EP0648863B1 - Emaillierbare Oxidschicht - Google Patents
Emaillierbare Oxidschicht Download PDFInfo
- Publication number
- EP0648863B1 EP0648863B1 EP94810572A EP94810572A EP0648863B1 EP 0648863 B1 EP0648863 B1 EP 0648863B1 EP 94810572 A EP94810572 A EP 94810572A EP 94810572 A EP94810572 A EP 94810572A EP 0648863 B1 EP0648863 B1 EP 0648863B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminium
- enamel
- substrate
- layer
- surface layer
- 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.)
- Expired - Lifetime
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
-
- 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
- C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
- C23D3/00—Chemical treatment of the metal surfaces prior to coating
Definitions
- the invention relates to an aluminum-containing substrate for enamel coatings containing at least on the surfaces provided for an enamel coating, a surface layer made of aluminum or an aluminum alloy and on this surface layer Oxide layer.
- the invention further relates to a method for producing the oxide layer and the use of the aluminum-containing substrate.
- Aluminum materials such as foils, strips or sheets, for example used as facade panels for facade and vehicle construction. Such cover plates are in usually anodized to be resistant to environmental influences.
- Alignment 54th year, 1978, volume 8, pages 527 and 528, W. Grosskopf, "overview about the application and implementation of the enamelling of aluminum ", is the enamelling of pure aluminum strips up to 0.3 mm thick. It was not found any aluminum material can be enamelled, and in particular magnesium-containing aluminum alloys are unsuitable for enamelling.
- UDSSR patent specification 1 120 034 A describes a process for enamelling aluminum alloys described, wherein the alloy is anodized and the anodized article coated with a sample of an enamel powder, dried and baked the enamel, around a decorative surface resp. to get a decorative pattern.
- Finishing Publication Ltd., Teddington, Middlesex, England, 5th edition, volume 2, 1987, page 1162 describes that on the one hand the worst results from the application of an enamel layer on one anodized aluminum would be achieved, on the other hand, anodized aluminum again a show much better bonding and resistance to thermal shock. So far therefore the problem of adhering to an aluminum-containing substrate for a long time Enamel layer not loosened. It is always to be feared that such a layer will appear soon after replaces or flakes off the order.
- the object of the present invention is to provide a substrate for To make available, which is suitable for the application of an enamel layer, as well to propose a method for producing the substrate and a use for the substrate.
- the object is achieved by the product according to claim 1.
- the method of manufacturing the product according to claim 1 is claimed in claim 9.
- the uses of the product according to claim 1 are claimed in claims 12 to 14.
- Advantageous embodiments of the product and the method are claimed in claims 2 to 8 or 10 and 11.
- Aluminum-containing substrates are, for example, sheet-like substrates made of aluminum or its alloys. Examples are foils, strips, sheets or profiles. The substrates but can also bodies of any shape with an aluminum surface or an aluminum-containing Surface. Other substrates are composite materials that at least a cover layer made of aluminum or an aluminum alloy. Preferably are foils, strips or sheets made of aluminum or aluminum alloys applied.
- the isotropic barrier layer can cover the entire surface of the aluminum or of the aluminum alloy extend or can be provided at least at the points to which the enamel coating should be applied.
- the isotropic barrier layer is a pore-free oxide layer and has a high temperature resistance as well as increased compared to aluminum or aluminum alloys chemical resistance. Enamel layers generally show good adhesion to oxides. Through time- and temperature-dependent diffusion processes, however, components can on the one hand the enamel layer and on the other hand also components of the aluminum-containing substrate, such as metallic alloy components or impurities, in the oxide layer arrive and form a layer that does not adhere well to the enamel layer Guaranteed aluminum-containing substrate. Such components (adhesion inhibitors), the one Reduce adhesion and thus, for example, also cause spalling problems in the enamel layer can be, for example, copper or magnesium. The diffusion of such adhesion inhibitors takes place in the oxide layer, due to the high baking temperature, essentially during the firing process of the enamel coating.
- Isotropic barrier layer prevents diffusion of adhesion inhibitors or at least in this way reduces that good adhesion of a deposited on the substrate according to the invention Enamel layer is guaranteed.
