EP1919632A1 - Coated articles - Google Patents

Coated articles

Info

Publication number
EP1919632A1
EP1919632A1 EP06778257A EP06778257A EP1919632A1 EP 1919632 A1 EP1919632 A1 EP 1919632A1 EP 06778257 A EP06778257 A EP 06778257A EP 06778257 A EP06778257 A EP 06778257A EP 1919632 A1 EP1919632 A1 EP 1919632A1
Authority
EP
European Patent Office
Prior art keywords
layer
dimers
oxide ceramic
ceramic layer
aluminum
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.)
Pending
Application number
EP06778257A
Other languages
German (de)
French (fr)
Inventor
Michael Froitzheim
Josef Heppekausen
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.)
Leybold GmbH
Original Assignee
Oerlikon Leybold Vacuum 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 Oerlikon Leybold Vacuum GmbH filed Critical Oerlikon Leybold Vacuum GmbH
Publication of EP1919632A1 publication Critical patent/EP1919632A1/en
Pending legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04D—NON-POSITIVE-DISPLACEMENT PUMPS
    • F04D29/00—Details, component parts, or accessories
    • F04D29/02—Selection of particular materials
    • F04D29/023—Selection of particular materials especially adapted for elastic fluid pumps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04D—NON-POSITIVE-DISPLACEMENT PUMPS
    • F04D19/00—Axial-flow pumps
    • F04D19/02—Multi-stage pumps
    • F04D19/04—Multi-stage pumps specially adapted to the production of a high vacuum, e.g. molecular pumps
    • F04D19/042—Turbomolecular vacuum pumps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B05D2202/25—Metallic substrate based on light metals based on Al
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/30—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/60—Adding a layer before coating
    • B05D2350/63—Adding a layer before coating ceramic layer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2230/00—Manufacture
    • F05D2230/30—Manufacture with deposition of material
    • F05D2230/31—Layer deposition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2230/00—Manufacture
    • F05D2230/90—Coating; Surface treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/17—Alloys
    • F05D2300/173—Aluminium alloys, e.g. AlCuMgPb
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/20—Oxide or non-oxide ceramics
    • F05D2300/21—Oxide ceramics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/40—Organic materials
    • F05D2300/43—Synthetic polymers, e.g. plastics; Rubber
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/60—Properties or characteristics given to material by treatment or manufacturing
    • F05D2300/611—Coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the invention relates to a method for coating articles made of valve metals from Al, Mg, Ti, Nb and / or Zr or their alloys and the articles thus obtainable.
  • EP 0 545 230 A1 relates to a process for the production of optionally modified oxide ceramic layers on barrier layer-forming metals and objects obtained therewith.
  • plasma chemical anodic oxidation is carried out in a chloride-free electrolyte bath having a pH of 2 to 8 at a constant current density of at least 1 A / dm 2 until the voltage is at a final level established.
  • an oxide ceramic layer consisting of corundum may be produced.
  • layer thicknesses of up to 150 ⁇ m are achieved.
  • DE 41 24 730 C2 relates to a process for the incorporation of fluoropolymers into microporous, produced by anodic oxidation surfaces of objects made of aluminum or its alloys, characterized in that an aqueous suspension of fluoropolymers or their precursor having a particle size of 1 to 50 nm in the Stored perpendicular to the metal capillaries of a Harteloxal harsh.
  • DE 42 39 391 C2 relates to articles made of aluminum, magnesium or titanium with an oxide ceramic layer filled with fluoropolymers and process for their preparation.
  • articles of the barrier layer forming metal having a thin adherent barrier layer on top of the metal having a sintered dense oxide ceramic layer thereon and an oxide ceramic layer having a wide-knit capillary system substantially filled with fluoropolymers.
  • the oxide ceramic layer has a thickness of 40 to 150 ⁇ m.
  • Examples of such articles are rotors for turbomolecular pumps, turbochargers for diesel or gasoline engines, components of vacuum or plasma technology, rollers for corona discharges and ultrasound isotopes, each made of aluminum or aluminum alloys.
  • particles of the fluoropolymer or its precursor to be introduced into the outer oxide ceramic layer are introduced as a solution or suspension in a suitable solvent.
  • the essential core of this description is to expose the particles of fluoropolymers in a suitable solvent to changing pressure conditions, for which an impregnation system is suitable in which the air is first removed from the capillary system of the oxide-ceramic layer by means of a vacuum and subsequently under the influence of the vacuum, the particles penetrate into the pores and after the vacuum is released, pressed by the atmospheric pressure in pores and thus also to achieve fine ramifications.
  • fluoropolymers are described in particular the polymers and copolymers of tetrafluoroethylene, hexane fluoropropene, vinylidene fluoride, vinyl fluoride and trifluorochloroethylene. These fluoropolymers are known to be soluble in virtually no solvent, so it can be assumed that according to DE 42 39 391 C2 these are introduced for polymers in the form of dispersions in the surface.
  • a corrosion-resistant structure is characterized in that in an aluminum / alloy part of a turbomolecular pump for discharging chlorine gas in semiconductor manufacturing apparatuses in contact with chlorine gas, a plated layer of Ni-P alloy having a thickness of about 20 ⁇ m is provided a fluororesin protective layer is formed on the plated layer by dipping a rotor and a stator of the turbomolecular pump in a liquid for forming the layer of fluororesin, and then drying them.
  • EP 1 485 622 B1 relates to a process for coating articles of valve metals of aluminum, magnesium, titanium, niobium and / or zirconium and their alloys with a thin barrier layer of the metal and an oxide ceramic layer thereon whose surface is coated with fluoropolymers, the process being characterized in that the fluoropolymers in the form of a solution are introduced by vacuum impregnation into the capillary system of the oxide-ceramic layer and dried after the removal of the non-crosslinking solvent components.
