CN116479492A - Preparation method of anodic aluminum oxide alloy with high antibacterial property and durability - Google Patents
Preparation method of anodic aluminum oxide alloy with high antibacterial property and durability Download PDFInfo
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- CN116479492A CN116479492A CN202310426457.8A CN202310426457A CN116479492A CN 116479492 A CN116479492 A CN 116479492A CN 202310426457 A CN202310426457 A CN 202310426457A CN 116479492 A CN116479492 A CN 116479492A
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- aluminum substrate
- hole sealing
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- antibacterial
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 77
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 5
- 239000000956 alloy Substances 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 59
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000758 substrate Substances 0.000 claims abstract description 58
- 238000007789 sealing Methods 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 18
- -1 silver ions Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008021 deposition Effects 0.000 claims abstract description 12
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 66
- 229910000838 Al alloy Inorganic materials 0.000 claims description 40
- 238000005530 etching Methods 0.000 claims description 25
- 238000004043 dyeing Methods 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 238000005238 degreasing Methods 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 7
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 239000004519 grease Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 9
- 239000010407 anodic oxide Substances 0.000 abstract description 20
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 15
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001431 copper ion Inorganic materials 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- 229910052709 silver Inorganic materials 0.000 abstract description 9
- 239000004332 silver Substances 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 230000036571 hydration Effects 0.000 abstract description 6
- 238000006703 hydration reaction Methods 0.000 abstract description 6
- 238000002161 passivation Methods 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 230000035515 penetration Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 229910021645 metal ion Inorganic materials 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- HAIMOVORXAUUQK-UHFFFAOYSA-J zirconium(iv) hydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Zr+4] HAIMOVORXAUUQK-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
-
- 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
- C25D11/16—Pretreatment, e.g. desmutting
-
- 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
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
An anodic aluminum oxide alloy with high antibacterial durability is prepared by immersing an aluminum substrate with an anodic porous layer in an antibacterial hole sealing mixed solution for hole sealing treatment, wherein the antibacterial hole sealing mixed solution is prepared by mixing antibacterial liquid and hole sealing liquid in a preset ratio. In the hole sealing treatment, silver ions, copper ions and zinc ions are diffused and precipitated into the anodic oxide film holes, hydroxide and crystalline aluminum oxide are respectively generated through nickel acetate hydrolysis and hydration expansion to seal the anodic oxide film holes, and the sealing effect is improved through the mutual penetration of the crystalline aluminum oxide and hydroxide and the copper ions and the zinc ions and the mutual deposition in the anodic oxide film holes, and the porous layer is subjected to passivation treatment by the copper ions and the zinc ions to form a composite passivation layer, so that the corrosion resistance of the aluminum substrate finished product is further improved.
Description
Technical Field
The invention relates to the technical field of aluminum alloy surface treatment, in particular to a preparation method of an anodic aluminum oxide alloy with high antibacterial durability.
Background
The aluminum alloy has the advantages of light weight, corrosion resistance, good processing formability and the like, and is widely applied to civil products such as kitchen appliances, food containers, home decoration materials, public transportation, large building air inlets and the like. In daily use, with the increasing use time of aluminum alloy, aluminum alloy is very easy to breed bacteria in moist air, causes potential bacterial infection danger to the user of aluminum alloy utensil to, the bacterial breeding department easily forms the corrosion phenomenon, seriously influences aluminum alloy's use and decorative effect. Therefore, the aluminum alloy with antibacterial property becomes an important point for improving civil materials, and aims to keep the original mechanical property, corrosion resistance, surface finish and other advantages of the aluminum alloy matrix, and meanwhile, the aluminum alloy matrix needs to have a long-term effective strong antibacterial effect.
At present, various preparation methods of antibacterial aluminum alloy exist for solving the problems, but the methods cannot meet the requirement of large-scale popularization. For example, in the first method, the antibacterial property is provided by an impregnation method, and referring to a surface treatment method of an aluminum alloy disclosed in chinese patent CN109881235a, an aluminum alloy having undergone pretreatment is anodized, then the aluminum alloy having an oxide film is immersed in a nano silver solution for ultrasonic treatment, ultrasonic and baking operations are repeated for 4-5 times, and the antibacterial treated aluminum alloy is obtained after natural cooling. Although the method can endow the aluminum alloy with antibacterial property, the operation process is complex, the efficiency is low, and the equipment occupies large space, so that the large-scale popularization of the mode is difficult.
