EP0857227B1 - Colmatage a chaud, de courte duree, de surfaces metalliques anodisees - Google Patents

Colmatage a chaud, de courte duree, de surfaces metalliques anodisees Download PDF

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Publication number
EP0857227B1
EP0857227B1 EP96934587A EP96934587A EP0857227B1 EP 0857227 B1 EP0857227 B1 EP 0857227B1 EP 96934587 A EP96934587 A EP 96934587A EP 96934587 A EP96934587 A EP 96934587A EP 0857227 B1 EP0857227 B1 EP 0857227B1
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EP
European Patent Office
Prior art keywords
acid
acids
aqueous solution
diphosphonic acid
diphosphonic
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
Application number
EP96934587A
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German (de)
English (en)
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EP0857227A1 (fr
Inventor
Torsten Körner
Josef Kresse
Wolf-Achim Roland
Jürgen Lindener
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Filing date
Publication date
Priority claimed from DE19538777A external-priority patent/DE19538777A1/de
Priority claimed from DE1996121819 external-priority patent/DE19621819A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0857227A1 publication Critical patent/EP0857227A1/fr
Application granted granted Critical
Publication of EP0857227B1 publication Critical patent/EP0857227B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers

Definitions

  • the invention is in the field of producing anti-corrosion and / or decorative coatings on metals by anodic oxidation. It affects one improved process for compacting the electrochemically produced porous Anodizing layers to further improve their properties.
  • the electrochemical anodic oxidation of metals in suitable electrolytes is a widely used process for the formation of anti-corrosion and / or decorative coatings on suitable metals. These procedures are for example in "Ullmann's Encyclopedia of Industrial Chemistry", 5th Edition, Vol. 9 (1987), pp. 174 - 176 briefly characterized. Accordingly, titanium, magnesium and Aluminum and their alloys can be anodized, the anodization of Aluminum and its alloys have the greatest technical importance.
  • the Electrolytically produced anodizing layers protect the aluminum surfaces the influences of weather and other corrosive media. Furthermore Anodizing layers applied to obtain a harder surface and thus to achieve increased wear resistance of the aluminum.
  • the aluminum is anodized in an acidic electrolyte, with sulfuric acid being the most common.
  • Other suitable electrolytes are phosphoric acid, oxalic acid and chromic acid.
  • the Properties of the anodizing layers can be determined by the choice of the electrolyte, its temperature as well as the current density and the anodizing time within wide limits vary.
  • the anodization is usually carried out with direct current or with a AC-superimposed DC.
  • the fresh anodizing layers can be immersed in a suitable solution Dye or by an AC treatment in a metal salt containing are preferably subsequently colored in a tin-containing electrolyte.
  • colored anodizing layers can be used obtained by so-called color anodization processes, for which the Anodization in solutions of organic acids, such as sulfophthalic acid in particular or sulfanilic acid, optionally in a mixture with sulfuric acid, used.
  • DE-A-38 20 650 certain can also be Phosphonic acids, for example 1-phosphonopropane-1,2,3-tricarboxylic acid use.
  • EP-A-122 129 is the use of further Phosphonic acids known.
  • DE-C-22 11 553 describes a method for Compacting anodic oxide layers on aluminum and aluminum alloys in aqueous ones containing phosphonic acids or their salts and calcium ions Solutions, the molar ratio of calcium ions to phosphonic acid is set at least 2: 1. A higher ratio of calcium ions is preferred to phosphonic acids from about 5: 1 to about 500: 1.
