CN108315795A - A kind of production method of antibacterial aluminium - Google Patents
A kind of production method of antibacterial aluminium Download PDFInfo
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- CN108315795A CN108315795A CN201810182244.4A CN201810182244A CN108315795A CN 108315795 A CN108315795 A CN 108315795A CN 201810182244 A CN201810182244 A CN 201810182244A CN 108315795 A CN108315795 A CN 108315795A
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- aluminium
- antibacterial
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- production method
- washing
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/12—Iodine, e.g. iodophors; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
Abstract
The invention discloses a kind of production methods of antibacterial aluminium, include the following steps：S1, anodic oxidation：It is placed in acid solution as anode, is aoxidized using pending aluminium；S2, electrochemical deposition：Aluminium after step S1 oxidations is immersed as anode plate in the aqueous solution containing elemental iodine, iodide ion and povidon iodine, electrochemical deposition is carried out；Wherein, in the aqueous solution elemental iodine mass fraction≤3%, mass fraction≤30% of povidon iodine, mass fraction≤2% of iodide ion.Compared with prior art, this method has many advantages, such as good anti-bacterial effect and anti-microbial property is lasting.
Description
Technical field
The present invention relates to metal material processing technical fields, and in particular to a kind of production method of antibacterial aluminium.
Background technology
With the progress of the development and science and technology of economic society, people increasingly pay attention to for resisting germ, especially
In recent years, various anti-biotic materials are gradually applied to a variety of life related fields such as weaving, medicine, ceramics, plastics and cultivation.Mesh
Before, antibacterial metallic materials are mainly based on steel, and the application of antiseptic aluminum or aluminum alloy materials is relatively fewer, mostly also in research
Stage.In the prior art, the production method of antiseptic aluminum or aluminum alloy materials is mainly sunk in anodic oxidation film surface or hole
Product Ag+、Cu2+、Zn2+And TiO2Equal antibacterial materials, wherein due to Ag+With stronger broad spectrum antibacterial, therefore, contain metal
The antiseptic aluminum or aluminum alloy materials of silver surface are that current application is a kind of more antiseptic aluminums or aluminum alloy materials.However, filling gold
The aluminium anode oxide film anti-microbial property for belonging to silver can only achieve 99% or so, and since silver belongs to precious metal so that production cost
It is higher so that silver-containing antibacterial aluminum alloy materials are difficult to obtain wide spread in the application range of sphere of life.Cu2+And Zn2+It is anti-
Bacterium effect and Ag+Compared to poor, TiO2Need just have the function of sterilization and degradation of organic substances, these offices under ultraviolet light
The sex-limited application range for strongly limiting existing Antibacterial aluminum alloy.
Iodine is since with antibacterial effect, strong, has a broad antifungal spectrum, the characteristics such as fast and small toxicity that sterilize are recognized by the world as answer already
With universal and the most safe and reliable fungicide, and iodine is also micro- necessary to human body.If iodine can be deposited on
Aluminum or aluminum alloy material surface, the anti-microbial property that will make aluminum or aluminum alloy material that there is wide spectrum.However, since iodine is a kind of pole
Therefore how the substance easily to distil is realized and iodine is deposited in the micropore of anode oxide film, and keep the antibacterial of continuous and effective
Performance is always global problem, and up to the present, all there has been no the relevant reports of such research application both at home and abroad.
Invention content
The technical problem to be solved by the present invention is to：There is provided that a kind of sterilization effect is good and the antibacterial aluminium of durable antibacterial effect
Production method.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of production method of antibacterial aluminium, packet
Include following steps：S1, anodic oxidation：It is placed in acid solution as anode, is aoxidized using pending aluminium；
S2, electrochemical deposition：Aluminium after step S1 oxidations is immersed as anode plate containing elemental iodine, iodine
In the aqueous solution of ion and povidon iodine, electrochemical deposition is carried out；Wherein, in the aqueous solution elemental iodine quality
Score≤3%, mass fraction≤30% of povidon iodine, mass fraction≤2% of iodide ion.