For example, in a second method, antibacterial property is provided by electrolytic deposition, and an antibacterial aluminum alloy is obtained by anodic oxidation of an aluminum alloy, then electrolytic deposition by immersing the oxidized aluminum alloy in a solution containing silver nitrate, and then hole sealing with boiling water, as disclosed in chinese patent CN107130276 a. The adoption of the electrolytic deposition can lead to deeper deposition of antibacterial silver ions, so that antibacterial performance cannot be ensured, meanwhile, the color of an oxide film of the aluminum alloy can be changed in the electrolytic process, the colorful decorative property of the oxide film of the aluminum alloy is affected, in addition, electric energy is wasted in the electrolytic process, and the stability of the silver nitrate electrolytic coloring liquid is poor.
For example, in a third method, antibacterial property is provided by changing oxidation mode, referring to a preparation method of anodic oxidation of aluminum alloy disclosed in chinese patent CN111647926a, an antibacterial aluminum alloy is obtained by first performing anodic oxidation and deposition of antibacterial substance on the pretreated aluminum alloy by using pulse alternating current, and then performing hole sealing operation on the film layer. In practical application, the aluminum alloy oxide film is difficult to deposit antibacterial metal due to weak conductivity, so that antibacterial performance cannot be ensured, energy consumption is increased by alternating current oxidation, and operation is complex.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of an anodic aluminum alloy with high antibacterial durability, so that the prepared aluminum alloy substrate finished product has a long-term effective strong antibacterial effect, and the preparation method is simple.
In order to achieve the above purpose, the invention provides a preparation method of an anodic aluminum alloy with high antibacterial durability, which comprises the following steps:
step s1, soaking an aluminum substrate in degreasing solution for degreasing treatment so as to remove grease on the surface of the aluminum substrate;
step s2, immersing the aluminum substrate in an alkaline etching solution for alkaline etching treatment to remove an oxide film on the surface of the aluminum substrate;
step s3, immersing the aluminum substrate in an ash removal solution for ash removal treatment to remove hydroxide deposition generated in the alkaline etching treatment, and neutralizing the residual alkaline etching solution on the surface of the aluminum substrate;
step s4, immersing the aluminum substrate in an anodic oxidation solution, and electrifying in the anodic oxidation solution to form a porous layer on the surface of the aluminum substrate;
step 5, soaking the aluminum substrate in an antibacterial hole sealing mixed solution for hole sealing treatment, wherein the antibacterial hole sealing mixed solution is prepared by mixing antibacterial solution and hole sealing solution in a preset ratio; the antibacterial liquid comprises silver salt 0.01-1.0g/l, copper salt 0.01-1.0g/l and zinc salt 0.01-1.0 g/l; the hole sealing liquid comprises 5-10g/l nickel acetate, 0.5-1.5g/l methylene dinaphthyl sodium sulfonate concentration, 0.2-1g/l sodium acetate and 0.1-0.5g/l boric acid;
and step S6, carrying out high-temperature drying treatment on the aluminum substrate to remove the water on the surface of the aluminum substrate.
Further, between step s4 and step s5, the aluminum substrate is immersed in a dyeing solution to be dyed.
Further, the dyeing solution comprises 0.1-10g/l of dyeing toner, wherein the dyeing toner is organic dyeing toner; the temperature of the dyeing solution is 35-55 ℃; the dyeing treatment time is 0.5-5min.
Further, the degreasing solution comprises 10-25g/l sodium phosphate, 5-15g/l sodium carbonate and 1-5g/l polyoxyethylene polyoxypropylene ether; the temperature of the degreasing solution is 30-60 ℃; degreasing treatment time is 3-10min.
Further, the alkaline etching solution comprises 40-70g/l sodium hydroxide, 10-20g/l sodium phosphate and 10-20g/l sodium carbonate; the temperature of the alkaline etching solution is 65-70 ℃; the alkali etching treatment time is 1-3min.
