EP0700340A1 - Process for producing print rolls made of a metallic core cylinder and a plasma-sprayed copper or copper alloy coating - Google Patents

Process for producing print rolls made of a metallic core cylinder and a plasma-sprayed copper or copper alloy coating

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Publication number
EP0700340A1
EP0700340A1 EP94915549A EP94915549A EP0700340A1 EP 0700340 A1 EP0700340 A1 EP 0700340A1 EP 94915549 A EP94915549 A EP 94915549A EP 94915549 A EP94915549 A EP 94915549A EP 0700340 A1 EP0700340 A1 EP 0700340A1
Authority
EP
European Patent Office
Prior art keywords
copper
cylinder
copper alloy
plasma
range
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.)
Granted
Application number
EP94915549A
Other languages
German (de)
French (fr)
Other versions
EP0700340B1 (en
Inventor
Heinrich Kuehn
Dieter Jaculi
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.)
Hoechst AG
Original Assignee
Hoechst AG
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Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0700340A1 publication Critical patent/EP0700340A1/en
Application granted granted Critical
Publication of EP0700340B1 publication Critical patent/EP0700340B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/16—Curved printing plates, especially cylinders
    • B41N1/20—Curved printing plates, especially cylinders made of metal or similar inorganic compounds, e.g. plasma coated ceramics, carbides
    • 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
    • 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
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • 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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • 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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • 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

Definitions

  • the invention relates to a method for producing printing rollers with a core cylinder made of metal and a plasma-sprayed homogeneous, low-oxide and adhesive copper or copper alloy coating made of powdery materials.
  • copper-coated metal cylinders are of particular technical importance and can be found e.g. used as a gravure cylinder.
  • the copper layer can be machined and engraved either chemically, mechanically or using laser technology.
  • Electrochemical deposition is known for the application of copper for the stated purpose.
  • the environmental protection costs for the wastewater produced increase the cost of this process.
  • the production times for e.g. a layer thickness of 1 mm is about 8 to 12 hours and can be shortened in the interests of flexible production.
  • the coating must be homogeneous and mechanically machinable so that the surface quality is comparable to galvanic copper coatings. It must be possible to insert the engravings for printing rollers into this surface without loss of quality.
  • the metallic basic cylinder is preferably made of steel.
  • Other metals and metal alloys e.g. Aluminum or high-strength aluminum alloys can be used.
  • the basic cylinder can also be made with chemically or electrochemically deposited metals such as nickel, copper, etc. be coated.
  • the surface of the pressure cylinder is first subjected to a roughening process.
  • a roughening of the surface with sandblasting devices can preferably be provided, with mineral blasting material such as aluminum oxide, electro-corundum, silicon carbide, zirconium corundum, etc., being suitable as the abrasive.
  • Preferred blasting conditions are a blasting pressure in the range from 2 to 6 bar, a grain size in the range from 0.1 to 1.5 mm, preferably 0.5 to 1.2 mm, a distance from the nozzle to the nozzle treating surface in the range of 90 to 150 mm and a movement of the nozzle across the treated surface at a speed in the range of 0.5 to 1 m / sec.
  • the micro surface roughness R a of the base body treated in this way is in the range from 5 to 15 measured according to DIN 4768. The macro structure remains unchanged.
  • the roughening process is expediently followed by a cleaning process using compressed air or in a cleaning bath, if appropriate with the assistance of ultrasound.
  • the cleaning process ensures within the scope of the invention that any contaminants still present on the surface are effectively removed.
  • copper and copper alloys are applied by thermal spraying of powdery, spherical, microfine material with a particle diameter D BQ of 6 to 12 which is determined by the Cilas laser diffraction method.