A kind of production method of antibacterial aluminium, includes the following steps：Pending aluminium is made by following operation successively
Antibacterial aluminium：Washing → anodic oxidation → washing → the electrochemistry of acid deoiling → washing → alkali cleaning → washing → light extraction → twice is heavy
Product → washing；
Wherein, it is in an acidic solution, to be carried out using pending aluminium as anode plate in the anodic oxidation operating process
DC anodizing, the technological parameter in oxidation process are as follows：Free sulfuric acid be 160~180g/L, aluminium ion concentration be 1~
5g/L, temperature≤20 DEG C, current density are 1.3~1.4A/dm2, the time is 10~50min；
In the electrochemical deposition operating process, immersed using pending aluminium as anode plate containing elemental iodine, iodide ion
In the aqueous solution of povidon iodine, electrochemical deposition is carried out using corrosion resistant pole plate as cathode plate, electrochemistry is heavy
Technological parameter during product is as follows：Mass fraction≤3% of elemental iodine in the aqueous solution, the matter of povidon iodine
Measure score≤30%, mass fraction≤2% of iodide ion, voltage >=80V.
The beneficial effects of the present invention are：Medical treatment device can be widely applied to using antibacterial aluminium made from the method for the present invention
The fields such as tool, special building place, household electrical appliances, food processing and daily use chemicals, greatly expand the application field of the aluminiums such as aluminum or aluminum alloy,
Pass through electro-deposition iodine to anodic oxidation membrane micropore and surface so that aluminium anode oxide film can show excellent anti-microbial property；
Iodine be deposited in anodic oxidation membrane micropore and surface on after, have a stronger binding ability with anode oxide film, illumination and
Boiling water is all difficult to all detach iodine from aluminium alloy anode oxide film surface, thus it is speculated that its main cause may be iodine and anodic oxidation
The oxygen atom in oxygen atom and polyvinylpyrrolidone in film is present in aluminum alloy surface in the form of coordinate bond, since I has
Free 5d electron orbits, and O has lone pair electrons, under the voltage effect of anode, the electronics of I atoms shifts, and presents
Positive charge, it is easier to receive the lone pair electrons above O.
Description of the drawings
Fig. 1 is the schematic diagram of antibacterial aluminium made from the embodiment of the present invention 1~3；
Fig. 2 is the antibacterial layer surface SEM shape appearance figures of antibacterial aluminium made from the embodiment of the present invention 1；
Fig. 3 is the antibiotic layer side section SEM shape appearance figures of antibacterial aluminium made from the embodiment of the present invention 1；
Fig. 4 is the energy spectrum analysis figure of the antibacterial layer surface of antibacterial aluminium made from the embodiment of the present invention 1；
Fig. 5 is a side section microcell energy spectrum analysis of the antibacterial layer surface of antibacterial aluminium made from the embodiment of the present invention 1
Figure；
Fig. 6 is another side section microcell power spectrum point of the antibacterial layer surface of antibacterial aluminium made from the embodiment of the present invention 1
Analysis figure；
Fig. 7 is the escherichia coli test result figure of antibacterial aluminium made from the embodiment of the present invention 4；
Fig. 8 is the escherichia coli test result figure of antibacterial aluminium sample one made from the embodiment of the present invention 4；
Fig. 9 is the escherichia coli test result figure of antibacterial aluminium sample two made from the embodiment of the present invention 4；
Figure 10 is the escherichia coli test result figure of antibacterial aluminium sample three made from the embodiment of the present invention 4；
Figure 11 is the escherichia coli test result figure of female plate sample in the embodiment of the present invention 4；
Figure 12 is the escherichia coli test result figure of positive plates sample (blank plate) in the embodiment of the present invention 4.
Specific implementation mode
To explain the technical content, the achieved purpose and the effect of the present invention in detail, below in conjunction with embodiment and coordinate attached
Figure is explained.
The design of most critical of the present invention is：Using electrochemical method in profiled aluminium micropore and surface deposition one
The complex compound of layer iodine so that aluminium has good sterilization ability；Meanwhile iodine is present in aluminium material surface in the form of complex compound,
So that its with antibacterial persistently etc. characteristics.
A kind of production method of antibacterial aluminium, includes the following steps：S1, anodic oxidation：It is placed in acid with pending aluminium
Property solution in be used as anode, aoxidized；
S2, electrochemical deposition：Aluminium after step S1 oxidations is immersed as anode plate containing elemental iodine, iodine
In the aqueous solution of ion and povidon iodine, electrochemical deposition is carried out；Wherein, in the aqueous solution elemental iodine quality
Score≤3%, mass fraction≤30% of povidon iodine, mass fraction≤2% of iodide ion.