Further, the components of the ash removal solution comprise 5-20g/l ferric nitrate and 50-100g/l nitric acid; the temperature of the ash removal solution is 25-30 ℃; the ash removal treatment time is 1-3min.
Further, the anodic oxidation solution comprises 150-200g/l sulfuric acid and 2-15g/l aluminum sulfate; the temperature of the anodic oxidation solution is 18-23 ℃; the energizing voltage is 13-20v, and the energizing time is 3-15min.
Further, the predetermined proportion in the step s5 is 2-5%.
Further, the temperature of the antibacterial hole sealing mixed liquid is 70-95 ℃, and the hole sealing treatment time is 5-15min.
In step s6, the aluminum substrate is subjected to high-temperature drying treatment by an oven, wherein the temperature of the high-temperature drying treatment is 80-100 ℃, and the time of the high-temperature drying treatment is 1-2min.
The beneficial effects of the invention are as follows: in hole sealing treatment, silver ions, copper ions and zinc ions are diffused and precipitated into the anodic oxide film holes, hydroxide and crystalline aluminum oxide are respectively generated through nickel acetate hydrolysis and hydration expansion to seal the anodic oxide film holes, and the crystalline aluminum oxide and hydroxide are mutually penetrated with the copper ions and the zinc ions and are jointly deposited in the anodic oxide film holes, so that the sealing effect is improved, the concentration and activity of antibacterial metal ions in a composite anodic oxidation process are improved, meanwhile, an aluminum substrate finished product can release the metal ions with antibacterial property more slowly, the safety is higher, the antibacterial time is longer, the preparation process is simple, and the operation is convenient. In addition, the porous layer is passivated by copper ions and zinc ions, and the corrosion resistance of the aluminum substrate finished product is further improved through the composite passivation layer.
Drawings
FIG. 1 is a schematic diagram of the steps of the preparation method.
Detailed Description
In order that the invention may be understood more fully, the invention will be described with reference to the accompanying drawings. The drawings illustrate preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete.
Referring to fig. 1, in this embodiment, a method for preparing an anodized aluminum alloy having high antimicrobial durability includes the steps of:
step s1, immersing an aluminum substrate in a degreasing solution for degreasing treatment, wherein the degreasing solution comprises 10-25g/l of sodium phosphate, 5-15g/l of sodium carbonate and 1-5g/l of polyoxyethylene polyoxypropylene ether; the temperature of the degreasing solution is 30-60 ℃; degreasing treatment time is 3-10min. Grease, fingerprint marks and the like caused by machining the surface of the aluminum alloy workpiece are effectively removed through degreasing treatment, and meanwhile, the surface is wetted, so that the subsequent alkaline etching treatment is not interfered by the grease. In addition, the degreasing treatment is performed by the degreasing solution of the embodiment, the cleaning rate is high, the corrosiveness is weak, substances harmful to human bodies are not contained, and the safety is high.
Step s2, immersing the aluminum substrate in an alkaline etching solution for alkaline etching treatment, wherein the alkaline etching solution comprises 40-70g/l sodium hydroxide, 10-20g/l sodium phosphate and 10-20g/l sodium carbonate; the temperature of the alkaline etching solution is 65-70 ℃; the alkali etching treatment time is 1-3min. The thin oxide film naturally formed on the surface of the aluminum alloy workpiece is effectively removed through alkaline etching treatment, and the alkaline etching solution is adopted to conduct alkaline etching treatment, so that the etching amount is low, the etched surface is uniform, and machining traces can be effectively removed.
Step 3, immersing the aluminum substrate in an ash removal solution for ash removal treatment, wherein the ash removal solution comprises 5-20g/l ferric nitrate and 50-100g/l nitric acid; the temperature of the ash removal solution is 25-30 ℃; the ash removal treatment time is 1-3min. The hydroxide deposition generated in the alkaline etching process is effectively removed through the ash removal treatment, meanwhile, the residual alkali liquor is neutralized, the ash removal treatment temperature is low, the heat energy consumption is low, the treatment time is short, the effect of thorough ash removal can be achieved, and the surface gloss of the aluminum substrate is not affected.
