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EP1888805B1 - Coated member, especially roller, made of carbon fiber-reinforced plastic (CFRP) for paper machines and printing presses, and method for the production of such a member - Google Patents

Coated member, especially roller, made of carbon fiber-reinforced plastic (CFRP) for paper machines and printing presses, and method for the production of such a member Download PDF

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Publication number
EP1888805B1
EP1888805B1 EP06722499.8A EP06722499A EP1888805B1 EP 1888805 B1 EP1888805 B1 EP 1888805B1 EP 06722499 A EP06722499 A EP 06722499A EP 1888805 B1 EP1888805 B1 EP 1888805B1
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EP
European Patent Office
Prior art keywords
layer
anyone
oxide ceramics
adhesion promoter
hard metal
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.)
Active
Application number
EP06722499.8A
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German (de)
French (fr)
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EP1888805A1 (en
Inventor
Gerhard Johner
Markus Kirst
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.)
Praxair ST Technology Inc
Praxair Technology Inc
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Praxair ST Technology Inc
Praxair Technology Inc
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Publication of EP1888805A1 publication Critical patent/EP1888805A1/en
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Classifications

    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41F—PRINTING MACHINES OR PRESSES
    • B41F13/00—Common details of rotary presses or machines
    • B41F13/08—Cylinders
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/341—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one carbide layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/347—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with layers adapted for cutting tools or wear applications
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21G—CALENDERS; ACCESSORIES FOR PAPER-MAKING MACHINES
    • D21G1/00—Calenders; Smoothing apparatus
    • D21G1/02—Rolls; Their bearings
    • D21G1/0246—Hard rolls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N2207/00—Location or type of the layers in shells for rollers of printing machines
    • B41N2207/02—Top layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N2207/00—Location or type of the layers in shells for rollers of printing machines
    • B41N2207/10—Location or type of the layers in shells for rollers of printing machines characterised by inorganic compounds, e.g. pigments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N7/00—Shells for rollers of printing machines

