JPS63247396A - Method for making anodic oxide film or aluminum opaque and white - Google Patents
Method for making anodic oxide film or aluminum opaque and whiteInfo
- Publication number
- JPS63247396A JPS63247396A JP7753587A JP7753587A JPS63247396A JP S63247396 A JPS63247396 A JP S63247396A JP 7753587 A JP7753587 A JP 7753587A JP 7753587 A JP7753587 A JP 7753587A JP S63247396 A JPS63247396 A JP S63247396A
- Authority
- JP
- Japan
- Prior art keywords
- treatment
- aqueous solution
- film
- opaque
- oxide film
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000010407 anodic oxide Substances 0.000 title claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 title claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 23
- 238000011282 treatment Methods 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims description 52
- 238000007654 immersion Methods 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 abstract description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 230000035515 penetration Effects 0.000 abstract 1
- 238000009736 wetting Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- -1 fluorine ions Chemical class 0.000 description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 230000002087 whitening effect Effects 0.000 description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 238000007743 anodising Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 3
- 229940094800 barium oxalate Drugs 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229940079864 sodium stannate Drugs 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940010048 aluminum sulfate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 229960003390 magnesium sulfate Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、白色をしたアルミニウム陽極酸化皮膜を水に
濡れた状態でも透明状にならずに不透明白色を維持し得
るアルミニウム陽極酸化皮膜の不透明白色化方法に関す
るものである。Detailed Description of the Invention [Field of Industrial Application] The present invention is an opaque aluminum anodic oxide film that can maintain an opaque white color without becoming transparent even when the white aluminum anodic oxide film is wet with water. This invention relates to a whitening method.
アルミニウムの着色皮膜材は久しく透明着色皮膜のもの
が汎用されて来たが、近年になり、不透明なパステル調
の色調のものが要望されて来た。Transparent colored coating materials for aluminum have been widely used for a long time, but in recent years, there has been a demand for opaque pastel colored coating materials.
そのために基調となる酸化皮膜を白色化し、さらに染色
処理や電解着色処理を行なう方法が提案され、酸浴やア
ルカリ浴中での電解処理により白色皮膜を形成する方法
が試みられたが２種々の理由で実用化されていない。For this purpose, a method was proposed in which the basic oxide film was whitened, and then dyed or electrolytically colored, and a method of forming a white film by electrolytic treatment in an acid bath or an alkaline bath was attempted, but two different methods were used. It has not been put into practical use for some reason.
クロム酸浴やエマタール浴でアルミニウム材を陽極酸化
すると不透明白色皮膜が形成されると言われているが、
高純度アルミニウム材以外の場合は、灰色味を帯びて純
白な不透明白色皮膜が得られない。又９強くエツチング
したアルミニウム材を陽極酸化すると白色味のある酸化
皮膜が得られるが、不透明度が弱く、電流回復法による
陽極酸化によっても白色味のある酸化皮膜が形成される
が、これも白色味と不透明度が弱いものである。It is said that an opaque white film is formed when aluminum material is anodized in a chromic acid bath or an ematal bath.
In the case of materials other than high-purity aluminum, a pure opaque white film with a grayish tinge cannot be obtained. Also, when a strongly etched aluminum material is anodized, a whitish oxide film is obtained, but its opacity is weak, and a whitish oxide film is also formed by anodic oxidation using the current recovery method, but this is also white. The taste and opacity are weak.
さらに、陽極酸化皮膜を形成させた後、カルシウム塩、
バリウム塩、アルミニウム塩などの水溶液中で浸漬又は
電解して不透明白色皮膜を得る方法が知られている。し
かしながら、この方法において不透明白色度を増加させ
ると、酸化皮膜の硬度や耐食性が劣化するという問題が
あり、白色化処理が強過ぎるとアルミニウム上に、いわ
ゆる「粉ふき」が発生することが知られており、白色生
成物を生成させる浴の管理が難しい、水にぬれたときに
透明化するなどといった問題があった。Furthermore, after forming an anodic oxide film, calcium salt,
A method of obtaining an opaque white film by immersion or electrolysis in an aqueous solution of barium salt, aluminum salt, etc. is known. However, increasing the opaque whiteness using this method has the problem of deteriorating the hardness and corrosion resistance of the oxide film, and it is known that if the whitening treatment is too strong, so-called "powdering" will occur on the aluminum. However, there were problems such as difficulty in controlling the bath in which the white product was produced and the fact that it became transparent when wet with water.