  • the object of the present invention is thus in a
  • the above object is achieved in a first embodiment by a method for coating articles of valve metals of aluminum, magnesium, titanium, niobium and / or zirconium and their alloys with an oxide ceramic layer formed from the metal, which has a thin barrier layer as a boundary layer to the metal whose surface is coated with polymers, characterized in that the polymers in the form of dimers or halogenated dimers of the general formula I
  • Ri is one or more hydrogen or halogen radicals
  • R.2 each represents hydrogen or halogen
  • R. 3 together represents a corresponding xylyl radical to complete a dimeric structure, introduced by vacuum deposition in the capillary system of the oxide ceramic layer and the dimers polymerized.
  • the general formula (I) represents the monomer of the dimer structure.
  • the properties with respect to the tightness of the protective layers can be substantially improved compared with the prior art.
  • Another advantage of using the polymers obtained is their extremely high resistance to aggressive and corrosive media. These media can be gaseous, for example, when using turbomolecular pumps in plasma etchers but also include liquids or vapors of acids or alkalis.
  • dimers first monomerize and then polymerize the radicals so formed.
  • the treated surfaces are characterized by special properties such as the repellency of dirt or dust particles as well as non-wettability by media such as water, oils or other liquids.
  • the advantages of the coatings according to the invention are on the one hand in the very low surface energy, on the other hand in an optimal resistance and impermeability to almost all solvents and gases, which include in particular solvents, oils (including silicone oils) and water-based fluids. Even solids are very difficult to deposit on the surface of the film.
  • the property of the polymerization also causes a very good adhesion to the valve metals, as well as on their previously described oxide ceramic layers. Also worthy of note are the high chemical, thermal and electrical stability, which is unaffected by the usual operating conditions to which the treated surfaces are exposed.
  • valve metal aluminum, magnesium, titanium, niobium or zirconium and their alloys are used as valve metal aluminum, magnesium, titanium, niobium or zirconium and their alloys. Particularly noteworthy here are aluminum and aluminum alloys, which are often used for the production of rotors in turbomolecular pumps.
  • aluminum and its alloys are understood to be pure aluminum and alloys of the groups 2 ⁇ 3xx, 3 ⁇ x, 5 ⁇ x, 6 ⁇ x and 7 ⁇ x according to DIN EN 5731-4 and casting alloys in accordance with DIN EN 1706.
  • magnesium casting alloys of the ASTM designations AS41, AM60, AZ61, AZ63, AZ81, AZ91, AZ92, HK31, QE22, ZE41, ZH62, ZK51, ZK61, EZ33, HZ32 and the wrought alloys AZ31 are also suitable for the purposes of the invention , AZ61, AZ80, MI ZK60, ZK40.
  • titanium or titanium alloys such as TiAl 6 V 4, TiAl 5 Fe 2 also, 5 and others are using.
  • the oxide ceramic layer is made of a more or less graded material in which the oxide ceramic layer has a dense barrier layer as a boundary layer to the valve metal, which adjoins a microporous layer structure, which terminates in a marmaschig linked capillary structure to the surface.
  • Corresponding oxide ceramic layers are known, for example, from DE 42 39 391 C2.
  • plasma-chemical oxide ceramic layers but also other oxide layers, such as For example, applied by electrochemical anodization, used with a thickness of 10 to 50 .mu.m, in particular 20 to 40 microns, as they are also known from DE 42 39 391 C2.
  • the monomers or halogenated monomers which can be used in the context of the present invention are preferably selected from dimers of the para-xylylene or dimers of the halogenated para-xylylene of the general formula I.
  • Parylene TM is used by Parylene Coating Services Inc. or Uniglobal Kisco Inc. to distribute xylylene derivatives as a coating material for a variety of purposes
  • Parylene TM coatings are hydrophobic, chemically resistant coatings with good barrier properties against inorganic and organic media, strong acids, alkalis, gases and water vapor. They have excellent electrical insulation with high dielectric strength and low dielectric constant .
  • the coatings are micropore and pinhol e-free from a layer thickness of 0.2 ⁇ m.
  • Thin and transparent coatings with high splitting properties are suitable for complex substrates, even on edges.
  • the coating of the substrates is carried out without exposure to heat, in particular at room temperature in a vacuum.
  • the coatings are temperature resistant up to 220 0 C.
  • the starting materials are usually present as dimer (di-para-xylylene) and are heated to about 150 0 C. These are converted into the corresponding gaseous monomer.
  • the layer thickness and the uniformity are controlled by the amount and purity of the dimer used.
  • the layers of poly-para-xylylene in a thickness of 0.5 to 15 .mu.m, in particular 5 to 10 microns are applied.
  • the invention in a further embodiment comprises articles of the valve metals obtainable by the above-mentioned process.
  • Particularly preferred for the purposes of the present invention are components for turbomolecular pumps, in particular rotors or stators, which are usually made of aluminum or aluminum alloys.
  • articles characterized by extremely low surface admittance can be obtained, as evidenced by comparative measurements of the admittance of untreated oxide layers and vacuum impregnated oxide layers.
  • a measuring cell with a contact area of 2.3 mm diameter was used.
  • the auxiliary electrolyte used was a potassium sulfate solution.
