EP1593758A1 - Verfahren zur ausbildung einer anodischen oxidbeschichtung auf der oberfläche von aluminium oder aluminiumlegierung - Google Patents

Verfahren zur ausbildung einer anodischen oxidbeschichtung auf der oberfläche von aluminium oder aluminiumlegierung Download PDF

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Publication number
EP1593758A1
EP1593758A1 EP04705515A EP04705515A EP1593758A1 EP 1593758 A1 EP1593758 A1 EP 1593758A1 EP 04705515 A EP04705515 A EP 04705515A EP 04705515 A EP04705515 A EP 04705515A EP 1593758 A1 EP1593758 A1 EP 1593758A1
Authority
EP
European Patent Office
Prior art keywords
aluminum
aluminum alloy
oxide layer
anodic oxide
bath liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04705515A
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English (en)
French (fr)
Other versions
EP1593758A4 (de
Inventor
Yoshiyuki Mitani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kirihata Takashi
Nihon Alumina Kakou KK
Original Assignee
Kirihata Takashi
Nihon Alumina Kakou KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kirihata Takashi, Nihon Alumina Kakou KK filed Critical Kirihata Takashi
Publication of EP1593758A1 publication Critical patent/EP1593758A1/de
Publication of EP1593758A4 publication Critical patent/EP1593758A4/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon

Definitions

  • the present invention relates to an improvement of a method for forming an anodic oxide layer on a surface of aluminum or an aluminum alloy.
  • a method for forming a corrosion-resistant oxide layer by anodizing aluminum or an alloy thereof in an electrolytic solution such as an aqueous solution of nitric acid, sulphuric acid or chromic acid for the purpose of mainly improving corrosion resistance thereof is known as an alumite treatment.
  • Articles subjected to the alumite treatment are widely utilized in various fields with a central focus on daily commodities such as a pan and a teakettle.
  • the layer to be formed by a conventional method is restricted to have a comparably small thickness of about 30 to about 50 ⁇ m, a low hardness and the like and, accordingly, there is a given limitation upon applications thereof.
  • the present invention has been achieved in order to solve these problems and an object of the present invention is to provide a method for treating a surface of aluminum or an aluminum alloy which can treat various types of aluminum alloys involving not only aluminum itself, but also duralumin and a die cast alloy, can apply a thick layer of 300 to 500 ⁇ m and has a number of advantages such that the layer to be obtained has a high surface hardness, an excellent heat resistance, an antibiotic action and the like and can produce various types of aluminum materials which can be utilized in a far wide field compared with a conventional one.
  • the above-described object according to the present invention can be attained by performing an anodic oxidation treatment by using a bath liquid, which involves an aqueous solution containing 250 gr/l to 350 gr/l of sulfuric acid and 15 gr/l to 25 gr/l of nickel sulfate under the following conditions:
  • the above-described treatment according to the present invention is referred to as “the present treatment (1)” and a product to be obtained thereby is referred to as “present product (1)”.
  • the object according to the present invention can be performed more favorably by using a bath liquid in which the bath liquid to be used in the present treatment (1) is further added with a low polymerization acrylic resin composition in the range of from 280 gr/l to 320 gr/l.
  • the above-described treatment according to the present invention is referred to as “the present treatment (2)” and a product to be obtained thereby is referred to as “present product (2)”.
  • anodic oxide layer is formed on the surface of aluminum or the aluminum alloy by any one of the above-described various types of treating methods
  • it is recommended to impregnate silver in the anodic oxide layer by performing a treatment using a bath liquid which involves an aqueous solution further containing 10 gr/l to 30 gr/l of silver sulfate or silver nitrate, 15 gr/l to 20 gr/l of boric acid and 1 gr/l to 2 gr/l of nickel sulfate under the following conditions:
  • the above-described treatment according to the present invention is referred to as “the present treatment (3)” and a product to be obtained thereby is referred to as “present product (3)”.
  • the above-described object according to the present invention can be attained by a method for forming an anodic oxide layer on a surface of aluminum or an aluminum alloy which is characterized in that an anodic oxide layer having a thickness of 300 ⁇ m to 600 ⁇ m is formed on a surface of aluminum or an aluminum alloy by any one of the above-described various treating methods and, after the above-described silver impregnation is performed on the layer, a surface layer was removed by polishing by a thickness of 50 ⁇ m to 100 ⁇ m and, then, an ultra-hard flat surface is obtained.
  • reference numeral 1 denotes an electrolyte bath
  • reference numeral 2 denotes an AC power supply
  • reference numeral 3 denotes an aluminum or aluminum alloy member to be treated by the method according to the present invention
  • reference numeral 4 denotes a non-consumable electrode such as carbon or graphite
  • reference numeral 5 denotes a bath liquid involving a predetermined electrolytic solution.
  • the present treatment (1) performs an anodic oxidation treatment by using a device as shown in FIG. 1 and an aqueous solution containing 250 gr/l to 350 gr/l of sulfuric acid, 15 gr/l to 25 gr/l of nickel sulfate as a bath liquid under the following conditions:
  • the present invention is entirely different from the conventional method in the point that the anodic oxidation treatment is performed under the treating conditions of a high sulfuric acid ion concentration, a low temperature and a high current density.
  • Nickel sulfate is added for the purpose of enhancing hardness of the layer to be formed.
  • a desired anodic oxide layer can be formed by using any one of above-described bath liquids and adopting the following conditions:
  • a desired anodic oxide layer can be formed by adopting the following conditions:
  • the present invention When the present invention to be constituted as described above is compared with a conventional method, the present invention has such advantages as described below.
  • an aluminum material or an aluminum alloy material on which an anodic oxide layer is formed by the method according to the present invention can favorably be utilized in a wide field, for example, as a tray for ice-making or unfreezing, a rice cooker, a pan, a kettle, a teakettle and other cooking devices for heating, an instantaneous hot-water heater, a heat exchanger, an air-conditioner, a freezer, a refrigerator, an oil heater, a radiator, a cooling fin, an air- or water-cooled engine (acceleration of heat release), a wing of an airplane (de-icing), a heat sink for a semiconductor, a semiconductor package, a heat pipe, a bearing, various types of sliding members, a brake shoe, a manufacturing apparatus for popcorn or ice-cream, a chassis for an electric apparatus, a casing for a motor; an electric transformer or the like.
  • the anodic oxidation treatment is performed by using a bath liquid in which the bath liquid used in the above-described present treatment (1) is further added with a low polymerization acrylic resin composition in the range of from 280 gr/l to 320 gr/l.
  • the low polymerization acrylic resin composition to be added for example, an article containing, based on percentages, 68% of hydroxypropyl methacrylate, 10% of neopentyl glycol dimethacrylate, 19.5% of polypropylene glycol methacrylate, 1% of 1,6-hexanediol diglycidyl ether, 1% of butyl peroxyoctoate, 500 ppm of hydroquinone monmethyl ether and 0.3% of dicyandiamide is favorably used.
  • tartaric acid for the purpose of prevention of "burning", it is recommended to further add tartaric acid to the above-described bath liquid in the range of from 5 gr/l to 15 gr/l.