本発明は、前記従来の方法における皮膜の硬度や耐食性
の劣化や「粉ふき」あるいは浴管理の困難さ、水に濡れ
た状態では透明化するなどといったことを解決する間呟
点とし、純白な不透明皮膜及びパステル調呈色状不透明
皮膜を形成し得る手段を得ることを目的とするものであ
る。The present invention aims to solve the problems of the conventional methods, such as the deterioration of the hardness and corrosion resistance of the film, the difficulty of "dusting" or bath management, and the fact that it becomes transparent when wet with water. The object of the present invention is to obtain a means for forming an opaque film and a pastel colored opaque film.
本発明者は、前記問題点を解決し、前記目的を達成する
ために研究を重ね、アルミニウム酸化皮膜をカルシウム
塩、バリウム塩、アルミニウム塩などの水溶液中で浸漬
又は電解した場合には、生成する不透明白色化皮膜は、
前記金属イオンがアルマイト孔中に十分に浸入し得ない
ために不透明度が弱いことを認め、あらかじめ陽極酸化
皮膜を形成したアルミニウム材をフッ素イオン含有水溶
液や金属塩を添加したフッ素イオン含有水溶液で浸漬又
は電解処理することにより、又は、金属塩水溶液処理の
前あるいは後にフッ素イオン含有水溶液による処理を行
なうことによって目的を達し得ることを見出して本発明
をなしたものである。In order to solve the above-mentioned problems and achieve the above-mentioned object, the present inventor has conducted repeated research and found that when an aluminum oxide film is immersed or electrolyzed in an aqueous solution of calcium salt, barium salt, aluminum salt, etc. The opaque whitening film is
Recognizing that the opacity was weak because the metal ions could not sufficiently penetrate into the alumite pores, we immersed the aluminum material, on which an anodized film had been previously formed, in a fluorine ion-containing aqueous solution or a fluorine ion-containing aqueous solution containing metal salts. The present invention has been made based on the discovery that the object can be achieved by electrolytic treatment or by treatment with a fluorine ion-containing aqueous solution before or after the metal salt aqueous solution treatment.
すなわち９本発明は、あらかじめ陽極酸化処理したアル
ミニウム材を、フッ素イオン含有水溶液あるいは金属塩
添加フッ素イオン含有水溶液で処理する一段処理、又は
、金属塩水溶液で処理する前あるいは処理後にフッ素イ
オン含有水溶液で処理する二段処理によって不透明白色
化するアルミニウム陽極酸化皮膜の不透明白色化方法で
ある。In other words, the present invention provides a one-step treatment in which an aluminum material that has been anodized in advance is treated with an aqueous solution containing fluorine ions or an aqueous solution containing metal salts, or a treatment with an aqueous solution containing fluorine ions before or after treatment with an aqueous metal salt solution. This is a method for making an aluminum anodic oxide film opaque and white in a two-stage process.
本発明を適用し得るアルミニウム材は、その種類に制限
を受けることはなく、サツシ、カーテンウオール、イン
テリアあるいはイクステリアなどの建材、道路用資材、
航空機、車輛用ホイール。Aluminum materials to which the present invention can be applied are not limited in type, and include building materials such as sash, curtain walls, interior and exterior materials, road materials,
Wheels for aircraft and vehicles.
化粧品ケースや音響機器パネルなどの着色材の用途に応
じて各種の合金材が使用できるが、陽極酸化皮膜処理に
よって着色皮膜が生成するいわゆる自然発色材にも適用
し得るものであって、このような着色皮膜であっても本
発明処理によって白色味がかったパステル調色彩の皮膜
を得ることができるものである。Various alloy materials can be used depending on the purpose of coloring materials such as cosmetic cases and audio equipment panels, but they can also be applied to so-called natural coloring materials in which a colored film is formed by anodizing. Even if the film is a colored film, it is possible to obtain a film with a whitish pastel color by the treatment of the present invention.
しかして、このようなアルミニウム材にあらかじめ施行
される陽極酸化処理は、多孔性陽極酸化皮膜が形成され
る硫酸、りん酸、しゆう酸、クロ３０重量係、浴温２０
〜３０℃の浴を用いて、電流密度１〜３Ｖｄｍ＋電解電
圧１５〜１８Ｖの直流で１５〜６０分間陽極酸化処理を
行なうことによつてなされ、これによって通常材であれ
ば透明皮膜が、自然発色材であればその特性に応じた透
明着色皮膜が形成されるものであって、これを本発明処
理に使用する。Therefore, the anodizing treatment performed on such aluminum materials in advance requires sulfuric acid, phosphoric acid, oxalic acid, chlorine 30% by weight, and bath temperature 20% to form a porous anodic oxide film.
