CN100535182C - Method for preparing silver nano antibacterial material - Google Patents
Method for preparing silver nano antibacterial material Download PDFInfo
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- CN100535182C CN100535182C CNB2007101777281A CN200710177728A CN100535182C CN 100535182 C CN100535182 C CN 100535182C CN B2007101777281 A CNB2007101777281 A CN B2007101777281A CN 200710177728 A CN200710177728 A CN 200710177728A CN 100535182 C CN100535182 C CN 100535182C
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Abstract
The invention relates to process for preparing sliver-nanometer anti-bacteria material. The process comprises that an aluminum ion membrane is prepared on the surface of a substrate which is subsequently soaked into silver mirror reaction liquid, and then the substrate is taken out. The scheme employs that the aluminum ion membrane is prepared on the surface of the substrate, which enables the substrate to be covered with aluminum ion, and silver mirror reaction liquid is employed to produce aluminum hydroxide in ammoniated silver solution, which changes the growth velocity of different crystal surfaces of the silver, thereby inducing the growing of flaky silver nanometer slice structure, accomplishing the preparation of silver nanometer slice in a short time, and simplifying the industrial art. As the longer nanometer slice has growth vantage, the achieved nanometer slice structure is enabled to be preserved, thereby guaranteeing the regulation of the silver nanometer structure in silver nanometer anti-bacteria materials.
Description
Technical field
The present invention relates to a kind of preparation method of anti-biotic material, relate in particular to a kind of method for preparing silver nano antibacterial material.
Background technology
Inorganic antibacterial material mainly is divided three classes.The first kind is the photocatalyst-type inorganic antibacterial material, as TiO2, ZrO2, V2O3, ZnO, CdS, SeO2, GaP, SiC etc.They can produce conduction electrons and valence band hole under illumination condition, there is sucking action in the hole to electronics, has oxidation capacity, and very strong reactive behavior, can react with the H2O or the OH ion of surface adsorption, formation has the hydroxyl of strong oxidizing property, removes cell killing by the strong oxidizing property of hydroxyl, and penetrable cytolemma, destroys the toxin that membrane structure, degradation of cell produce.Second class is a metal ion metal oxide type inorganic antibacterial material.This class material mainly is a silver ions.The anti-microbial effect mechanism of silver type inorganic antibacterial material has two kinds of explanations, and the one, the antibiotic mechanism of slowly-releasing sterilization of silver ions, the 2nd, active oxygen sterilization mechanism.The antibiotic mechanism of silver ions slowly-releasing sterilization is meant in its use, antiseptic-germicide slowly releases Ag+, because Ag+ can destroy bacterial cell membrane or attract the thin base of zymoprotein in the bacterial body consumingly under lower concentration very, and the activity of the reduction cellular plasm organized enzyme that combines rapidly, have anti-microbial effect.Thereby by slowly-releasing Ag+, inorganic antibacterial material can be brought into play persistent antibacterial effect.The antibiotic mechanism of the active oxygen of silver ions shows: the reductibility of high oxidation state silver is high, under the effect of light, antiseptic-germicide and water or air effect, the active oxygen O-2 of generation and * OH, have very strong redoxomorphism.The 3rd class is rare-earth activated photochemical catalysis composite inorganic anti-biotic material.The nano composite rare earth anti-biotic material is added in the glaze formula, and rare earth element can be oxidized to water the living radical and the negative oxygen ion of strong oxidation capacity, when having an effect with bacterial cell membrane, can reach the purpose of kill bacteria.
At present, inorganic antibacterial material also is applied in a lot of fields, as anti-bacteria nylon toothbrush, polyethylene chopping block, food product packing film, polypropylene woven bag, food and drink tool, inner container of electric refrigerator, agitation wheel for washing machine etc., and, still in continuous broadened application scope, as sanitary towel, agricultural water-absorbing resin, food and drink tool, drug packing material, agricultural mulching, food shelf and Turnover Box, mobile phone and beeper shell, telephone casing and button, dishwasher, humidifier, toy teaching aid, syringe and tubing, culturing net, tables and chairs handrail etc.Silver is one of the most ancient known antimicrobial reagent.Silver type anti-biotic material does not have particular requirement to complete processing, can be widely used in the products such as plastics, pottery, fiber.
