EP3960899A1 - Säure- und laugenbeständige eloxalschichten - Google Patents
Säure- und laugenbeständige eloxalschichten Download PDFInfo
- Publication number
- EP3960899A1 EP3960899A1 EP21193393.2A EP21193393A EP3960899A1 EP 3960899 A1 EP3960899 A1 EP 3960899A1 EP 21193393 A EP21193393 A EP 21193393A EP 3960899 A1 EP3960899 A1 EP 3960899A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- substrate
- solution
- process according
- anodised aluminium
- anodised
- 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
Images
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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1245—Inorganic substrates other than metallic
Definitions
- the present invention relates to a surface treatment method for anodised aluminium or alloys thereof to make the anodised aluminium resistant to corrosion by acidic and/or alkaline agents, in particular for use in the automotive sector.
- the oxide layer is electrochemically formed on the metal by means of known processes in the sector. Once formed, the oxide layer has a porosity which can be useful if any colours are to be applied, but has the great disadvantage of not protecting the metal from corrosion. To overcome this problem, the anodised aluminium is usually subjected to a subsequent step of fixing the pores, for example by hot hydration or cold impregnation, which causes an expansion or swelling of the oxide layer and consequent closure of the pores.
- the hot fixing of the pores is normally carried out with hot water in the presence of any additives, or with steam, while the cold fixing involves temperatures of 30°C and the presence of nickel fluoride.
- anodised aluminium finishing treatment for window frames which consists of a transparent (possibly glossy) electrophoretic coating of the type known as "E.D. coat” or, simply ED.
- This coating would allow anodised aluminium to pass the tests of car manufacturers, but the polymer layer of paint is visible to the naked eye and therefore may not be accepted in this sector.
- EP1873278 discloses an aluminium treatment, anodised and fixed, with a solution of alkaline silicates.
- the treatment serves to increase the corrosion resistance of the aluminium for uses in the automotive sector.
- the silane coating ensures a resistance up to pH 13.5.
- JP2003183889 discloses a method for increasing the corrosion resistance of anodised aluminium. Such a method involves applying a silane solution to the surface of the aluminium.
- US2015/0034487 relates to a method for improving the corrosion resistance of anodised and partially fixed aluminium up to pH 13.5 which consists in applying a solution containing an orthosilicate and a non-alkali silicate to the surface of the aluminium and then heating to 200°C for one hour. This treatment may result in the irreversible rupture of the oxide layer.
- Anodised aluminium treatments are also known in which a first layer of alkaline silicate is applied, followed by a second layer of silane.
- the product obtained after treatment with silicates and silane in two steps exhibits a weight loss of at least 10 mg/dm 2 of surface when subjected to the alkali resistance test established by the rules of the car manufacturers. This result indicates that the treatment does not allow the product to pass the test without altering the functional and aesthetic properties thereof.
- the need remains in the sector to provide a surface treatment method of anodised aluminium (or alloys thereof) that allows to pass the tests at acidic and basic pHs (in particular at pH 1 and 13.5) established by car manufacturers without altering the aesthetic appearance and properties of the aluminium.
- This is in order to make such a substrate resistant to the atmospheric and chemical agents to which cars are subjected.
- the anodised aluminium components used for the construction of cars must withstand the products used in car washes which are solutions, foams, dispersions etc. which have a pH of about 13.5 or higher.
- the present invention relates to a process for coating an anodised aluminium comprising treating anodised aluminium with a solution containing silicates, silanes and siloxanes and subsequently heating it to a temperature comprised between 55°C and 80°C.
- the solution can also possibly comprise a surfactant.
- the anodised aluminium substrate can be treated with conventional methods for pore closure (fixing).
- the anodised aluminium substrate can be coloured by methods known in the sector.
- the invention also relates to an anodised aluminium substrate or alloys thereof coated with a coating derived from the process according to the invention.
- the aluminium substrate treated with the process of the invention passes, without alterations, the test established by the rules of car manufacturers, i.e., it resists unaltered at pHs from 1 to 13.5.
- the present invention relates to a process for coating an anodised aluminium substrate or anodised aluminium alloys, comprising:
- the anodised aluminium substrate (or alloys thereof) is preferably a component used for the construction of vehicles, in particular cars, such as windscreen wiper blades, body parts such as doors and hoods, wheels and other components which have an aesthetic value. These substrates can be subjected to extreme pH conditions especially when placed in contact with washing solutions which normally reach pHs even above 13.5.
- the anodised aluminium substrate can also be a furnishing component, a frame for a window, a door, a floor, a wall, a shower enclosure, or other furnishing items.
