EP1301656A1 - Verfahren zur oberflächenbehandlung von aluminium oder aluminium-legierungen mittels alkansulfonsäurehaltigen formulierungen - Google Patents
Verfahren zur oberflächenbehandlung von aluminium oder aluminium-legierungen mittels alkansulfonsäurehaltigen formulierungenInfo
- Publication number
- EP1301656A1 EP1301656A1 EP01960487A EP01960487A EP1301656A1 EP 1301656 A1 EP1301656 A1 EP 1301656A1 EP 01960487 A EP01960487 A EP 01960487A EP 01960487 A EP01960487 A EP 01960487A EP 1301656 A1 EP1301656 A1 EP 1301656A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminum
- acid
- electrolyte
- weight
- alkanesulfonic
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
- C25D11/22—Electrolytic after-treatment for colouring layers
Definitions
- the invention relates to a process for the surface treatment of aluminum or aluminum alloys by anodic oxidation of aluminum or aluminum alloys (anodization) and the use of an alkanesulfonic acid in a process for the anodic oxidation of aluminum or aluminum alloys, an electrolyte composition for the anodic oxidation of Aluminum or aluminum alloys and the use of the workpieces based on aluminum or aluminum alloys produced by the method according to the invention.
- Corrosion resistance can be increased by reinforcing the natural oxide skin using chemical or electrochemical processes.
- the reinforced oxide layer is absorbent so that it can be colored with water-soluble dyes or dye precursors.
- the oxide surfaces for paint coatings offer an excellent base for adhesion, and the abrasion resistance of workpieces is increased by anodic surface oxidation.
- the surface oxidation of the aluminum surface or the surface of aluminum alloys can be carried out chemically by dipping the workpieces in solutions of weakly attacking agents or by chromating and phosphating.
- anodic oxidation by electrochemical means is more advantageous since thicker oxide coatings are obtained than by chemical treatment.
- the most frequently used processes use sulfuric acid (S), oxalic acid (X) or chromic acid solutions as electrolytes.
- S sulfuric acid
- X oxalic acid
- chromic acid solutions as electrolytes.
- S sulfuric acid
- X oxalic acid
- WS or WX process alternating current
- the layer thickness of the oxide layer is approximately 10 to 30 ⁇ m in these processes.
- hard anodizing At low temperatures (up to approx. + 10 ° C, preferably 2 to 3 ° C), high current densities (up to 2.5 A / dm) and generally low sulfuric acid concentrations (up to approx. 10% by weight), optionally in a mixture with phosphoric acid, very hard, abrasion-resistant oxide layers are obtained (hard anodizing).
- a layer thickness of the oxide layer of> 50 ⁇ m can be achieved.
- workpieces obtained by hard anodizing are used in particular for die-cast aluminum parts, e.g. used for engine construction.
- There is a maximum achievable layer thickness which, for example, is approximately 45 ⁇ m in the GS process. At this maximum layer thickness, the rate of dissolution of the aluminum oxide is equal to its rate of formation.
- the object of the present invention is to provide an anodizing method for aluminum or aluminum alloys which is faster than the conventional methods of the prior art and which, moreover, is said to have better current efficiency, that is to say also lower energy losses through cooling.
- This process is said to be suitable both for anodization by means of immersion and for continuous anodization, for example of strips or wires by means of an electrolytic pulling process.
- the method is intended for a Hard anodization enables greater maximum layer thicknesses to be achieved than is possible with the methods of the prior art, for example with the GS method.
- This object is achieved on the basis of a process for the surface treatment of aluminum or aluminum alloys by anodic oxidation of the aluminum or aluminum alloys (anodization) in an electrolyte.
- the electrolyte contains 3 to 30% by weight of an alkanesulfonic acid.
- the electrolyte preferably contains 10 to 30% by weight, particularly preferably 10 to 25% by weight, of an alkanesulfonic acid.
- the electrolyte can contain further acids, in particular selected from sulfuric acid, phosphoric acid and oxalic acid.
- the electrolyte contains sulfuric acid in addition to an alkanesulfonic acid.
- an electrolyte based exclusively on an alkanesulfonic acid is used.
- alkanesulfonic acids in the surface treatment of aluminum or aluminum alloys is already known from the prior art.
