WO2023079671A1 - Matériau métallique d'aluminium présentant une excellente conductivité et son procédé de production - Google Patents

Matériau métallique d'aluminium présentant une excellente conductivité et son procédé de production Download PDF

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WO2023079671A1
WO2023079671A1 PCT/JP2021/040703 JP2021040703W WO2023079671A1 WO 2023079671 A1 WO2023079671 A1 WO 2023079671A1 JP 2021040703 W JP2021040703 W JP 2021040703W WO 2023079671 A1 WO2023079671 A1 WO 2023079671A1
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electrolysis
aluminum
film
anodized film
minutes
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PCT/JP2021/040703
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English (en)
Japanese (ja)
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成憲 田中
政弘 秋本
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株式会社アート１
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Priority to KR1020237028783A priority Critical patent/KR20230132583A/ko
Priority to PCT/JP2021/040703 priority patent/WO2023079671A1/fr
Priority to CA3208948A priority patent/CA3208948A1/fr
Priority to JP2022523191A priority patent/JP7165462B1/ja
Priority to CN202180097454.3A priority patent/CN117203378A/zh
Publication of WO2023079671A1 publication Critical patent/WO2023079671A1/fr

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    • 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
    • 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
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment

Definitions

  • the present invention relates to an aluminum metal material with excellent conductivity and a method for producing the same.
  • Aluminum anodized film (hereafter referred to as anodized aluminum) was developed as an electrically insulating material. played a part in its development. For example, decoration and corrosion-resistant technology can be used to create color panels for buildings, colored sashes for window frames, and colored daily necessities. Technology has made outdoor exteriors, underwater cameras, etc. lighter, and aluminum has come to be used in many ways. In order to further develop aluminum in the future, it is necessary not only to develop materials, but also to overcome the insulating material that is the starting point of anodized film, and use the advantages of conductivity, magnetism, etc. + light weight and easy processing. As a result, the development and practical application of an anodized film that has conductivity in addition to conventional properties has been eagerly awaited. For example, the anodized film can damage electronic circuits due to sparks caused by static electricity. However, heavy metals are generated during treatment, disposal, and recycling of the plating solution, and there is a problem in terms of LCA compatibility.
  • Patent Document 1 As for imparting conductivity to the anodized film of alumite, a method of treating it in an anodizing bath containing nitrate ions has been proposed (Patent Document 1).
  • the conductivity achieved by this method is on the level of 10 5 to 6 ⁇ or more in terms of resistance, and is described as having an antistatic function and can be used for various computer-related products.
  • the performance is insufficient to prevent accidents that damage electronic circuits due to sparks, and to demonstrate the magnetic shielding effect of medium to ultra-short waves used in smartphones, satellite broadcasting, taxi radios, etc.
  • this document does not describe the surface hardness, in reality only a hardness of about Hv 280 can be obtained, and it cannot be used in the application field of hard alumite due to insufficient hardness, and improvement is necessary.
  • the anodized aluminum film consists of a porous layer and a barrier layer (non-porous layer).
  • Anodized aluminum was originally developed as an insulating material at RIKEN and has continued to this day.
  • the barrier layer was removed from the Institute for Metals, and electro-coloring technology was used to deposit metal on the surface. A paper has been published.
  • Non-Patent Document 1 uses sulfuric acid as the electrolytic solution, drops the final voltage from 15 to 20 V at the time of film formation to around 0.05 V at once, and further dissolves the barrier layer after switching off, and then performs Ni electrodeposition to HV 50 to 50. It is described that a hardness increase of about 100 was achieved. They also reported that there is conduction between the Al substrate and the film surface by a tester. However, the film hardness of nickel electrodeposition by this manufacturing method is HV450 at maximum, and the biggest drawback is that it completely loses the corrosion resistance that is the greatest feature of anodized aluminum, making it a product that is difficult to use practically. On the other hand, zinc electrodeposition, which does not affect the corrosion resistance of the anodized film, is of no or almost no use in improving the film hardness.
  • the purpose of the present invention is to impart conductivity and hardness to alumite, which could not be used in the past, and to provide a method for manufacturing it as a lightweight material.
  • a material having an anodized film made of aluminum or its alloy having an electrical resistance of 1 ⁇ 10 ⁇ 2 ⁇ or less and a film cross-sectional hardness of HV470 or more and a method for producing the same.
  • the method for measuring the electrical resistance in the embodiment is the DC four-terminal method (voltage drop method), which is excellent for low resistance measurement, and the electrical resistance between the surface and the substrate is measured with a resistance meter RM3548 (manufactured by Hioki Electric Co., Ltd.). When measured, it is 1 ⁇ 10 ⁇ 2 ⁇ or less, and the cross-sectional hardness of the film is HV470 or more when measured by the JIS-Z2244 (Vickers hardness test) method with a load of 0.098 N (10 grf) and a holding time of 15 seconds.
  • the electrical resistance between the surface and the substrate is 1 ⁇ 10 -2 ⁇ or less
  • the film cross-sectional hardness is HV470 or more
  • the heat resistance test is performed at 300 ° C. for 2 weeks.
