DE29680628U1 - Microporous cover layers with embedded brines - Google Patents
Microporous cover layers with embedded brinesInfo
- Publication number
- DE29680628U1 DE29680628U1 DE29680628U DE29680628U DE29680628U1 DE 29680628 U1 DE29680628 U1 DE 29680628U1 DE 29680628 U DE29680628 U DE 29680628U DE 29680628 U DE29680628 U DE 29680628U DE 29680628 U1 DE29680628 U1 DE 29680628U1
- Authority
- DE
- Germany
- Prior art keywords
- lyosol
- silica
- microporous
- cover layer
- layer according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- OLGONLPBKFPQNS-UHFFFAOYSA-M sodium 2-(4-phenylphenyl)butanoate Chemical compound [Na+].CCC(C([O-])=O)c1ccc(cc1)-c1ccccc1 OLGONLPBKFPQNS-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 238000005260 corrosion Methods 0.000 claims abstract description 9
- 230000007797 corrosion Effects 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 239000004411 aluminium Substances 0.000 claims abstract 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 4
- 150000004756 silanes Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000012963 UV stabilizer Substances 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 239000005368 silicate glass Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 239000011247 coating layer Substances 0.000 abstract 4
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 9
- 238000007789 sealing Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000000499 gel Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 3
- 229910052574 oxide ceramic Inorganic materials 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000008131 herbal destillate Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- 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
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)
- Chemical Vapour Deposition (AREA)
- Physical Vapour Deposition (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Paints Or Removers (AREA)
- Saccharide Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Polyurethanes Or Polyureas (AREA)
- Materials For Medical Uses (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
Mikroporöse Dechschichten mit eingelagerten SolenMicroporous roof layers with embedded brines
BeschreibungDescription
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 dichten
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.
10Despite its high affinity for oxygen, aluminum is relatively corrosion-resistant in air because the metal surface is immediately covered in air with a 5 to 20 nm thick, firmly adhering and very dense oxide layer that prevents further oxygen from entering. Magnesium and titanium and their alloys are also protected against further oxidation by a thin oxide layer at normal temperatures.
10
Es ist bekannt, die natürlichen Oxidschichten der genannten Metalle durch anodische Oxidation erheblich zu verstärken. Dabei bilden sich Konversionsschichten.It is known that the natural oxide layers of the metals mentioned can be significantly strengthened by anodic oxidation. This creates conversion layers.
Bei Aluminium besteht der anodisch erzeugte Überzug zum Beispiel aus einer etwa 0,15 pm dicken zusammenhängenden Unterschicht (barrier layer) und einer mikroporösen Deckschicht, die von senkrecht zum Metall stehenden Kapillaren von 0,01 bis 0,05 pm (10 - 50 nm) in einem Abstand von etwa 0,3 pm 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),In the case of aluminum, for example, the anodically produced coating consists of a coherent base layer about 0.15 pm thick (barrier layer) and a microporous top layer, which is permeated by capillaries of 0.01 to 0.05 pm (10 - 50 nm) perpendicular to the metal at a distance of about 0.3 pm. After it has been produced, the microporous top layer has an inner surface of about 100 m /g and is chemically very reactive. This high chemical reactivity is caused by active centers formed by OH groups in the area of the microporous top layer close to the surface (cf. 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 pm zu erzeugen.p. 220). With newer anodic oxidation processes it is possible to produce microporous coatings up to about 200 pm on Al materials.
Auch durch anodische Oxidation von Magnesium lassen sich mikroporöse Deckschichten, die oxidischer Natur sind und gegebenenfalls Fluorid oder Phosphat enthalten, mit einer Dicke bis zu 30 pm und guter Verschleißbeständigkeit erzeugen (DE-A-38 08 610). Bekannt sind hierbei auch das HAE- und DOW 17-Verfahren (vgl. H. Simon,Microporous coatings that are oxidic in nature and may contain fluoride or phosphate can also be produced by anodic oxidation of magnesium, with a thickness of up to 30 pm and good wear resistance (DE-A-38 08 610). The HAE and DOW 17 processes are also well known (cf. H. Simon,
M. Thoma „Angewandte Oberflächentechnik für metallische Werkstoffe", Carl Hanser Verlag, München Wien 1985, S. 91 ff·)·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 mikroporöse Deckschichten mit verschieden oxidischer Zusammensetzung (vgl. Simon & Thoma).Anodic oxidation of titanium also produces microporous coatings with different oxide compositions (see Simon & Thoma).