This is done by anodic oxidation treatment for 15 to 60 minutes with a DC current density of 1 to 3 Vdm + electrolytic voltage of 15 to 18 V using a bath at ~30°C. As a result, the transparent film on ordinary materials becomes naturally colored. If it is a material, a transparent colored film will be formed depending on its characteristics, and this will be used in the treatment of the present invention.
生するものであれば、フッ化物のいずれでもよく八
たとえば、フッ化アンモニウム、フッ化ナトリウム、フ
ッ化アルミニウムなどが好ましく、その他フッ化カリウ
ム、ケイフッ化ナトリウム、フッ化バリウム、フッ化カ
ルシウムのようなフッ化物があげられ、これらをそれぞ
れ単独に、あるいは。For example, ammonium fluoride, sodium fluoride, aluminum fluoride, etc. are preferable, and other fluorides such as potassium fluoride, sodium silicofluoride, barium fluoride, and calcium fluoride may be used. Fluoride is mentioned, each of these alone or.
適宜２種類以上を混合した水溶液として使用するもので
ある。It is used as an aqueous solution in which two or more types are appropriately mixed.
１゛金属塩添加フツ素イオン含有水溶液、及び金属塩水
溶液用として使用する金属塩は、同一種類の塩類であっ
て、金属塩添加フッ素イオン含有水溶液は、前記フッ化
水素酸及び／又はフッ化物と金属塩との混合水溶液であ
り、金属塩は、たとえば。1゛The metal salt-added fluorine ion-containing aqueous solution and the metal salt used for the metal salt aqueous solution are the same type of salts, and the metal salt-added fluorine ion-containing aqueous solution contains the hydrofluoric acid and/or fluoride. It is a mixed aqueous solution of and a metal salt, and the metal salt is, for example.
硫酸アルミニウム、硫酸ニッケル、硫酸第一スズ。Aluminum sulfate, nickel sulfate, stannous sulfate.
硫酸マグネシウム、硫酸亜鉛のような硫酸塩、硝酸カル
シウム、硝酸バリウムのような硝酸塩、しゆう酸バリウ
ムのようなしゆう酸塩、モリブデン酸アンモニウムのよ
うなアンモニウム塩などの可溶性金属塩が使用し得、こ
れらのそれぞれを単独にあるいは適宜の二種類以上を組
合せて使用し得るものである。ただし、これらの複合添
加においてフッ素イオン含有水溶液に金属塩を共存させ
る場合における金属塩としては、 ＣｃＬＦ２として沈
降してしまうカルシウム塩はフッ素イオンによる効果を
なくすので好ましくない。Soluble metal salts such as sulfates such as magnesium sulfate, zinc sulfate, nitrates such as calcium nitrate, barium nitrate, oxalates such as barium oxalate, ammonium salts such as ammonium molybdate may be used; Each of these can be used alone or in a suitable combination of two or more. However, in the case where a metal salt is allowed to coexist in a fluorine ion-containing aqueous solution in these combined additions, a calcium salt that precipitates as CcLF2 is not preferable because it eliminates the effect of fluoride ions.
本発明の一段処理は、フッ素イオン含有水溶液あるいは
金属塩添加フッ素イオン含有水溶液による処理であって
、フッ化水素酸の場合は、 蔗０．ｏ１に調製して使用
するものであり、添加する場合の金属塩は、５〜飽和溶
解度、好ましくは、５〜１００ｇ／ｌの範囲で添加する
ものである。ここでフッ素イオン濃度が高ければ浸漬時
間あるいは電解時間を短縮し得るが、浴が強酸性や強ア
ルカリ性であると陽極酸化皮膜の溶解が進行するので、
ＰＨ２〜９の浴となるようにすることが望ましい。又。The one-stage treatment of the present invention is treatment with a fluorine ion-containing aqueous solution or a metal salt-added fluorine ion-containing aqueous solution, and in the case of hydrofluoric acid, 0. The metal salt is added in a range of 5 to saturated solubility, preferably 5 to 100 g/l. If the fluorine ion concentration is high, the immersion time or electrolysis time can be shortened, but if the bath is strongly acidic or alkaline, the anodic oxide film will dissolve.
It is desirable that the bath has a pH of 2 to 9. or.
フッ化物は溶解度の大きいものほど浴の管理が容易であ
るが、たとえばフッ化カルシウムのように溶解度が好ま
しい濃度範囲の下限値（５ｇ／１３ ）以下であっても
、前記範囲値内にあり、かつ、ＰＨ値が前記範囲値内に
あれば使用可能であり、良好な結果が得られるものであ
る。The higher the solubility of fluoride, the easier it is to manage the bath; however, even if the solubility of calcium fluoride is below the lower limit of the preferred concentration range (5 g/13), it is still within the above range. Moreover, if the pH value is within the above range, it can be used and good results can be obtained.
