CN114746579A - Aluminum alloy material and method for producing same - Google Patents
Aluminum alloy material and method for producing same Download PDFInfo
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- CN114746579A CN114746579A CN202080082571.8A CN202080082571A CN114746579A CN 114746579 A CN114746579 A CN 114746579A CN 202080082571 A CN202080082571 A CN 202080082571A CN 114746579 A CN114746579 A CN 114746579A
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 163
- 239000000956 alloy Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 14
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- 230000010287 polarization Effects 0.000 claims abstract description 28
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
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- 238000000576 coating method Methods 0.000 claims abstract description 10
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000005530 etching Methods 0.000 claims description 56
- 238000007739 conversion coating Methods 0.000 claims description 52
- 239000002253 acid Substances 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 39
- -1 titanium fluoride compound Chemical class 0.000 claims description 27
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- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 150000003609 titanium compounds Chemical class 0.000 claims description 12
- 150000003752 zinc compounds Chemical class 0.000 claims description 12
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 3
- 229940007718 zinc hydroxide Drugs 0.000 claims description 3
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000010349 cathodic reaction Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
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- 239000012466 permeate Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
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- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- 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
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The present invention provides an aluminum alloy material having: a base material composed of an aluminum alloy; and a chemical conversion treatment coating film on the surface of the base material, wherein the aluminum alloy material is measured at a scanning speed of 20 mV/min in a 5 wt% NaCl aqueous solution at 25 ℃ and pH5.5 with a silver-silver chloride electrode in saturated KCl as a reference electrode, and the absolute value of the current density in the obtained cathodic polarization curve reaches 10 muA/cm2The electrode potential of (b) is-1350 mV to-1150 mV.
Description
Technical Field
The invention relates to an aluminum alloy material and a manufacturing method thereof.
Background
Conventionally, in order to improve the surface characteristics of aluminum alloy materials, aluminum alloy materials subjected to various surface treatment methods have been proposed. Patent document 1 (jp 2014-62277 a) discloses an aluminum alloy sheet including an aluminum alloy substrate and an aluminum oxide film formed on a surface of the aluminum alloy substrate, the aluminum oxide film including at least one additive element having a P-B ratio (Pilling-Bedworth ratio) of 1.00 or more, 0.01 to 10 atomic% of zirconium, and 0.1 atomic% or more and less than 10 atomic% of magnesium.
Patent document 2 (jp 2015-206117 a) discloses a surface-treated aluminum alloy sheet including an aluminum alloy sheet containing magnesium and an oxide film formed on the surface of the aluminum alloy sheet, wherein chemical treatment (chemical treatment) is performed during use, and the thickness of the oxide film is 1 to 30nm, the magnesium concentration is 1 to 20 atomic%, the zirconium concentration is 0.2 to 10 atomic%, and the halogen concentration and the phosphorus concentration are each less than 0.1 atomic%.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-62277
Patent document 2: japanese patent laid-open publication No. 2015-206117
Disclosure of Invention
Problems to be solved by the invention
Although aluminum alloy materials subjected to various surface treatments have been proposed in the past, no sufficient study has been made on aluminum alloy materials in which the electrochemical activity of the surface is controlled. The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that an aluminum alloy material having a reduced surface electrochemical activity can be obtained by subjecting the surface of a base material to a specific surface treatment. Further, it has been found that the interface between the aluminum alloy material and another material is not easily deteriorated, and the adhesion durability between the aluminum alloy material and another material is improved, and the present invention has been completed. That is, an object of the present invention is to provide an aluminum alloy material having excellent adhesion durability to other materials and a method for producing the same.
Means for solving the problems
In order to solve the above problems, the present invention has the following embodiments.
[1] An aluminum alloy material having: a base material composed of an aluminum alloy; and a chemical conversion coating film on the surface of the substrate, wherein,
the aluminum alloy material was measured in a 5 wt% NaCl aqueous solution at 25 ℃ and pH5.5 with a silver-silver chloride electrode in saturated KCl as a reference electrode and at a scanning speed of 20 mV/min, and in the obtained cathodic polarization curve, the absolute value of the current density reached 10. mu.A/cm2The electrode potential of (b) is-1350 mV to-1150 mV.
[2] The aluminum alloy material according to the above [1], wherein,
the base material is composed of an aluminum alloy containing 0.3 to 5.0 wt% of Mg.
[3] The aluminum alloy material according to the above [1] or [2], wherein,
the chemical conversion treatment coating contains a titanium compound and a zinc compound,
the titanium compound is at least one of titanium oxide and titanium hydroxide,
the zinc compound is at least one of zinc oxide and zinc hydroxide,
the total amount of the titanium compound and the zinc compound in the chemical conversion coating film is 2 to 29mg/m in terms of the amount of the metal element2。
[4]A process for producing an aluminum alloy material, comprising measuring an aluminum alloy material in a 5 wt.% NaCl aqueous solution at 25 ℃ and pH5.5 with a silver-silver chloride electrode in saturated KCl as a reference electrode and at a scanning speed of 20 mV/min, and obtaining a cathodic polarization curve in which the absolute value of the current density reaches 10 μ A/cm2The electrode potential of (2) is-1350 mV to-1150 mV, the manufacturing method comprises:
a step of acid-etching a base material made of an aluminum alloy containing Mg; and
a step of forming a chemical conversion coating by subjecting the surface of the acid-etched substrate to a chemical conversion treatment,
the etching amount of the substrate in the step of performing the acid etching [ E: (mg/m)2)]Relative to the amount of Mg in the substrate [ M (wt%)]Satisfy the following requirementsE is more than or equal to 10M and less than or equal to 200M.
[5] The method for producing an aluminum alloy material according to [4], wherein in the step of forming the chemical conversion coating, a treatment liquid containing a titanium fluoride compound and a zirconium fluoride compound is used, and chemical conversion treatment is performed so that the total mass concentration [ C (ppm in terms of metal element amount) ] of the titanium fluoride compound and the zirconium fluoride compound in the treatment liquid and the treatment time [ t (sec) ] satisfy 50. ltoreq. Cxt. ltoreq.1500.
