EP3245317B2 - Behandlung von anodisierten aluminium und legierungen - Google Patents

Behandlung von anodisierten aluminium und legierungen Download PDF

Info

Publication number
EP3245317B2
EP3245317B2 EP15778287.1A EP15778287A EP3245317B2 EP 3245317 B2 EP3245317 B2 EP 3245317B2 EP 15778287 A EP15778287 A EP 15778287A EP 3245317 B2 EP3245317 B2 EP 3245317B2
Authority
EP
European Patent Office
Prior art keywords
treatment according
silanes
treatment
solution
och
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.)
Active
Application number
EP15778287.1A
Other languages
English (en)
French (fr)
Other versions
EP3245317A1 (de
EP3245317B1 (de
Inventor
Antonio Mangano
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.)
Asit Automotive Srl
Original Assignee
Asit Automotive Srl
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=51932269&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3245317(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Asit Automotive Srl filed Critical Asit Automotive Srl
Priority to RS20190991A priority Critical patent/RS59341B2/sr
Priority to PL15778287.1T priority patent/PL3245317T5/pl
Publication of EP3245317A1 publication Critical patent/EP3245317A1/de
Publication of EP3245317B1 publication Critical patent/EP3245317B1/de
Application granted granted Critical
Publication of EP3245317B2 publication Critical patent/EP3245317B2/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C25D11/16—Pretreatment, e.g. desmutting
    • 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
    • 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
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • 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
    • C25D11/243—Chemical after-treatment using organic dyestuffs