しかして、これらの水溶液による処理方法としては、浸
漬法と電解法とがあり、いずれかの方法で処理するもの
であって、浸漬法では、水溶液温１０〜７０℃で、５〜
６０分間浸漬処理するものであって、高濃度・高浴温で
は浸漬時間を短かく〜３０°Ｃで、電圧３〜１０ｖで１
〜１０分間処理するものである。Treatment methods using these aqueous solutions include the immersion method and the electrolytic method.
The immersion treatment is for 60 minutes, and if the concentration is high and the bath temperature is high, the immersion time is shortened to 30°C and the voltage is 3 to 10V.
The treatment is for ~10 minutes.
又、二段処理は、金属塩水溶液での処理前あるいは処理
後にフッ素イオン含有水溶液による処理を行なうもので
ある。この処理に使用するフッ素イオン含有水溶液は、
前記一段処理で使用するフッ素イオン含有水溶液と同濃
度のものを使用して。Further, the two-stage treatment is one in which treatment with a fluorine ion-containing aqueous solution is performed before or after treatment with a metal salt aqueous solution. The fluorine ion-containing aqueous solution used for this treatment is
Use a fluorine ion-containing aqueous solution with the same concentration as that used in the one-stage treatment.
前記一段処理と同条件で処理するものである。金属塩水
溶液は、濃度５ ｇ／ｌ〜飽和濃度、好ましくは５〜１
ｏ ｏ ｇ７１の範囲で、ＰＨ値が２〜９の範囲にな
るように調製して使用する。この濃度が高濃度では硫酸
塩の場合に陽極酸化皮膜を溶解するおそれがある。This process is performed under the same conditions as the one-stage process. The metal salt aqueous solution has a concentration of 5 g/l to saturation concentration, preferably 5 to 1
o o g71, and the pH value is adjusted to be in the range of 2 to 9 before use. If this concentration is high, there is a risk that the anodic oxide film will be dissolved in the case of sulfate.
しかして、これらの水溶液による処理方法としては、前
記一段処理の場合と同様に浸漬法と電解法とがある。浸
漬法では、水溶液温度２０〜８０゛Ｃで、５〜６０分間
浸漬するものであって、液温か低いと処理時間が長くな
る一方、高温すぎると皮膜が溶解するおそれがあり、処
理時間が短かいと不透明度が弱く、長時間では皮膜が溶
解するおそれがあり前記範囲内で処理するものである。As the treatment methods using these aqueous solutions, there are the immersion method and the electrolytic method, as in the case of the one-stage treatment. In the immersion method, immersion is performed for 5 to 60 minutes at an aqueous solution temperature of 20 to 80°C. If the liquid temperature is low, the processing time will be longer, but if the temperature is too high, the film may dissolve, and the processing time may be shortened. The opacity of the coating is low, and the coating may dissolve over a long period of time, so treatment should be carried out within the above range.
又。or.
電解法は、設備費はかかるが技術的には皮膜孔中へのフ
ッ素イオンの拡散や皮膜孔中の水素イオンの除去もより
促進されるので好ましく、浴温度１０〜３０℃、カーボ
ン対極を使用し、電流は交流でも直流でもよく、電圧３
〜１０ｖで、５〜６０分間電解する。Although the electrolytic method requires equipment costs, it is technically preferable because it promotes the diffusion of fluorine ions into the pores of the film and the removal of hydrogen ions from the pores of the film, and uses a bath temperature of 10 to 30°C and a carbon counter electrode. However, the current may be alternating current or direct current, and the voltage may be 3
Electrolyze for 5-60 minutes at ~10v.
このように、一段処理であれ、二段処理であれフッ素イ
オン含有水溶液処理をすることによって。In this way, whether it is a one-stage treatment or a two-stage treatment, treatment is performed with an aqueous solution containing fluorine ions.
フッ素イオンが皮膜孔壁の内部へルムホルッ層に吸着し
、これによって、陽極酸化皮膜の孔中のプラス帯電を中
和することによって、孔中へ金属塩が拡散・侵入し易く
なり、金属イオンが陽極酸化皮膜孔中で水酸化物や不溶
性フッ化物や不溶性複塩になって不透明度と白色度とを
増加さすことになり、かつ、陽極酸化皮膜を丈夫にする
ことにもなるのである。Fluorine ions are adsorbed to the Helmholt layer inside the pore walls of the film, and this neutralizes the positive charge in the pores of the anodic oxide film, making it easier for metal salts to diffuse and enter into the pores, causing metal ions to In the pores of the anodic oxide film, hydroxides, insoluble fluorides, and insoluble double salts are formed, increasing the opacity and whiteness, and also making the anodic oxide film durable.
