CN105408527A - Treated surface aluminum material and manufacturing method therefor - Google Patents
Treated surface aluminum material and manufacturing method therefor Download PDFInfo
- Publication number
- CN105408527A CN105408527A CN201480041347.9A CN201480041347A CN105408527A CN 105408527 A CN105408527 A CN 105408527A CN 201480041347 A CN201480041347 A CN 201480041347A CN 105408527 A CN105408527 A CN 105408527A
- Authority
- CN
- China
- Prior art keywords
- oxide scale
- aluminium
- scale film
- electrode
- solidity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
-
- 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
- C25D11/005—Apparatus specially adapted for electrolytic conversion coating
-
- 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
- C25D11/024—Anodisation under pulsed or modulated current or potential
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/007—Current directing devices
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
- H05K1/053—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an inorganic insulating layer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
To provide a treated surface aluminum material, on a portion of the surface of which a corrosion-resistant oxide film layer is formed and on the other areas of the surface of which a porous oxide film layer of excellent adhesiveness and closeness of adhesion is formed. A treated surface aluminum material and a manufacturing method therefor. The treated surface aluminum material comprises an aluminum material, a monolayer structure corrosion resistant oxide film formed on a portion of the surface of the aluminum material, and a porous oxide film formed on the other areas of the surface. The corrosion resistant oxide film has a 10-100 nm thickness and has specified FT-IR analysis characteristics. The porous oxide film is obtained from a 20-500 nm thick porous aluminum oxide film layer formed on the surface side and 3-30 nm barrier aluminum oxide film layer formed on the base side. Pores of 5-30 nm diameter are formed in the porous aluminum oxide film layer. The range of fluctuation in thickness in the overall porous oxide film formed on the surface of the aluminum material is within +/- 50% of the arithmetic mean thereof.
Description
Technical field
The present invention relates to one, to implement surface-treated fine aluminium material or aluminium alloy material (following, be designated as " aluminium ") and manufacture method, specifically, relate to a kind of surface treated aluminum material and manufacture method thereof, this surface treated aluminum material is formed with the solidity to corrosion oxide skin rete of corrosion resistance excellent in the part on surface, is formed with the porousness oxide skin rete of cementability and excellent adhesion at the position on the surface not being formed with this solidity to corrosion oxide skin rete.
Background technology
Aluminium lightweight and there is the mechanical characteristics of appropriateness, and there is the excellent feature such as aesthetic feeling, molding processibility, solidity to corrosion, therefore can be widely used in various container class, structured material, mechanical part, electronic unit etc.By implementing surface treatment to a part for these aluminiums, can give and improve the functions such as solidity to corrosion, wear resistant, resin closed, cementability, wetting ability, water-repellancy, germ resistance, intention, infrared emission, highly reflective, extensively utilize.
Such as, as the surface preparation improving solidity to corrosion and wear resistant, anodic oxidation treatment (so-called anodised aluminium process) is widely used.Specifically, as described in non-patent literature 1,2, by being bathed in acidic electrolysis by aluminium material impregnation and utilizing galvanic current to carry out electrolysis treatment and form anodic oxide coating, various treatment process is proposed according to purposes.
In addition, especially as the surface preparation making resin closed improve, in patent documentation 1, propose a kind of alkali alternating-current solution.That is, the bath temperature basic solution of 35 ~ 85 DEG C is used, with current density 4 ~ 50A/dm
2, electricity is more than 80C/dm
2time, carry out alternating current electrolysis process.Obtain thus and be formed with thickness
the printed wiring substrate of oxide scale film.
Prior art document
Non-patent literature
Non-patent literature 1: ア Le ミ ニ ウ system Ha Application De Block ッ Network the 7th edition, 179 ~ 190 pages, 2007, general society team legal person Japan ア Le ミ ニ ウ ム Association meeting
Non-patent literature 2: JIS JISH8601, " ア Le ミ ニ ウ system and び ア Le ミ ニ ウ system alloy Yang Very acidifying epithelium " (1999)
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 5-191001 publication
Summary of the invention
Invent problem to be solved
In prior art as above, be wired directly to after aluminium carries out electrolysis treatment, make aluminium itself become electrode.Therefore, surface treatment is implemented the regional integration that aluminium touches electrolytic solution.
When implementing the surface treatment of giving resin closed to a part for aluminium, by coating surface portion not implementing to process such as masking belts.To not implemented surface treatment by the part be coated to, therefore, resin closed improves.But do not implement surface treatment owing to eliminating coating part after surface treatment, therefore, this part, as preset, is not endowed resin closed, exists and does not obtain corrosion proof problem.
Now, after the surface treatment of raising resin closed is implemented to a part for aluminium material surface, corrosion proof surface treatment must be given to not implementing surface-treated part.Therefore, the coating surface-treated part implementing raising resin closed, carries out the surface treatment of the 2nd time once again.Therefore, carry out 2 times and coating not only cause cost to improve, also there is the operation that needs in addition to carry out the 2nd subsurface process thus reduce productive problem.
For solving the method for problem
The present inventor is repeated research to solve above-mentioned problem, found that and a kind ofly only form solidity to corrosion oxide scale film at specific part and form the surface treated aluminum material with the porousness oxide scale film of adaptation in the part not forming solidity to corrosion oxide scale film, and form the manufacture method of surface treated aluminum material of these solidity to corrosion oxide scale films and porousness oxide scale film, thus complete the present invention simultaneously.
Namely, the present invention is a kind of surface treated aluminum material in claim 1, it is characterized in that, comprising: aluminium, be formed at this aluminium material surface a part and there is the solidity to corrosion oxide scale film of single layer structure and be formed at the porousness oxide scale film not forming the position of solidity to corrosion oxide scale film of above-mentioned aluminium material surface, above-mentioned solidity to corrosion oxide scale film has the thickness of 10 ~ l00nm, if analyzing by FT-IR the peak absorption wavenumber obtained is b (cm
-1), when the peak specific absorption of peak absorption wavenumber b is a (%), meet l≤a≤95 and the relation of b>=3a+710, above-mentioned porousness oxide scale film comprises and is formed at face side and thickness is the multi-hole type aluminum oxidation skin membrane of 20 ~ 500nm, with be formed at substrate side and thickness is the isolation-type aluminum oxidation skin membrane of 3 ~ 30nm, the aperture of diameter 5 ~ 30nm is formed at above-mentioned multi-hole type aluminum oxidation skin membrane, be formed in the porousness oxide scale film entirety of aluminium material surface, the amplitude of fluctuation of the aggregate thickness of above-mentioned multi-hole type aluminum oxidation skin membrane and isolation-type aluminum oxidation skin membrane this aggregate thickness arithmetical av ± 50% within.
The present invention is as in claim 1 in claim 2, above-mentioned peak absorption wavenumber b (cm
-1) be the wave number at the peak of the strongest stretching vibration from Al-O, come across the scope of 720≤b≤995.
The present invention is as in claim 1 or 2 in claim 3, and total hole area of the aperture of above-mentioned multi-hole type aluminum oxidation skin membrane is 25 ~ 75% relative to the ratio of the surface-area on apparent.