- the density of the isotropic barrier layer is advantageously between 2.5 and 3.8 g / cm 3 and preferably has a dielectric constant between 8.5 and 10.
- substrates with a surface layer made of pure aluminum, essentially containing aluminum and the commercially available impurities or made of aluminum alloys are examples of aluminum-containing substrates.
- Aluminum substrates can, for example, be aluminum of a purity of 98.5% by weight and higher, preferably of 99.0% by weight and higher and in particular 99.5 wt .-% and higher, and the rest of commercial impurities contain.
- Wrought aluminum alloys are preferred for the substrates.
- Alloys include e.g. the types AlMg, AlMgSi, AlCuMg and AlZnMg.
- wrought aluminum alloys can contain: Up to 1.5 % By weight silicon, up to 1.0% by weight iron, up to 4.0% by weight copper, up to 1.5% by weight of manganese, up to 6.0% by weight of magnesium, up to 7.0% by weight Zinc, up to 0.2% by weight of titanium and up to 1.6% by weight of other elements, Rest aluminum.
- Substrates made of an aluminum alloy are particularly preferred, containing 0.25 to 1.5 wt .-% silicon, up to 0.3 wt .-% Iron, up to 0.25% by weight copper, 0.1 to 0.8% by weight manganese, 2.7 - 5.0 %
- Examples from the practice of substrates are aluminum alloys AlMg3, AlMg3Si, AlMg5, AlMg5Si and AlMg10.
- Aluminum casting alloys are also preferred for the substrates.
- Alloys include e.g. the types: AlSi, AlSiMg, AlSiCuMg, AlMgSi-CuMg, AlMgSi and AlZnMg.
- Cast aluminum alloys containing: up to 11.0% by weight silicon, up to 1.0% by weight iron, up to 5.2% by weight copper, up to 0.5% by weight Manganese, up to 7.5% by weight of magnesium, up to 10% by weight of zinc, up to 0.3 %
- titanium up to 1.2% by weight nickel, up to 0.03% by weight lead, up to 0.03% by weight of tin and up to 0.05% by weight of other elements, the rest being aluminum.
- the substrates can only use this aluminum or aluminum-containing surface layer and on this surface layer, at least partially, the have oxide layer according to the invention, or e.g. for the purpose of a composite or a laminate further aluminum-containing layers or layers of other materials on the back of the surface layer be arranged while the oxide layer according to the invention on the front is arranged.
- the aluminum or aluminum-containing surface layer must be on the surface, so that the inventive Oxide layer in an appropriate manner on it. can be attached to it.
- the inventive The oxide layer then forms the layer that is now exposed on the outside for further use Coating with the enamel layer.
- the present invention also relates to a process for producing the aluminum-containing one Substrates for enamel coatings.
- the method is carried out in such a way that that the oxide layer at least in the areas provided for the enamel coating by means of anodic oxidation (anodizing) in an electrolyte with a pH value in Range between 5 and 7 in the temperature range of 30 to 80 ° C is formed, with the anodic oxidation the surface layer of aluminum or an aluminum alloy or at least the area intended for the enamel coating in an electrolyte is given, and between the surface layer and a second, in the same electrolyte a voltage is applied to the electrode.
- the aluminum-containing substrate or at least the areas provided for the enamel coating are placed in an electrolyte and be switched as a positive electrode (anode).
- a negative electrode cathode
- another electrode in the same electrolyte is used, for example stainless steel or lead. If an electrical voltage is applied to the electrodes, then hydrogen gas develops at the cathode, at the anode or in the electrolyte submerged aluminum-containing substrate oxygen gas. This oxygen reacts with the Aluminum to aluminum oxide, which forms an oxide layer on the surface layer.
- the process of producing the oxide layer used in practice runs essentially so that the substrate and in particular the surface to be coated with enamel of aluminum or an aluminum alloy is subjected to a pretreatment, wherein the surface is first degreased, then rinsed and finally stained, with the pickling for example with a sodium hydroxide solution in a concentration of 50 to 200 g / l 40 to 60 ° can be carried out for one to ten minutes. Then can rinsed the surface and with an acid such as Nitric acid, especially a concentration of 25 to 35% by weight in the room temperature range of typically 20 - Neutralized at 25 ° C for 20-60 s, rinsed again and if necessary be dried.