As can be seen from the above description, the beneficial effects of the present invention are：It can be wide using antibacterial aluminium made from the method for the present invention
It is general to be applied to the fields such as medical instrument, special building place, household electrical appliances, food processing and daily use chemicals, greatly expand aluminum or aluminum alloy etc.
The application field of aluminium passes through electro-deposition iodine to anodic oxidation membrane micropore and surface so that aluminium anode oxide film can show
Excellent anti-microbial property；Iodine be deposited in anodic oxidation membrane micropore and surface on after, have with anode oxide film stronger
Binding ability, illumination and boiling water are all difficult to all detach iodine from aluminium alloy anode oxide film surface, thus it is speculated that its main cause can
Can be that iodine is present in aluminium with the oxygen atom in the oxygen atom and polyvinylpyrrolidone in anode oxide film in the form of coordinate bond
Alloy surface, since I has empty 5d electron orbits, and O has lone pair electrons, under the voltage effect of anode, the electricity of I atoms
Son shifts, and positive charge is presented, it is easier to receive the lone pair electrons above O.
In the solution, I3The oxygen atom among iodine and polyvinylpyrrolidone in ion is formed compound with electrostatic attraction
Object (if giving the solution illumination, the iodine molecule in solution will distil and decompose quickly)；Under certain voltage, in anode
(Process on Aluminum Alloy Oxidation Film) surface deposits iodine, polyvinylpyrrolidone in the form of coordinate bond, and cathode generates hydrogen.Infer pole plate
Following (the R of reactionA(B)Represent different polyvinylpyrrolidonemolecules molecules)：
Anode reaction：RA-O…I3 -+RB-O…I3 --2e→RA-O→I2+RB-O→I2+I2
Al-O+RA(B)-O→I2→RA(B)-O→I-I←O-Al
Al-O+I2→I2←O-Al
Cathode reaction：2H++2e→H2↑
Iodine has a stronger penetration and oxidizing force to germ, iodine can penetration cell wall quickly, by replacing on C, N, O and S
Hydrogen and hinder the amino acid, protein and nucleic acid of germ to synthesize, simultaneously also by oxidation change germ cell in C and S
The chemical valence of atom is to make the enzymatic activity of germ lose, to have the function that antibacterial.It deposited the aluminium alloy of iodo-complexes
Anti-biotic material can buffer and release I2, make it have fast and strong antibacterial effect.Since iodine release is slow, iodine is complete
Release needs the long period, and it is also preferable to deduce its antibacterial endurance quality from the anti-microbial property of colourless Sample.
Further, in the step S2, electrodeposition time is not more than 8min.
Preferably, the electrodeposition time is 0.5~5min, it is highly preferred that the electrodeposition time is 2~5min.
As can be seen from the above description, the beneficial effects of the present invention are：Sedimentation time is control anode oxide film surface color
The method of the depth, with the increase of sedimentation time, color is gradually deepened from colourless-light yellow-yellow-yellowish-brown-dark brown,
3min is comparatively fast deepened with the color of inner membrance, and between 3~8min, color change is more slow, but to after 8min, electric current is down to
The color of about 0.05A, film are close to or up to limit color concentration, and subsequent amplitude of variation is smaller or is basically unchanged, therefore, according to
The difference and solution concentration of time is different, the antimicrobial sample that can be of different shades.
Further, in the step S2, voltage >=80V in electrochemical deposition process.
Further, in the step S2, in electrochemical deposition process, cathode plate is corrosion-resistant pole plate.
Further, the cathode plate is steel plate, aluminium sheet, copper coin or carbon electrode plate etc..
Further, in the step S1, anodic oxidation operation uses DC anodizing method.
Further, in the step S1, when anode oxidation process, aluminum ions a concentration of 1~5g/L, temperature is less than 20
DEG C, current density is 1.3~1.4A/dm2, the time is 10~50min.
Further, in the step S1, the acid solution is sulfuric acid solution.
As can be seen from the above description, the beneficial effects of the present invention are：Anode oxidation process to alumilite process film quality and
Microcellular structure has significant effect, and present invention process parameter is used to carry out the micropore of the anode oxide film of anodic oxidation acquisition for after
The sedimentary of sequence technique provides good mechanical adhesion.
Further, the sulfuric acid concentration to dissociate in the sulfuric acid solution is 160~180g/L.
Further, the pending aluminium is made of aluminum or aluminum alloy material.
Further, the aluminum alloy materials are aluminium alloy extrusions or aluminum alloy plate materials.