  • the color difference ( ⁇ E) before and after heating is 3.0 or less, preferably 2.5 or less
  • the color difference ( ⁇ E) before and after heating is 3.0 or less, preferably 2, even in a heat resistance test at 500° C. for 1 hour. 0.5 or less, and no cracks on the surface of the film are observed when viewed from the front after heating in air at 200° C. for 30 minutes.
  • the film of the present invention is a material made of aluminum or its alloy having excellent conductivity, hardness and heat resistance, and a method for producing the same.
  • an aluminum metal material that has high electrical conductivity, a relatively high degree of durability, and a method for manufacturing the same.
  • FIG. 2 is a diagram showing a cross section and surface state of an anodized film manufactured according to the present embodiment;
  • FIG. 4 is a conceptual diagram showing film formation on the bottom of micropores in the third electrolysis in the manufacturing process of the present embodiment.
  • FIG. 4 is a conceptual diagram showing deposition of metal in the fourth electrolysis in the manufacturing process of the present embodiment;
  • FIG. 4 is a conceptual diagram showing a method of measuring the electrical resistance of aluminum containing an anodized film in the present embodiment.
  • FIG. 4 is a diagram showing various characteristics of an anodized film produced according to the present embodiment;
  • the corrosion resistance test of this embodiment is performed using a JIS-Z2371 neutral salt spray tester STP-90V-4 (manufactured by Suga Test Instruments Co., Ltd.) after one month of continuous spraying (720 hours).
  • JIS-H8679-1 Evaluation method of pitting corrosion generated in anodized film of aluminum and aluminum alloy-Part 1: Rating number method (RN). The rating number applies only to pitting corrosion that has penetrated the coating and reached the metal substrate.
  • RN10 is 0% (no pitting corrosion)
  • RN9.8 is over 0.00 and 0.02% or less
  • RN9.5 is over 0.02%
  • RN9.3 is more than 0.05% and 0.07% or less
  • the criterion is JIS-H8603-5.6 (hard anodized film of aluminum and aluminum alloy-corrosion resistance)
  • H8603-4 Classified as shown in Table 1 according to type (material).
  • one type is specified as having no pitting corrosion (pitting corrosion) after 336 hours of spray test using a neutral salt spray tester (RN10). stipulated in the agreement between In this embodiment, the above regulation is met, and a criterion for 720 hours (one month) is added. Actually, after removing from the salt spray tester, the corrosion products on the surface are physically and chemically removed, washed thoroughly with water, and after confirming that there is no deposit on the surface, it is dried, and the size and number of pitting corrosion are rated. Evaluate by comparing with number standard chart.
  • the material of this embodiment is conductive and has a cross-sectional hardness of HV470 or higher. According to Non-Patent Document 1, it has conductivity and high hardness, but in terms of corrosion, it states that "pits were generated in the salt spray test for 24 hours, and the surface was considerably covered with corrosion products after 240 hours.” There were only materials that were not corrosion resistant.
  • the material of the present invention has a corrosion resistance that achieves RN 9.5 or higher for type 1 and type 2-(a) materials, RN 7 or higher for type 2-(b), and 8 or higher for type 3-(a) materials. It has
  • the thickness of the anodized film is 6 to 50 ⁇ m, preferably 10 to 30 ⁇ m, particularly preferably 10 to 30 ⁇ m, when measured after calibration with a calibration standard plate (plastic film) using JIS-H8680-2 (eddy current measurement method). is 20 to 30 ⁇ m, and forms a film with a color tone of light brown to dark brown to black.
  • anodized aluminum film tends to turn from brown to black as the film thickness increases. When the film thickness exceeds 80 ⁇ m, the film turns black.
  • the coating of the present embodiment is thinner and blacker than the conventional coating, and has hardness, so that the occurrence of cracks cannot be visually observed.
  • the manufacturing process of this embodiment includes four steps of electrolysis and a post-treatment.
  • the electrolytic solution removes the valley layer at the bottom of the film of the micropores (Fig. 3), the third electrolysis creates the film again (Fig. 4), and the fourth electrolysis deposits the metal into the micropores (Fig. 5). ).
  • the electric resistance is 1 ⁇ 10 -2 ⁇ or less by performing work such as sealing as a post-treatment
  • the film cross-sectional hardness is HV 470 or more in the Vickers hardness test method
  • the color tone is A material composed of aluminum or an alloy thereof that forms an anodized film having a light brown to dark brown to black tone can be produced.
  • the first electrolysis of the present embodiment is a step of forming a base film, and the liquid composition is preferably a solution of an organic acid as a main component, and an inorganic acid and / or an organic acid other than the organic acid as the main component, and optionally Electrolysis is performed in an electrolytic solution containing additives as required.
  • the electrolysis method is DC waveform, liquid temperature 0 to 40°C, current density 0.6 to 3.0A/dm 2 , 10 to 120 minutes, preferably liquid temperature 10 to 30°C, current density 0.8 to 2.0A. /dm 2 , electrolysis time 20-90 minutes, pulse waveform, PR pulse waveform, AC waveform, average current density of positive current 0.1-10 A / dm 2 in one cycle, average current of negative current 0 0 to 10 A/dm 2 , a liquid temperature of 0 to 40° C.