Along with the development of nanotechnology, silver nano antibacterial material nano lamellar silver type inorganic antibacterial material appearred in recent years, i.e..It is neutral that this anti-biotic material is in water, water insoluble and organic solvent, and acidproof, salt tolerant and weak base to the light and heat good stability, also are to be abutted against that to touch the reaction destroy microorganisms active, and its antimicrobial component is a silver ions, and antibacterial effect is lasting; Simultaneously, under the effect of light, silver ions can play the effect of catalytic active center, activate the oxygen in the water and air, produce active oxygen ion, and active oxygen ion has very strong oxidation capacity, can destroy the multiplication capacity of bacterium at short notice, cause necrocytosis, thereby reach antibiotic purpose.
In the prior art, the preparation method of silver nano antibacterial material adsorbs to make in porous materials such as zeolite, the stem pith of the rice-paper plant, algae, the preparation method who provides for the patent document of CN1395829, CN1279825C as publication number, its Yin Nami that makes mostly is powder morphology greatly, the high temperature instability, easily oxidation, easy to change.In addition publication number is that the patent document of CN1267006C has been announced and a kind ofly prepared the nanometer silver fluorapatite with coprecipitation method, strengthens the anti-biotic material that carries silver-colored effect by high-temperature calcination.But preparation process also needs 1000 degree high temperature sinterings.The problem that prior art exists is: these method complex process, and silver nanostructured in the silver nano antibacterial material by these methods preparations all be amorphous structure.
Summary of the invention
The objective of the invention is to propose a kind of method for preparing silver nano antibacterial material, to prepare the silver nano antibacterial material of compound with regular structure simply, fast.
For achieving the above object, the invention provides a kind of method for preparing silver nano antibacterial material, comprising:
With aluminum salt solution pre-treatment is carried out in substrate; To be dipped in the silver mirror reaction liquid of preparation through pretreated described substrate; Take out described substrate.
The described method for preparing silver nano antibacterial material specifically comprises: in the substrate surface preparation aluminum ion thin film, described aluminum ion thin film is generated by aluminum metal and acidic solution reaction, and described aluminum metal is the aluminum metal that contains in the described substrate or is the layer of aluminum that is arranged on described substrate surface; Have the described substrate of aluminum ion thin film to be dipped in silver mirror reaction liquid preparation, described silver mirror reaction liquid is that the adding glucose solution obtained after titration ammoniacal liquor to precipitation disappeared in silver nitrate solution; Take out described substrate.
This programme passes through in the substrate surface preparation aluminum ion thin film, make and be coated with aluminum ion in the substrate, and in silver ammino solution, generate aluminium hydroxide by silver mirror reaction, change the speed of growth of silver-colored different crystal faces, thereby induced sheet Nano silver piece structural growth, finished the preparation of Nano silver piece at short notice, technology is simple; And because long nanometer sheet has growth vigor, the nanometer sheet structure that obtains is maintained, has guaranteed in the silver nano antibacterial material silver nanostructured regular.
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Description of drawings
Fig. 1 prepares the schema of the method embodiment one of silver nano antibacterial material for the present invention;
Fig. 2 prepares the schema of the method embodiment two of silver nano antibacterial material for the present invention;
Fig. 3 prepares the schema of the method embodiment three of silver nano antibacterial material for the present invention;
Fig. 4 prepares the schema of the method embodiment four of silver nano antibacterial material for the present invention;
Fig. 5 prepares the schema of the method embodiment five of silver nano antibacterial material for the present invention.
