the metal substrate, the antibacterial ions are evenly distributed and change consistently, and thus a complete and uniform antibacterial effect can be obtained; the antibacterial metal products obtained have high strength, good impact resistance, and good resistance to Escherichia coli, Staphylococcus aureus, etc. The process of the preparation method is easy to control, can be widely applied to the industrialization of various manufacturers, has low investment, low cost, and is easy to promote industrialization.

[0031] Preferably, in step (2), the metal product is subjected to preliminary treatment before being placed on the negative electrode of the electrolytic cell, and the preliminary treatment includes any one or more of etching, friction or high-pressure cleaning of the metal product.

[0032] Preferably, the water temperature for cleaning the metal products in step (4) is controlled at 1-15°, and this temperature range can quickly lock the antibacterial ions on the surface of the metal products; and also includes a cleaning solution recovery device, which recovers the water solution after cleaning to the electrolytic cell for reuse. The electrolytic cell is heated before or after the electrolytic reaction starts, and the temperature is controlled between 30-100 degrees; the anode of the electrolytic cell is any one of silver, copper, zinc, and magnesium, and the electrolyte is a salt solution corresponding to the anode metal.

[0033] Compared with the prior art, the present invention has at least the following beneficial effects: in this scheme, a micro-arc oxidation ceramic layer is arranged on the metal substrate, so that the surface of the metal substrate has excellent mechanical properties. At the same time, an antibacterial layer is arranged outside the micro-arc oxidation ceramic layer, so that the pores of the micro-arc oxidation ceramic layer can be well sealed. Through the close combination of the antibacterial layer and the micro-arc oxidation ceramic layer, the antibacterial stability is increased, it is not easy to fall off, the bactericidal effect is more sustainable, and the antibacterial cost is low, the operation is simple, and it has universal applicability. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the technical solutions in the specific embodiments of the present invention, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0035] Figure 1 It is a flow chart of the present invention. DETAILED DESCRIPTION

[0036] The technical solutions in the specific embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0037] Example 1

[0038] The present embodiment provides an antibacterial metal product, including a metal substrate, a micro-arc oxidation ceramic layer and an antibacterial layer; the micro-arc oxidation ceramic layer is arranged on at least part of the surface of the metal substrate, the antibacterial layer is arranged on the surface of the metal substrate or the surface of the micro-arc oxidation ceramic layer, and the main component of the antibacterial layer is an antibacterial composition. The metal substrate can be cast iron, stainless steel, zinc, aluminum, magnesium, copper and alloys thereof commonly seen in the market. By arranging the micro-arc oxidation ceramic layer and the antibacterial layer on the surface of the above-mentioned metal substrate, the mechanical properties of the surface of the metal substrate are increased. At the same time, the antibacterial layer is arranged outside the micro-arc oxidation ceramic layer, which can well seal the micro-arc oxidation ceramic layer. Through the close combination of the antibacterial layer and the micro-arc oxidation ceramic layer, the antibacterial stability is increased, it is not easy to fall off, the bactericidal effect is more sustainable, and the antibacterial cost is low, the operation is simple, and it has universal applicability.

[0039] In this embodiment, the antibacterial layer may include any one or more of silver nitrate, silver acetate or silver halide, and the antibacterial layer may also include any one or more of calcium oxide, iron oxide and zinc oxide; the antibacterial layer also includes phosphorus pentoxide, calcium phosphate and sodium oxide; in a preferred embodiment, titanium dioxide may also be included, and the antibacterial property of silver ions may inactivate the surface proteins of bacteria and viruses, and the antibacterial property of calcium, iron and zinc may further be used to extinguish bacteria and viruses, thereby achieving a sterilization effect; phosphorus pentoxide, calcium phosphate and sodium oxide are added to the antibacterial material, so that the antibacterial material can be combined to form phosphate, and the phosphate has a unique network structure of phosphorus-oxygen tetrahedron, so that the phosphate obtains a sustained-release property, and the antibacterial ions are loaded through the network structure of the phosphate. Adding titanium dioxide can further improve the network structure of the antibacterial layer, increase the loading performance, and the antibacterial material can be released evenly and slowly, effectively extending the antibacterial durability.