  • the average current density of positive current is 0.6 to 3.0 A/dm 2 and the average current of negative current is 0.0 to 3.0 A/dm 2 in one cycle.
  • Anodizing is performed at 0 A/dm 2 and at a liquid temperature of 10 to 30° C. using a current or voltage waveform of a DC waveform, an AC waveform pulse waveform, and a PR pulse waveform alone or a combination of two or more of them.
  • FIG. 1 An overall image of the anodized film formed here is shown in FIG. 1, and its cross section (FIG. 2(A)) and surface field view (FIG. 2(b)) are shown in FIG.
  • the power is maintained for 1 to 5 minutes without turning off the power, and then the voltage is gradually lowered to 0V.
  • the method is to lower the final voltage by 1 to 10V, hold it for 10 to 120 seconds, lower it further by 1 to 10V, hold it for 10 to 120 seconds, and then lower it to 10V, and then lower it to 5V, 3V, 2V, 1V, and 0V in order.
  • the holding time is 40 seconds each, and the total voltage effect time is 5 to 60 minutes.
  • the voltage is lowered by 2 to 5 V, held for 20 to 20 seconds, and reached 0 V in 10 to 40 minutes. is desirable. This step removes the barrier layer at the lower portion of the pores.
  • This schematic diagram is shown in FIG.
  • the third electrolysis of the present embodiment is an electrolytic solution obtained by adding an additive to an alkaline solution, with a DC waveform, a voltage of 1 to 30 V, a time of 5 to 20 minutes, a liquid temperature of 0 to 20 ° C., and a voltage of preferably 5 to 15 V. , for 10 to 15 minutes at 10 to 15°C.
  • the cell shape (160 nm) peculiar to the alkali film is about four times that of the sulfuric acid film (44 nm), and the electrical conductivity is good, and a film of 2 ⁇ m or less is formed at the bottom of the micropores. A schematic diagram of this is shown in FIG.
  • the fourth electrolysis is performed with an electrolytic solution containing an acid solution containing a metal salt and an additive.
  • the metal salt is dissolved and used as metal ions.
  • Electrolysis is carried out by AC, DC, pulse, PR pulse waveforms alone or in combination of two or more, the voltage is 5 to 40 V, the time is 3 to 30 minutes, the liquid temperature is -10 to 40 ° C., preferably 10 to 25 V. , 5 to 15 minutes at 16 to 30 ° C. If the power source has polarity, set the (member to be treated) on the cathode side, electrolyze the anode side using a carbon plate electrode, and wash with water before and after electrolytic coloring. deionized or pure water is sufficient. In this process, metal is deposited in the micropores of the anodized film. This schematic diagram is shown in FIG.
  • the electrolytic solution used in the first and second electrolysis of the present embodiment is preferably a single or mixed system mainly composed of aliphatic or aromatic sulfonic acid and/or carboxylic organic acid.
  • it is an electrolytic solution obtained by adding an inorganic acid and/or an organic acid different from the organic acid mainly used above, or an additive if necessary.
  • These liquid concentrations are preferably 0.1 to 4.5 mol/L.
  • the electrolytic solution used in the third electrolysis of the present embodiment is an alkaline solution to which an alkaline compound alone or two or more is added, and an organic compound is added as an additive.
  • an alkaline compound alone or two or more is added, and an organic compound is added as an additive.
  • sodium hydroxide, sodium carbonate, sodium phosphate and the like are used as the electrolytic solution for anodization, either singly or in combination of two or more.
  • the concentration of these liquids is 0.05 to 2.0 mol/L, preferably 0.1 to 0.5 mol/L.
  • carboxylates, carbonates, phosphates, fluorides, aluminates, and the like are used singly or in combination of two or more.
  • ammonium tartrate, sodium tartrate, ammonium carbonate, sodium carbonate, sodium polyphosphate, sodium fluoride, ammonium fluoride, sodium aluminate, etc. with a liquid concentration of 0.05 to 1.0 mol/L, preferably 0.1 to 0.5 mol/L.
  • the electrolytic solution used in the fourth electrolysis consists of an acid solution containing metal salts and additives, and the metal salts are used in the form of soluble metal ions.
  • Typical acidic liquids are mainly composed of sulfuric acid compounds and oxalic acid compounds, and carboxylic acid organic acids, boric acid, etc. are added as additives.
  • Metal salt compounds to be added include gold, silver, and copper. , platinum, tin, cobalt, nickel, iron, tungsten, molybdenum, chromium, zinc, palladium, zirconium, rhodium, ruthenium, vanadium, titanium and manganese. Zinc is most preferred to maintain the excellent corrosion resistance of the anodized coating of the resulting material.
  • a light brown to dark brown to black anodized film is formed. It is not colored, but formed by metal deposition in the fourth electrolysis. Even if this film is heat-treated at 300° C. for 2 weeks or heated at 500° C. for 1 hour, almost no change in color tone is visually observed, and it has high stability.