Further, when the pending aluminium is made of aluminum alloy materials, the cathode plate is aluminium sheet, steel plate, copper coin
Or carbon electrode plate.
Further, the production method further includes carrying out anodic oxidation pending aluminium to be placed in acid solution
Preceding also to have carried out pretreatment operation to pending aluminium, the pretreatment operation includes the following steps：
Acid deoiling → washing → alkali cleaning → washing → light extraction → is washed twice.
As can be seen from the above description, the beneficial effects of the present invention are：Aluminium is subjected to cleaning treatment before anodic oxidation,
In, the main purpose of light extraction operation is to neutralize the alkaline matter for removing aluminium material surface, inhibits the rate for generating oxidation film once again, together
When be not involved in alkaline reaction when can remove alkaline etching again and be but still adsorbed on the loose ash shape substance of aluminium material surface and more firm
The impurity such as free silica.
Further, the production method further includes by the aluminium after anodic oxidation operates and after electrochemical deposition operation
The step of carrying out water washing operations respectively.
A kind of production method of antibacterial aluminium, includes the following steps：Pending aluminium is made by following operation successively
Antibacterial aluminium：Washing → anodic oxidation → washing → the electrochemistry of acid deoiling → washing → alkali cleaning → washing → light extraction → twice is heavy
Product → washing；
Wherein, it is in an acidic solution, to be carried out using pending aluminium as anode plate in the anodic oxidation operating process
DC anodizing, the technological parameter in oxidation process are as follows：Free sulfuric acid be 160~180g/L, aluminium ion concentration be 1~
5g/L, temperature≤20 DEG C, current density are 1.3~1.4A/dm2, the time is 10~50min；
In the electrochemical deposition operating process, immersed using pending aluminium as anode plate containing elemental iodine, iodide ion
In the aqueous solution of povidon iodine, using the pole plate of the corrosion resistances such as steel plate, aluminium sheet, copper coin or carbon as cathode plate into
Row electrochemical deposition, the technological parameter in electrochemical deposition process are as follows：The mass fraction of elemental iodine in the aqueous solution≤
3%, mass fraction≤30% of povidon iodine, mass fraction≤2% of iodide ion, voltage >=80V.
The embodiment of the present invention one is：A kind of production method of antibacterial aluminium, includes the following steps：By pending aluminium according to
It is secondary that antibacterial aluminium is made by following operation：Washing → the anodic oxygen of acid deoiling → washing → alkali cleaning → washing → light extraction → twice
Change → washing → electrochemical deposition → washing；
Wherein, it is in an acidic solution, to be carried out using pending aluminium as anode plate in the anodic oxidation operating process
DC anodizing, the pending aluminium are aluminum alloy plate materials, and the technological parameter in oxidation process is as follows：Free sulfuric acid is
160g/L, aluminium ion concentration 1g/L, temperature are 20 DEG C, current density 1.4A/dm2, time 30min；
In the electrochemical deposition operating process, immersed using pending aluminium as anode plate containing elemental iodine, iodide ion
In the aqueous solution of povidon iodine, electrochemical deposition is carried out using aluminium sheet as cathode plate, in electrochemical deposition process
Technological parameter it is as follows：The mass fraction of elemental iodine is 0.03% in the aqueous solution, the quality point of povidon iodine
Number is 0.4%, and the mass fraction of iodide ion is 0.015%, voltage 100V, electrodeposition time 2min.
The embodiment of the present invention two is：A kind of production method of antibacterial aluminium differs only in electricity with embodiment one
Sedimentation time is 5min.
The embodiment of the present invention three is：A kind of production method of antibacterial aluminium differs only in electricity with embodiment one
Sedimentation time is 0.5min.
Examples 1 to 3 is respectively such as Fig. 1 (1), 1 (2) and 1 (3), wherein treated that aluminum alloy materials are in shallow for embodiment one
Yellow, treated the aluminum alloy materials of embodiment two are in dark brown, and treated is silvery white in color for embodiment three.
1, aluminum alloy surface pattern and constituent analysis
With scanning electron microscope (Scanning Electron Microscope, SEM) to treated the aluminium alloy of embodiment one
Sample is tested, and the antibiotic layer surface free processing of Antibacterial aluminum alloy is directly scanned Electronic Speculum test, and side section uses water
It is tested after mill and polishing, test result difference is as shown in Figures 2 and 3.