又、金属塩水溶液処理をすることによって、白色度の向
上又はパステル調色彩をより一層よく得ることができる
ものである。すなわち、金属塩を陽極酸化皮膜の孔中に
充填することによって、生成する皮膜の白色度を高める
ものであり、したがって、電解法による処理の場合でも
、孔中に金属が析出するような強い電解処理を行なう必
要はなく、軽度の電解によって孔中への金属塩の吸着・
充填を促進する程度に行なえばよい。しかしながら、あ
る程度の電解着色現象が発生した場合でも白色化は行な
われ、パステル調色彩の皮膜が得られるので、多少の電
解着色が発生する程度に電解が行なわれてもよく、パス
テル調を目的として処理することも可能である。Furthermore, by treatment with an aqueous metal salt solution, it is possible to improve the whiteness or obtain a pastel color. In other words, by filling the pores of the anodic oxide film with metal salts, the whiteness of the resulting film is increased. Therefore, even in the case of electrolytic treatment, strong electrolysis that causes metal to precipitate in the pores is not possible. There is no need to carry out any treatment, and the metal salts can be adsorbed into the pores by mild electrolysis.
This may be done to the extent that it promotes filling. However, even if a certain degree of electrolytic coloring occurs, whitening will still occur and a pastel-colored film will be obtained. It is also possible to process.
このようにして陽極酸化皮膜を不透明白色化して得た皮
膜は、瀬戸物のような滑らかな外観を有し、水に濡れて
も透明化せず、硬度や耐食性にすぐれたものである。The film obtained by making the anodic oxide film opaque and white has a smooth appearance similar to chinaware, does not become transparent even when wet with water, and has excellent hardness and corrosion resistance.
本発明方法による処理を行なった後は、常法に”゛よっ
て封孔処理、又は、透明樹脂たとえばアクリ°゛、’７
’ル樹脂の電着塗装のようなりリアー塗装仕上げ処理を
行なって製品とする。After the treatment according to the method of the present invention, sealing treatment is carried out by a conventional method or transparent resin such as acrylic resin, '7
The product is manufactured by applying a rear paint finish process similar to electro-deposition of resin.
本発明は１通常の陽極酸化処理をしたアルミニウム材を
、−膜処理又は二段処理によってフッ素イオン含有水溶
液で処理するものであるから、水で濡れた場合でも透明
化せず白色を維持できる従来にない不透明白色皮膜が得
られる不透明白色化をなし得、陽極酸化皮膜が着色した
ものであればパステル調とすることができ、これらが、
従来の表面処理ラインに、フッ素イオン含有水溶液槽を
増設するだけで既存の電解着色浴などをそのまま活用で
き、既存プロセスの改造を最小に押えながら目的を容易
に達成し得るなど優れた効果が認められる。The present invention is to treat an aluminum material that has been subjected to a normal anodizing treatment with an aqueous solution containing fluorine ions through a membrane treatment or a two-stage treatment, so that even when wet with water, it does not become transparent and maintains its white color. If the anodic oxide film is colored, it can be made into a pastel tone.
By simply adding a fluorine ion-containing aqueous solution tank to a conventional surface treatment line, existing electrolytic coloring baths can be used as is, and the system has been recognized for its excellent effects, such as being able to easily achieve the objective while minimizing modifications to the existing process. It will be done.
次に９本発明の実施例を述べる。 Next, nine embodiments of the present invention will be described.
実施例 １
純度９９．５ｑ６のアルミニウム材を１５重量％Ｈ２Ｓ
Ｏ４浴（２０℃）中で直流電圧１８Ｖで６０分間゛ト陽
極酸化処理を行な・て厚さ２０μ・の皮膜を形成ヅ
′させた後、それぞれ５ ｇ／１１のフッ化アンモニウ
ム。Example 1 Aluminum material with purity 99.5q6 was mixed with 15% by weight H2S
After anodizing for 60 minutes at a DC voltage of 18 V in an O4 bath (20°C) to form a film with a thickness of 20 μm, 5 g/11 ammonium fluoride was added.
フッ化ナトリウム、フッ化カリウムの水溶液を使用して
、２０℃で２０分間浸漬した。この結果。It was immersed for 20 minutes at 20°C using an aqueous solution of sodium fluoride and potassium fluoride. As a result.
いずれの水溶液を使用した場合でも陽極酸化皮膜は不透
明白色化され、耐食性も優れていた。No matter which aqueous solution was used, the anodic oxide film was opaque and white and had excellent corrosion resistance.