Definitions

  • the invention relates to a coated body, in particular roller, carbon fiber reinforced plastic (CFRP) for paper and printing machines, with a primer layer and applied to the primer layer, wear-protective layer of hard metal or oxide ceramic and a method for producing such a body.
  • CFRP carbon fiber reinforced plastic
  • CFRP roller bodies are enjoying increasing popularity in paper machines and printing machines due to their low weight and at the same time extreme flexural rigidity.
  • the disadvantage is only the need for a coating, generally against wear or other stresses that drives the price in the current state of the art in the air.
  • coatings ceramic and hard metal coatings have prevailed, which are mainly produced by thermal spraying, namely plasma and flame spraying.
  • Elaborate and thus price increasing are less these known coating methods as the hitherto customary primer preparation, eg in DE 41 16 641 A1 or in EP 0 514 640 B1 such as EP 1 129 787 A and DE 101 27 908 A is described.
  • the CFRP roller is covered with another layer of synthetic resin into which previously large volumes of a typical adhesion promoter, for example NiAl or NiCr powder, have been dispersed.
  • a typical adhesion promoter for example NiAl or NiCr powder
  • a first grinding takes place, so that the dispersed-in adhesive promoter particles are ground.
  • ground primer particles are, so to speak, the adhesion points for further treatment by thermal spraying by means of NiCr or NiAl adhesion promoters and subsequent application of the functional layer of ceramic or hard metal.
  • Such coatings are only possible if the thermal load of the CFRP roller body is kept correspondingly low by adequate cooling measures, so that no delamination of the carbon fibers in the synthetic resin matrix occurs or the latter is damaged.
  • Out DE 93 05 806 U1 is a gravure roll with a sleeve of thermally wound fiber-reinforced thermoplastics known, wherein the fiber reinforcement may consist inter alia of carbon fibers.
  • a layer of copper or a copper alloy by thermal spraying, in particular plasma spraying or high-speed flame spraying, applied directly. In the copper layer, the necessary for the gravure printing engraving is introduced.
  • DE 100 37 212 A1 describes a particular for sports equipment, for example in the field of a golf club head, certain, at least partially thermally coated, fiber-reinforced plastic.
  • a primer layer of zinc, zinc alloys, aluminum alloys and / or exothermic acting materials during the injection process such as nickel-aluminum or molybdenum is applied to a carbon fiber-reinforced plastic base body for example by means of a thermal spraying process.
  • Thermal spray on the primer layer is a wear protection layer of metals, metal alloys, Oxides, carbides, borides, plastics or mixtures of said substances applied.
  • JP 02 270 954 A describes a method in which a CFRP cylinder intended for paper machines is preheated and provided by plasma spraying with a molybdenum base layer, and in which a ceramic protective layer is applied by flame spraying onto the molybdenum base layer thus produced.
  • Out GB 887,366 is a method of multilayer coating of plastics with metals or alloys by flame spraying, in which the first deposited layer has a thermal expansion coefficient which is greater than that of the plastic, while the subsequent layer or layers has a coefficient of thermal expansion (smaller than) which is the plastic.
  • Body in particular rolls of CFK in EP 0514640 B1 or in DE 3427554 C2 described type and nevertheless provide a bonding agent that causes a permanent tight fit on the body and other wear-resistant coatings of oxide ceramics or carbide securely fixed on the body.
  • the object underlying the invention is achieved by the coated body according to claim 1 and by the method according to claim 7.
  • the adhesion promoter layer consists of ductile metal selected from the group consisting of copper, lead and tin and applied by plasma spraying or flame spraying.
  • the adhesive layer of ductile metal is suitably applied in a thickness of 0.01 mm to 3.0 mm, preferably about 0.1 mm.
  • wear-protective layers of oxide ceramics such as chromium oxide (Cr 2 O 3 ), aluminum oxide (Al 2 O 3 ), titanium dioxide (TiO 2 ), quartz-containing mullite (eg 3Al 2 O 3 2SiO 2 to 2Al 2 O 3 - SiO 2 ), zirconium oxide (ZrO 2 ) and mixtures thereof, as well as wear-resistant hard metals, for example from the group tungsten carbide / cobalt (WC / Co), tungsten carbide / nickel (WC / Ni), titanium carbide / nickel (TiC / Ni), nickel-chromium / chromium carbide (Cr 3 C 2 / NiCr), nickel-chromium-boron-silicon (NiCrBSi), molten carbide (pure chromium carbide), chromium, molybdenum with oxygen, etc. preferably by thermal spraying methods such as plasma spraying, flame spraying and High speed flame spraying
  • outer coatings may also, as known ( EP 0 999 043 A1 ), get a non-stick seal.
  • the oxide ceramic or cemented carbide layer protecting against wear does not have to be applied by thermal spraying, but can also be applied by coating processes such as PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), sintering, hot isostatic pressing, electroplating, explosive plating, build-up welding, brazing, adhesive techniques or reactors be applied, provided that no delamination of the carbon fibers in the plastic matrix or damage the latter occurs.
  • PVD Physical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • sintering hot isostatic pressing
  • electroplating electroplating
  • explosive plating build-up welding
  • brazing adhesive techniques or reactors be applied, provided that no delamination of the carbon fibers in the plastic matrix or damage the latter occurs.
  • the wear-resistant coating has a thickness of 0.01 to 3.0 mm, preferably 0.1 mm.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Ceramic Engineering (AREA)
  • Coating By Spraying Or Casting (AREA)

Description

Die Erfindung betrifft einen beschichteten Körper, insbesondere Walze, aus Kohlefaser verstärktem Kunststoff (CFK) für Papier- und Druckmaschinen, mit einer Haftvermittlerschicht und einer auf die Haftvermittlerschicht aufgetragenen, vor Verschleiß schützenden Schicht aus Hartmetall oder Oxidkeramik sowie ein Verfahren zum Herstellen eines solchen Körpers.The invention relates to a coated body, in particular roller, carbon fiber reinforced plastic (CFRP) for paper and printing machines, with a primer layer and applied to the primer layer, wear-protective layer of hard metal or oxide ceramic and a method for producing such a body.