- these known processes essentially relate to the use of alkanesulfonic acids in the electrolytic metal salt coloring of aluminum, in which an alkanesulfonic acid is used as an additive or as the base of an acidic electrolytic solution, and not to the use of alkanesulfonic acids in the anodic oxidation (anodization) of aluminum or an aluminum alloy.
- No. 4,128,460 relates to a process for coloring aluminum or aluminum alloys by electrolysis, comprising the anodization of the aluminum or aluminum alloys using customary methods and the subsequent electrolysis in a bath, which comprises an aliphatic sulfonic acid and a metal salt, in particular a tin salt. , Copper, lead or silver salt containing sulfonic acid.
- a bath which comprises an aliphatic sulfonic acid and a metal salt, in particular a tin salt. , Copper, lead or silver salt containing sulfonic acid.
- the stability of the electrolysis bath is increased by an increased oxidation stability of the metal salts used and a uniform coloring of the surface of the aluminum or the aluminum alloys.
- BR 9501255-9 Only in BR 9501255-9 are special reaction conditions for anodizing the surface of aluminum disclosed, mentioning the use of methanesulfonic acid as an additive in an electrolyte based on sulfuric acid. Methanesulfonic acid is contained therein in an amount of 10 parts by weight in relation to sulfuric acid, i.e. less than 2 wt .-% of the electrolyte used. A further reference to the use of alkanesulfonic acids in the anodizing step or advantages of such an use are not disclosed in BR 9501255-9.
- anodizing takes place more quickly than with the methods of the prior art.
- a subsequent electrolytic coloring of the anodized surface since in such a two-stage process, comprising anodizing and subsequent coloring of the anodized surface, anodizing is the rate-determining step.
- it is 5 to 50 times slower than the subsequent coloring.
- Increasing the speed of the anodizing step thus leads to a more economical implementation of the method, since higher throughputs per unit of time can be achieved in this way.
- the electrolysis time to achieve an optimum aluminum oxide layer thickness for a subsequent dyeing step of generally 10 to 30 ⁇ m, preferably 15 to 25 ⁇ m, is generally 5 to 40 minutes, preferably 10 to 30 minutes, the exact time being dependent, inter alia, on the current density is dependent.
- alkanesulfonic acids have a significantly less corrosive effect on the aluminum oxide layer formed during the anodization than, for example, the sulfuric acid usually used. It is thus possible to achieve greater layer thicknesses in a shorter time with the method according to the invention, in particular with hard anodizing, than with the methods of the prior art.
- Another great advantage of the method according to the invention is the significantly lower energy consumption during anodizing, since a voltage that is significantly lower than that of pure sulfuric acid electrolytes is obtained at the same current strength. This also has the consequence that the energy required to cool the anodizing bath is significantly lower.
- the method according to the invention is suitable both for anodizing aluminum or aluminum alloys by means of the electro-immersion method and for continuous anodizing, for example of strips, tubes or wires, by means of an electrolytic pull-through method, e.g. for the production of aluminum sheet for the production of cans.
- the method according to the invention can be operated both with direct current and with alternating current, the method is preferably operated with direct current.
- the electrolyte can contain further acids, for example sulfuric acid, phosphoric acid or oxalic acid.
- the electrolyte contains either the only acid an alkanesulfonic acid or a mixture of sulfuric acid and alkanesulfonic acid.
- the electrolyte preferably contains 20 to 100 parts by weight of an alkanesulfonic acid and 80 to 0 parts by weight of a further acid selected from sulfuric acid, phosphoric acid or oxalic acid, the sum of alkanesulfonic acid and sulfuric acid, phosphoric acid or oxalic acid being 100 parts by weight and makes up a concentration of 3 to 30 wt .-% of the electrolyte.
- the electrolyte particularly preferably contains 20 to 90 parts by weight of an alkanesulfonic acid and 80 to 10 parts by weight of sulfuric acid.
- the use of alkanesulfonic acid as the only acid in the electrolyte is also possible.
- Alkanesulfonic acids for the purposes of the present invention are understood to mean aliphatic sulfonic acids. Their aliphatic radicals can optionally be substituted with functional groups or heteroatoms, for example hydroxyl groups. Alkanesulfonic acids of the general formulas are preferred
- R is a hydrocarbon radical which can be branched or unbranched, having 1 to 12 carbon atoms, preferably having 1 to 6 carbon atoms, particularly preferably an unbranched hydrocarbon radical having 1 to 3 carbon atoms, very particularly preferably having 1 carbon atom, that is to say methanesulfonic acid.