The present invention is a kind of manufacture method of surface treated aluminum material in claim 4, it is characterized in that: use and want the electrode of surface-treated aluminium, to electrode and the conduction material being wired to above-mentioned aluminium electrode, using pH9 ~ 13, liquid temperature 35 ~ 85 DEG C and molten deposit aluminum concentration be more than 5ppm, below l000ppm alkaline aqueous solution as electrolytic solution, at frequency 10 ~ 100Hz, current density 4 ~ 50A/dm
2alternating current electrolysis process is carried out with under the electrolysis time condition of 5 ~ 60 seconds, form porousness oxide scale film with to the above-mentioned aluminium material surface of electrode contraposition thus, and form solidity to corrosion oxide scale film at the above-mentioned aluminium material surface opposed with the conduction material being wired to aluminium electrode simultaneously.
The present invention is as in claim 4 in claim 5, above-mentioned want surface-treated aluminium electrode with tabular is to electrode, the above-mentioned area being wired to the conduction material of aluminium electrode in electrolytic solution is 80 ~ 150% of the area for forming solidity to corrosion oxide scale film, and the distance of above-mentioned conduction material and aluminium is 1 ~ 50mm.
The present invention is as in claim 4 or 5 in claim 6, and the above-mentioned conduction material being wired to aluminium electrode is made up of stainless steel or copper material.
The present invention is as in any one in claim 4 ~ 6 in claim 7, conduction material is configured at the side, a face of above-mentioned aluminium electrode, make it opposed with this face, another side, face of aluminium electrode will be configured to electrode, make it opposed with this face, form solidity to corrosion oxide scale film in an above-mentioned face of aluminium electrode thus, form porousness oxide scale film in another face above-mentioned.
The present invention is as in any one in claim 4 ~ 6 in claim 8, another side, face of above-mentioned aluminium electrode will be configured to electrode, make it opposed with this face, conduction material is configured in this another face and between electrode, make it opposed with the part in another face of aluminium electrode, by above-mentioned electrode is configured to opposed with other position of the above-mentioned part in another face being complementary to aluminium electrode, solidity to corrosion oxide scale film is formed thus in the above-mentioned part in another face of aluminium electrode, porousness oxide scale film is formed at other position above-mentioned of aluminium electrode.
The effect of invention
Pass through the present invention, a kind of surface treated aluminum material and manufacture method thereof can be provided, the feature of this surface treated aluminum material is, is formed with solidity to corrosion oxide scale film in the part on surface, is formed with the porousness oxide scale film with adaptation at the position not being formed with solidity to corrosion oxide scale film.
Accompanying drawing explanation
Fig. 1 is the diagrammatic cross-section of a part for surface treated aluminum material of the present invention.
Fig. 2 is the diagrammatic cross-section at other position of surface treated aluminum material of the present invention.
Fig. 3 is the frontview of an embodiment of the electrolyzer showing aluminium of the present invention.
Fig. 4 is the frontview of another embodiment of the electrolyzer showing aluminium of the present invention.
Embodiment
Below, details of the present invention is sequentially described.
As shown in Figure 1, solidity to corrosion oxide scale film 3 is formed with in the part on the surface of surface treated aluminum material 1 of the present invention.In addition, as shown in Figure 2, porousness oxide scale film 4 is formed with in the surface portion of the aluminium 2 not being formed with solidity to corrosion oxide scale film 3.
A. about aluminium
As the aluminium used in the present invention, pure aluminum or aluminum alloy can be used.There is no particular restriction for the composition of aluminium alloy, can use the various alloys comprising the alloy specified in JIS.With regard to shape, be not particularly limited, from the viewpoint of stablizing formation processing epithelium, be applicable to using tabular.
B. about the solidity to corrosion oxide scale film structure of aluminium material surface
As shown in Figure 1, it is 10 ~ l00nm, the atypic solidity to corrosion oxide scale film 3 being preferably 20 ~ 80nm that the part on the surface of the aluminium 2 used in the present invention forms thickness.This solidity to corrosion oxide scale film 3 is the epithelium of single layer structure.If the multilayered structure of non-single layer structure, crevice corrosion occurs between top layer and middle layer, therefore sufficient solidity to corrosion cannot be shown.In addition, also solidity to corrosion oxide scale film 3 can be formed whole of aluminium 2.When the thickness of solidity to corrosion oxide scale film 3 is less than l0nm, sufficient solidity to corrosion cannot be obtained.On the other hand, controlling solidity to corrosion oxide scale film thickness more than being then difficult to during l00nm, process occurring uneven.
The peak absorption wavenumber b (cm of the infrared absorption spectrum when film quality of this solidity to corrosion oxide scale film 3 is by analyzing with FT-IR (fourier transform formula Infrared spectrophotometer)
-1) and the peak specific absorption (a%) that obtained by the baseline in this peak absorption wavenumber and give feature.Here, peak absorption wavenumber b (cm
-1) be the absorption wavenumber at the peak of the strongest stretching vibration from Al-O.In addition, peak absorption wavenumber b (cm
-1) usually come across the scope of 720≤b≤995.
In solidity to corrosion oxide scale film used in the present invention, regulation: the above-mentioned peak specific absorption a (%) when utilizing FT-IR to analyze is l≤a≤95, is preferably 2≤a≤75.When this peak specific absorption is less than 1%, the thickness of solidity to corrosion oxide scale film is less than 10nm, makes solidity to corrosion not enough.If this peak specific absorption is more than 95%, then the thickness of solidity to corrosion oxide scale film is more than l00nm, is difficult to control solidity to corrosion oxide scale film thickness, easily causes process uneven.In addition, in the present invention, peak specific absorption a (%) and peak absorption wavenumber b (cm
-1) meet b>=3a+710, be preferably the relation of b>=3a+720.When not meeting this relation, the epithelium shape of solidity to corrosion oxide scale film becomes Porous shape, causes solidity to corrosion to reduce.
C. about the porousness oxide scale film structure of aluminium material surface
As shown in Figure 2, porousness oxide scale film 4 is formed with at the aluminium material surface at the position not being formed with solidity to corrosion oxide scale film.Porousness oxide scale film 4 comprises the isolation-type aluminum oxidation skin membrane 41 of the substrate side of aluminium 2 and the multi-hole type aluminum oxidation skin membrane 42 of side, top layer.
C-1. multi-hole type aluminum oxidation skin membrane
The thickness of multi-hole type aluminum oxidation skin membrane 42 is 20 ~ 500nm.When being less than 20nm, thickness is insufficient, and therefore the formation of small structure described later easily becomes insufficient, and bonding force or closing force are reduced.On the other hand, if more than 500nm, multi-hole type aluminum oxidation skin membrane easily aggegation itself destroys and bonding force or closing force is reduced.The thickness of multi-hole type aluminum oxidation skin membrane 42 is preferably 30 ~ 400nm.
In addition, multi-hole type aluminum oxidation skin membrane 42 possesses the aperture 420 deep towards depth direction from its surface.The diameter of aperture 420 is 5 ~ 30nm, is preferably 10 ~ 20nm.This aperture plays the effect making resin layer and caking agent etc. and the contact area of aluminum oxidation epithelium increase, its bonding force or closing force are increased.If hole diameter is less than 5nm, then contact area is not enough, so cannot obtain sufficient bonding force or closing force.On the other hand, if hole diameter is more than 30nm, then multi-hole type aluminum oxidation skin membrane entirety can become fragile, and produces aggegation and destroys, and bonding force or closing force are reduced.