Figure it is seen that alumilite process film surface covers layer of substance；One layer is can be clearly seen that from Fig. 3
Film thickness is 10 μm or so anode oxide films.
Energy disperse spectroscopy (Energy Dispersive are carried out to the post-depositional oxidation film layer of iodine anode electrochemical
Spectrdmeter, EDS) detection and analysis, as shown in figures 4-6, Fig. 4 is the energy spectrum analysis figure of aluminium alloy antibacterial layer surface；Fig. 5
It is the microcell energy spectrum analysis figure in aluminium alloy antibiotic layer side section oxidation film section with 6.Figure 4, it is seen that aluminium alloy is anti-
Bacterium layer surface contains iodine, and the substance for illustrating to aoxidize film surface covering is iodine substance；From Figures 5 and 6 as can be seen that offside cuts open
The micro-zone analysis of surface oxidation film sectional drawing detects that, containing elements such as I, S, Al and O, it is micro- that wherein S enters oxidation film when being anodic oxidation
The SO in hole4 2-, can not clean in washing, match with the ingredient of alumite completely；Therefore, it is detected in oxidation film film
Higher iodine content, also illustrates that iodine has been deposited in the micropore of aluminium anode oxide film, and with the coating containing iodine on surface
It is closely linked.
2, electric depositing solution residual components are analyzed：Solution composition of the electro-deposition after complete is analyzed, using thio sulphur
Elemental iodine content in sour sodium titrimetry tank liquor, using the content of iodide ion in sodium hydrogensulfite titrimetry tank liquor, specifically
Operation is as follows：
1) elemental iodine assay：50ml tank liquors are taken, 1ml (9 → 100) hydrochloric acid are added, with the Na of 0.01mol/L2S2O3Drop
Determine to nearly terminal, adds 0.5% starch indicator solution 2ml, continue to be titrated to blue disappearance, according to the consumption of sodium thiosulfate titrating solution
Amount calculates tank liquor concentration.
The calculation formula of elemental iodine content is following (g/L)：
V(Na2S2O3)×C(Na2S2O3)×253.81÷2÷50
It is calculated, the content of elemental iodine is 0.34g/L in the remaining tank liquor of embodiment one.
2) iodide ion content measures：50ml tank liquors are taken, after adding water 50ml, add solution of sodium bisulfite (10g/30ml) extremely molten
Liquid color disappears, and adds nitric acid 10ml, and 10.00ml silver nitrate titrations liquid (0.1mol/L) is added, and 0.5ml ferric sulfate is added after shaking up
Ammonium indicator (8g/100ml) is titrated to solution with ammonium thiocyanate titrating solution (0.1mol/L) and shows light brick-red, and by titrating solution
Result corrected with blank assay.
The calculation formula (g/L) of iodide ion content：(V (silver nitrate) × C (silver nitrate)-V (ammonium thiocyanate) × C (thiocyanic acids
Ammonium)) × 253.81 ÷ 50- content of iodine
It is calculated, the content of iodide ion is 0.15g/L in the remaining tank liquor of embodiment one.
3) content analysis of polyvinylpyrrolidone：Polyvinylpyrrolidone solid content (g/L)：10ml tank liquors are taken, 130
It is dried to constant weight to 180 DEG C, weighs residue weight m, m ÷ 10 × 1000.
It is calculated, the content of polyvinylpyrrolidone is 3.4g/L in the remaining tank liquor of embodiment one.
The feature of aluminium alloy anode oxide film multifunctionality is originated from the regular and controllable porosity type of anode oxide film
Structure, different functional materials is filled in porous structure can obtain the functional anode oxide film of various characteristics, anode
The micropore of oxidation film can provide good mechanical adhesion for sedimentary.Such as Electrodeposition Bath of Iron, nickel, cobalt magnetic metal, sun
Pole oxidation film just will present magnetism, can be applied to data storage or other magnetic recordings；Electrodeposited Silver can make oxidation film itself also at
For a good conductor, the anode oxide film for filling silver in recent years is also applied as anti-biotic material.As a same reason, electric
Iodine is deposited to anodic oxidation membrane micropore and surface, so that it may aluminium anode oxide film be made to show excellent anti-microbial property.