  • an "Anotest YD" from Fischer was used.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Structures Of Non-Positive Displacement Pumps (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention relates to a method for coating articles from valve metals from aluminum, magnesium, titanium, niobium and/or zirconium and the alloys thereof with an oxide ceramic layer constituted of the metal and having a thin barrier layer as the boundary layer to the metal, the surface of said barrier layer being coated with polymers. The inventive method is characterized by introducing, by vacuum-coating, the polymers into the capillary system of the oxide ceramic layer in the form of dimers or halogenated dimers of the general formula (I), wherein R<SUB>1</SUB> represents one or more hydrogen or halogen groups, R<SUB>2</SUB> represents hydrogen or halogen and R<SUB>3</SUB> together represents a corresponding xylyl group for completing a dimeric structure, and polymerizing the dimers.

Description

BESCHICHTETE GEGENSTÄNDE COATED ARTICLES
Die Erfindung betrifft ein Verfahren zur Beschichtung von Gegenständen aus Ventilmetallen aus AI, Mg, Ti, Nb und/oder Zr oder deren Legierungen sowie die so erhältlichen Gegenstände.The invention relates to a method for coating articles made of valve metals from Al, Mg, Ti, Nb and / or Zr or their alloys and the articles thus obtainable.
Die EP 0 545 230 Al betrifft ein Verfahren zur Erzeugung von gegebenenfalls modifizierten Oxidkeramikschichten auf Sperrschichtbildenden Metallen und damit erhaltene Gegenstände. Um die Dicke und Verschleißfestigkeit von Oxidkeramikschichten auf Sperrschichtbildenden Metallen zu erhöhen, wird eine plasmachemische anodische Oxidation in einem chloridfreien Elektrolytbad mit einem pH-Wert von 2 bis 8 bei konstanter Stromdichte von mindestens 1 A/dm2 durchgeführt, bis sich die Spannung auf einen Endwert einstellt. Auf Gegenständen aus Aluminium oder Aluminiumlegierungen kann eine Oxidkeramikschicht erzeugt werden, die aus Korund besteht. Auch auf Magnesium und Titanium werden Schichtdicken bis zu 150 μm erreicht.EP 0 545 230 A1 relates to a process for the production of optionally modified oxide ceramic layers on barrier layer-forming metals and objects obtained therewith. In order to increase the thickness and wear resistance of oxide ceramic layers on barrier layer forming metals, plasma chemical anodic oxidation is carried out in a chloride-free electrolyte bath having a pH of 2 to 8 at a constant current density of at least 1 A / dm 2 until the voltage is at a final level established. On articles of aluminum or aluminum alloys, an oxide ceramic layer consisting of corundum may be produced. Also on magnesium and titanium, layer thicknesses of up to 150 μm are achieved.
Für viele Anwendungen müssen hochbelastete Bauteile aus Ventilmetallen auch unter extremen Bedingungen korrosionsbeständig und verschleißfest sein. Das gelingt, in dem man derartige Gegenstände mit einer Oxidkeramikschicht mit einem weitmaschigen verknüpften Kapillarsystem versieht, Teilchen von Fluorpolymeren einbringt, die wenigstens in einer Dimension kleiner sind als der Durchmesser der Kapillaren und den Gegenstand mit dem vorgefüllten Kapillarsystem wechselnden Druckbedingungen aussetzt. DE 41 24 730 C2 betrifft ein Verfahren zur Einlagerung von Fluorpolymeren in mikroporöse, durch anodische Oxidation hergestellte Oberflächen von Gegenständen aus Aluminium oder dessen Legierungen, dadurch gekennzeichnet, dass eine wässrige Suspension von Fluorpolymeren oder deren Vorstufe mit einer Teilchengröße von 1 bis 50 nm in die senkrecht zum Metall stehenden Kapillaren einer Harteloxalschicht eingelagert werden.For many applications, highly stressed valve metal components must be resistant to corrosion and wear, even under extreme conditions. This is achieved by providing such articles with an oxide ceramic layer having a wide-meshed linked capillary system, introducing particles of fluoropolymers which are at least one dimension smaller than the diameter of the capillaries and exposing the article to the prefilled capillary system under varying pressure conditions. DE 41 24 730 C2 relates to a process for the incorporation of fluoropolymers into microporous, produced by anodic oxidation surfaces of objects made of aluminum or its alloys, characterized in that an aqueous suspension of fluoropolymers or their precursor having a particle size of 1 to 50 nm in the Stored perpendicular to the metal capillaries of a Harteloxalschicht.