  • Aluminum has a recrystallization temperature of about 250°C, and after this temperature, rough crystals, which are the cause of work hardening (work strain that occurs when deformation processing such as rolling at room temperature) remain in aluminum processed products, are generated. At 250° C. or higher, the crystal grains soften and recrystallize and become stable without internal strain. Practically, an operation of softening at about 350° C. to reduce the internal stress, that is, annealing is required.
  • Cold working is the process of working aluminum below the recrystallization temperature. In this working method, work hardening always occurs, so annealing is required. Since it is rarely used above, if there is no abnormality in color fading in a heat test at 300 ° C., which is the starting point of softening, it can be used without problems in terms of fading in practical terms. .
  • the momentary heat resistance test is set at 500°C for 1 hour because the material itself will be abnormal if it is performed for a long time at 300°C or higher, which is the starting point of softening, so 1 hour is the practical limit. Therefore, it was determined that heat resistance during this period was sufficient.
  • the organic acid preferably used in the first electrolysis and the second electrolysis in the present embodiment is an aliphatic or aromatic sulfonic acid and/or carboxylic acid alone or in a mixed system, specifically oxalic acid, malonic acid, and succinic acid.
  • One or a combination of two or more of these is used as an electrolytic solution for anodization.
  • the electrolysis method is DC waveform, liquid temperature 0-40°C, current density 0.6-3.0A/dm 2 , 10-120 minutes, preferably liquid temperature 10-30°C, current density 0.8-2.0A/dm 2 . dm 2 , electrolysis time 20-90 minutes, pulse waveform, PR pulse waveform, AC waveform, average current density of positive current 0.1-10 A/dm 2 , average current of negative current 0.1-10 A/dm 2 in one cycle. 0 to 10 A/dm 2 , liquid temperature 0 to 40° C.
  • the thickness of the anodized film is produced to be 6 to 50 ⁇ m.
  • the current density of DC electrolysis which is usually used, refers to the value obtained by dividing the amount of electricity (A sec) by the electrolysis time (sec) and the surface area (dm 2 ) of the object to be treated. ), current density and average current density are used synonymously, and the unit is A/dm 2 , because the current does not change with time for the object to be processed.
  • current density and average current density are used synonymously, and the unit is A/dm 2 , because the current does not change with time for the object to be processed.
  • pulse and PR pulse waveforms depending on the time, "positive current”, “0 (no current flow)", or “negative current” with reversed polarity flows, so the average current density in the waveform is the current In one period (cycle) of the waveform, the positive current average current density and negative It is necessary to display the current as the average current density.
  • one cycle of the waveform is set to 10 seconds, and a positive current of 2 A is applied for 4 seconds, followed by a negative current of 1 A for 6 seconds. and the average current densities of negative current are 0.4 A/dm 2 and 0.3 A/dm 2 , respectively.
  • the average current density of negative current is 0.0 A/dm 2 .
  • What can be added as an additive to the electrolytic solution mainly composed of an organic acid is one or more compounds of an inorganic acid type or an organic acid type.
  • the organic acid-based compound is the above-described aliphatic or aromatic sulfonic acid and/or carboxylic acid-based compound. use.
  • alcohol compounds such as ethylene glycol, diethylene glycol, glycerin, etc. can also be used as solvents, the amount of which is up to 60%, and these alcohol compounds can be used together with water as part of the solvent.
  • Inorganic acid compounds include boric acid, silicic acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid or salts thereof, pyrophosphoric acid, sulfamic acid or salts thereof, fluoride salts, bifluoride salts, permanganic acid.
  • One or two or more can be used, such as salt.
  • the amount of these additives used is less than the amount of the organic acid used in the electrolytic solution, and the concentration of the liquid is preferably 0.001 to 0.9 mol/L.
  • the fourth electrolysis of the present embodiment can produce a light brown to black anodized film with excellent weather resistance and fading resistance and excellent surface hardness.
  • the electrolysis conditions of the fourth electrolysis are as follows.
  • the temperature is -10 to 40 ° C., preferably 10 to 25 V, 5 to 15 minutes, 16 to 30 ° C.
  • the (member to be treated) is set on the cathode side, and the anode side is a carbon plate. Electrolysis is performed using electrodes, and washing before and after electrolysis is sufficiently performed with deionized water or pure water.
  • the color difference ( ⁇ E) used in this embodiment as a measure of the degree of fading is a quantitative representation of the "color difference" that could only be evaluated sensory in the past. For example, even if they look the same to the human eye, a colorimeter is used to three-dimensionally measure the hue, saturation, and lightness of the point of the reference color, and the point of the sample color is measured in the same way. This is a method of expressing the distance between points as a color difference.
  • the anodized film of this embodiment is a conventional product, it will begin to fade to a brownish color when heated at a temperature exceeding 200°C, and at 300°C, the color difference ⁇ E will exceed 3.0 in about 1 hour.
  • ⁇ E can be maintained at 3.0 or less even after a two-week heat resistance test at the same temperature, and similar results can be obtained in a one hour heat resistance test at 500° C. for a short period of time.