Definitions

  • Anodized aluminum has low resistance to alkalis and to acids.
  • domains such as automotive and building there is a pressing need for anodized articles the surface of which, while preserving their characteristic appearance, can withstand contact with strong alkaline solutions, and possibly also with strong acid solutions.
  • Treatments to improve this resistance are notably the subject of standards, such as those of the European Aluminum Anodisers Association, these are referred as "Qualanod" standards.
  • standards such as those of the European Aluminum Anodisers Association
  • products treated in accordance to these standards mainly directed to buildings material, prove not to pass the tests of the automotive industry.
  • the present invention aims at solving this problem. If in the first place the products for automotive industry are concerned, the invention also applies to any type of anodized product including those intended for building or domestic appliances.
  • the anodized aluminum product treated first is one obtained that presents no prior defects, to that effect the anodization must follow the best known practices.
  • usage anodization is carried out in electrolytic solution that includes an inorganic acid.
  • acids most common is sulfuric acid.
  • Other acids are also of interest notably those that are less susceptible to dissolve the anodic oxide film created.
  • the anodization conditions such as voltage, temperature are well known from prior art that gives products free of any defects but need a precise control especially when using sulfuric acid solution. For example to low temperature corresponds a slow rate forming of the oxide layer, but if the temperature is too high the dissolution rate is increased. The temperature is usually not above 24°C.
  • the anodic solution is immediately removed and the product washed to prevent further dissolution of the oxide film.
  • the usual thickness selected must be sufficient to allow for the necessary resistance, chemical and mechanical. This is normally above 5 ⁇ m, and preferably above 10 ⁇ m. The thickness is preferably not above 50 ⁇ m to prevent possible defect formation such as cracks.
  • Anodization leads to an oxide layer the structure resulting in a porous system that has poor resistance notably to acids or alkaline solutions. It is common to prevent these corrosive chemicals to penetrate the porous structure by sealing the pores.
  • the usual sealing is made by hydration of the aluminum oxide that swells and obstructs the pores. Hydration may be made by way of hot water or steam. ("hot sealing"). This is done at temperature above 95°C.
  • hot sealing Another possibility called “cold sealing” is starting with an impregnation step that includes contact with a first solution e.g. of nickel fluoride used for its properties to form insoluble complexes with aluminium and plug the pores, producing a good sealing.
  • Other metallic salts notably of chromium may substitute to those of nickel. In this cold impregnation the temperature is not above 30°C. The impregnation is followed by ageing in a hot water treatment. Impregnation needs also careful control notably of nickel and fluoride respective concentrations.
  • a first post treatment is using a solution of silicates in which the products are immersed under conditions that result in a further sealing or coating with "silicates polymers".
  • a second treatment is following that includes using specific silanes solutions that adds another coating.
  • this type of treatment using silicate is still to be improved.
  • the invention provides for conditions to carry out this step, that makes both more efficient control and prevent possible defects.
  • the treated products must be free of any powder deposit at the surface of the material that could alter the final aesthetic appearance.
  • the products are thus immersed in the silicates solution.
  • the silicate solution used is preferably one of alkaline metal, sodium, potassium or lithium or mixture thereof. These, notably sodium and potassium, are readily available in commerce and extensively used in many industrial sectors, notably as thickening agents.
  • the solutions are containing an amount of silicate that depends on the stability. When increasing the concentration there is a limit above which the solution turns a gel. The concentration that allows remaining stable for long period of time are also depending on the nature of the silicate including the molar ratio SiO 2 /M 2 O (M standing for Na, K or Li). The higher this ratio, the lower the possible amount of silicate when trying to prevent the gel formation.
  • the ratio is at least of 2.5, and preferably at least of 3.
  • the silicate solution is preferably at pH above 5 and preferably above 6.
  • This concentration for sodium silicate is preferably higher than 1g/l and preferably from 10 to 30g/l.
  • the coating also depends on temperature of the solution. Faster deposition of silicates is obtained with the highest temperature. For easiness of control over the process, the temperature is preferably higher than 40°C and does not exceed 95°C. The best temperature range according to the invention is from 60 to 80°C.
  • the processing time depends on the previous parameters and is most usually between 5 and 50 minutes.
  • the next step according to the invention is a treatment with a solution of one or more silanes or silanols that result from hydrolysis of these silanes.
  • silanes used according to the invention are alkoxysilanes that may be hydrolyzed to give in silanols that may react with hydroxyl groups leading to covalent bonds according to the known general mechanism: Al-OH+R-SiOH ⁇ Al-O-Si-R +H 2 O
  • silanols are seldom available as such for reason that, to be stable, they need to be in greatly diluted solutions. For this reason it is most often necessary to have the silanols prepared when needed.
  • the silanes used according to the invention are preferably of the general formula: R'(CH 2 )nSi(OR) 3 with n at most equal to 4 where -OR is one of: -OCH 3 , -OC 2 H 5 , -OCOCH 3 and R' is a radical from: vinyl, epoxy, methacrylate, primary amine, diamine, mercapto.
  • CH 2 CHSi(OCH 3 ) 3
  • CH 2 CHSi(OC 2 H5) 3 CH 2 CH-CH 2 O-(CH 2 ) 3 Si(OCH 3 ) 3
  • CH 2 C(CH 3 )-COO-(CH 2 ) 3 Si(OCH 3 ) 3 H 2 N(CH 2 ) 2 Si(OCH 3 ) 3 H 2 N(CH 2 ) 2 NH(CH 2 ) 3 Si(OCH 3 ) 3 N 2 HCN(O)H(CH2) 3 Si HS(CH 2 ) 3 Si(OCH 3 ) 3 .
  • the silanes that are used may also be bis-silanes of the general formula: (RO) 3 -Si(CH 2 )nR'(CH 2 )n-Si(OR) 3 with R, R' and n , having the same significance as indicated above.
  • the bis-silanes preferred ones are: (C 2 H 5 O) 3 Si(CH 2 )Si(OC 2 H 5 ) 3 (C 2 H 5 O) 3 Si(CH 2 ) 3 -S 4 -(CH 2 ) 3 Si(OC 2 H 5 ) 3 (C 2 H 5 O) 3 Si(CH 2 ) 3 -NH-(CH 2 ) 3 Si(OC 2 H 5 ) 3 .
  • the concentration in silanes is less than 8% by weight of the solution, and most preferably less than 5% by weight. At these concentrations the hydrolysis tends to get to completion. To limit the processing time the concentration is preferably no less than 0.1% by weight.
  • organo-silanes that are useful have a limited solubility as such in water.
  • Using a water alcohol mixture enhance the solubility to the necessary concentration.
  • the presence of alcohol may also regulate the hydrolysis of the silanes, and possibly makes the final drying easier.
  • the content of alcohol may be up to 15% by weight of the mixture.
  • hydrolysis of silanes needs time and depends on various factors notably the type of organo-silanes, the medium of the reaction and the pH. Hydrolysis in water proceeds more quickly than in mixture of water and organic solvent such as ethanol, and tends to completion. Playing with pH may catalyze the hydrolysis and enhance its speed.