- an acid such as Nitric acid
- the properties of the oxide layer formed largely depend on the Electrolysis conditions such as electrolyte composition, pH value, electrolyte temperature, applied voltage and the electrolysis current from.
- electrolysis conditions such as electrolyte composition, pH value, electrolyte temperature, applied voltage and the electrolysis current from.
- an acidic electrolyte one forms Oxide layer, which is essentially a non-porous base or barrier layer and contains a porous outer layer.
- Oxide layer which is essentially a non-porous base or barrier layer and contains a porous outer layer.
- anodic Oxidation in acidic electrolytes forms on the substrate surface a pore-free base or barrier layer and at the same time the during the anodic oxide layer formed on the outside partially dissolved chemically by field-induced redissolving.
- an oxide layer with fine pores forms on the surface for example, perpendicular to the surface and against the surface are open.
- the thickness of the oxide layer reaches its upper limit if growth and solution are balanced, what of the
- pH-neutral or approximately pH-neutral electrolytes are solutions that have a pH in the range between 5 and 7.
- Typical examples of such electrolytes are boric acid (H 3 BO 3 ) or aqueous solutions of ammonium salts with borates, phosphates, tartrates, citrates, vanadates or molybdate and mixtures thereof.
- electrolytes such as aqueous solutions with 1% by weight NH 4 H 2 PO 4 (9% phosphate), 10% by weight H 3 BO 3 (7% borate), 5% by weight NH 4 molybdate (2.5% Mo oxide) or 2% by weight NH 4 vanadate (2% vanadium oxide), with the information in parentheses the compounds typical of the individual electrolytes in atomic percentages which are in the oxide layer and in particular to be built into their outer surface.
- the surfaces to be treated come into contact with the electrolyte brought and by means of direct current, pulse current, alternating current or asymmetrical AC anodized. Also be under DC currents of practically the same type, for example through full-wave rectification a single-phase alternating current or by rectifying one Three-phase alternating current are generated, understood.
- asymmetrical AC types can include, for example, sinusoidal AC a voltage / time curve with unequal amplitudes in the positive and negative part, rectangular alternating current with a Voltage / time curve with equally high amplitudes and unequal lengths Time shares of the positive and negative part, rectangular alternating current with a voltage / time curve with unequal amplitudes in the positive and negative range or rectangular alternating current with a voltage / time curve with unequal amplitudes and unequal long time portions of the positive and negative part can be applied.
- sinusoidal alternating current curves with phase gating in positive and negative part and also other asymmetrical alternating currents be used with interrupted current flow, e.g. with triangular Alternating current.
- the anodic oxidation in pH-neutral or approximately pH-neutral electrolytes is expediently carried out with a voltage up to 600 V, preferably up to 500 V, and a current density up to 120 A / m 2 , preferably up to 100 A / m 2 .
- the anodic oxidation in pH-neutral or approximately pH-neutral electrolytes can be carried out, for example, by continuously increasing the applied voltage up to the maximum value such that the current density is kept constant at this level after an initially continuous increase up to the predetermined value. After reaching the maximum voltage, the current density then decreases due to the increasingly thick oxide layer and reaches a residual current density after a certain time.
- the method according to the invention is preferably carried out until the current density has fallen to a value between 1 and 10 A / m 2 after the maximum voltage has been applied.
- the thickness of the oxide layer obtained is voltage-dependent and lies in the range between 10 and 16 ⁇ / V and in particular between 11 and 15 ⁇ / V.
- the oxide layer can have a small surface area Contain concentration of ions. This ion concentration becomes essentially determined by the electrolyte and is therefore on the outer Surface area of the oxide layer limited.
- the inventive Oxide layer is particularly low in magnesium and prevents during and after the enamel coating has burned in, another diffusion of magnesium from the surface layer.