  • Phosphonic acids are suitable, for example: 1-hydroxypropane, 1-hydroxybutane, 1-hydroxypentane, 1-hydroxyhexane-1,1-diphosphonic acid and 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid and preferably 1-hydroxyethane-1,1-diphosphonic acid, 1-aminoethane, 1-amino-1-phenylmethane, Dimethylaminoethane, dimethylaminobutane, diethylaminomethane, propyl and Butylaminomethane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, Diethylenetriaminepentamethylenephosphonic acid, Aminotri- (2-propylene-2-phosphonic acid), phosphonosuccinic acid, 1-phosphono-1-methyl succinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. According to the Embodiments of this patent are conventional Hot
  • nickel salts in particular fluorides, some of which are used in practice (EP-A-171 799), Nitrosylpentacyanoferrate, complex fluorides of titanium and zirconium as well Chromates or chromic acid, optionally in conjunction with other additives.
  • Nitrosylpentacyanoferrate complex fluorides of titanium and zirconium as well Chromates or chromic acid, optionally in conjunction with other additives.
  • the hydrophobization of the Oxide layer using long-chain carboxylic acids or waxes recommended as well as the Treatment with acrylamides to be polymerized in the pore space. Closer Information on this can be found in the above-mentioned literature reference by S. Wernick et al. be removed. With the exception of consolidation, these suggestions could do not enforce with nickel compounds in practice.
  • Nickel fluoride Because of the toxic properties of nickel salts, this will result however, complex measures for wastewater treatment are required.
  • a short-term hot compression process in which the anodized metal parts are immersed in a lithium-containing aqueous solution.
  • the lithium concentration is preferably in the range from 0.01 to 50 g / l and especially in the range of 0.01 to 5 g / l.
  • the Compression solution also contains a sealant inhibitor. This is preferably present and in a concentration between 0.1 and 10 g / l preferably an aromatic disulfonate.
  • US-A-5 478 415 which to the same priority as the above cited US-A-5 411 607 may be one Brief hot compression with an aqueous solution, which is at least 0.01 g / l Contains lithium ions and from 0.1 to 10 g / l of a sealing deposit inhibitor.
  • the sealant inhibitor is preferably an aromatic disulfonate.
  • the contact of the treatment solutions with the anodized metals can by spraying the solutions onto the metal surfaces or preferably by immersing the metal parts in the solutions.
  • Anodizing layer thickness of about 20 microns are the required treatment times only in the range of 20 to 40 minutes. According to the invention, it is therefore preferred that the anodized metal for a period between 1 and 2 minutes per Micrometer anodizing layer thickness with the aqueous solution defined above in Touches.
  • the temperature of the treatment solution is preferably in the Range between 90 ° C and the boiling point and especially in the range from 94 to 98 ° C, for example at 96 ° C.
  • the pH of the aqueous solution is preferably in the range 5.5 to 7, especially in the range 5.5 to 6.5.
  • the adjustment of the pH value can if necessary with ammonia or acetic acid. With ammonium acetate as a buffer it can be kept in the required area.
  • Lithium and magnesium are particularly suitable as metal ions of group a).
  • the metals can be in the form of their concentration range water-soluble salts are used, for example as acetate, lactate, sulfate, Oxalate and / or nitrate. Acetates are particularly suitable.
  • the organic acids of group b) selected from saturated or unsaturated or aromatic carbocyclic Six-ring carboxylic acids with 3 to 6 carboxyl groups.
  • Preferred examples such acids are trimesic acid, trimellitic acid, pyromellitic acid, mellitic acid and the particularly preferred cyclohexane hexacarboxylic acid.
  • the total amount such carboxylic acids are preferably in the range from 0.0005 to 0.2 g / l, in particular from 0.001 to 0.1 g / l, and particularly preferably in the range of 0.001 up to 0.05 g / l.