ADVANTAGEOUS EFFECTS OF INVENTION
An aluminum alloy material excellent in adhesion durability with other materials and a method for producing the same can be provided.
Drawings
Fig. 1 is a diagram showing a plate-shaped aluminum alloy material used for measurement of a cathodic polarization curve.
FIG. 2 is a graph showing a cathodic polarization curve of the aluminum alloy material of example 2.
Detailed Description
1. Aluminum alloy material
The aluminum alloy material of the invention comprises: a base material composed of an aluminum alloy; and a chemical conversion coating film on the surface of the substrate. In addition, in a cathodic polarization curve obtained by measuring an aluminum alloy material in a 5 wt% NaCl aqueous solution at 25 ℃ and pH5.5 with a silver-silver chloride electrode in saturated KCl as a reference electrode and at a scanning speed of 20 mV/min, the absolute value of the current density reached 10. mu.A/cm2The electrode potential of (b) is-1350 mV to-1150 mV.
For example, in the case where a conventional aluminum alloy material is bonded to another member via an adhesive (another material), if tensile stress is applied to the interface between the aluminum alloy material and the adhesive during use, deterioration of the bonding interface between the aluminum alloy material and the adhesive (interface deterioration) is accelerated. The interface deterioration is caused by the infiltration of moisture or salt from the bonding end face to cause corrosion of the aluminum alloy material, or by the reaction of the infiltrated moisture with the aluminum alloy material to cause the growth of a surface oxide film. In addition to the gradual permeation of moisture from the bonding interface, the permeation of moisture also occurs as water vapor permeates through the adhesive. Further, in an actual use environment of the adhesive, the bonded portion is always under a tensile stress and is also exposed to a corrosive environment. That is, mechanical deterioration that physically cracks the bonding interface and chemical deterioration that causes moisture and salt to permeate into the bonding interface are superimposed and occur simultaneously, and a severe deterioration environment beyond that assumed in the past is formed. As a result, the conventional surface treatment method has insufficient adhesion durability under such a severe environment.
In contrast, the aluminum alloy material of the present invention can suppress deterioration of the interface between the aluminum alloy material and the adhesive due to load of tensile stress or corrosion, and can suppress deterioration due to penetration of moisture, salt, or the like by controlling the electrochemical properties of the surface to an appropriate range. The electrochemical properties of the surface of the aluminum alloy material can be measured by measurement of a polarization curve, and with the aluminum alloy material of the present invention, the absolute value of the current density in the cathodic polarization curve reaches 10. mu.A/cm2The electrode potential of (b) is-1350 mV to-1150 mV. In addition, since the aluminum alloy material of the present invention has the characteristics of the cathodic polarization curve as described above even when the interface is formed with a material other than the adhesive, the interface deterioration due to the load tensile stress, corrosion, penetration of moisture and salt, and the like can be suppressed.
The principle of the influence of the electrochemical properties of the surface of the aluminum alloy material on the interface deterioration is as follows. A dense natural oxide film having a thickness of about several nm, which is generated by a reaction with air or water, is present on the surface of the aluminum alloy. The natural oxide film is an insulating film and has high protective properties, and therefore, the corrosion resistance of the aluminum alloy can be ensured. However, the natural oxide film has a defect portion and becomes a starting point of corrosion. When the aluminum alloy corrodes, the following anodic reaction and cathodic reaction are simultaneously performed.
(anodic reaction) Al → Al3++3e-
(cathode reaction) O2+2H2O+4e-→4OH-
2H++2e-→H2
This is because electrons generated by ionization (dissolution) of metallic aluminum, which is an anode reaction, need to be consumed in a cathode reaction (reduction reaction of dissolved oxygen or hydrogen ions) in order to satisfy the electrically neutral condition. As described above, the defect portion in the natural oxide film on the surface of the aluminum alloy functions as an active site for the anodic reaction and the cathodic reaction. However, in the defect portion of these films, a substance functioning as a site of a cathode reaction is limited to a crystal precipitate or the like having a high potential existing on the surface of the aluminum alloy. That is, the rate of corrosion of the aluminum alloy depends on the degree of activity of the cathodic reaction of the surface (cathode activity). The principle of the continuous reaction between the aluminum alloy surface and water to grow the surface oxide film is also the same as described above. Therefore, in order to effectively suppress deterioration of the bonding interface, it is effective to appropriately control the electrochemical properties, particularly the cathode activity, of the aluminum alloy surface.
When the cathode activity on the surface of the aluminum alloy is high, a corrosion reaction is likely to occur on the surface of the aluminum alloy, and deterioration of the adhesion interface is accelerated. Therefore, by forming a chemical conversion coating on the surface of the aluminum alloy by chemical conversion treatment, the cathode activity on the surface can be appropriately reduced, and deterioration of the adhesion interface can be suppressed. However, when a thick film is unnecessarily formed on the surface of the aluminum alloy due to excessive chemical conversion treatment, the cathode activity on the surface is greatly reduced, but the chemical conversion treatment film itself is easily deteriorated, and the chemical conversion treatment film is easily broken or peeled off, resulting in a decrease in adhesion durability. Therefore, in the present invention, deterioration of the bonding interface and reduction of the bonding durability can be suppressed by appropriately adjusting the electrochemical characteristics of the aluminum alloy surface. Here, the electrochemical properties of the aluminum alloy surface can be evaluated by measurement of a polarization curve.