CFK-Walzenkörper erfreuen sich zunehmender Beliebtheit in Papiermaschinen und Druckmaschinen aufgrund ihres geringen Gewichts bei gleichzeitig extremer Biegesteifigkeit. Der Nachteil ist nur die Notwendigkeit einer Beschichtung, im allgemeinen gegen Verschleiß oder andere Beanspruchungen, die nach heutigem Stand der Technik den Preis in die Höhe treibt. Als Beschichtungen haben sich Keramik- und Hartmetallbeschichtungen durchgesetzt, die hauptsächlich durch Thermisches Spritzen, namentlich Plasma- und Flammspritzen, hergestellt werden. Aufwändig und damit preiserhöhend sind weniger diese bekannten Beschichtungsverfahren als vielmehr die bislang übliche Haftgrundvorbereitung, die z.B. in DE 41 16 641 A1 bzw. in EP 0 514 640 B1 sowie EP 1 129 787 A und DE 101 27 908 A beschrieben ist. Dabei wird die CFK-Walze mit einer weiteren Schicht aus Kunstharz belegt, in die zuvor große Volumina eines typischen Haftvermittlers z.B NiAl- oder NiCr-Pulver eindispergiert wurden. Nach dem Aushärten dieser äußeren Kunstharzbeschichtung erfolgt ein erstes Anschleifen, so dass die eindispergierten Haftvermittlerpartikel angeschliffen werden. Diese angeschliffenen Haftvermittlerpartikel sind sozusagen die Haftpunkte für die weitere Behandlung durch Thermisches Spritzen mittels NiCr- oder NiAl- Haftvermittler und anschließendem Auftrag der Funktionsschicht aus Keramik oder Hartmetall. Derartige Beschichtungen sind nur möglich, wenn die thermische Belastung des CFK-Walzenkörpers durch adäquate Kühlmaßnahmen entsprechend niedrig gehalten wird, so dass keinesfalls eine Delamination der Karbonfasern in der Kunstharzmatrix auftritt oder Letztere Schaden nimmt. Versuche, diese aufwändige Haftgrundvorbereitung gemäß EP 0 514 640 B1 , z.B. durch Drahtspritzen von Zink zu umgehen, scheiterten häufig an der mangelhaften Duktilität von Zink mit der Folge von Rissbildungen in der angestrebten Haftvermittlerschicht, die letztlich zu Schichtabhebungen vom zu beschichtenden CFK-Körper führten.CFRP roller bodies are enjoying increasing popularity in paper machines and printing machines due to their low weight and at the same time extreme flexural rigidity. The disadvantage is only the need for a coating, generally against wear or other stresses that drives the price in the current state of the art in the air. As coatings ceramic and hard metal coatings have prevailed, which are mainly produced by thermal spraying, namely plasma and flame spraying. Elaborate and thus price increasing are less these known coating methods as the hitherto customary primer preparation, eg in DE 41 16 641 A1 or in EP 0 514 640 B1 such as EP 1 129 787 A and DE 101 27 908 A is described. The CFRP roller is covered with another layer of synthetic resin into which previously large volumes of a typical adhesion promoter, for example NiAl or NiCr powder, have been dispersed. After curing of this outer synthetic resin coating, a first grinding takes place, so that the dispersed-in adhesive promoter particles are ground. These ground primer particles are, so to speak, the adhesion points for further treatment by thermal spraying by means of NiCr or NiAl adhesion promoters and subsequent application of the functional layer of ceramic or hard metal. Such coatings are only possible if the thermal load of the CFRP roller body is kept correspondingly low by adequate cooling measures, so that no delamination of the carbon fibers in the synthetic resin matrix occurs or the latter is damaged. Try this elaborate primer preparation according to EP 0 514 640 B1 For example, bypassing by wire spraying of zinc, often failed due to the lack of ductility of zinc with the result of cracking in the desired adhesive layer, which ultimately led to Schichtabhebungen of the CFRP body to be coated.