  • the phosphorus content of the copper or copper alloy is in the range from 0.08 to 0.15% by weight and is determined photometrically, while the oxygen content is in the range from 0.2 to 0.3% and is determined by hot extraction in an inert gas stream.
  • a phosphorus content of preferably 0.10 to 0.12% by weight as a deoxidizer has positive effects on the oxidation behavior of the applied copper layer.
  • copper alloys can also be used, such as copper-zinc, copper-tin, copper-aluminum, copper-nickel or copper-nickel-zinc, which can additionally contain further alloy components such as iron, manganese, silicon or lead.
  • an inert gas or an inert gas mixture is used as the plasma gas, preferably argon in an amount in the range from 30 to 60 l / min.
  • the micro-grain of the application material means that the plasma torch can be operated at low electrical power.
  • the preferred electrical power of the plasma torch is 10 to 15 kW, particularly preferably 12 kW.
  • the burner is moved past the rotationally symmetrical base body at a distance in the range from 40 to 100 mm, preferably from 40 to 70 mm, at a speed of 10 to 100 mm / min. Under such conditions, an application rate in the range of 2 to 8 kg / h is achieved.
  • the pressure rollers provided for the coating are preferably cooled during the coating process in order to keep the oxide formation low and to prevent residual stresses both in the coating and in the base body.
  • CO 2 is preferably used in a finely crystalline form at a high pressure of approximately 40 to 60 bar.
  • Layers applied by the process according to the invention can have a layer thickness in the range from 50 to 2000 ⁇ m, preferably from 100 to 1000 ⁇ m, in a single operation, the thickness uniformity fluctuating only by 5 to 10%.
  • the application in one layer means that the layer has no oxidic intermediate layers.
  • FIG. 1 shows a schematic illustration according to which the coating method according to the invention can be carried out.
  • the plasma torch 1, into which the plasma gas 2 is introduced, is shown in detail with reference numerals.
  • the copper powder 3 is placed in a metering device 4, is introduced into the hot gas jet with a powder carrier gas 5 and is then deposited on the metallic surface 6.
  • the rotationally symmetrical body is set in rotation by a device 7.
  • carbonic acid 8 is used for cooling and non-sticking Particles emitted through fine crystals.
  • the plasma torch 1 is guided along the coating body by a moving device 9 in a transition with respect to the longitudinal axis. After this process, the metallic body is coated with a copper layer 10.
  • the coated metallic cylinders obtained by the production process according to the invention are particularly well suited for mechanical processing for use as engraved printing rollers, in particular the non-engraved, polished, shadow-free surface having a roughness R a ⁇ 0.1 mm (DIN 4768 ) having.
  • the closed surface can be galvanically or chemically coated with metals such as Nickel, chrome, copper, etc. and provided with metal alloys.
  • the surface of a steel pressure cylinder with a diameter of 1 13.2 mm and a length of 375 mm was roughened by sandblasting to apply the copper layer.
  • Electro-corundum was used as the blasting agent, an aluminum oxide powder with a content of 3% titanium dioxide and a grain size in the range from 1 to 1.2 mm.
  • the jet pressure was 2.5 bar with a jet spacing of 120 mm and with a jet nozzle diameter of 8 mm. After roughening, the surface was cleaned with cleaned compressed air.
  • the surface of the base body treated in this way was coated by plasma spraying with a copper powder with a grain size D 1 in the range from 8 to 10 ⁇ m.
  • Argon was used as the plasma gas.
  • the burner output was 12 kW and the burner was placed at a distance of 60 mm with a speed of 22 mm / min moved over the rotating base body at a speed of 320 rpm.
  • the surface of the base body was cooled in the C0 2 under a pressure of 60 bar in the area of the plasma flame and non-adhesive material is removed by blasting with CO 2 particles.
  • the copper layer produced in this way had a layer thickness of 1 mm.
  • the copper surface could be machined very well with polycrystalline diamond. After a reduction in diameter of 0.15 mm, a pore-free surface having a roughness R a was achieved of 0.3 mm.
  • the surface quality of the subsequent finishing by diamond film lapping was R a ⁇ 0.04 mm.
  • the roughness was measured according to DIN 4768.
  • the shape deviation of the finished cylinder was 0.01 mm, while its position deviation was 0.01 mm, in each case in accordance with DIN ISO 1 101.

