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
  • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
• • 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

Definitions

• the present invention relates to an improvement in a method for forming an anodic oxide film on the surface of aluminum or an aluminum alloy. Background technology
• Anodizing aluminum or its alloy in an electrolytic solution such as nitric acid, sulfuric acid, or chromic acid aqueous solution mainly to improve its corrosion resistance to form a corrosion-resistant oxide film is alumite.
• an electrolytic solution such as nitric acid, sulfuric acid, or chromic acid aqueous solution mainly to improve its corrosion resistance to form a corrosion-resistant oxide film
• alumite Known as a treatment, the alumite-treated product thus obtained is widely used in various fields, mainly for daily necessities such as pots and kettles.
• the upper layer of the alumite film is generally porous, the corrosion resistance is still insufficient, and the abrasion resistance, the ease of coloring and the like have not been satisfactory.
• Patent Documents 1 to 3 below disclose a technique for forming a composite film of an aluminum oxide film and an acryl resin composition, and further relates to a shape of an object to be processed.
• a technique for forming a dense composite film in a short period of time, and a technique for improving its coloring property are disclosed.
• Patent Document 1 Japanese Patent Publication No. 0 1—0 1 9 4 7 9
• Patent Document 2 Japanese Patent Application Laid-Open No. H02-09976998
• Patent Document 3 Japanese Patent Publication No. 0 5—0 1 4 0 3 3
• anodic oxide film can be easily formed on an A1-Mn-based alloy, but a treatment can be performed on a duralumin-die-cast alloy. It is impossible, and there is a problem that it is difficult to treat other aluminum alloys.
• Films formed by the conventional method are also relatively thin, about 30 to 50 / m in thickness, and have low hardness and other limitations.
• the present invention has been made to solve the above-mentioned problems, and has an object In addition to aluminum itself, it can be applied to all kinds of aluminum alloys including duralumin and die-casting alloys. Surface treatment of aluminum or aluminum alloy, which has many advantages such as high heat resistance, excellent heat resistance and antibacterial properties, and can produce various aluminum materials that can be used in a much wider range of fields than before It is to provide a method.
• the above object of the present invention is to
• process of the present invention (1) for convenience of description, and the product obtained thereby is referred to as “product of the present invention (1)”.
• product of the present invention (1) By using a bath solution to which a low-polymerized acrylic resin composition is added in the range of 280 gr / 1 to 320 gr / 1 to the bath solution used in the above treatment (1) of the present invention, The object can be achieved more suitably.
• present invention processing (2) This processing according to the present invention is referred to as “present invention processing (2)” for convenience of explanation, and the product obtained thereby is referred to as “present invention product (2)”.
• a bath solution containing tartaric acid in the range of 5 gr / 1 or more and 15 gr Z1 or less may be used for the bath solution. Recommended.
• process of the present invention (3) Such a process according to the present invention is referred to as “process of the present invention (3)” for convenience of explanation, and a product obtained thereby is referred to as “product of the present invention (3)”.
• the object of the present invention is further to form an anodic oxide film having a thickness of 300 m or more and 600 m or less on the surface of aluminum or an aluminum alloy by the above-mentioned various treatment methods, and further performing the silver impregnation thereon,
• the method can also be achieved by forming an anodized film on the surface of aluminum or aluminum alloy, characterized in that the surface layer is removed to a thickness of 50 m or more and 100 m or less by polishing to obtain a superhard smooth surface.
• FIG. 1 is an explanatory view showing one embodiment of an apparatus for implementing a method for forming an anodized film on a surface of aluminum or an aluminum alloy according to the present invention.
• FIG. 2 is an enlarged sectional view of a portion to be coated with aluminum or an aluminum alloy which has been subjected to the treatment (2) of the present invention.
• 1 is an electrolytic cell
• 2 is an AC power supply
• 3 is an aluminum or aluminum alloy member to be treated by the method of the present invention
• 4 and 4 are non-consumable electrodes such as rubber and graphite
• 5 Is a bath solution composed of a predetermined electrolytic solution.
• an apparatus as shown in Fig. 1 was used, and as a bath solution, sulfuric acid of 250 gr / 1 or more and 350 gr / l or less, and 15 gr / 1 or more and 25 gr / 1 or less Using an aqueous solution containing sulphate nigel,
• the anodizing treatment is performed under the conditions described above.
• the present invention is completely different from the conventional method in that the anodic oxidation treatment is performed under the processing conditions of high sulfate ion concentration, low temperature, and high current density.
• Nigel sulfate is added to improve the hardness of the formed film.
• Examples of the aluminum or aluminum alloy material forming the anodic oxide film by the treatment method of the present invention include those listed in Table 1 below. table 1
• an anodic oxide film could be easily formed on A1-Mn alloys, but it was not possible to treat duralumin and die cast alloys, and to treat other alloys. Was difficult.
• the method of the present invention can be applied to all kinds of aluminum alloys such as duralumin, die cast alloys and the like.
• the film formed by the conventional method has a hard surface layer (however, a Pickers hardness of 400 or less), but has a porous inside and low hardness.