- the substrate or the treated surface can other treatments, such as Rinsing or impregnation will.
- Such an aftertreatment without rinsing is provided, for example, by Impregnation of the oxide surface with a flux.
- a flux can contain compounds or ions, which are very important in enamel are easily soluble and therefore, for example, better enamel anchoring effect on the oxide surface.
- the oxide surfaces can be such Compounds or ions, such as vanadium oxide, ammonium vanadate, Molybdenum oxide, ammonium molybdate, ammonium borate, ammonium phosphate etc. already contained by the anodic oxidation. In this case their effect is achieved by applying an appropriate flux supported. Fluxes can also affect the wettability of the oxide surface increase and / or lower the melting point of the enamel frit.
- the present invention also relates to the use of the inventive Product as a substrate for enamel coatings.
- the substrate according to the present invention for enamel coatings can be used as a melting point of 480 ° C to or near the melting point Melting point of the substrate can be used. With close to the melting point For example, temperatures between 20 or 10 ° C below the Melting point described.
- the product is useful as a substrate for enamel coatings based on alkali-silico-titanates, if necessary with baking temperature-reducing additives, e.g. the connections, such as oxides, lithium, barium, antimony, cadmium, bismuth or Vanadium applied.
- the present relates Invention the use of the product as a substrate for Enamel coatings from a frit containing the oxides of silicon in amounts of 27 to 33% by weight, preferably 30% by weight, of the potassium of 9 to 12% by weight, preferably 9.5 to 11.5% by weight, of the titanium from 18 to 22 %
- the potassium of 9 to 12% by weight, preferably 9.5 to 11.5% by weight
- the titanium from 18 to 22 %
- 20 to 22% by weight of sodium from 18 to 22% by weight, preferably 20 to 22% by weight of the aluminum of 0.5 to 3.2% by weight, preferably 2.8 to 3.2% by weight of the lithium from 3.5 to 4.2% by weight is preferred 3.8 to 4.2% by weight of boron from 5 to 8% by weight, preferably 6.5 to 8% by weight of the zircon from 0.05 to 3% by weight, preferably from 2.3 to 3 %
- the zinc from 0.8 to 2.0% by weight, preferably 0.8 to 1.5 %
- the magnesium from 1 to 1.5% by weight,
- Enamel coatings which are used as frit with additives on the Applied and by heat treatment or baking in a substrate
- the enamel coating in turn, for example, from a mixture of oxides are generated in the specified proportions.
- the oxides usually lie as a frit, i.e. as a mixture that was ground in front. This frit can in turn be used with processing aids such as for example boric acid, sodium metasilicate, potassium hydroxide, titanium dioxide and pigments are added.
- Typical example of a frit composition contains: 100 parts frit, about 4 parts boric acid, one Part with sodium metasilicate, part with potassium hydroxide, five to fifteen Parts of titanium dioxide and one to seven parts of pigment.
- the enamelling can, for example comprise a layer, a layer of a frit composition is applied to the substrate surface and in one firing process branded, i.e. is transferred into the enamel coating.
- Further methods are also within the scope of the invention, according to which two Layers in two burns, three layers in three burns resp. multiple layers can be applied in multiple firing processes. Other methods of applying enamel layers are by applying of two or more frit layers or frit compositions with just one burn.
- the frit can be, for example, a medium one Grain size of less than 74 microns and suitably less than 44 microns.
- the frit can be sprinkled, sprayed, dipped or Slurries are applied. Electrostatic is another option Spraying or electrophoresis. Occasionally, the frit, if it was applied with a suspension aid such as water, be dried. After drying, the coated substrate can be in a furnace, the combustion process being continuous or can be done gradually. Typical burning times are between 3 and 10 minutes, with burn times between 3 and 6 minutes preferred will. Typical firing temperatures are between 480 and 560 ° C. All procedures can be carried out step by step or continuously will.
- Oxide layers represent a substrate which is used for an enamel coating is particularly suitable since the wetting by the components of the Enamel coating in particular during the baking process is pronounced and thus the use of frits with lower Melting point, i.e. with a melting point of up to 20, for example ° C below the usual range.