  • an electrolytically colored film there is a proposal for a film in which nickel or cobalt is deposited in porous pores, and there is no change in discoloration at 400° C. for 100 hours (4 days). No material has yet been found that shows ⁇ E of 3.0 or less after heat treatment of an oxide film at 300° C. for 2 weeks. Furthermore, the surface hardness is about HV470, and practically, it also prevents scratch resistance.
  • the anodized film of this embodiment also has a hardness of HV470 or more in a Vickers hardness test. In addition, it has an excellent electromagnetic wave shielding effect at the frequency of 500 kHz to 1000 MHz, which is equivalent to that of the aluminum base.
  • Electromagnetic shielding effect measurement of the anodized film manufactured by this embodiment is the result of electrolysis and magnetic field measurement up to 100 kHz-1000 MHz (1 GHz) by the KEC method at the KEC Kansai Electronic Industry Promotion Center, Test Division. , 500kHz-1000MHz (1GHz) as a guaranteed value is 30db or more, which is the same value as the aluminum base, and has a shielding effect equivalent to the limit value of aluminum. As a result, it has heat resistance and corrosion resistance, so it is difficult to corrode, the shielding effect is maintained stably for a long time, and it is hard to be scratched. Conceivable.
  • Electromagnetic waves are waves (waves) formed by changes in the electric and magnetic fields in space.
  • Light and radio waves are a type of electromagnetic waves.
  • radio waves have longer wavelengths (mm or longer) than infrared rays, up to about 1 ⁇ m. is called infrared rays, 0.7 to 0.3 ⁇ m is called visible light, shorter wavelengths up to several nm are called ultraviolet rays, and 10 nm to 1 pm is called X-rays.
  • Electromagnetic waves have both wave and particle properties, and show various wave properties such as scattering, reflection, refraction, and interference depending on the wavelength.
  • the radio waves used in this embodiment are long waves (LF), medium waves (MF), short waves (HF), very high frequencies (VHF), ultrahigh frequencies (UHF), centimeter waves (SHF), and millimeter waves (EHF).
  • LF long waves
  • MF medium waves
  • HF very high frequencies
  • UHF ultrahigh frequencies
  • SHF centimeter waves
  • EHF millimeter waves
  • submillimeter waves of which 500KHz to 1000MHz (1GHz) from medium waves to ultrashort waves, which are mainly used for mobile phones, smartphones, TVs, taxi radios, aircraft phones, AM radios, FM broadcasting, ships, international broadcasting.
  • the purpose is to shield the wavelength range used for beacons for ships and aircraft.
  • EMC countermeasures which accepts necessary electromagnetic waves and eliminates (shields) unnecessary electromagnetic waves, has become more and more enhanced.
  • shields unnecessary electromagnetic waves
  • the electromagnetic wave shield is generally called RF and targets frequencies of about 300Hz to 3THz.
  • the basis of electromagnetic wave shielding is to raise the performance of the shield from multiple reflection losses of reflection loss, absorption loss or a combination thereof.
  • Reflection loss is the loss (attenuation) due to reflection on the surface of the shield when an electromagnetic wave enters the shield material and is transmitted through it. Reflection loss is measured by assembling multiple shielding materials in layers, and when an electromagnetic wave penetrates inside the shielding material, part of it is reflected, part of it is transmitted, it propagates to the next shielding material, and reflection, penetration, and transmission occur again. Attenuates by repeating and enhances the shield effect.
  • the electromagnetic shielding effect is expressed using decibels (dB). It is a unit that relatively expresses how much electromagnetic waves are attenuated before and after shielding, and is derived from the following formula.
  • Typical methods for evaluating the performance of electromagnetic shielding materials include the "KEC method” developed by the Kansai Electronics Industry Center and the “Advantest method” developed by Advantest Co., Ltd. Either method is used in this embodiment. can do.
  • Table 2 shows the relationship between the decibel, the shield rate, and the attenuation rate.
  • the anodized film of aluminum was originally developed as an insulating material, and after many years of improvement, it became the anodized film of today, and there is no doubt that it contributed to the development of aluminum. Density has risen markedly, and along with this, the miniaturization of electronic equipment has progressed rapidly.For this reason, the space that was not a problem in the past has become extremely narrow, and static electricity sparks occur, which is a serious problem for electronic equipment. It has resulted in damage. In order to solve this problem, there has been a demand for a film that is a conductor, has hardness, and satisfies the LCA, so that the static electricity does not accumulate on the surface and can always be dropped to the ground.
  • the electrical resistance was measured by using the direct-current four-terminal method (voltage drop method), which is excellent in low resistance measurement, as shown in FIG.
  • An ohmmeter RM3548 (manufactured by Hioki Electric Co., Ltd.) 6 is placed on the surface 12 of the anodized film and the substrate 3, and an electrode 11 made of gold-plated copper with a thickness of 1 cm 2 is placed, and a weight of 50 g/cm 2 is applied to the surface to measure the electrical resistance.
  • the Vickers hardness test shows the average film hardness measured under a load of 10 gf for 15 seconds using a micro-hardness tester (HMV-G-XY-D) manufactured by Shimadzu Corporation by microscopic cross-section measurement.