  • the preferred cyclohexane hexacarboxylic acid exists in the form different stereoisomers. As known from DE-A-26 50 989 those cyclohexane hexacarboxylic acids preferred, the 5 cis and 1 trans or which carry 4 cis and 2 trans carboxyl groups.
  • Group b) preferably contains 0.1 to 5 g / l of the aqueous treatment solution in particular 0.2 to 2.5 g / l of metal ions of group a).
  • the organic acids are of the group b) selected from the phosphonic acids: 1-phosphonopropane-1,2,3-tricarboxylic acid, 1,1-diphosphonopropane-2,3-dicarboxylic acid, 1-hydroxypropane-1,1-diphosphonic acid, 1-hydroxybutane-1,1-diphosphonic acid, 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenylmethane-1,1-diphosphonic acid, Dimethylaminoethane-1,1-diphosphonic acid, propylaminoethane-1,1-diphosphonic acid, Butylaminoethane-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminotetra (methylenephosphonic acid), Diethylenetriamineopenta (
  • 1-phosphonopropane-1,2,3-tricarboxylic acid 1,1-diphosphonopropane-2,3-dicarboxylic acid and the aminotri (methylenephosphonic acid) is particularly preferred.
  • Polyphosphinocarboxylic acids as organic acids of group b) in particular preferably suitable as copolymers of acrylic acid and hypophosphites can be understood.
  • An example of this is Belclene ® 500 from FMC Corporation, UK.
  • the above-mentioned phosphonic acids and polyphosphinocarboxylic acids are preferred as acids of group b) in an amount of 0.003 to 0.1 and used in particular in an amount of 0.003 to 0.05 g / l.
  • acids of group b) acids contain the aqueous treatment solution preferably 0.0001 to 0.01 g / l and in particular a maximum of 0.005 g / l Group a) metal ions.
  • the aqueous compression solution additionally contains approximately as an optional component 0.001 to 0.05 g / l surfactants, selected from the group of the cationic, non-ionic or anionic surfactants.
  • cationic surfactants for example, quaternary ammonium salts.
  • anionic surfactants such as alkyl or alkylaryl sulfates or -sulfonates used.
  • linear alkyl sulfates such as for example lauryl sulfate, is preferred.
  • the anionic surfactants are called Alkali metal salts are used, with lithium salts being particularly preferred.
  • nonionic surfactants can use fatty amine or fatty alcohol ethoxylates become. Fatty alcohol ethoxylates with 4-8 ethylene oxide units are preferred.
  • concentration of the surfactants is preferably in the range from 0.002 to 0.02 g / l.
  • the compression bath suitable for the compression process according to the invention can in principle by dissolving the components in - preferably fully desalinated - Water in the required concentration range can be produced on site. However, one is preferably used to prepare the compression baths aqueous concentrate that already contains all the necessary components of the Compression bath in the right proportions and from which one can Dilute with water by a factor between 10 and 1000 receives the ready-to-use solution. If necessary, the pH value adjusted to the range according to the invention with ammonia or with acetic acid become.
  • the invention accordingly also includes an aqueous concentrate for preparation the aqueous solution for use in the short-term hot compression process according to the invention, taking the concentrate by diluting it with water a factor between 10 and 1000 the ready-to-use aqueous Solution results.
  • compacted anodizing layers can be produced in their Layer properties are not inferior to those conventionally produced.
  • test parameters for the layer quality are in particular the removal of acid in Chromic acid, the apparent conductance and the color drop test are important. This Quality indicators of the layers are checked according to standard test procedures that are given in the example section.