- the substrates according to the present invention with the enamel coatings have an extremely smooth surface. Thanks to the enamel coating is the substrate against mechanical, physical, chemical and actinic Influences and, for example, largely protected against environmental influences.
- the surface is smooth, shiny and extremely hard.
- the smooth surface can, for example, dirt, dyes, solvent-based Dyes or in a carrier medium Dyes do not penetrate pores and the appearance of the surface change or deface. The great hardness of the surface protects against Abrasion and other mechanical influences.
- substrates with an enamel coating are suitable, for example in building construction as facade panels for indoor and outdoor applications, as an outer layer on composite panels for facades or for interior work, as cladding panels or body parts for vehicles, such as Railway wagons, buses and other road and rail vehicles and for Corrosive atmosphere applications. They are also suitable substrates coated with enamel according to the present invention for furniture in public areas such as poster pillars, letter boxes, Vending machine boxes and the like, e.g. due to vandalism an increased Are at risk.
- the enamel coatings on the inventive can have such a smooth surface show that just by weathering a strong self-cleaning of the enamel coated substrates.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Glass Compositions (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Description
Claims (14)
- Aluminiumhaltiges Substrat für Emailbeschichtungen, enthaltend wenigstens auf den für eine Emailbeschichtung vorgesehenen Flächen eine Oberflächenschicht aus Aluminium oder einer Aluminiumlegierung und unmittelbar auf dieser Oberflächenschicht eine porenfreie Oxidschicht, die eine isotrope Sperrschicht einer Dicke von 0,01 bis 0,5 µm mit einer Dielektrizitätskonstanten zwischen 5 und 10 darstellt.
- Aluminiumhaltiges Substrat nach Anspruch 1, wobei die Dichte der isotropen Sperrschicht zwischen 2,5 und 3,8 g/cm3 beträgt.
- Aluminiumhaltiges Substrat nach Anspruch 1, wobei die isotrope Sperrschicht eine Dielektrizitätskonstante zwischen 8,5 und 10 aufweist.
- Aluminiumhaltiges Substrat nach Anspruch 1, wobei die Oberflächenschicht eine Aluminiumknetlegierung darstellt.
- Aluminiumhaltiges Substrat nach Anspruch 4, wobei die Aluminiumknetlegierung bis zu 1,5 Gew.-% Silicium, bis zu 1,0 Gew.-% Eisen, bis zu 4,0 Gew.-% Kupfer, bis zu 1,5 Gew.-% Mangan, bis zu 6,0 Gew.-% Magnesium, bis zu 7,0 Gew.-% Zink, bis zu 0,2 Gew.-% Titan und bis zu 1,6 Gew.-% andere Elemente, Rest Aluminium, enthält.
- Aluminiumhaltiges Substrat nach Anspruch 4, wobei die Oberflächenschicht eine Aluminiumknetlegierung darstellt, enthaltend 0,25 bis 1,5 Gew.-% Silicium, bis zu 0,3 Gew.-% Eisen, bis zu 0,25 Gew.-% Kupfer, 0,1 bis 0,8 Gew.-% Mangan, 2,7 bis 5,0 Gew.-% Magnesium, bis zu 1,0 Gew.-% Zink, 0,01 bis 0,2 Gew.-% Titan, bis 0,2 Gew.-% Chrom und bis zu 1,5 Gew.-% andere Elemente, Rest Aluminium.
- Aluminiumhaltiges Substrat nach Anspruch 1, wobei die Oberflächenschicht eine Aluminiumgusslegierung darstellt.
- Aluminiumhaltiges Substrat nach Anspruch 7, wobei die Aluminiumlegierungen bis zu 11,0 Gew.-% Silicium, bis zu 1,0 Gew.-% Eisen, bis zu 5,2 Gew.-% Kupfer, bis zu 0,5 Gew.-% Mangan, bis zu 7,5 Gew.-% Magnesium, bis zu 10 Gew.-% Zink, bis zu 0,3 Gew.-% Titan, bis zu 1,2 Gew.-% Nickel, bis zu 0,03 Gew.-% Blei, bis zu 0,03 Gew.-% Zinn und bis zu 0,05 Gew.-% andere Elemente, Rest Aluminium, enthalten.