There is no particular restriction relative to the ratio of the surface-area of multi-hole type aluminum oxidation skin membrane for total hole area of aperture.Total hole area of the aperture of multi-hole type aluminum oxidation skin membrane is preferably 25 ~ 75% relative to the ratio of the surface-area (not considering the minute asperities etc. on surface, the area with long and wide product representation) on apparent.When being less than 25%, contact area may be not enough and cannot obtain sufficient bonding force or closing force.On the other hand, if more than 75%, multi-hole type aluminum oxidation skin membrane entirety may become fragile, and produces aggegation and destroys, and bonding force or closing force are reduced.
C-2. isolation-type aluminum oxidation skin membrane
Isolation-type aluminum oxidation skin membrane 41 asks the oxide scale film of the densification of thickness 3 ~ 30nm.When thickness is less than 3nm, cannot give sufficient bonding force as the combination of interposed layers to multi-hole type aluminum oxidation skin membrane 4 and aluminium base 2, the bonding force especially under the harsh and unforgiving environments of high temperature and humidity etc. becomes insufficient.On the other hand, if more than 30nm, easily affect by its compactness, make isolation-type aluminum oxidation skin membrane 3 that aggegation occur and destroy, bonding force or closing force can be made on the contrary to reduce.In addition, the thickness of isolation-type aluminum oxidation skin membrane 41 is preferably 5 ~ 25nm.
C-3. the amplitude of fluctuation of the integral thickness of porousness oxide scale film
The thickness of the isolation-type aluminum oxidation skin membrane 41 recorded in the multi-hole type aluminum oxidation skin membrane 42 recorded in the integral thickness of porousness oxide scale film 4, i.e. C-1 and C-2 adds up to, no matter measure in any position being formed with porousness oxide scale film 4, its amplitude of fluctuation must within ± 50%, preferably within ± 20%.Namely, (expectation is more than 10 positions, place in any number of positions being located on aluminium material surface, being desirably in these each position is the measuring point of more than 10) arithmetical av of porousness oxide scale film integral thickness that records is when being T (nm), these are multiple locate whole in porousness oxide scale film integral thickness must in the scope of (0.5 × T) ~ (1.5 × T).If there is the position being less than (0.5 × T), the porousness oxide scale film of its position is than thin around it.Thus, in the position that this film is thin easily should bonding caking agent or should be closely sealed resin layer etc. and porousness oxide scale film between produce gap, sufficient contact area cannot be guaranteed, bonding force or closing force are reduced.
On the other hand, if there is the position exceeding (1.5 × T), then the porousness oxide scale film of its position is thicker than the surrounding of surrounding.Thus, concentrating the stress from answering closely sealed resin layer etc. in the position of this thickness, causing and destroying in the aggegation of porousness oxide scale film, bonding force or closing force are reduced.
In addition, be thin position or thick position at the integral thickness of porousness oxide scale film as above, compared with surrounding, its optical characteristics is different, therefore sometimes can be visually observed the change of the tone such as dark brown or gonorrhoea look.
D. about the manufacture method of aluminium
The method meeting the solidity to corrosion oxide scale film of above condition and the surface treated aluminum material of porousness oxide scale film is possessed as being manufactured on surface, described method can be listed below: use and want surface-treated aluminium electrode, be wired to aluminium and the conduction material be arranged near aluminium material surface and the electrode as the aftermentioned material to electrode, using pH9 ~ 13, liquid temperature 35 ~ 85 DEG C and molten deposit aluminum concentration be more than 5ppm, below 1000ppm alkaline aqueous solution as electrolytic solution, at frequency 10 ~ 100Hz, current density 4 ~ 50A/dm
2carry out alternating current electrolysis process with under the electrolysis time condition of 5 ~ 60 seconds, form solidity to corrosion oxide scale film at the position of the aluminium material surface opposed with conduction material thus, form porousness oxide scale film at the position with the aluminium material surface to electrode contraposition.In addition, also by making the total surface of aluminium opposed with conduction material, solidity to corrosion oxide scale film can only be formed on its surface.
Surface treated aluminum material of the present invention, uses and wants surface-treated aluminium electrode, is wired to the conduction material of aluminium electrode and to electrode, carries out alternating current electrolysis process.Be wired to and want the conduction material of surface-treated aluminium electrode to be configured in electrolytic solution near the aluminium material surface part of wish formation solidity to corrosion oxide scale film, make it opposed with this surface portion.In not opposed with conduction material aluminium material surface part, form porousness oxide scale film.In addition, in electrolytic solution, the conduction face opposed with aluminium amasss 80 ~ 150% of the aluminium area for making formation solidity to corrosion oxide scale film, is preferably 90 ~ 130%.In addition, the distance of opposed with aluminium conduction material is 1 ~ 50mm.When the area of conduction material is less than 80% of the aluminium area for forming solidity to corrosion oxide scale film, porousness oxide scale film may be formed in the part for forming solidity to corrosion oxide scale film; If more than 150%, then also may form solidity to corrosion oxide scale film in the part for forming porousness oxide scale film.When the distance of the conduction material opposed with aluminium is less than 1mm, between conduction material and opposed aluminium, be difficult to the convection current causing electrolytic solution, the process that solidity to corrosion oxide scale film easily occurs is uneven.On the other hand, if this distance is more than 50mm, the interval of conduction material and opposed aluminium is wide, causes forming porousness oxide scale film whole of aluminium.
In alternating current electrolysis treatment process, as the alkaline aqueous solution that electrolytic solution uses, the phosphoric acid salt such as sodium phosphate, potassium hydrogen phosphate, trisodium phosphate, potassium pyrophosphate and sodium-metaphosphate can be used; The alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; The carbonate such as sodium carbonate, sodium bicarbonate, salt of wormwood; Ammonium hydroxide; Or the aqueous solution of these mixtures.As described later, considering from needing the pH of electrolytic solution to be remained on specified range, preferably using the alkali aqueous solution containing the phosphate-based material can expecting buffering effect.In this alkaline aqueous solution, the concentration of contained alkali composition can suitably adjust, and makes the pH of electrolytic solution become expected value, is generally 1 × l0
-4~ 1 mol/L, is preferably l × l0
-3~ 0.8 mol/L.In addition, in these alkaline aqueous solutions, in order to improve soil removability, tensio-active agent can be added.
The pH of electrolytic solution must be set to 9 ~ 13, is preferably set to 9.5 ~ 12.PH lower than 9 time, the alkaline etching power of electrolytic solution is not enough, therefore, makes porousness oxide scale film become unsetting epithelium, makes the formation of the multi-hole type aluminum oxidation skin membrane of regulation and isolation-type aluminum oxidation skin membrane incomplete.In addition, pH lower than 9 time, be difficult to the thickness controlling solidity to corrosion oxide scale film, process easily occur uneven.On the other hand, if pH is more than 13, alkaline etching power is superfluous, and oxide skin rete is difficult to grow up, and the porousness oxide scale film desired by obstruction is formed.
Electrolytic solution temperature must be set to 35 ~ 85 DEG C, is preferably set to 40 ~ 70 DEG C.When electrolytic bath temperature is lower than 35 DEG C, alkaline etching power is not enough, and the formation of porousness oxide scale film is incomplete.On the other hand, if more than 85 DEG C, alkaline etching power is superfluous, hinders the formation of porousness oxide scale film and solidity to corrosion oxide scale film.