  • hydrolysis is faster with the smallest alkoxy group of the silanes, e.g. hydrolysis of methoxy-silanes is 6 to 10 times faster than ethoxy-silanes of the same structure.
  • the treatment may be started when the concentration of silanols is sufficient, this corresponding to the solution becoming clear showing a true solution where before it was mostly a suspension.
  • Application on the surface may be e.g. by dipping or by spraying.
  • the necessary contact time depends notably on the temperature. For example, at a temperature of 15 to 35°C, this contact may be from 0.5 to 5 minutes.
  • Silanols reacts with hydroxyl groups linked to the metal, but may also give rise to condensation reactions of the silanols themselves to forms silanes films.
  • the former are increasing the adhesion to the substrate when the silanols condensates are promoting formation of a film the thickness of which depends on the concentration of the silanes solutions. Typical thickness may be up to 400nm.
  • the structure of the film is possibly cross-linked depending on the specific silanes used (or mixture of silanes). The cross-linking is normally high with bis-silanes and better protection is obtained.
  • the aluminum article is dried at temperature that may be from ambient to as high as 120°C, preferably from 40 to 120°C.
  • temperature may be from ambient to as high as 120°C, preferably from 40 to 120°C.
  • the above mentioned reactions are going n during the drying step.
  • Anodized aluminum and aluminum alloys treated by the process according to the invention exhibit specific resistance to the corrosive action that are the subject of the tests specified by the automotive industry. They notably have a weight loss at most of 10mg/dm 2 surface and preferably at most 5 mg/dm 2 , and most preferably at most 1mg/dm 2 when submitted to acid followed by alkaline test according to the specifications of the corrosion test 9.57448 from Fiat group. This weight loss is notably obtained for corrosion tests in which the acid is at a pH 1 and the alkali solution is at pH 13.5.
  • Samples of aluminum profile are prepared prior to anodic oxidation by cleaning the pieces and polishing up to a surface roughness R a of 0.6 ⁇ m.
  • Chemical pickling or electrochemical treatment of surface may be preferred to confer another appearance, notably etched appearance to other samples.
  • the anodization bath is containing 200 ⁇ 10g/l sulfuric acid. This solution is maintained at about 15°C. The current density is about 1.8 A/dm 2 .
  • the anodization is carried out till the oxide layer is 20 ⁇ m. At the indicated current density this needs about 45 minutes.
  • the anodized article is thoroughly washed in deionized water to remove any adhering solution.
  • a sealing process is then made to close the pore of the oxide layer.
  • the sealing is of the "cold sealing" type including an impregnation with nickel ions.
  • the example is made with Ni2+ at 1.2g/l and fluoride ions at 0.250g/l.
  • the temperature selected is 28°C and treatment is maintained for 20 minutes.
  • the solution is continuously filtered to remove any precipitate.
  • the anodized samples are immersed in an aqueous solution of sodium silicate.
  • the solution is prepared by diluting to 1l, 10ml of a sodium silicate solution containing by weight:
  • the pH is 8.0.
  • Treatment of the samples is by immersion at a temperature of 70°C.
  • the immersion time is 10 minutes.
  • the various parameters are selected so that no precipitation occurs during the treatment.
  • continuous filtration of the solution is carried out.
  • the samples are washed in tap water then in demineralized water and dried.
  • Careful examination of the product is done to control that no defects such as spots or powdery appearance of the surface may be detected.
  • Table 1 The conditions recited in table 1 for anodization and sealing and silicate treatment are other possible examples substitutes to the ones indicated above. Table 1. It includes various conditions relating to the steps: anodization, sealing and treatment with silicates. Preliminary treatment Anodizing parameters Coloring Sealing Additional treatment Application A Chemical polishing H 2 SO 4 200g/l Organic dying Impregnation Sealing Sodium silicate sol. Automotive Al dissolved "Black MLW" 1 Ni 2+ 1.2 g/l (waterglass) 7g/l 20 ⁇ 1 °C 10g/145°C F - 0.250g/l 10ml/l 1.5 A/dm 2 10 minutes 28°C 70 °C 45 minutes 20 minutes 20min B Chemical polishing H 2 SO 4 200g/l None Medium Temp. sealing.
  • Temperature sealing chemical specialties available on the market are based on a solution of about 10 g/nickel acetate and 0.2-05 g/l of a surfactant acting as a "bloom preventer" (i.e. it avoid the formation of powder on the anodic layer surface). Temperature 85-90 °C, dipping time 1 minute / ⁇ m (i.e. 20 min) 3 - Hot sealing chemical specialties available on the market contains essentially a mixture of surfactant used at a concentration of 1-2 ml/l acting as a "bloom preventer” (i.e. it avoid the formation of powder on the anodic layer surface). Temperature > 95 °C, dipping time 2 minute / micron (i.e. 40 min) 4 - Additives known to stabilize the tin ions solution, hampering its oxidation and/or precipitation.
  • silanes composition is the one sold by the company CHEMETAL under the name "OXILAN MM 0706".
  • the solution contains 3% by weight of this composition of silanes in water with addition of ethanol (5% by weight).
  • the samples are immersed in the solution at room temperature during 2 minutes. After this the samples are removed from the tank and without washing directly dried in a hot air flow at 60°C for 20 minutes.
  • the product made by the process according to the invention was analyzed at each stage of the preparation. This allows to confirm that the product in itself may be the subject of identification without having recourse to the process for making it.
  • a possible investigation includes an X-ray photoelectron spectrometry (XPS).
  • XPS X-ray photoelectron spectrometry
  • This method allows for identification of the elements entering in the surface layer of the product.
  • the method permit analysis of very thin layers (around 20-30 ⁇ ) preventing a possible confusion with elements from under-layers. Nevertheless when the layers considered exhibit average thicknesses that are less than these figures, and/or the roughness of the surface is noticeable, part of the measurements may indicate a limited amount of elements from under-layers.
  • each analysis is distinct according to the stage of the preparation. This confirm that the method definitely permits analysis of each top layer whatever the layers located underneath. This is notably the case of the silane top layer (4) including nitrogen (the starting silane is an amino-silane). It also contains an amount of carbon that clearly exceeds the amount of the previous layers, as the silane contains organic parts.
  • the anodized part (1) includes carbon and nitrogen corresponding to the black coating part. Sealing in (2) appears notably through the presence of Ni and F. These elements are also appearing but definitely at a lower concentration in the product at the silicate treatment step (3) making clear that the layer of silicate is a thin one and possibly intervening to further sealing the pores. This layer also indicates that Al content is less than in sub-layers (2).
  • Silanes of 4-7 above are sold pre-hydrolyzed and thus directly water soluble.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (17)