Embodiment
Substrate can be metal productss such as aluminium, copper, iron, aluminium alloy, stainless steel, also can be on-metallic articles such as synthetic glass, by on substrate surface, preparing aluminum ion thin film, when participating in silver mirror reaction, change the speed of growth of the different crystal faces of silver, thereby induce sheet Nano silver piece structural growth, because long nanometer sheet has growth vigor, and the nanometer sheet structure that obtains is maintained.When in the substrate during aluminiferous metals, can use acidic solution that substrate surface is handled, generate aluminum ion thin film; When in the substrate not during aluminiferous metals, can at first layer of aluminum be set, and then handle with acidic solution at substrate surface, generate aluminum ion thin film at substrate surface.Wherein, acidic solution can be hydrochloric acid, nitric acid etc., and concentration is the best with 0.005mol/L to 5mol/L.Acidic solution changes to some extent to treatment time of aluminium flake, aluminium alloy or aluminium film difference because of the concentration of acidic solution, is generally more than 2 seconds.When acidic solution concentration was higher, the treatment time was shorter relatively; When acidic solution concentration was low, the treatment time was more than 1 hour.Because silver mirror reaction speed is very fast, the reaction times that surface preparation has the substrate of aluminum ion thin film and silver mirror reaction liquid minute is the best with 2 seconds to 10.
Fig. 1 is the schema that the present invention prepares the method embodiment one of silver nano antibacterial material,, specifically comprises for the substrate preparation silver nano antibacterial material is an example with aluminium:
After glucose solution adds silver ammino solution, aluminium flake after will handling immediately is dipped in this reaction solution, specifically can be with the local silver mirror reaction liquid that immerses of this aluminium flake, base need prepare one of Yin Nami with aluminium flake and face down and immerse the reaction solution liquid level and leave standstill, aluminium flake one side up just can not be dipped into silver mirror reaction liquid, as has been dipped into reaction solution, silver mirror reaction can take place yet, produce silver nano-grain, but effect is not so good; If the aluminium flake surface all needs to prepare Yin Nami, also the whole immersion silver mirror reaction of aluminium flake liquid can be left standstill.In the present embodiment, at room temperature whole or local the leaving standstill in silver mirror reaction liquid 2 minutes with aluminium flake after reaction finishes, has silver mirror to generate on the wall of container of Sheng reaction solution, has Yin Nami to generate on the aluminium flake.
Fig. 2 is that substrate preparation silver nano antibacterial material be example with aluminium alloy as 6063 for the present invention prepares the schema of the method embodiment two of silver nano antibacterial material, specifically comprises:
Step 201, aluminium alloy (6063) the sheet a slice of getting 1cm * 1cm;
Step 202, aluminum alloy sheet is handled: aluminum alloy sheet was soaked in hydrochloric acid nearly 1 minute, the aluminum alloy sheet that takes out is cleaned, clean the hydrochloric acid of aluminum alloy sheet remained on surface with deionized water with the hydrochloric acid of 0.005mol/L.
Step 203, aluminum alloy sheet is dipped in the silver mirror reaction liquid liquid level of preparation.At first prepare silver mirror reaction liquid: get the silver nitrate solution of 20ml 0.12mol/L, with the extremely precipitation disappearance of ammonia water titration of 1.1mol/L.The glucose solution of getting 30mL 0.56mol/L joins in the silver ammino solution of above-mentioned new system, makes silver mirror reaction liquid.Preparation silver mirror reaction liquid can carry out simultaneously at the processing aluminum alloy sheet equally, to save time.
After glucose solution added silver ammino solution, the aluminum alloy sheet after will cleaning immediately was dipped in reaction solution.Finish after at room temperature leaving standstill for 30 seconds, have silver mirror to generate on the wall of container, having has Yin Nami to generate on the aluminum alloy sheet.
Step 204, taking-up aluminum alloy sheet are cleaned with deionized water, and it is dry to put into vacuum drying oven.The aluminum alloy sheet surface becomes taupe.There are a lot of nanometer sheet structures on the aluminum alloy sheet surface, and is deposited in together.
