[go: up one dir, main page]

WO1997005302A1 - Process for depôtsols into microporous coating layers - Google Patents

Process for depôtsols into microporous coating layers Download PDF

Info

Publication number
WO1997005302A1
WO1997005302A1 PCT/DE1996/001188 DE9601188W WO9705302A1 WO 1997005302 A1 WO1997005302 A1 WO 1997005302A1 DE 9601188 W DE9601188 W DE 9601188W WO 9705302 A1 WO9705302 A1 WO 9705302A1
Authority
WO
WIPO (PCT)
Prior art keywords
lyosol
silica
microporous
pores
capillaries
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.)
Ceased
Application number
PCT/DE1996/001188
Other languages
German (de)
French (fr)
Inventor
Ulrich Reininghaus
Peter Kurze
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.)
Electro Chemical Engineering GmbH
Original Assignee
Electro Chemical Engineering GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Electro Chemical Engineering GmbH filed Critical Electro Chemical Engineering GmbH
Priority to DE29680628U priority Critical patent/DE29680628U1/en
Priority to EP96922737A priority patent/EP0842309B1/en
Priority to DE19680596A priority patent/DE19680596C1/en
Priority to AU63527/96A priority patent/AU6352796A/en
Priority to DE59608600T priority patent/DE59608600D1/en
Priority to AT96922737T priority patent/ATE212075T1/en
Publication of WO1997005302A1 publication Critical patent/WO1997005302A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C25D11/18—After-treatment, e.g. pore-sealing
    • 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
    • C25D11/30—Anodisation of magnesium or alloys based thereon
    • 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
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • 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
    • C25D11/026—Anodisation with spark discharge

Definitions

  • aluminum is relatively corrosion-resistant because the metal surface in the air is immediately covered with a 5 to 20 nm thick, firmly adhering and very dense oxide layer which prevents further oxygen access.
  • Magnesium and titanium and their alloys are also protected against further oxidation by a thin oxide layer at normal temperature.
  • the anodically produced coating consists, for example, of a coherent sub-layer (barrier layer) about 0.15 ⁇ m thick and a microporous cover layer, which consists of capillaries perpendicular to the metal of 0.01 to 0.05 ⁇ m (10 - 50 nm) is penetrated at a distance of about 0.3 ⁇ m.
  • the microporous cover layer has an inner surface of about 100 m / g after its production and is very chemically reactive. This high chemical reactivity is caused by active centers, which are formed by OH groups in the near-surface area of the microporous cover layer (see Peri, J.B .: J.Phsy.Chem. 69 (1965), p. 220). With newer methods of anodic oxidation, microporous cover layers down to about 200 ⁇ m can be created on Al materials.
  • Anodic oxidation of magnesium can also be used to produce microporous cover layers which are oxidic in nature and, if appropriate
  • Anodic oxidation of titanium also forms microporous cover layers with different oxidic compositions
  • the pores are of different sizes. They range in size from 10 nm to 30 ⁇ m.
  • Coating film on the corrosion-resistant anodized surface film of aluminum products in which this includes subjected to a sealing treatment of the micropores in the oxide film by immersing them in an aqueous sealing liquid containing dispersed silica and then coating them with a thermosetting acrylic resin.
  • the purpose of this process is to be able to use coating agents with a drying or curing temperature of 140 ° C. or above due to the sealing treatment, in which problems of cracking and insufficient adhesion previously occurred.
  • Oxide films by immersing the aluminum objects in the aqueous sealing liquid containing silica or silicate should also close the micropores so that, for example, sulfuric acid remaining therein can no longer escape; but it was not possible or intends to fill the vertical capillaries with the silica.
  • the aim of the invention is to avoid the corrosion caused by the pores and to produce a stable bond between the microporous oxide cover layer and at least one compound forming an inorganic network.
  • the invention relates to a process for the treatment of microporous top layers produced by anodic oxidation or by plasma-chemical anodic oxidation on objects made of aluminum, magnesium, titanium or their alloys, in the form of silica in the pores or capillaries of the microporous top layer a lyosol is introduced in which the colloidally distributed Si0 2 particles are at least one dimension smaller than the diameter of the pores or capillaries and the introduced and applied silica lyosol is then coagulated or reacted with the cover layer.
  • a lyosol is a colloidal solution in which a solid substance is dispersed in a finely divided form in a liquid.
  • Organosols and hydrosols can also be used for the purposes of the invention, depending on whether it is a suspension of the silica in organic liquids, such as alcohols, preferably C 1 -C 6 -alcohols, or water.
  • organic liquids such as alcohols, preferably C 1 -C 6 -alcohols, or water.
  • the silica lyosol is a silica sol (see Römpp, chemistry lexicon, key words brine and silica sol).
  • the sol In order to achieve an incorporation of the sol into the pores or capillaries, it is introduced according to the invention in a form in which the SiO 2 particles are at least one dimension smaller than that
  • the size of the particles of colloidal silica in the sol is accordingly about 1 to 50 nm, preferably 1 to 10 nm.
  • the particles of the colloidal silica to be introduced are Appropriately as an aqueous and / or organic dispersion.
  • the film formers such as alcohols and / or silanes and / or salts of organic acids, which tend to polymerize or polycondense, are added to the SiO 2 sols.
  • Silica sols suitable for the purposes of the invention are known. They are produced by in situ growth of Si0 2 micro-nuclei and are then present as a concentrated aqueous dispersion of colloidally distributed pore-free amorphous Si0 2 particles. These Si0 2 dispersions generally contain minor amounts of alkali, which negatively charge the surface of the Si0 2 particles. As a result, the particles repel each other and bring about the stability of the solution. Silica sols which are suitable for the purposes of the invention are commercially available, for example, under the name KLEBOSOL. These can also be modified by other film-forming oxides of the third to eighth group of the periodic system of the elements, for example aluminum, indium, zirconium, titanium, iron, nickel and rare earths. Modification with mono- or polyhydric alcohols, eg diethylene glycol, is also possible. The silica lyosols can be produced by in situ growth of Si0 2 micro-nuclei and are then present as a concentrated aqueous dispersion
  • Substances especially alcohols and silanes, are added which form films with the silica.
  • the sols can also contain fillers, corrosion inhibitors, dyes, lubricants, surface-active substances, UV stabilizers in amounts which do not affect the reactivity of the sol with the microporous top layer.
  • Solids concentration of the silica sol is advantageously 15 to 60%, preferably 30 to 50%.
  • Objects with such oxide cover layers are immersed in the lyosol, in particular silica sol, sprayed or painted with them.
  • the introduction can be improved in that the object provided with the oxide layer and immersed in the lyosol changes Exposed to pressure conditions.
  • An impregnation system is suitable for this, in which the air is first removed from the pores or capillaries using a vacuum. Under the action of the vacuum, the lyosol penetrates into the pores and, after the vacuum is released, is pressed into the pores by atmospheric pressure and thus also reaches the bottom of the vertical capillaries of the anodically produced coatings of aluminum or the finest branches of the microporous cover layers on magnesium or titanium materials or on the oxide ceramic layers produced by plasma chemical oxidation.
  • the change from vacuum and pressure, which can also exceed atmospheric pressure, is repeated one or more times if necessary.
  • Devices suitable for introducing the particles into the microporous cover layer of the objects are available, for example, in the form of the Maldaner impregnation system.
  • microporous cover layers such as hard anodized layers or oxide ceramic layers, which are less than 24 hours old, accelerate the incorporation of the silica sol to the bottom of the capillaries and pores by anodic oxidation or by plasma-chemical anodic oxidation.
  • Coagulation of the silica lyosol according to the sol-gel process known per se for the film formation of such brine (Sol-Gel Technology for thin Films, Fibers, Preforms, Electronics, and Specialty Shapes, edited by Lisa Klein, Noyes Publications, S. 50 ff., Sect. 4, Helmut Dislich, Thin Films from the Sol-Gel Process). Coagulation takes place by withdrawing the liquid from the lyosol, in particular the silica sol.
  • This silicate glass layer formed on the surface of the microporous cover layer from the Si0 2 particles is provided with pins protruding vertically into the capillaries of the anodized layer and having a diameter of 10 to 50 nm or in the manner of roots which penetrate the capillaries of other oxide layers, in particular ceramic layers. protrude, firmly anchored in the microporous top layer. That is probably the reason for the high corrosion and scratch resistance.
  • the invention also relates to components made of aluminum,
  • the surface of the microporous cover layer is preferably also covered with a film of these gels and connected to the gels in the pores or capillaries.
  • magnesium casting alloys of the ASTM designation are also suitable for the purposes of the invention.
  • EP-B-333 084 were treated according to the ORMOCER process in order to fill the capillaries and pores and to seal the surface of the microporous cover layer.
  • a scanning electron micrograph on a cross-section shows that the pores and capillaries are filled with the silicon dioxide formed after the thermal treatment or its reaction products.
  • the outer sealing layer has a thickness of approximately 5 ⁇ m.
  • plates After immersion in soda water glass and subsequent silicification in a CO 2 atmosphere, plates likewise had an approximately 5 ⁇ m thick sealing layer and in the neutral salt spray test mentioned only a service life of approx. 200 hours.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Materials For Medical Uses (AREA)
  • Physical Vapour Deposition (AREA)
  • Chemical Vapour Deposition (AREA)
  • Paints Or Removers (AREA)
  • Saccharide Compounds (AREA)

Abstract

A process is disclosed for treating microporous coating layers deposited by anodic oxidation or plasmachemical anodic oxidation on objects made of aluminium, magnesium, titanium or their alloys. The process is useful to permanently seal the microporous coating layer and thus to protect the base material against corrosion and wear. For that purpose, silicic acid in the form of a silicic acid lyosol is deposited into the pores or capillaries of the microporous coating layer. In the silicic acid lyosol, the colloidally distributed SiO2 particles have at least one dimension smaller than the diameter of the pores or capillaries. The sol thus deposited into the pores is then coagulated or made to react with the coating layer.

Description

Verfahren zur Einlagerung von Solen in mikroporöse Deckschichten Process for the storage of brines in microporous cover layers

B e s c h r e i b u n gDescription

Aluminium ist trotz der hohen Affinität gegenüber Sauerstoff an der Luft relativ korrosionsbeständig, weil sich die Metalloberfläche an der Luft sofort mit einer 5 bis 20 nm dicken, festhaftenden und sehr dich¬ ten Oxidschicht bedeckt, die den weiteren Sauerstoffzutritt verhindert. Auch Magnesium und Titanium und deren Legierungen sind durch eine dünne Oxidschicht bei normaler Temperatur gegen weitere Oxidation geschützt.Despite the high affinity for oxygen in the air, aluminum is relatively corrosion-resistant because the metal surface in the air is immediately covered with a 5 to 20 nm thick, firmly adhering and very dense oxide layer which prevents further oxygen access. Magnesium and titanium and their alloys are also protected against further oxidation by a thin oxide layer at normal temperature.

Es ist bekannt, die natürlichen Oxidschichten der genannten Metalle durch anodische Oxidation erheblich zu verstärken. Dabei bilden sich Konversionsschichten .It is known to significantly strengthen the natural oxide layers of the metals mentioned by anodic oxidation. Conversion layers are formed.

Bei Aluminium besteht der anodisch erzeugte Überzug zum Beispiel aus einer etwa 0,15 μm dicken zusammenhängenden Unterschicht (barrier layer) und einer mikroporösen Deckschicht, die von senkrecht zum Metall stehenden Kapillaren von 0,01 bis 0,05 μm (10 - 50 nm) in einem Abstand von etwa 0,3 μm durchsetzt ist. Die mikroporöse Deckschicht hat nach ihrer Erzeugung eine innere Oberfläche von etwa 100 m /g und ist chemisch sehr reaktionsfähig. Diese hohe chemische Reaktivität wird durch aktive Zentren, die durch OH- Gruppen im oberflächennahen Bereich der mikroporösen Deckschicht gebildet sind, verursacht (vgl. Peri, J.B.: J.Phsy.Chem. 69 (1965), S. 220). Mit neueren Verfahren der anodischen Oxidation gelingt es, auf Al-Werkstoffen mikroporöse Deckschichten bis etwa 200 μm zu erzeugen.In the case of aluminum, the anodically produced coating consists, for example, of a coherent sub-layer (barrier layer) about 0.15 μm thick and a microporous cover layer, which consists of capillaries perpendicular to the metal of 0.01 to 0.05 μm (10 - 50 nm) is penetrated at a distance of about 0.3 μm. The microporous cover layer has an inner surface of about 100 m / g after its production and is very chemically reactive. This high chemical reactivity is caused by active centers, which are formed by OH groups in the near-surface area of the microporous cover layer (see Peri, J.B .: J.Phsy.Chem. 69 (1965), p. 220). With newer methods of anodic oxidation, microporous cover layers down to about 200 μm can be created on Al materials.

Auch durch anodische Oxidation von Magnesium lassen sich mikro- poröse Deckschichten, die oxidischer Natur sind und gegebenenfallsAnodic oxidation of magnesium can also be used to produce microporous cover layers which are oxidic in nature and, if appropriate

Fluorid oder Phosphat enthalten, mit einer Dicke bis zu 30 μm und guter Verschleißbeständigkeit erzeugen (DE-A-38 08 610). Bekannt sind hierbei auch das HAE- und DOW 17-Verfahren (vgl. H. Simon, M. Thoma „Angewandte Oberflächentechnik für metallische Werk¬ stoffe", Carl Hanser Verlag, München Wien 1985, S. 91 ff.).Contain fluoride or phosphate, with a thickness of up to 30 μm and good wear resistance (DE-A-38 08 610). The HAE and DOW 17 processes are also known (cf. H. Simon, M. Thoma "Applied surface technology for metallic materials", Carl Hanser Verlag, Munich Vienna 1985, p. 91 ff.).

Durch anodische Oxidation von Titanium bilden sich auch mikro- poröse Deckschichten mit verschieden oxidischer ZusammensetzungAnodic oxidation of titanium also forms microporous cover layers with different oxidic compositions

(vgl. Simon & Thoma).(see Simon & Thoma).

Auf Aluminium-, Magnesium- oder Titanwerkstoffen lassen sich durch plasmachemische anodische Oxidation mikroporöse Deckschichten als Oxidkeramikschichten mit hoher Reaktionsfähigkeit erzeugen (EP-B-On aluminum, magnesium or titanium materials, plasma-chemical anodic oxidation can be used to produce microporous cover layers as oxide ceramic layers with high reactivity (EP-B-

280 886, 333 048, 545 230). Die Poren sind hier von unterschiedlicher Größe. Sie reichen von einer Größe von 10 nm bis 30 μm.280 886, 333 048, 545 230). The pores here are of different sizes. They range in size from 10 nm to 30 μm.

Es hat nicht an Versuchen gefehlt, die mikroporöse Deckschicht dauerhaft zu versiegeln, um den Grundwerkstoff gegen Korrosion undThere has been no lack of attempts to permanently seal the microporous cover layer in order to protect the base material against corrosion and

Verschleiß zu schützen. Dazu sind verschiedene Verfahren, wie Sealing in heißem Wasser, Tränken in Ölen und Wachsen bis hin zu einem Auftrag von organischen Lacken, bekannt. Diese Verfahren genügen keineswegs den heutigen Anforderungen. Das gleiche gilt für das aus der DE-A-28 12 116 bekannte Verfahren zur Herstellung einesTo protect wear. Various processes are known for this, such as sealing in hot water, soaking in oils and waxes and applying organic paints. These processes do not meet today's requirements. The same applies to the method for producing a known from DE-A-28 12 116

Überzugfilms auf dem korrosionsbeständigen anodisch oxidierten Oberflächenfilm von Alurniniumerzeugnissen, bei dem dieser u.a. einer Versiegelungsbehandlung der Mikroporen in dem Oxidfilm durch Eintauchen in eine dispergierte Kieselsäure enthaltende wäßrige Versiegelungsflüssigkeit unterworfen und anschließend mit einem wärmehärtenden Acrylharz überzogen wird. Zweck dieses Verfahrens ist es, aufgrund der Versiegelungsbehandlung Überzugsmittel mit einer Trocknungs- oder Härtungstemperatur von 140 °C oder darüber ver¬ wenden zu können, bei denen vorher Probleme der Rißbildung und ungenügende Haftung auftraten. Die Versiegelungsbehandlung desCoating film on the corrosion-resistant anodized surface film of aluminum products, in which this includes subjected to a sealing treatment of the micropores in the oxide film by immersing them in an aqueous sealing liquid containing dispersed silica and then coating them with a thermosetting acrylic resin. The purpose of this process is to be able to use coating agents with a drying or curing temperature of 140 ° C. or above due to the sealing treatment, in which problems of cracking and insufficient adhesion previously occurred. The sealing treatment of the

Oxidfilms durch Eintauchen der Aluminiumgegenstände in die Kiesel¬ säure oder Silikat enthaltende wäßrige Versiegelungsflüssigkeit soll zwar auch die Mikroporen verschließen, damit z.B. darin verbliebene Schwefelsäure nicht mehr austreten kann; es war aber nicht möglich oder beabsichtigt, die senkrechten Kapillaren mit der Kieselsäure zu füllen.Oxide films by immersing the aluminum objects in the aqueous sealing liquid containing silica or silicate should also close the micropores so that, for example, sulfuric acid remaining therein can no longer escape; but it was not possible or intends to fill the vertical capillaries with the silica.

Ziel der Erfindung ist es, die durch die Poren bedingte Korrosion zu vermeiden und einen stabilen Verbund zwischen der mikroporösen oxidischen Deckschicht und mindestens einer ein anorganisches Netzwerk bildenden Verbindung herzustellen.The aim of the invention is to avoid the corrosion caused by the pores and to produce a stable bond between the microporous oxide cover layer and at least one compound forming an inorganic network.

Gegenstand der Erfindung ist ein Verfahren zur Behandlung von mikroporösen, durch anodische Oxidation oder durch plasmachemi¬ sche anodische Oxidation hergestellten Deckschichten auf Gegenstän¬ den aus Aluminium, Magnesium, Titanium oder deren Legierungen, bei dem Kieselsäure in die Poren oder Kapillaren der mikroporösen Deckschicht in Form eines Lyosols eingebracht wird, in dem die kolloidal verteilten Si02-Teilchen wenigstens in einer Dimension kleiner sind, als der Durchmesser der Poren oder Kapillaren und das eingebrachte und aufgetragene Kieselsäure-Lyosol anschließend koaguliert oder mit der Deckschicht zur Reaktion gebracht wird. Ein Lyosol ist definitionsgemäß eine kolloidale Lösung, in der ein fester Stoff in feinster Verteilung in einer Flüssigkeit dispergiert ist.The invention relates to a process for the treatment of microporous top layers produced by anodic oxidation or by plasma-chemical anodic oxidation on objects made of aluminum, magnesium, titanium or their alloys, in the form of silica in the pores or capillaries of the microporous top layer a lyosol is introduced in which the colloidally distributed Si0 2 particles are at least one dimension smaller than the diameter of the pores or capillaries and the introduced and applied silica lyosol is then coagulated or reacted with the cover layer. By definition, a lyosol is a colloidal solution in which a solid substance is dispersed in a finely divided form in a liquid.

Auch für die Zwecke der Erfindung sind Organosole und Hydrosole brauchbar, je nachdem, ob es sich um eine Suspension der Kieselsäure in organischen Flüssigkeiten, wie z.B. Alkoholen, bevor¬ zugt Ci- bis C6-Alkoholen, oder Wasser handelt. In diesem Fall ist das Kieselsäure-Lyosol ein Kieselsol (s. Römpp, Chemie-Lexikon, Stich¬ worte Sole und Kieselsol).Organosols and hydrosols can also be used for the purposes of the invention, depending on whether it is a suspension of the silica in organic liquids, such as alcohols, preferably C 1 -C 6 -alcohols, or water. In this case the silica lyosol is a silica sol (see Römpp, chemistry lexicon, key words brine and silica sol).

Um eine Einlagerung des Sols in die Poren oder Kapillaren zu errei¬ chen, wird es erfindungsgemäß in einer Form eingeführt, in der die Si02-Teilchen wenigstens in einer Dimension kleiner sind als derIn order to achieve an incorporation of the sol into the pores or capillaries, it is introduced according to the invention in a form in which the SiO 2 particles are at least one dimension smaller than that

Durchmesser der Poren oder Kapillaren der mikroporösen oxidischen Deckschicht. Die Größe der Teilchen kolloidaler Kieselsäure im Sol beträgt demzufolge etwa 1 bis 50 nm, vorzugsweise 1 bis 10 nm. Die einzubringenden Teilchen der kolloidalen Kieselsäure liegen zweckmäßig als wäßrige und/oder organische Dispersion vor. Um eine gute Filmbildung zu erreichen, sind den Si02-Solen zur Polymerisation bzw. Polykondensation neigende Filmbildner wie Alkohole und/oder Silane und/oder Salze organischer Säuren zuge- setzt.Diameter of the pores or capillaries of the microporous oxide cover layer. The size of the particles of colloidal silica in the sol is accordingly about 1 to 50 nm, preferably 1 to 10 nm. The particles of the colloidal silica to be introduced are Appropriately as an aqueous and / or organic dispersion. In order to achieve good film formation, the film formers, such as alcohols and / or silanes and / or salts of organic acids, which tend to polymerize or polycondense, are added to the SiO 2 sols.

Für die Zwecke der Erfindung geeignete Kieselsole sind bekannt. Sie werden durch in situ Wachstum von Si02-Mikrokeimen hergestellt und liegen dann als konzentrierte wäßrige Dispersion von kolloidal verteil- ten porenfreien amoφhen Si02-Teilchen vor. Diese Si02-Dispersionen enthalten in der Regel geringfügige Alkalimengen, die die Oberfläche der Si02-Partikel negativ laden. Dadurch stoßen sich die Teilchen gegenseitig ab und bewirken die Stabilität der Lösung. Für die Zwecke der Erfindung geeignete Kieselsole sind beispielsweise unter der Bezeichnung KLEBOSOL im Handel. Diese können auch durch andere filmbildende Oxide der dritten bis achten Gruppe des periodischen Systems der Elemente, z.B. des Aluminiums, Indiums, Zirkons, Titaniums, Eisens, Nickels und der Seltenen Erden modifiziert sein. Ebenso ist die Modifizierung mit ein- oder mehrwertigen Alkoholen, z.B. Diethylenglycol, möglich. Den Kieselsäure-Lyosolen könnenSilica sols suitable for the purposes of the invention are known. They are produced by in situ growth of Si0 2 micro-nuclei and are then present as a concentrated aqueous dispersion of colloidally distributed pore-free amorphous Si0 2 particles. These Si0 2 dispersions generally contain minor amounts of alkali, which negatively charge the surface of the Si0 2 particles. As a result, the particles repel each other and bring about the stability of the solution. Silica sols which are suitable for the purposes of the invention are commercially available, for example, under the name KLEBOSOL. These can also be modified by other film-forming oxides of the third to eighth group of the periodic system of the elements, for example aluminum, indium, zirconium, titanium, iron, nickel and rare earths. Modification with mono- or polyhydric alcohols, eg diethylene glycol, is also possible. The silica lyosols can

Substanzen, insbesondere Alkohole und Silane, zugesetzt werden, die mit der Kieselsäure Filme bilden. Die Sole können auch Füllstoffe, Korrosionsinhibitoren, Farbstoffe, Gleitmittel, oberflächenaktive Sub¬ stanzen, UV-Stabilisatoren in Mengen enthalten, die das Sol in seiner Reaktivität mit der mikroporösen Deckschicht nicht beeinflussen. DieSubstances, especially alcohols and silanes, are added which form films with the silica. The sols can also contain fillers, corrosion inhibitors, dyes, lubricants, surface-active substances, UV stabilizers in amounts which do not affect the reactivity of the sol with the microporous top layer. The

Feststoffkonzentration des Kieselsols beträgt zweckmäßig 15 bis 60 %, vorzugsweise 30 bis 50 %.Solids concentration of the silica sol is advantageously 15 to 60%, preferably 30 to 50%.

Zum Einbringen der kolloidal verteilten Si02-Teilchen des Lyosols in die Poren oder Kapillaren der mikroporösen Deckschicht werden dieTo introduce the colloidally distributed Si0 2 particles of the lyosol into the pores or capillaries of the microporous cover layer, the

Gegenstände mit solchen oxidischen Deckschichten in das Lyosol, insbesondere Kieselsol, getaucht, damit bespritzt oder gestrichen. Das Einbringen läßt sich dadurch verbessern, daß der mit der Oxidschicht versehene, in das Lyosol eingetauchte Gegenstand wechselnden Druckbedingungen ausgesetzt wird. Hierfür eignet sich ein Imprägniersystem, bei dem zunächst mittels Vakuum die Luft aus den Poren oder Kapillaren entfernt wird. Unter Einwirkung des Vakuums dringt das Lyosol in die Poren ein und wird, nachdem das Vakuum aufgehoben ist, durch den atmosphärischen Druck in die Poren gepreßt und erreicht so auch den Boden der senkrechten Kapillaren der anodisch erzeugten Überzüge von Aluminium oder die feinsten Verästelungen der mikroporösen Deckschichten auf Magnesium- oder Titanwerkstoffen bzw. der durch plasmachemische Oxidation herge- stellten Oxidkeramikschichten. Der Wechsel vom Vakuum und Druck, der auch über den atmosphärischen Druck hinausgehen kann, wird erforderlichenfalls ein oder mehrmals wiederholt. Für dieses Einbringen der Teilchen in die mikroporöse Deckschicht der Gegenstände geeignete Vorrichtungen stehen z.B. in Form des Maldaner-Imprägniersystems zur Verfügung.Objects with such oxide cover layers are immersed in the lyosol, in particular silica sol, sprayed or painted with them. The introduction can be improved in that the object provided with the oxide layer and immersed in the lyosol changes Exposed to pressure conditions. An impregnation system is suitable for this, in which the air is first removed from the pores or capillaries using a vacuum. Under the action of the vacuum, the lyosol penetrates into the pores and, after the vacuum is released, is pressed into the pores by atmospheric pressure and thus also reaches the bottom of the vertical capillaries of the anodically produced coatings of aluminum or the finest branches of the microporous cover layers on magnesium or titanium materials or on the oxide ceramic layers produced by plasma chemical oxidation. The change from vacuum and pressure, which can also exceed atmospheric pressure, is repeated one or more times if necessary. Devices suitable for introducing the particles into the microporous cover layer of the objects are available, for example, in the form of the Maldaner impregnation system.

Überraschenderweise hat sich gezeigt, daß durch anodische Oxidation oder durch plasmachemische anodische Oxidation frisch hergestellte mikroporöse Deckschichten, wie Harteloxalschichten oder Oxid- keramikschichten, die weniger als 24 Stunden alt sind, die Einlagerung des Kieselsols bis an den Grund der Kapillaren und Poren beschleu¬ nigen.Surprisingly, it has been shown that freshly produced microporous cover layers, such as hard anodized layers or oxide ceramic layers, which are less than 24 hours old, accelerate the incorporation of the silica sol to the bottom of the capillaries and pores by anodic oxidation or by plasma-chemical anodic oxidation.

Wenn die Poren oder Kapillaren der Deckschichten so gut wie mög- lieh mit den kolloidalen Si02-Teilchen gefüllt sind, sorgt man für eineIf the pores or capillaries of the cover layers are filled with the colloidal Si0 2 particles as well as possible, you will be taken care of

Koagulation des Kieselsäure-Lyosols, nach dem für die Filmbildung solcher Sole an sich bekannten Sol-Gel-Prozeß (Sol-Gel Technology for thin Films, Fibers, Preforms, Electronics, and Specialty Shapes, edited by Lisa Klein, Noyes Publications, S. 50 ff., Abschn. 4, Helmut Dislich, Thin Films from the Sol-Gel Process). Die Koagulation erfolgt durch Entzug der Flüssigkeit des Lyosols, insbesondere des Kieselsols. Schon aufgrund der bevorzugten Reaktion frisch hergestellter oxidischer Deckschichten wird angenommen, daß es bei der Koagulation durch Erwärmen auf Temperaturen bis zu 300 °C, vorzugsweise bis zu 150 °C, zugleich zu Reaktionen zwischen den mikroporösen oxidischen Deckschichten und den sehr feinen und damit auch sehr reaktionsfähigen Si02-Teilchen in den Poren und an der Oberfläche der Deckschichten kommt. Die Si02-Schichten sind vermutlich glasähnlich und amorph und haben eine Dicke bis zuCoagulation of the silica lyosol, according to the sol-gel process known per se for the film formation of such brine (Sol-Gel Technology for thin Films, Fibers, Preforms, Electronics, and Specialty Shapes, edited by Lisa Klein, Noyes Publications, S. 50 ff., Sect. 4, Helmut Dislich, Thin Films from the Sol-Gel Process). Coagulation takes place by withdrawing the liquid from the lyosol, in particular the silica sol. Already due to the preferred reaction of freshly produced oxidic cover layers, it is assumed that during coagulation by heating to temperatures up to 300 ° C, preferably up to 150 ° C, at the same time there are reactions between the microporous oxide cover layers and the very fine and thus also very reactive Si0 2 particles in the pores and on the surface of the cover layers. The Si0 2 layers are presumably glass-like and amorphous and have a thickness of up to

5 μm, insbesondere 0,5 bis 2 mm. Diese an der Oberfläche der mikroporösen Deckschicht aus den Si02-Paιtikeln gebildete Silikat¬ glasschicht ist mit senkrecht in die Kapillaren der Eloxalschicht hineinragenden Stiften von 10 bis 50 nm Durchmesser bzw. nach Art von Wurzeln, die in die Kapillaren anderer Oxidschichten, insbesondere Keramikschichten, hineinragen, fest in der mikroporösen Deckschicht verankert. Das ist vermutlich die Ursache für die hohe Korrosions- und Kratzfestigkeit.5 μm, in particular 0.5 to 2 mm. This silicate glass layer formed on the surface of the microporous cover layer from the Si0 2 particles is provided with pins protruding vertically into the capillaries of the anodized layer and having a diameter of 10 to 50 nm or in the manner of roots which penetrate the capillaries of other oxide layers, in particular ceramic layers. protrude, firmly anchored in the microporous top layer. That is probably the reason for the high corrosion and scratch resistance.

Gegenstand der Erfindung sind auch Bauteile aus Aluminium-,The invention also relates to components made of aluminum,

Magnesium- oder Titanwerkstoffen mit einer durch anodische Oxida¬ tion oder plasmachemisch anodischen Oxidation erzeugten mikro¬ porösen Deckschicht, deren Poren oder Kapillaren im wesentlichen mit dem, gegebenenfalls modifizierten, Si02-Gel gefüllt sind. Vorzugsweise ist auch die Oberfläche der mikroporösen Deckschicht mit einem Film dieser Gele überzogen und mit den Gelen in den Poren oder Kapillaren verbunden.Magnesium or titanium materials with a microporous cover layer produced by anodic oxidation or plasma chemical anodic oxidation, the pores or capillaries of which are essentially filled with the optionally modified SiO 2 gel. The surface of the microporous cover layer is preferably also covered with a film of these gels and connected to the gels in the pores or capillaries.

Unter Aluminiumwerkstoffen werden im Rahmen der Erfindung Reinstaluminium und Legierungen AlMn; AlMnCu; AlMgl; AlMgl,5; E-Within the scope of the invention, pure aluminum and alloys AlMn; AlMnCu; AlMgl; AlMgl, 5; E-

AlMgSi; AlMgSi0,5; AlZnMgCu0,5, AlZnMgCul,5; G-A1SÜ2; G-AlSi5Mg; G-AlSi8Cu3; G-AlCu4Ti; G-AlCu4TiMg verstanden.AlMgSi; AlMgSi0.5; AlZnMgCu0.5, AlZnMgCul, 5; G-A1SÜ2; G-AlSi5Mg; G-AlSi8Cu3; G-AlCu4Ti; G-AlCu4TiMg understood.

Für die Zwecke der Erfindung eignen sich ferner außer Reinmagne- sium, insbesondere Magnesiumgußlegierungen der ASTM-BezeichnungIn addition to pure magnesium, magnesium casting alloys of the ASTM designation are also suitable for the purposes of the invention

AS41; AM60; AZ6l; AZ63; AZ81; AZ91; AZ92; HK31; QE22; ZE41; ZH62, ZK51; ZK61, EZ33; HZ33 sowie die Knetlegierungen AZ31; AZ61; AZ80; Ml, ZK60; ZK40. Als Titanwerkstoffe eignen sich Rein- titanium oder die Legierung TiAl6V4. BeispielAS41; AM60; AZ6l; AZ63; AZ81; AZ91; AZ92; HK31; QE22; ZE41; ZH62, ZK51; ZK61, EZ33; HZ33 and the wrought alloys AZ31; AZ61; AZ80; Ml, ZK60; ZK40. Pure titanium or the alloy TiAl6V4 are suitable as titanium materials. example

Platten aus der Magnesiumlegierung AZ91HP der Größe 100 x 50 x 2 mm, die beidseitig durch plasmachemische anodische Oxidation mit einer mikroporösen Deckschicht von 20 μm nach demSheets made of AZ91HP magnesium alloy, size 100 x 50 x 2 mm, which are covered on both sides by plasma chemical anodic oxidation with a microporous cover layer of 20 μm

Verfahren der EP-B-333 084 versehen worden waren, wurden nach dem ORMOCER-Verfahren behandelt, um die Kapillaren und Poren auszufüllen und die mikroporöse Deckschicht oberflächlich zu versie¬ geln. Eine raster-elektronenmikroskopische Aufnahme an einem Quer- schliff zeigt, daß die Poren und Kapillaren mit dem nach der thermi¬ schen Behandlung gebildeten Siliciumdioxid oder dessen Reaktions¬ produkten gefüllt sind. Die äußere Versiegelungsschicht hat eine Dicke von etwa 5 μm.Processes of EP-B-333 084 were treated according to the ORMOCER process in order to fill the capillaries and pores and to seal the surface of the microporous cover layer. A scanning electron micrograph on a cross-section shows that the pores and capillaries are filled with the silicon dioxide formed after the thermal treatment or its reaction products. The outer sealing layer has a thickness of approximately 5 μm.

Die so erhaltene Platte wurde dem neutralen Salznebeltest nach DINThe plate thus obtained was subjected to the neutral salt spray test according to DIN

SS 50021 unterworfen. Sie hatte eine Standzeit von 1500 Stunden. Auch als der Test abgebrochen wurde, hatten einige Platten noch nicht einmal einen einzigen Korrosionspunkt.Subjected to SS 50021. It had a service life of 1500 hours. Even when the test was stopped, some panels did not even have a single point of corrosion.

Die gleichen, mit der gleichen oxidischen Deckschicht versehenenThe same, provided with the same oxidic top layer

Platten hatten nach dem Tauchen in Natronwasserglas und anschließender Auskieselung in einer C02-Atmosphäre gleichfalls eine etwa 5 μm dicke Versiegelungsschicht und in dem erwähnten neutra¬ len Salznebeltest nur eine Standzeit von ca. 200 Stunden. After immersion in soda water glass and subsequent silicification in a CO 2 atmosphere, plates likewise had an approximately 5 μm thick sealing layer and in the neutral salt spray test mentioned only a service life of approx. 200 hours.

Claims

P a t e n t a n s p r ü c h e Patent claims 1. Verfahren zur Behandlung von mikroporösen, durch anodische Oxida¬ tion oder durch plasmachemische anodische Oxidation hergestellten Deckschichten auf Gegenständen aus Aluminium, Magnesium, Titanium oder deren Legierungen, dadurch gekennzeichnet, daß Kieselsäure in die Poren oder Kapillaren der mikroporösen Deckschicht in Form eines Lyosols eingebracht wird, in dem die kolloidal verteilten Si02-Teilchen wenigstens in einer Dimension kleiner sind als der Durchmesser der Poren oder Kapillaren und daß das Kieselsäure-Lyosol koaguliert oder mit der Deckschicht zur Reaktion gebracht wird.1. A process for the treatment of microporous top layers produced by anodic oxidation or by plasma chemical anodic oxidation on objects made of aluminum, magnesium, titanium or their alloys, characterized in that silica is introduced into the pores or capillaries of the microporous top layer in the form of a lyosol is in which the colloidally distributed Si0 2 particles are at least one dimension smaller than the diameter of the pores or capillaries and that the silica lyosol is coagulated or reacted with the cover layer. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Kiesel¬ säure-Lyosol ein Kieselsol ist.2. The method according to claim 1, characterized in that the Kiesel¬ acid lyosol is a silica sol. 3- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das flüssige Medium des Lyosols ein Alkohol ist.3- The method according to claim 1, characterized in that the liquid medium of the lyosol is an alcohol. 4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß der Alkohol ein aliphatischer Cr bis C6-Alkohol ist.4. The method according to claim 3, characterized in that the alcohol is an aliphatic C r to C 6 alcohol. 5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Durchmesser der Si02-Teilchen im Lyosol 1 bis 50 nm, vorzugs¬ weise 1 bis 10 nm, beträgt.5. The method according to any one of claims 1 to 4, characterized in that the diameter of the Si0 2 particles in the lyosol is 1 to 50 nm, preferably 1 to 10 nm. 6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Koagulation oder die Reaktion mit der Deckschicht durch Erwärmen auf Temperaturen bis zu 300 °C, vorzugsweise bis zu 150 °C, erfolgt.6. The method according to any one of claims 1 to 5, characterized in that the coagulation or the reaction with the cover layer is carried out by heating to temperatures up to 300 ° C, preferably up to 150 ° C. 7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Feststoffkonzentration des Kieselsols 15 bis 60 %, vorzugsweise 30 bis 50 %, beträgt. 7. The method according to any one of claims 1 to 6, characterized in that the solids concentration of the silica sol is 15 to 60%, preferably 30 to 50%. 8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß dem Kieselsäure-Lyosol Substanzen, insbesondere Alkohole und Silane, zugesetzt werden, die mit der Kieselsäure Filme bilden.8. The method according to any one of claims 1 to 7, characterized in that the silica-lyosol substances, in particular alcohols and silanes, are added, which form films with the silica. 9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß dem Kieselsäure-Lyosol Füllstoffe, Korrosionsinhibitoren, Farb¬ stoffe, Gleitmittel, oberflächenaktive Substanzen oder UV-Stabilisatoren zugesetzt werden.9. The method according to any one of claims 1 to 8, characterized in that fillers, corrosion inhibitors, dyes, lubricants, surface-active substances or UV stabilizers are added to the silica-lyosol. 10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß Deckschichten behandelt werden, die nicht älter als 24 Stunden sind.10. The method according to any one of claims 1 to 9, characterized in that cover layers are treated which are not older than 24 hours. 11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeich¬ net, daß die Behandlung der mikroporösen Schicht mit dem Lyosol nach der Koagulation gegebenenfalls mehrfach wiederholt wird.11. The method according to any one of claims 1 to 10, characterized gekennzeich¬ net that the treatment of the microporous layer with the lyosol after the coagulation is optionally repeated several times. 12. Gegenstände aus Aluminium, Magnesium, Titanium oder deren Legie¬ rungen mit einer mikroporösen, durch anodische Oxidation oder durch plasmachemische anodische Oxidation erzeugten Deckschicht, dadurch gekennzeichnet, daß die Poren oder Kapillaren der Deckschicht im wesentlichen mit Siliciumdioxid gefüllt sind.12. Objects made of aluminum, magnesium, titanium or their alloys with a microporous top layer produced by anodic oxidation or by plasma chemical anodic oxidation, characterized in that the pores or capillaries of the top layer are essentially filled with silicon dioxide. 13. Gegenstände nach Anspruch 12, dadurch gekennzeichnet, daß die Oberfläche der mikroporösen Deckschicht mit einer an den Si02-Parti- keln gebildete Silikatglasschicht bedeckt ist. 13. Objects according to claim 12, characterized in that the surface of the microporous cover layer is covered with a silicate glass layer formed on the Si0 2 particles.
PCT/DE1996/001188 1995-07-28 1996-07-02 Process for depôtsols into microporous coating layers Ceased WO1997005302A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE29680628U DE29680628U1 (en) 1995-07-28 1996-07-02 Microporous cover layers with embedded brines
EP96922737A EP0842309B1 (en) 1995-07-28 1996-07-02 Process for deposition of sols into microporous coating layers
DE19680596A DE19680596C1 (en) 1995-07-28 1996-07-02 Process for the storage of sols in microporous cover layers on objects made of aluminum, magnesium, titanium or their alloys and objects made of magnesium, titanium or their alloys with sol-treated cover layers
AU63527/96A AU6352796A (en) 1995-07-28 1996-07-02 Process for depotsols into microporous coating layers
DE59608600T DE59608600D1 (en) 1995-07-28 1996-07-02 METHOD FOR STORING SOLES IN MICROPOROUS COATING LAYERS
AT96922737T ATE212075T1 (en) 1995-07-28 1996-07-02 METHOD FOR INCORPORATING BRINES IN MICROPOROUS COVER LAYERS

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19527688.4 1995-07-28
DE19527688 1995-07-28

Publications (1)

Publication Number Publication Date
WO1997005302A1 true WO1997005302A1 (en) 1997-02-13

Family

ID=7768067

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1996/001188 Ceased WO1997005302A1 (en) 1995-07-28 1996-07-02 Process for depôtsols into microporous coating layers

Country Status (7)

Country Link
EP (1) EP0842309B1 (en)
AT (1) ATE212075T1 (en)
AU (1) AU6352796A (en)
DE (3) DE19680596C1 (en)
ES (1) ES2168491T3 (en)
PT (1) PT842309E (en)
WO (1) WO1997005302A1 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999015474A3 (en) * 1997-09-20 1999-05-27 Bosch Gmbh Robert Composite based on a porous material
EP1231299A4 (en) * 1999-08-17 2006-08-02 Isle Coat Ltd Light alloy-based composite protective multifunction coating
EP1903124A3 (en) * 2006-09-22 2009-07-22 Innovent e.V. Technologieentwicklung Method for manufacturing an inorganic-inorganic or inorganic-organic gradient composite coating
WO2008152077A3 (en) * 2007-06-12 2009-11-05 Siemens Aktiengesellschaft Method for introducing nanoparticles into an anodized aluminum surface
GB2469115A (en) * 2009-04-03 2010-10-06 Keronite Internat Ltd Process for the enhanced corrosion protection of valve metals
CN102199785A (en) * 2011-06-29 2011-09-28 上海理工大学 Microarc oxidation solution of titanium alloy wear-resistant coating and application thereof
GB2513575A (en) * 2013-04-29 2014-11-05 Keronite Internat Ltd Corrosion and erosion-resistant mixed oxide coatings for the protection of chemical and plasma process chamber components
CN106435685A (en) * 2016-09-18 2017-02-22 佛山科学技术学院 Method for preparing low-absorptivity high-hemispherical-emissivity oxidation film on surface of aluminum through electro-deposition
WO2021058916A1 (en) * 2019-09-27 2021-04-01 Liebherr-Aerospace Toulouse Sas Method for manufacturing a fire-resistant part of an air conditioning system and part produced by such a method
US11312107B2 (en) * 2018-09-27 2022-04-26 Apple Inc. Plugging anodic oxides for increased corrosion resistance

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008011298A1 (en) 2007-03-16 2008-09-18 Süddeutsche Aluminium Manufaktur GmbH Partial pigmentation of a cover layer to avoid interference with aluminum components or aluminum-containing components
EP2166200A1 (en) 2008-09-23 2010-03-24 Franz Rübig & Söhne GmbH & Co. KG Valve spring disc and method for its manufacture
DE102017207589A1 (en) * 2017-05-05 2018-11-08 Federal-Mogul Nürnberg GmbH Thermally insulating coating for an aluminum piston

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR802421A (en) * 1936-02-26 1936-09-04 Protection of magnesium against corrosion by vitrification
US4421789A (en) * 1981-06-30 1983-12-20 Occidental Chemical Corporation Process for treating the surfaces of aluminum heat exchangers
EP0410003A1 (en) * 1989-02-14 1991-01-30 Sumitomo Electric Industries, Ltd. Insulated electric wire

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5959896A (en) * 1982-09-28 1984-04-05 Nippon Light Metal Co Ltd Method for sealing aluminum anodic oxide film
JPS59179798A (en) * 1983-03-30 1984-10-12 Mitsubishi Heavy Ind Ltd Aluminum and its alloy member
JPS61250193A (en) * 1985-04-26 1986-11-07 Pentel Kk Surface treatment of formed aluminum or aluminum alloy body to provide antislipping property
DE3808610A1 (en) * 1988-03-15 1989-09-28 Electro Chem Eng Gmbh PROCESS FOR SURFACE FINISHING OF MAGNESIUM AND MAGNESIUM ALLOYS
JPH0327043A (en) * 1989-06-23 1991-02-05 Fuji Photo Film Co Ltd Photosensitive planographic printing plate requiring no dampening water
JPH04311595A (en) * 1991-04-08 1992-11-04 Nippon Parkerizing Co Ltd Ceramic coating method for aluminum
JPH06316787A (en) * 1993-04-28 1994-11-15 Kojundo Chem Lab Co Ltd Treatment of surface of anodized alminum layer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR802421A (en) * 1936-02-26 1936-09-04 Protection of magnesium against corrosion by vitrification
US4421789A (en) * 1981-06-30 1983-12-20 Occidental Chemical Corporation Process for treating the surfaces of aluminum heat exchangers
EP0410003A1 (en) * 1989-02-14 1991-01-30 Sumitomo Electric Industries, Ltd. Insulated electric wire

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999015474A3 (en) * 1997-09-20 1999-05-27 Bosch Gmbh Robert Composite based on a porous material
EP1231299A4 (en) * 1999-08-17 2006-08-02 Isle Coat Ltd Light alloy-based composite protective multifunction coating
EP1903124A3 (en) * 2006-09-22 2009-07-22 Innovent e.V. Technologieentwicklung Method for manufacturing an inorganic-inorganic or inorganic-organic gradient composite coating
WO2008152077A3 (en) * 2007-06-12 2009-11-05 Siemens Aktiengesellschaft Method for introducing nanoparticles into an anodized aluminum surface
GB2469115B (en) * 2009-04-03 2013-08-21 Keronite Internat Ltd Process for the enhanced corrosion protection of valve metals
WO2010112914A1 (en) 2009-04-03 2010-10-07 Keronite International Ltd Process for the enhanced corrosion protection of valve metals
GB2469115A (en) * 2009-04-03 2010-10-06 Keronite Internat Ltd Process for the enhanced corrosion protection of valve metals
US9816188B2 (en) 2009-04-03 2017-11-14 Keronite International Limited Process for the enhanced corrosion protection of valve metals
CN102199785A (en) * 2011-06-29 2011-09-28 上海理工大学 Microarc oxidation solution of titanium alloy wear-resistant coating and application thereof
CN102199785B (en) * 2011-06-29 2012-12-12 上海理工大学 Microarc oxidation solution of titanium alloy wear-resistant coating and application thereof
GB2513575B (en) * 2013-04-29 2017-05-31 Keronite Int Ltd Corrosion and erosion-resistant mixed oxide coatings for the protection of chemical and plasma process chamber components
US9765440B2 (en) 2013-04-29 2017-09-19 Keronite International Limited Corrosion and erosion-resistant mixed oxide coatings for the protection of chemical and plasma process chamber components
GB2513575A (en) * 2013-04-29 2014-11-05 Keronite Internat Ltd Corrosion and erosion-resistant mixed oxide coatings for the protection of chemical and plasma process chamber components
CN106435685A (en) * 2016-09-18 2017-02-22 佛山科学技术学院 Method for preparing low-absorptivity high-hemispherical-emissivity oxidation film on surface of aluminum through electro-deposition
US11312107B2 (en) * 2018-09-27 2022-04-26 Apple Inc. Plugging anodic oxides for increased corrosion resistance
WO2021058916A1 (en) * 2019-09-27 2021-04-01 Liebherr-Aerospace Toulouse Sas Method for manufacturing a fire-resistant part of an air conditioning system and part produced by such a method
FR3101361A1 (en) * 2019-09-27 2021-04-02 Liebherr-Aerospace Toulouse Sas PROCESS FOR MANUFACTURING A FIRE-RESISTANT PART OF AN AIR CONDITIONING SYSTEM AND PART OBTAINED BY SUCH A PROCESS
US20220372628A1 (en) * 2019-09-27 2022-11-24 Liebherr-Aerospace Toulouse Sas Method for manufacturing a fire-resistant part of an air conditioning system and part produced by such a method
US12428734B2 (en) 2019-09-27 2025-09-30 Liebherr-Aerospace Toulouse Sas Method for manufacturing a fire-resistant part of an air conditioning system and part produced by such a method

Also Published As

Publication number Publication date
EP0842309A4 (en) 1996-09-30
DE19680596D2 (en) 1997-09-18
PT842309E (en) 2002-07-31
ATE212075T1 (en) 2002-02-15
DE59608600D1 (en) 2002-02-21
ES2168491T3 (en) 2002-06-16
EP0842309B1 (en) 2002-01-16
EP0842309A1 (en) 1998-05-20
DE29680628U1 (en) 1998-11-05
AU6352796A (en) 1997-02-26
DE19680596C1 (en) 2001-08-23

Similar Documents

Publication Publication Date Title
DE102007057777B4 (en) Method for producing a component from aluminum and / or an aluminum alloy and use of the method
EP0842309A1 (en) Process for dep tsols into microporous coating layers
EP0545230A1 (en) Process for preparing modified oxide ceramic coatings on barrier-layer metals and products obtained
Kiele et al. Methyl–modified hybrid organic-inorganic coatings for the conservation of copper
DE102008062881A1 (en) Process for producing a hollow glass molded body
DE4311772A1 (en) Biocompatible implants comprising titanium@ for bone surgery - are prepd. by anodic oxidation of etched surface treated with phosphate-contg. soln., and then heat treating
EP1150620A1 (en) Osteophilic implants
Simka et al. Anodic oxidation of Ti–13Nb–13Zr alloy in silicate solutions
EP2828421A2 (en) Treatment of an anodically oxidized surface
EP3019644B1 (en) Method for producing a corrosion-resistant, wear-resistant aluminium substrate
EP3175018B1 (en) Metallic workpiece of titanium and/or a titanium alloy and/or nickel-titanium alloys and also nitinol with a porous surface and production process
DE4116910A1 (en) METHOD FOR PRODUCING OXIDE-CERAMIC SURFACE LAYERS ON LIGHT METAL CAST ALLOYS
Csokan Some observations on the growth mechanism of hard anodic oxide coatings on aluminium
EP0347663B1 (en) Method for sealing-in anodised films on aluminium and aluminium alloys
EP2151481A1 (en) Aqueous solution and method for coating metallic surfaces and use of modified silicic acids and concentrate compound for preparing an aqueous coating solution
DE112008002441B4 (en) Metal materials with hybrid-stabilized oxide layer, process for the production and their use
Menchaca-Campos et al. Smart protection of polymer-inhibitor doped systems
EP2236163A2 (en) Implant made of biocorrodible metallic material with a silane coating containing nanoparticles and accompanying production method
DE102011106764B4 (en) A method of making an adhesion promoting layer on a surface of a titanium material by anodic oxidation, using an anodic oxidation solution and adhesion promoting layer
JPS62129110A (en) Production of microfilter
WO2023110154A1 (en) Method for producing a highly abrasion-resistant, coated material with a conversion layer on an, in particular strip-shaped, aluminium substrate
DE102011055644A1 (en) Production of black ceramic oxide surface layer on component, involves forming surface layer by plasma chemical anodic oxidation using aqueous electrolyte of aqueous ammonia, citric acid, cobalt acetate and nickel acetate on component
WO2009135635A1 (en) Method for compressing a component made of aluminum and/or an aluminum alloy
DE102006011348B4 (en) A process for producing a physiological environment corrosion inhibiting layer on a molding
DE102008038671B3 (en) Surface compression process for automotive aluminium or aluminium alloy components in a hot mixture of distilled water and alcohol

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AT AU AZ BB BG BR BY CA CH CN CZ CZ DE DE DK DK EE EE ES FI FI GB GE HU IL IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SK TJ TM TR TT UA UG US UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

CFP Corrected version of a pamphlet front page
CR1 Correction of entry in section i

Free format text: PAT.BUL.08/97 UNDER INID (54) "TITLE",REPLACE THE EXISTING TEXT BY "PROCESS FOR DEPOSITING SOLS INTO MICROPOROUS COATING LAYERS"

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REF Corresponds to

Ref document number: 19680596

Country of ref document: DE

Date of ref document: 19970918

WWE Wipo information: entry into national phase

Ref document number: 19680596

Country of ref document: DE

WWE Wipo information: entry into national phase

Ref document number: 1996922737

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1996922737

Country of ref document: EP

NENP Non-entry into the national phase

Ref document number: 97507072

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: CA

WWG Wipo information: grant in national office

Ref document number: 1996922737

Country of ref document: EP