- R is a hydrocarbon test which can be branched or unbranched, having 2 to 12 carbon atoms, preferably having 2 to 6 carbon atoms, particularly preferably an unbranched hydrocarbon radical having 2 to 4 carbon atoms, it being possible for the hydroxyl group and the sulfonic acid group to be bonded to any carbon atom the restriction that they are not bound to the same carbon atom.
- Methanesulfonic acid is very particularly preferably used according to the invention as alkanesulfonic acid.
- aluminum and aluminum alloys can be anodically oxidized.
- Particularly suitable aluminum alloys are alloys of aluminum with silicon, manganese, zinc, copper and / or magnesium. Silicon, manganese, zinc, copper and / or magnesium can be used in a proportion of 15% by weight (Si), 4% by weight (Mn), 5% by weight (Zn), 5% by weight ( Cu) or 5% by weight (Mg) may be contained in the alloy, cast alloys also being included.
- Some aluminum materials show a tendency to pitting corrosion when using electrolytes containing alkanesulfonic acid.
- this pre-anodizing step is carried out for a time of 3 s to 5 min., Preferably for 1 min. up to 3 min. carried out.
- the present invention accordingly furthermore relates to a process in which the anodic oxidation is carried out in two stages, comprising:
- Oxidation in an electrolyte according to the invention containing an alkanesulfonic acid Oxidation in an electrolyte according to the invention containing an alkanesulfonic acid.
- the process conditions of the pre-anodization preferably correspond to the conditions of the classic GS (direct current sulfuric acid) or also GSX (direct current sulfuric acid oxalic acid) electrolysis known from the prior art.
- the anodic oxidation is preferably carried out at temperatures from 0 to 30 ° C. If excessive temperatures are used, an irregular deposition of the oxide layer occurs, which is undesirable.
- hard anodizing in which thick oxide layers with low porosity and thus high hardness and high protection of the aluminum surface are desired, is carried out at low temperatures of generally 0 to 5 ° C., preferably 0 to 3 ° C. Because of the less corrosive property of the alkanesulfonic acids compared to aluminum oxide compared to pure sulfuric acid, large layer thicknesses of the oxide layer of> 30 ⁇ m, preferably from 40 to 100 ⁇ m, particularly preferably from 50 to 80 ⁇ m, are possible in shorter times with the aid of the method according to the invention than when used of pure sulfuric acid as the basis of the electrolyte. These aluminum oxide surfaces obtained by hard anodization are generally not used for a subsequent surface coloring step.
- the anodization according to the invention for obtaining a porous aluminum oxide surface is generally carried out at temperatures from 17 to 30 ° C., preferably at 18 to 28 ° C.
- the process according to the invention is distinguished from the processes of the prior art in that it can be carried out at a higher temperature than the processes of the prior art. Usually, unusable, uneven oxide layers are obtained even at temperatures above approximately 24 ° C., while the process according to the invention enables the process to be carried out at temperatures up to 30 ° C. The possibility of being able to carry out the process at elevated temperatures saves on energy costs.
- cooling of the electrolyte solution is necessary during the anodization because the anodization is exothermic. With this embodiment of the method according to the invention at temperatures of generally 17 to 30 ° C., depending on the current density and the electrolysis time, layer thicknesses of 5 to 40 ⁇ m, preferably 10 to 30 ⁇ m, are achieved.
- the process according to the invention is generally carried out at a current density of 0.5 to 5 A / dm 2 , preferably 0.5 to 3 A / dm 2 , particularly preferably 1 to 2.5 A / dm 2 .
- the voltage is generally 1 to 30 V, preferably 2 to 20 V.
- the electrolyte In addition to the alkanesulfonic acid used according to the invention or a mixture of alkanesulfonic acid and sulfuric acid, the electrolyte generally contains water and, if necessary, further additives such as aluminum sulfate.
- Suitable devices for carrying out the process according to the invention are generally all known devices which are suitable for electro-immersion or for the continuous anodic oxidation of aluminum or aluminum alloys, for example by means of an electrolytic drawing process.