Molten aluminum concentration of depositing contained in electrolytic solution must be set to more than 5ppm, below l000ppm, is preferably set to more than l0ppm, below 500ppm.Molten when depositing aluminum concentration lower than 5ppm, the forming reactions of the oxide scale film at electrolytic reaction initial stage sharply occurs, and therefore may be partially formed the porousness oxide scale film of thick film, and produces uneven at solidity to corrosion oxide scale film.On the other hand, deposit aluminum concentration more than l000ppm if molten, the viscosity of electrolytic solution increases, and hinders the even convective near aluminium material surface in electrowinning process, and molten aluminium of depositing is had an effect in the direction of suppression porousness oxide scale film formation simultaneously.Its result, forms thinner porousness oxide scale film locally.Deposit aluminum concentration if molten and exceed above-mentioned scope, in the porousness oxide scale film entirety being formed at aluminium material surface, the amplitude of fluctuation being difficult to the aggregate thickness making above-mentioned multi-hole type aluminum oxidation skin membrane and isolation-type aluminum oxidation skin membrane this aggregate thickness arithmetical av ± 50% within.Its result, causes the bonding force of the porousness oxide scale film of acquisition, closing force reduces.
The frequency used is 10 ~ 100Hz.During lower than 10Hz, with regard to electricity decomposes, the key element of direct current can improve, and result cannot carry out the formation of multi-hole type aluminum oxidation skin membrane, becomes dense structure.On the other hand, if more than 100Hz, the reversion of anode and negative electrode is too fast, and the formation of oxide scale film entirety is extremely slowed down, and makes porousness oxide scale film and solidity to corrosion oxide scale film all become the time needing extremely to grow in order to the thickness obtaining regulation.In addition, the frequency of use is preferably set to 20 ~ 80Hz.
Current density must be set to 4 ~ 50A/dm
2.Current density is lower than 4A/dm
2time, preferential only formation isolation-type aluminum oxidation skin membrane in porousness oxide scale film, so cannot obtain multi-hole type aluminum oxidation skin membrane.On the other hand, if more than 50A/dm
2, electric current is excessive, is difficult to the thickness controlling porousness oxide scale film and solidity to corrosion oxide scale film, easily causes process uneven.In addition, current density is preferably set to 5 ~ 30A/dm
2.
Electrolysis time must be set to 5 ~ 60 seconds.Lower than under the treatment time of 5 seconds, the formation of porousness oxide scale film excessively sharply, fully cannot form multi-hole type aluminum oxidation skin membrane, form the oxide scale film be made up of unsetting aluminum oxide.On the other hand, if more than 60 seconds, oxide scale film dissolves again, and therefore, fully cannot form solidity to corrosion oxide skin rete, productivity also reduces, so not preferred.In addition, electrolysis time is preferably set to 10 ~ 50 seconds.
An electrode in the pair of electrodes used in alternating current electrolysis process is the aluminium that should be surface treated through electrolysis treatment.As another to electrode, such as, the known electrodes such as graphite, aluminium, Ti electrode can be used, must use and can not produce deterioration, excellent electric conductivity and itself can not cause the material of electrochemical reaction to the alkali composition of electrolytic solution or temperature.From this point to consider, be applicable to using Graphite Electrodes to electrode.This is because Graphite Electrodes is chemically being stablized, and easily to obtain at a low price, and, utilize the effect being present in a large amount of pores of Graphite Electrodes, make power line appropriateness diffusion in alternating current electrolysis operation, therefore easily make porousness oxide scale film become even together with solidity to corrosion oxide scale film.
Be wired to the conduction material of the part forming solidity to corrosion oxide scale film on aluminium by electrolysis treatment, compared with aluminium, its electropotential is necessary for noble potential.Carry out electrolysis by by electropotential compared with aluminium being the conduction material of noble potential and aluminium wiring and being arranged near aluminium, cause the cathodic reaction of alternating current electrolysis on conduction material surface, cause anodic reaction at aluminium and conduction material surface.Therefore, the solidity to corrosion oxide scale film utilizing anodic reaction to obtain is formed at aluminium material surface.Electropotential is the conduction material of noble potential compared with aluminium, such as, be gold, platinum, copper, iron, stainless steel, nickel etc., in the present invention, is applicable to using stainless steel or copper.This is due to these corrosion resistance excellents in alkaline solution, low price and be easy to processing.
In the present invention, preferably through the aluminium of electrolysis treatment and all should use tabular to electrode, make opposed aluminium roughly the same with to the opposed faces size each other of electrode, under static state electrolysis procedure is carried out to two electrodes.As shown in Figure 3, preferably prepare electrode 5, with the mode relative to battery lead plate 5, surface treated aluminium 2 surface is arranged to parallel with to the surface of electrode 5.In addition, in figure, 7 is AC power, and in figure, 8 is electrolytic solution.
Need not be tabular with the flat shape of the conduction material 6 of aluminium 2 wiring of electrolysis treatment of wanting, also can be netted or vesicular.As shown in Figure 3, such as wanting a face (face on the left of in figure) the side configuration conduction material 6 of surface-treated aluminium 2, make it opposed with this face, configure electrode 5 in another face (face on the right side of in the figure) side of aluminium 2, make it opposed with this face, carry out alternating current electrolysis, thus, solidity to corrosion oxide scale film can be formed in an above-mentioned face of aluminium 2, form porousness oxide scale film in another face above-mentioned.
Replace the situation of Fig. 3, as shown in Figure 4, also can want another face of surface-treated aluminium 2 (face on the right side of in figure) and corresponding with this face to electrode 5 between configure and conduct electricity material 6.Now, make the part in another face of aluminium 2 (the upside half part in figure) opposed with conduction material 6, other position (the downside half part in figure) in another face of aluminium 2 is not opposed but opposed with to electrode 5 with conduction material 6.By carrying out alternating current electrolysis with above-mentioned configuration, solidity to corrosion oxide scale film can be formed in the part in another face of the aluminium opposed with conduction material 6, form porousness oxide scale film at other position in another face of opposed with to electrode 5 and not opposed with conduction material 6 aluminium, same at aluminium 2 forms solidity to corrosion oxide scale film and porousness oxide scale film.In addition, in the diagram, by making the part in another face of aluminium 2 (the downside half part in figure) opposed with conduction material 6, other position (the upside half part in figure) in another face of aluminium 2 is configured to not opposed but opposed with to electrode 5 with conduction material 6, also the part in another face above-mentioned can form solidity to corrosion oxide scale film, form porousness oxide scale film at other position in another face above-mentioned.
In addition, as another face of aluminium 2 a part and make itself and the opposed part of conduction material 6, arbitrary shape, size and position can be set to.And, can its position opposed with to electrode 5 be made other position in another face as aluminium 2 to be set to part complementary with an above-mentioned part in another face.
The structure observation of porousness oxide scale film of the present invention and solidity to corrosion oxide scale film and thickness measurement, applicable use utilizes the section of penetrating type electron microscope (TEM) to observe.Specifically, the thickness of porousness oxide scale film and solidity to corrosion oxide scale film and the hole diameter of porousness oxide skin rete by being processed into thin slice with ultramicrotome etc., can carry out tem observation to measure.
Embodiment
Below, based on embodiment and comparative example, suitable embodiment of the present invention is described.