Daneben ist es bekannt ( DE 34 27 554 A1 ), CFK-Körper galvanisch zu verkupfern, die Kupferschicht durch Tauchen in einen sauren Elektrolyten zu aktivieren, eine Zwischenspülung in deionisiertem Wasser vorzunehmen, auf der aktivierten Kupferschicht in einem sauren Elektrolyten eine haftvermitteinde Metallschicht aus Nickel, Kobalt, Eisen oder Zinn galvanisch derart abzuscheiden, dass auf der Oberfläche verästelte baumartige Strukturelemente entstehen, eine weitere Zwischenspülung in deionisiertem Wasser vorzunehmen, die mit Strukturelementen versehenen Oberfläche durch Tauchen in einen Elektrolyt zu stabilisieren, erneut in deionisiertem Wasser zu spülen und dann die Metallschicht an Luft zu trocknen. Ein solches Vorgehen ist umständlich und daher gleichfalls preissteigernd.In addition, it is known ( DE 34 27 554 A1 ) To electroplate CFRP body, to activate the copper layer by immersion in an acidic electrolyte, to carry out an intermediate rinse in deionized water, to electrodeposit an electrically conductive metal layer of nickel, cobalt, iron or tin on the activated copper layer in an acidic electrolyte, that on the surface branched tree-like structural elements arise to make a further intermediate rinse in deionized water to stabilize the surface provided with structural elements by immersion in an electrolyte to rinse again in deionized water and then to dry the metal layer in air. Such a procedure is cumbersome and therefore also price-increasing.

Aus DE 93 05 806 U1 ist eine Tiefdruckwalze mit einer Hülse aus thermisch gewickelten, faserverstärkten Thermoplasten bekannt, wobei die Faserverstärkung unter anderem aus Kohlefasern bestehen kann. Auf die zuvor aufgeraute äußere Oberfläche eines Grundkörpers aus thermoplastischem faserverstärktem Kunststoffmaterial ist eine Schicht aus Kupfer oder einer Kupferlegierung durch thermisches Spritzen, insbesondere Plasmaspritzen oder Hochgeschwindigkeitsflammspritzen, direkt aufgebracht. In die Kupferschicht wird die für das Tiefdruckverfahren notwendige Gravur eingebracht.Out DE 93 05 806 U1 is a gravure roll with a sleeve of thermally wound fiber-reinforced thermoplastics known, wherein the fiber reinforcement may consist inter alia of carbon fibers. On the previously roughened outer surface of a base body made of thermoplastic fiber-reinforced plastic material, a layer of copper or a copper alloy by thermal spraying, in particular plasma spraying or high-speed flame spraying, applied directly. In the copper layer, the necessary for the gravure printing engraving is introduced.

DE 100 37 212 A1 beschreibt einen insbesondere für Sportgeräte, zum Beispiel im Bereich eines Golfschlägerkopfes, bestimmten, zumindest teilweise thermisch beschichteten, faserverstärkten Kunststoff. Dabei ist auf einen zum Beispiel kohlefaserverstärkten Kunststoffgrundkörper mittels eines thermischen Spritzverfahrens eine Haftgrundschicht aus Zink, Zinklegierungen, Aluminiumlegierungen und/oder beim Spritzprozess exotherm wirkenden Materialien wie Nickel-Aluminium oder Molybdän aufgetragen. Auf die Haftgrundschicht ist durch thermisches Spritzen eine Verschleißschutzschicht aus Metallen, Metall-Legierungen, Oxiden, Carbiden, Boriden, Kunststoffen oder Mischungen der genannten Stoffe aufgebracht. DE 100 37 212 A1 describes a particular for sports equipment, for example in the field of a golf club head, certain, at least partially thermally coated, fiber-reinforced plastic. In this case, a primer layer of zinc, zinc alloys, aluminum alloys and / or exothermic acting materials during the injection process such as nickel-aluminum or molybdenum is applied to a carbon fiber-reinforced plastic base body for example by means of a thermal spraying process. Thermal spray on the primer layer is a wear protection layer of metals, metal alloys, Oxides, carbides, borides, plastics or mixtures of said substances applied.