- Verfahren zur Herstellung eines aluminiumhaltigen Substrates für Emailbeschichtungen gemäss Anspruch 1, in dem
die Oxidschicht gemäß Anspruch 1 wenigstens an den für die Emailbeschichtung vorgesehenen Bereichen mittels anodischer Oxidation in einem Elektrolyten mit einem pH-Wert im Bereich zwischen 5 und 7 im Temperaturbereich von 30 bis 80 °C gebildet wird, wobei bei der anodischen Oxidation die Oberflächenschicht aus Aluminium oder einer Aluminiumlegierung oder wenigstens der für die Emailbeschichtung vorgesehene Bereich in einen Elektrolyten gegeben wird, und zwischen der Oberflächenschicht und einer zweiten, im selben Elektrolyten befindlichen Elektrode eine Spannung angelegt wird. - Verfahren nach Anspruch 9, in dem anodische Oxidation bei einer angelegten Spannung bis zu 600 V und einer Stromdichte bis zu 120 A/m2 durchgeführt wird.
- Verfahren nach Anspruch 10, in dem die anodische Oxidation solange durchgeführt wird, bis nach erfolgter Anlegung der Maximalspannung die Stromdichte auf einen Wert zwischen 1 und 10 A/m2 gefallen ist.
- Verwendung des Erzeugnisses nach Anspruch 1 als Substrat für Emailbeschichtungen mit einem Schmelzpunkt von 480 °C bis zum Schmelzpunkt des Substrates.
- Verwendung des Erzeugnisses nach Anspruch 1 als Substrat für Emailbeschichtungen, enthaltend die Oxide des Siliciums in Mengen von 27 bis 33 Gew.-%, bevorzugt 30 Gew.-%, des Kaliums von 9 bis 12 Gew.-%, bevorzugt 9,5 bis 11,5 Gew.-%, des Titans von 18 bis 22 Gew.-%, bevorzugt 20 bis 22 Gew.-%, des Natriums von 18 bis 22 Gew.-%, bevorzugt 20 bis 22 Gew.-%, des Aluminiums von 0,5 bis 3,2 Gew.-%, bevorzugt 2,8 bis 3,2 Gew.-%, des Lithiums von 3,5 bis 4,2 Gew.-%, bevorzugt 3,8 bis 4,2 Gew.-%, des Bors von 5 bis 8 Gew.-%, bevorzugt 6,5 bis 8 Gew.-%, des Zirkons von 0,05 bis 3 Gew.-%, vorzugweise von 2,3 bis 3 Gew.-%, des Zinks von 0,8 bis 2,0 Gew.-%, vorzugsweise 0,8 bis 1,5 Gew.-%, und gegebenenfalls eines oder mehrere der Oxide des Magnesiums von 1 bis 1,5 Gew.-%, des Cadmiums von 0 bis 5 Gew.-%, des Antimons von 0 bis 2,8 Gew.-%, des Strontiums von 0 bis 1,5 Gew.-% und des Phosphors von 0 bis 2,5 Gew.-%.