Die DE 42 39 391 C2 betrifft Gegenstände aus Aluminium, Magnesium oder Titan mit einer mit Fluorpolymeren gefüllten Oxidkeramikschicht und Verfahren zu ihrer Herstellung. Beschrieben werden Gegenstände aus dem Sperrschicht-bildenden Metall mit einer dünnen festhaftenden Sperrschicht auf dem Metall, auf der sich eine gesinterte dichte Oxidkeramikschicht und darauf eine Oxidkeramikschicht mit einem weitmaschig verknüpften Kapillarsystem befindet, das im wesentlichen mit Fluorpolymeren gefüllt ist. Die Oxidkeramikschicht hat insbesondere ein Dicke von 40 bis 150 μm. Beispiele solcher Gegenstände sind Rotoren für Turbomolekularpumpen, Turbolader für Diesel- oder Benzinmotoren, Bauteile aus Vakuum- oder Plasmatechnik, Walzen für Koronarentladungen und Ultraschallisonotoden, jeweils aus Aluminium oder Aluminiumlegierungen. Es wird beschrieben, dass man in die äußere Oxidkeramikschicht einzubringende Teilchen des Fluorpolymeren oder seiner Vorstufe, sofern es sich nicht um Flüssigkeiten handelt, als Lösung oder Suspension in einem geeigneten Lösungsmittel einbringt. Wesentlicher Kern dieser Beschreibung ist es, die Teilchen von Fluorpolymeren in einem geeigneten Lösungsmittel wechselnden Druckbedingungen auszusetzen, wofür sich ein Imprägniersystem eignet, bei dem zunächst mittels Vakuum die Luft aus dem Kapillarsystem der Oxidkeramikschicht entfernt wird und anschließend unter Einwirkung des Vakuums, die Teilchen in die Poren eindringen und nach dem das Vakuum aufgehoben ist, durch den atmosphärischen Druck in Poren gepresst und somit auch feine Verästelungen erreichen sollen.DE 42 39 391 C2 relates to articles made of aluminum, magnesium or titanium with an oxide ceramic layer filled with fluoropolymers and process for their preparation. Disclosed are articles of the barrier layer forming metal having a thin adherent barrier layer on top of the metal having a sintered dense oxide ceramic layer thereon and an oxide ceramic layer having a wide-knit capillary system substantially filled with fluoropolymers. In particular, the oxide ceramic layer has a thickness of 40 to 150 μm. Examples of such articles are rotors for turbomolecular pumps, turbochargers for diesel or gasoline engines, components of vacuum or plasma technology, rollers for corona discharges and ultrasound isotopes, each made of aluminum or aluminum alloys. It is described that particles of the fluoropolymer or its precursor to be introduced into the outer oxide ceramic layer, if they are not liquids, are introduced as a solution or suspension in a suitable solvent. The essential core of this description is to expose the particles of fluoropolymers in a suitable solvent to changing pressure conditions, for which an impregnation system is suitable in which the air is first removed from the capillary system of the oxide-ceramic layer by means of a vacuum and subsequently under the influence of the vacuum, the particles penetrate into the pores and after the vacuum is released, pressed by the atmospheric pressure in pores and thus also to achieve fine ramifications.
Als besonders geeignete Fluorpolymere werden insbesondere die Polymeren und Copolymeren von Tetrafluorethylen, Hexanfluorpropen, Vinylidenfluorid, Vinylfluorid und Trifluorchlorethylen beschrieben. Diese Fluorpolymere sind bekanntermaßen in praktisch keinem Lösungsmittel löslich, so dass davon auszugehen ist, dass gemäß der DE 42 39 391 C2 diese für Polymere in Form von Dispersionen in die Oberfläche eingebracht werden.Particularly suitable fluoropolymers are described in particular the polymers and copolymers of tetrafluoroethylene, hexane fluoropropene, vinylidene fluoride, vinyl fluoride and trifluorochloroethylene. These fluoropolymers are known to be soluble in virtually no solvent, so it can be assumed that according to DE 42 39 391 C2 these are introduced for polymers in the form of dispersions in the surface.
Ein ähnliches Verfahren wird in dem japanischen Patent JP 2,913,537 beschrieben. Ein korrosionsbeständiger Aufbau ist dadurch gekennzeichnet, dass in einem in Kontakt mit Chlorgas kommenden Aluminium/Legierungsteil einer Turbomolekularpumpe zum Entlassen von Chlorgas bei Halbleiterherstellungs-Vorrichtungen eine plattierte Schicht aus Ni-P-Legierung mit einer Dicke von etwa 20 μm vorgesehen ist, und das auf der plattierten Schicht eine Fluorharz-Schutzschicht dadurch gebildet ist, dass ein Rotor und ein Stator der Turbomolekularpumpe in eine Flüssigkeit zum Bilden der Schicht aus Fluorharz eingetaucht und daraufhin getrocknet werden.A similar method is described in Japanese Patent JP 2,913,537. A corrosion-resistant structure is characterized in that in an aluminum / alloy part of a turbomolecular pump for discharging chlorine gas in semiconductor manufacturing apparatuses in contact with chlorine gas, a plated layer of Ni-P alloy having a thickness of about 20 μm is provided a fluororesin protective layer is formed on the plated layer by dipping a rotor and a stator of the turbomolecular pump in a liquid for forming the layer of fluororesin, and then drying them.
EP 1 485 622 Bl betrifft ein Verfahren zur Beschichtung von Gegenständen aus Ventilmetallen aus Aluminium, Magnesium, Titan, Niob und/oder Zirkonium und deren Legierungen mit einer dünnen Sperrschicht aus dem Metall und einer darauf befindlichen Oxidkeramikschicht, deren Oberfläche mit Fluorpolymeren beschichtet ist, wobei das Verfahren dadurch gekennzeichnet ist, dass man die Fluorpolymere in Form einer Lösung durch Vakuumimprägnierung in das Kapillarsystem der Oxidkeramikschicht einbringt und nach der Entfernung der nicht vernetzenden Lösungsanteile trocknet.EP 1 485 622 B1 relates to a process for coating articles of valve metals of aluminum, magnesium, titanium, niobium and / or zirconium and their alloys with a thin barrier layer of the metal and an oxide ceramic layer thereon whose surface is coated with fluoropolymers, the process being characterized in that the fluoropolymers in the form of a solution are introduced by vacuum impregnation into the capillary system of the oxide-ceramic layer and dried after the removal of the non-crosslinking solvent components.
Dem vorgenannten Stand der Technik ist gemeinsam, dass sich die Fluorpolymere im wesentlichen auf der äußeren Oberfläche der oxidkeramischen befindlichen Schicht, jedoch nur zu einem geringen Anteil in die Verästelungen eindringen.The above-mentioned prior art has in common that the fluoropolymers penetrate essentially on the outer surface of the oxide-ceramic layer, but only to a small extent in the branches.
Die Aufgabe der vorliegenden Erfindung besteht somit in einerThe object of the present invention is thus in a
Verbesserung der Gleichmäßigkeit, Beschichtung und damit derImprovement of uniformity, coating and thus the
Abdichtung von Gegenständen, insbesondere oxidkeramischen Schichten.Sealing of objects, in particular oxide-ceramic layers.
Die vorgenannte Aufgabe wird in einer ersten Ausführungsform gelöst durch ein Verfahren zur Beschichtung von Gegenständen aus Ventilmetallen aus Aluminium, Magnesium, Titan, Niob und/oder Zirkonium und deren Legierungen mit einer aus dem Metall gebildeten Oxidkeramikschicht, die eine dünne Sperrschicht als Grenzschicht zum Metall aufweist, deren Oberfläche mit Polymeren beschichtet ist, dadurch gekennzeichnet, dass man die Polymere in Form von Dimeren oder halogenierten Dimeren der allgemeinen Formel IThe above object is achieved in a first embodiment by a method for coating articles of valve metals of aluminum, magnesium, titanium, niobium and / or zirconium and their alloys with an oxide ceramic layer formed from the metal, which has a thin barrier layer as a boundary layer to the metal whose surface is coated with polymers, characterized in that the polymers in the form of dimers or halogenated dimers of the general formula I
(I) wobei (I) in which
Ri für einen oder mehrere Wasserstoff- oder Halogenreste,Ri is one or more hydrogen or halogen radicals,
R.2 jeweils für Wasserstoff oder Halogen undR.2 each represents hydrogen or halogen and
R.3 gemeinsam für einen entsprechenden Xylylrest zur Vervollständigung einer dimeren Struktur steht, durch Vakuumbeschichten in das Kapillarsystem der Oxidkeramikschicht einbringt und die Dimere polymerisiert.R. 3 together represents a corresponding xylyl radical to complete a dimeric structure, introduced by vacuum deposition in the capillary system of the oxide ceramic layer and the dimers polymerized.
Die allgemeine Formel (I) stellt das Monomer der dimeren Struktur dar.The general formula (I) represents the monomer of the dimer structure.
Durch die Nachbehandlung von insbesondere anodisch erzeugtem Oxidoder Keramikschichten mittels Vakuumbeschichtung mit Dimeren oder halogenierten Dimeren können die Eigenschaften bezüglich der Dichtigkeit der Schutzschichten gegenüber dem Stand der Technik wesentlich verbessert werden. Ein weiterer Vorteil bei der Anwendung der erhaltenen Polymere liegt in deren extrem hohen Beständigkeiten gegenüber aggressiven und korrosiven Medien. Diesen Medien können beispielsweise beim Einsatz von Turbomolekularpumpen in Plasmaätzern gasförmig sein aber auch Flüssigkeiten oder Dämpfe von Säuren oder Alkalien umfassen.By the aftertreatment of in particular anodically produced oxide or ceramic layers by means of vacuum coating with dimers or halogenated dimers, the properties with respect to the tightness of the protective layers can be substantially improved compared with the prior art. Another advantage of using the polymers obtained is their extremely high resistance to aggressive and corrosive media. These media can be gaseous, for example, when using turbomolecular pumps in plasma etchers but also include liquids or vapors of acids or alkalis.
Es wird angenommen, dass die Dimere zunächst monomerisieren und die so gebildeten Radikale dann polymerisieren.It is believed that the dimers first monomerize and then polymerize the radicals so formed.
In gleicher Weise ist auch der Einsatz von Monomeren oder halogenierten Monomeren direkt möglich, ohne die Notwendigkeit der vorherigen Beschichtung oxidischer oder keramischer Art. Auch die so behandelten Oberflächen zeichnen sich durch besondere Eigenschaften wie das Abweisen von Schmutz oder Staubpartikeln sowie Unbenetzbarkeit durch Medien wie Wasser, Öle oder andere Flüssigkeiten aus.In the same way, the use of monomers or halogenated monomers is directly possible, without the need of the previous coating oxide or ceramic type. The treated surfaces are characterized by special properties such as the repellency of dirt or dust particles as well as non-wettability by media such as water, oils or other liquids.
Mit Hilfe der vorliegenden Erfindung ist es möglich, gegenüber dem Stand der Technik die Gleichmäßigkeit der Beschichtung poröser Oberflächen signifikant zu verbessern. Hierzu ist es besondere hilfreich, dass die Aufbringung der obengenannten Schichten unter Vakuum erfolgt, bei der gasförmige Monomere oder halogenierte Monomere in die Poren bzw. mikroskopisch kleine Hohlräume der Schichten eindringen und dort polymerisieren.With the aid of the present invention it is possible to significantly improve the uniformity of the coating of porous surfaces compared with the prior art. For this purpose, it is particularly helpful that the application of the above-mentioned layers takes place under vacuum, in which gaseous monomers or halogenated monomers penetrate into the pores or microscopically small cavities of the layers and polymerize there.
Die Vorteile der erfindungsgemäßen Beschichtungen liegen einerseits in der sehr niedrigen Oberflächenenergie, andererseits in einer optimalen Resistenz und Undurchlässigkeit gegenüber beinahe allen Lösungsmitteln und Gasen, zu denen insbesondere Lösemittel, Öle (auch Silikonöle) sowie Flüssigkeiten auf Wasserbasis zählen. Auch Feststoffe können sich nur sehr schwer auf der Oberfläche des Films ablagern. Die Eigenschaft der Polymerisation bewirkt darüber hinaus eine sehr gute Haftung auf den Ventilmetallen, wie auch auf ihren zuvor beschriebenen oxidkeramischen Schichten. Weiterhin sind hervorzuheben die hohe chemische, thermische und elektrische Stabilität, die von den üblichen Betriebsbedingungen unbeeinflusst bleibt, denen die behandelten Oberflächen ausgesetzt sind.The advantages of the coatings according to the invention are on the one hand in the very low surface energy, on the other hand in an optimal resistance and impermeability to almost all solvents and gases, which include in particular solvents, oils (including silicone oils) and water-based fluids. Even solids are very difficult to deposit on the surface of the film. The property of the polymerization also causes a very good adhesion to the valve metals, as well as on their previously described oxide ceramic layers. Also worthy of note are the high chemical, thermal and electrical stability, which is unaffected by the usual operating conditions to which the treated surfaces are exposed.
Im Sinne der vorliegenden Erfindung wird als Ventilmetall Aluminium, Magnesium, Titan, Niob oder Zirkonium und deren Legierungen einsetzt. Besonders hervorzuheben sind an dieser Stelle Aluminium und Aluminiumlegierungen, die häufig für die Herstellung von Rotoren in Turbomolekularpumpen eingesetzt werden.For the purposes of the present invention is used as valve metal aluminum, magnesium, titanium, niobium or zirconium and their alloys. Particularly noteworthy here are aluminum and aluminum alloys, which are often used for the production of rotors in turbomolecular pumps.
Unter Aluminium und dessen Legierungen werden im Rahmen der vorliegenden Erfindung Reinstaluminium und Legierungen der Gruppen 2xxx, 3xxx, 5xxx, 6xxx und 7xxx gemäß DIN EN5731-4 sowie Gusslegierungen gemäß DIN EN1706 verstanden.For the purposes of the present invention, aluminum and its alloys are understood to be pure aluminum and alloys of the groups 2 × 3xx, 3 × x, 5 × x, 6 × x and 7 × x according to DIN EN 5731-4 and casting alloys in accordance with DIN EN 1706.
Für die Zwecke der Erfindung eignen sich ferner außer Reinmagnesium insbesondere die Magnesiumgusslegierungen der ASTM-Bezeichnungen AS41, AM60, AZ61, AZ63, AZ81, AZ91, AZ92, HK31, QE22, ZE41, ZH62, ZK51, ZK61, EZ33, HZ32 sowie die Knetlegierungen AZ31, AZ61, AZ80, Ml ZK60, ZK40.In addition to pure magnesium, the magnesium casting alloys of the ASTM designations AS41, AM60, AZ61, AZ63, AZ81, AZ91, AZ92, HK31, QE22, ZE41, ZH62, ZK51, ZK61, EZ33, HZ32 and the wrought alloys AZ31 are also suitable for the purposes of the invention , AZ61, AZ80, MI ZK60, ZK40.
Des weiteren lassen sich Reintitanium oder auch Titanlegierungen wie TiAI6V4, TiAI5Fe2,5 und andere einsetzen.Furthermore, let pure titanium or titanium alloys such as TiAl 6 V 4, TiAl 5 Fe 2 also, 5 and others are using.
Besonders bevorzugt im Sinne der vorliegenden Erfindung ist die Oxidkeramikschicht aus einem mehr oder weniger gradiertem Material hergestellt, bei dem die Oxidkeramikschicht eine dichte Sperrschicht als Grenzschicht zum Ventilmetall aufweist, der sich eine mikroporöse Schichtstruktur anschließt, die in eine weitmaschig verknüpfte Kapillarstruktur zur Oberfläche hin ausläuft. Entsprechende Oxidkeramikschichten sind beispielsweise aus der DE 42 39 391 C2 bekannt.Particularly preferred according to the present invention, the oxide ceramic layer is made of a more or less graded material in which the oxide ceramic layer has a dense barrier layer as a boundary layer to the valve metal, which adjoins a microporous layer structure, which terminates in a weitmaschig linked capillary structure to the surface. Corresponding oxide ceramic layers are known, for example, from DE 42 39 391 C2.
Auch im Sinne der vorliegenden Erfindung werden plasmachemische Oxidkeramikschichten, aber auch andere oxidische Schichten, wie beispielsweise durch elektrochemische Anodisation aufgebrachte, mit einer Dicke von 10 bis 50 μm, insbesondere 20 bis 40 μm eingesetzt, wie sie auch aus der DE 42 39 391 C2 bekannt sind.Also within the meaning of the present invention are plasma-chemical oxide ceramic layers, but also other oxide layers, such as For example, applied by electrochemical anodization, used with a thickness of 10 to 50 .mu.m, in particular 20 to 40 microns, as they are also known from DE 42 39 391 C2.
Die Monomere oder halogenierten Monomere, die im Sinne der vorliegenden Erfindung eingesetzt werden können, sind vorzugsweise ausgewählt aus Dimeren des para-Xylylens oder Dimeren des halogenierten para-Xylylens der allgemeinen Formel I.The monomers or halogenated monomers which can be used in the context of the present invention are preferably selected from dimers of the para-xylylene or dimers of the halogenated para-xylylene of the general formula I.
Unter der Bezeichnung „Parylene™" werden von der Firma Parylene Coating Services Inc. oder auch von der Uniglobal Kisco Inc. Xylylen- Derivate als Beschichtungsmaterial für verschiedenste Zwecke vertrieben. Parylene™ ist eine Beschichtung, die im Vakuum durch Kondensation aus der Gasphase als porenfreier und transparenter Polymerfilm auf das Substrat aufgetragen wird. Praktisch jedes Substratmaterial, beispielsweise Metall, Glas, Papier, Lack, Kunststoff, Keramik, Ferrit und Silikone ist mit Parylene™ beschichtbar. In einem Arbeitsgang können Beschichtungsdicken von 0,1 bis 50 μm aufgebracht werden. Parylene™- Beschichtungen stellen hydrophobe, chemisch resistente Beschichtungen mit guter Barriere Wirkung gegenüber anorganischen und organischen Medien, starken Säuren, Laugen, Gasen und Wasserdampf dar. Sie besitzen eine hervorragende elektrische Isolation mit hoher Spannungsfestigkeit und niedriger Dielektrizitätskonstante. Die Beschichtungen sind Mikroporen- und Pinhole-frei ab einer Schichtdicke von 0,2 μm. Dünne und transparente Beschichtungen mit hoher Spaltgängigkeit sind geeignet für komplex gestaltete Substrate auch auf Kanten. Die Beschichtung der Substrate erfolgt ohne Temperaturbelastung, insbesondere bei Raumtemperatur im Vakuum. Die Beschichtungen sind temperaturbeständig bis zu 220 0C. Die Ausgangsstoffe liegen üblicherweise als Dimer (Di-para-Xylylen) vor und werden auf etwa 150 0C erhitzt. Hierbei werden diese in das entsprechende gasförmige Monomer umgewandelt. Die Schichtdicke und die Gleichförmigkeit werden durch die Menge und die Reinheit des verwendeten Dimers kontrolliert.The name "Parylene ™" is used by Parylene Coating Services Inc. or Uniglobal Kisco Inc. to distribute xylylene derivatives as a coating material for a variety of purposes Virtually any substrate material, such as metal, glass, paper, paint, plastic, ceramic, ferrite, and silicones, can be coated with Parylene ™ to provide coating thicknesses of 0.1 to 50 μm in a single pass. Parylene ™ coatings are hydrophobic, chemically resistant coatings with good barrier properties against inorganic and organic media, strong acids, alkalis, gases and water vapor. They have excellent electrical insulation with high dielectric strength and low dielectric constant .The coatings are micropore and pinhol e-free from a layer thickness of 0.2 μm. Thin and transparent coatings with high splitting properties are suitable for complex substrates, even on edges. The coating of the substrates is carried out without exposure to heat, in particular at room temperature in a vacuum. The coatings are temperature resistant up to 220 0 C. The starting materials are usually present as dimer (di-para-xylylene) and are heated to about 150 0 C. These are converted into the corresponding gaseous monomer. The layer thickness and the uniformity are controlled by the amount and purity of the dimer used.
Besonders bevorzugt im Sinne der vorliegenden Erfindung werden die Schichten der Poly-para-Xylylene in einer Dicke von 0,5 bis 15 μm, insbesondere 5 bis 10 μm aufgebracht.Particularly preferred according to the present invention, the layers of poly-para-xylylene in a thickness of 0.5 to 15 .mu.m, in particular 5 to 10 microns are applied.
Die Erfindung umfasst in einer weiteren Ausführungsform Gegenstände aus den Ventilmetallen, die nach dem obengenannten Verfahren erhältlich sind. Besonders bevorzugt im Sinne der vorliegenden Erfindung handelt es sich dabei um Bauteile für Turbomolekularpumpen, insbesondere Rotoren oder Statoren, die meist aus Aluminium oder Aluminiumlegierungen hergestellt werden.The invention in a further embodiment comprises articles of the valve metals obtainable by the above-mentioned process. Particularly preferred for the purposes of the present invention are components for turbomolecular pumps, in particular rotors or stators, which are usually made of aluminum or aluminum alloys.
Mit Hilfe der vorliegenden Erfindung werden Gegenstände erhältlich, die sich durch einen äußerst niedrigen Scheinleitwert der Oberfläche auszeichnen, wie durch vergleichende Messungen des Scheinleitwerts von unbehandelten Oxidschichten und Vakuum-imprägnierten Oxidschichten gezeigt werden konnte.By means of the present invention, articles characterized by extremely low surface admittance can be obtained, as evidenced by comparative measurements of the admittance of untreated oxide layers and vacuum impregnated oxide layers.
Bei der Vakuumbeschichtung ist die komplette Beschichtung der Poren in der oxidischen Schicht und somit der gesamten Oberfläche gewährleistet. Bei den Porenabmessungen von plasmachemisch erzeugten Schichten, aber auch bei anodischen Oxidschichten, ist diese Vorgehensweise besonders vorteilhaft. Die klassische Tauchbehandlung erreicht nur die benetzbare Oberfläche, dringt aber nicht in die Poren (hier besonders in die Poren hartanodischer Schichten) ein. Hierzu wurden Tests an plasmaoxidischen Schichten durchgeführt, die einen Unterschied zeigten:In the case of vacuum coating, the complete coating of the pores in the oxidic layer and thus the entire surface is ensured. In the pore dimensions of plasma-chemically generated layers, but also in anodic oxide layers, this procedure is particularly advantageous. The classic dip treatment reaches only the wettable surface, but does not penetrate into the pores (especially in the pores of hard anodic layers). For this purpose tests were carried out on plasma-oxidic layers which showed a difference:
Ein Scheinleitwert von 42 μS wurde bei einer üblichen Beschichtung gegenüber 7 μS bei einer erfindungsgemäßen Vakuumbeschichtung ermittelt.An admittance of 42 μS was determined in a conventional coating against 7 μS in a vacuum coating according to the invention.