• the coating formed by the method of the present invention has a high surface hardness and a Vickers hardness of about 450 to 500.
• the lower layer is denser and harder than the surface, and when removed from the surface by 50 to 150 m, the Vickers hardness becomes 800 to 1000.
• the film formed by the method of the present invention has high thermal conductivity, which is comparable to that of copper.
• the coating formed by the method of the present invention has low surface heat transmission resistance.
• the ice melts twice as fast as an untreated tray. Therefore, for example, it can be suitably used as a tray for thawing frozen foods.
• the time from the start of heating to the first explosion of the popcorn is reduced from 6 minutes of the conventional product to 3 minutes.
• the film formed by the method of the present invention has a high heat resistance and is about 800 ° C.
• the film formed by the method of the present invention has antibacterial properties.
• the aluminum material or aluminum alloy material on which the anodized film is formed by the method of the present invention is, for example, a tray for ice making and thawing, a rice cooker, a pot, a pot, a kettle, other heating cookers, and an instantaneous boiling water.
• a low-polymerized acrylic resin composition is further added to the bath used in the treatment (1) of the present invention in a range of 280 gr / 1 or more and 320 gr / 1 or less. Anodizing treatment is performed using the added bath solution.
• Examples of the low-polymerized acrylic resin composition to be added include, for example, 68% of hydroxypropyl methacrylate, 10% of neopentyl dalichol dimethacrylate, 19.5% of polypropylene glycol methyl acrylate, and 6 Hexanediol diglycidyl ether 1%, butyl peroxyctoate 1%, hydroquinone monomethyl ether 500ppra, and dicyandiamide 0.3% are preferably used.
• tartaric acid be further added to the above bath solution in a range of 5 gr / 1 or more and 15 gr / 1 or less.
• an oxide film in which aluminum oxide and the acrylic resin composition are combined is formed. That is, since the porous oxide film on the metallurgy and the acrylic resin fabric are polymerized by acid ionization to form a strong and dense composite film, the corrosion resistance and the abrasion resistance are greatly improved. In addition, since the film is generated while evacuating the gas from the pinholes, the number of pinholes is extremely small. Furthermore, the oxide film is formed slowly at low temperatures, so it has excellent denseness and the film is hard to peel off, so it is machined. And the surface roughness does not change.
• reference numeral 21 denotes a base metal aluminum or aluminum alloy material
• 22 denotes an anodized film
• 23 denotes a barrier layer thereof
• 24 denotes a porous film portion
• 25 denotes an acrylic resin composition film portion.
• the anodic oxide film 22 is composed of a barrier layer 23 formed on an aluminum material or an aluminum alloy material 21, a porous film portion 24 formed thereon, and an acryl resin composition penetrated and fixed in the porous layer. And a coating layer 25.
• a strong and dense composite coating is formed by the coating layers 24 and 25. Since the hardness of the composite coating increases as the portion is closer to the barrier layer 23 and becomes denser, a region closer to the surface can be removed by machining to obtain a surface with higher hardness as described later.
• the process (3) of the present invention will be described.
• the decrease in silver ion concentration with the progress of processing is compensated for by replenishment of silver sulfate or silver nitrate.
• Boric acid is mainly added for adjusting the conductivity of the electrolyte.
• the processing efficiency is poor. If the voltage is more than 15 V, silver is deposited too rapidly, so that the porous layer of the oxide film is not sufficiently impregnated. Almost occur.
• silver ions are formed in the porous anodic oxide film. Penetrates deeply (electrolytically impregnated by AC voltage), and forms a strong and dense composite film by combining with aluminum oxide, so the surface has excellent thermal conductivity, corrosion resistance, abrasion resistance, antibacterial properties, etc. A coating is formed.
• the surface coating is conductive, has a low coefficient of friction on the surface, and has little change in color over time. It also has the effect of generating far infrared rays and removing static electricity.
• the treatment (3) of the present invention can be applied to all aluminum materials or aluminum alloy materials, and a thick film having the above-mentioned various excellent properties can be formed on the surface thereof.
• the present invention further provides an anodic oxide film having a thickness of not less than 300 m and not more than 600 im on the surface of aluminum or an aluminum alloy by the above various treatment methods, and further performing the above silver impregnation thereon.
• the present invention provides an aluminum material or an aluminum alloy material having a superhard smooth surface by removing a surface layer from 50 / xm to 100 m by polishing.
• the coating formed by the method of the present invention has a high surface hardness, and has a Vickers hardness of about 450 to 500.
• the lower layer is denser and harder than the surface. Therefore, removing 50 to 50 L from the surface gives an aluminum or aluminum alloy material with a smooth surface with a Vickers hardness of 800 to 1000, which is very hard.
• Table 2 shows the properties of the products treated according to the present invention for each material.
• the thermal conductivity is 0.9 for the product of the present invention, 0.94 for copper, and 0.53 for aluminum, assuming that silver is 1. Therefore, the thermal conductivity of the product of the present invention is higher than that of aluminum of the base material and about the same as that of copper.
• This property indicates that it is excellent as a material for various heat transfer members, heat transmission members, and heat radiation members.