  • the film thickness is 20 ⁇ m or less
  • the film thickness is the average thickness measured by an eddy current film thickness meter (LH-373) manufactured by Kett Science Laboratory Co., Ltd.
  • the corrosion resistance test was performed using a JIS-Z2371 neutral salt spray tester (manufactured by Suga Test Instruments Co., Ltd.), and after one month of continuous spraying (720 hours), the evaluation method was JIS-H8679-1 (aluminum and aluminum alloy Evaluation method of pitting corrosion generated in the anodized film of - Part 1: Performed by the rating number method (RN).
  • Electromagnetic shield effect measurement is the result of electric field and magnetic field measurement up to 100KHz-1000MHz (1GHz) by the KEC method at KEC Kansai Electronics Industry Promotion Center, Test Division, and thermal emissivity is infrared emissivity measurement.
  • the temperature of the object to be measured is 100 ° C., and the emissivity of the black body is 100%.
  • the emissivity and the total emissivity in the middle to far infrared region with a wavelength of 3 to 25 ⁇ m are measured and expressed in %.
  • a test piece of aluminum A1050 material (Si 0.25%, Mn 0.05% or less) of 50 ⁇ 100 ⁇ t 1.0 mm is pretreated by emulsion degreasing / 45 ° C ⁇ 5 minutes - 5% nitric acid / room temperature ⁇ 3 minutes - Etching 20% sodium hydroxide/room temperature x 1 minute - desmutting/10% sulfuric acid/room temperature x 3 minutes;
  • the liquid temperature was 25 ⁇ 1° C.
  • the current density was 1.4 ⁇ 0.1 A/dm 2
  • the current density was 1.4 ⁇ 0.1 A/dm 2 for 70 minutes.
  • the final voltage of the first electrolysis was maintained at 70 V for 2 minutes without turning off the power, then lowered by 5 V, held for 60 seconds, then lowered again by 5 V and held for 60 seconds, repeatedly up to a voltage of 10 V, then 7 V, 5 V, The voltage was gradually lowered to 3 V, 2 V, 1 V, and 0 V, and the holding time at this time was 60 seconds each, and 0 V was reached in 17 minutes.
  • the liquid composition was 0.3 mol/L of sodium hydroxide, and 0.05 mol/L of ammonium tartrate was added as an additive, and the liquid temperature was 5°C. Density was 0.8 A/dm 2 and electrolysis time was 10 minutes.
  • the liquid composition is 300 g/L of zinc sulfate, 28 g/L of ammonium sulfate, and 25 g/L of boric acid. Electrolysis was performed for 20 minutes at ⁇ 1° C. and a current density of 1.0 A/dm 2 .
  • the first electrolysis is 98 g / dm 3 sulfuric acid aqueous solution , 30° C., voltage 20 V (approximately 3 A/dm 2 ), time 30 minutes, electrolysis using carbon as the counter electrode, barrier removal in the second electrolysis, the bath voltage was lowered to 0.08 V in 3 minutes before the end of the electrolysis, and the power was turned off.
  • the sample was galvanically dissolved in the liquid for 15 minutes.
  • the resulting anodized film had an electrical resistance of 4 ⁇ 10 ⁇ 1 ⁇ , a cross-sectional film hardness of HV380, a cross-sectional average film thickness of 26 ⁇ m, a corrosion resistance of RN9.0, and cracks after heating and cooling to 200° C.
  • resistance, hardness, corrosion resistance, electromagnetic wave shielding effect, heat resistance and infrared emissivity were not sufficient, and the desired material could not be obtained.
  • test piece A1100 material 100 ⁇ 100 ⁇ t1.0, after organic degreasing, desmutting is performed by etching with 50 g/L sodium hydroxide at 70° C. for 30 seconds and immersing in a 30% nitric acid solution at room temperature for 10 seconds.
  • the obtained anodized film had an average film thickness of 22 ⁇ m, an average electrical resistance of 1.67 ⁇ 10 ⁇ 1 ⁇ , a hardness of HV 380 by the Knoop method, a corrosion resistance of RN8, and a heat resistance of 300° C.-2.
  • Example 2 The materials, pretreatment, first electrolysis, fourth electrolysis, sealing treatment, and film measurement were performed in the same manner as in Example 1. Except for the second and third electrolysis, the fourth electrolysis treatment was performed, and when the surface was observed, spalling occurred. However, the film looked like a volcanic crater, so the subsequent processes were stopped.
  • Example 1 The materials, pretreatment, fourth electrolysis, sealing treatment, and measurement of the film were performed in the same manner as in Example 1 . 16 V, bath temperature 19 to 20° C., electrolysis time 60 min.
  • the resulting anodized film had a uniform dark brown color, and was an insulator with an electrical resistance of 10 6 ⁇ or more between the film surface and the aluminum substrate.
  • Corrosion resistance is RN10
  • no corrosion is 45 dB for electric field
  • 28 dB for magnetic field
  • heat resistance test is 300 ° C - 14 days
  • color difference ( ⁇ E) in L * a * b * color space before and after heat treatment is 3 2.