From analysis of experimental results, iodine be deposited in anodic oxidation membrane micropore and surface on, it and anode oxide film knot
Conjunction ability is strong, and illumination and boiling water are difficult that iodine is made all to be detached from aluminium alloy anode oxide film surface.From the power analysis of key, can push away
Disconnected iodine is present in aluminium alloy with the oxygen atom in the oxygen atom and polyvinylpyrrolidone in oxidation film in the form of coordinate bond
Surface.Main cause may be I, and there is empty 5d electron orbits, O to have lone pair electrons, under the voltage effect of anode, I atoms
Electronics shift, present positive charge, it is easier to receive the lone pair electrons above O.
In the solution, I3 -The oxygen atom among iodine and polyvinylpyrrolidone in ion forms compound with electrostatic attraction
(if giving the solution illumination, the iodine molecule in solution will distil and decompose quickly)；Under certain voltage, in anode (aluminium
Alloy oxide film) surface deposits iodine, polyvinylpyrrolidone in the form of coordinate bond, and cathode generates hydrogen.Infer what pole plate occurred
Following (the R of reactionA(B)Represent different polyvinylpyrrolidonemolecules molecules)：
Anode reaction：RA-O…I3 -+RB-O…I3 --2e→RA-O→I2+RB-O→I2+I2
Al-O+RA(B)-O→I2→RA(B)-O→I-I←O-Al
Al-O+I2→I2←O-Al
Cathode reaction：2H++2e→H2↑
In the tank liquor of electro-deposition, iodide ion is formed with elemental iodine and is balanced, and the addition of elemental iodine will influence the dense of iodide ion
Degree, therefore in order to keep the concentration of elemental iodine and iodide ion that need to only add elemental iodine.In antibacterial aluminium manufacturing process, iodine
Consumption be more than the consumption of povidon iodine, and elemental iodine is insoluble in water, in order to solve this problem, needs adding
A certain proportion of elemental iodine and povidon iodine are mixed before adding and mill it is broken after, be dissolved in water and be added in tank liquor.
Anti-microbial property test：According to GB/T21866-2008 antibiotic paints (paint film) antibacterial assay method and antibacterial effect into
Tongbiao Standard Technology Service Co., Ltd (SGS) state is entrusted in the measurement of row anti-escherichia coli and Staphylococcus aureus, the test
Border profession testing agency is detected.
The aluminum alloy materials (being labeled as sample one) for not carrying out electro-deposition and the embodiment of the present invention one are taken (to be labeled as sample respectively
Product two), embodiment two (be labeled as sample three) Antibacterial aluminum alloy that treated carry out anti-microbial property test, test result such as table 1
It is shown.
1 anti-microbial property test table of table
Wherein, the negative and blank control sample is：GB/T21866-2008 antibiotic paints (paint film) antibacterial measurement side
Reference substance as defined in method and antibacterial effect.
The embodiment of the present invention four is：A kind of production method of antibacterial aluminium, includes the following steps：By pending aluminium according to
It is secondary that antibacterial aluminium is made by following operation：Washing → the anodic oxygen of acid deoiling → washing → alkali cleaning → washing → light extraction → twice
Change → washing → electrochemical deposition → washing；
Wherein, it is in an acidic solution, to be carried out using pending aluminium as anode plate in the anodic oxidation operating process
DC anodizing, the pending aluminium are aluminium alloy extrusions, and the technological parameter in oxidation process is as follows：Free sulfuric acid is
180g/L, aluminium ion concentration 5g/L, temperature are 18 DEG C, current density 1.3A/dm2, time 25min；
In the electrochemical deposition operating process, immersed using pending aluminium as anode plate containing elemental iodine, iodide ion
In the aqueous solution of povidon iodine, electrochemical deposition is carried out using aluminium sheet as cathode plate, in electrochemical deposition process
Technological parameter it is as follows：The mass fraction of elemental iodine is 0.03% in the aqueous solution, the quality point of povidon iodine
Number is 0.4%, and the mass fraction of iodide ion is 0.015%, voltage 100V, electrodeposition time 5min.
The Antibacterial aluminum alloy Surface of profile made from embodiment 4 applies 8.0 × 105The escherichia coli of the order of magnitude is after 1 hour
Also it is not detected bacterium, detection is as shown in fig. 7, taken multiple samples to be tested, arbitrary extracting wherein three (sample one, samples
This two and sample three), after the 1h of respective sample surface dilute 2000 times culture 24 hours after result as seen in figs. 8-10, the test
In Nanping City in Fujian province, food and medicine examines inspection center to carry out.