• the hardness (Hv) is 80 for aluminum, 200 for stainless steel, and 450 for the product of the present invention, and the product of the present invention has twice or more the hardness of stainless steel.
• the heat resistance temperature (t :) is 260 ° C for polytetrafluoroethylene, 660 ° C for aluminum, and 800 ° C for the surface coating of the product of the present invention.
• the amount of abrasion of the product of the present invention was 1 Z10 of ordinary hard alumite.
• an abrasion test was performed with the test piece on the rotating side and the resin-based oilless bearing material on the fixed side.
• the test conditions were a vibration speed of 1 mZs, a surface pressure of 20 kgf cm2 and a test time of 3 hr.
• the wear amount of the hard anodized was 2.5 m
• the wear amount of the product of the present invention was 0.25 m.
• the seizure surface pressure of the product of the present invention was twice that of ordinary hard alumite.
• the wear coefficient was measured with the test piece on the rotating side and the resin-based oil-free bearing material on the fixed side, and the load at which the wear coefficient increased sharply was evaluated as the seizure limit load.
• ordinary hard alumite was 160 kgf / cm2
• that of the product of the present invention was 320 kgf / cm2.
• the product of the present invention showed that the initial cracks were smaller than that of Tafram (trade name; a product in which hard alumite was sintered and impregnated with polytetrafluoroethylene). The number of cracks increased by heating was small.
• the product of the present invention was 0 before heating, but became 12 after heating, whereas the evening flam was before heating. From 263 to 321 after heating. An antibacterial test was performed. The contents are as follows.
• sample a sample
• viable cell count of the sample after storage at 35 ° C. for 24 hours was measured.
• Escherichia coli IFO 3301 E. coli
• Staphylococcus aureus IFO 12732 Staphylococcus aureus
• Vibrio parahaemolyticus RIMD 2210100 Vibrio parahaemolyticus
• Salmonella enteritidis IFO 3313 (Salmonella)
• NA medium normal agar medium
• NB medium normal broth medium supplemented with 0.2% meat extract
• SA medium Standard agar medium
• test bacteria were cultured in NA medium at 35 ° C for 16 to 24 hours, they were inoculated again into NA medium and cultured at 35 ° C for 16 to 20 hours. After the cultivation, so Nigosa suspended bacterial cells obtained test bacteria to 1 Z200 concentration NB medium, appropriately diluted with 1/200 concentration NB medium so that the number of bacteria is 10 5 to 10 6 ml, was used as a cell solution .
• an NA medium and a 1Z200 concentration NB medium supplemented with 3% of sodium chloride were used for Vibrio parahaemolyticus.
• test surface of the sample was gently wiped with absorbent cotton containing 99.9% (V / V) ethanol, and then thoroughly dried.
• Test operation 0.5 ml of the bacterial solution was added dropwise to the sample, and a polyethylene film was adhered to the sample. The solution was stored at 35 ° C, and the number of viable cells after storage for 24 hours was measured. Also, 0.5 ml of the bacterial solution was dropped on a plastic dish, and a polyethylene film was adhered to the sample, which was used as a control sample for the same test. The trial was performed three times in parallel measurement.
• SCDLP medium Nahon Pharmaceutical Co., Ltd.
• the number of viable bacteria was measured by a pour plate method (cultured at 35 ° C. for 48 hours) using an SA medium and converted to a sample.
• SCDLP medium and SA medium supplemented with 3% of salt were used.
• an anodic oxide film could be easily formed on A1-Mn alloy.
• Duralumin and die casting alloys could not be treated, and other alloys were difficult to treat.
• the method of the present invention can be applied to all kinds of aluminum alloys such as duralumin, die cast alloys and the like.
• the film formed by the conventional method has a hard surface layer (however, a Pickers hardness of 400 or less), but has a porous inside and low hardness.
• the coating formed by the method of the present invention has a high surface hardness and a Vickers hardness of about 450 to 500.
• the lower layer is denser and harder than the surface, and when removed from the surface by 50 to 150 m, the pickers hardness becomes 800 to 1000.
• the film formed by the method of the present invention has high thermal conductivity, which is comparable to that of copper.
• the coating formed by the method of the present invention has low surface heat transmission resistance.
• the ice melts twice as fast as an untreated tray. Therefore, for example, it can be suitably used as a tray for thawing frozen foods.
• the aluminum heating container for popcorn is treated by the method of the present invention, the time from the start of heating to the first explosion of the popcorn is reduced from 6 minutes to 3 minutes of the conventional product.
• the film formed by the method of the present invention has a high heat resistance and is about 800 ° C.
• the film formed by the method of the present invention has antibacterial properties. Therefore, as described above, the aluminum material or the aluminum alloy material on which the anodized film is formed by the method of the present invention is, for example, a tray for ice making and thawing, a rice cooker, a pot, a pot, a kettle and other heating cookers, Water heaters, heat exchangers, air conditioners, refrigerators, refrigerators, oil heaters, radiators, cooling fins, air-cooled and water-cooled engines (promoting heat dissipation), aircraft wings (anti-icing prevention), semiconductor heat dissipation boards, Semiconductor packages, heat pipes, bearings, various sliding members, plastics, popcorn and ice cream It can be suitably used in a wide range of fields, such as manufacturing equipment, electrical equipment chassis, motors and casings for transformers, etc.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Other Surface Treatments For Metallic Materials (AREA)
• Laminated Bodies (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• ing And Chemical Polishing (AREA)