- the aluminium substrate (or alloys thereof) is subjected to a conventional anodising process. Such a process can comprise some preliminary steps of preparing the substrate selected from:
- the substrate is anodised by immersing the piece in an acid bath, preferably of sulphuric acid, and applying a current having a density usually comprised between 1.0 and 3.0 A/dm 2 , preferably between 1.5 and 2.0 A/dm 2 .
- the acid bath is maintained at a temperature comprised between 15°C and 23°C, preferably between 18°C and 21 °C, thermostated ⁇ 0.5 with respect to the chosen temperature.
- the treatment time is comprised between 30 and 60 minutes, preferably between 40 and 50 minutes.
- a colour can be applied, if necessary, for the desired applications.
- an organic colour is used which is absorbed by the oxide or an electrolytic colouring is performed.
- the colour is applied by immersing the substrate in the dye, the colour must be pre-fixed by immersing the coloured substrate in a solution containing nickel acetate.
- the nickel ion binds to the dye molecule and forms nickel hydroxide within the pore of the aluminium oxide, preventing the dye from bleeding with the consequent discolouration of the dyed substrate.
- a solution of 5-10 g/L of nickel acetate is used.
- the solution is heated at a temperature comprised between 60° and 75°C.
- the aluminium oxide thickness which forms can vary from 5 to 25 ⁇ m.
- the fixing can be done by hydration with boiling water, optionally in the presence of additives, or by means of steam or by impregnation with a solution containing nickel ions and fluoride ions.
- a solution containing nickel ions and fluoride ions is particularly useful if a colour is applied to the anodised substrate.
- the fixing used for the present invention is a fixing with nickel fluoride at a temperature comprised between 25°C and 30°C.
- a treatment with nickel acetate can be carried out at a temperature between 70°C and 90°C.
- the pores can be fixed by immersion in hot water, optionally with appropriate additives, at a temperature between 90°C and 100°C.
- the fixing takes place for a time comprised between 1 to 3 min/ ⁇ m of oxide thickness.
- a solution comprising at least one alkaline silicate, at least one siloxane and at least one silane is applied.
- the alkaline silicate is present in the solution in an amount comprised between 0.5 and 10 g/l, preferably between 1 -4 g/l.
- the silanes have a general formula: R'(CH 2 ) n Si(OR) 3 wherein:
- n is equal to 3 or 4
- R' is vinyl, epoxy or glycidyloxy
- OR is a methoxy group (OCH 3 ).
- the silane used in the solution of the invention is 3-glycidyloxypropyltrimethoxysilane having the formula given above.
- Silane is present in the solution of the invention in an amount comprised between 0.5 g/L and 4 g/L, preferably between 1 g/L and 3 g/L.
- Siloxanes are a class of chemical compounds in the structure of which the functional group R 2 SiO is repeated, wherein R is a hydrogen or an alkyl or aryl group.
- R is a hydrogen or an alkyl or aryl group.
- siloxane comes from the combination of silicon, oxygen and alkane. They are considered part of the class of organo-siliceous compounds.
- Siloxanes have a main, linear or branched chain, in which silicon and oxygen atoms -Si-O-Si-O- alternate with the R side chains bound to the silicon atoms.
- Polymers of siloxanes wherein R is an alkyl group are commonly known as silicones or "polysiloxanes".
- silicones or "polysiloxanes”.
- the most representative examples of these polymers are [SiO(CH 3 ) 2 ] n (polydimethylsiloxane) and [SiO(C 6 H 5 ) 2 ] n (polydiphenylsiloxane).
- the synthesis of silicones generally begins with the hydrolysis of methyl chlorosilanes forming cyclosiloxanes: tetramethylchlorosilane, hexamethylchlorosilane, usually referred to as D4, D6 respectively.
- Cyclosiloxanes can be considered the "monomers" of silicone polymerisation.
- the polymerisation takes place in the presence of highly basic catalysts in a particular synthesis process which allows other siloxanes with alkyl, phenyl and vinyl terminations to be inserted into the polymer chain. With these introductions, the characteristics of the final polymer change considerably and, above all, can be modulated according to the needs of use with appropriate dosages.
- the siloxane used in the solution of the invention is a siloxane and/or a polysiloxane.
- the siloxane is preferably selected from:
- the polysiloxane is preferably selected from polyether siloxane and polyetheredimethylsiloxane.
- the solution comprises a siloxane preferably selected from: hexamethyldisiloxane and polydimethylsiloxane and a polysiloxane preferably selected from: polyether siloxane and polyetheredimethylsiloxane.
- Siloxane is comprised in the solution in an amount from 0.1 to 1g/L, preferably 0.2 to 0.5 g/L.
- the polysiloxane is comprised in the solution in an amount from 0.1 to 1g/L, preferably 0.2 to 0.5 g/L.
