EP1464733A1 - Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium - Google Patents

Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium Download PDF

Info

Publication number: EP1464733A1
Authority: EP; European Patent Office
Prior art keywords: bath; clogging; molybdenum oxide; hydration; carried out
Prior art date: 2002-02-15
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Granted

Application number

EP02290376A

Other languages

English (en)

French (fr)

Other versions

EP1464733B1 (de

Inventor

désignation de l'inventeur n'a pas encore été déposée La

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.)

Aalberts Surface Technologies SAS

Original Assignee

Societe de Galvanoplastie Industrielle SAS

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.)

2002-02-15

Filing date

2002-02-15

Publication date

2004-10-06

2002-02-15 Application filed by Societe de Galvanoplastie Industrielle SAS filed Critical Societe de Galvanoplastie Industrielle SAS

2002-02-15 Priority to AT02290376T priority Critical patent/ATE294265T1/de

2002-02-15 Priority to EP02290376A priority patent/EP1464733B1/de

2002-02-15 Priority to ES02290376T priority patent/ES2238058T3/es

2002-02-15 Priority to DE60203945T priority patent/DE60203945T8/de

2004-10-06 Publication of EP1464733A1 publication Critical patent/EP1464733A1/de

2005-04-27 Application granted granted Critical

2005-04-27 Publication of EP1464733B1 publication Critical patent/EP1464733B1/de

2022-02-15 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

238000000034 method Methods 0.000 title claims abstract description 23
229910052782 aluminium Inorganic materials 0.000 title claims abstract description 11
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 11
239000004411 aluminium Substances 0.000 title abstract 3
238000007789 sealing Methods 0.000 title description 10
239000010407 anodic oxide Substances 0.000 title 1
MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title 1
230000036571 hydration Effects 0.000 claims abstract description 19
238000006703 hydration reaction Methods 0.000 claims abstract description 19
238000005260 corrosion Methods 0.000 claims abstract description 18
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
238000007654 immersion Methods 0.000 claims abstract description 14
JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 11
229910000838 Al alloy Inorganic materials 0.000 claims abstract description 9
239000003795 chemical substances by application Substances 0.000 claims abstract description 9
238000002360 preparation method Methods 0.000 claims abstract 2
QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
229910000476 molybdenum oxide Inorganic materials 0.000 claims description 14
PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 14
150000003839 salts Chemical class 0.000 claims description 13
APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 8
235000018660 ammonium molybdate Nutrition 0.000 claims description 8
239000011609 ammonium molybdate Substances 0.000 claims description 8
229940010552 ammonium molybdate Drugs 0.000 claims description 8
229910021529 ammonia Inorganic materials 0.000 claims description 7
238000007743 anodising Methods 0.000 claims description 7
USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
239000005695 Ammonium acetate Substances 0.000 claims description 4
229940043376 ammonium acetate Drugs 0.000 claims description 4
235000019257 ammonium acetate Nutrition 0.000 claims description 4
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
150000001412 amines Chemical class 0.000 claims description 2
229910052700 potassium Inorganic materials 0.000 claims description 2
239000011591 potassium Substances 0.000 claims description 2
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 claims 1
VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims 1
229910052708 sodium Inorganic materials 0.000 claims 1
239000011734 sodium Substances 0.000 claims 1
238000002048 anodisation reaction Methods 0.000 abstract description 2
238000007596 consolidation process Methods 0.000 abstract 2
238000012360 testing method Methods 0.000 description 19
230000007797 corrosion Effects 0.000 description 12
239000007921 spray Substances 0.000 description 11
239000003973 paint Substances 0.000 description 9
ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
238000010521 absorption reaction Methods 0.000 description 7
229910045601 alloy Inorganic materials 0.000 description 7
239000000956 alloy Substances 0.000 description 7
239000000975 dye Substances 0.000 description 7
JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
229910052804 chromium Inorganic materials 0.000 description 3
239000011651 chromium Substances 0.000 description 3
239000000463 material Substances 0.000 description 3
229910052751 metal Inorganic materials 0.000 description 3
239000002184 metal Substances 0.000 description 3
239000004814 polyurethane Substances 0.000 description 3
230000015572 biosynthetic process Effects 0.000 description 2
239000011248 coating agent Substances 0.000 description 2
238000000576 coating method Methods 0.000 description 2
150000001875 compounds Chemical class 0.000 description 2
229910052750 molybdenum Inorganic materials 0.000 description 2
239000011733 molybdenum Substances 0.000 description 2
230000003647 oxidation Effects 0.000 description 2
238000007254 oxidation reaction Methods 0.000 description 2
229920002635 polyurethane Polymers 0.000 description 2
230000001681 protective effect Effects 0.000 description 2
229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
239000002253 acid Chemical class 0.000 description 1
239000000337 buffer salt Substances 0.000 description 1
230000000711 cancerogenic effect Effects 0.000 description 1
231100000315 carcinogenic Toxicity 0.000 description 1
KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
239000002131 composite material Substances 0.000 description 1
230000008021 deposition Effects 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
239000003112 inhibitor Substances 0.000 description 1
230000005764 inhibitory process Effects 0.000 description 1
238000004519 manufacturing process Methods 0.000 description 1
238000005259 measurement Methods 0.000 description 1
150000004682 monohydrates Chemical class 0.000 description 1
238000009659 non-destructive testing Methods 0.000 description 1
RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
229920000642 polymer Polymers 0.000 description 1
239000011148 porous material Substances 0.000 description 1
229910052761 rare earth metal Inorganic materials 0.000 description 1
-1 rare earth salts Chemical class 0.000 description 1
239000011347 resin Substances 0.000 description 1
229920005989 resin Polymers 0.000 description 1
238000005096 rolling process 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
238000004381 surface treatment Methods 0.000 description 1
231100000331 toxic Toxicity 0.000 description 1
230000002588 toxic effect Effects 0.000 description 1
230000001131 transforming effect Effects 0.000 description 1
LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
229910001928 zirconium oxide Inorganic materials 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers

Definitions

the present invention relates to a method of clogging by hydration of the oxide layer obtained by anodizing aluminum or an aluminum alloy, free of hexavalent chromium.
Aluminum alloys are, despite the development of composites, the most used on airframe and helicopter cells. Corrosion protection and assembly by bonding of these materials therefore remain the concerns main.
chromate ion is one of the most corrosion inhibitors more effective for aluminum.
the inhibition is due to the formation on the surface of the metal of a protective film formed by the reduction of the chromate ion.
the inventors have set themselves the goal find a non-harmful substitute for hexavalent chromium, while maintaining the resistance properties in corrosion of the material and its ability to adhere to paint systems.
molybdenum oxide could be used as a substitute for chromium hexavalent in the sealing process.
the rate of hydration represents by mass the quantity of water fixed during clogging with respect to the total mass of the coating (alumina + water).
molybdenum oxide is present in the form of salt, preferably in the form of sodium molybdate, potassium or ammonium, or as a complex, preferably in the form of an amine and acid complex molybdic.
the molybdenum oxide is present in the form of ammonium molybdate.
the ammonium molybdate can be used directly in the form of a salt containing 85% of MoO 3 or can be used in the form of pure molybdenum oxide supplemented with ammonia according to the following equation: 7 MoO 3 + 6 NH 4 OH ⁇ (NH 4 ) 6 Mo 7 O 24 + 3 H 2 O
the pH of the sealing baths used in the process according to the invention is stabilized at 6 +/- 1 by addition of a buffer salt such as for example acetate ammonium.
the sealing process according to the invention can be used on pure aluminum or alloys aluminum type 2024 T3, 5086 or 7075 T73 previously anodized using an anodizing method conventional, such as methods sulfuric, chromic, alkaline or anodizing sulfoborique.
the parts obtained after clogging according to the present invention have very good resistance to corrosion, between 500 and 750 hours and the hydration levels correspond to those observed with classic clogging in the presence of chromium Hexavalent.
the paint system offers perfect adhesion, as well as excellent resistance to salt spray corresponding to that obtained with chromic oxidation followed by clogging with hexavalent chromium.
the hydration rate is measured by a gravimetric measurement of the hydration of the coating.
the thickness of the layer is measured by a test according to ISO 2360 standard; clogging is measured by the method dye absorption referenced NF A 91408, and the layer continuity is measured by the test ISO 2085 standard.
the adhesion of the paint was measured according to the technique described by the company PRC-De Soto which includes successive application of a primer coat P99, based on phenolic butyral, then the deposition of a PAC 33 anticorrosion primer, then a layer PU 66 finishing coat based on polyurethane, above designations being registered trademarks of the PRC-De Soto company.
the first layer has a thickness of 4 to 11 ⁇ m, the total of the first two layers a thickness of 14 to 29 ⁇ m, and the total of the three layers a thickness of 39 to 64 ⁇ m.
a "Q + S" adhesion test according to the ISO standard 2409-1976 is measured after 14 days of immersion in the water.
a pilot line is used with tanks of 250 l volume; the alloy used is 2024 T3 alloy in the form of a test piece of dimension 120 x 60 x 08 mm, rough rolling.
the test specimens are anodized for approximately 40 minutes to one hour in a bath containing 35 to 60 g / l of chromic acid at a voltage between 5 and 90 volts and an electric current density of 0.5 to 50 amps / cm 2 .
the anodized part is rinsed for approximately 2 minutes and immersed in a sealing bath containing either ammonium molybdate at 85% in MoO 3 added directly in the bath, or ammonium molybdate prepared by adding ammonia to MoO 3 according to the equation 7 MoO 3 + 6 NH 4 OH ⁇ (NH 4 ) 6 Mo 7 O 24 + 3 H 2 O
the duration of immersion in the sealing bath is 20 minutes and the bath temperature is 97 ° C.
the sealing bath comprises 3.6 g / l of MoO 3 to which NH 4 OH ammonia and ammonium acetate have been added.
the bath temperature is 97 ° C and the immersion time is 40 minutes.
the test pieces used are 2024 T3 and 7075 T7 test pieces.
a series of test pieces is used to measure the adhesion of the paint, the other series is used to assess the resistance corrosion.
the paint system provides perfect adhesion before and after immersion in water, as well as excellent resistance to salt spray.
the parts treated by the process of the invention have a thickness, a layer continuity, a absorption of dyes identical to those used obtained after chromic anodization and clogging with hexavalent chromium.
the corrosion resistance measured by the behavior of the salt spray is quite satisfactory and well over 500 hours of exposure.
the paint system offers a perfect adhesion and excellent resistance to salt spray also corresponding to that which one obtained after chromic oxyanodization and clogging with hexavalent chromium.