In the cathode polarization curve of the aluminum alloy material, the absolute value of the current density reaches 10 muA/cm2The electrode potential of (b) is-1350 mV to-1150 mV. In the cathode polarization curve of the aluminum alloy material, the absolute value of the current density reaches 10 muA/cm2When the electrode potential of (2) is more than-1150 mV, the inhibition of the cathode activity on the aluminum alloy surface is insufficient, and the adhesion durability is thereby insufficientAnd (4) descending. Unless otherwise stated, the electrode potential in the present specification means a value measured with a silver-silver chloride electrode (SSE) in saturated KCl at 25 ℃ as a reference electrode. In addition, in the cathodic polarization curve of the aluminum alloy material of the present invention, the absolute value of the current density reached 10. mu.A/cm2When the electrode potential of (2) is less than-1350 mV, the thickness of the formed chemical conversion coating film becomes more than necessary, resulting in a decrease in adhesion durability. Therefore, the electrode potential is preferably-1330 mV to-1175 mV, and more preferably-1310 mV to-1200 mV. In the cathodic polarization curve, the absolute value of the current density reached 10. mu.A/cm2The electrode potential of (b) is within the above range, so that the aluminum alloy material can have more excellent adhesion durability. In addition, by performing appropriate surface treatment on the base material composed of an aluminum alloy, the electrochemical properties of the surface can be controlled, and the absolute value of the current density in the cathodic polarization curve can be made to 10 μ A/cm2The electrode potential of (2) is controlled within the above range. Specifically, as the surface treatment, various conditions of acid etching, chemical conversion treatment, and treatment accompanied by the surface treatment as necessary are appropriately controlled, whereby the electrochemical properties of the surface of the aluminum alloy material can be optimized.
The cathodic polarization curve of the aluminum alloy material of the present invention was measured in the following manner. First, a container opened in the atmosphere at a temperature of 25 ℃ was prepared, and 300ml of a 5 mass% NaCl aqueous solution at 25 ℃ and pH5.5 was poured into the container and allowed to stand. In this case, the pH of the NaCl aqueous solution may be adjusted to pH5.5 with NaOH or HCl. The container used for the measurement has a depth that allows the test piece to be sufficiently immersed, and is not particularly limited as long as the aspect ratio (the ratio of the bottom surface diameter to the height) is not an extreme value, and a beaker having a volume of 500mL or the like is suitable as an example. Fig. 1 is a drawing showing a plate-like aluminum alloy material used for measurement of a cathodic polarization curve, fig. 1A is a front view, and fig. 1B is a back view. As shown in FIG. 1, the aluminum alloy used for the measurement was cut into a plate-like test piece of 5 cm. times.2 cm by a shear. Selecting a test piece without damage and dirt. The plate-like test piece 10 is separated by about 5mm from one end in the longitudinal directionThe right position was exposed 1cm × 1cm as a measurement surface (the measurement surface was provided only at 1 position on the surface of the test piece), and the remaining portion was masked with a silicone resin to define an evaluation area 11. At this time, one end 12 in the longitudinal direction of the test piece on the side opposite to the area evaluation portion 11 is exposed by about 5mm in advance, and a measurement terminal is connected thereto. Next, the test piece and the electrode plate (platinum electrode) were immersed in the NaCl aqueous solution and left standing for 30 minutes. At this time, the test piece was immersed under the liquid surface at about half of the length direction thereof. At this time, the contact portion with the measurement terminal is not wetted, and the measurement surface is immersed to 1cm or more below the water surface. The platinum electrode is not particularly limited as long as it is an electrode used for ordinary dynamic potential polarization measurement, and examples thereof include the following methods: a platinum wire having a diameter of 0.7mm and a length of 120mm was used, and the wire was immersed below the liquid surface for 5cm or more in the measurement. In addition, no degassing and stirring were performed during the measurement. Further, a silver-silver chloride electrode (HS-205C, manufactured by tokyo DKK corporation) in saturated KCl at 25 ℃ was used as a reference electrode, and a polarization curve was obtained by a three-electrode method. 30 minutes after the start of immersion of the test piece, the potential was scanned in a decreasing direction from the natural potential of the test piece by a potentiostat (SDPS-511U, Shrinks co., ltd.) to measure the cathodic polarization curve. At this time, the potential scanning speed was set to 20 mV/min. Furthermore, the absolute value of the current density reached 10. mu.A/cm2The electrode potential at that time was measured. Here, the absolute value of the current density was 10. mu.A/cm2The positive and negative marks are removed from the measured current value, and the cathode current density reaches 10 muA/cm2. For example, in a measuring apparatus in which the cathode current is represented by a negative sign, the measured value of the cathode current density is represented by-10. mu.A/cm2Therefore, the minus sign is removed and expressed as 10. mu.A/cm2. The evaluation area 11 of the test piece was accurately measured, and the current density was calculated by dividing the measured current by the actual evaluation area 11. Preferably, the above measurement is performed for 3 different test pieces and the average value thereof is selected. In addition, it was confirmed that the current density reached 10. mu.A/cm2If the current density reaches 10. mu.A/cm instantaneously due to noise or the like at the potential of (1)2It is ignored as an abnormal value. Therefore, it is necessary to perform polarization until it can be confirmed that the current density sufficiently exceeds 10. mu.A/cm2The potential of (b) is preferably measured to-1600 mV or less.
Hereinafter, each part constituting the aluminum alloy material according to one embodiment will be described.
(substrate)
The base material is not particularly limited as long as it is composed of an aluminum alloy, and examples thereof include 1000 series aluminum alloys (pure aluminum alloys), 2000 series aluminum alloys (Al — Cu — Mg series aluminum alloys), 3000 series aluminum alloys (Al — Mn series aluminum alloys), 4000 series aluminum alloys (Al — Si series aluminum alloys), 5000 series aluminum alloys (Al — Mg series aluminum alloys), 6000 series aluminum alloys (Al — Mg — Si series aluminum alloys), and 7000 series aluminum alloys (Al — Zn — Mg series aluminum alloys). From the viewpoint of strength and corrosion resistance of the base material made of an aluminum alloy, an aluminum alloy containing 0.3 to 5.0 wt% of Mg is preferably used.