  1. Chemische Behandlung, angewendet an Produkten aus Aluminium oder Aluminiumlegierungen, die zuvor anodischer Oxidation und Porenversiegelung gemäß bekannten Verfahren im Stand der Technik unterzogen worden sind, umfassend zwei zusätzliche Schritte:
    - eine Behandlung mit einer Alkalisilicatlösung;
    - eine Behandlung mit Silanlösungen.
  2. Behandlung gemäß Anspruch 1, wobei die Dicke der anodischen Oxidschicht nicht weniger als 5 µm beträgt.
  3. Behandlung gemäß Anspruch 1, wobei die Behandlung in Alkalilösung in einer stabilen wässrigen Lösung durchgeführt wird, die ein oder mehrere Silicate von Natrium, Kalium oder Lithium oder Gemische davon enthält.
  4. Behandlung gemäß Anspruch 3, wobei das Molverhältnis von SiO2/M2O so ist, dass die Lösung einen pH-Wert von über 6 aufweist, vorzugsweise über 8, wobei M für Na, K oder Li steht.
  5. Behandlung gemäß Anspruch 4, wobei das Alkalisilicat Natriumsilicat ist, wobei das Molverhältnis von SiO2/Na2O wenigstens 3 beträgt.
  6. Behandlung gemäß einem der vorstehenden Ansprüche, wobei die Lösung von 1,0 g/l bis zu der Löslichkeitsgrenze, vorzugsweise von 10 bis 30 g/l, Alkalisilicat enthält.
  7. Behandlung gemäß einem der vorstehenden Ansprüche, wobei die Alkalisilicatbehandlung bei einer Temperatur von 40 bis 95 °C, vorzugsweise von 60 bis 80 °C, durchgeführt wird.
  8. Behandlung gemäß einem der vorstehenden Ansprüche, wobei das Produkt für 5 bis 50 Minuten in der Alkalisilicatlösung gehalten wird.
  9. Behandlung gemäß einem der vorstehenden Ansprüche, wobei das Produkt in einer wässrigen oder wässrigalkoholischen Lösung eines Silans oder eines Gemischs von Silanen behandelt wird.
  10. Behandlung gemäß Anspruch 9, wobei die Silane Monosilane der allgemeinen Formel:

            R'(CH2)nSi(OR)3

    sind, wobei n höchstens gleich 4 ist,
    wobei -OR eines von:

            -OCH3, -OC2H5, -OCOCH3

    ist und R' ein Rest von: Vinyl, Epoxy, Methacrylat, primäres Amin, Diamin, Mercapto ist.
  11. Behandlung gemäß Anspruch 10, wobei die Silane eines oder mehrere von:

            CH2=CHSi(OCH3)3

            CH2=CHSi(OC2H5)3

            CH2CH-CH2O-(CH2)3Si(OCH3)3

            \0/

            CH2=C(CH3)-COO-(CH2)3Si(OCH3)3

            H2N(CH2)2Si(OCH3)3

            H2N(CH2)2NH(CH2)3Si(OCH3)3

            N2HCN(O)H(CH2)3Si

            HS (CH2)3Si(OCH3)3

    sind.
  12. Behandlung gemäß Anspruch 9, wobei die Silane Bissilane der allgemeinen Formel:

            (RO)3-Si(CH2)nR'(CH2)nSi(OR)3

    sind, wobei R, R' und n die gleiche Bedeutung wie in Anspruch 10 haben.
  13. Behandlung gemäß Anspruch 12, wobei die Bissilane eines von:

            (C2H5O)3Si(CH2)Si (OC2H5)3

            (C2H5O)3Si(CH2)3-S4-(CH2)3Si(OC2H5)3

            (C2H5O)3Si(CH2)3-NH-(CH2)3Si(OC2H5)3

    sind.
  14. Behandlung gemäß einem der Ansprüche 9 bis 13, wobei die Lösung von 0,1 bis 5 Gew.-% Silane enthält.
  15. Behandlung gemäß einem der Ansprüche 9 bis 14, wobei die Lösung von 0,1 bis 15 Gew.-% an aliphatischem Alkohol enthält.
  16. Behandlung gemäß einem der Ansprüche 9 bis 15, wobei die Kontaktdauer mit der Lösung von 0,5 bis 5 min beträgt und die Temperatur von 15 bis 35 °C beträgt.
  17. Behandlung gemäß einem der Ansprüche 9 bis 16, wobei das Produkt bei einer Temperatur von Umgebungstemperatur bis 120 °C getrocknet wird.
EP15778287.1A 2014-11-21 2015-10-08 Behandlung von anodisierten aluminium und legierungen Active EP3245317B2 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
RS20190991A RS59341B2 (sr) 2014-11-21 2015-10-08 Obrada anodiranog aluminijuma i legura
PL15778287.1T PL3245317T5 (pl) 2014-11-21 2015-10-08 Obróbka anodyzowanego aluminium i stopów

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14194333.2A EP3023522A1 (de) 2014-11-21 2014-11-21 Behandlung von anodisierten Aluminium und Legierungen
PCT/EP2015/073271 WO2016078826A1 (en) 2014-11-21 2015-10-08 Treatment of anodized aluminum and alloys

Publications (3)