[0040] The metal substrate is also provided with a hydrophobic antibacterial layer, which includes at least one of dimethylsiloxane polyurethane, polypropylene and polyethylene. The hydrophobic antibacterial layer is mainly composed of organic compounds, has good hydrophobic properties, can be well combined with the metal substrate, and is not easy to fall off; by providing the hydrophobic antibacterial layer, the hydrophobicity of the metal substrate surface can be improved, impurities are not easily loaded, and it is easy to clean.

[0041] Example 2

[0042] Micro-arc oxidation (MAO), also known as plasma electrolytic oxidation (PEO), is developed from the anodizing technology, and the coating formed is better than anodizing. The micro-arc oxidation (MAO) process mainly relies on the matching and adjustment of the electrolyte and electrical parameters. Under the instantaneous high temperature and high pressure generated by arc discharge, a modified ceramic coating mainly composed of matrix metal oxide and supplemented by electrolyte components grows on the surface of valve metals such as aluminum, magnesium, titanium and their alloys. Its corrosion resistance and wear resistance are significantly better than traditional anodized coatings. This embodiment provides a method for setting a micro-arc oxidation ceramic layer on a metal substrate, and the specific steps are as follows:

[0043] (1) cleaning the surface of the metal substrate;

[0044] (2) preparing a micro-arc oxidation electrolyte for standby use, using at least one of aluminate, sodium hydroxide and metaaluminate to prepare the micro-arc oxidation electrolyte, wherein the concentration of the aluminate and the metaaluminate is 11-28 g / L, and the concentration of the sodium hydroxide is 3-10 g / L; adding additives to the micro-arc oxidation electrolyte, wherein the concentrations of the additives are: sodium tungstate 2-12 g / L, sodium molybdate 0.5-2.5 g / L, sodium citrate 2-6 g / L, and disodium ethylenediaminetetraacetic acid 4-12 g / L;

[0045] (3) placing the metal substrate into a prepared micro-arc oxidation electrolyte and treating it at room temperature for 30-60 minutes, so that the metal substrate obtains a micro-arc oxidation ceramic layer.

[0046] Through this method, the micro-arc oxidation ceramic layer is covered on the surface of the metal substrate. The micro-arc oxidation ceramic layer is evenly distributed on the surface of the metal substrate. The thickness of the metal substrate surface varies uniformly, which increases the mechanical properties of the metal substrate surface. At the same time, the porous characteristics of the micro-arc oxidation ceramic layer also provide favorable conditions for the subsequent addition of antibacterial ions, making it less likely to fall off and the antibacterial effect more lasting.

[0047] In a preferred embodiment, the micro-arc oxidation electrolyte in step (3) can be heated and the temperature maintained at 40-90 degrees, which can accelerate the reaction, improve the reaction efficiency and save time.

[0048] Example 3

[0049] This embodiment provides an antibacterial composition, which can be combined with the surface of the substrate so that the surface of the substrate has an antibacterial function. The substrate described here can be a metal product or other types of items, such as glass products, ceramic products or plastic products. The antibacterial composition mainly comprises the following components by weight: 12-20 parts of silver compound, 2-3 parts of citric acid, 1-3 parts of glycerol, 2-3 parts of collagen, 3-6 parts of stabilizer, 5-10 parts of colloidal silica, and in a preferred embodiment, the stabilizer is selected from glycerol. The silver compound can also be replaced by a zinc compound or a copper compound; or any one or more of silver compounds, zinc compounds or copper compounds can be selected for use. The collagen substance mainly refers to collagen, preferably type I, II, and III collagen molecules, which can increase the viscosity of the antibacterial composition, improve the ability of the antibacterial composition to bind to the surface of the substrate, and improve the antibacterial effect and durability of the antibacterial composition.

[0050] Example 4

[0051] The present embodiment provides an antibacterial composition, which can be arranged on the surface of a substrate so that the substrate surface has an antibacterial function. The substrate described herein can be a metal product, or it can be other types of articles, such as glass products, ceramic products or plastic products. The antibacterial composition mainly comprises the following components: a biguanide antibacterial agent, a quaternary ammonium salt, and ethanol. In a preferred embodiment, the weight ratio of the biguanide antibacterial agent, the quaternary ammonium salt, and the ethanol is 5-16:12-23:20-30; the biguanide antibacterial agent is selected from any one or more of chlorhexidine and polyhexamethyleneguanidine hydrochloride. The quaternary ammonium salt is selected from any one of chlorhexidine, benzalkonium bromide, a chloride-type quaternary ammonium salt, a bromide-type quaternary ammonium salt, and an organosilicon quaternary ammonium salt.