(chemical conversion coating)
The chemical conversion coating is a coating obtained by subjecting the surface of the substrate to a chemical conversion treatment described later. The chemical conversion coating film preferably contains an inorganic compound, and more preferably contains a titanium compound and a zinc compound. Preferably, the titanium compound is at least one of titanium oxide and titanium hydroxide, and preferably the zinc compound is at least one of zinc oxide and zinc hydroxide. When the chemical conversion coating film contains a titanium compound and a zinc compound, the total amount of the titanium compound and the zinc compound in the chemical conversion coating film is preferably 2 to 29mg/m in terms of the amount of the metal element2More preferably 3 to 27mg/m2More preferably 4 to 20mg/m2. When the total amount of the titanium compound and the zinc compound is within the above range, the aluminum alloy material can have excellent adhesion durability. The amount of each of the titanium compound and the zinc compound is preferably at least 1mg/m in terms of the amount of the metal element2More preferably at least 1.5mg/m2. The above "conversion to the amount of the metal element" means that the amount is 1m per unit2The amount of Ti element and Zr element in the chemical conversion coating film. The film thickness of the chemical conversion treatment film is preferably less than 50nm, more preferably less than 30nm, and still more preferably less than 50nmThe step is preferably 1nm to 20 nm. About every 1m2The total amount of Ti and Zr elements in the chemical conversion coating of (2) can be measured by a fluorescent X-ray analyzer (XRF) by drawing a calibration curve based on a reference plate in which the coating amount is known. The film thickness of the chemical conversion coating can be measured by GD-OES (Glow Discharge Optical Emission Spectroscopy), and when the value at which the Emission intensity of aluminum sufficiently reaches the main body (substrate) is taken as a reference value, the sputtering depth at the time when 50% of the reference value is reached can be taken as the film thickness.
2. Method for manufacturing aluminum alloy material
According to the method for producing an aluminum alloy material of the present invention, the following aluminum alloy material is produced: the aluminum alloy material was measured in a 5 wt% NaCl aqueous solution at 25 ℃ and pH5.5 with a silver-silver chloride electrode in saturated KCl as a reference electrode and at a scanning speed of 20 mV/min, and the absolute value of the current density in the obtained cathodic polarization curve reached 10. mu.A/cm2The electrode potential of (b) is-1350 mV to-1150 mV. The manufacturing method comprises: a step of acid-etching a base material made of an aluminum alloy containing Mg; and a step of forming a chemical conversion coating by subjecting the surface of the acid-etched substrate to a chemical conversion treatment. In addition, the etching amount of the substrate in the step of performing acid etching [ E: (mg/m)2)]Relative to the amount of Mg in the substrate [ M (wt%)]Acid etching is performed so as to satisfy the relationship of E being 10M or more and 200M or less. With respect to the aluminum alloy material produced by the method of producing an aluminum alloy material of the present invention, the absolute value of the current density in the cathodic polarization curve is 10. mu.A/cm2The electrode potential of (B) is-1350 mV to-1150 mV. Therefore, deterioration of the interface between the aluminum alloy material and the adhesive due to tensile stress and corrosion can be suppressed, and deterioration due to penetration of moisture, salt, or the like can be suppressed. In addition, since the aluminum alloy material of the present invention has the characteristics of the cathodic polarization curve as described above even when the interface is formed with a material other than an adhesive, it is possible to suppress interface degradation due to load tensile stress, corrosion, penetration of moisture, salt, and the like. In addition, the E is more than 10M, so that the surface of the base material after acid etching becomes cleanThe chemical conversion coating film can be formed to be in good contact with the surface of the substrate. On the other hand, if E exceeds 200M and is excessively increased, surface irregularities and dirt (fine particles of insoluble matter generated by the acid remaining after etching) generated by etching affect the adhesion durability. This is because the dirt enters the inside of the surface irregularities and cannot be easily removed, thereby affecting the adhesion to the adhesive. Therefore, when E is 200M or less, unnecessary increase in surface unevenness and excessive occurrence of dirt can be suppressed, and the adhesion durability between the aluminum alloy material and another material can be improved. The respective steps of the method for producing an aluminum alloy material of the present invention will be described in detail below.
(Rolling and Heat treatment)
In one example, after forming an aluminum alloy into an ingot according to a conventional method, homogenization treatment, hot rolling, cold rolling, intermediate annealing, cold rolling, or homogenization treatment, hot rolling, and cold rolling are sequentially performed, and an aluminum alloy sheet rolled to a final thickness is used as a base material. Next, the aluminum alloy sheet rolled to the final sheet thickness is subjected to heat treatment. In this case, when the heat treatment is performed in the air, magnesium, which is an easily oxidizable element in the aluminum alloy, diffuses on the surface and bonds with oxygen, thereby forming a layer containing a large amount of magnesium oxide on the surface of the aluminum alloy sheet.
(degreasing Process)
The degreasing step may be optionally performed before the acid etching step. The purpose is to remove rolling oil, processing oil, lubricating oil, and the like, which have adhered to the surface of the aluminum alloy sheet in the step before pickling. The solution used in the washing step is not particularly limited, but an alkali cleaning agent, a surfactant, or a mixture thereof, or an organic solvent may be used as appropriate, and the washing step may be performed thereafter. In the case where the amount of oil or the like adhering to the surface of the aluminum alloy sheet is small, the cleaning step may be omitted. In addition, when the degreasing step is performed, if an alkali degreasing agent is used, a certain amount of dissolution of the base aluminum alloy occurs. If the amount of dissolution of the base material in the cleaning step is excessively increased, a large amount of dirt may adhere to the surface of the plate, and the subsequent steps may be affected. Therefore, in the case of performing the degreasing process, the aluminum alloy is subjected to a degreasing processThe amount of gold dissolved is preferably 50mg/m2Hereinafter, more preferably 40mg/m2The following. Further, in etching with alkali, a substance having low solubility in alkali, such as magnesium oxide on the surface of the aluminum alloy sheet, cannot be removed, and therefore, the acid etching step cannot be replaced with alkali etching.