- Devices made of metals which are resistant to alkanesulfonic acids are particularly preferred are, or devices that are lined with plastic, such as polyethylene or polypropylene.
- Another object of the present invention is a method for the surface treatment of aluminum or aluminum alloys, comprising the following steps: a) pretreatment of the aluminum or aluminum alloys; b) anodic oxidation according to the method according to the invention (anodization); c) optionally coloring the oxidized surface of the aluminum or the aluminum alloys; d) aftertreatment of the workpiece obtained after steps a), b) and optionally c); e) if appropriate, recovery of the alkanesulfonic acid and / or its salts used, step e) being able to follow each step in which an alkanesulfonic acid can be used, in particular steps b) and / or optionally c), or in parallel to these Steps can be performed.
- the pretreatment of aluminum or aluminum alloys is a crucial step, since it determines the optical quality of the end product. Since the oxide layer produced during anodizing is transparent and this transparency is also retained during the coloring process in step c), any surface defect of the metallic workpiece remains visible up to the finished part.
- the pretreatment is carried out using customary methods such as mechanical and / or electropolishing, dewaxing with neutral surfactants or organic solvents, glosses or pickling. Then it is generally rinsed with water.
- solutions containing alkanesulfonic acid are also used in step a).
- alkanesulfonic acids have already been used for an application in the anodizing step (step b)) mentioned.
- Methanesulfonic acid is particularly preferably used.
- Step h) Step b) relates to the anodizing process according to the invention, which follows the pretreatment of the aluminum or the aluminum alloy. This method according to the invention has already been explained in detail above.
- Step c) If the anodized aluminum or the anodized aluminum alloy is not to be used directly without coloring the aluminum oxide layer, which e.g. in the case of hard anodizing in general, with dense, thick layers being obtained, the aluminum oxide layer obtained in step b) can be colored.
- the dyeing of the alumina layer is achieved by the inclusion of organic or inorganic dyes in the kapillarf 'RMIG pores formed by the anodization in step b) the obtained oxide layer.
- step c) it is generally possible to use all of the processes known from the prior art for coloring anodized aluminum. A distinction is usually made between chemical and electrolytic coloring.
- anodized aluminum or aluminum alloy is colored in the aqueous phase with suitable organic or inorganic compounds without the effect of electricity.
- Organic dyes anodized dyes, for example dyes from the Alizarin series or indigo dyes
- Inorganic dyes can be deposited in the pores during chemical coloring by precipitation reactions or by hydrolysis of heavy metal salts.
- the processes involved are difficult to control, and there are often problems with reproducibility, that is, maintaining the same color shades. Hence have For a long time now, the electrolytic processes for coloring aluminum oxide layers have become more common.
- Step c) of the method according to the invention is therefore preferably carried out by an electrolytic method in an electrolyte containing metal salts.
- the aluminum oxide layers obtained after step b) of the process according to the invention are colored in a metal salt-containing electrolyte by means of direct or alternating current, preferably by means of alternating current.
- Metal is deposited from the metal salt solution at the pore base of the oxide layer.
- the use of salts from different metals and different working conditions create different colors. The colorations achieved are very lightfast.
- Suitable metal salts are generally salts selected from tin, copper, silver, cobalt, nickel, bismuth, chromium, palladium and lead or mixtures of two or more of these metal salts. Tin, copper or silver salts or mixtures thereof are preferably used in the process according to the invention.
- Additives can also be added to the electrolyte to improve the scatter and reduce the oxidation of the metal ions used, e.g. the oxidation of tin (II) to insoluble tin (IV).
- the electrolyte contains 20 to 100 parts by weight of an alkanesulfonic acid and 80 to 0 parts by weight of sulfuric acid, the sum of alkanesulfonic acid and sulfuric acid being 100 parts by weight and a concentration of 0.1 makes up to 20 wt .-%, preferably 0.1 to 15 wt .-% of the electrolyte.
- the electrolyte very particularly preferably contains 100 parts by weight of an alkanesulfonic acid.
- Alkanesulfonic acids suitable for the process according to step c) have already been disclosed above for use in the anodization (step b)). Methanesulfonic acid is particularly preferred. Compared to purely sulfuric acid electrolytes, electrolytes based on alkanesulfonic acids have a higher electrical conductivity, cause a quicker coloring, show a reduced oxidation effect, whereby the precipitation of e.g. tin (IV) salts from a tin (II) salt-containing Electrolytes are prevented and the addition of additives such as the environmentally harmful phenolic or toluenesulfonic acid is not necessary.