Priority Applications (7)

Applications Claiming Priority (2)

Publications (1)

Family

ID=32820698

Family Applications (1)

Country Status (11)

Cited By (3)

Families Citing this family (18)

Citations (5)

Family Cites Families (8)

• 2004
  • 2004-01-27 BR BR0407080-1A patent/BRPI0407080A/pt not_active IP Right Cessation
  • 2004-01-27 EP EP04705515A patent/EP1593758A4/en not_active Withdrawn
  • 2004-01-27 AU AU2004207220A patent/AU2004207220A1/en not_active Abandoned
  • 2004-01-27 US US10/542,533 patent/US20070267299A1/en not_active Abandoned
  • 2004-01-27 WO PCT/JP2004/000684 patent/WO2004067807A1/ja active Application Filing
  • 2004-01-27 KR KR1020057013998A patent/KR20050103284A/ko not_active Application Discontinuation
  • 2004-01-27 MX MXPA05008032A patent/MXPA05008032A/es unknown
  • 2004-01-27 CN CNA2004800033090A patent/CN1745200A/zh active Pending
  • 2004-01-27 JP JP2005504706A patent/JP4069135B2/ja not_active Expired - Fee Related
  • 2004-01-27 CA CA002514271A patent/CA2514271A1/en not_active Abandoned
  • 2004-01-29 TW TW093101996A patent/TW200417635A/zh unknown

Patent Citations (5)

Also Published As

Similar Documents

Legal Events