(step of acid etching)
In the step of performing acid etching, the base material made of an aluminum alloy containing Mg is acid etched. The acid etching is performed under conditions such that the etching amount of the substrate [ E: (mg/m)2)]Relative to the amount of Mg in the substrate before acid etching [ M (wt%)]The condition that E.ltoreq.10 M.ltoreq.200M is satisfied is not particularly limited. By performing acid etching under conditions satisfying the relationship of E.ltoreq.10 M.ltoreq.200M, the brittle layer existing on the surface of the aluminum alloy base material can be removed, and the adhesion durability can be improved. The brittle layer is a mixture of a surface-modified layer generated in a mechanical process such as a rolling process and a substance such as aluminum oxide or magnesium oxide grown on the surface of the aluminum alloy in a heat treatment process. When the bonding is performed in a state where these brittle layers remain, the bonding durability is reduced. In the case of an aluminum alloy containing magnesium as an easily oxidizable element in a large amount, magnesium oxide is easily generated in the heat treatment step, and the brittle layer tends to be formed thick. Therefore, in order to optimize the etching amount according to the magnesium alloy content of the base material, E/M is set to 10 to 200. E/M is preferably 20 to 150, more preferably 30 to 100. In addition, M is preferably 0.3 to 5.0 wt%, more preferably 1.0 to 5.0 wt%, and further preferably 2.0 to 5.0 wt%. The method can be implemented by H1305: the emission spectroscopic analysis method defined in 2005 measures the amount of Mg in the substrate before etching, but any method may be used as long as it can obtain the same degree of accuracy. In addition, when the manufactured base material is purchased, the Mg amount can be calculated from the Mg content disclosed in the base material. The etching amount E of the base material can be calculated by measuring the dry mass before and after etching using a test piece obtained by cutting the base material into an appropriate size, and dividing the difference in the measurement results (mass before etching-mass after etching) by the area of the test piece and converting the result into a numerical value per unit area. The size of the test piece in this case may be arbitrary, but when the area is small, the weight changesAnd the influence on the measurement precision is reduced. Therefore, it is necessary to set the area of the test piece to an appropriate size in consideration of the accuracy of the balance used for weighing. As the etching liquid for acid etching, an acid of nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, or a mixed solution thereof can be used. The etching solution may optionally contain an etching assistant (oxidizing agent), a surfactant, a chelating agent, and the like. The acid concentration in the etching solution (total concentration of the acid solutions in the case of a mixed solution) is preferably 0.01 to 30 wt%, more preferably 0.03 to 25 wt%, and still more preferably 0.05 to 20 wt%. The temperature of the etching solution is preferably 30-90 ℃, more preferably 40-90 ℃, and further preferably 45-90 ℃. The etching time is preferably 1 to 30 seconds, more preferably 1 to 25 seconds, and further preferably 1 to 20 seconds. The acid etching step is preferably followed by a water washing step. In the water washing step, water having a conductivity of 500mS/m or less at a temperature of 20 ℃ is preferably used. When water having high electrical conductivity is used, various ions contained in the water may be adsorbed on the surface of the aluminum alloy, which may cause deterioration in adhesion durability. The water temperature in the water washing step is preferably 30 to 90 ℃, more preferably 40 to 85 ℃, and still more preferably 45 to 80 ℃. This is because many substances have high solubility in water at high temperatures, and therefore are effective for cleaning the surface of the aluminum alloy substrate after etching. When the temperature of the washing water is high, the washing effect is increased, but the energy cost may be increased. When the temperature of the washing water exceeds 90 ℃, a hydration reaction may occur between the aluminum alloy substrate and water to form an aluminum hydrous oxide film on the surface. Further, if the time of the water washing step is too long, the aluminum surface may gradually react with the water washing water to form an aluminum oxide, and if it is too short, the treatment chemical attached to the surface may not be sufficiently removed. Therefore, the time for the water washing step is preferably 0.5 to 30 seconds, and more preferably 1 to 20 seconds.
(Process for Forming chemical conversion coating film)
In the step of forming the chemical conversion coating, the chemical conversion treatment is performed on the surface of the base material after the acid etching to form the chemical conversion coating. The surface after the acid etching step has a plurality of sites for cathodic reaction, and the adhesion durability can be improved by forming an appropriate chemical conversion coating. The chemical conversion coating is preferably an inorganic chemical conversion coating because the chemical conversion coating can be formed by an electrochemical reaction between ions dissolved in the treatment liquid and the surface of the aluminum alloy. This is because the sites of the cathodic reaction present on the surface of the aluminum alloy substrate also function as sites at which the film is easily formed during the formation of the chemical conversion coating. Therefore, when a chemical conversion coating is formed by an electrochemical reaction with ions dissolved in a solution through an aluminum alloy, it is possible to efficiently cover the cathode reaction sites on the surface of the aluminum alloy. In addition, even in the chemical conversion coating of inorganic substances, both titanium and zirconium are preferably contained. This is because titanium oxide or hydroxide and zirconium oxide or hydroxide formed as the chemical conversion coating are chemically stable, and are less likely to cause chemical changes even in a deteriorating environment, and are effective for preventing a decrease in adhesion durability. Further, when the chemical conversion treatment film is formed on the surface of the aluminum alloy base material, the film is formed gradually from the cathode reaction site on the surface as described above, and therefore the electrochemical characteristics of the aluminum alloy surface fluctuate all the time in the process. Therefore, by blending elements having different solubilities and electrode potentials in the solution, i.e., titanium and zirconium, in the treatment solution, it is possible to widely cope with the surface of the aluminum alloy which varies at every moment during the formation of the chemical conversion coating film, and it is possible to effectively and optimally cover the surface of the aluminum alloy with the chemical conversion coating film.