  • the resulting anodized film had an electrical resistance of 36.2 ⁇ between the surface of the film and the aluminum substrate, an average film hardness of HV438 measured by microscopic cross-section measurement, an average film thickness of 21 ⁇ m, a deep brownish black color, and corrosion resistance.
  • electromagnetic wave shielding effect was 42 dB for electric field and 27 dB for magnetic field
  • heat resistance was L * a * b * color before and after heating at 300°C.
  • the spatial color difference ( ⁇ E) is 3.3, and the color difference ( ⁇ E) is 3.1 at 500°C.
  • the total emissivity in the middle to far infrared region was 73.4%, and no cracks were observed. material was not obtained.
  • Example 2 The materials, pretreatment, first electrolysis, second electrolysis, third electrolysis, sealing treatment, and measurement of the film were performed in the same manner as in Example 1.
  • the electrical resistance between the film surface and the aluminum substrate was 10 6 ⁇ or more
  • the average film hardness measured by microscopic cross section measurement is HV437
  • the average film thickness is 19 ⁇ m
  • the color tone is brown
  • the corrosion resistance is RN6 (corrosion area rate exceeds 0.50%, 1.00% after 720 hours). %)
  • the electromagnetic wave shielding effect is 43 dB for the electric field and 26 dB for the magnetic field
  • the heat resistance is L * a * b * before and after heating at 300°C.
  • the materials, pretreatment, first electrolysis, second electrolysis, third electrolysis, sealing treatment, and film measurement were performed in the same manner as in Example 1.
  • the fourth electrolysis was performed with a DC waveform, and the solution composition was 10 g of stannous sulfate.
  • L, nickel sulfate hexahydrate 15 g/L, sulfuric acid 15 g/L, tartaric acid 8 g/L, PH 1, bath temperature 23 ° C., electrolysis voltage 16 V, secondary electrolysis for 20 minutes, and further as sealing treatment
  • the electric resistance between the film surface and the aluminum substrate was 0.3 ⁇ , and sufficient electrical conductivity was not obtained.
  • the average film hardness measured by microscopic cross-section measurement is HV478, the average film thickness is 21 ⁇ m, the color is dark brown, the corrosion resistance is RN8 (corrosion area rate exceeds 0.10%, 0.25% or less) after 720 hours, and electromagnetic waves
  • the shielding effect is 33 dB for electrolysis , 30 dB for magnetic field, and the heat resistance is 3.5 before and after heating at 300°C .
  • the infrared emissivity is 64.8% in the mid-infrared wavelength region of 3 to 6 ⁇ m, and 87.5% in the middle to far infrared region of 3 to 25 ⁇ m, and no cracks are observed. I didn't. However, in Comparative Example 7, except for hardness and medium to far infrared reflectance, the corrosion resistance and electromagnetic wave shielding effect of infrared rays were insufficient, and the desired material could not be obtained.
  • the materials, pretreatment, second electrolysis, third electrolysis, fourth electrolysis, sealing treatment, and film measurement were performed in the same manner as in Example 1.
  • the liquid composition of the first electrolysis was the same, and the electrolysis conditions were a PR pulse waveform.
  • the positive side current density is 2.0 A/dm 2
  • the negative side current density is 0.5 A/dm 2
  • the positive side maximum voltage is 70 V
  • the negative side maximum voltage is ⁇ 15 V
  • 1 pulse is 3.3 ms. 20 pulses, 3 pulses on the negative side, and a rest period of 3 pulses when the polarity changes. This is regarded as one cycle.
  • the electrical resistance of the film surface and the aluminum substrate was 2 ⁇ 10 -3 ⁇
  • the average film hardness was HV480
  • the average film thickness was The thickness is 21 ⁇ m
  • the color is dark brownish black
  • the corrosion resistance is RN9.8 after 720 hours
  • the electromagnetic wave shielding effect is 38 dB for electric field and 32 dB for magnetic field
  • the heat resistance is L * a * b * color space before and after heating at 300°C.
  • the color difference ( ⁇ E) is 2.6, which is 2.2 at 500°C.
  • a total emissivity of 93.4% was obtained, no cracks were observed, and an anodized film with good properties was obtained.
  • the materials, pretreatment, second electrolysis, third electrolysis, fourth electrolysis, sealing treatment, and film measurement were performed in the same manner as in Example 1.
  • the liquid composition of the first electrolysis was 3% oxalic acid, and the electrolysis conditions were AC/DC superposition.
  • the current density is 1.5 A/dm 2 on the + side and 0.5 A/dm 2 on the - side, the voltage is 50 V for DC and 90 V for AC, bath temperature is 25° C., and electrolysis time is 60 minutes.
  • the electrical resistance of the film surface and the aluminum substrate was 3 ⁇ 10 ⁇ 3 ⁇
  • the average cross-sectional hardness was HV475, the dark brown black
  • the average film thickness was 36 ⁇ m
  • the corrosion resistance was RN9.5 after 720 hours
  • the electromagnetic shielding was achieved.
  • the effect is an electric field of 35 dB or more, a magnetic field of 32 dB or more
  • the heat resistance is L * a * b * before and after heating at 300°C.