  • an oxide layer which is a composite of aluminum oxide and the acrylic resin composition is formed. Namely, a metallurgical porous oxide layer and the acrylic resin composition are acid-ionized and polymerized therebetween and, then, form a tough and dense composite layer to thereby enhance corrosion resistance and abrasion resistance to a great extent. Further, since the layer is formed while drawing out a gas in a pinhole portion, the layer has characteristics such that pinholes are small in number and, further, since the oxide layer is slowly formed at a low temperature, it is excellent in density and, since the layer is hard to be peeled off, it can be subjected to machining and a surface roughness thereof remains unchanged.
  • the anodic oxide layer obtained by the present treatment (2) is now explained with reference to an enlarged cross-sectional view showing a layer portion of FIG. 2.
  • reference numeral 21 denotes an aluminum material or aluminum alloy material as a base metal
  • reference numeral 22 denotes an anodic oxide layer
  • reference numeral 23 denotes a barrier layer
  • reference numeral 24 denotes a porous layer portion
  • reference numeral 25 denotes an acrylic resin composition layer portion.
  • the anodic oxide layer 22 involves a barrier layer 23 formed on the aluminum material or aluminum alloy material 22, a porous layer portion 24 formed thereon and an acrylic resin composition layer portion 25 which is impregnated inside the porous layer and fixed therein.
  • a tough and dense composite layer is formed.
  • the composite layer as a portion thereof is closer to the barrier layer 23, the portion comes to have a higher hardness and becomes denser and, as described below, by removing a region close to a surface by machining, the surface having a further higher hardness can be obtained.
  • the present treatment (3) is performed, after the anodic oxide layer is formed on a surface of an aluminum or aluminum alloy by any one of the above-described various types of treating methods, it is characterized in that silver is impregnated in the anodic oxide layer by performing an anodic oxidation treatment using a bath liquid which involves an aqueous solution further containing 10 gr/l to 30 gr/l of silver sulfate or silver nitrate, 15 gr/l to 20 gr/l of boric acid and 1 gr/l to 2 gr/l of nickel sulfate under the following conditions:
  • Boric acid is added mainly for adjustment of electric conductivity of the electrolytic solution.
  • a silver ion is deeply impregnated inside the porous anodic oxide layer (electrolytically impregnated by alternating voltage) and, then, combines with aluminum oxide, to thereby form a tough dense composite layer.
  • the surface layer excellent in the heat conductance, the corrosion resistance, the abrasion resistance, the antibiotic action and the like can be formed.
  • the surface layer has the electric conductance and has a small coefficient of friction and a small color change in time.
  • the layer has effects such as far-infrared emission, removal of static electricity and the like.
  • Such present treatment (3) can be performed on all types of aluminum material and aluminum alloy material and can form a thick layer having various types of excellent characteristics as described above on the surface thereof.
  • an anodic oxide layer having a thickness of 300 ⁇ m to 600 ⁇ m is formed on a surface of aluminum or an aluminum alloy by the above-described various types of treating methods and, then, further, the above-described silver impregnation is performed and, thereafter, a surface layer is removed by polishing in a depth of from 50 to 100 ⁇ m from the surface and, subsequently, an aluminum material or aluminum alloy material having a ultra-hard smooth surface can be provided.
  • a surface hardness is high and is about 450 to about 500 in terms of Vicker's hardness.
  • a lower layer is denser than the surface and is higher in hardness.
  • the heat conductivity of the present product is higher than that of aluminum as a base metal and is comparable with that of copper.
  • This property shows that the present product is excellent as a raw material for various types of heat transfer members, diathermal members, heat releasing members.
  • the hardness (Hv) that of aluminum is 80, that of stainless steel is 200, that of the present product is 450. Accordingly, the hardness of the present product is more than twice that of stainless steal.
  • the upper temperature limit (°C) that of polytetrafluoro-ethylene is 260°C; that of aluminum is 660°C; and that of the surface layer of the present product is 800°C.
  • the present product can provide a flame-retardant shutter, heat-resistant wall material and the like.
  • an abrasion amount of the present product was one tenth the abrasion amount of ordinary hard-type alumite.
  • the abrasion test was conducted by arranging a test piece to be in a rotating side and a resin-type oil-less bearing material in a fixing side. Testing conditions were as follows: vibration speed: 1m/s; face pressure 20 kgf/cm 2 ; and test duration: 3 hours. As a result, the abrasion amount of the hard-type alumite was 2.5 ⁇ m while that of the present product was 0.25 ⁇ m.
  • a wear coefficient was measured by arranging the test piece to be in a rotating side and a resin-type oil-less bearing material in a fixing side. A load at the time the wear coefficient showed an abrupt increase was evaluated as a critical load of the burning-down.
  • the critical load of the ordinary hard-type alumite was 160 kgf/cm 2
  • that of the present product was 320 kgf/cm 2 .
  • TUFRAM trademark: a product prepared by subjecting hard-type alumite to a sintering treatment and, then, impregnating the resultant alumite with polytetrafluoroethylene.
  • an aluminum material or an aluminum alloy material on which an anodic oxide layer is formed by the method according to the present invention can favorably be utilized in a wide field, for example, as a tray for ice-making or unfreezing, a rice cooker, a pan, a kettle, a teakettle and other cooking devices for heating, an instantaneous hot-water heater, a heat exchanger, an air-conditioner, a freezer, a refrigerator, an oil heater, a radiator, a cooling fin, an air- or water-cooled engine (acceleration of heat release), a wing of an airplane (de-icing), a heat sink for a semiconductor a semiconductor package, a heat pipe, a bearing, various types of sliding members, a brake shoe, a manufacturing apparatus for popcorn or ice-cream, a chassis for an electric apparatus, a casing for a motor, an electric transformer or the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • ing And Chemical Polishing (AREA)
EP04705515A 2003-01-30 2004-01-27 Verfahren zur ausbildung einer anodischen oxidbeschichtung auf der oberfläche von aluminium oder aluminiumlegierung Withdrawn EP1593758A4 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2003022682 2003-01-30
JP2003022682 2003-01-30
PCT/JP2004/000684 WO2004067807A1 (ja) 2003-01-30 2004-01-27 アルミニウム又はアルミニウム合金の表面に陽極酸化皮膜を形成する方法