Further, it is preferable to keep the aluminum alloy surface wet with the water washing without drying or blowing between the water washing step in the acid etching step and the step of forming the chemical conversion treatment film. This is because the various oxides on the surface of the aluminum alloy removed in the acid etching step can be prevented from contacting air and growing again thickly. However, if the aluminum alloy is in contact with the washing water for a long time, various oxides start to grow on the surface of the aluminum alloy. Therefore, the step of forming the chemical conversion treatment film is preferably started within 30 seconds after the completion of the water washing step in the acid etching step, more preferably within 10 seconds, and even more preferably within 5 seconds. Further, it is most preferably within 2 seconds.
In the step of forming the chemical conversion coating film, it is preferable to use a treatment liquid containing a titanium hydride compound and a zirconium fluoride compound so that the total mass concentration [ C (ppm in terms of the amount of the metal element) of the titanium fluoride compound and the zirconium fluoride compound in the treatment liquid is set to]Treatment time [ t (seconds)]The chemical conversion treatment is performed in a manner satisfying 50. ltoreq. Cxt. ltoreq.1500. The C × t is in the above range, and an optimal chemical conversion coating can be formed on the surface of the aluminum alloy after the acid etching step. As the titanium fluoride compound, 6-fluorotitanic acid (H) can be mentioned2TiF6) And salts thereof (particularly potassium salt, sodium salt, ammonium salt) and the like. As the zirconium fluoride compound, 6-fluorozirconic acid (H) can be mentioned2ZrF6) And salts thereof (particularly potassium salt, sodium salt, ammonium salt) and the like. Preferably 50. ltoreq. Cxt. ltoreq.1500, more preferably 80. ltoreq. Cxt. ltoreq.1400, and further preferably 100. ltoreq. Cxt. ltoreq.1300. When C × t is less than 50, a chemical conversion coating may not be sufficiently formed on the surface of the aluminum alloy. When C × t exceeds 1500, the chemical conversion treatment film may be formed too thick, and the adhesion durability may be reduced. The total mass concentration C (in terms of the amount of metal element) of the titanium fluoride compound and the zirconium fluoride compound in the treatment liquid is preferably 20 to 400ppm, more preferably 30 to 350ppm, and still more preferably 40 to 300 ppm. The time t is preferably 0.5 to 30 seconds, more preferably 1 to 25 seconds, and further preferably 1.5 to 20 seconds. The mass concentration of the titanium fluoride compound in the treatment liquid is preferably 10 to 400ppm, more preferably 15 to 300ppm, and further preferably 20 to 200ppm in terms of the metal element. The mass concentration of the zirconium fluoride compound in the treatment liquid is preferably 10 to 400ppm, more preferably 15 to 300ppm, and still more preferably 20 to 200 ppm. The temperature of the treatment liquid is preferably 30 to 80 ℃, more preferably 35 to 70 ℃, and further preferably 40 to 65 ℃. When the concentration of the titanium fluoride compound and the zirconium fluoride compound in the treatment solution, the treatment time and the treatment temperature are within the above-mentioned ranges, [ C (ppm in terms of the amount of the metal element) ]]Treatment time [ t (seconds)]Within the above range, the chemical conversion coating on the surface of the aluminum alloy can be optimally adhered.
Further, as the treatment area of the aluminum alloy substrate increases, Al ions eluted from the substrate in the treatment solution for chemical conversion treatment gradually increase. When the amount of Al ions increases, the formation of the chemical conversion coating is inhibited. The concentration of Al ions in the treatment liquid is preferably 600ppm or less, more preferably 500ppm or less, until the concentration of Al ions in the treatment liquid reaches about 800ppm without affecting the formation of the chemical conversion treatment film.
In one example, the step of forming the chemical conversion coating is immediately followed by a step of washing with water. This enables the treatment liquid remaining on the surface to be quickly removed, and the thickness of the chemical conversion coating film can be appropriately adjusted by controlling the reaction time between the substrate surface and the treatment liquid. Further, the components of the treatment liquid can be prevented from remaining on the surface of the chemical conversion coating film. If the components of the treatment liquid remain on the surface of the chemical conversion coating, the adhesion durability is reduced, and discoloration of the substrate surface occurs. The time from the step of forming the chemical conversion coating to the step of washing with water is preferably 2 seconds or less, and more preferably 1 second or less. The electric conductivity of the water used in the water washing step is preferably 100mS/m or less, more preferably 50mS/m or less, at a temperature of 20 ℃. When water having high electrical conductivity is used, various ions contained in the water remain on the surface of the substrate, which causes a decrease in adhesion durability and discoloration of the substrate surface. For the measurement of the electrical conductivity, for example, an ac 2-pole method can be used.
Since the water washing step after the step of forming the chemical conversion coating film affects the final quality of the substrate surface, it is preferable to provide the water washing step a plurality of times in 2 stages or more. When the water washing step after the step of forming the chemical conversion coating is provided a plurality of times, the time between the water washing steps is preferably 2 seconds or less, more preferably 1 second or less. In addition, it is preferable that the conductivity of water in the water washing step to be performed thereafter is equal to or lower than the conductivity of water used in the first water washing step after the step of forming the chemical conversion coating film. This makes it possible to sufficiently remove components in the chemical conversion treatment liquid that cannot be completely removed in the 1 st washing step. If the time of the water washing step is too long, the surface of the aluminum alloy substrate may gradually react with the water to form aluminum oxide, but if the time of the water washing step is too short, the cleaning effect cannot be sufficiently obtained. Therefore, the total time of the water washing step performed after the step of forming the chemical conversion coating film is preferably 0.5 to 30 seconds, and more preferably 1 to 20 seconds. Further, since the solubility of most substances in water increases at a high water temperature, the cleaning effect is improved at a high water temperature in the water washing step after the step of forming the chemical conversion coating film. When the water temperature in the water washing step exceeds 90 ℃, energy costs may be increased, and in addition, a hydration reaction between the aluminum alloy substrate and water may occur to form an aluminum hydrous oxide film on the surface of the substrate. Therefore, the water temperature in the first water washing step after at least the step of forming the chemical conversion coating is preferably 30 to 90 ℃, more preferably 40 to 85 ℃, and still more preferably 50 to 85 ℃. The water temperature in the subsequent water washing step may be in the range of 10 to 90 ℃. Preferably, after the water washing step, hot air drying or the like is performed to remove water droplets remaining on the surface of the aluminum alloy base material.