Step s4, immersing the aluminum substrate in an anodic oxidation solution, wherein the anodic oxidation solution comprises 150-200g/l sulfuric acid and 2-15g/l aluminum sulfate; the temperature of the anodic oxidation solution is 18-23 ℃, then the anodic oxidation solution is electrified, the electrified voltage is 13-20v, and the electrified time is 3-15min. The honeycomb porous layer is formed on the surface of the aluminum substrate through electrolysis, so that the adsorptivity, corrosion resistance and hardness of the surface of the aluminum substrate are improved, the components of the adopted anodic oxidation solution are simple, the anodic oxidation solution is easy to manage and control, and the anodic oxidation film holes formed on the surface of the aluminum substrate are uniform and compact, so that the dye adsorption of the subsequent dyeing treatment is promoted.
After step s4, soaking the aluminum substrate in a dyeing solution for dyeing treatment, wherein the dyeing solution comprises 0.1-10g/l of dyeing toner, and the dyeing toner is organic dyeing toner; the temperature of the dyeing solution is 35-55 ℃; the dyeing treatment time is 0.5-5min. The color of the aluminum base material is endowed by dyeing treatment, so that the decorative property of the aluminum base material is improved.
Step s5, soaking the aluminum substrate in an antibacterial hole sealing mixed solution for hole sealing treatment, wherein the antibacterial hole sealing mixed solution is prepared by mixing antibacterial solution and hole sealing solution in a preset ratio. The predetermined ratio is a ratio of 5%. The antibacterial liquid comprises 1.0g/l silver salt, 1.0g/l copper salt and 1.0g/l zinc salt; the hole sealing liquid comprises 10g/l nickel acetate, 1.5g/l methylene dinaphthyl sodium sulfonate, 1g/l sodium acetate and 0.1-0.5g/l boric acid. The temperature of the antibacterial hole sealing mixed solution is 95 ℃, and the hole sealing treatment time is 15min.
In the hole sealing treatment process of the step s5, silver ions, copper ions and zinc ions diffuse into the anodic oxide film holes, then, the silver ions react with alumina in the anodic oxide film to generate hydroxyl groups, and the hydroxyl groups are combined with part of the silver ions, copper ions and zinc ions diffused into the anodic oxide film holes to generate hydroxide to deposit on the film holes to block holes, so that a stable coating film is formed, wherein the release process of the silver ions, the copper ions and the zinc ions is slowed down through the coating film, so that an aluminum substrate finished product can continuously and slowly provide antibacterial metal ions, the risk of loss of the antibacterial metal ions caused by friction and vibration is reduced, and the antibacterial performance of the aluminum substrate finished product is improved. In addition, by the adsorption and deposition of high Wen Cujin silver ions, copper ions and zinc ions of the antibacterial hole sealing mixed solution into the anodic oxide film holes, the deposition amount of antibacterial substances on the surface of the composite anodic oxide film is increased, the antibacterial performance of the aluminum substrate finished product is further improved, and the porous layer is passivated by the copper ions and the zinc ions to form the composite passivation layer.
Further, in the hole sealing treatment process of the step s5, the anodic oxide film holes are sealed through nickel acetate hydrolysis and hydration expansion, wherein hydroxide deposition is generated through the nickel acetate hydrolysis, and crystalline alumina is generated through the nickel acetate hydration expansion; by depositing crystalline aluminum oxide and hydroxide on the anodic oxide film pores and the zirconium-based conversion film, zirconium salt hydroxide and nickel salt hydroxide are made to interpenetrate and co-deposit to achieve the anodic oxide film pores of the closed porous layer. During the sealing process by the crystallized alumina and hydroxide, the crystallized alumina and hydroxide and copper ions and zinc ions are mutually penetrated and are jointly deposited in the anodic oxide film holes, and the deposited copper ions and zinc ions are embedded by the alumina and hydroxide, and meanwhile, the anodic oxide film holes are sealed, so that the release of antibacterial metal ions in the aluminum substrate finished product is further slowed down, and the aim of continuously and stably releasing the antibacterial metal ions is fulfilled.