Ausführungsbeispiele:EXAMPLES
Beispiel 1 :Example 1 :
Ein Probeblech aus der 2xxx Legierungsgruppe mit einer Kepla-Coat- Beschichtung (25 μm) und einem Scheinleitwert von 55 μS wurde mit <10 μm Parylene™C nach dem für Parylene üblichen Herstellungsverfahren beschichtet.A sample plate of the 2xxx alloy group with a Kepla coat coating (25 μm) and an admittance of 55 μS was coated with <10 μm Parylene ™ C according to the production method customary for parylene.
Es ergab sich ein nicht mehr messbarer Scheinleitwert nach dem Vakuumbeschichten.The result was a no longer measurable admittance after vacuum coating.
Zur Bestimmung des Scheinleitwertes wurde eine Messzelle mit einer Kontaktfläche von 2,3 mm Durchmesser verwendet. Als Hilfselektrolyt diente eine Kaliumsulfatlösung. Für die Messung selbst wurde ein "Anotest YD" der Firma Fischer eingesetzt. To determine the admittance, a measuring cell with a contact area of 2.3 mm diameter was used. The auxiliary electrolyte used was a potassium sulfate solution. For the measurement itself, an "Anotest YD" from Fischer was used.

Claims

Patentansprüche: claims:
1. Verfahren zur Beschichtung von Gegenständen aus Ventil metallen aus Aluminium, Magnesium, Titan, Niob und/oder Zirkonium und deren Legierungen mit einer aus dem Metall gebildeten Oxidkeramikschicht, die eine Sperrschicht als Grenzschicht zum Metall aufweist, deren Oberfläche mit Polymeren beschichtet ist, dadurch gekennzeichnet, dass man die Polymere in Form von Dimeren oder halogenierten Dimeren der allgemeinen Formel I1. A method for coating objects made of valve metal aluminum, magnesium, titanium, niobium and / or zirconium and their alloys with an oxide ceramic layer formed from the metal having a barrier layer as a boundary layer to the metal whose surface is coated with polymers, characterized in that the polymers in the form of dimers or halogenated dimers of the general formula I
wobeiin which
Ri für einen oder mehrere Wasserstoff- oder Halogenreste,Ri is one or more hydrogen or halogen radicals,
R.2 jeweils für Wasserstoff oder Halogen undR.2 each represents hydrogen or halogen and
R.3 gemeinsam für einen entsprechenden Xylylrest zur Vervollständigung einer dimeren Struktur steht, durch Vakuumbeschichten in das Kapillarsystem der Oxidkeramikschicht einbringt und die Dimere polymerisiert.R. 3 together represents a corresponding xylyl radical to complete a dimeric structure, introduced by vacuum deposition in the capillary system of the oxide ceramic layer and the dimers polymerized.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man eine Oxidkeramikschicht einsetzt, die eine Sperrschicht als Grenzschicht zum Ventilmetall aufweist, der sich eine Schichtstruktur anschließt, die in eine Kapillarstruktur zur Oberfläche hin ausläuft, die durch plasmachemische anodische Oxidation aufgebracht wurde.2. The method according to claim 1, characterized in that one uses an oxide ceramic layer having a barrier layer as a boundary layer to the valve metal, which adjoins a layer structure, the leaking into a capillary structure towards the surface, which was deposited by plasma chemical anodic oxidation.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass man eine plasmachemische Oxidkeramikschicht mit einer Dicke von 10 bis 50 μm, insbesondere 20 bis 40 μm einsetzt.3. The method according to claim 1 or 2, characterized in that one uses a plasma-chemical oxide ceramic layer with a thickness of 10 to 50 .mu.m, in particular 20 to 40 microns.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass man Dimere einsetzt, die ausgewählt sind aus dimeren Fluor-Xylylenen, Chlor-Xylylenen und/oder Wasserstoff- Xylylenen.4. The method according to any one of claims 1 to 3, characterized in that one uses dimers which are selected from dimeric fluorine xylylenes, chloro-xylylenes and / or hydrogen xylylenes.
5. Gegenstand aus Ventilmetallen erhältlich nach einem Verfahren gemäß einem der Ansprüche 1 bis 4.5. An article of valve metals obtainable by a process according to one of claims 1 to 4.
6. Gegenstand nach Anspruch 5, dadurch gekennzeichnet, dass er einen Rotor aus Aluminium oder Aluminiumlegierungen einer Turbomolekularpumpe umfasst.6. An article according to claim 5, characterized in that it comprises a rotor made of aluminum or aluminum alloys of a turbomolecular pump.
7. Gegenstand nach Anspruch 5 oder 6, dadurch gekennzeichnet, dass die Schichtdicke der Polymere 0,5 bis 15 μm, insbesondere 5 bis 10 μm beträgt. 7. An article according to claim 5 or 6, characterized in that the layer thickness of the polymers is 0.5 to 15 .mu.m, in particular 5 to 10 microns.
EP06778257A 2005-08-27 2006-08-17 Coated articles Pending EP1919632A1 (en)

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DE200510040648 DE102005040648A1 (en) 2005-08-27 2005-08-27 Process for coating valve metal or alloy for e.g. aluminum or alloy rotor for turbomolecular pump involves vapor coating with optionally halogenated xylylene dimer and polymerization in capillary system of surface film of oxide ceramic
PCT/EP2006/065402 WO2007025868A1 (en) 2005-08-27 2006-08-17 Coated articles

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US8119243B2 (en) 2012-02-21
TW200712264A (en) 2007-04-01
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WO2007025868A1 (en) 2007-03-08
RU2008111634A (en) 2009-10-10

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