Fig. 3 is the schema that the present invention prepares the method embodiment three of silver nano antibacterial material,, specifically comprises for the substrate preparation silver nano antibacterial material is an example with the stainless steel substrates:
Step 301, the stainless steel substrates a slice of getting 1cm * 1cm;
Step 302, plate layer of aluminum with electro-plating method on the stainless steel substrates surface, thickness is about 50um;
Step 303, the stainless steel substrates that aluminium has been plated on the surface with the hydrochloric acid of 0.05mol/L are handled: stainless steel substrates is soaked to advance for 30 seconds in hydrochloric acid, with deionized water the stainless steel substrates that takes out is cleaned, clean the hydrochloric acid of stainless steel substrates remained on surface.
Step 304, stainless steel substrates is dipped in the silver mirror reaction liquid liquid level of preparation.At first prepare silver mirror reaction liquid: get the silver nitrate solution of 20ml 0.12mol/L, with the extremely precipitation disappearance of ammonia water titration of 1.1mol/L.The glucose solution of getting 30mL 0.56mol/L joins in the silver ammino solution of above-mentioned new system, makes silver mirror reaction liquid.Preparation silver mirror reaction liquid can carry out when handling stainless steel substrates equally, to save time.
Glucose solution is dipped in reaction solution with the cleaned stainless steel sheet after adding silver ammino solution immediately.At room temperature leave standstill after 1 minute and finish, have silver mirror to generate on the wall of container, having has Yin Nami to generate on the stainless steel substrates.
Step 305, taking-up stainless steel substrates are cleaned with deionized water, and it is dry to put into vacuum drying oven.The stainless steel substrates surface becomes taupe.There are a lot of nanometer sheet structures on the stainless steel substrates surface, and is deposited in together.
Fig. 4 is that the substrate preparation silver nano antibacterial material is an example for the present invention prepares the schema of the method embodiment four of silver nano antibacterial material with the synthetic glass sheet, specifically comprises:
After glucose solution added silver ammino solution, the synthetic glass sheet after will cleaning immediately was dipped in reaction solution.At room temperature leave standstill after 5 minutes and finish, have silver mirror to generate on the wall of container, have Yin Nami to generate on the synthetic glass sheet.
Fig. 5 is that the substrate preparation silver nano antibacterial material is an example for the present invention prepares the schema of the method embodiment five of silver nano antibacterial material with the synthetic glass sheet, specifically comprises:
After glucose solution added silver ammino solution, the synthetic glass sheet after will cleaning immediately was dipped in reaction solution.At room temperature leave standstill after 10 minutes and finish, have silver mirror to generate on the wall of container, have Yin Nami to generate on the synthetic glass sheet.
The above embodiment of the present invention utilizes the acidic solution pack processing to contain the substrate of aluminum metal or the substrate that the surface is coated with the aluminium film, make substrate surface cover the layer of aluminum ionic membrane, and prepare Nano silver piece at metal and nonmetallic surface by silver mirror reaction, make trivalent aluminium ion in silver ammino solution, generate aluminium hydroxide, changed the speed of growth of silver-colored different crystal faces, thereby induced sheet Nano silver piece structural growth, silver nano-grain can generate in 5 seconds, must high temperature sintering etc. complicated technology, technology is simple, finished the preparation of Nano silver piece at short notice, and adhered to stable, high temperature resistant.Nano silver piece compound with regular structure, the sheet cluster of utilizing this method to make, but not unbodied silver-colored particle make silver-colored Nanosurface long-pending bigger.Nanometer sheet is constantly grown become big.And, the nanometer sheet structure that obtains is maintained because long nanometer sheet has growth vigor.
It should be noted that at last: above embodiment only in order to technical scheme of the present invention to be described, is not intended to limit; Although with reference to previous embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that: it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (16)
1, a kind of method for preparing silver nano antibacterial material is characterized in that, comprising:
In the substrate surface preparation aluminum ion thin film, described aluminum ion thin film is generated by aluminum metal and acidic solution reaction, and described aluminum metal is the aluminum metal that contains in the described substrate or is the layer of aluminum that is arranged on described substrate surface;
Have the described substrate of aluminum ion thin film to be dipped in silver mirror reaction liquid preparation, described silver mirror reaction liquid is that the adding glucose solution obtained after titration ammoniacal liquor to precipitation disappeared in silver nitrate solution;
Take out described substrate.