And step S6, carrying out high-temperature drying treatment on the aluminum substrate through an oven to remove water on the surface of the aluminum substrate, wherein the temperature of the high-temperature drying treatment is 80-100 ℃, and the time of the high-temperature drying treatment is 1-2min. Residual moisture of the aluminum substrate can be effectively removed by performing high-temperature treatment on the aluminum substrate after the step s5 is completed, hydration inside the anodic oxide film holes can be quickened by the high-temperature treatment, the sealing effect is further improved, the surface hardness of the aluminum alloy workpiece is improved, and the service life is prolonged.
The silver ions, the copper ions and the zinc ions diffuse and precipitate into the anodic oxide film holes, hydroxide and crystalline alumina are respectively generated through nickel acetate hydrolysis and hydration expansion to seal the anodic oxide film holes, and the crystalline alumina and hydroxide are mutually penetrated with the copper ions and the zinc ions and are jointly deposited in the anodic oxide film holes, so that the sealing effect is improved, the concentration and the activity of antibacterial metal ions in the composite anodic oxidation process are improved, meanwhile, the aluminum substrate finished product can release the antibacterial metal ions more slowly, the safety is higher, the antibacterial time is longer, the preparation process is simple, and the operation is convenient. In addition, the corrosion resistance of the aluminum substrate finished product is further improved through the composite passivation layer.
Example two
The difference from the first embodiment is that: the predetermined ratio in step s5 is a ratio of 4%. The antibacterial liquid comprises 0.5g/l silver salt, 0.5 copper salt and 0.5g/l zinc salt; the hole sealing liquid comprises 8g/l nickel acetate, 1.2g/l methylene dinaphthyl sodium sulfonate concentration, 0.7g/l sodium acetate and 0.4g/l boric acid. The temperature of the antibacterial hole sealing mixed solution is 90 ℃, and the hole sealing treatment time is 12min.
Example III
The difference from the first embodiment is that: the predetermined ratio in step s5 is a ratio of 3%. The antibacterial liquid comprises 0.1g/l silver salt, 0.1g/l copper salt and 0.1g/l zinc salt; the hole sealing liquid comprises 6g/l nickel acetate, 1g/l methylene dinaphthyl sodium sulfonate concentration, 0.4g/l sodium acetate and 0.2g/l boric acid. The temperature of the antibacterial hole sealing mixed solution is 80 ℃, and the hole sealing treatment time is 9min.
Example IV
The difference from the first embodiment is that: the predetermined ratio in step s5 is a ratio of 2%. The antibacterial liquid comprises 0.01g/l silver salt, 0.01 copper salt and 0.01g/l zinc salt; the hole sealing liquid comprises 5g/l nickel acetate, 0.5g/l methylene dinaphthyl sodium sulfonate concentration, 0.2g/l sodium acetate and 0.1g/l boric acid. The temperature of the antibacterial hole sealing mixed solution is 70 ℃, and the hole sealing treatment time is 5min.
Comparative example
The difference from the first embodiment is that: the components of the antibacterial liquid comprise 1.0g/l silver salt.
The aluminum substrate finished products obtained in examples one to four and the aluminum substrate finished products obtained in comparative examples were subjected to performance tests, and the test results are shown in the following table.
In the above table, as can be seen from the comparison between the test results of examples one to four, the higher the concentration of each component of the antibacterial solution and the concentration of each component of the sealing solution, the higher the antibacterial rate of the obtained aluminum substrate finished product, the stronger the antibacterial durability, and the stronger the corrosion resistance. As can be seen from the comparison between the test results of the comparative example and the test results of the first example, the aluminum substrate finished product prepared in the comparative example is weaker in the antibacterial durability and corrosion resistance test than the aluminum substrate finished product prepared in the first example, so that it can be judged that the antibacterial durability and corrosion resistance of the aluminum substrate finished product are poor due to the fact that the copper salt and zinc salt are not included in the antibacterial liquid of the comparative example, and the surface of the aluminum substrate finished product prepared in the comparative example is not provided with the composite passivation layer.
The above-described embodiments are merely preferred embodiments of the present invention, and are not intended to limit the present invention in any way. Any person skilled in the art, using the disclosure above, may make many more possible variations and modifications of the technical solution of the present invention, or make many more modifications of the equivalent embodiments of the present invention without departing from the scope of the technical solution of the present invention. Therefore, the protection of the present invention should be covered by equivalent changes made according to the inventive concept without departing from the technical scheme of the present invention.