[0052] The antibacterial composition provided in this embodiment has excellent antibacterial ability, and has the advantages of being non-irritating to the skin and mucous membranes, having good stability, being harmless, and being environmentally friendly. At the same time, the antibacterial composition has good adhesion to the surface of the substrate, is not easy to fall off, has a good bactericidal effect, and does not affect the original performance of the substrate.

[0053] Example 5

[0054] This embodiment also provides a method for preparing an antibacterial metal product, comprising the following steps:

[0055] (a) Pretreatment: removing the oxidation layer of the antibacterial metal substrate under vacuum;

[0056] (b) crushing the antibacterial metal or antibacterial ion-containing compound under vacuum, putting it into a nano-fine grinder for full grinding for 1-2 hours, stably controlling the temperature at 10-25 degrees, opening the nano-fine grinder every 10 minutes and taking out the ground particles, and detecting the particle size and shape of the particles by a particle size and shape measuring instrument;

[0057] (c) dissolving the fine powder obtained by grinding in 0.5-1.2% acetic acid solution, placing the fine powder in a mixer and stirring the mixture for 10-20 minutes, monitoring the temperature in real time, and maintaining the temperature at 10-25° C. during mixing to form an antibacterial suspension for use;

[0058] (d) applying the antibacterial suspension evenly on the surface of the metal product, and repeatedly rubbing and / or increasing the pressure on the surface of the metal product during the application process to accelerate the penetration of the antibacterial suspension into the surface of the metal product.

[0059] In this embodiment, the antibacterial metal or the compound containing antibacterial ions is ground and pulverized by a grinder, thereby reducing the average particle size of the antibacterial material, so that the surface of the metal substrate with the same area can be covered with more antibacterial ions, thereby increasing the density of the antibacterial ions and further improving the killing effect on bacteria, viruses, etc.

[0060] Example 6

[0061] This embodiment provides a method for preparing an antibacterial metal product, such as Figure 1 As shown, the following steps are included:

[0062] (1) placing a metal substrate in a micro-arc oxidation electrolyte, adding an additive for micro-arc oxidation, and treating at room temperature for 30 to 60 minutes to obtain a micro-arc oxidation ceramic layer;

[0063] (2) cleaning, drying, sensitization and activation pretreatment;

[0064] (3) The treated metal substrate is placed in the cathode of the prepared electrolytic cell to allow the antibacterial ions of the cathode to enter the surface of the ceramic layer and treated for 30 to 60 minutes to obtain an antibacterial metal product with high antibacterial properties.

[0065] The micro-arc oxidation electrolyte described in step (1) is one or more of silicate, borate and phosphate, and the concentration used is: the concentration of silicate and phosphate is 1-35g / L, and the concentration of borate is 1-8g / L. The additives in the micro-arc oxidation electrolyte and their concentrations are: sodium tungstate 4-18g / L, sodium silicate 3-10g / L, sodium hydroxide 1-3g / L, sodium ethylenediaminetetraacetate 1-4g / L, potassium sodium tartrate 0.2-6g / L, boric acid 0.4-1g / L, cerium nitrate 0.1-0.4g / L, the pH value of the micro-arc oxidation electrolyte is 8-10, and in a preferred embodiment, the pH value of the micro-arc oxidation electrolyte is 9.

[0066] This embodiment uses electroplating silver to prepare an antibacterial layer on a micro-arc oxidation ceramic layer. Since the micro-arc oxidation layer has good mechanical properties such as hardness, wear resistance and corrosion resistance, and the antibacterial ions have good antibacterial properties, the antibacterial metal products obtained by this method have both excellent mechanical properties and high-efficiency antibacterial properties; at the same time, the antibacterial ions can effectively seal the micro-arc oxidation ceramic layer. The micro-arc oxidation ceramic layer has a porous surface structure, and the antibacterial ions can fully enter the pores of the ceramic layer by using the electroplating silver process, so that the coating is dense and uniform. The method has low cost, can be carried out at room temperature, saves energy, is simple to operate, and can be generally applied to most metal products.