- tin (IV) salts from a tin (II) salt-containing Electrolytes are prevented and the addition of additives such as the environmentally harmful phenolic or toluenesulfonic acid is not necessary.
- the metal salts are generally used in the electrolyte in a concentration of 0.1 to 50 g / 1, preferably 0.5 to 20 g / 1, particularly preferably 0.2 to 10 g / 1, based on the metal used ,
- the electrolyte In addition to the corresponding acid, preferably sulfuric acid or an alkanesulfonic acid or a mixture of the two acids, and the metal salt used or a mixture of several metal salts, the electrolyte generally contains water and, if necessary, further additives, such as spreading improvers. In particular, when using electrolytes containing alkanesulfonic acid, the addition of additives is generally not necessary.
- the electrolysis time in step c) is 0.1 to 10 minutes, preferably 0.5 to 8 minutes, particularly preferably 0.5 to 5 minutes, the electrolysis time depending on the metal salts used and the desired depth of color.
- the electrolytic coloring in step c) is usually carried out with alternating current.
- the current density is generally 0.1 to 2 A / dm 2 , preferably 0.2 to 1 A / dm 2 .
- the voltage is generally 3 to 30 V, preferably 5 to 20 V.
- the electrodes which are usually suitable in a method for the electrolytic coloring of aluminum oxide layers, such as stainless steel or graphite electrodes, are suitable as electrodes.
- An electrode made of the metal to be deposited, for example tin, silver or copper, can also be used.
- a gold coloring of the oxidized surface of the aluminum or of the aluminum alloys is achieved in an electrolyte containing silver salts, optionally in a mixture with tin and / or copper salts.
- Such gold-colored aluminum workpieces are of particular interest for the production of decorative objects, since the demand for gold-colored objects made of aluminum is great.
- gold-colored aluminum oxide surfaces are preferably obtained by dyeing in step c) at a concentration of an alkyl sulfonate of the silver, calculated as Ag + , from 2 to 50 g / 1, preferably from 3 to 20 g / 1, and a product of current density and tension of 0.5 to 10 AV / dm 2 , preferably of 1 to 5 AV / dm 2 over a period of generally 0.05 to 4 minutes, preferably 0.3 to 3 minutes.
- a precise description of the production of gold-colored aluminum oxide layers can be found in the simultaneously filed application DE-A .... entitled "Process for the production of gold-colored surfaces of aluminum or aluminum alloys using silver-containing formulations".
- the workpieces are generally rinsed with water, in particular with running water. This rinsing step follows both step b) and step c), if this is carried out.
- the pores of the oxide layer produced are generally sealed after step b), if step c) is not carried out, or after step c), if this is carried out, in order to obtain good corrosion protection.
- This re-sealing can be achieved by immersing the workpieces in boiling, distilled water for approx. 30 to 60 minutes.
- the oxide layer swells, which closes the pores.
- the water can also contain additives.
- the workpieces are post-treated in steam at 4 to 6 bar instead of in boiling water.
- the sealing is preferably carried out by means of water or steam.
- the alkanesulfonic acid and / or its salts used can be recovered. This recovery can follow every step in which an alkanesulfonic acid can be used or can be carried out in parallel with these steps. Recovery is possible, for example, together with the rinsing step (dl)) following step b) and, if this is carried out, step c). Such recovery can e.g. by means of electrolytic membrane cells, by cascade rinsing, or by simple concentration e.g. of the rinsing solutions.
- Another object of the present invention is the use of an alkanesulfonic acid in a process for the anodic oxidation of aluminum or aluminum alloys (anodization) to increase the rate of anodic oxidation.
- anodic oxidation aluminum or aluminum alloys
- the use of alkanesulfonic acids as the base of the electrolyte enables thicker layers to be obtained in a shorter time than when pure sulfuric acid is used as the electrolyte base.
- the Energy consumption significantly lower, since a lower voltage is set and less cooling is required.
- an electrolyte composition for the anodic oxidation of aluminum or aluminum alloys is claimed, the electrolyte containing 3 to 30% by weight of an alkanesulfonic acid.
