EP0648863B2 - Emaillierbare Oxidschicht - Google Patents
Emaillierbare Oxidschicht Download PDFInfo
- Publication number
- EP0648863B2 EP0648863B2 EP94810572A EP94810572A EP0648863B2 EP 0648863 B2 EP0648863 B2 EP 0648863B2 EP 94810572 A EP94810572 A EP 94810572A EP 94810572 A EP94810572 A EP 94810572A EP 0648863 B2 EP0648863 B2 EP 0648863B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminium
- enamel
- layer
- aluminum
- weight
- 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
- 239000010410 layer Substances 0.000 claims abstract description 63
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 239000002320 enamel (paints) Substances 0.000 claims abstract description 32
- 239000002344 surface layer Substances 0.000 claims abstract description 18
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 17
- 230000004888 barrier function Effects 0.000 claims abstract description 12
- 239000004411 aluminium Substances 0.000 claims abstract 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 210000003298 dental enamel Anatomy 0.000 abstract description 17
- 239000003792 electrolyte Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- -1 pH value Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- 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 the use of an aluminum-containing substrate for enamel coatings containing at least on the areas intended for an enamel coating a surface layer of aluminum or one Aluminum alloy and on this surface layer an oxide layer.
- Aluminum materials such as foils, Strips or sheets are used, for example, for facade and vehicle construction used as cover plates.
- cover plates are usually anodized to to be resistant to environmental influences.
- Magazine “Aluminum” 54th year, 1978, number 8, pages 527 and 528, W. Grosskopf, “Overview of application and carrying out the enamelling of aluminum” is the enamelling of pure aluminum strips up to 0.3 mm thick. It was found, that not every aluminum material can be enamelled, and especially magnesium-containing aluminum alloys are unsuitable for enamelling.
- the object of the present invention is a substrate to make that available for the application with an enamel layer.
- Aluminum-containing substrates are, for example, sheet-like Substrates made of aluminum or its alloys. Examples are foils, strips, sheets or Profiles.
- the substrates can also be any body Build with an aluminum surface or be aluminum-containing surface.
- Other substrates are composite materials that have at least one top layer made of aluminum or an aluminum alloy consist. Foils, tapes are preferred or sheets of aluminum or aluminum alloys applied.
- the isotropic barrier layer can overlap the whole area of aluminum or aluminum alloy extend or can at least at the points be provided on which the enamel coating to be applied.
- the isotropic barrier layer provides a non-porous one Oxide layer and has a high temperature resistance as well as one versus aluminum or aluminum alloys increased chemical resistance.
- Enamel layers generally show good results on oxides Liability. Through time and temperature dependent diffusion processes can on the one hand be part of the Enamel layer and on the other hand also components of the aluminum-containing substrate, such as metallic Alloy components or impurities, get into the oxide layer and form a layer, which does not adhere well to the enamel layer Guaranteed aluminum-containing substrate.
- Such components (Detention inhibitors) that reduce adhesion and thus, for example, spalling problems of the Enamel layer can, for example Copper or magnesium.
- the diffusion of such adhesion inhibitors into the oxide layer, the high baking temperature because of, essentially during Firing process of the enamel coating.
- 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 can be used as the aluminum-containing substrate with a surface layer made of pure aluminum, containing essentially aluminum and the commercially available Impurities or aluminum alloys be applied.
- Aluminum substrates can, for example an aluminum with 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 commercially available Contain impurities.
- Wrought aluminum alloys are preferred for the substrates. These alloys include e.g. the guys AlMg, AlMgSi, AlCuMg and AlZnMg.
- Wrought aluminum alloys can, for example 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 Manganese, up to 6.0% by weight magnesium, up to 7.0 % By weight zinc, up to 0.2% by weight titanium and up to 1.6 % By weight of other elements, balance aluminum.
- Especially substrates made of an aluminum alloy are preferred, containing 0.25 to 1.5 wt .-% silicon, up to 0.3% by weight iron, up to 0.25% by weight copper, 0.1 to 0.8% by weight of manganese, 2.7 - 5.0% by weight of magnesium, to 1% by weight zinc, 0.01 to 0.2% by weight titanium, up to 0.2 Wt% chromium, and up to 1.5 wt% other elements, Rest aluminum.
- Examples from the practice of substrates are aluminum alloys AlMg3, AlMg3Si, AlMg5, AlMg5Si and AlMg10.