[0067] Example 7

[0068] This embodiment provides a method for preparing an antibacterial metal product, comprising the following steps:

[0069] (1) providing an electrolytic cell, wherein an electrolyte is provided in the electrolytic cell, wherein the main component of the electrolyte is a salt solution containing antibacterial ions;

[0070] (2) applying a preset voltage to the electrolytic cell so that the antibacterial ions are gathered at the negative electrode of the electrolytic cell under the action of the voltage, wherein the preset voltage ranges from 20 V to 700 V;

[0071] (3) providing a metal product and placing it at the negative electrode of the electrolytic cell; antibacterial ions enter the surface of the metal product;

[0072] (4) After a period of time, the metal product is taken out, cleaned, and dried to obtain an antibacterial metal product.

[0073] In step (2), the metal product is pre-treated before being placed on the negative electrode of the electrolytic cell, and the pre-treatment includes any one or more of etching, friction or high-pressure cleaning of the metal product. In a preferred embodiment, the voltage in step (2) is selected to be 120V.

[0074] The water temperature for cleaning the metal products in step (4) is controlled at 1-15°, and this temperature range can quickly lock the antibacterial ions on the surface of the metal products; and also includes a device for recovering the cleaning solution, and recovers the aqueous solution after cleaning to the electrolytic cell for reuse. The electrolytic cell is heated before or after the electrolytic reaction starts, and the temperature is controlled between 30-100 degrees; the anode of the electrolytic cell is any one of silver, copper, zinc, and magnesium, and the electrolyte is a salt solution corresponding to the anode metal.

[0075] In this embodiment, the surface of the metal substrate is covered with a micro-arc oxidation ceramic layer by an electrolytic method. The method has low cost, can be performed at room temperature, saves energy, is simple to operate, and can be generally applied to most metal products.

[0076] The invention principle of the present invention is described in this paper by using specific examples, and the description of the above embodiments is only used to help understand the method and core idea of ​​the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. An antibacterial metal product, characterized in that: It includes a metal substrate, a micro-arc oxidation ceramic layer and an antibacterial layer; the micro-arc oxidation ceramic layer is arranged on at least part of the surface of the metal substrate, the antibacterial layer is arranged on the surface of the metal substrate or the surface of the micro-arc oxidation ceramic layer, and the main component of the antibacterial layer is an antibacterial composition.

2. The antibacterial metal product according to claim 1, characterized in that: The antibacterial layer includes any one or more of silver nitrate, silver acetate or silver halide, and the antibacterial layer also includes any one or more of calcium oxide, iron oxide and zinc oxide; the antibacterial layer also includes phosphorus pentoxide, calcium phosphate and sodium oxide; a hydrophobic antibacterial layer is also provided outside the metal substrate, and the hydrophobic antibacterial layer includes at least one of dimethylsiloxane-based polyurethane, polypropylene and polyethylene.

3. The antibacterial metal product according to claim 1, characterized in that: The steps of providing the micro-arc oxidation ceramic layer on the metal substrate are: (1) cleaning the surface of the metal substrate; (2) preparing a micro-arc oxidation electrolyte for standby use, using at least one of aluminate, sodium hydroxide and metaaluminate to prepare the micro-arc oxidation electrolyte, wherein the concentration of the aluminate and the metaaluminate is 11-28 g / L, and the concentration of the sodium hydroxide is 3-10 g / L; adding additives to the micro-arc oxidation electrolyte, wherein the concentrations of the additives are: sodium tungstate 2-12 g / L, sodium molybdate 0.5-2.5 g / L, sodium citrate 2-6 g / L, and disodium ethylenediaminetetraacetic acid 4-12 g / L; (3) placing the metal substrate into a prepared micro-arc oxidation electrolyte and treating it at room temperature for 30-60 minutes, so that the metal substrate obtains a micro-arc oxidation ceramic layer.

4. An antibacterial composition, characterized in that The main components are as follows in parts by weight: 12-20 parts of any one or more of silver compound, zinc compound or copper compound, 2-3 parts of citric acid, 1-3 parts of glycerol, 2-3 parts of collagen, 3-6 parts of stabilizer, 5-10 parts of colloidal silicon dioxide, wherein the stabilizer is glycerol.