(method of treating Each step)
As the degreasing step, the step of performing acid etching, the step of forming a chemical conversion treatment coating film, and the step of washing with water in association with the respective steps, a method of spraying a treatment liquid onto the surface of the aluminum alloy, a method of passing the aluminum alloy through a treatment tank filled with the treatment liquid (immersion method), and the like are suitably employed.
(method of Using aluminum alloy Material)
The aluminum alloy material of the present invention can be used as a member for automobiles, construction machines, and conveyors by providing an adhesive layer on the surface of the chemical conversion coating film and then further adhering the aluminum alloy material to another aluminum alloy material. The aluminum alloy material of the present invention has excellent adhesion durability to other materials, and therefore can be firmly adhered to other aluminum alloy materials via an adhesive, and can maintain adhesion for a long period of time. Examples of the adhesive include epoxy resins, acrylic resins, urethane resins, and the like, and thermosetting epoxy resins are preferably used. The thickness of the adhesive layer provided on the surface of the chemical conversion coating is not particularly limited, but is preferably 10 to 5000 μm, more preferably 20 to 3000 μm, and still more preferably 30 to 1000 μm.
Examples
The present invention will be described in detail below based on examples. The present invention is not limited to the examples described below, and the configuration thereof may be modified as appropriate within a range not to impair the gist of the present invention.
(examples 1 to 8)
A substrate having a thickness of 1mm and a size of 7cm × 15cm shown in Table 1 below was prepared, and acid etching was performed on the substrate under the following conditions. Examples 1 to 3 were acid-etched for 6 seconds under the conditions shown in table 1 using an etching solution having a composition of 0.5 mass% sulfuric acid +0.05 mass% hydrofluoric acid at 60 ℃. Similarly, in examples 4 to 7, acid etching was performed for 4 seconds under the conditions shown in Table 1 using an etching solution having a composition of 0.5 mass% sulfuric acid +0.05 mass% hydrofluoric acid at 60 ℃. In example 8, acid etching was performed for 4 seconds under the conditions shown in table 1 using an etching solution having a composition of 10 mass% sulfuric acid at 80 ℃. After the acid etching, the substrate was water-washed with ion-exchanged water having a conductivity of 0.2mS/m at a temperature of 20 ℃ and a temperature of 70 ℃. Next, chemical conversion treatment was immediately performed under the conditions of temperature, composition, and treatment time shown in table 1, thereby obtaining an aluminum alloy material having a base material and a chemical conversion treatment coating film in the amount of the coating film shown in table 1. The titanium fluoride compound and the zirconium fluoride compound used in examples 1 to 8 were 6-fluorotitanic acid and 6-fluorozirconic acid, respectively. Immediately after the chemical conversion treatment, the substrate was washed with 70 ℃ ion exchange water having a conductivity of 0.2mS/m at 20 ℃ and further washed with room temperature (specifically, 20 ℃) ion exchange water having a conductivity of 0.1mS/m at 20 ℃, and then dried by spraying hot air at 50 ℃. The electrical conductivity of the water was measured by a portable conductivity meter ES-71 manufactured by horiba, Ltd.
Comparative examples 1 to 2
In comparative example 1, a base material having the same size as that used in the examples shown in table 1 below was prepared, the base material was acid-etched for 4 seconds using an etching solution having a composition of 80 ℃ and 10 mass% sulfuric acid under the conditions shown in table 1, and the substrate was water-washed using ion exchange water having an electric conductivity of 0.2mS/m at 20 ℃ and a temperature of 70 ℃, thereby obtaining an aluminum alloy base material. In comparative example 1, no chemical conversion treatment was performed. In comparative example 2, the aluminum alloy material having the base material and the conversion-treated coating film in the amount of the coating film shown in table 1 was obtained by performing acid etching for 1 second using an etching solution containing sulfuric acid at a concentration of 10 mass% and 50 ℃ under the conditions shown in table 1, washing the substrate with water after the acid etching using ion-exchanged water having an electric conductivity of 0.2mS/m at a temperature of 20 ℃ and a temperature of 70 ℃, and immediately performing the conversion treatment under the conditions shown in table 1. The titanium fluoride compound and the zirconium fluoride compound used in comparative example 2 were 6-fluorotitanic acid and 6-fluorozirconic acid, respectively. After the chemical conversion treatment, the substrate was immediately washed with 70 ℃ ion exchange water having a conductivity of 0.2mS/m at 20 ℃, further washed with room temperature (specifically, 20 ℃) ion exchange water having a conductivity of 0.1mS/m at 20 ℃, and then dried by spraying hot air at 50 ℃.
[ TABLE 1]
The cathode polarization curve of the aluminum alloy material of each example obtained in the above manner was measured by the above method. FIG. 2 is a view showing the cathodic polarization curve of the aluminum alloy material of example 2 measured in the above manner.