- An electrolyte composition is preferred in which the electrolyte contains 20 to 100 parts by weight of an alkanesulfonic acid and 80 to 0 parts by weight of a sulfuric acid, the sum of alkanesulfonic acid and sulfuric acid being 100 parts by weight and a concentration of 3 to 30 parts by weight .-% of the electrolyte.
- Suitable alkanesulfonic acids have already been mentioned above.
- the alkanesulfonic acid methanesulfonic acid used is particularly preferred.
- electrolyte compositions are outstandingly suitable for use in a process for the anodic oxidation of aluminum or aluminum alloys and lead to a faster aluminum oxide deposition than the processes of the prior art and to a thicker aluminum oxide layer in a shorter time, which is of particular interest in the case of hard anodizing and reduced energy consumption.
- the workpieces produced according to the invention based on aluminum or aluminum alloys can be used, for example, in construction, in particular for the production of window profiles or facade components, in automobile or aircraft construction, both for the production of body parts and for the production of die-cast aluminum parts, e.g. in engine construction, and in packaging, in particular for the production of cans, for example by a continuous electrolytic drawing process, e.g. continuous tape anodization can be used.
- Anodizing electrolytes were prepared, each containing 18% by weight of an acid or an acid mixture and 8 g / 1 aluminum.
- the electrolytes were used to anodize pure aluminum sheets, each of which was pre-anodized in the classic GS process for 2 minutes, anodizing being carried out at a current of 1.2 A / dm 2 for 30 minutes.
- the anodizing bath was thermostatted to 20 ° C. in each case.
- the aluminum oxide layer thickness, the porosity or MiloO structure of the surface and the microhardness were determined on the anodized workpieces. Table 1 below shows the layer thicknesses of the oxide layer obtained as a function of the electrolyte used and the anodizing voltage and any cooling which may be necessary:
- the layers consistently showed a significantly lower porosity and increased hardness compared to Example 1.
- the sheets anodized in MA (methanesulfonic acid) Compared to the sheets anodized in H 2 SO 4 , the layer thickness was increased by 20% and the hardness increased by approximately 10%.
- the layers consistently showed a significantly increased porosity and reduced hardness, the porosity of the sheets 3 and 4 (according to the invention, the acid in the electrolyte corresponding to the compositions given in Table 1 under No. 3 and 4 respectively) being lower than that of the others.
- MSA methanesulfonic acid
- 57g / l methanesulfonic acid At a current density of 0.2 A / dm 2 and a voltage of approx. 8 V, the sheets anodized according to No. 3 and 4 in Table 1 were colored for different lengths. The colorations listed in Table 2 below were obtained for both sheets:
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10033435A DE10033435A1 (de) | 2000-07-10 | 2000-07-10 | Verfahren zur Oberflächenbehandlung von Aluminium oder Aluminium-Legierungen mittels alkansulfonsäurehaltigen Formulierungen |
DE10033435 | 2000-07-10 | ||
PCT/EP2001/007932 WO2002004716A1 (de) | 2000-07-10 | 2001-07-10 | Verfahren zur oberflächenbehandlung von aluminium oder aluminium-legierungen mittels alkansulfonsäurehaltigen formulierungen |
Publications (2)
Publication Number | Publication Date |
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EP1301656A1 true EP1301656A1 (de) | 2003-04-16 |