2, method according to claim 1 is characterized in that, described substrate is metal products or on-metallic article.
3, method according to claim 1 is characterized in that, is specially in the substrate surface preparation aluminum ion thin film:
Described substrate is soaked in the acidic solution.
4, method according to claim 1 is characterized in that, is specially in the substrate surface preparation aluminum ion thin film:
Electroplate layer of aluminum at described substrate surface;
The described substrate that is coated with aluminium is soaked in the acidic solution.
5, method according to claim 1 is characterized in that, is specially in the substrate surface preparation aluminum ion thin film:
Apply one deck conducting polymer composite at described substrate surface;
Electroplate layer of aluminum at the described substrate surface that scribbles conducting polymer composite;
The described substrate that is coated with aluminium is soaked in the acidic solution.
6, method according to claim 1 is characterized in that, is specially in the substrate surface preparation aluminum ion thin film:
Plate layer of aluminum with the vacuum electroplating method at described substrate surface;
The described substrate that is coated with aluminium is soaked in the acidic solution.
According to each described method among the claim 3-6, it is characterized in that 7, described acidic solution is a hydrochloric acid soln.
According to each described method among the claim 3-6, it is characterized in that 8, described acidic solution concentration is 0.005mol/L to 5mol/L.
9, according to each described method among the claim 3-6, it is characterized in that time＞2 second that described substrate is soaked in acidic solution.
10, according to each described method among the claim 3-6, it is characterized in that, described substrate be soaked in acidic solution also comprise afterwards:
With the described substrate of washed with de-ionized water through soaking.
11, according to each described method among the claim 3-6, it is characterized in that, described substrate be soaked in acidic solution also comprise afterwards:
Soak described substrate with aluminum salt solution.
12, according to each described method among the claim 1-6, it is characterized in that having the described substrate of aluminum ion thin film to be dipped in silver mirror reaction liquid preparation and also comprise before: preparation silver mirror reaction liquid.
13, method according to claim 1 is characterized in that, has the described substrate of aluminum ion thin film to be dipped in silver mirror reaction liquid preparation and is specially:
The part of described substrate is left standstill in described silver mirror reaction liquid.
14, method according to claim 1 is characterized in that, will be dipped in silver mirror reaction liquid through pretreated described substrate and be specially: described substrate integral body is left standstill in described silver mirror reaction liquid.
According to claim 13 or 14 described methods, it is characterized in that 15, time of repose is 2 seconds to 10 minute.
16, according to each described method among the claim 1-6, it is characterized in that, also comprise:
With the described substrate after the washed with de-ionized water taking-up;
Drying treatment is carried out in described substrate after cleaning.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007101777281A CN100535182C (en) | 2007-11-20 | 2007-11-20 | Method for preparing silver nano antibacterial material |
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| CNB2007101777281A CN100535182C (en) | 2007-11-20 | 2007-11-20 | Method for preparing silver nano antibacterial material |
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| CN101187018A CN101187018A (en) | 2008-05-28 |
| CN100535182C true CN100535182C (en) | 2009-09-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103044611B (en) * | 2012-12-17 | 2015-06-10 | 上海师范大学 | Preparation of polymer antibacterial nano-particles and magnetic antibacterial nano-particles containing halamine functional groups |
| CN103350236B (en) * | 2013-07-25 | 2015-03-18 | 湖南科技大学 | Method for compounding hexagon silver nanosheet |
| CN106630037A (en) * | 2015-10-30 | 2017-05-10 | 青岛海尔智能技术研发有限公司 | Sterilization element, water heater and foam electrode preparation method |
| CN109848436A (en) * | 2019-03-01 | 2019-06-07 | 淮海工学院 | A method of preparing silver nanoparticle band |
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