As the adhesion evaluation, the aluminum alloy materials obtained in the respective examples were evaluated by a method based on a modified APGE test described in japanese patent application publication No. 2018-527467, and Cy of the adhesion breaking period was measured. The detailed sequence of the changed APGE test is as follows. 2 test pieces 52.5mm in length × 25mm in width were bonded with an epoxy adhesive so that the length of the bonded portion became 12.5mm and the bonding thickness became 0.2 mm. In order to prevent the test piece having a thickness of 1mm from being deformed during the test, the same kind of plate was previously bonded with the same kind of adhesive. Next, 6 pairs of test pieces prepared in this order were connected to each other at their respective ends by stainless steel bolts. In order to prevent contact corrosion of dissimilar metals caused by contact between the test piece and the stainless bolt, insulation is performed by winding a seal tape around the bolt or another suitable method. The state was maintained in which tensile stress of 2400N was always applied to both ends of the 6 pairs of connected bodies. The connected body in a state of being applied with stress was immersed in a 5 mass% NaCl aqueous solution for 15 minutes, taken out at a room temperature of 25 ℃ and allowed to dry naturally within 105 minutes, and then placed in a constant temperature and humidity chamber having a relative humidity of 90% RH at 50 ℃ and maintained for 22 hours. According to the method, durability in a very severe bonding interface deterioration environment in which tensile stress and corrosive environment are simultaneously superimposed can be evaluated. The time from when the tensile stress of 2400N was applied to the end of the 22-hour retention in the constant temperature and humidity chamber was counted as 1 cycle, and the test was performed for 1 cycle within 1 day of the working day. In addition, the link was kept in the constant temperature and humidity chamber for 48 hours on the rest day, and was not counted as a test period. When the joint state of the sample was confirmed at the start of the next cycle, and fracture was observed in any 1 pair of the bonded portions of 6 pairs of the connected test pieces, the 1 st fracture (fracture of the 1 st pair) was determined as the cycle number at that time. Even when the test piece was broken during the period from the time when the test piece was loaded with 2400N stress to the time when the test piece was set in the constant temperature and humidity chamber, the 1 st breakage was set to the cycle number at that time. The broken test piece was removed, a single plate of the same size as 1 pair of test pieces was inserted and fastened to the other test pieces with bolts, and the test cycle was restarted by applying stress again. In addition, when the bonding portions of the plurality of test pieces are simultaneously broken, the same number of cycles is counted for each test piece. For example, when the test piece is not broken at the time when 18 cycles end and 2 pairs of the 6 pairs of test pieces are broken at the time when the 20 th cycle starts, 20 cycles are set for the 1 st break and the 2 nd break, respectively, and the breakage is changed to the 3 rd break. This sequence was repeated until the 4 th breakage (any 4 pairs of breakage out of 6 pairs of connected test pieces) and the test was continued. Then, the average value of the number of cycles from 1 st to 4 th fractures (rounding of the 1 st position after the decimal point) was obtained and set as Cy. The case of Cy < 18 was evaluated as "poor", the case of 18. ltoreq. Cy < 20 was evaluated as "good", and the case of 20. ltoreq. Cy was evaluated as "excellent". The measurement results are shown in table 2 below.
[ TABLE 2]
As is clear from table 2, the adhesion evaluation was "good" or "excellent" in examples 1 to 8, and the adhesion evaluation was "x" in comparative examples 1 to 2. From this, it is understood that the aluminum alloy material of the present invention achieves excellent adhesion durability.
Claims (5)
1. An aluminum alloy material, having: a base material composed of an aluminum alloy; and a chemical conversion coating film on the surface of the substrate, wherein,
the aluminum alloy material was measured in a 5 wt% NaCl aqueous solution at 25 ℃ and pH5.5 with a silver-silver chloride electrode in saturated KCl as a reference electrode and at a scanning speed of 20 mV/min, and the absolute value of the current density in the obtained cathodic polarization curve reached 10. mu.A/cm2The electrode potential of (b) is-1350 mV to-1150 mV.
2. The aluminum alloy material according to claim 1, wherein the base material is composed of an aluminum alloy containing 0.3 to 5.0 wt% of Mg.
3. The aluminum alloy material according to claim 1 or 2, wherein the chemical conversion treatment coating film contains a titanium compound and a zinc compound,
the titanium compound is at least one of titanium oxide and titanium hydroxide,
the zinc compound is at least one of zinc oxide and zinc hydroxide,
the total amount of the titanium compound and the zinc compound in the chemical conversion coating film is 2 to 29mg/m in terms of the amount of the metal element2。
4. A method for producing an aluminum alloy material, wherein the aluminum alloy material is measured at 25 ℃ in a 5 wt% NaCl aqueous solution at pH5.5 with a silver-silver chloride electrode in saturated KCl as a reference electrode and at a scanning speed of 20 mV/min, and the absolute value of the current density in the obtained cathodic polarization curve is 10 muA/cm2The electrode potential of (2) is-1350 mV to-1150 mV, and the production method comprises the following steps:
a step of acid-etching a base material made of an aluminum alloy containing Mg; and
a step of forming a chemical conversion coating by subjecting the surface of the acid-etched substrate to a chemical conversion treatment,
the etching amount E of the base material in the step of performing the acid etching satisfies a relation of 10M or more and E or less and 200M with respect to the amount M of Mg in the base material, wherein the unit of E is Mg/M2And M has the unit of wt%.
5. The method of manufacturing an aluminum-alloy material according to claim 4,
in the step of forming the chemical conversion coating film, a chemical treatment is performed with a treatment liquid containing a titanium fluoride compound and a zirconium fluoride compound, in such a manner that the total mass concentration C of the titanium fluoride compound and the zirconium fluoride compound in the treatment liquid satisfies 50. ltoreq. Cxt. ltoreq.1500, and the treatment time t is C in ppm in terms of the amount of the metal element, and t in seconds.
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| JP2019-177015 | 2019-09-27 | ||
| JP2019177015 | 2019-09-27 | ||
| JP2020075335A JP6846558B1 (en) | 2019-09-27 | 2020-04-21 | Aluminum alloy material and its manufacturing method |
| JP2020-075335 | 2020-04-21 | ||
| PCT/JP2020/035953 WO2021060346A1 (en) | 2019-09-27 | 2020-09-24 | Aluminum alloy material and method for manufacturing same |
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| CN114746579A true CN114746579A (en) | 2022-07-12 |
| CN114746579B CN114746579B (en) | 2024-10-25 |
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| US20220290304A1 (en) | 2022-09-15 |
| WO2021060346A1 (en) | 2021-04-01 |
| EP4036274A1 (en) | 2022-08-03 |
| EP4036274A4 (en) | 2023-11-22 |
| JP6846558B1 (en) | 2021-03-24 |
| JP2021055178A (en) | 2021-04-08 |
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