  • the compression method according to the invention is preferably for anodized Aluminum or anodized aluminum alloys used. However, it can also on the anodizing layers of other anodizable metals, such as, for example Use titanium and magnesium or their alloys. It is for both undyed anodizing layers can be used as well for those after conventional methods such as integral staining, one Adsorptive staining using organic dyes, a reactive one Coloring with the formation of inorganic color pigments, an electrochemical Coloring using metal salts, especially tin salts, or interference staining. With adsorptively colored anodizing layers The inventive method has the further advantage that the shorter compaction time is possible with conventional hot compaction Bleeding of the dye can be reduced.
  • Al 99.5 aluminum sheets were conventionally anodized (Direct current / sulfuric acid, one hour, layer thickness 20 ⁇ m) and if necessary colored electrochemically or with organic dipping colors. Then the Sheets for times between 30 and 60 minutes in the invention Compaction solutions or comparative solutions dipped according to the tables.
  • the Solutions had a temperature of 96 ° C.
  • Following the treatment according to Tables were the plates immersed in boiling demineralized water for one minute and then dried. After that, the quality of compaction with checked the usual quality tests described below. Their Results are also shown in the tables. They show that with the The inventive method after only 30 minutes of compression results can be obtained, which experience has shown with a conventional Hot compression bath only after an hour. In contrast, they are Compaction results after half an hour of treatment with comparison solutions insufficient quality.
  • the apparent conductance Y 20 was determined in accordance with the German standard DIN 50949 using an Anotest YD 8.1 measuring device from Fischer.
  • the measuring system consists of two electrodes, one of which is conductively connected to the base material of the sample.
  • the second electrode is immersed in an electrolyte cell that can be placed on the layer to be examined.
  • This cell is designed as a rubber ring with an inner diameter of 13 mm and a thickness of approximately 5 mm, the ring surface of which is self-adhesive.
  • the measuring area is 1.33 cm 2 .
  • a potassium sulfate solution (35 g / l) in deionized water is used as the electrolyte.
  • the apparent conductance readable on the measuring device is converted according to the specifications of DIN 50949 to a measuring temperature of 25 ° C and to a layer thickness of 20 ⁇ m.
  • the values obtained, which should preferably be in the range between approximately 10 and approximately 20 ⁇ S, are entered in the tables.
  • the stained test area is marked by Rub off using a mild powder detergent from loosely adhering Dye exempted. After drying the surface becomes a relative Reflection measurement made by the measuring head of a light reflection measuring device (Micro Color from Dr. Lange) once on an undyed part of the Surface and second is placed on the stained measuring surface.
  • the Residual reflection in% is obtained by taking the quotient from the measured value of the colored area divided by the measured value of the uncolored area with a hundred multiplied. Residual reflection values between 95 and 100% are good evidence Compaction quality, while values below 95% are considered unacceptable. The higher the values of the residual reflection, the higher the compression quality.
  • the found values are entered in the tables.
  • the acid removal was measured based on ISO 3210.
  • the test plate is weighed to the nearest 0.1 mg and then immersed for 15 minutes at 38 ° C in an acid solution containing 35 ml of 85% phosphoric acid and 20 g of chromium (VI) oxide per liter.
  • the sample is rinsed with deionized water and dried in a drying cabinet at 60 ° C. for 15 minutes.
  • the sample is then weighed again.
  • Comparison 1 had fingerprints. The rest For example, the appearance of the layers was good.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Claims (14)