As the aluminium wanting electrolysis treatment, use the flat board of the JIS5052 of vertical 500mm × horizontal 500mm × thickness of slab 1.0mm.Use this aluminium sheet as an electrode, in electrode, use graphite cake or the titanium plate of vertical 500mm × horizontal 550mm × thickness of slab 2.0mm.In embodiment 1 ~ 23 and comparative example 1 ~ 13, as shown in Figure 3, will be arranged to parallel to each other to electrode 5 and aluminium 2.Aluminium alloy plate 2 with the face to electrode 5 opposition side near configure and conduct electricity material 6, one whole in conduction material 6 side of aluminium alloy plate 2 forms solidity to corrosion oxide scale film, is forming porousness oxide scale film to whole of electrode side.In addition, in embodiment 24, as shown in Figure 4, be arranged to and make the part (the upside half part in figure) in another face, the surface of aluminium 2 (face on the right side of in figure) opposed with conduction material, make other position in another face, surface of aluminium 2 (the downside half part in figure) not opposed and opposed with to electrode 5 with conduction material 6, form solidity to corrosion oxide scale film and porousness oxide scale film at the same face of aluminium 2.
In conduction material, in embodiment 1 ~ 14,18 ~ 21 and comparative example 1 ~ 13, use the SUS304 stainless steel plate of vertical 500mm × horizontal 500mm × thickness of slab 0.5mm.In embodiment 15, use the copper coin of vertical 500mm × horizontal 500mm × thickness of slab 0.5mm.In embodiment 16, use the stainless steel-gold network of SUS304 of 10 meshes of vertical 500mm × horizontal 500mm, wire diameter 0.5mm, porosity 64.5%.In embodiment 17, use the SUS304 stainless steel punch metal of vertical 500mm × horizontal 500mm, aperture 6mm, distance between borehole (spacing) 8mm.In embodiment 22, use the SUS304 stainless steel plate of vertical 480mm × horizontal 480mm × thickness of slab 0.5mm.In embodiment 23, use the SUS304 stainless steel plate of vertical 570mm × horizontal 570mm × thickness of slab 0.5mm.In embodiment 24, use the SUS304 stainless steel plate of vertical 250mm × horizontal 500mm × thickness of slab 0.5mm.In addition, the distance of conduction material and aluminium alloy plate is set to 5mm in embodiment 1 ~ 17,22 ~ 24 and comparative example 1 ~ 13.In embodiment 18, be set to 2mm, in embodiment 19, be set to 45mm, in embodiment 20, be set to 0.5mm, in embodiment 21, be set to 55mm.In addition, in the area ratio of the conduction material shown in table 1 relative to aluminium area, conduction face amasss by the length in length and breadth ignoring hole portion and obtains.
In electrolytic solution, use and there is pH shown in table 1, temperature and moltenly deposit aluminum concentration and take trisodium phosphate as the alkaline aqueous solution of principal constituent.In addition, the pH of electrolytic solution is adjusted with the NaOH aqueous solution of 0.1 mol/L.The alkali constituent concentration of alkaline aqueous solution is set to 0.1 mol/L.In addition, implement electrolysis treatment under the alternating current electrolysis treatment condition shown in table 1, the surface being produced on aluminium sheet is formed with solidity to corrosion oxide scale film, is formed with the confession examination material of the surface treated aluminum material of porousness oxide scale film on another surface.
[table 1]
[thickness measurement of solidity to corrosion oxide scale film]
Trying material to operating supplying of obtaining as mentioned above, being implemented the section observation of solidity to corrosion oxide scale film by TEM.Specifically, measure the thickness of solidity to corrosion oxide scale film, and observe the structure (whether skin membrane is single layer structure) of solidity to corrosion oxide scale film.In order to the structure observation of the thickness measurement and solidity to corrosion oxide scale film that carry out solidity to corrosion oxide scale film, ultramicrotome is used to make section observation thin slice test portion from for trying material.Then, any 100 points in field of view (1 μm × 1 μm) are selected in this thin slice test portion, observed by TEM section, measure the thickness of solidity to corrosion oxide scale film and whether observe solidity to corrosion oxide scale film be single layer structure (be designated as 〇 during single layer structure, be designated as during non-single layer structure ×).The thickness of solidity to corrosion oxide scale film be 10 ~ l00nm and solidity to corrosion oxide scale film is single layer structure time be evaluated as qualified (〇), the thickness of solidity to corrosion oxide scale film is not evaluated as defective (×) when the scope of 10 ~ l00nm and the non-at least arbitrary result for during single layer structure of solidity to corrosion oxide scale film.Above result is represented at table 2.
[table 2]
[determining film thickness of porousness oxide scale film]
In porousness oxide skin rete, implement section by TEM and observe.Specifically, multi-hole type aluminum oxidation skin membrane in porousness oxide skin rete and the thickness of isolation-type aluminum oxidation skin membrane and the hole diameter of porousness oxide skin rete is measured.In order to measure these, ultramicrotome is used to make section observation thin slice test portion from for examination material.Then, any 100 points in field of view (1 μm × 1 μm) are selected in this thin slice test portion, observed by TEM section, measure multi-hole type aluminum oxidation skin membrane in porousness oxide skin rete and the thickness of isolation-type aluminum oxidation skin membrane and the hole diameter of porousness oxide skin rete at each point.Obtain the maximum value, minimum value and the arithmetical av that operate the multi-hole type aluminum oxidation skin membrane of 100 that record and the aggregate thickness of isolation-type aluminum oxidation skin membrane like this.In addition, the amplitude of fluctuation studying the aggregate thickness of multi-hole type aluminum oxidation skin membrane and isolation-type aluminum oxidation skin membrane whether arithmetical av ± 50% within.Specifically, if when arithmetical av is T (nm), the whole aggregate thickness comprising maximum value and minimum value are all designated as qualified (〇) when the scope of (0.5 × T) ~ (1.5 × T), are not designated as defective (×) when this scope.In addition, in embodiment 24, use and the side to electrode contraposition.Represent above result in table 2.
[Evaluation of Corrosion Resistance of solidity to corrosion oxide scale film]
Prepare 10 from each confession examination material and be cut to long 50mm and the test film of wide 50mm.Corrosion resistant test carries out according to the CASS test recorded in salt spray testing method (JISZ2371).CASS test is implemented to obtained anodic oxidation treatment product, takes out after 3 hours, measure the corroded area of solidity to corrosion oxide scale film, carry out the evaluation of corroded area rate.Here, corroded area rate (%) is [(corroded area)/(total area of solidity to corrosion oxide scale film)] × l00.
〇: corroded area rate is lower than 10%
△: corroded area rate is more than 10%, lower than 50%
×: corroded area rate is more than 50%
Represent result in table 3.In the table, represent respectively above-mentioned 〇, △ in 10 test films, × number, it is qualified to be judged to be when whole result is 〇, and result is in addition judged to be defective.
[table 3]
[Phosphatizing film assessing of solidity to corrosion oxide scale film]
The peak absorption wavenumber b (cm of solidity to corrosion oxide scale film is measured by FT-IR
-1) and the peak specific absorption a (%) of peak absorption wavenumber b.The detector (detector) of FT-IR uses the wave number that can measure to be wide scope (400 ~ 4000cm
-1) detector, test portion area is set to 30mm × 50mm.Represent result in table 3.In the table, peak specific absorption a (%) and peak absorption wavenumber b (cm
-1) meet 1≤a≤95 and peak specific absorption a (%) and peak absorption wavenumber b (cm
-1) the relation result that meets b>=3a+710 be designated as qualified (〇), be not designated as defective (×) in the result of scope.