- Verwendung des Erzeugnisses nach Anspruch 1 als Substrat für Emailbeschichtungen, die als Fritte mit Zusätzen auf das Substrat aufgebracht und durch Wärmebehandlung in eine Emailbeschichtung einer Dicke von 50 bis 200 µm, bevorzugt 50 bis 120 µm, und insbesondere 70 bis 100 µm, übergeführt wird.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH308193 | 1993-10-13 | ||
CH3081/93 | 1993-10-13 | ||
CH308193A CH686374A5 (de) | 1993-10-13 | 1993-10-13 | Emaillierbare Oxidschicht. |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0648863A1 EP0648863A1 (de) | 1995-04-19 |
EP0648863B1 true EP0648863B1 (de) | 1998-01-14 |
EP0648863B2 EP0648863B2 (de) | 2001-05-02 |
Family
ID=4248209
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94810572A Expired - Lifetime EP0648863B2 (de) | 1993-10-13 | 1994-09-30 | Emaillierbare Oxidschicht |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0648863B2 (de) |
AT (1) | ATE162234T1 (de) |
CH (1) | CH686374A5 (de) |
DE (1) | DE59405021D1 (de) |
DK (1) | DK0648863T5 (de) |
ES (1) | ES2112505T5 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20210073708A (ko) * | 2019-12-10 | 2021-06-21 | 김준수 | 에나멜 코팅용 알루미늄 합금 및 다이캐스팅법에 의해 제조된 알루미늄 합금 프라이팬의 제조방법 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2585273B1 (fr) * | 1985-07-24 | 1988-05-13 | Daussan & Co | Revetement pour proteger l'interieur d'un recipient metallurgique et procede pour realiser ce revetement |
DE69939474D1 (de) | 1999-11-23 | 2008-10-16 | Pemco Brugge Nv | Emaillierung von Aluminiumlegierungsoberflächen |
CN102575413B (zh) * | 2009-10-09 | 2015-09-16 | Bsh家用电器有限公司 | 特别是用于蒸汽熨斗的熨斗基底 |
DE102009045522A1 (de) * | 2009-10-09 | 2011-04-14 | BSH Bosch und Siemens Hausgeräte GmbH | Bügeleisensohle, insbesondere für ein Dampfbügeleisen |
ES2390028B1 (es) * | 2011-04-08 | 2013-10-21 | BSH Electrodomésticos España S.A. | Procedimiento para recubrir una superficie de aluminio de un elemento de aluminio, elemento de aluminio y suela de plancha de aluminio |
CN115177385B (zh) * | 2022-07-15 | 2023-08-22 | 成都贝施美生物科技有限公司 | 一种类天然牙根色的种植体 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0611834A1 (de) * | 1993-02-18 | 1994-08-24 | Alusuisse-Lonza Services Ag | Aluminiumhaltiges Substrat für Emailbeschichtungen |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR440516A (fr) * | 1911-05-05 | 1912-07-12 | Paul Auguste Felix De Saint Ma | Aluminium oxyde en couche profonde, procédé d'obtention de cet oxyde d'aluminium et application de cet aluminium oxyde et nu comme conducteur électrique isolé |
US2991234A (en) * | 1958-08-11 | 1961-07-04 | Croname Inc | Enameled aluminum and process for manufacture thereof |
JPS63270482A (ja) * | 1987-04-28 | 1988-11-08 | Nisshin Steel Co Ltd | アルミめつきホ−ロ−鋼板 |
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1993
- 1993-10-13 CH CH308193A patent/CH686374A5/de not_active IP Right Cessation
-
1994
- 1994-09-30 EP EP94810572A patent/EP0648863B2/de not_active Expired - Lifetime
- 1994-09-30 ES ES94810572T patent/ES2112505T5/es not_active Expired - Lifetime
- 1994-09-30 DK DK94810572T patent/DK0648863T5/da active
- 1994-09-30 AT AT94810572T patent/ATE162234T1/de not_active IP Right Cessation
- 1994-09-30 DE DE59405021T patent/DE59405021D1/de not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0611834A1 (de) * | 1993-02-18 | 1994-08-24 | Alusuisse-Lonza Services Ag | Aluminiumhaltiges Substrat für Emailbeschichtungen |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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KR20210073708A (ko) * | 2019-12-10 | 2021-06-21 | 김준수 | 에나멜 코팅용 알루미늄 합금 및 다이캐스팅법에 의해 제조된 알루미늄 합금 프라이팬의 제조방법 |
Also Published As
Publication number | Publication date |
---|---|
DE59405021D1 (de) | 1998-02-19 |
CH686374A5 (de) | 1996-03-15 |
DK0648863T3 (da) | 1998-09-14 |
ES2112505T3 (es) | 1998-04-01 |
EP0648863B2 (de) | 2001-05-02 |
EP0648863A1 (de) | 1995-04-19 |
ES2112505T5 (es) | 2001-07-01 |
ATE162234T1 (de) | 1998-01-15 |
DK0648863T5 (da) | 2001-01-29 |
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