Landscapes

Chemical & Material Sciences (AREA)
General Chemical & Material Sciences (AREA)
Engineering & Computer Science (AREA)
Chemical Kinetics & Catalysis (AREA)
Electrochemistry (AREA)
Materials Engineering (AREA)
Metallurgy (AREA)
Organic Chemistry (AREA)
Chemical Treatment Of Metals (AREA)
Preventing Corrosion Or Incrustation Of Metals (AREA)
Paints Or Removers (AREA)
Sealing Material Composition (AREA)
Other Surface Treatments For Metallic Materials (AREA)

EP02290376A 2002-02-15 2002-02-15 Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium Expired - Lifetime EP1464733B1 (de)

Priority Applications (4)

Application Number	Priority Date	Filing Date	Title
AT02290376T ATE294265T1 (de)	2002-02-15	2002-02-15	Verwendung eines molybdats in einem verfahren zur versieglung von anodischen oxidschichten auf aluminium
EP02290376A EP1464733B1 (de)	2002-02-15	2002-02-15	Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium
ES02290376T ES2238058T3 (es)	2002-02-15	2002-02-15	Utilizacion de molibdato en un procedimiento de colmatado de una capa de oxido obtenida por anodizacion de aluminio.
DE60203945T DE60203945T8 (de)	2002-02-15	2002-02-15	Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
EP02290376A EP1464733B1 (de)	2002-02-15	2002-02-15	Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium

Publications (2)

Publication Number	Publication Date
EP1464733A1 true EP1464733A1 (de)	2004-10-06
EP1464733B1 EP1464733B1 (de)	2005-04-27

Family

ID=32842681

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP02290376A Expired - Lifetime EP1464733B1 (de)	2002-02-15	2002-02-15	Verwendung eines Molybdats in einem Verfahren zur Versieglung von anodischen Oxidschichten auf Aluminium

Country Status (4)

Country	Link
EP (1)	EP1464733B1 (de)
AT (1)	ATE294265T1 (de)
DE (1)	DE60203945T8 (de)
ES (1)	ES2238058T3 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
WO2023076564A1 (en)	2021-10-29	2023-05-04	Raytheon Technologies Corporation	Coating for aluminum alloy aerostructures

Citations (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4225398A (en) *	1977-03-30	1980-09-30	Yoshida Kogyo K.K.	Method of improving the corrosion resistance of an anodically oxidized surface film on aluminum articles
US4515919A (en) *	1983-05-09	1985-05-07	Lockheed Corporation	Protective coating composition and process for aluminum and aluminum alloys
JPH0225592A (ja) *	1988-07-14	1990-01-29	Fujitsu Ltd	陽極酸化皮膜の封孔処理方法
US5205922A (en) *	1990-11-20	1993-04-27	The United States Of America As Represented By The Secretary Of The Navy	Formation of pitting resistant anodized films on aluminum

2002
- 2002-02-15 AT AT02290376T patent/ATE294265T1/de not_active IP Right Cessation
- 2002-02-15 DE DE60203945T patent/DE60203945T8/de active Active
- 2002-02-15 ES ES02290376T patent/ES2238058T3/es not_active Expired - Lifetime
- 2002-02-15 EP EP02290376A patent/EP1464733B1/de not_active Expired - Lifetime

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4225398A (en) *	1977-03-30	1980-09-30	Yoshida Kogyo K.K.	Method of improving the corrosion resistance of an anodically oxidized surface film on aluminum articles
US4515919A (en) *	1983-05-09	1985-05-07	Lockheed Corporation	Protective coating composition and process for aluminum and aluminum alloys
JPH0225592A (ja) *	1988-07-14	1990-01-29	Fujitsu Ltd	陽極酸化皮膜の封孔処理方法
US5205922A (en) *	1990-11-20	1993-04-27	The United States Of America As Represented By The Secretary Of The Navy	Formation of pitting resistant anodized films on aluminum

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 014, no. 176 (C - 0707) 9 April 1990 (1990-04-09) *

Also Published As

Publication number	Publication date
ATE294265T1 (de)	2005-05-15
ES2238058T3 (es)	2005-08-16
DE60203945D1 (de)	2005-06-02
DE60203945T8 (de)	2006-07-27
DE60203945T2 (de)	2006-02-23
EP1464733B1 (de)	2005-04-27

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