  1. Procédé de colmatage de surfaces métalliques, anodisées
    caractérisé en ce que
    l'on met en contact le métal anodisé pendant une durée comprise entre 0,5 et 2 minutes par micromètre d'épaisseur de couche d'anodisation, avec une solution aqueuse qui présente une température comprise entre 75°C et le point d'ébullition et une valeur de pH comprise dans la plage allant de 5,5 à 8,5, et contenant :
    a) globalement de 0, 0001 à 5 g/l d'un ou plusieurs ions métalliques alcalins et/ou alcalino-terreux, et
    b) globalement de 0,0005 à 0,5 g/l d'un ou plusieurs acides organiques, sélectionnés parmi les acides polycarboniques cycliques ayant de 3 à 6 groupes carboxyle et/ou les acides phosphoniques et/ou les acides polyphosphinocarboniques,
    la solution contenant une quantité d'ions métalliques du groupe a) supérieure à ce qui est nécessaire pour neutraliser complètement les acides du groupe b).
  2. Procédé selon la revendication 1
    caractérisé en ce que
    la solution aqueuse présente une température située dans la plage de 94 à 98°C.
  3. Procédé selon l'une ou les deux des revendications 1 et 2,
    caractérisé en ce que
    la solution aqueuse a une valeur de PH comprise dans la plage allant de 5,5 à 7.
  4. Procédé selon l'une ou plusieurs des revendications 1 à 3,
    caractérisé en ce que
    les ions métalliques du groupe a) sont sélectionnés parmi Li et Mg.
  5. Procédé selon l'une ou plusieurs des revendications 1 à 4,
    caractérisé en ce que
    les acides organiques du qroupe b) sont sélectionnés parmi des acides carboniques carbocycliques, à six atomes de carbon, saturés ou insaturés, ou aromatiques ayant de 3 à 6 groupes carboxyle.
  6. Procédé selon la revendication 5, caractérisé en ce que les acides carboniques sont sélectionnés parmi l'acide trimésinique, l'acide triméllitique, l'acide pyromellitique, l'acide mellitique et l'acide cyclohexanehexacarbonique.
  7. Procédé selon l'une ou les deux des revendications 5 et 6,
    caractérisé en ce que
    la solution aqueuse contient les acides carboniques en une quantité globale de 0,001 à 0,05 g/l.
  8. Procédé selon l'une ou plusieurs des revendications 5 à 7,
    caractérisé en ce que
    la solution aqueuse contient globalement de 0,2 à 2,5 g/l d'ions métalliques du groupe a).
  9. Procédé selon l'une ou plusieurs des revendications 1 à 4,
    caractérisé en ce que
    les acides organiques du groupe b) sont choisis parmi l'acide 1-phosphonopropane-1,2,3-tricarbonique, l'acide 1,1-diphosphonopropane-2,3-dicarbonique, l'acide 1-hydroxypropane-1,1-disphosphonique, l'acide 1-hydroxybutane-1,1-diphosphonique, l'acide 1-hydroxy 1-phénylméthane-1,1-disphosphonique, l'acide 1-hydroxyéthane-1,1-disphosphonique, l'acide 1-aminoéthane-1,1-diphosphonique, l'acide 1-amino-1-phénylméthane-1,1-diphosphonique, l'acide diméthylaminoéthane-1,1-diphosphonique, l'acide propylaminoéthane-1,1-diphosphonique, l'acide butylaminoéthane-1,1-diphosphonique, l'aminotri (acide méthylène phosphonique), l'éthylène diamine tétra(acide méthylènephosphonique), le diéthylènetriaminopenta (acide méthylènephosphonique), l'hexaméthylènediaminotétra (acide méthylènephosphonique), le n-propyliminodi (acide méthylènephosphonique), l'amino-tri(2-propylène-2-acide phosphonique), l'acide phosphosuccinique, l'acide 1-phosphono-1 méthylsuccinique, l'acide 1-phosphonobutane-1,2,4-tricarbonique et les acides polyphosphinocarboniques.
  10. Procédé selon la revendication 9,
    caractérisé en ce que
    la solution aqueuse contient les acides du groupe b) en une quantité de 0,003 à 0,05 g/l.
  11. Procédé selon l'une ou les deux revendications 9 et 10,
    caractérisé en ce que
    la solution aqueuse contient globalement jusqu'à 0,005 g/l d'ions métalliques du groupe a).
  12. Procédé selon l'une ou plusieurs des revendications 1 à 11,
    caractérisé en ce que
    la solution aqueuse contient en plus de 0,001 à 0,05 g/l de tensio-actifs non ioniques ou anioniques.
  13. Procédé de colmatage de surfaces métalliques anodisées,
    caractérisé en ce que
    les surfaces métalliques, après traitement selon une ou plusieurs des revendications de 1 à 12, sont immergées pendant une durée comprise entre 30 et 120 secondes dans de l'eau complètement déminéralisée, à une température supérieure à 90°C.
  14. Concentrat aqueux pour la préparation de la solution aqueuse à utiliser dans le procédé selon l'une ou plusieurs des revendication 1 à 13, donnant la solution aqueuse prête à l'application par dilution à l'eau, d'un facteur compris entre 10 et 1000.
EP96934587A 1995-10-18 1996-10-09 Colmatage a chaud, de courte duree, de surfaces metalliques anodisees Expired - Lifetime EP0857227B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19538777A DE19538777A1 (de) 1995-10-18 1995-10-18 Kurzzeit-Heißverdichtung anodisierter Metalloberflächen
DE19538777 1995-10-18
DE19621819 1996-05-31
DE1996121819 DE19621819A1 (de) 1996-05-31 1996-05-31 Kurzzeit-Heißverdichtung anodisierter Metalloberflächen
PCT/EP1996/004373 WO1997014828A1 (fr) 1995-10-18 1996-10-09 Colmatage a chaud, de courte duree, de surfaces metalliques anodisees