- Aluminum casting alloys are also preferred for the substrates. These alloys include e.g. the types: AlSi, AlSiMg, AlSiCuMg, AlMgSi-CuMg, AlMgSi and AlZnMg. Of these types are in turn particularly preferably aluminum casting 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 magnesium, up to 10% by weight Zinc, up to 0.3% by weight titanium, up to 1.2% by weight nickel, up to 0.03% by weight of lead, up to 0.03% by weight of tin and up to 0.05% by weight of other elements, balance aluminum.
- AlSi, AlSiMg, AlSiCuMg, AlMgSi-CuMg, AlMgSi and AlZnMg Of these types are in turn particularly preferably aluminum casting alloys containing: Up to 11.0% by weight silicon, up to 1.0% by weight Iron, up
- the substrates can only use these aluminum or aluminum-containing surface layer and on top of it Surface layer, at least partially, according to the invention
- Oxide layer or e.g. in the sense of a composite or a laminate layers containing aluminum or layers of others Materials arranged on the back of the surface layer be while the oxide layer according to the invention is arranged on the front.
- the aluminum or aluminum-containing surface layer must be analogous are on the surface so that the inventive Oxide layer on it appropriately resp. can be attached to it.
- the inventive The oxide layer then forms the. outside exposed layer for further coating with the enamel layer.
- the manufacturing process is carried out such that the oxide layer at least on the enamel coating Areas by means of anodic oxidation (anodizing) in an electrolyte with a pH in the range between 5 and 7 in the temperature range from 30 to 80 ° C is formed, the anodic oxidation Surface layer made of aluminum or an aluminum alloy or at least that for the enamel coating intended area in an electrolyte is given, and between the surface layer and a second one located in the same electrolyte A voltage is applied to the electrode.
- anodic oxidation anodizing
- the production process used in practice the oxide layer essentially runs such that the substrate and especially the one with enamel Coating surface made of aluminum or one Pretreated aluminum alloy the surface is degreased first, then rinsed and finally pickling, the pickling for example with a sodium hydroxide solution in one Concentration from 50 to 200 g / l at 40 to 60 ° during one to ten minutes can be done. Subsequently can be rinsed and cleaned with a Acid such as Nitric acid, especially a concentration from 25 to 35% by weight in the room temperature range typically 20 - 25 ° C during 20 - Neutralized for 60 s, rinsed again and if necessary be dried.
- a Acid such as Nitric acid
- the properties of the oxide layer formed depend largely from the electrolysis conditions such as for example electrolyte composition, pH value, Electrolyte temperature, applied voltage and the Electrolysis current.
- electrolysis conditions such as for example electrolyte composition, pH value, Electrolyte temperature, applied voltage and the Electrolysis current.
- an acidic Electrolyte forms an oxide layer, which is essentially a non-porous base or barrier layer and one contains porous outer layer.
- anodic Oxidation in acidic electrolytes forms on the A non-porous base or barrier layer and at the same time that during the anodic Oxidation formed oxide layer on the outside partly chemical due to field-induced redissolving dissolved again.
- the thickness of the oxide layer reached their upper limit when there is growth and solution balance what of the electrolyte composition, depends on the current density and the temperature.
- pH-neutral or approximately pH-neutral electrolyte the oxide is not or only very slightly redissolved during the electrolysis process and no pores are formed.
- solutions which have a pH in the range between 5 and 7 are referred to as pH-neutral or approximately pH-neutral electrolytes.
- 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.
- asymmetrical AC types can for example sinusoidal alternating current with a Voltage / time curve with unevenly high Amplitudes in the positive and negative part, more rectangular AC with a voltage / time curve with equally high amplitudes and unequal lengths of time of the positive and negative part, more rectangular AC with a voltage / time curve with unequal amplitudes in the positive and negative Area or rectangular alternating current with a Voltage / time curve with unequal amplitudes and unequal time shares of positive and negative Partly applied.
- sinusoidal AC curves with leading edge in positive and negative part and also other asymmetrical Alternating currents with interrupted current flow are used, 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 depends on the voltage and is in the range between 10 and 16 ⁇ / V and especially between 11 and 15 ⁇ / V.
- the Oxide layer can have a slight on its free surface Contain concentration of ions. This ion concentration is essentially due to the electrolyte is determined and is therefore on the outer surface area the oxide layer limited.