Auf Aluminium-, Magnesium- oder Titanwerkstoffen lassen sich durch plasmachemische anodische Oxidation mikroporöse Deckschichten als Oxidkeramikschichten mit hoher Reaktionsfähigkeit erzeugen (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 pm.Microporous cover layers can be produced as oxide ceramic layers with high reactivity on aluminum, magnesium or titanium materials by plasma-chemical anodic oxidation (EP-B-280 886, 333 048, 545 230). The pores here are of different sizes. They range from 10 nm to 30 pm.
Es hat nicht an Versuchen gefehlt, die mikroporöse Deckschicht dauerhaft zu versiegeln, um den Grundwerkstoff gegen Korrosion und 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 eines Überzugfilms auf dem korrosionsbeständigen anodisch oxidierten Oberflächenfilm von Aluminiumerzeugnissen, 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 0C oder darüber verwenden zu können, bei denen vorher Probleme der Rißbildung und ungenügende Haftung auftraten. Die Versiegelungsbehandlung des Oxidfilms durch Eintauchen der Aluminiumgegenstände in die Kieselsäure 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 möglichThere has been no lack of attempts to permanently seal the microporous top layer in order to protect the base material against corrosion and wear. Various methods are known for this, such as sealing in hot water, soaking in oils and waxes, and even applying organic paints. These methods do not meet today's requirements. The same applies to the method known from DE-A-28 12 116 for producing a coating film on the corrosion-resistant anodically oxidized surface film of aluminum products, in which the latter is subjected to a sealing treatment of the micropores in the oxide film by immersion in an aqueous sealing liquid containing dispersed silica and then coated with a heat-curing acrylic resin. The purpose of this process is to be able to use coating agents with a drying or hardening temperature of 140 0 C or more, which previously had problems with cracking and insufficient adhesion. The sealing treatment of the oxide film by immersing the aluminum objects in the aqueous sealing liquid containing silica or silicate is also intended to close the micropores so that, for example, any sulfuric acid remaining in them cannot escape; however, it was not possible
oder beabsichtigt, die senkrechten Kapillaren mit der Kieselsäure zu füllen.or intended 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 corrosion caused by the pores and to create a stable bond between the microporous oxide covering layer and at least one compound forming an inorganic network.
Gegenstand der Erfindung sind mikroporöse, durch anodische Oxidation oder durch plasmachemische anodische Oxidation
hergestellte Deckschichten auf Gegenständen aus Aluminium, Magnesium, Titanium oder deren Legierungen, bei dem Kieselsäure in
die Poren oder Kapillaren der mikroporösen Deckschicht in Form eines Lyosols eingebracht sind, in dem die kolloidal verteilten SiO2-Teilchen
wenigstens in einer Dimension kleiner sind, als der Durchmesser der Poren oder Kapillaren und das eingebrachte und
aufgetragene Kieselsäure-Lyosol anschließend koaguliert ist oder mit der Deckschicht reagierte.
Ein Lyosol ist definitionsgemäß eine kolloidale Lösung, in der ein fester Stoff in feinster Verteilung in einer Flüssigkeit dispergiert ist.
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, bevorzugt C1-bis
Cg-Alkoholen, oder Wasser handelt. In diesem Fall ist das Kieselsäure-Lyosol
ein Kieselsol (s. Römpp, Chemie-Lexikon, Stichworte Sole und Kieselsol).The invention relates to microporous covering layers produced by anodic oxidation or by plasma-chemical anodic oxidation on objects made of aluminum, magnesium, titanium or their alloys, in which silica is introduced into the pores or capillaries of the microporous covering layer in the form of a lyosol, in which the colloidally distributed SiO 2 particles are smaller in at least one dimension than the diameter of the pores or capillaries and the introduced and applied silica lyosol is subsequently coagulated or reacted with the covering layer.
By definition, a lyosol is a colloidal solution in which a solid substance is dispersed in a liquid in a very fine distribution. Organosols and hydrosols are also suitable for the purposes of the invention, depending on whether the silica is suspended in organic liquids, such as alcohols, preferably C 1 to C 8 alcohols, or water. In this case, the silica lyosol is a silica sol (see Römpp, Chemistry Dictionary, keywords brine and silica sol).
Um eine Einlagerung des Sols in die Poren oder Kapillaren zu erreichen, wird es erfindungsgemäß in einer Form eingeführt, in der die SiO2-Teilchen wenigstens in einer Dimension kleiner sind als der 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 liegenIn order to achieve an incorporation of the sol into the pores or capillaries, according to the invention it is introduced in a form in which the SiO 2 particles are smaller in at least one dimension than the diameter of the pores or capillaries of the microporous oxidic covering layer. The size of the particles of colloidal silica in the sol is therefore approximately 1 to 50 nm, preferably 1 to 10 nm. The particles of colloidal silica to be introduced are
— 4 ——4—
zweckmäßig als wäßrige und/oder organische Dispersion vor. Um eine gute Filmbildung zu erreichen, sind den SiO2-Solen zur Polymerisation bzw. Polykondensation neigende Filmbildner wie Alkohole und/oder Silane und/oder Salze organischer Säuren zugesetzt. advantageously in the form of an aqueous and/or organic dispersion. In order to achieve good film formation, film formers that tend to polymerize or polycondense, such as alcohols and/or silanes and/or salts of organic acids, are added to the SiO 2 sols.
Für die Zwecke der Erfindung geeignete Kieselsole sind bekannt. Sie werden durch in situ Wachstum von SiO2-Mikrokeimen hergestellt und liegen dann als konzentrierte wäßrige Dispersion von kolloidal verteilten porenfreien amorphen SiO2-Teilchen vor. Diese SiO2-Dispersionen enthalten in der Regel geringfügige Alkalimengen, die die Oberfläche der SiO2-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 können Substanzen, insbesondere Alkohole und Silane, zugesetzt werden, die mit der Kieselsäure Filme bilden. Die Sole können auch Füllstoffe, Korrosionsinhibitoren, Farbstoffe, Gleitmittel, oberflächenaktive Substanzen, UV-Stabilisatoren in Mengen enthalten, die das Sol in seiner Reaktivität mit der mikroporösen Deckschicht nicht beeinflussen. Die Feststoffkonzentration des Kieselsols beträgt zweckmäßig 15 bis 60 %, vorzugsweise 30 bis 50 %.Silica sols suitable for the purposes of the invention are known. They are produced by in situ growth of SiO 2 micro-nuclei and are then present as a concentrated aqueous dispersion of colloidally distributed, pore-free amorphous SiO 2 particles. These SiO 2 dispersions generally contain small amounts of alkali, which negatively charge the surface of the SiO 2 particles. This causes the particles to repel each other and ensures the stability of the solution. Silica sols suitable for the purposes of the invention are available commercially under the name KLEBOSOL, for example. These can also be modified by other film-forming oxides from the third to eighth groups of the periodic table of elements, e.g. aluminum, indium, zirconium, titanium, iron, nickel and the rare earths. Modification with mono- or polyhydric alcohols, e.g. diethylene glycol, is also possible. Substances, in particular alcohols and silanes, which form films with the silica can be added to the silica lyosols. The sols can also contain fillers, corrosion inhibitors, dyes, lubricants, surface-active substances, UV stabilizers in amounts that do not affect the sol's reactivity with the microporous covering layer. The solids concentration of the silica sol is suitably 15 to 60%, preferably 30 to 50%.
Zum Einbringen der kolloidal verteilten SiO2-Teilchen des Lyosols in die Poren oder Kapillaren der mikroporösen Deckschicht werden die 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 wechselndenIn order to introduce the colloidally distributed SiO 2 particles of the lyosol into the pores or capillaries of the microporous covering layer, the objects with such oxide covering layers are dipped into the lyosol, in particular silica sol, or are sprayed or painted with it. The introduction can be improved by subjecting the object provided with the oxide layer and immersed in the lyosol to alternating
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 hergestellten 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.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 effect of the vacuum, the lyosol penetrates into the pores and, after the vacuum is released, is pressed into the pores by the atmospheric pressure and thus also reaches the bottom of the vertical capillaries of the anodically produced aluminum coatings or the finest branches of the microporous covering layers on magnesium or titanium materials or the oxide ceramic layers produced by plasma-chemical oxidation. The alternation of vacuum and pressure, which can also exceed atmospheric pressure, is repeated once or several times if necessary. Suitable devices for this introduction of the particles into the microporous covering 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 Oxidkeramikschichten, die weniger als 24 Stunden alt sind, die Einlagerung des Kieselsols bis an den Grund der Kapillaren und Poren beschleunigen. Surprisingly, it has been shown that microporous covering layers, such as hard anodized layers or oxide ceramic layers, freshly produced by anodic oxidation or by plasma-chemical anodic oxidation, which are less than 24 hours old, accelerate the deposition of the silica sol down to the bottom of the capillaries and pores.
Wenn die Poren oder Kapillaren der Deckschichten so gut wie möglieh mit den kolloidalen SiO2-Teilchen gefüllt sind, sorgt man für eine 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 0C,When the pores or capillaries of the cover layers are filled as well as possible with the colloidal SiO 2 particles, the silica lyosol is coagulated using the sol-gel process known for the film formation of such sols (Sol-Gel Technology for thin Films, Fibers, Preforms, Electronics, and Specialty Shapes, edited by Lisa Klein, Noyes Publications, p. 50 ff., section 4, Helmut Dislich, Thin Films from the Sol-Gel Process). Coagulation occurs by removing the liquid from the lyosol, in particular the silica sol. Based on the preferred reaction of freshly produced oxidic cover layers, it is assumed that coagulation by heating to temperatures of up to 300 0 C,
-6--6-
vorzugsweise bis zu 150 0C, zugleich zu Reaktionen zwischen den mikroporösen oxidischen Deckschichten und den sehr feinen und damit auch sehr reaktionsfähigen SiO2-Teilchen in den Poren und an der Oberfläche der Deckschichten kommt. Die SiO2-Schichten sind vermutlich glasähnlich und amorph und haben eine Dicke bis zu 5 pm, insbesondere 0,5 bis 2 mm. Diese an der Oberfläche der mikroporösen Deckschicht aus den SiO2-Partikeln gebildete Silikatglasschicht 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.preferably up to 150 0 C, at the same time reactions occur between the microporous oxide covering layers and the very fine and therefore very reactive SiO 2 particles in the pores and on the surface of the covering layers. The SiO 2 layers are presumably glass-like and amorphous and have a thickness of up to 5 pm, in particular 0.5 to 2 mm. This silicate glass layer formed from the SiO 2 particles on the surface of the microporous covering layer is firmly anchored in the microporous covering layer by pins with a diameter of 10 to 50 nm that protrude vertically into the capillaries of the anodized layer or like roots that protrude into the capillaries of other oxide layers, in particular ceramic layers. This is presumably the reason for the high corrosion and scratch resistance.
Gegenstand der Erfindung sind auch Bauteile aus Aluminium-, Magnesium- oder Titanwerkstoffen mit einer durch anodische Oxidation oder plasmachemisch anodischen Oxidation erzeugten mikroporösen Deckschicht, deren Poren oder Kapillaren im wesentlichen mit dem, gegebenenfalls modifizierten, SiO2-GeI 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.The invention also relates to components made of aluminum, magnesium or titanium materials with a microporous covering 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. Preferably, the surface of the microporous covering layer is also coated 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; AlMgI; AlMgI,5; E-AlMgSi; AlMgSiO.5; AlZnMgCu0,5, AlZnMgCuI,5; G-A1SÜ2; G-AlSi5Mg; G-AlSi8Cu3; G-AlCu4Ti; G-AlCu4TiMg verstanden.For the purposes of the invention, aluminum materials are understood to mean ultrapure aluminum and alloys AlMn; AlMnCu; AlMgI; AlMgI,5; E-AlMgSi; AlMgSiO.5; AlZnMgCu0,5, AlZnMgCuI,5; G-A1SÜ2; G-AlSi5Mg; G-AlSi8Cu3; G-AlCu4Ti; G-AlCu4TiMg.
Für die Zwecke der Erfindung eignen sich ferner außer Reinmagnesium, insbesondere Magnesiumgußlegierungen der ASTM-Bezeichnung AS41; AM60; AZ6l; AZ63; A281; AZ91; AZ92; HK31; QE22; ZEAl; ZH62, ZK51; ZK61, EZ33; HZ33 sowie die Knetlegierungen AZ31; AZ61; AZ80; Ml, ZK60; ZK40. Als Titanwerkstoffe eignen sich Reintitanium oder die Legierung TiAl6V4.In addition to pure magnesium, magnesium cast alloys of the ASTM designation AS41; AM60; AZ61; AZ63; A281; AZ91; AZ92; HK31; QE22; ZEAl; ZH62, ZK51; ZK61, EZ33; HZ33 and the wrought alloys AZ31; AZ61; AZ80; Ml, ZK60; ZK40 are also suitable for the purposes of the invention. Pure titanium or the alloy TiAl6V4 are suitable as titanium materials.
-7--7-
Platten aus der Magnesiumlegierung AZ91HP der Größe 100 &khgr; 50 &khgr; 2 mm, die beidseitig durch plasmachemische anodische 5 Oxidation mit einer mikroporösen Deckschicht von 20 pm nach dem 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 versiegeln. Eine raster-elektronenmikroskopische Aufnahme an einem Querschliff zeigt, daß die Poren und Kapillaren mit dem nach der thermischen Behandlung gebildeten Siliciumdioxid oder dessen Reaktionsprodukten gefüllt sind. Die äußere Versiegelungsschicht hat eine Dicke von etwa 5 pm.Plates made of the magnesium alloy AZ91HP measuring 100 x 50 x 2 mm, which had been provided on both sides with a microporous covering layer of 20 pm by plasma-chemical anodic oxidation according to the method of EP-B-333 084, were treated using the ORMOCER method in order to fill the capillaries and pores and to seal the surface of the microporous covering layer. A scanning electron microscope image of 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 about 5 pm.
Die so erhaltene Platte wurde dem neutralen Salznebeltest nach 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.The resulting plate was subjected to the neutral salt mist test according to DIN SS 50021. It had a service life of 1500 hours. Even when the test was stopped, some plates did not have even a single corrosion point.
Die gleichen, mit der gleichen oxidischen Deckschicht versehenen Platten hatten nach dem Tauchen in Natronwasserglas und anschließender Auskieselung in einer CO2-Atmosphäre gleichfalls eine etwa 5 pm dicke Versiegelungsschicht und in dem erwähnten neutralen Salznebeltest nur eine Standzeit von ca. 200 Stunden.The same plates, provided with the same oxide top layer, also had a sealing layer about 5 pm thick after immersion in sodium silicate and subsequent desilting in a CO 2 atmosphere and only had a service life of about 200 hours in the neutral salt mist test mentioned above.
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE29680628U DE29680628U1 (en) | 1995-07-28 | 1996-07-02 | Microporous cover layers with embedded brines |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19527688 | 1995-07-28 | ||
| PCT/DE1996/001188 WO1997005302A1 (en) | 1995-07-28 | 1996-07-02 | Process for depôtsols into microporous coating layers |
| DE29680628U DE29680628U1 (en) | 1995-07-28 | 1996-07-02 | Microporous cover layers with embedded brines |
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| Publication Number | Publication Date |
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| DE29680628U1 true DE29680628U1 (en) | 1998-11-05 |
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| DE19680596A Expired - Fee Related 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 |
| DE29680628U Expired - Lifetime DE29680628U1 (en) | 1995-07-28 | 1996-07-02 | Microporous cover layers with embedded brines |
| DE59608600T Expired - Fee Related DE59608600D1 (en) | 1995-07-28 | 1996-07-02 | METHOD FOR STORING SOLES IN MICROPOROUS COATING LAYERS |
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| DE19680596A Expired - Fee Related 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 |
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| DE59608600T Expired - Fee Related DE59608600D1 (en) | 1995-07-28 | 1996-07-02 | METHOD FOR STORING SOLES IN MICROPOROUS COATING LAYERS |
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| EP (1) | EP0842309B1 (en) |
| AT (1) | ATE212075T1 (en) |
| AU (1) | AU6352796A (en) |
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| ES (1) | ES2168491T3 (en) |
| PT (1) | PT842309E (en) |
| WO (1) | WO1997005302A1 (en) |
Cited By (1)
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|---|---|---|---|---|
| EP2166200A1 (en) | 2008-09-23 | 2010-03-24 | Franz Rübig & Söhne GmbH & Co. KG | Valve spring disc and method for its manufacture |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19741580A1 (en) * | 1997-09-20 | 1999-04-01 | Bosch Gmbh Robert | Composite |
| ATE541962T1 (en) * | 1999-08-17 | 2012-02-15 | Isle Coat Ltd | MULTIFUNCTIONAL LIGHT METAL-BASED COMPOSITE PROTECTIVE COATING |
| DE102006045617B4 (en) * | 2006-09-22 | 2010-06-10 | Innovent E.V. Technologieentwicklung | Process for producing an inorganic-inorganic gradient composite layer |
| 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 |
| DE102007027628B3 (en) * | 2007-06-12 | 2008-10-30 | Siemens Ag | Method of introducing nanoparticles into anodized aluminum surface |
| GB2469115B (en) | 2009-04-03 | 2013-08-21 | Keronite Internat Ltd | Process for the enhanced corrosion protection of valve metals |
| 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 |
| CN106435685B (en) * | 2016-09-18 | 2018-09-07 | 佛山科学技术学院 | The method that aluminium surface electro-deposition prepares low absorptivity and high hemispherical emissivity oxidation film |
| DE102017207589A1 (en) * | 2017-05-05 | 2018-11-08 | Federal-Mogul Nürnberg GmbH | Thermally insulating coating for an aluminum piston |
| US11312107B2 (en) * | 2018-09-27 | 2022-04-26 | Apple Inc. | Plugging anodic oxides for increased corrosion resistance |
| FR3101361B1 (en) * | 2019-09-27 | 2022-01-14 | Liebherr Aerospace Toulouse Sas | METHOD FOR MANUFACTURING A FIRE-RESISTANT PART OF AN AIR CONDITIONING SYSTEM AND PART OBTAINED BY SUCH A PROCESS |
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| FR802421A (en) * | 1936-02-26 | 1936-09-04 | Protection of magnesium against corrosion by vitrification | |
| JPS582596A (en) * | 1981-06-30 | 1983-01-08 | Nippon Parkerizing Co Ltd | Surface treatment for heat exchanger made of aluminum |
| JPS5959896A (en) * | 1982-09-28 | 1984-04-05 | Nippon Light Metal Co Ltd | Sealing of anodic oxidized film of aluminum |
| 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 |
| EP0410003B1 (en) * | 1989-02-14 | 1994-11-02 | Sumitomo Electric Industries, Ltd. | Insulated electric wire |
| 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 aluminium |
| JPH06316787A (en) * | 1993-04-28 | 1994-11-15 | Kojundo Chem Lab Co Ltd | Treatment of surface of anodized alminum layer |
-
1996
- 1996-07-02 AT AT96922737T patent/ATE212075T1/en not_active IP Right Cessation
- 1996-07-02 DE DE19680596A patent/DE19680596C1/en not_active Expired - Fee Related
- 1996-07-02 ES ES96922737T patent/ES2168491T3/en not_active Expired - Lifetime
- 1996-07-02 DE DE29680628U patent/DE29680628U1/en not_active Expired - Lifetime
- 1996-07-02 DE DE59608600T patent/DE59608600D1/en not_active Expired - Fee Related
- 1996-07-02 AU AU63527/96A patent/AU6352796A/en not_active Abandoned
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- 1996-07-02 PT PT96922737T patent/PT842309E/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2166200A1 (en) | 2008-09-23 | 2010-03-24 | Franz Rübig & Söhne GmbH & Co. KG | Valve spring disc and method for its manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6352796A (en) | 1997-02-26 |
| EP0842309A1 (en) | 1998-05-20 |
| ATE212075T1 (en) | 2002-02-15 |
| DE19680596C1 (en) | 2001-08-23 |
| WO1997005302A1 (en) | 1997-02-13 |
| DE59608600D1 (en) | 2002-02-21 |
| ES2168491T3 (en) | 2002-06-16 |
| EP0842309B1 (en) | 2002-01-16 |
| PT842309E (en) | 2002-07-31 |
| DE19680596D2 (en) | 1997-09-18 |
| EP0842309A4 (en) | 1996-09-30 |
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