Take culture dish as female plate sample, market arbitrarily purchase without anti-microbial property proximate matter as positive plates (blank plate)
Sample, wherein the positive plates sample is：Aluminum alloy plate materials after following pretreatment operation：Acid deoiling → washing → alkali cleaning →
Washing → light extraction → is washed twice, and wherein acid deoiling, washing, alkali cleaning and light extraction, sealing of hole operation are according to the routine of this field
Technological parameter operates, and the technological parameter of positive plates sample and the processing operation of sample one, two, three are completely the same.
8.0 × 10 are applied equally in female plate and positive plates sample5The escherichia coli of the order of magnitude is after 1 hour, testing result
It is as shown in FIG. 11 and 12 respectively, take multiple blank samples and positive plates sample to carry out above-mentioned test, wherein Figure 11 and 12 is arbitrarily choosing
Two sample results taken, should the result is that bacterium 2000 times of cultures 24 hours of dilution behind respective sample surface 1 hour pictures.
Comparison diagram 8-12 goes back a large amount of escherichia coli groups of remnants it is found that result is shown in female plate and positive plates sample,
And treated the Antibacterial aluminum alloy proximate matter of embodiment 4 can kill bacterium completely in 1 hour.
In addition, also by antibacterial aluminium made from the embodiment of the present invention 4, according to GB/T21866-2008 antibiotic paints (paint film)
Antibacterial assay method and antibacterial effect carry out anti-escherichia coli performance test, and 10 are applied in antibacterial Surface of profile7The order of magnitude it is big
Bacterium is also not detected after 24 hours in the uncommon bacterium of intestines angstrom, it can be deduced that product of the present invention equally has stronger anti-microbial property.
After the antibacterial aluminium made according to the method for the present invention is stored 1 year, according to GB/T21866-2008 antibiotic paints
(paint film) antibacterial assay method and antibacterial effect carry out anti-escherichia coli performance test, and 10 are applied in antibacterial Surface of profile7Quantity
After 24 hours bacterium is equally not detected, it can thus be seen that antibacterial aluminium made from the method for the present invention in the escherichia coli of grade
Still there is good anti-microbial property after one year, show that the anti-microbial property of antibacterial aluminium prepared by production method of the present invention has and hold
Long property.
The embodiment of the present invention five is：A kind of production method of antibacterial aluminium, includes the following steps：By pending aluminium according to
It is secondary that antibacterial aluminium is made by following operation：Washing → the anodic oxygen of acid deoiling → washing → alkali cleaning → washing → light extraction → twice
Change → washing → electrochemical deposition → washing；
Wherein, it is in an acidic solution, to be carried out using pending aluminium as anode plate in the anodic oxidation operating process
DC anodizing, the pending aluminium are aluminium sheet, and the technological parameter in oxidation process is as follows：Free sulfuric acid is 170g/L,
Aluminium ion concentration is 3g/L, and temperature is 15 DEG C, current density 1.35A/dm2, time 50min；
In the electrochemical deposition operating process, immersed using pending aluminium as anode plate containing elemental iodine, iodide ion
In the aqueous solution of povidon iodine, electrochemical deposition is carried out using steel plate as cathode plate, in electrochemical deposition process
Technological parameter it is as follows：The mass fraction of elemental iodine is 3% in the aqueous solution, and the mass fraction of povidon iodine is
25%, the mass fraction of iodide ion is 0.5%, voltage 120V, electrodeposition time 3min.
The embodiment of the present invention six is：A kind of production method of antibacterial aluminium, includes the following steps：By pending aluminium according to
It is secondary that antibacterial aluminium is made by following operation：Washing → the anodic oxygen of acid deoiling → washing → alkali cleaning → washing → light extraction → twice
Change → washing → electrochemical deposition → washing；
Wherein, it is in an acidic solution, to be carried out using pending aluminium as anode plate in the anodic oxidation operating process
DC anodizing, the pending aluminium are aluminium sheet, and the technological parameter in oxidation process is as follows：Free sulfuric acid is 170g/L,
Aluminium ion concentration is 3g/L, and temperature is 15 DEG C, current density 1.35A/dm2, time 10min；
In the electrochemical deposition operating process, immersed using pending aluminium as anode plate containing elemental iodine, iodide ion
In the aqueous solution of povidon iodine, electrochemical deposition is carried out using steel plate as cathode plate, in electrochemical deposition process
Technological parameter it is as follows：The mass fraction of elemental iodine is 3% in the aqueous solution, and the mass fraction of povidon iodine is
30%, the mass fraction of iodide ion is 2%, voltage 120V, electrodeposition time 3min.