[the caking agent cementability of porousness oxide scale film is evaluated]
Long 50mm is cut to and the test film of wide 25mm from preparing 2 for examination material.The forming surface of porousness oxide scale film is overlapped each other with adhesion width 10mm one another along total width direction for examination material by these 2, utilize the two-pack type epoxy adhesive (host=upgrading epoxy resin, solidifying agent=upgrading polyimide, Mixing ratio by weight=host 100/ solidifying agent 100) sold that lap is bonding, make shearing test sheet.Tensile testing machine is utilized to supply the end of the length direction of examination material to stretch in the opposite direction along its length with the speed of 10mm/ minute, according to its loading (being converted into shear-stress) and the state of stripping, with following benchmark evaluation caking agent cementability by 2.In addition, about shearing test sheet, make 10 groups of test films, evaluate for each group.In addition, in embodiment 24, use and the side to electrode contraposition.
〇: shear-stress is 20N/mm
2above and bond layer itself in aggegation destroy state
△: shear-stress is 20N/mm
2above, but bond layer with for trying the state that material is interface peel
×: shear-stress is lower than 20N/mm
2and bond layer tries with confession the state that material is interface peel
Represent result in table 3.In the table, represent respectively above-mentioned 〇, △ in 10 test films, × number, it is qualified to be judged to be when whole result is 〇, and result is in addition judged to be defective.
[the film adaptation of porousness oxide scale film is evaluated]
At the large Japanese coating of surface coated (strain) system " VFlon#2000 " of the above-mentioned porousness oxide scale film side for examination material, make its drying (160 DEG C, 20 minutes), make the fitness test sheet being formed with the resin coating film of thickness 30 μm.With the method according to JIS-K5600-5-6, use is cut off cutter and is cut out 1mm checkerboard indentation at the resin coating film of this fitness test sheet.Then, after the distiller dip treating of 30 minutes is implemented at 125 DEG C to test film, take out from treatment solution at once, erasing moisture.The stripping test utilizing transparent pressure sensitive jointing tape is implemented to this test film.According to film survival rate, with following benchmark evaluation adaptation.In addition, about fitness test sheet, make 10 test films from identical for examination material, evaluate for each test film.In addition, in embodiment 24, use and the side to electrode contraposition.
〇: film survival rate is 100%
△: film survival rate is more than 75%, lower than 100%
×: film survival rate is lower than 75%
Represent result in table 3.In the table, represent respectively above-mentioned 〇, △ in 10 test films, × number, it is qualified to be judged to be when whole result is 〇, and result is in addition judged to be defective.
[comprehensive evaluation]
The caking agent cementability of the Evaluation of Corrosion Resistance of solidity to corrosion oxide scale film and Phosphatizing film assessing and porousness oxide scale film evaluates and the evaluation of film adaptation is all eligible, it is qualified that its comprehensive evaluation is designated as, these respectively evaluate at least any one is then designated as defective for underproof comprehensive evaluation.
As Table 2,3, in embodiment 1 ~ 24, owing to meeting underlying condition of the present invention, therefore the solidity to corrosion of solidity to corrosion oxide scale film and film quality good, and the caking agent cementability of porousness oxide scale film and film adaptation good, comprehensive evaluation is qualified.On the other hand, in comparative example 1 ~ 13, because not meeting underlying condition of the present invention, at least one item in above-mentioned each evaluation is defective, and comprehensive evaluation is defective.
Specifically, in comparative example 1, because the pH of the electrolytic solution in alternating current electrolysis is too low, therefore alkaline etching power is not enough.Therefore, the hole diameter in multi-hole type aluminum oxidation skin membrane is not enough, and the thickness of isolation-type aluminum oxidation skin membrane becomes blocked up, and the amplitude of fluctuation of porousness oxide scale film thickness is excessive.Its result, caking agent cementability and the film adaptation of porousness oxide scale film are defective, and comprehensive evaluation is defective.
In comparative example 2, because the pH of the electrolytic solution in alternating current electrolysis is too high, thus excessively cause alkaline etching.Therefore, the thickness of solidity to corrosion oxide scale film is not enough, and the thickness of multi-hole type aluminum oxidation skin membrane is not enough, and hole diameter is excessive, and in addition, the thickness of isolation-type aluminum oxidation skin membrane is not enough.Its result, the solidity to corrosion of solidity to corrosion oxide scale film is defective, and the caking agent cementability of porousness oxide scale film and film adaptation defective, comprehensive evaluation is defective.
In comparative example 3, because the temperature of the electrolytic solution in alternating current electrolysis is too low, thus alkaline etching power is not enough.Therefore, the thickness of isolation-type aluminum oxidation skin membrane is thickening.In addition, the hole diameter of multi-hole type aluminum oxidation skin membrane diminishes.Its result, caking agent cementability and the film adaptation of porousness oxide scale film are defective, and comprehensive evaluation is defective.
In comparative example 4, because the temperature of the electrolytic solution in alternating current electrolysis is too high, thus excessively cause alkaline etching.Therefore, the thickness of solidity to corrosion oxide scale film and the thickness deficiency of multi-hole type aluminum oxidation skin membrane and isolation-type aluminum oxidation skin membrane.Its result, solidity to corrosion and the film quality of solidity to corrosion oxide scale film are defective, and the caking agent cementability of porousness oxide scale film and film adaptation defective, comprehensive evaluation is defective.
In comparative example 5, do not exist in the electrolytic solution of alternating current electrolysis and moltenly deposit aluminium.Therefore, sharply there is the forming reactions of porousness oxide scale film in the electrolytic reaction initial stage, and the amplitude of fluctuation of porousness oxide scale film thickness becomes large.In addition, the formation of solidity to corrosion oxide scale film also becomes uneven, and thickness is not enough.Its result, solidity to corrosion and the film quality of solidity to corrosion oxide scale film are defective, and the caking agent cementability of porousness oxide scale film and film adaptation defective, comprehensive evaluation is defective.
In comparative example 6, exist in the electrolytic solution of alternating current electrolysis and a large amount of moltenly deposit aluminium.Therefore, the formation of isolation-type aluminum oxidation skin membrane becomes uneven, forms the part of thickness locally, and the hole diameter of multi-hole type aluminum oxidation skin membrane diminishes.In addition, the amplitude of fluctuation of porousness oxide scale film thickness becomes large.Its result, caking agent cementability and the film adaptation of porousness oxide scale film are defective, and comprehensive evaluation is defective.
In comparative example 7, due to the underfrequency of alternating current electrolysis, thus the flip-flop of electric current strengthens.Therefore, the formation of multi-hole type aluminum oxidation skin membrane is suppressed, and thickness is not enough.Its result, caking agent cementability and the film adaptation of porousness oxide scale film are defective, and comprehensive evaluation is defective.
In comparative example 8, because the frequency of alternating current electrolysis is too high, thus the formation of solidity to corrosion oxide scale film and multi-hole type aluminum oxidation skin membrane is suppressed, and respective thickness is not enough.Its result, solidity to corrosion and the film quality of solidity to corrosion oxide scale film are defective, and the caking agent cementability of porousness oxide scale film and film adaptation defective, comprehensive evaluation is defective.