EP1301656B1 EP1301656B1 (de) | 2005-01-26 |
Family
ID=7648388
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP01960487A Expired - Lifetime EP1301656B1 (de) | 2000-07-10 | 2001-07-10 | Verfahren zur oberflächenbehandlung von aluminium oder aluminium-legierungen mittels alkansulfonsäurehaltigen formulierungen |
Country Status (14)
Country | Link |
---|---|
US (1) | US20040004003A1 (de) |
EP (1) | EP1301656B1 (de) |
JP (1) | JP2004502877A (de) |
CN (1) | CN1192128C (de) |
AT (1) | ATE287977T1 (de) |
AU (1) | AU2001281971A1 (de) |
BR (1) | BR0112434A (de) |
CA (1) | CA2415556A1 (de) |
DE (2) | DE10033435A1 (de) |
ES (1) | ES2234870T3 (de) |
MX (1) | MXPA03000233A (de) |
PL (1) | PL360817A1 (de) |
TW (1) | TWI243864B (de) |
WO (1) | WO2002004716A1 (de) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005028121A1 (de) * | 2005-06-10 | 2006-12-14 | Decoma (Germany) Gmbh | Verfahren zum Behandeln einer Oberfläche |
DE102006052170A1 (de) * | 2006-11-02 | 2008-05-08 | Steinert Elektromagnetbau Gmbh | Anodische Oxidschicht für elektrische Leiter, insbesondere Leiter aus Aluminium, Verfahren zur Erzeugung einer anodischen Oxidschicht und elektrischer Leiter mit anodischer Oxidschicht |
DE102008011298A1 (de) * | 2007-03-16 | 2008-09-18 | Süddeutsche Aluminium Manufaktur GmbH | Teilpigmentierung einer Deckschicht zur Vermeidung von Interferenzen bei Aluminiumbauteilen oder Aluminium aufweisenden Bauteilen |
WO2009017039A1 (ja) * | 2007-07-27 | 2009-02-05 | Mitsubishi Electric Corporation | 熱交換器およびその製造方法 |
CN103374742A (zh) * | 2012-04-18 | 2013-10-30 | 靖江先锋半导体科技有限公司 | 铝镁合金的增强型阳极氧化表面处理工艺 |
PE20161103A1 (es) | 2013-11-19 | 2016-11-19 | Aqua Metals Inc | Dispositivos y metodos de reciclaje de baterias acidas de plomo sin necesidad de fundicion |
CN104152969B (zh) * | 2014-08-04 | 2016-07-27 | 石狮市星火铝制品有限公司 | 一种铝合金交流电解沉积银铜的着色方法 |
CN208087763U (zh) | 2014-08-29 | 2018-11-13 | 苹果公司 | 包括阳极氧化物涂层以及促进粘附的阳极氧化物层的部件 |
US9359686B1 (en) | 2015-01-09 | 2016-06-07 | Apple Inc. | Processes to reduce interfacial enrichment of alloying elements under anodic oxide films and improve anodized appearance of heat treatable alloys |
CN104651905B (zh) * | 2015-01-28 | 2017-11-07 | 永保纳米科技(深圳)有限公司 | 一种阳极铝匀染缓染助剂及其操作液,和阳极铝匀染缓染处理工艺 |
WO2016160036A1 (en) | 2015-04-03 | 2016-10-06 | Apple Inc. | Process for evaluation of delamination-resistance of hard coatings on metal substrates |
US20160289858A1 (en) * | 2015-04-03 | 2016-10-06 | Apple Inc. | Process to mitigate grain texture differential growth rates in mirror-finish anodized aluminum |
PT3294916T (pt) | 2015-05-13 | 2021-02-19 | Aqua Metals Inc | Sistemas e métodos para a recuperação de chumbo de baterias de chumbo-ácido |
RS62200B1 (sr) | 2015-05-13 | 2021-08-31 | Aqua Metals Inc | Sistem zatvorene petlje i metod za reciklažu olovnih akumulatora |
WO2016183431A1 (en) | 2015-05-13 | 2016-11-17 | Aqua Metals Inc. | Electrodeposited lead composition, methods of production, and uses |
US10760176B2 (en) | 2015-07-09 | 2020-09-01 | Apple Inc. | Process for reducing nickel leach rates for nickel acetate sealed anodic oxide coatings |
US10711363B2 (en) | 2015-09-24 | 2020-07-14 | Apple Inc. | Anodic oxide based composite coatings of augmented thermal expansivity to eliminate thermally induced crazing |
US9970080B2 (en) | 2015-09-24 | 2018-05-15 | Apple Inc. | Micro-alloying to mitigate the slight discoloration resulting from entrained metal in anodized aluminum surface finishes |