実施例 ２
純度９９．５％のアルミニウム材を実施例１と同様に６
０分間陽極酸化処理して厚さ２０μｍの皮膜を形成させ
た後、６０°Ｃの５０ ｇ／ｌフッ化アルアルミニウム
水溶液中０分間浸漬した。この結果。Example 2 An aluminum material with a purity of 99.5% was prepared in the same manner as in Example 1.
After anodic oxidation treatment for 0 minutes to form a film with a thickness of 20 μm, it was immersed in a 50 g/l aluminum fluoride aqueous solution at 60°C for 0 minutes. As a result.
実施例１と同様に耐食性不透明白化皮膜が得られたＯ
実施例 ３
アルミニウム材として６０６３合金を使用して実施例１
と同様に陽極酸化処理を行なった後、実施例１と同様に
フッ素イオン含有水溶液に浸漬処理を行なった。この結
果、実施例１と同様に耐食性不透明白色化皮膜が得られ
た。A corrosion-resistant opaque whitening film was obtained in the same manner as in Example 1. Example 3 Example 1 using 6063 alloy as the aluminum material
After performing anodization treatment in the same manner as in Example 1, immersion treatment in a fluorine ion-containing aqueous solution was performed in the same manner as in Example 1. As a result, as in Example 1, a corrosion-resistant, opaque, whitened film was obtained.
実施例 ４
６０６３合金材に実施例１と同様にして３０分間陽極酸
化処理して厚さ１０μｍの陽極酸化皮膜を形成させた後
、５ｇ／ｌフッ化アル化工ルミニウム水溶液れぞれ５０
９／ｌの硫酸アルミニウム、硫酸亜鉛、硫酸ニッケル、
硫酸コバルト、硫酸マグネシウム、硫酸第１スズ、硝酸
アルミニウム、硝酸バリウム、しゆう酸バリウム、スズ
酸ナトリウム。Example 4 A 6063 alloy material was anodized for 30 minutes in the same manner as in Example 1 to form an anodic oxide film with a thickness of 10 μm, and then treated with 5 g/l aqueous aluminum fluoride solution at 50% each.
9/l aluminum sulfate, zinc sulfate, nickel sulfate,
Cobalt sulfate, magnesium sulfate, stannous sulfate, aluminum nitrate, barium nitrate, barium oxalate, sodium stannate.
モリブデン酸アンモニウムなどの水溶液を添加したそれ
ぞれ別個の水溶液を使用して、６０℃で２０分間浸漬処
理した。この結果、実施例１と同様に耐食性不透明白色
化皮膜が得られた。A 20 minute immersion treatment was carried out at 60° C. using separate aqueous solutions to which ammonium molybdate and other aqueous solutions were added. As a result, as in Example 1, a corrosion-resistant, opaque, whitened film was obtained.
実施例 ５
実施例４における金属塩添加フッ素イオン水溶液による
浸漬処理の代りに、浴温４０°Ｃの実施例４記載の各水
溶液を使用して、交流電圧１０ｖ。Example 5 Instead of the immersion treatment with the metal salt-added fluorine ion aqueous solution in Example 4, each aqueous solution described in Example 4 with a bath temperature of 40°C was used, and an AC voltage of 10 V was used.
あるいは、直流電圧−５Ｖで電解処理した。この結果は
いずれも実施例１と同様に耐食性不透明白色化皮膜が得
られた。Alternatively, electrolytic treatment was performed at a DC voltage of -5V. In all of these results, similar to Example 1, a corrosion-resistant, opaque, whitened film was obtained.
実施例 ６
純度９９．５％のアルミニウム材を、実施例２と同様に
して厚さ２０μｍの陽極酸化皮膜を形成させた後、５０
ｇ／ｌフッ化アルミニウム、！＝ ５０９／ｌａ酸アル
ミニウムとの混合溶液を使用して、６０’Ｃで２０分間
浸漬処理した。この結果、実施例１と同様に耐食性不透
明白色化皮膜が得られた。Example 6 After forming an anodic oxide film with a thickness of 20 μm on an aluminum material with a purity of 99.5% in the same manner as in Example 2,
g/l aluminum fluoride,! = 509/la A mixed solution with aluminum acid was used for immersion treatment at 60'C for 20 minutes. As a result, as in Example 1, a corrosion-resistant, opaque, whitened film was obtained.