Claims (10)
1. A preparation method of an anodic aluminum oxide alloy with high antibacterial durability is characterized by comprising the following steps: the method comprises the following steps:
step s1, soaking an aluminum substrate in degreasing solution for degreasing treatment so as to remove grease on the surface of the aluminum substrate;
step s2, immersing the aluminum substrate in an alkaline etching solution for alkaline etching treatment to remove an oxide film on the surface of the aluminum substrate;
step s3, immersing the aluminum substrate in an ash removal solution for ash removal treatment to remove hydroxide deposition generated in the alkaline etching treatment, and neutralizing the residual alkaline etching solution on the surface of the aluminum substrate;
step s4, immersing the aluminum substrate in an anodic oxidation solution, and electrifying in the anodic oxidation solution to form a porous layer on the surface of the aluminum substrate;
step 5, soaking the aluminum substrate in an antibacterial hole sealing mixed solution for hole sealing treatment, wherein the antibacterial hole sealing mixed solution is prepared by mixing antibacterial solution and hole sealing solution in a preset ratio; the antibacterial liquid comprises silver salt 0.01-1.0g/l, copper salt 0.01-1.0g/l and zinc salt 0.01-1.0 g/l; the hole sealing liquid comprises 5-10g/l nickel acetate, 0.5-1.5g/l methylene dinaphthyl sodium sulfonate concentration, 0.2-1g/l sodium acetate and 0.1-0.5g/l boric acid;
and step S6, carrying out high-temperature drying treatment on the aluminum substrate to remove the water on the surface of the aluminum substrate.
2. The method for producing an anodized aluminum alloy having high antibacterial activity and durability according to claim 1, characterized by: between step s4 and step s5, the aluminum substrate is immersed in a dyeing solution to be dyed.
3. The method for producing an anodized aluminum alloy having high antibacterial activity and durability according to claim 2, characterized by: the dyeing solution comprises 0.1-10g/l of dyeing toner, wherein the dyeing toner is organic dyeing toner; the temperature of the dyeing solution is 35-55 ℃; the dyeing treatment time is 0.5-5min.
4. The method for producing an anodized aluminum alloy having high antibacterial activity and durability according to claim 1, characterized by: the degreasing solution comprises 10-25g/l sodium phosphate, 5-15g/l sodium carbonate and 1-5g/l polyoxyethylene polyoxypropylene ether; the temperature of the degreasing solution is 30-60 ℃; degreasing treatment time is 3-10min.
5. The method for producing an anodized aluminum alloy having high antibacterial activity and durability according to claim 1, characterized by: the alkaline etching solution comprises 40-70g/l sodium hydroxide, 10-20g/l sodium phosphate and 10-20g/l sodium carbonate; the temperature of the alkaline etching solution is 65-70 ℃; the alkali etching treatment time is 1-3min.
6. The method for producing an anodized aluminum alloy having high antibacterial activity and durability according to claim 1, characterized by: the components of the ash removal solution comprise 5-20g/l ferric nitrate and 50-100g/l nitric acid; the temperature of the ash removal solution is 25-30 ℃; the ash removal treatment time is 1-3min.
7. The method for producing an anodized aluminum alloy having high antibacterial activity and durability according to claim 1, characterized by: the anodic oxidation solution comprises 150-200g/l sulfuric acid and 2-15g/l aluminum sulfate; the temperature of the anodic oxidation solution is 18-23 ℃; the energizing voltage is 13-20v, and the energizing time is 3-15min.
8. The method for producing an anodized aluminum alloy having high antibacterial activity and durability according to claim 1, characterized by: the predetermined proportion in the step s5 is 2-5%.
9. The method for producing an anodized aluminum alloy having high antibacterial activity and durability according to claim 1, characterized by: the temperature of the antibacterial hole sealing mixed solution is 70-95 ℃, and the hole sealing treatment time is 5-15min.
10. The method for producing an anodized aluminum alloy having high antibacterial activity and durability according to claim 1, characterized by: in the step s6, high-temperature drying treatment is performed on the aluminum substrate through an oven, wherein the temperature of the high-temperature drying treatment is 80-100 ℃, and the time of the high-temperature drying treatment is 1-2min.
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