In comparative example 9, because the current density of alternating current electrolysis is too low, thus the formation of solidity to corrosion oxide scale film and multi-hole type aluminum oxidation skin membrane is suppressed, and respective thickness is not enough.Its result, solidity to corrosion and the film quality of solidity to corrosion oxide scale film are defective, and the caking agent cementability of porousness oxide scale film and film adaptation defective, comprehensive evaluation is defective.
In comparative example 10, because the current density of alternating current electrolysis is too high, thus the formation of porousness oxide scale film and solidity to corrosion oxide scale film becomes uneven.Therefore, the thickness of solidity to corrosion oxide scale film and the thickness of multi-hole type aluminum oxidation skin membrane and isolation-type aluminum oxidation skin membrane thickening.In addition, the amplitude of fluctuation of porousness oxide scale film thickness becomes large.Its result, solidity to corrosion and the film quality of solidity to corrosion oxide scale film are defective, and the caking agent cementability of porousness oxide scale film and film adaptation defective, comprehensive evaluation is defective.
In comparative example 11, because the electrolysis time of alternating current electrolysis is too short, the thus thickness of solidity to corrosion oxide scale film and the thickness deficiency of multi-hole type aluminum oxidation skin membrane.In addition, the amplitude of fluctuation of porousness oxide scale film thickness becomes large.Its result, solidity to corrosion and the film quality of solidity to corrosion oxide scale film are defective, and the caking agent cementability of porousness oxide scale film and film adaptation defective, comprehensive evaluation is defective.
In comparative example 12, because the electrolysis time of alternating current electrolysis is long, thus the thickness of skin membrane and isolation-type aluminum oxidation skin membrane is thickening.Its result, caking agent cementability and the film adaptation of porousness oxide scale film are defective, and comprehensive evaluation is defective.
In comparative example 13, in the electrolytic solution of alternating current electrolysis, molten aluminium of depositing is lower than 5ppm.Therefore, sharply there is the forming reactions of porousness oxide scale film in the electrolytic reaction initial stage, and the amplitude of fluctuation of porousness oxide scale film thickness becomes large.In addition, the formation of solidity to corrosion oxide scale film also becomes uneven, and thickness is not enough.Its result, the solidity to corrosion of solidity to corrosion oxide scale film is defective, and the caking agent cementability of porousness oxide scale film and film adaptation defective, comprehensive evaluation is defective.
Industrial utilizability
According to the present invention, the surface treated aluminum material of a kind of a part of corrosion resistance excellent of aluminium material surface and other position cementability of aluminium material surface and excellent adhesion can be obtained.Thus, surface treated aluminum material of the present invention is applicable to being used in the aluminium of the part needs cementability of only aluminium and adaptation-resin-bonded parts and printed wiring substrate etc.
Nomenclature
1 ... surface treated aluminum material
2 ... aluminium
3 ... solidity to corrosion oxide scale film
4 ... porousness oxide scale film
41 ... isolation-type aluminum oxidation skin membrane
42 ... multi-hole type aluminum oxidation skin membrane
420 ... aperture
5 ... to electrode
6 ... conduction material
7 ... AC power
8 ... electrolytic solution
Claims (8)
1. a surface treated aluminum material, is characterized in that, comprising:
Aluminium,
Solidity to corrosion oxide scale film, it is formed at a part for this aluminium material surface and has single layer structure, and
Porousness oxide scale film, it is formed at the position not forming solidity to corrosion oxide scale film of described aluminium material surface,
Described solidity to corrosion oxide scale film has the thickness of 10 ~ l00nm, if analyzing by FT-IR the peak absorption wavenumber obtained is b (cm
-1), the peak specific absorption of peak absorption wavenumber b is when being a (%), meets l≤a≤95 and the relation of b>=3a+710,
Described porousness oxide scale film comprises and is formed at face side and thickness is the multi-hole type aluminum oxidation skin membrane of 20 ~ 500nm and is formed at substrate side and thickness is the isolation-type aluminum oxidation skin membrane of 3 ~ 30nm, the aperture of diameter 5 ~ 30nm is formed at described multi-hole type aluminum oxidation skin membrane, be formed in the porousness oxide scale film entirety of aluminium material surface, the amplitude of fluctuation of the aggregate thickness of described multi-hole type aluminum oxidation skin membrane and isolation-type aluminum oxidation skin membrane this aggregate thickness arithmetical av ± 50% within.
2. surface treated aluminum material as claimed in claim 1, is characterized in that:
Described peak absorption wavenumber b (cm
-1) be the wave number at the peak of the strongest stretching vibration from Al-O, come across the scope of 720≤b≤995.
3. surface treated aluminum material as claimed in claim 1 or 2, is characterized in that:
Total hole area of the aperture of described multi-hole type aluminum oxidation skin membrane is 25 ~ 75% relative to the ratio of the surface-area on apparent.
4. a manufacture method for surface treated aluminum material, is characterized in that:
Use and want the electrode of surface-treated aluminium, to electrode and the conduction material being wired to described aluminium electrode, using pH9 ~ 13, liquid temperature 35 ~ 85 DEG C and molten deposit aluminum concentration be more than 5ppm, below l000ppm alkaline aqueous solution as electrolytic solution, at frequency 10 ~ 100Hz, current density 4 ~ 50A/dm
2alternating current electrolysis process is carried out with under the electrolysis time condition of 5 ~ 60 seconds, form porousness oxide scale film with to the described aluminium material surface of electrode contraposition thus, and form solidity to corrosion oxide scale film at the described aluminium material surface opposed with the conduction material being wired to aluminium electrode simultaneously.
5. the manufacture method of surface treated aluminum material as claimed in claim 4, is characterized in that:
Described want surface-treated aluminium electrode with tabular is to electrode, the area being wired to the conduction material of aluminium electrode described in electrolytic solution is 80 ~ 150% of the area for forming solidity to corrosion oxide scale film, and the distance of described conduction material and aluminium is 1 ~ 50mm.
6. the manufacture method of the surface treated aluminum material as described in claim 4 or 5, is characterized in that:
The described conduction material being wired to aluminium electrode is made up of stainless steel or copper material.
7. the manufacture method of the surface treated aluminum material according to any one of claim 4 to 6, is characterized in that:
Conduction material is configured at the side, a face of described aluminium electrode, make it opposed with this face, another side, face of aluminium electrode will be configured to electrode, make it opposed with this face, form solidity to corrosion oxide scale film in a described face of aluminium electrode thus, form porousness oxide scale film in another face described.