実施例 ７
純度９９．５ ％のアルミニウム材を実施例４と同様に
陽極酸化処理して厚さ１０μｍの陽極酸化皮膜を形成さ
せた後、 ５０９／ｌの硫酸アルミニウム水溶液に、そ
れぞれ１０ ｇ／ｌのフッ化バリウム、フッ化ナトリウ
ム、ケイフッ化ナトリウムの水溶液を添加したそれぞれ
別個の水溶液を調製し、液温５０℃で２０分間浸漬処理
した。この結果は、実施例１と同様に耐食性不透明白色
化皮膜が得られた０
実施例 ８
６０６３合金材を実施例２と同様に陽極酸化処５′−４
理して厚さ２０μｍの陽極酸化皮膜を形成させた後。Example 7 An aluminum material with a purity of 99.5% was anodized in the same manner as in Example 4 to form an anodic oxide film with a thickness of 10 μm, and then 10 g/l of each was added to a 509/l aluminum sulfate aqueous solution. Separate aqueous solutions were prepared by adding barium fluoride, sodium fluoride, and sodium fluorosilicate aqueous solutions, respectively, and immersion treatment was performed at a liquid temperature of 50° C. for 20 minutes. This result shows that a corrosion-resistant opaque whitening film was obtained in the same manner as in Example 1.
After processing to form a 20 μm thick anodic oxide film.
２．−・ダ
ニゾニ段処理の第１次処理として、それぞれ５ ｇ／ｌ
のフッ化ナトリウム、フッ化アンモニウム、フッ化カリ
ウム、ケイフッ化ナトリウムの水溶液をそれぞれ別個に
使用して、２０℃で１０分間浸漬処理し、ついで、第２
次処理として、それぞれ５０ ｇ／ｌの硫酸アルミニウ
ム、硫酸亜鉛、硫酸ニッケル。2. - 5 g/l each as the first treatment of the Danizoni stage treatment.
Aqueous solutions of sodium fluoride, ammonium fluoride, potassium fluoride, and sodium silicofluoride were used separately and immersed at 20°C for 10 minutes.
As a subsequent treatment, 50 g/l each of aluminum sulfate, zinc sulfate and nickel sulfate.
硫酸マグネ７ウム、硫酸コバルト、硫酸第１スズ。Magnesium sulfate, cobalt sulfate, stannous sulfate.
硝酸アルミニウム、硝酸バリウム、しゆう酸バリウム、
スズ酸ナトリウム、モリブデン酸ナトリウムの水溶液の
いずれかを使用して、第１次処理をした陽極酸化皮膜を
、液温６０℃で１０分間第２次浸漬処理を行なった。第
１次処理の使用水溶液と第２次処理の使用水溶液とを任
意に選択して組合せて試験した結果、いずれも実施例１
と同様に耐食性不透明白色化皮膜が得られた。Aluminum nitrate, barium nitrate, barium oxalate,
The anodized film that had been subjected to the first treatment using either an aqueous solution of sodium stannate or sodium molybdate was subjected to a second immersion treatment at a solution temperature of 60° C. for 10 minutes. As a result of testing by arbitrarily selecting and combining the aqueous solution used in the primary treatment and the aqueous solution used in the secondary treatment, both were tested in Example 1.
A corrosion-resistant, opaque, whitened film was obtained in the same manner.
実施例 ９
実施例８における使用水溶液の使用順序を逆にして、実
施例８において第２次処理に使用した金属塩水溶液を第
１次処理用水溶液として６０°Ｃ９１０分間の第１次処
理を行ない、ついで、実施例）８において第１次処理に
使用したフッ素イオン含有水溶液を第２次用水溶液とし
て６０°Ｃ９１０分間の第２次処理を行なう試験を、実
施例８と同様に任意の組合せで行なった。これらの結果
は、いずれも実施例１と同様に耐食性不透明白色化皮膜
が得られた。Example 9 The order of use of the aqueous solutions used in Example 8 was reversed, and the metal salt aqueous solution used for the secondary treatment in Example 8 was used as the aqueous solution for the first treatment, and the first treatment was carried out at 60°C for 10 minutes. Then, as in Example 8, a test was carried out in which the fluorine ion-containing aqueous solution used for the first treatment in Example 8 was used as a second aqueous solution and a second treatment was performed at 60°C for 910 minutes using any combination as in Example 8. I did it. In all of these results, similar to Example 1, a corrosion-resistant, opaque, whitened film was obtained.
実施例 １０
しゆう酸浴を使用して形成した陽極酸化皮膜について、
実施例１乃至実施例９と同様な処理を行なったが、いず
れも黄色味のある不透明白色化皮膜（パステル調皮膜）
が形成されていることが認められた。Example 10 Regarding the anodic oxide film formed using an oxalic acid bath,
The same treatments as in Examples 1 to 9 were performed, but in all cases, a yellowish opaque white coating (pastel-like coating) was obtained.
was observed to be formed.