In conclusion a kind of production method of antibacterial aluminium provided by the invention, this method has good anti-bacterial effect and resists
The advantages that bacterium consistency of performance.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalents made by bright specification and accompanying drawing content are applied directly or indirectly in relevant technical field, include similarly
In the scope of patent protection of the present invention.
Claims (10)
1. a kind of production method of antibacterial aluminium, it is characterised in that：Include the following steps：S1, anodic oxidation：With pending aluminium
Material, which is placed in acid solution, is used as anode, is aoxidized；
S2, electrochemical deposition：Aluminium after step S1 oxidations is immersed as anode plate containing elemental iodine, iodide ion
In the aqueous solution of povidon iodine, electrochemical deposition is carried out；Wherein, in the aqueous solution elemental iodine mass fraction
≤ 3%, mass fraction≤30% of povidon iodine, mass fraction≤2% of iodide ion.
2. the production method of antibacterial aluminium according to claim 1, it is characterised in that：In the step S2, when electro-deposition
Between be not more than 8min.
3. the production method of antibacterial aluminium according to claim 1, it is characterised in that：In the step S2, electrochemistry is heavy
Voltage >=80V during product.
4. the production method of antibacterial aluminium according to claim 1, it is characterised in that：In the step S2, electrochemistry is heavy
During product, cathode plate is corrosion resistance pole plate.
5. the production method of antibacterial aluminium according to claim 1, it is characterised in that：In the step S1, anodic oxidation
When process, aluminum ions a concentration of 1~5g/L, temperature is less than 20 DEG C, and current density is 1.3~1.4A/dm2, the time be 10~
50min。
6. the production method of antibacterial aluminium according to claim 5, it is characterised in that：In the step S1, the acidity
Solution is sulfuric acid solution.
7. the production method of antibacterial aluminium according to claim 6, it is characterised in that：The sulphur to dissociate in the sulfuric acid solution
Acid concentration is 160~180g/L.
8. the production method of antibacterial aluminium according to claim 1, it is characterised in that：The pending aluminium is by aluminium or aluminium
Alloy material is made.
9. the production method of antibacterial aluminium according to claim 1, it is characterised in that：The production method further includes inciting somebody to action
Pending aluminium is placed in acid solution and has also carried out pretreatment operation to pending aluminium before progress anodic oxidation, described
Pretreatment operation includes the following steps：
Acid deoiling → washing → alkali cleaning → washing → light extraction → is washed twice.
10. a kind of production method of antibacterial aluminium, it is characterised in that：Include the following steps：Pending aluminium is passed through such as successively
Antibacterial aluminium is made in lower operation：Acid deoiling → washing → alkali cleaning → washing → light extraction → washing → anodic oxidation → washing twice
→ electrochemical deposition → washing；
Wherein, it is in an acidic solution, direct current to be carried out using pending aluminium as anode plate in the anodic oxidation operating process
Anodic oxidation, the technological parameter in oxidation process are as follows：Free sulfuric acid is 160~180g/L, and aluminium ion concentration is 1~5g/L,
Temperature≤20 DEG C, current density are 1.3~1.4A/dm2, the time is 10~50min；In the electrochemical deposition operating process,
It is immersed in the aqueous solution containing elemental iodine, iodide ion and povidon iodine using pending aluminium as anode plate, with resistance to
Corrosivity pole plate carries out electrochemical deposition as cathode plate, and the technological parameter in electrochemical deposition process is as follows：The aqueous solution
Mass fraction≤3% of middle elemental iodine, mass fraction≤30% of povidon iodine, the mass fraction of iodide ion≤
2%, voltage >=80V.
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| CN109487317A (en) * | 2018-11-08 | 2019-03-19 | 石狮市青灿兴五金工艺品有限公司 | A kind of antibacterial belt fastener and its manufacturing method |
| CN111647926A (en) * | 2020-05-14 | 2020-09-11 | 东南大学 | Preparation method of antibacterial aluminum alloy by anodic oxidation |
| CN114540909A (en) * | 2022-03-03 | 2022-05-27 | 福建省南平铝业股份有限公司 | Surface treatment method for aluminum profile for antibacterial and mildewproof cabinet |
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