- the inventive The oxide layer is particularly poor in Magnesium and prevents during and after baking the enamel coating a further diffusion of magnesium from the surface layer.
- the substrate or the treated surface of further treatments such as. Rinsing or impregnation.
- Such post-treatment without rinsing represents, for example, the impregnation of the oxide surface with a flux.
- a flux can Compounds or ions contained in the enamel are very easily soluble and therefore, for example, one cause better enamel anchoring 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 brought about by the application of a corresponding Flux supported. You can also Flux increase the wettability of the oxide surface and / or lower the melting point of the enamel frit.
- the substrate is according to the present invention for enamel coatings with a melting point of 480 ° C to the melting point or near the melting point of the substrate used. With will be close to the melting point for example temperatures between 20 or 10 ° C below the melting point. Appropriately becomes the product as a substrate for enamel coatings based on alkali-silico-titanates, if necessary with baking temperature-reducing additives, e.g. the compounds, such as oxides, lithium, barium, Antimons, cadmiums, bismuths or vanadiums applied.
- the compounds such as oxides, lithium, barium, Antimons, cadmiums, bismuths or vanadiums applied.
- the present invention relates the present 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 from 9 to 12% by weight, preferably 9.5 to 11.5% by weight, of the titanium from 18 to 22% by weight, preferably 20 to 22 %
- sodium from 18 to 22% by weight is preferred 20 to 22% by weight of aluminum from 0.5 to 3.2% by weight, preferably 2.8 to 3.2% by weight of the lithium of 3.5 to 4.2% by weight, preferably 3.8 to 4.2% by weight, of the boron from 5 to 8% by weight, preferably 6.5 to 8% by weight, of the Zircons from 0.05 to 3% by weight, preferably from 2.3 to 3% by weight of the zinc from 0.8 to 2.0% by weight, preferably 0.8 to 1.5% by weight of the magnesium from 1 to 1.5% by weight of the cadmium from 0 to 5% by weight of the Antimons from 0 to 2.6% by
- Enamel coatings which are used as frit, are preferred applied to the substrate with additives and through Heat treatment or baking in an enamel coating a thickness of 50 to 200 microns, preferred from 50 to 120 ⁇ m and in particular 70 to 100 ⁇ m, be transferred.
- the enamel coating on your part can, for example, from a mixture of oxides in the specified proportions are generated.
- the oxides are usually fritted, i.e. as Mixture that was ground. This frit can in turn with processing aids such as 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, a portion of potassium hydroxide, five to fifteen Parts of titanium dioxide and one to seven parts of pigment.
- Coloring pigments can be used in the enamelling be applied.
- the enamelling can, for example comprise a layer, one layer a frit composition on the substrate surface is applied and burned in one burning process, 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 firing processes, three layers in three firing processes respectively. multiple layers applied in multiple firing processes become.
- Other methods of application of enamel layers consists of applying two or further frit layers or frit compositions with just one burn.
- the frit can for example an average grain size of less than 74 ⁇ m and suitably less than 44 ⁇ m.
- the frit can be sprinkled, sprayed, dipped or slurries are applied. More options are electrostatic spraying or electrophoresis. In some cases, the frit, provided that it is Suspension aids such as water applied was dried. After drying can the coated substrate is placed in an oven, the combustion process being continuous or gradual can be done. Typical burning times are in the Range between 3 and 10 minutes, with burning times between 3 and 6 minutes are preferred. Typical Firing temperatures are between 480 and 560 ° C. All procedures can be gradual or continuous be performed.
- the surface layer and the oxide layer arranged above constitutes a substrate which is particularly suitable for an enamel coating is suitable because the wetting by the components the enamel coating during the baking process is particularly pronounced and thereby the use of fries with lower Melting point, i.e. with a melting point of, for example up to 20 ° C below the usual range, is made possible.
- the substrates according to the present invention with the Enamel coatings have an extremely smooth surface on.
- the substrate is through the enamel coating against mechanical, physical, chemical and actinic influences and, for example, against environmental influences largely protected.
- the surface is smooth, shiny and of great hardness. Because of the smooth Surface can, for example, dirt, dyes, solvent-based dyes or in a carrier medium Any dyes found do not penetrate pores and change or deface the appearance of the surface.
- the great hardness of the surface protects against Abrasion and other mechanical influences.