Aus EP 0 850 899 A1 ist ferner ein Verfahren zum Beschichten von Kohlenstoffsubstraten oder nichtmetallischen, kohlenstoffhaltigen Substraten bekannt, bei dem auf eine auf 500°C bis 2500°C erhitzte Substratoberfläche durch Plasmaspritzen eine Grundschicht aus Rhenium, Molybdän, Zirkon, Titan, Chrom, Niob, Tantal, Hafnium, Vanadium, Platin, Rhodium oder Iridium aufgetragen und danach mittels Plasmaspritzen eine Deckschicht aufgebracht wird, die zumindest teilweise aus hochschmelzendem Metall besteht.Out EP 0 850 899 A1 Furthermore, a method for coating carbon substrates or non-metallic, carbon-containing substrates is known, in which at a heated to 500 ° C to 2500 ° C substrate surface by plasma spraying a base layer of rhenium, molybdenum, zirconium, titanium, chromium, niobium, tantalum, hafnium, Vanadium, platinum, rhodium or iridium and then applied by plasma spraying a cover layer is applied, which consists at least partially of refractory metal.

JP 02 270 954 A beschreibt ein Verfahren, bei dem ein für Papiermaschinen bestimmter CFK-Zylinder vorerhitzt und durch Plasmaspritzen mit einer Molybdängrundschicht versehen wird, und bei dem auf die so erzeugte Molybdän-, grundschicht eine Keramik-Schutzschicht durch Flammspritzen aufgebracht wird. JP 02 270 954 A describes a method in which a CFRP cylinder intended for paper machines is preheated and provided by plasma spraying with a molybdenum base layer, and in which a ceramic protective layer is applied by flame spraying onto the molybdenum base layer thus produced.

Aus GB 887 366 ist ein Verfahren zum mehrlagigen Beschichten von Kunststoffen mit Metallen oder Legierungen durch Flammspritzen bekannt, bei dem die zuerst aufgebrachte Lage einen Wärmeausdehnungskoeffizienten hat, der größer als der des Kunststoffes ist, während die nachfolgende Lage oder Lagen einen Wärmeausdehnungskoeffizienten aufweist (aufweisen), der kleiner als der des Kunststoffes ist.Out GB 887,366 is a method of multilayer coating of plastics with metals or alloys by flame spraying, in which the first deposited layer has a thermal expansion coefficient which is greater than that of the plastic, while the subsequent layer or layers has a coefficient of thermal expansion (smaller than) which is the plastic.

Der Erfindung liegt nun die Aufgabe zugrunde, einen für den Einsatz bei Papier- und Druckmaschinen bestimmten beschichteten Körper, insbesondere Walze, aus Kohlefaser verstärktem Kunststoff (CFK) und ein Verfahren zum Herstellen eines solchen Körpers zu schaffen, die ohne eine aufwändige Oberflächenvorbehandlung für CFK-Körper, insbesondere Walzen aus CFK der in EP 0514640 B1 oder in DE 3427554 C2 beschriebenen Art auskommen und gleichwohl eine Haftvermittlung bereitstellen, die einen dauerhaft festen Sitz auf dem Körper bewirkt und weitere verschleißhemmende Beschichtungen aus Oxidkeramik oder Hartmetall auf dem Körper sicher fixiert.It is an object of the present invention to provide a coated body, in particular a roller, made of carbon fiber reinforced plastic (CFRP) intended for use in paper and printing machines and a method for producing such a body, which can be used without complex surface pretreatment for CFRP. Body, in particular rolls of CFK in EP 0514640 B1 or in DE 3427554 C2 described type and nevertheless provide a bonding agent that causes a permanent tight fit on the body and other wear-resistant coatings of oxide ceramics or carbide securely fixed on the body.