Claims (1)
ッ素イオン含有水溶液あるいは金属塩添加フッ素イオン
含有水溶液で処理する一段処理、又は、金属塩水溶液で
処理する前あるいは処理後にフッ素イオン含有水溶液で
処理する二段処理によって不透明白色化することを特徴
とするアルミニウム陽極酸化皮膜の不透明白色化方法。1) One-stage treatment in which pre-anodized aluminum material is treated with a fluorine ion-containing aqueous solution or a metal salt-added fluorine ion-containing aqueous solution, or a two-stage treatment in which an anodic oxidized aluminum material is treated with a fluorine ion-containing aqueous solution before or after treatment with a metal salt aqueous solution. A method for making an aluminum anodic oxide film opaque and white, characterized by making it opaque and white through treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7753587A JPS63247396A (en) | 1987-04-01 | 1987-04-01 | Method for making anodic oxide film or aluminum opaque and white |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7753587A JPS63247396A (en) | 1987-04-01 | 1987-04-01 | Method for making anodic oxide film or aluminum opaque and white |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63247396A true JPS63247396A (en) | 1988-10-14 |
Family
ID=13636679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7753587A Pending JPS63247396A (en) | 1987-04-01 | 1987-04-01 | Method for making anodic oxide film or aluminum opaque and white |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63247396A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102834551A (en) * | 2011-03-08 | 2012-12-19 | 纳米及先进材料研发院有限公司 | Method for producing white anodized aluminum oxide |
| CN109112595A (en) * | 2018-10-15 | 2019-01-01 | 南京工程学院 | A kind of magnesium alloy surface composite film differential of the arc fluorination preparation method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51137633A (en) * | 1975-05-24 | 1976-11-27 | Hokusei Aluminium Co Ltd | Coloring process for aluminum or aluminum alloy |
| JPS5253740A (en) * | 1975-10-30 | 1977-04-30 | Hokusei Aluminium Co Ltd | Process for coloring aluminum or its alloy |
| JPS56152994A (en) * | 1980-04-25 | 1981-11-26 | Yoshida Kogyo Kk <Ykk> | Method for forming opaque white film on aluminum surface |
| JPS5732396A (en) * | 1980-07-31 | 1982-02-22 | Yoshida Kogyo Kk <Ykk> | Method for forming opaque colored film on aluminum surface |
| JPS5956597A (en) * | 1982-09-24 | 1984-04-02 | Pilot Pen Co Ltd:The | Surface treatment of aluminum or aluminum alloy |
| JPS6021397A (en) * | 1983-07-15 | 1985-02-02 | Pilot Pen Co Ltd:The | Surface treatment of aluminum or aluminum alloy |
| JPS60197897A (en) * | 1984-03-22 | 1985-10-07 | Pilot Pen Co Ltd:The | Formation of opaque white anodized film of aluminum or aluminum alloy |
-
1987
- 1987-04-01 JP JP7753587A patent/JPS63247396A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51137633A (en) * | 1975-05-24 | 1976-11-27 | Hokusei Aluminium Co Ltd | Coloring process for aluminum or aluminum alloy |
| JPS5253740A (en) * | 1975-10-30 | 1977-04-30 | Hokusei Aluminium Co Ltd | Process for coloring aluminum or its alloy |
| JPS56152994A (en) * | 1980-04-25 | 1981-11-26 | Yoshida Kogyo Kk <Ykk> | Method for forming opaque white film on aluminum surface |
| JPS5732396A (en) * | 1980-07-31 | 1982-02-22 | Yoshida Kogyo Kk <Ykk> | Method for forming opaque colored film on aluminum surface |
| JPS5956597A (en) * | 1982-09-24 | 1984-04-02 | Pilot Pen Co Ltd:The | Surface treatment of aluminum or aluminum alloy |
| JPS6021397A (en) * | 1983-07-15 | 1985-02-02 | Pilot Pen Co Ltd:The | Surface treatment of aluminum or aluminum alloy |
| JPS60197897A (en) * | 1984-03-22 | 1985-10-07 | Pilot Pen Co Ltd:The | Formation of opaque white anodized film of aluminum or aluminum alloy |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102834551A (en) * | 2011-03-08 | 2012-12-19 | 纳米及先进材料研发院有限公司 | Method for producing white anodized aluminum oxide |
| CN102834551B (en) * | 2011-03-08 | 2015-07-01 | 纳米及先进材料研发院有限公司 | Method for producing white anodized aluminum oxide |
| CN109112595A (en) * | 2018-10-15 | 2019-01-01 | 南京工程学院 | A kind of magnesium alloy surface composite film differential of the arc fluorination preparation method |
| CN109112595B (en) * | 2018-10-15 | 2020-06-05 | 南京工程学院 | Micro-arc fluorination preparation method of magnesium alloy surface composite film |
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