5. An antibacterial composition, characterized in that The invention mainly comprises the following components: a biguanide antibacterial agent, a quaternary ammonium salt and ethanol, wherein the weight ratio of the biguanide antibacterial agent, the quaternary ammonium salt and the ethanol is 5-16:12-23:20-30, and the quaternary ammonium salt is selected from any one of chlorhexidine, benzalkonium bromide, chloride-type quaternary ammonium salt, bromide-type quaternary ammonium salt and organosilicon quaternary ammonium salt.

6. A method for preparing an antibacterial metal product, characterized in that: The steps include: (a) Pretreatment: removing the oxidation layer of the antibacterial metal substrate under vacuum; (b) crushing the antibacterial metal or antibacterial ion-containing compound under vacuum, putting it into a nano-fine grinder for full grinding for 1-2 hours, stably controlling the temperature at 10-25 degrees, opening the nano-fine grinder every 10 minutes and taking out the ground particles, and detecting the particle size and shape of the particles by a particle size and shape measuring instrument; (c) dissolving the fine powder obtained by grinding in 0.5-1.2% acetic acid solution, placing the fine powder in a mixer and stirring the mixture for 10-20 minutes, monitoring the temperature in real time, and maintaining the temperature at 10-25° C. during mixing to form an antibacterial suspension for use; (d) applying the antibacterial suspension evenly on the surface of the metal product, and repeatedly rubbing and / or increasing the pressure on the surface of the metal product during the application process to accelerate the penetration of the antibacterial suspension into the surface of the metal product.

7. A method for preparing an antibacterial metal product, characterized in that: The steps include: (1) placing a metal substrate in a micro-arc oxidation electrolyte, adding an additive for micro-arc oxidation, and treating at room temperature for 30 to 60 minutes to obtain a micro-arc oxidation ceramic layer; (2) cleaning, drying, sensitization and activation pretreatment; (3) The treated metal substrate is placed in the cathode of the prepared electrolytic cell to allow the antibacterial ions of the cathode to enter the surface of the ceramic layer and treated for 30 to 60 minutes to obtain an antibacterial metal product with high antibacterial properties.

8. The preparation method according to claim 7, characterized in that: The micro-arc oxidation electrolyte described in step (1) is one or more of silicate, borate and phosphate, and the concentration used is: the concentration of silicate and phosphate is 1-35g / L, and the concentration of borate is 1-8g / L. The additives and their concentrations in the micro-arc oxidation electrolyte are: sodium tungstate 4-18g / L, sodium silicate 3-10g / L, sodium hydroxide 1-3g / L, sodium ethylenediaminetetraacetate 1-4g / L, potassium sodium tartrate 0.2-6g / L, boric acid 0.4-1g / L, cerium nitrate 0.1-0.4g / L, and the pH value of the micro-arc oxidation electrolyte is 8-10.

9. A method for preparing an antibacterial metal product, characterized in that: The steps include: (1) providing an electrolytic cell, wherein an electrolyte is provided in the electrolytic cell, wherein the main component of the electrolyte is a salt solution containing antibacterial ions; (2) applying a preset voltage to the electrolytic cell so that the antibacterial ions are gathered at the negative electrode of the electrolytic cell under the action of the voltage, wherein the preset voltage ranges from 20 V to 700 V; (3) providing a metal product and placing it at the negative electrode of the electrolytic cell; antibacterial ions enter the surface of the metal product; (4) After a period of time, the metal product is taken out, cleaned, and dried to obtain an antibacterial metal product.

10. The preparation method according to claim 9, characterized in that: In the step (2), the metal product is subjected to preliminary treatment before being placed on the negative electrode of the electrolytic cell. The preliminary treatment includes any one or more of etching, friction or high-pressure cleaning of the metal product.

11. The preparation method according to claim 9, characterized in that: The water temperature for cleaning the metal products in step (4) is controlled at 1-15°, and this temperature range can quickly lock the antibacterial ions on the surface of the metal products; and also includes a cleaning liquid recovery device to recover the cleaned aqueous solution to the electrolytic cell for reuse.

12. The preparation method according to claim 9, characterized in that: The electrolytic cell is heated before or after the electrolytic reaction starts, and the temperature is controlled between 30 and 100 degrees. The anode of the electrolytic cell is any one of silver, copper, zinc, and magnesium, and the electrolyte is a salt solution corresponding to the anode metal.

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