- the solution can comprise an anionic surfactant, preferably a disulphonate. If present, the surfactant is added in an amount comprised between 0.1 and 1% with respect to the volume of the solution, preferably between 0.2% and 0.5%.
- the surfactant has the function of homogenising and making the solution clear and is particularly useful if anodised substrates with a glossy aesthetic effect are to be prepared, while if the substrates are frosted, the surfactant can also not be added, as on frosted surfaces (i.e., opaque and non-reflective), any aesthetic alterations are not visible.
- the solution of the invention is applied to the substrate by immersing the same in the solution.
- the application time is comprised between 5 and 20 minutes, preferably between 7 and 15 minutes.
- the solution is heated at a temperature comprised between 40°C and 85°C, preferably between 50°C and 80°C.
- the piece After immersion of the anodised substrate in the solution, the piece is dried, preferably without rinsing, at a temperature comprised between 55°C and 80°C, preferably between 60°C and 70°C.
- the drying is preferably carried out with hot air.
- the thickness of the layer obtained is comprised between 0.5 and 3 ⁇ m.
- the process is self-limiting, as the thickness which is formed is not directly proportional to the immersion time; i.e., when a certain value is reached which depends on the operating conditions, the layer no longer increases.
- the anodised substrate treated with the solution of the invention has been shown to pass the tests required by the FCA specifications, which envisage subjecting the anodised aluminium samples to the following test cycle:
- the substrate does not have and must not have aesthetic alterations.
- the invention also relates to an anodised aluminium substrate (or alloys thereof) coated with a coating layer obtainable by the application of the process according to the present invention.
- Such a substrate is characterised in that it passes, without aesthetic alterations, the test established by the car manufacturers of resistance to acidic pHs equal to 1 and to basic pHs up to 13.5.
- the anodised aluminium substrate (or alloys thereof) has an aluminium oxide thickness from 0.3 ⁇ m to 30 ⁇ m.
- the thickness of the coating layer according to the present invention can vary from 0.5 to 3 ⁇ m.
- the total thickness of the anodised aluminium substrate coated with the coating according to the present invention is comprised between 3 and 35 ⁇ m.
- silicate solution sodium, lithium or potassium silicate
- frosted colour simply perform: a passage of 15 min in colour (e.g., orange, blue, turquoise, etc.) at the temperature recommended by the dye producer.
- colour e.g., orange, blue, turquoise, etc.
- Figure 1 shows the initial step of a resistance test at pH 13.5 of two anodised aluminium substrates: left substrate (black coloured) not treated with the coating of the invention and right substrate (silver) treated with the coating of the invention.
- the part of the substrate immersed in the alkaline solution is delimited by a mark with a black marker.
- Figure 2 shows the end of the immersion test of figure 1 . It is clear that the untreated coloured substrate has completely lost colour and the aluminium oxide layer has been dissolved by the high alkalinity; instead the silver substrate treated with the coating of the invention has not been affected at all. In fact, the basic solution has remained clear and colourless.
- Figure 3 shows black-coloured anodised aluminium substrates after immersion in a solution at pH 13.5.
- the left substrate was not coated with the coating of the invention: the right substrate was coated with the coating.
- the substrate on the left has a total dissolution of the colour and of the oxide layer, while the substrate on the right is intact for both the colour and the oxide layer.
- Figure 4 shows uncoloured anodised aluminium substrates subjected to immersion tests in basic solution at pH 13.5.
- the left substrate was not coated with the coating of the invention while two right substrates were coated.
- the aluminium oxide layer of the left substrate has been completely dissolved from the basic solution, while the right substrates are intact.