CN105239133A (zh) * | 2015-10-08 | 2016-01-13 | 昆明理工大学 | 一种钛及钛合金表面阳极氧化着色方法 |
US10316420B2 (en) | 2015-12-02 | 2019-06-11 | Aqua Metals Inc. | Systems and methods for continuous alkaline lead acid battery recycling |
JP6579520B2 (ja) * | 2016-03-01 | 2019-09-25 | 松田製綱株式会社 | ワイヤーロープ圧縮止め用アルミ製クランプ管の製造方法及び玉掛けワイヤーロープにおけるアルミ製クランプ管の製造方法並びに曳網用ワイヤーロープ |
US10174436B2 (en) | 2016-04-06 | 2019-01-08 | Apple Inc. | Process for enhanced corrosion protection of anodized aluminum |
US11352708B2 (en) | 2016-08-10 | 2022-06-07 | Apple Inc. | Colored multilayer oxide coatings |
US11242614B2 (en) | 2017-02-17 | 2022-02-08 | Apple Inc. | Oxide coatings for providing corrosion resistance on parts with edges and convex features |
IT201700080501A1 (it) * | 2017-07-17 | 2019-01-17 | Tramec S R L | Riduttore. |
CN107815716B (zh) * | 2017-09-12 | 2019-09-20 | 广东长盈精密技术有限公司 | 对工件的表面进行处理的方法 |
US11549191B2 (en) | 2018-09-10 | 2023-01-10 | Apple Inc. | Corrosion resistance for anodized parts having convex surface features |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1426423A (en) * | 1974-12-04 | 1976-02-25 | Fujisash Ind Ltd | Method of producing coloured anodic coating on aluminum and its alloys |
US4128460A (en) * | 1976-09-13 | 1978-12-05 | Daiwa Kasei Kenkyujo Kabushiki Kaisha | Coloring by electrolysis of aluminum or aluminum alloys |
JPS57126993A (en) * | 1981-01-29 | 1982-08-06 | Daiwa Kasei Kenkyusho:Kk | Coloring anodic oxidation treatment bath and method of aluminum or aluminum alloy |
JP2720224B2 (ja) * | 1990-06-15 | 1998-03-04 | 富士写真フイルム株式会社 | 感光性平版印刷版 |
US5980723A (en) * | 1997-08-27 | 1999-11-09 | Jude Runge-Marchese | Electrochemical deposition of a composite polymer metal oxide |
-
2000
- 2000-07-10 DE DE10033435A patent/DE10033435A1/de not_active Withdrawn
-
2001
- 2001-07-10 BR BR0112434-0A patent/BR0112434A/pt not_active IP Right Cessation
- 2001-07-10 PL PL36081701A patent/PL360817A1/xx not_active Application Discontinuation
- 2001-07-10 AU AU2001281971A patent/AU2001281971A1/en not_active Abandoned
- 2001-07-10 ES ES01960487T patent/ES2234870T3/es not_active Expired - Lifetime
- 2001-07-10 CA CA002415556A patent/CA2415556A1/en not_active Abandoned
- 2001-07-10 WO PCT/EP2001/007932 patent/WO2002004716A1/de active IP Right Grant
- 2001-07-10 US US10/332,586 patent/US20040004003A1/en not_active Abandoned
- 2001-07-10 AT AT01960487T patent/ATE287977T1/de not_active IP Right Cessation
- 2001-07-10 DE DE50105209T patent/DE50105209D1/de not_active Expired - Fee Related
- 2001-07-10 EP EP01960487A patent/EP1301656B1/de not_active Expired - Lifetime
- 2001-07-10 TW TW090116875A patent/TWI243864B/zh active
- 2001-07-10 CN CNB018139329A patent/CN1192128C/zh not_active Expired - Fee Related
- 2001-07-10 JP JP2002509566A patent/JP2004502877A/ja not_active Withdrawn
- 2001-07-10 MX MXPA03000233A patent/MXPA03000233A/es not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO0204716A1 * |
Also Published As
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CN1446273A (zh) | 2003-10-01 |
BR0112434A (pt) | 2003-07-15 |
MXPA03000233A (es) | 2003-08-20 |
DE50105209D1 (de) | 2005-03-03 |
AU2001281971A1 (en) | 2002-01-21 |
CN1192128C (zh) | 2005-03-09 |
CA2415556A1 (en) | 2003-01-09 |
JP2004502877A (ja) | 2004-01-29 |
DE10033435A1 (de) | 2002-01-24 |
ATE287977T1 (de) | 2005-02-15 |
US20040004003A1 (en) | 2004-01-08 |
EP1301656B1 (de) | 2005-01-26 |
WO2002004716A1 (de) | 2002-01-17 |
ES2234870T3 (es) | 2005-07-01 |
TWI243864B (en) | 2005-11-21 |
PL360817A1 (en) | 2004-09-20 |
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