Die der Erfindung zu Grunde liegende Aufgabe wird durch den beschichteten Körper gemäß Anspruch 1 sowie durch das Verfahren gemäß Anspruch 7 gelöst.The object underlying the invention is achieved by the coated body according to claim 1 and by the method according to claim 7.

. Dabei besteht bei einem beschichteten Körper der eingangs genannten Art erfindungsgemäß die Haftvermittlerschicht aus duktilem Metall, das aus der Gruppe Kupfer, Blei und Zinn ausgewählt und durch Plasmaspritzen oder Flammspritzen aufgetragen ist (wird)., According to the invention, in the case of a coated body of the type mentioned at the outset, the adhesion promoter layer consists of ductile metal selected from the group consisting of copper, lead and tin and applied by plasma spraying or flame spraying.

Es wurde gefunden, dass eine solche Haftvermittlerschicht vergleichsweise einfach und rasch ausgebildet werden kann sowie einen hervorragenden Haftgrund für darüber aufgebrachte Schutzschichten bildet.It has been found that such a primer layer can be formed comparatively easily and rapidly and forms an excellent primer for protective layers applied over it.

Vorteilhafte weitere Ausgestaltungen der Erfindung ergeben sich aus den Unteransprüchen.Advantageous further embodiments of the invention will become apparent from the dependent claims.

So wird die Haftvermittlerschicht aus duktilem Metall zweckmäßig in einer Dicke von 0,01 mm bis 3,0 mm, vorzugsweise etwa 0,1 mm, aufgetragen.Thus, the adhesive layer of ductile metal is suitably applied in a thickness of 0.01 mm to 3.0 mm, preferably about 0.1 mm.

Als besonders günstig hat es sich erwiesen, während des Auftragens der Haftvermittlerschicht den durch zweckentsprechende Kühlmaßnahmen auf einer Temperatur von höchstens 200 °C gehaltenen CFK-Körper, insbesondere Walzenkörper, auf einer Umfangsgeschwindigkeit von mindestens 0,3m/s zu halten. Auf diese Weise wird rasch ein geschlossener, rissfreier Metallring um den CFK-Walzenkörper herum ausgebildet, und durch die abkühlungsbedingte Volumenschrumpfung dieses Metallrings ergibt sich eine fest haftende, kraftschlüssige Verbindung mit dem CFK-Walzenkörper.It has proved to be particularly favorable, during the application of the primer layer, to keep the CFRP body, in particular the roller body, held at a temperature of at most 200 ° C. by appropriate cooling measures at a circumferential speed of at least 0.3 m / s. In this way, a closed, crack-free metal ring is formed around the CFK roller body around quickly, and the volume shrinkage caused by the cooling of this metal ring results in a firmly adhering, frictional connection with the CFRP roller body.

In einem weiteren Schritt werden dann vor Verschleiß schützende Schichten aus Oxidkeramiken wie Chromoxid (Cr2O3), Aluminiumoxid (Al2O3), Titandioxid (TiO2), quarzhaltiges Mullit (z. B. 3Al2O3 2SiO2 bis 2Al2O3 - SiO2), Zirkonoxid (ZrO2) und deren Mischungen, sowie aus verschleißarmen Hartmetallen wie zum Beispiel aus der Gruppe Wolframkarbid/Kobalt (WC/Co), Wolframkarbid/Nickel (WC/Ni), Titankarbid/Nickel (TiC/Ni), Nickel-Chrom/Chromkarbid (Cr3C2/NiCr), NickelChrom-Bor-Silizium (NiCrBSi), Schmelzkarbid (reines Chromkarbid), Chrom, Molybdän mit Sauerstoff, etc. vorzugsweise durch thermische Spritzverfahren wie Plasmaspritzen, Flammspritzen und Hochgeschwindigkeitsflammspritzen aufgebracht.In a further step, wear-protective layers of oxide ceramics such as chromium oxide (Cr 2 O 3 ), aluminum oxide (Al 2 O 3 ), titanium dioxide (TiO 2 ), quartz-containing mullite (eg 3Al 2 O 3 2SiO 2 to 2Al 2 O 3 - SiO 2 ), zirconium oxide (ZrO 2 ) and mixtures thereof, as well as wear-resistant hard metals, for example from the group tungsten carbide / cobalt (WC / Co), tungsten carbide / nickel (WC / Ni), titanium carbide / nickel (TiC / Ni), nickel-chromium / chromium carbide (Cr 3 C 2 / NiCr), nickel-chromium-boron-silicon (NiCrBSi), molten carbide (pure chromium carbide), chromium, molybdenum with oxygen, etc. preferably by thermal spraying methods such as plasma spraying, flame spraying and High speed flame spraying applied.