8. the manufacture method of the surface treated aluminum material according to any one of claim 4 to 6, is characterized in that:
Another side, face of described aluminium electrode will be configured to electrode, make it opposed with this face, conduction material is configured in this another face and between electrode, make it opposed with the part in another face of aluminium electrode, by described electrode is configured to opposed with other position of the described part in another face being complementary to aluminium electrode, form solidity to corrosion oxide scale film in the described part in another face of aluminium electrode thus, described in aluminium electrode, other position forms porousness oxide scale film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-160561 | 2013-08-01 | ||
| JP2013160561 | 2013-08-01 | ||
| PCT/JP2014/003880 WO2015015768A1 (en) | 2013-08-01 | 2014-07-23 | Treated surface aluminum material and manufacturing method therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105408527A true CN105408527A (en) | 2016-03-16 |
| CN105408527B CN105408527B (en) | 2018-07-13 |
Family
ID=52431327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480041347.9A Active CN105408527B (en) | 2013-08-01 | 2014-07-23 | Surface treated aluminum material and its manufacturing method |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP6563336B2 (en) |
| KR (1) | KR102155398B1 (en) |
| CN (1) | CN105408527B (en) |
| MY (1) | MY177082A (en) |
| TW (1) | TWI656223B (en) |
| WO (1) | WO2015015768A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110312824A (en) * | 2017-02-22 | 2019-10-08 | 株式会社Uacj | Surface treated aluminum material and preparation method thereof, and surface treated aluminum material/engaging member conjugant including the engaging member such as the surface treated aluminum material and resin and preparation method thereof |
| CN111742083A (en) * | 2018-03-22 | 2020-10-02 | 株式会社Uacj | Surface-treated aluminum alloy material and method for producing same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY185682A (en) * | 2015-08-13 | 2021-05-30 | Uacj Corp | Surface-treated aluminum material having excellent adhesiveness to resins, method for manufacturing the same, and surface-treated aluminum material-resin bonded body |
| JP6829961B2 (en) | 2015-08-13 | 2021-02-17 | 株式会社Uacj | Surface-treated aluminum material with excellent resin adhesion and its manufacturing method, and surface-treated aluminum material / resin joint |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0413894A (en) * | 1990-05-03 | 1992-01-17 | Sky Alum Co Ltd | Aluminum alloy material to be coated for automobile and its production |
| JP2001020082A (en) * | 1999-07-07 | 2001-01-23 | Kobe Steel Ltd | Aluminum alloy material for zinc phosphate treatment |
| JP2011021260A (en) * | 2009-07-17 | 2011-02-03 | Furukawa-Sky Aluminum Corp | Aluminum substrate and method of manufacturing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2630858B2 (en) | 1991-02-26 | 1997-07-16 | スカイアルミニウム株式会社 | Manufacturing method of printed wiring board |
-
2014
- 2014-07-22 TW TW103125145A patent/TWI656223B/en active
- 2014-07-23 WO PCT/JP2014/003880 patent/WO2015015768A1/en active Application Filing
- 2014-07-23 KR KR1020157035097A patent/KR102155398B1/en active IP Right Grant
- 2014-07-23 CN CN201480041347.9A patent/CN105408527B/en active Active
- 2014-07-23 MY MYPI2016700061A patent/MY177082A/en unknown
- 2014-07-23 JP JP2015529376A patent/JP6563336B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0413894A (en) * | 1990-05-03 | 1992-01-17 | Sky Alum Co Ltd | Aluminum alloy material to be coated for automobile and its production |
| JP2001020082A (en) * | 1999-07-07 | 2001-01-23 | Kobe Steel Ltd | Aluminum alloy material for zinc phosphate treatment |
| JP2011021260A (en) * | 2009-07-17 | 2011-02-03 | Furukawa-Sky Aluminum Corp | Aluminum substrate and method of manufacturing the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110312824A (en) * | 2017-02-22 | 2019-10-08 | 株式会社Uacj | Surface treated aluminum material and preparation method thereof, and surface treated aluminum material/engaging member conjugant including the engaging member such as the surface treated aluminum material and resin and preparation method thereof |
| US11230785B2 (en) | 2017-02-22 | 2022-01-25 | Uacj Corporation | Surface-treated aluminum material and method for manufacturing same; and bonded body of surface-treated aluminum material and bonding member comprising said surface-treated aluminum material, and bonding member such as resin, and method for manufacturing said bonded body |
| CN110312824B (en) * | 2017-02-22 | 2022-03-22 | 株式会社Uacj | Preparation method of surface-treated aluminum material |
| CN111742083A (en) * | 2018-03-22 | 2020-10-02 | 株式会社Uacj | Surface-treated aluminum alloy material and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2015015768A1 (en) | 2017-03-02 |
| JP6563336B2 (en) | 2019-08-21 |
| CN105408527B (en) | 2018-07-13 |
| MY177082A (en) | 2020-09-04 |
| KR102155398B1 (en) | 2020-09-11 |
| TW201510233A (en) | 2015-03-16 |
| TWI656223B (en) | 2019-04-11 |
| WO2015015768A1 (en) | 2015-02-05 |
| KR20160040458A (en) | 2016-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105408527A (en) | Treated surface aluminum material and manufacturing method therefor | |
| El Sawy et al. | Nano-porous iridium and iridium oxide thin films formed by high efficiency electrodeposition | |
| Ren et al. | Glucose sensor based on porous Ni by using a graphene bottom layer combined with a Ni middle layer | |
| Shang et al. | Corrosion resistance of micro-arc oxidation/graphene oxide composite coatings on magnesium alloys | |
| US20170014043A1 (en) | Electrodermal Activity Sensor | |
| CN103331440A (en) | Silver-gold porous nanorod array, preparation method and purpose of silver-gold porous nanorod array | |
| Premlatha et al. | Electrodeposition of a 3D hierarchical porous flower-like cobalt–MWCNT nanocomposite electrode for non-enzymatic glucose sensing | |
| He et al. | Dynamic gas bubble template electrodeposition mechanisms and amperometric glucose sensing performance of three kinds of three-dimensional honeycomb-like porous nano-golds | |
| CN104114752A (en) | Surface treated aluminum material, method for producing same, and resin-coated surface treated aluminum material | |
| Chung et al. | Fabrication of composite Cu2O/Au inverse opals for enhanced detection of hydrogen peroxide: Synergy effect from structure and sensing mechanism | |
| Xue et al. | Nanoporous gold chemically de-alloyed from Au-based amorphous thin film for electrochemical nonenzymatic H2O2 sensing | |
| Singh et al. | Nanopatterning of transition metal surfaces via electrochemical dimple array formation | |
| Huang et al. | Morphology control of cathodically deposited TiO2 films | |
| Rashkov et al. | NiW/TiOx composite layers as cathode material for hydrogen evolution reaction | |
| CN104988541A (en) | Flower-shaped submicron silver hemisphere array, and preparation method and application of array | |
| Tanaka et al. | Preparation and characterization of microporous layers on titanium | |
| Graham et al. | Nanostructured electrodes for biocompatible CMOS integrated circuits | |
| Klosová et al. | Advanced electrodes with nanostructured surfaces for electrochemical microsensors | |
| Myrzak et al. | On size effect of rate of corrosion of copper nanowire ensemble: Part 2. Size effect of rate of corrosion of copper in pyrophosphate solution | |
| CN107709631B (en) | The excellent surface treated aluminum material of resin adhesion and its manufacturing method and surface treated aluminum material/resin conjugant | |
| JP6575968B2 (en) | Surface-treated aluminum material, method for producing the same, and surface-treated aluminum material / resin layer assembly | |
| Durut et al. | Phenomenological Model for Gold-Copper Electrodeposition: Application to Thick Coatings | |
| JP5218964B2 (en) | Plating thickness measurement method | |
| Tzaneva et al. | Conductive silver layers on anodic aluminum oxide | |
| Jiang et al. | Electrolytic Metal Atoms Enabled Manufacturing of Nanostructured Sensor Electrodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |