CN108677171A - A kind of preparation method of antibacterial aluminium product - Google Patents
A kind of preparation method of antibacterial aluminium product Download PDFInfo
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- CN108677171A CN108677171A CN201810619891.7A CN201810619891A CN108677171A CN 108677171 A CN108677171 A CN 108677171A CN 201810619891 A CN201810619891 A CN 201810619891A CN 108677171 A CN108677171 A CN 108677171A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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Abstract
The present invention relates to a kind of preparation methods of antibacterial aluminium product, include the following steps：Aluminum products are immersed intermediary layer and generated in solution, chemical plating is carried out to matrix by intermediary layer generation step, form intermediary layer, and the intermediary layer generates oxide of the solution containing the active metal between silver, aluminium；Activation process step immerses the aluminum products for generating intermediary layer in activated solution, the intermediary layer metal phase in etch away parts region, and aluminum products surface will have some activation and defective region；Antibacterial coating liquid containing silver salt is coated on aluminum products surface by antibacterial coating step, by forming effective antibacterial functions layer under absorption, reduction and liquid deposition reaction and outer force effect.The present invention is by liquid deposition and chemical method directly aluminum products Surface Creation binding force is good, high-efficiency broad spectrum silver-containing antibacterial layer；By the configuration of antibacterial coating solution, the Argent grain conducive to aluminum products adsorption is formed, antimicrobial component, basal body binding force is good, is not required to be heat-treated, cost-effective.
Description
【Technical field】
The present invention relates to a kind of preparation methods of antibacterial product, more particularly, to a kind of preparation method of antibacterial aluminium product.
【Background technology】
Now with social development and improvement of living standard, people are gradual to health, health, cleaning, fungi-proofing consciousness
Enhancing, market are constantly increasing the demand of antimicrobial product, and people expect that daily necessities have energy antibacterial functions,
Therefore popularization and application of the antibacterial metal product in life, will cause the new revolution of health field.
Most metal ions have very strong sterilizing power, but after addition metal material, are formed with parent metal ion molten altogether
The metal alloy compositions of type, so there are when bacterium contacting metal surface, sterilization that cannot be effectively lasting or bacteriostasis, until making
Its antibacterial effect cannot be played or be kept in metal surface.At present there are two types of the preparation methods of antibacterial metal：When by antiseptic with
Addition phase identity is added in the liquid phase of metal alloy, is molded with liquid postcooling by uniformly stirring, metal is made to have
Anti-microbial property；Second is that the method by carrying out antimicrobial treatment to metal surface, metal surface is coated in by antibacterial granule.The first
The antibacterial granule of method has mutually formed stronger chemical interactions with parent metal, therefore the antibiotic layer that this method is formed is water-soluble
Cannot be continuously precipitated in liquid, antibacterial effect cannot be lasting, exist simultaneously antiseptic dosage is big, of high cost and antibacterial granule from
The shortcomings of problem effectively, is persistently precipitated in matrix, is unfavorable for antibacterial metal large-scale production and application；Second of preparation method is general
Including ion beam depositing (IBAD), physical vapour deposition (PVD) (PVD), chemical vapor deposition (CVD), electro-deposition and chemical collosol and gel
Etc. processes, related art can be referring to entitled《A method of manufacture antibacterial metal product》Chinese invention patent
It is ZL 98801747.4, entitled《Anti-biotic material》Chinese invention patent ZL 94194799.8 etc., however, this method
The antibacterial product made there is also the lasting precipitation problem of antibacterial granule and and the problem of basal body binding force, and in most cases
Heat treatment process is needed, power consumption is big, and equipment investment scale is big.
【Invention content】
For solve the problems, such as it is above-mentioned it is in the prior art exist, the present invention provides a kind of preparation method of antibacterial aluminium product,
Its preparation process is simple, at low cost, is easy to industrialized production, and the good anti-bacterial effect of the antibacterial aluminium product prepared.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：A kind of preparation side of antibacterial aluminium product is provided
Method includes the following steps：
Aluminum products are immersed intermediary layer and generated in solution, carried out chemical plating to matrix, form intermediary by intermediary layer generation step
Layer, so that antibacterial Argent grain can preferably be combined with matrix, the intermediary layer generates solution containing active between silver, the aluminium
The oxide of metal；
The aluminum products for generating intermediary layer are immersed in activated solution and carry out activation process, make part by activation process step
The intermediary layer metal phase in region is corroded, and finally making aluminum products surface, there are some activation and defective region, Zhi Houyong
Clear water cleans, and removes surface raffinate；
The advance prepared antibacterial coating liquid containing silver salt is coated on through aforementioned each step process mistake by antibacterial coating step
Aluminum products surface, by product surface forming effective antibacterial under absorption, reduction and liquid deposition reaction and outer force effect
Functional layer.
Being further improved for above-mentioned technical proposal be：It further includes acid etch processing step before intermediary layer generation step
Suddenly：Aluminum products are immersed into acidleach etching treatment fluid, oxidation on metal surface layer is made to remove and be formed active region；Acid etch processing is stirred
Mix rotating speed is 50~200 revs/min, and the time of acid etch processing is 5~60 seconds, and the main component of acidleach etching treatment fluid at least contains
A kind of reagent in nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid.
Being further improved for above-mentioned technical proposal be：It further includes cleaning before acid etch processing step, cleaning
Step again include at least it is following step by step in one step by step：
Chemical polishing step by step, aluminum products is immersed in chemical polishing soln, remove the residue on surface, at chemical polishing
The temperature of reason is 70~105 DEG C, the time of chemical polishing processing：With flowing, clear water is clear under room temperature after 2 seconds~2 minutes
It washes, removes the residue on surface, basic chemical polishing liquid or acidic chemical polishing liquid may be selected in used chemical polishing soln.
Step by step, aluminum products are immersed in degreasant solution for ungrease treatment, remove surface residue, keep aluminum products surface dry
Only, no-sundries are cleaned with clear water later, and wherein the temperature of ungrease treatment is 60~80 DEG C, and the time of ungrease treatment is 10~30
Second, degreasing metal inorganic agent or degreasant solution as following formula can be selected in ungrease treatment：
Solvent is water；
Sodium carbonate：20~40 grams per liters；
Sodium phosphate：20~40 grams per liters；
Sodium metasilicate：5~10 grams per liters.
Being further improved for above-mentioned technical proposal be：The antibacterial coating step again include following two step by step：
Prepare antibacterial coating liquid step by step, the ingredient and its content that used antibacterial coating liquid contains are：
Silver salt：0.13~13 grams per liter；
Surface complexing agent：Molar concentration is 1.0mol/L；
Reducing agent：0.02~2.0 grams per liter；
Wherein, the control of the concentration molar ratio of silver ion and reducing agent is at 1: 2~1: 4.5, preparation, first by silver salt and surface
Complexing agent is configured and is mixed according to concentration requirement, under stirring after mixing fully, is slowly added to a certain concentration
Reducing agent, and continuously stir 1 hour；
Step by step, at room temperature, antibacterial coating liquid is coated on through the processed aluminum products of above steps for coating processing
Surface allows antibacterial coating liquid to be come into full contact with aluminum products surface, and so that antibacterial granule is deposited to matrix under external force
Surface active and defect area can make antibacterial granule be combined with matrix closely, and coating time need to be at 0.5 minute or more, later
After being washed with clear water, spontaneously dries, form antibacterial metal layer.
Being further improved for above-mentioned technical proposal be：The silver salt can select silver nitrate, silver chlorate, silver sulfide, silver sulfate,
One kind in silver orthophosphate, organic acid silver salt.
Being further improved for above-mentioned technical proposal be：Three hexanol amine, hexamethylene diamine, citric acid, six can be selected in surface complexing agent
Any one in sodium metaphosphate.
Being further improved for above-mentioned technical proposal be：The reducing agent can select potassium borohydride, sodium borohydride, peroxidating
One kind in hydrogen, hydrazine hydrate, sodium hypophosphite.
Being further improved for above-mentioned technical proposal be：Stirring, friction, brushing, roller coating, spray can be used in the mode of coating processing
One kind in painting.
Being further improved for above-mentioned technical proposal be：In intermediary layer generation step, treatment temperature is room temperature, and processing time is
20~60 seconds, speed of agitator was 100~500 revs/min, and the solvent that intermediary layer generates solution is water, wherein the main component contained
And its content is：
Sodium hydroxide：100~140 grams per liters；
Sodium nitrate：1~4 grams per liter；
Ferric trichloride：1~4 grams per liter；
Sodium potassium tartrate tetrahydrate：40~60 grams per liters；
The oxide of metal of the activity between silver, aluminium：The oxide of metal of the activity between silver, between aluminium can be with
Be the zinc oxide of 15~30 grams per liters, the copper oxide of 15~30 grams per liters or 25~50 grams per liters tin oxide in any one.
Being further improved for above-mentioned technical proposal be：The activated solution is that volumn concentration is the cleaning of 40~70% nitric acid
Solution.
Due to the adoption of the above technical scheme, the present invention has the advantages that：
The present invention, in aluminum metal Surface Creation antibacterial functions layer, keeps antibacterial granule phase disperse uniform by using chemical method
It is distributed in aluminiferous metal article surface, antibacterial phase is combined that power is stronger, and after testing, antibacterial granule is distributed in aluminium gold with aluminum metal substrate
Belong in 3 μm of superficial layers below of matrix surface, antibacterial granule is very tiny, reaches 200nm or less.And antibacterial is mutually in matrix surface
Weight percent when reaching 2 percent or more, so that it may keep the metal surface of rich antiseptic elements exposed when outer, make and surface
The bacterio protein of contact is denaturalized, and so as to effectively kill bacterium, sterilizing rate can reach 90% or more.
Heat treatment process is not needed in the technical process of the present invention, saves the cost of antimicrobial component input.
Moreover, in antibacterial metal preparation process of the present invention, for the first time with liquid phase deposition process directly in aluminum products table
Face generates that binding force is good, high-efficiency broad spectrum silver-containing antibacterial layer.The grain size of the antibacterial granule of generation is not more than 1 μm, wherein antibacterial granule
Be after pretreatment aluminum products by contacting in antiseptic solution or suspension, its surface will generate and be embedded in up antibacterial at
Point, and by the configuration of antibacterial coating solution, be formed with conducive to the Argent grain of aluminum products adsorption, rather than silver ion
Or silver atoms, antimicrobial component and basal body binding force are preferable.
Simple production process of the present invention, at low cost, good anti-bacterial effect is easy to industrialized production.This technology is closed suitable for aluminium
Golden arts can be more convenient in metal finishing industry application, more save and efficient.The product that the technology can be used has
The aluminum products such as aluminium plate, aluminium section bar and aluminum alloy part, such as tap, door and window, aluminium alloy tableware, lamps and lanterns, air-conditioning, hand
The various aluminum products for needing antibacterial functions of table, heat sink of air conditioner, medical instrument, household appliances etc..
【Specific implementation mode】
The present invention provides a kind of preparation method for the antibacterial aluminium product for making aluminiferous metal article have anti-microbial property, is mainly
Using the surfacing process being chemically and physically combined, with reference to the preparation process of common alloy product, from original
Following two big steps can be divided into reason mechanism：
Pre-treatment step carries out some pretreatments to aluminum products surface, and aluminium surface is made to be formed conducive to adsorption antibacterial particle
Surface active layer；
Antibacterial coating step, by being formed in product surface under absorption, reduction and liquid deposition reaction and outer force effect
Effective antibacterial functions layer.In combination with the means such as stirring action or friction, brushing, roller coating, spraying when coating, antibacterial granule is made to pass through
Molecular Adsorption, stirring or external pressure effect under, disperse is adsorbed on the regions such as microflute, activation or the defect on aluminum products surface, from
And it is formed and the stronger antibacterial functions layer of basal body binding force on aluminiferous metal article surface.
A kind of preparation method of antibacterial aluminium product of the present invention is described in detail below, a kind of antibacterial aluminium product of the present invention
Preparation method include the following steps：
A, cleaning
The cleaning is removed pollutant, chemical polishing, ungrease treatment etc. clearly primarily with respect to the surface of aluminum products
Clean processing mechanical processing, surface oxidation or due to catching spot etc., needs to be located in advance primarily directed to aluminum products
Reason, makes the aluminum substrates such as clean, clean and tidy expose.Surface is also needed to carry out in advance there are the aluminum products of oxide, spot
Sand paper is polished and electrochemical deoiling decontamination, and chemical polishing and ungrease treatment can be used later, keep surface clean, smooth.And in reality
In production, if the aluminum products used have met clean, smooth surface requirements, the cleaning can be omitted.According to cleaning
The different disposal process of step, but can be subdivided into it is the following step by step：
1) chemical polishing is step by step
Existing chemical polishing reagent may be selected when handling in chemical polishing, and basic chemical polishing liquid or acidification also can be selected
Optical polishing liquid, in a preferred embodiment of the invention, the acidic chemical polishing liquid of use contain as follows according to percent by volume
Ingredient：
Phosphoric acid：80-90%, best 85%；
Nitric acid：3-8%, best 5%；
Ethyl alcohol：7-12%, best 10%；
Wherein chemical polishing processing temperature be：80~105 DEG C；
The time of chemical polishing processing：2 seconds~2 minutes；
Three kinds of chemical reagent are subjected to preparation solution, and electricity consumption stove heat according to percentage by volume, reach 90 degree in temperature
Afterwards, aluminum products are put into solution, then need with flowing under room temperature clear water clean, remove the residue on surface.This point
Step is relatively rough primarily directed to aluminum products surface, the pre-treating technology step carried out when rough and uneven in surface, and for
For smooth, smooth, the clean aluminum products in surface surface, the step can be omitted.
2) ungrease treatment is step by step
Existing ungrease treatment agent can be selected, also can oneself configuration degreasant solution, solvent is water, wherein each ingredient for containing and
Its content is：
Sodium carbonate：20~40 grams per liters
Sodium phosphate：20~40 grams per liters
Sodium metasilicate：5~10 grams per liters
The temperature of ungrease treatment is：60~80 DEG C
The time of ungrease treatment is：10~30 seconds
Aluminum products after polishing treatment are immersed in the solution system of above-mentioned ungrease treatment condition, remove remained on surface
Object, makes that aluminum products surface is clean, no-sundries, needs to use clear water cleaning treatment later, moreover, also can omit this step by step when necessary.
B, acid etch processing step
The speed of agitator of acid etch processing is 50~200 revs/min, and the time of acid etch processing is 5~60 seconds, at acid etch
The main component of liquid is managed at least containing a kind of reagent in nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid, or it is main to select by them
The acid etch agent of constituent.
In the preferred embodiment for the present invention, the solvent of the acidleach etching treatment fluid of preparation is water, wherein the main component contained
Volumn concentration be：
Nitric acid：50~80%；
Hydrofluoric acid：50~20%.
Surface is clean, smooth, smooth aluminum products immerse in above-mentioned acidleach etching treatment fluid, and aluminium gold metal surface is made to form one
A little active regions, in favor of in subsequent processing steps, an intermediary layer is generated in these active regions.It needs to adopt after acid etch processing
It washes with water, removes the solution of remained on surface.When the aluminum products surface of offer has had some active regions, can also incite somebody to action
Acid etch processing step is omitted.
C, intermediary layer generation step
The solvent of the solution used in this step is water, wherein containing following main component：
Sodium hydroxide：100~140 grams per liters
Sodium nitrate：1~4 grams per liter
Ferric trichloride：1~4 grams per liter
Sodium potassium tartrate tetrahydrate：40~60 grams per liters
Zinc oxide：15~30 grams per liters
Treatment temperature is：Room temperature
Processing time is：20~60 seconds
Speed of agitator is：100~500rpm (rev/min)
The aluminum products of above-mentioned activation are put into above-mentioned solution, chemical plating is carried out, intermediary layer are formed, to make antimicrobial silver
Particle can preferably be combined with matrix, be cleaned later with tap water, and the solution of remained on surface is removed.
In this step, the metals such as the oxide, such as zinc, copper, tin of metal of the activity between silver, aluminium can be used
Oxide is converted, primarily to antibacterial Argent grain is enable more preferably to be combined with matrix, while they itself have again it is certain
Anti-microbial property, so needing this process step by step.If because of the not no intermediary layer, the metal active between silver and aluminium
It differs larger, electrochemical redox reaction easily occurs, therefore be unfavorable for the two and muchly combine, and the electrode potential of the two
Differ larger, band structure difference is larger, and the Argent grain for directly adsorbing in aluminium surface in the antimicrobial solution is easy to fall off, binding force
It is small, and the activity of zinc, copper, tin then falls between, and can be combined well with aluminium and silver respectively.Therefore intermediary layer be have it is dual
The function intermediary layer of effect.It is the zinc oxide for having selected 15~30 grams per liters in above-mentioned solution composition, it is of course also possible to select
The oxide of other metals of the activity between silver, aluminium is selected, such as：The copper oxide of 15~30 grams per liters or 25~50 grams per liters
Tin oxide can equally get a desired effect.
D, activation process step
The activating solution used is 40~70% nitric acid cleaning solutions for volumn concentration
Aluminum products through aforementioned each step process are immersed in the activating solution, the intermediary layer metal phase of subregion can be rotten
Eating away makes aluminum products surface form some activation and defective region, and can be conducive to grow antibiotic layer at this.At activation
It is cleaned with tap water after reason, removes the solution of remained on surface.
Above-mentioned A~D steps are all the set-up procedures before antibacterial coating, are conducive to adsorption antibacterial to make aluminium surface be formed
Grain surface active layer, therefore, from principle mechanisms for, A~D steps can be summarized as pre-treatment step.
E, antibacterial coating step
1) antibacterial coating liquid is prepared step by step
Used antibacterial coating liquid contains following ingredient：
Silver salt：0.13~13 grams per liter
Surface complexing agent：Molar concentration is 1.0mol/L
Reducing agent：0.02~2.0 grams per liter (sodium borohydride：0.014~1.4 grams per liter)
Wherein, for antimicrobial component therein -- silver salt, can be selected it is following in any one：Silver nitrate, silver chlorate, sulphur
Change silver, silver sulfate, silver orthophosphate, organic acid silver salt etc.；For surface complexing agent, three hexanol amine, hexamethylene diamine, lemon also can be selected
Any one in acid, calgon, poly- hexylene glycol (400,500) etc., molar concentration is generally 1.0mol/L, such as selects
With three hexanol amine, then its a concentration of 149 grams per liter, and if select hexamethylene diamine, a concentration of 60 grams per liter；And for reducing agent,
Then can be selected it is following in any one：Potassium borohydride, sodium borohydride, hydrogen peroxide, hydrazine hydrate, sodium hypophosphite etc.；Moreover, silver-colored
The concentration molar ratio of ion and reducing agent is controlled in 1: 2~1: 4.5, most preferably 1: 3.Should be when configuring antibacterial coating solution
First silver salt and surface complexing agent are configured and mixed according to concentration requirement, under stirring after mixing fully, is delayed
Slowly certain density reducing agent is added, and continuously stirs a period of time, typically about 1 hour.
In originally step by step, antibacterial coating liquid is prepared according to the content of above-mentioned each ingredient, and make under stirring
Solution forms colourless or yellow solution.
2) coating processing is step by step
It is mainly effectively anti-by being formed in product surface under absorption, reduction and liquid deposition reaction and outer force effect
Bacterium functional layer.When coating, antimicrobial silver particle solution will be contacted through the processed aluminum products of above-mentioned each pre-treatment step, and allow antimicrobial fluid
It is come into full contact with aluminum products surface, so that antibacterial granule is deposited to matrix surface activation and defect area, and in outer force effect
Under antibacterial granule can be made to be combined with matrix closely, be not readily separated, fall off；Coating time need to can be used later at 0.5 minute or more
After clear water is washed, spontaneously dries, be formed antibacterial metal layer.Temperature when coating is room temperature.
The external force mode of action such as stirring, friction, brushing, roller coating, spraying can be used in coating processing.In general, using stirring
When the means of mixing are coated, mechanical agitation instrument can be used to carry out, speed of agitator control is 100~500rpm (rev/min)；Choosing
When with friction, then antibiotic layer can be promoted to generate using gauze, polishing cloth, sand paper or polishing machine etc.；And for selecting spraying, rolling
It applies and brushes, you can using with relevant liquid coating equipments such as spray gun, roller and hairbrush.It is primarily directed to different
Aluminum products shape or produce reality situation and select the different force mode of action.For example, for aluminium plate or aluminum slice, it can
The means such as roller coating, brushing or mantle friction are selected to promote to generate antibiotic layer；And for complex-shaped aluminum products part and
Speech, is carried out using mechanical agitation or spraying equipment.
It can be seen from the above, a kind of preparation method of antibacterial aluminium product of the present invention is mainly using chemical method in aluminum metal table
Face generates antibacterial functions layer, and antibacterial granule phase disperse is made to be evenly distributed on aluminiferous metal article surface, antibacterial phase and aluminum metal substrate
It is stronger to be combined power, after testing, antibacterial granule is distributed in the superficial layer below of 3 μm of aluminum metal substrate surface, and antibacterial granule is very
It is tiny, reach 200nm or less.And antibacterial phase is when the weight percent of matrix surface reaches 2 percent or more, so that it may make
The metal surface of rich antiseptic elements is exposed when outer, and the bacterio protein contacted with surface is made to be denaturalized, thin so as to effectively kill
Bacterium, sterilizing rate can reach 90% or more.
Heat treatment process is not needed in the technical process of the present invention, saves the cost of antimicrobial component input.
Moreover, in antibacterial metal preparation process of the present invention, for the first time with liquid phase deposition process directly in aluminum products table
Face generates that binding force is good, high-efficiency broad spectrum silver-containing antibacterial layer.The grain size of the antibacterial granule of generation is not more than 1 μm, wherein antibacterial granule
Be after pretreatment aluminum products by contacting in antiseptic solution or suspension, its surface will generate and be embedded in up antibacterial at
Point, and by the configuration of antibacterial coating solution, be formed with conducive to the Argent grain of aluminum products adsorption, rather than silver ion
Or silver atoms, antimicrobial component and basal body binding force are preferable.
Simple production process of the present invention, at low cost, good anti-bacterial effect is easy to industrialized production.This technology is closed suitable for aluminium
Golden arts can be more convenient in metal finishing industry application, more save and efficient.The product that the technology can be used has
The aluminum products such as aluminium plate, aluminium section bar and aluminum alloy part, such as tap, door and window, aluminium alloy tableware, lamps and lanterns, air-conditioning, hand
The various aluminum products for needing antibacterial functions of table, heat sink of air conditioner, medical instrument etc..
Claims (10)
1. a kind of preparation method of antibacterial aluminium product, includes the following steps：
Aluminum products are immersed intermediary layer and generated in solution, carried out chemical plating to matrix, form intermediary layer by intermediary layer generation step,
So that antibacterial Argent grain can preferably be combined with matrix, the intermediary layer generates solution containing the active gold between silver, aluminium
The oxide of category；
The aluminum products for generating intermediary layer are immersed in activated solution and carry out activation process, make subregion by activation process step
Intermediary layer metal phase be corroded, finally make aluminum products surface there are some activation and defective region, use clear water later
Cleaning removes surface raffinate；
The advance prepared antibacterial coating liquid containing silver salt is coated on the aluminium crossed through aforementioned each step process by antibacterial coating step
Product surface, by forming effective antibacterial functions in product surface under absorption, reduction and liquid deposition reaction and outer force effect
Layer.
2. a kind of preparation method of antibacterial aluminium product as described in claim 1, it is characterised in that：It is in intermediary layer generation step
Further include acid etch processing step before：Aluminum products are immersed into acidleach etching treatment fluid, oxidation on metal surface layer is made to remove and be formed
Active region；The speed of agitator of acid etch processing is 50~200 revs/min, and the time of acid etch processing is 5~60 seconds, acid etch
The main component for the treatment of fluid is at least containing a kind of reagent in nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid.
3. a kind of preparation method of antibacterial aluminium product as claimed in claim 2, it is characterised in that：It is in acid etch processing step
Further include cleaning before, cleaning include at least again it is following step by step in one step by step：
Step by step, aluminum products are immersed in chemical polishing soln for chemical polishing, remove the residue on surface, chemical polishing processing
Temperature is 70~105 DEG C, and the time of chemical polishing processing is 2 seconds~2 minutes, and with flowing, clear water cleans under room temperature later,
Remove the residue on surface, basic chemical polishing liquid or acidic chemical polishing liquid may be selected in used chemical polishing soln；
Step by step, aluminum products are immersed in degreasant solution for ungrease treatment, remove surface residue, make aluminum products surface it is clean,
No-sundries are cleaned with clear water later, and wherein the temperature of ungrease treatment is 60~80 DEG C, and the time of ungrease treatment is 10~30 seconds,
Existing degreasing metal inorganic agent or degreasant solution as following formula can be selected in ungrease treatment：
Solvent is water；
Sodium carbonate：20~40 grams per liters；
Sodium phosphate：20~40 grams per liters；
Sodium metasilicate：5~10 grams per liters.
4. a kind of preparation method of antibacterial aluminium product as claimed in claim 1,2 or 3, it is characterised in that：Antibacterial coating step
Suddenly and including following two step by step：
Prepare antibacterial coating liquid step by step, the ingredient and its content that used antibacterial coating liquid contains are：
Silver salt：0.13~13 grams per liter；
Surface complexing agent：Molar concentration is 1.0mol/L；
Reducing agent：0.02~2.0 grams per liter；
Wherein, first silver salt and surface are complexed at 1: 2~1: 4.5, preparation for the control of the concentration molar ratio of silver ion and reducing agent
Agent is configured and is mixed according to concentration requirement, under stirring after mixing fully, is slowly added to certain density go back
Former agent, and continuously stir 1 hour；
Step by step, at room temperature, antibacterial coating liquid is coated on through the processed aluminum products surface of above steps for coating processing,
It allows antibacterial coating liquid to be come into full contact with aluminum products surface, and antibacterial granule is enable to deposit to matrix surface work under external force
Change and defect area, can make antibacterial granule be combined with matrix closely, coating time need to use clear water later at 0.5 minute or more
After washing, spontaneously dries, form antibacterial metal layer.
5. a kind of preparation method of antibacterial aluminium product as claimed in claim 4, it is characterised in that：The silver salt can select nitric acid
One kind in silver, silver chlorate, silver sulfide, silver sulfate, silver orthophosphate, organic acid silver salt.
6. a kind of preparation method of antibacterial aluminium product as claimed in claim 4, it is characterised in that：Surface complexing agent can be selected three
Any one in hexanol amine, hexamethylene diamine, citric acid, calgon, poly- hexylene glycol.
7. a kind of preparation method of antibacterial aluminium product as claimed in claim 4, it is characterised in that：The reducing agent can select boron
One kind in hydrofining, sodium borohydride, hydrogen peroxide, hydrazine hydrate, sodium hypophosphite.
8. a kind of preparation method of antibacterial aluminium product as claimed in claim 4, it is characterised in that：The mode of coating processing can adopt
With one kind in stirring, friction, brushing, roller coating, spraying.
9. a kind of preparation method of antibacterial aluminium product as described in claim 1, it is characterised in that：In intermediary layer generation step,
Treatment temperature is room temperature, and processing time is 20~60 seconds, and speed of agitator is 100~500 revs/min, and intermediary layer generates the molten of solution
Agent is water, wherein the main component and its content that contain are：
Sodium hydroxide：100~140 grams per liters；
Sodium nitrate：1~4 grams per liter；
Ferric trichloride：1~4 grams per liter；
Sodium potassium tartrate tetrahydrate：40-60 grams per liters；
The oxide of metal of the activity between silver, aluminium：The oxide of the activity then metal between silver, between aluminium can be
Any one in the tin oxide of the zinc oxide of 15~30 grams per liters, the copper oxide of 15~30 grams per liters or 25~50 grams per liters.
10. a kind of preparation method of antibacterial aluminium product as described in claim 1, it is characterised in that：The activated solution is volume
Percentage composition is 40~70% nitric acid cleaning solutions.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110684968A (en) * | 2019-10-31 | 2020-01-14 | 济南大学 | Surface modification method for preventing white eggs in fish breeding earthen pot |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110684968A (en) * | 2019-10-31 | 2020-01-14 | 济南大学 | Surface modification method for preventing white eggs in fish breeding earthen pot |
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