Diese äußeren Beschichtungen können auch noch, wie an sich bekannt ( EP 0 999 043 A1 ), eine Antihaftversiegelung bekommen.These outer coatings may also, as known ( EP 0 999 043 A1 ), get a non-stick seal.

Die vor Verschleiß schützende Oxidkeramik oder Hartmetallschicht muss nicht durch thermisches Spritzen aufgebracht sein, sondern kann auch durch Beschichtungsprozesse wie PVD (Physical Vapour Deposition), CVD (Chemical Vapour Deposition), Sintern, Heißisostatpressen, Galvanik, Sprengplattieren, Auftragschweißen, Auflöten, Klebetechniken oder Reaktiwerfahren aufgebracht werden, sofern dabei keine Delamination der Karbonfasern in der Kunststoffmatrix oder ein Schädigung Letzterer auftritt.The oxide ceramic or cemented carbide layer protecting against wear does not have to be applied by thermal spraying, but can also be applied by coating processes such as PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), sintering, hot isostatic pressing, electroplating, explosive plating, build-up welding, brazing, adhesive techniques or reactors be applied, provided that no delamination of the carbon fibers in the plastic matrix or damage the latter occurs.

In der bevorzugten Ausführungsform weist die vor Verschleiß schützende Beschichtung eine Dicke von 0,01 bis 3,0 mm, vorzugsweise 0,1 mm, auf.In the preferred embodiment, the wear-resistant coating has a thickness of 0.01 to 3.0 mm, preferably 0.1 mm.

Je nach Anwendungsfall sind Oberflächengüten erforderlich, die einen Schleif- und Poliervorgang nach dem Beschichten erfordern, so dass bei der vor Verschleiß schützenden Beschichtung eine Oberflächenrauhigkeit funktionsgerecht eingestellt werden kann, die vorzugsweise zwischen 1,0 µm < Rz < 90 µm, insbesondere bei Rz = 15 bis 20 µm liegt.Depending on the application surface finishes are required, which require a grinding and polishing process after coating, so that in the wear-protective coating, a surface roughness can be adjusted functionally, preferably between 1.0 .mu.m <R z <90 .mu.m, in particular at R z = 15 to 20 microns.

Claims (16)