  • a total emissivity of 76.3% in the middle infrared wavelength region of 3 to 6 ⁇ m and a total emissivity of 82.1% in the middle to far infrared region of 3 to 25 ⁇ m were obtained, and no cracks were observed.
  • An anodized film with excellent properties was obtained.
  • the material of the present embodiment is an anodized aluminum film having both a low resistance film of 1 ⁇ 10 0 ⁇ or less and a hardness of HV450 or more. Prevents breakage due to sparks, shielding effect especially against magnetic fields from 500KHz to 1000MHz, heat resistance with color difference ⁇ E of 3.0 or less after heat treatment at 300°C for 2 weeks and 500°C for 1 hour, and is lightweight as an unused energy temperature zone material. It is expected that it will be used as a conductor material with hard slidability.
  • Micropores 2 1. Micropores 2 . wall3. Material (aluminum) 4. porous layer 5 . barrier layer 6 . Recoating7. 8. Metal deposition in micropores; Resistance meter: RM3548 9. DC constant voltage power supply 10 . voltage system 11 . Gold plated electrode 12 . Anodized film

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Abstract

Le problème décrit par la présente invention est de développer un matériau dans lequel un revêtement d'oxyde anodique d'aluminium a été imprimé avec une conductivité électrique et est au moins aussi dur que l'alumite. La solution selon l'invention consiste à retirer une couche barrière qui sert de matériau isolant dans un revêtement d'oxyde anodique d'aluminium et à former ensuite un revêtement ayant une bonne conductivité électrique et déposer en outre un métal afin de maintenir une résistance électrique de 1×10-2 Ω ou moins, conférer une dureté HV de 470 ou plus et améliorer la résistance à la corrosion, la présente invention apporte un matériau ayant une faible résistance et une excellente dureté que l'on ne trouve pas dans les matériaux d'aluminium classiques. Le matériau peut être produit par la mise en œuvre d'une électrolyse en quatre étapes.
PCT/JP2021/040703 2021-11-05 2021-11-05 Matériau métallique d'aluminium présentant une excellente conductivité et son procédé de production WO2023079671A1 (fr)

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PCT/JP2021/040703 WO2023079671A1 (fr) 2021-11-05 2021-11-05 Matériau métallique d'aluminium présentant une excellente conductivité et son procédé de production
CA3208948A CA3208948A1 (fr) 2021-11-05 2021-11-05 Materiau d'aluminium presentant une bonne conductivite et methode de fabrication connexe
JP2022523191A JP7165462B1 (ja) 2021-11-05 2021-11-05 導電性に優れたアルミニウム金属材料およびその製造方法
CN202180097454.3A CN117203378A (zh) 2021-11-05 2021-11-05 导电性优异的铝金属材料及其制造方法

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000001865A1 (fr) 1998-07-07 2000-01-13 Izumi Techno Inc. Procede pour traiter la surface d'une preforme en aluminium
JP2002332578A (ja) * 2001-05-10 2002-11-22 Canon Inc ナノ構造体の製造方法
JP2006291259A (ja) * 2005-04-07 2006-10-26 Kumabo Metal:Kk 帯電を抑制するアルミニウムまたはアルミニウム合金表面形成方法及び帯電を抑制するアルミニウムまたはアルミニウム合金部材
JP2019147988A (ja) * 2018-02-27 2019-09-05 富士フイルム株式会社 金属膜、構造体、複合材料、金属膜の製造方法、構造体の製造方法、および複合材料の製造方法
JP2021070865A (ja) * 2019-10-29 2021-05-06 株式会社アート１ 耐熱性に優れたアルミニウム金属材料およびその製造法。
JP2021181609A (ja) * 2020-05-18 2021-11-25 株式会社アート１ 導電性に優れたアルミニウム金属材料およびその製造法。

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000001865A1 (fr) 1998-07-07 2000-01-13 Izumi Techno Inc. Procede pour traiter la surface d'une preforme en aluminium
JP2002332578A (ja) * 2001-05-10 2002-11-22 Canon Inc ナノ構造体の製造方法
JP2006291259A (ja) * 2005-04-07 2006-10-26 Kumabo Metal:Kk 帯電を抑制するアルミニウムまたはアルミニウム合金表面形成方法及び帯電を抑制するアルミニウムまたはアルミニウム合金部材
JP2019147988A (ja) * 2018-02-27 2019-09-05 富士フイルム株式会社 金属膜、構造体、複合材料、金属膜の製造方法、構造体の製造方法、および複合材料の製造方法
JP2021070865A (ja) * 2019-10-29 2021-05-06 株式会社アート１ 耐熱性に優れたアルミニウム金属材料およびその製造法。
JP2021181609A (ja) * 2020-05-18 2021-11-25 株式会社アート１ 導電性に優れたアルミニウム金属材料およびその製造法。

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* Cited by examiner, † Cited by third party
Title
JOURNAL OF THE SURFACE FINISHING SOCIETY OF JAPAN, vol. 33, no. 5, 1982, pages 232 - 237

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