Publications (2)

Publication Number Publication Date
EP1593758A1 true EP1593758A1 (de) 2005-11-09
EP1593758A4 EP1593758A4 (de) 2006-11-29

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EP04705515A Withdrawn EP1593758A4 (de) 2003-01-30 2004-01-27 Verfahren zur ausbildung einer anodischen oxidbeschichtung auf der oberfläche von aluminium oder aluminiumlegierung

Country Status (11)

Country Link
US (1) US20070267299A1 (de)
EP (1) EP1593758A4 (de)
JP (1) JP4069135B2 (de)
KR (1) KR20050103284A (de)
CN (1) CN1745200A (de)
AU (1) AU2004207220A1 (de)
BR (1) BRPI0407080A (de)
CA (1) CA2514271A1 (de)
MX (1) MXPA05008032A (de)
TW (1) TW200417635A (de)
WO (1) WO2004067807A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
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CN109943873A (zh) * 2017-12-21 2019-06-28 李文熙 电镀金属前处理的厚膜铝电极

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JP2009030736A (ja) * 2007-07-27 2009-02-12 Nitto Seiko Co Ltd 高硬度アルミニウム合金製ねじ部品
JP5301810B2 (ja) * 2007-11-13 2013-09-25 住友電気工業株式会社 陽極酸化アルミナ自立膜およびその製造方法
CN101629316B (zh) * 2009-06-19 2011-06-08 常州佳得顺抗菌材料科技有限公司 铝或铝合金材料的抗菌抗腐蚀及抗变色表面处理工艺
IT1398287B1 (it) * 2009-09-18 2013-02-22 Unical A G S P A Metodo di anodizzazione di leghe metalliche, particolarmente per scambiatori di calore in leghe di alluminio e simili per caldaie a condensazione.
CN101886285A (zh) * 2010-06-25 2010-11-17 广东工业大学 一种制备表面抗菌不锈钢的方法
CN101994142B (zh) * 2010-12-09 2012-05-30 沈阳大学 一种铝材表面制备二氧化钛/铜纳米复合抗菌涂层的方法
CN102888643B (zh) * 2011-07-18 2015-09-02 汉达精密电子(昆山)有限公司 铝合金硬质阳极氧化电解液及方法
JP5441082B2 (ja) 2011-07-21 2014-03-12 国立大学法人東北大学 ガス排気用ポンプのスクリューローター及びその製造方法、並びにそのスクリューローターを備えるガス排気用ポンプ及びその製造方法及び組立方法
CN102312263A (zh) * 2011-08-22 2012-01-11 吴江市精工铝字制造厂 铝件的瓷质氧化方法
JP2013211523A (ja) * 2012-03-02 2013-10-10 Canon Components Inc フレキシブル回路基板
JP6029764B2 (ja) * 2013-08-30 2016-11-24 富士フイルム株式会社 金属充填微細構造体の製造方法
CN103498179B (zh) * 2013-10-22 2014-08-06 哈尔滨三泳金属表面技术有限公司 一种铝或铝合金表面氧化膜及其制备方法
CN105530785B (zh) 2014-12-26 2016-11-23 比亚迪股份有限公司 一种形成有天线槽的电子产品金属壳体及其制备方法
CN107164797A (zh) * 2017-04-11 2017-09-15 浙江洋铭工贸有限公司 一种压铸铝采暖散热片的电泳工艺
CN113089049A (zh) * 2017-06-26 2021-07-09 石狮市星火铝制品有限公司 一种抗菌铝及其制造方法
CN107937953B (zh) * 2017-12-12 2019-10-25 北京小米移动软件有限公司 铝合金壳体及其制备方法
WO2020067500A1 (ja) 2018-09-28 2020-04-02 株式会社三菱ケミカルホールディングス 抗菌材、積層体、抗菌性積層体、医療用部材、抗菌材の製造方法、抗菌性積層体の製造方法及び抗菌方法
CN111778537A (zh) * 2020-07-06 2020-10-16 上海脉诺金属表面处理技术有限公司 一种抗菌防霉型铝合金的常温硬质氧化液
CN114260312A (zh) * 2021-12-22 2022-04-01 福建省欧麦鑫自动化科技有限公司 一种高强度无菌型金属罐及其加工工艺

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CN109943873A (zh) * 2017-12-21 2019-06-28 李文熙 电镀金属前处理的厚膜铝电极

Also Published As

Publication number Publication date
US20070267299A1 (en) 2007-11-22
EP1593758A4 (de) 2006-11-29
TW200417635A (en) 2004-09-16
MXPA05008032A (es) 2006-01-27
CA2514271A1 (en) 2004-08-12
AU2004207220A1 (en) 2004-08-12
CN1745200A (zh) 2006-03-08
JPWO2004067807A1 (ja) 2006-05-18
JP4069135B2 (ja) 2008-04-02
BRPI0407080A (pt) 2006-01-24
WO2004067807A1 (ja) 2004-08-12
KR20050103284A (ko) 2005-10-28

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