Publications (2)

Publication Number Publication Date
EP0857227A1 EP0857227A1 (fr) 1998-08-12
EP0857227B1 true EP0857227B1 (fr) 2000-01-26

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EP96934587A Expired - Lifetime EP0857227B1 (fr) 1995-10-18 1996-10-09 Colmatage a chaud, de courte duree, de surfaces metalliques anodisees

Country Status (7)

Country Link
US (1) US5935656A (fr)
EP (1) EP0857227B1 (fr)
AR (1) AR004035A1 (fr)
AU (1) AU7287896A (fr)
DE (1) DE59604329D1 (fr)
ES (1) ES2142619T3 (fr)
WO (1) WO1997014828A1 (fr)

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DE19804124A1 (de) * 1998-02-03 1999-08-05 Bayer Ag Phosphorhaltige Verbindungen auf Basis der 1-Hydroxypropan-1,3-diphosphonsäure
US6379523B1 (en) * 1998-07-07 2002-04-30 Izumi Techno Inc. Method of treating surface of aluminum blank
DE10161478A1 (de) * 2001-12-14 2003-06-26 Henkel Kgaa Verfahren zum Verdichten von anodisierten Metalloberflächen im mittleren Temperaturbereich
USD790918S1 (en) 2015-07-27 2017-07-04 Whirlpool Corporation Food processing attachment
USD790917S1 (en) 2015-07-27 2017-07-04 Whirlpool Corporation Food processing attachment
CN105040067B (zh) * 2015-09-09 2017-09-29 佛山市海化表面处理科技有限公司 环保型无镍无氟中温封闭剂及封闭方法
ITUB20160646A1 (it) * 2016-02-10 2017-08-10 Italtecno S R L Metodo per il fissaggio dell'ossido anodico.
US10138566B2 (en) * 2017-01-13 2018-11-27 Macdermid Acumen, Inc. Sealing anodized aluminum using a low-temperature nickel-free process
US10480093B2 (en) 2017-05-12 2019-11-19 United Technologies Corporation Sealing process for an anodized aluminum-alloy surface
USD867051S1 (en) 2017-10-04 2019-11-19 Whirlpool Corporation Grinder attachment for a stand mixer
USD885822S1 (en) 2018-12-14 2020-06-02 Whirlpool Corporation Food grinder

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Publication number Priority date Publication date Assignee Title
BE792852A (fr) * 1971-12-17 1973-06-15 Henkel & Cie Gmbh Procede de traitement de surfaces d'aluminium par oxydation suivie d'une densification
DE2211553C3 (de) * 1972-03-10 1978-04-20 Henkel Kgaa, 4000 Duesseldorf Verfahren zum Verdichten von anodischen Oxidschichten auf Aluminium und Aluminiumlegierungen
DE2650989C2 (de) * 1976-11-08 1985-01-24 Henkel KGaA, 4000 Düsseldorf Verfahren zur Behandlung von Aluminiumoberflächen durch Oxidation mit einer nachfolgenden Verdichtung
US4202706A (en) * 1979-03-12 1980-05-13 Minnesota Mining And Manufacturing Company Corrosion resistance treatment of aluminum with N-alkyl-fluoroaliphaticsulfonamidophosphonic acids and salts thereof
US4376000A (en) * 1980-11-28 1983-03-08 Occidental Chemical Corporation Composition for and method of after-treatment of phosphatized metal surfaces
GB8309571D0 (en) * 1983-04-08 1983-05-11 Albright & Wilson Accelerated sealing of anodised aluminium
US4647347A (en) * 1984-08-16 1987-03-03 Amchen Products, Inc. Process and sealant compositions for sealing anodized aluminum
DE3820650A1 (de) * 1988-06-18 1989-12-21 Henkel Kgaa Verfahren zum verdichten von anodisierten oxidschichten auf aluminium und aluminiumlegierungen
US5411607A (en) * 1993-11-10 1995-05-02 Novamax Technologies Holdings, Inc. Process and composition for sealing anodized aluminum surfaces
CN1125271A (zh) * 1994-12-23 1996-06-26 华东冶金学院 铝和铝合金低温快速封闭剂及封闭工艺

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Publication number Publication date
US5935656A (en) 1999-08-10
ES2142619T3 (es) 2000-04-16
AR004035A1 (es) 1998-09-30
DE59604329D1 (de) 2000-03-02
EP0857227A1 (fr) 1998-08-12
AU7287896A (en) 1997-05-07
WO1997014828A1 (fr) 1997-04-24

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