- substrates with an enamel coating are suitable, for example, in facade construction as facade panels for indoor and outdoor applications, as an outer layer on composite panels for facades or for the Interior, as cladding panels or body parts for vehicles such as railroad cars, buses and other road and rail vehicles and for applications in areas of corrosive atmosphere.
- the substrates coated with enamel are suitable according to the present invention for furniture in public Areas such as poster pillars, post boxes, vending machines and the like, e.g. through vandalism are exposed to an increased risk.
- the Enamel coatings on the inventive can be so smooth Have surface that just by weathering a strong self-cleaning of the email-coated Substrates.
Landscapes
- 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)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH308193A CH686374A5 (de) | 1993-10-13 | 1993-10-13 | Emaillierbare Oxidschicht. |
CH308193 | 1993-10-13 | ||
CH3081/93 | 1993-10-13 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0648863A1 EP0648863A1 (de) | 1995-04-19 |
EP0648863B1 EP0648863B1 (de) | 1998-01-14 |
EP0648863B2 true 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 (es) |
AT (1) | ATE162234T1 (es) |
CH (1) | CH686374A5 (es) |
DE (1) | DE59405021D1 (es) |
DK (1) | DK0648863T5 (es) |
ES (1) | ES2112505T5 (es) |
Families Citing this family (7)
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 |
DE102009045522A1 (de) * | 2009-10-09 | 2011-04-14 | BSH Bosch und Siemens Hausgeräte GmbH | Bügeleisensohle, insbesondere für ein Dampfbügeleisen |
RU2535274C2 (ru) * | 2009-10-09 | 2014-12-10 | Бсх Бош Унд Сименс Хаусгерете Гмбх | Подошва утюга, в частности парового утюга |
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 |
KR102273220B1 (ko) * | 2019-12-10 | 2021-07-05 | 김준수 | 에나멜 코팅용 알루미늄 합금 및 다이캐스팅법에 의해 제조된 알루미늄 합금 프라이팬의 제조방법 |
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 |
Family Cites Families (4)
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 |
CH687989A5 (de) * | 1993-02-18 | 1997-04-15 | Alusuisse Lonza Services Ag | Aluminiumhaeltiges Substrat. |
-
1993
- 1993-10-13 CH CH308193A patent/CH686374A5/de not_active IP Right Cessation
-
1994
- 1994-09-30 ES ES94810572T patent/ES2112505T5/es not_active Expired - Lifetime
- 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
- 1994-09-30 EP EP94810572A patent/EP0648863B2/de not_active Expired - Lifetime
- 1994-09-30 DK DK94810572T patent/DK0648863T5/da active
Non-Patent Citations (8)
Title |
---|
B. Castel: "Les alumines et leurs applications", 1990, Aluminium Pechiney/Techno-Nathan, Seiten 51 und 56 † |
G.E. Thompson et al: "Anodic films on aluminium" in G.C. Sculley: "Corrosion: Aqueous process and passive films", 1983, Academic Press, New York(US), Seite 229 † |
L. Young: "Anodic Oxide Films", 1961, Academic Press, New York(US), Seiten 211-218 † |
P. Barrand et al: "L'aluminium", Band 2, 1964, Editions Eyrolles, Paris (FR), Seiten 617 und 676-679 † |
R. Irmann: "Aluminiumguss in Sand und Kokille" 6.Auflage, 1959, Aluminium-Verlag GmbH, Düsseldorf(DE), Seiten 215-216 † |
R.C. Weast: "Handbook of chemistry and physics" 53.Auflage, 1972-1973, CRC Press, Cleveland(US), Seite E-48 † |
S. Wernick et al:"The surface treatment and finishing of aluminium and its alloys"3. Auflage, 1964, Robert Draper Ltd., Teddington (GB), Seiten 260-266 † |
W Hufnagel: "Aluminium-Taschenbuch", 14.Auflage, 1983, Aluminium-Verlag GmbH, Düsseldorf(DE), Seite 748 † |
Also Published As
Publication number | Publication date |
---|---|
ES2112505T3 (es) | 1998-04-01 |
EP0648863A1 (de) | 1995-04-19 |
ES2112505T5 (es) | 2001-07-01 |
EP0648863B1 (de) | 1998-01-14 |
DE59405021D1 (de) | 1998-02-19 |
DK0648863T5 (da) | 2001-01-29 |
ATE162234T1 (de) | 1998-01-15 |
DK0648863T3 (da) | 1998-09-14 |
CH686374A5 (de) | 1996-03-15 |
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