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Catalysts (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT102020000020590A IT202000020590A1 (it) | 2020-08-28 | 2020-08-28 | Strati anodizzati resistenti agli acidi ed agli alcali |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3960899A1 true EP3960899A1 (de) | 2022-03-02 |
Family
ID=73139249
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP21193393.2A Pending EP3960899A1 (de) | 2020-08-28 | 2021-08-26 | Säure- und laugenbeständige eloxalschichten |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3960899A1 (de) |
IT (1) | IT202000020590A1 (de) |
WO (1) | WO2022043977A1 (de) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003183889A (ja) | 2001-12-14 | 2003-07-03 | Shimano Inc | 塗装部品 |
US20060099332A1 (en) * | 2004-11-10 | 2006-05-11 | Mats Eriksson | Process for producing a repair coating on a coated metallic surface |
EP1873278A1 (de) | 2006-06-30 | 2008-01-02 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur Behandlung von verdichteten anodisierten Aluminiumschichten mit Silikat |
US20150034487A1 (en) | 2012-03-22 | 2015-02-05 | Nanogate Ag | Treatment of an anodically oxidized surface |
EP3023522A1 (de) * | 2014-11-21 | 2016-05-25 | AGC Glass Europe | Behandlung von anodisierten Aluminium und Legierungen |
CN106400085A (zh) * | 2016-06-21 | 2017-02-15 | 武汉风帆电化科技股份有限公司 | 一种铝及铝合金阳极氧化膜后处理用封孔剂及后处理方法 |
-
2020
- 2020-08-28 IT IT102020000020590A patent/IT202000020590A1/it unknown
-
2021
- 2021-08-26 EP EP21193393.2A patent/EP3960899A1/de active Pending
- 2021-09-29 WO PCT/IB2021/058928 patent/WO2022043977A1/en active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003183889A (ja) | 2001-12-14 | 2003-07-03 | Shimano Inc | 塗装部品 |
US20060099332A1 (en) * | 2004-11-10 | 2006-05-11 | Mats Eriksson | Process for producing a repair coating on a coated metallic surface |
EP1873278A1 (de) | 2006-06-30 | 2008-01-02 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur Behandlung von verdichteten anodisierten Aluminiumschichten mit Silikat |
US20150034487A1 (en) | 2012-03-22 | 2015-02-05 | Nanogate Ag | Treatment of an anodically oxidized surface |
EP3023522A1 (de) * | 2014-11-21 | 2016-05-25 | AGC Glass Europe | Behandlung von anodisierten Aluminium und Legierungen |
EP3245317A1 (de) | 2014-11-21 | 2017-11-22 | ASIT AUTOMOTIVE S.r.L | Behandlung von eloxiertem aluminium und legierungen |
CN106400085A (zh) * | 2016-06-21 | 2017-02-15 | 武汉风帆电化科技股份有限公司 | 一种铝及铝合金阳极氧化膜后处理用封孔剂及后处理方法 |
Also Published As
Publication number | Publication date |
---|---|
IT202000020590A1 (it) | 2022-02-28 |
WO2022043977A1 (en) | 2022-03-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104160070B (zh) | 阳极氧化表面处理 | |
KR101020526B1 (ko) | 금속의 부식 방지 | |
KR101362969B1 (ko) | 금속용 보호 코팅 | |
US6162498A (en) | Method for providing a metal surface with a vitreous layer | |
KR101055596B1 (ko) | 부식 방지를 위한 금속 피복용 조성물 | |
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 | |
US20140262790A1 (en) | Colored, corrosion-resistant aluminum alloy substrates and methods for producing same | |
CA2696919C (en) | Corrosion resistant aluminum alloy substrates and methods of producing the same | |
JP2004538364A (ja) | マグネシウム表面の耐腐食性を改善するための処理 | |
CN106906462B (zh) | 一种金属表面前处理剂及其制备方法、应用 | |
WO2013171582A1 (en) | Radiation curable composition, and method for preparing a hybrid sol-gel layer on a surface of a substrate using said composition | |
EP2850139A1 (de) | Radikalisch und kationisch strahlungshärtbare zusammensetzung und verfahren zur herstellung einer hybriden sol-gel-schicht auf einer oberfläche eines substrats unter verwendung der besagten zusammensetzung | |
EP3960899A1 (de) | Säure- und laugenbeständige eloxalschichten | |
US4235638A (en) | Sulfonato-organosilanol compounds and aqueous solutions | |
JP2009513824A (ja) | 塗装酸化アルミニウム層の耐食性および耐光堅牢度を改良する方法 | |
CN106835093B (zh) | 一种q型poss改性的金属表面前处理剂及其制备方法、应用 | |
CA3168087C (en) | Decorative and protective coating composition for metal, glass and plastics substrates | |
CN106894009B (zh) | 一种环氧基poss改性的金属表面前处理剂及其制备方法、应用 | |
US4267213A (en) | Sulfonato-organosilanol compounds and aqueous solutions thereof | |
JP6667191B2 (ja) | アルミニウムの表面処理方法 | |
EP3245317B1 (de) | Behandlung von anodisierten aluminium und legierungen | |
CN111100335B (zh) | 一种橡胶用有机硅烷涂敷钢丝复合物、制备方法及涂覆方法 | |
US11035052B2 (en) | Highly alkali-resistant aluminum member | |
CN116161873A (zh) | 一种玻璃基底透明超疏水防污功能涂层的制备方法 | |
CN117244767A (zh) | 一种金属或合金的表面处理方法及金属或合金制品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
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: THE APPLICATION HAS BEEN PUBLISHED |
|
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 |
|
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: 20220729 |
|
RBV | Designated contracting states (corrected) |
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 |