Publication Number Publication Date
EP3245317A1 EP3245317A1 (de) 2017-11-22
EP3245317B1 EP3245317B1 (de) 2019-05-08
EP3245317B2 true EP3245317B2 (de) 2022-05-18

Family

ID=51932269

Family Applications (2)

Application Number Title Priority Date Filing Date
EP14194333.2A Withdrawn EP3023522A1 (de) 2014-11-21 2014-11-21 Behandlung von anodisierten Aluminium und Legierungen
EP15778287.1A Active EP3245317B2 (de) 2014-11-21 2015-10-08 Behandlung von anodisierten aluminium und legierungen

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP14194333.2A Withdrawn EP3023522A1 (de) 2014-11-21 2014-11-21 Behandlung von anodisierten Aluminium und Legierungen

Country Status (6)

Country Link
EP (2) EP3023522A1 (de)
EA (1) EA037385B1 (de)
ES (1) ES2741525T5 (de)
PL (1) PL3245317T5 (de)
RS (1) RS59341B2 (de)
WO (1) WO2016078826A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3899086A1 (de) * 2018-12-21 2021-10-27 AGC Glass Europe Verfahren zum beschichten von metall
IT202000020590A1 (it) * 2020-08-28 2022-02-28 Ossidazione Anodica S R L Strati anodizzati resistenti agli acidi ed agli alcali

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3061467A (en) † 1962-10-30 Method of coating metals with an aque-
US6261638B1 (en) † 1997-01-09 2001-07-17 University Of Cincinnati Method of preventing corrosion of metals using silanes
JP2003183889A (ja) † 2001-12-14 2003-07-03 Shimano Inc 塗装部品
EP1780313A2 (de) † 2005-10-25 2007-05-02 Goodrich Corporation Behandeltes Aluminium und Herstellungsverfahren dafür
ITMI20052278A1 (it) † 2005-11-29 2007-05-30 Italfinish S P A Procedimento elettrolitico polivalente per il trattamento superficiale di materiali metallici non ferrosi
ITMI20062199A1 (it) † 2006-11-15 2008-05-16 Italfinish S P A Uso di organo-silani preidrolizzati per il trattamento dei metalli
WO2013139899A2 (de) † 2012-03-22 2013-09-26 Nanogate Ag Behandlung einer anodisch oxidierten Oberfläche

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5124292B2 (de) * 1972-10-06 1976-07-23
EP1873278A1 (de) 2006-06-30 2008-01-02 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur Behandlung von verdichteten anodisierten Aluminiumschichten mit Silikat
DE102007057777B4 (de) * 2007-11-30 2012-03-15 Erbslöh Ag Verfahren zur Herstellung eines Bauteils aus Aluminium und/oder einer Aluminiumlegierung sowie Verwendung des Verfahrens

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3061467A (en) † 1962-10-30 Method of coating metals with an aque-
US6261638B1 (en) † 1997-01-09 2001-07-17 University Of Cincinnati Method of preventing corrosion of metals using silanes
JP2003183889A (ja) † 2001-12-14 2003-07-03 Shimano Inc 塗装部品
EP1780313A2 (de) † 2005-10-25 2007-05-02 Goodrich Corporation Behandeltes Aluminium und Herstellungsverfahren dafür
ITMI20052278A1 (it) † 2005-11-29 2007-05-30 Italfinish S P A Procedimento elettrolitico polivalente per il trattamento superficiale di materiali metallici non ferrosi
EP1793019A2 (de) † 2005-11-29 2007-06-06 Italfinish S.p.A. Multivalentes elektrolytisches verfahren für die oberflächenbehandlung von nichteisenhaltigen metallischen werkstoffen
ITMI20062199A1 (it) † 2006-11-15 2008-05-16 Italfinish S P A Uso di organo-silani preidrolizzati per il trattamento dei metalli
WO2013139899A2 (de) † 2012-03-22 2013-09-26 Nanogate Ag Behandlung einer anodisch oxidierten Oberfläche