  1. Coated body of carbon fiber reinforced plastic (CFP) for paper machines and printing machines, particularly roller, comprising an adhesion promoter layer applied onto the carbon fiber reinforced plastic body and a wear protective layer of hard metal or oxide ceramics which is applied onto the adhesion promoter layer, characterized in that the adhesion promoter layer consists of ductile metal selected from the group consisting of copper, lead and tin and is applied by plasma spraying or flame spraying.
  2. Coated body according to claim 1, characterized in that the adhesion promoter layer of ductile metal has a thickness from 0.01 mm to 3.0 mm, and preferably of about 0.1 mm.
  3. Coated body according to claim 1 or claim 3, characterized in that the wear protective layer of hard metal or oxide ceramics has a thickness from 0.01 mm to 3.0 mm, and preferably of 0.2 mm.
  4. Coated body according to anyone of the preceding claims, characterized in that the wear protective layer of hard metal or oxide ceramics has a surface roughness of between 1.0 µm<Rz<90 µm, and particularly of Rz=15 µm to 20 µm.
  5. Coated Body according to anyone of the preceding claims, characterized in that the hard metal layer consists of WC/Co, WC/Ni, TiC/Ni, Cr3C2/Ni, NiCrBSi or molybdenum or of mixtures of said hard metals.
  6. Coated body according to anyone of claims 1 to 4, characterized in that the oxide ceramics layer consists of Al2O2, Cr2O3, TiO2, SiO2, or ZrO2 or of mixtures thereof.
  7. Method for producing a coated body of carbon fiber reinforced plastic (CFP) for paper machines and printing machines, particularly roller, wherein an adhesion promoter layer of ductile metal selected from the group consisting of copper, lead and tin is applied by plasma spraying or flame spraying onto a CFP body, whilst the body is maintained by cooling measures at a temperature not exceeding 200°C, and wherein in a further step a wear protective layer of hard metal or oxide ceramics is applied onto the adhesion promoter layer.
  8. Method according to claim 7, wherein, during the coating step, the CFP roller body is maintained at a circumferential speed of at least 0.3 m/sec.
  9. Method according to claim 7 or claim 8, wherein the adhesion promoter layer is applied at a thickness from 0.01 mm to 3.0 mm, and preferably of about 0.1 mm.
  10. Method according to anyone of claims 7 to 9, wherein the wear protective layer of hard metal or oxide ceramics is applied at a thickness from 0.01 mm to 3.0 mm, and preferably of 0.2 mm.
  11. Method according to anyone of claims 7 to 10, wherein the surface roughness of the wear protective layer of hard metal or oxide ceramics is adjusted by grinding and polishing to a value of between 1.0 µm<Rz<90 µm, and particularly of Rz=15 µm to 20 µm.
  12. Method according to anyone of claims 7 to 11, including the further step of applying onto the adhesion promoter layer a hard metal layer of WC/Co, WC/Ni, TiC/Ni, Cr3C2/Ni, NiCrBSi or molybdenum or of mixtures of said hard metals.
  13. Method according to anyone of claims 7 to 12, wherein the hard metal layer is applied by thermal spraying such as plasma spraying, flame spraying and high velocity flame spraying.
  14. Method according to anyone of claims 7 to 11, wherein an oxide ceramics layer of Al2O2, Cr2O3, TiO2, SiO2, or ZrO2 or of mixtures thereof is applied in said further method step onto the adhesion promoter layer.
  15. Method according to anyone of claims 7 to 11 or 14, wherein the oxide ceramics layer is applied by thermal spraying such as plasma spraying and flame spraying.
  16. Method according to anyone of claims 7 to 12 or 14, wherein the wear protective layer of hard metal or oxide ceramics is applied in a further method step by coating processes, such as PVD (physical vapour deposition), CVD (chemical vapour deposition), sintering, hot isostatic pressing, electroplating, explosive plating, surface welding, soldering, brazing, adhesive bonding techniques or reactive processes, under conditions at which a delamination of the carbon fibers wherein the plastic matrix and a damaging of the latter is avoided.
EP06722499.8A 2005-02-24 2006-02-16 Coated member, especially roller, made of carbon fiber-reinforced plastic (CFRP) for paper machines and printing presses, and method for the production of such a member Active EP1888805B1 (en)

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DE102005008487A DE102005008487C5 (en) 2005-02-24 2005-02-24 Coated body of carbon fiber reinforced plastic for paper and printing machines, in particular roller, and method for producing such a body
PCT/DE2006/000287 WO2006089519A1 (en) 2005-02-24 2006-02-16 Coated member, especially roller, made of carbon fiber-reinforced plastic (cfk) for paper machines and printing presses, and method for the production of such a member

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US20090023567A1 (en) 2009-01-22
EP1888805A1 (en) 2008-02-20
DE102005008487A1 (en) 2006-09-07
DE102005008487B4 (en) 2008-06-26
WO2006089519A1 (en) 2006-08-31
DE102005008487C5 (en) 2011-08-18

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