Also Published As

Publication number Publication date
EP3245317A1 (de) 2017-11-22
RS59341B2 (sr) 2022-10-31
EP3245317B1 (de) 2019-05-08
WO2016078826A1 (en) 2016-05-26
ES2741525T3 (es) 2020-02-11
RS59341B1 (sr) 2019-10-31
PL3245317T5 (pl) 2023-01-30
EA037385B1 (ru) 2021-03-23
PL3245317T3 (pl) 2019-12-31
ES2741525T5 (es) 2022-10-13
EP3023522A1 (de) 2016-05-25
EA201791723A1 (ru) 2017-12-29

Similar Documents

Publication Publication Date Title
CN104233428B (zh) 一种提高铝或铝合金材料表面阳极氧化膜耐碱性能的方法
DK2265441T3 (en) Protective coating for metals
CN110359044B (zh) 一种钢基体表面超疏水膜的制备方法
US10385470B2 (en) Treatment of an anodically oxidized surface
CN102575356A (zh) 制备耐碱的阳极氧化铝表面的多步骤方法
HUT75966A (en) Metal pretreated with an aqueous solution containing a dissolved inorganic silicate or aluminate, an organofunctional silane and a non-functional silane for enhanced corrosion resistance
KR101606844B1 (ko) 금속 표면 처리 방법 및 조성물
EP3245317B2 (de) Behandlung von anodisierten aluminium und legierungen
KR19990023387A (ko) 금속 호일의 부착력 증대방법
JP2014173128A (ja) アルミニウム系部材の修復方法、修復処理液、アルミニウム系材料およびその製造方法
EP0101820B1 (de) Verfahren zum schützenden Verdichten von anodisch oxydiertem Aluminium und seinen Legierungen
JP6733810B2 (ja) 銀鏡膜形成液及びその還元液の作製方法
JP4176581B2 (ja) 表面処理アルミニウム材及びアルミニウム成形体
EP3960899A1 (de) Säure- und laugenbeständige eloxalschichten
CN116334603A (zh) 一种铝基超疏水防腐涂层及其制备方法
KR100213562B1 (ko) 알루미늄 또는 그 합금의 표면처리방법
CN114717630A (zh) 一种铝及铝合金阳极氧化膜新型环保封闭剂及其制备方法
JP4133129B2 (ja) 硬質膜の製造方法
US20190040541A1 (en) Highly alkali-resistant aluminum member
JPH04311595A (ja) アルミニウムのセラミックコーティング方法
WO2019121178A1 (en) A method for increasing corrosion resistance of a substrate comprising an outermost chromium alloy layer
JP4221340B2 (ja) 大気環境中において変色を生じにくいチタンおよびチタン合金とその製造方法
TW201831736A (zh) 用於鎂的深色電子陶瓷塗層
Brace et al. Production and Properties of Opaque Coatings by Chromic Acid Anodising
JPS5913589B2 (ja) シリカ質皮膜を有する製品の製法

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20171009

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180801

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ASIT AUTOMOTIVE S.R.L.

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTC Intention to grant announced (deleted)
INTG Intention to grant announced

Effective date: 20190116

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1130271

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190515

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602015029978

Country of ref document: DE

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20190508

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190908

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190808

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

REG Reference to a national code

Ref country code: SK

Ref legal event code: T3

Ref document number: E 31843

Country of ref document: SK

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190809

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190808

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1130271

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602015029978

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2741525

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20200211

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

26 Opposition filed

Opponent name: DELBARBA, MR ANDREA

Effective date: 20200207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191031

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191008

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191031

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20191031

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190908

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20151008

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBY Invitation to file observations in appeal sent

Free format text: ORIGINAL CODE: EPIDOSNOBA2O

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20220518

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 602015029978

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190508

REG Reference to a national code

Ref country code: SK

Ref legal event code: T5

Ref document number: E 31843

Country of ref document: SK

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Ref document number: 2741525

Country of ref document: ES

Kind code of ref document: T5

Effective date: 20221013

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20250912

Year of fee payment: 11

Ref country code: IT

Payment date: 20250922

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20250904

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250908

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: RS

Payment date: 20250917

Year of fee payment: 11

Ref country code: CZ

Payment date: 20250923

Year of fee payment: 11

Ref country code: IE

Payment date: 20250909

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: RO

Payment date: 20250922

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SK

Payment date: 20250912

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250902

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20251002

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20251107

Year of fee payment: 11