Abstract

A process is disclosed for producing print rolls made of a metallic core cylinder and a plasma-sprayed copper or copper alloy coating which may be easily shaped by mechanical means into an only slightly rough, homogeneous closed surface into which high quality engravings may be incorporated. The process is characterised in that finely ground copper or a copper alloy powder with particles having a mean diameter of 12 mu m or less is applied by plasma spraying on the surface of the roll by means of a low power plasma torch, without oxidized intermediate layers.

Description

Verfahren zur Herstellung von Druckwalzen aus einem metallischen Kernzylinder und einer plasmagespritzten Kupfer- oder KupferlegierungsauflageProcess for the production of printing rollers from a metallic core cylinder and a plasma-sprayed copper or copper alloy coating
Die Erfindung betrifft ein Verfahren zur Herstellung von Druckwalzen mit einem Kernzyiinder aus Metall und einer plasmagespritzten homogenen, oxidarmen und haftfesten Kupfer- oder Kupferlegierungsauflage aus pulverförmigen Werkstoffen.The invention relates to a method for producing printing rollers with a core cylinder made of metal and a plasma-sprayed homogeneous, low-oxide and adhesive copper or copper alloy coating made of powdery materials.
Auf dem Gebiet der Drucktechnik sind kupferbeschichtete Metalizylinder von besonderer technischer Bedeutung und finden z.B. als Tiefdruckzγlinder Verwendung. Die Kupferschicht läßt sich mechanisch bearbeiten und entweder chemisch, mechanisch oder mit Hilfe der Lasertechnik gravieren.In the field of printing technology, copper-coated metal cylinders are of particular technical importance and can be found e.g. used as a gravure cylinder. The copper layer can be machined and engraved either chemically, mechanically or using laser technology.
Für das Aufbringen von Kupfer für den genannten Zweck ist die elektrochemische Abscheidung bekannt. Die Umweltschutzaufwendungen für das dabei anfallende Abwasser verteuern dieses Verfahren aber in zunehmender Form. Die Produktionszeiten für z.B. eine Schichtdicke von 1 mm betragen etwa 8 bis 12 Stunden und sind in Sinne einer flexiblen Fertigung zu verkürzen.Electrochemical deposition is known for the application of copper for the stated purpose. However, the environmental protection costs for the wastewater produced increase the cost of this process. The production times for e.g. a layer thickness of 1 mm is about 8 to 12 hours and can be shortened in the interests of flexible production.
Kupferlegierungen lassen sich galvanisch nur sehr schwer mit konstant gleichbleibender Legierungszusammensetzung auf einem Zylinderkörper abscheiden. Femer müssen für die einzelnen Legierungsarten unterschiedliche Elektrolytbäder verwendet werden. Unterschiedliche Metalle oder Legierungen des Grundzylinders bedürfen einer getrennten Vorbehandlung vor der galvanischen Auftragung.It is very difficult to electroplate copper alloys on a cylinder body with a constant alloy composition. Different electrolyte baths must also be used for the individual types of alloy. Different metals or alloys of the base cylinder require separate pretreatment before galvanic application.
Das Aufbringen von Kupfer durch Flamm- oder Plasmaspritzen auf metallische Körper zum Zwecke der Herstellung einer lötbaren Verbindung oder zur Verbesserung des elektrischen Übergangswiderstands sind bekannt. Die bisher erzeugten grobfladigen Schichten sind in ihrer Zusammensetzung inhomogen und für eine hochwertige Gravur für Druckzylinder ungeeignet. Die geeigneteren Spritzprozesse unter Vakuum, Schutzgaskammern und Schutzgasummantelungen sind in technischer Hinsicht sehr aufwendig.The application of copper by flame or plasma spraying to metallic bodies for the purpose of producing a solderable connection or to improve the electrical contact resistance is known. The coarse-layered layers produced to date are inhomogeneous in their composition and unsuitable for high-quality engraving for printing cylinders. The more suitable spraying processes under vacuum, protective gas chambers and Protective gas jackets are very complex from a technical point of view.
Aufgabe der vorliegenden Erfindung war es daher ein Verfahren bereitzustellen, welches es ermöglicht, daß auf einen metallischen Grundkörper mit einem einzigen Verfahren Kupfer- wie Kupferlegierungsbeschichtungen mit geringeren Entsorgungskosten und hoher Produktivität unabhängig von der chemischen Zusammensetzung des metallischen Grundkörpers aufgebracht werden können. Die Beschichtung muß homogen und mechanisch so bearbeitbar sein, daß die Oberflächenbeschaffenheit vergleichbar mit galvanischen Kupferbeschichtungen ist. In diese Oberfläche muß es möglich sein, die Gravuren für Druckwalzen ohne Qualitätsverluste einzubringen.It was therefore an object of the present invention to provide a process which makes it possible to apply copper and copper alloy coatings to a metallic base body in a single process, with lower disposal costs and high productivity, regardless of the chemical composition of the metallic base body. The coating must be homogeneous and mechanically machinable so that the surface quality is comparable to galvanic copper coatings. It must be possible to insert the engravings for printing rollers into this surface without loss of quality.
Gelöst wird diese Aufgabe durch ein Verfahren nach Anspruch 1 , dessen nährere Ausgestaltungen in den Ansprüchen 2 bis 9 angegeben sind. Nach der Beschichtung wird die Schicht zu einer geschlossenen homogenen Oberfläche mechanisch bearbeitet und die Gravuren mit hoher Güte eingebracht.This object is achieved by a method according to claim 1, the more detailed embodiments of which are given in claims 2 to 9. After coating, the layer is mechanically processed into a closed, homogeneous surface and the engravings are made with high quality.
Der metallische Grundzγlinder besteht vorzugsweise aus Stahl. Es können auch andere Metalle und Metall-Legierungen z.B. Aluminium oder hochfeste Aluminiumlegierungen verwendet werden.The metallic basic cylinder is preferably made of steel. Other metals and metal alloys e.g. Aluminum or high-strength aluminum alloys can be used.
Zusätzlich kann der Grundzylinder auch mit chemisch oder elektrochemisch abgeschiedenen Metallen wie Nickel, Kupfer u.a. beschichtet sein.In addition, the basic cylinder can also be made with chemically or electrochemically deposited metals such as nickel, copper, etc. be coated.
Nach einer zweckmäßigen Ausgestaltung des erfindungsgemäßen Verfahrens wird die Oberfläche des Druckzγlinders zunächst einem Aufrauhprozeß unterzogen. Vorzugsweise kann hierzu eine Aufrauhung der Oberfläche mit Sandstrahlgeräten vorgesehen sein, wobei als Strahlmittel vorzugsweise mineralisches Strahlgut wie Aluminiumoxid, Elektrokorund, Siliciumcarbid, Zirkonkorund u.a. in Frage kommen. Bevorzugte Strahlbedingungen sind dabei ein Strahldruck im Bereich von 2 bis 6 bar, eine Korngröße im Bereich von 0,1 bis 1 ,5 mm, bevorzugt 0,5 bis 1 ,2 mm, ein Abstand der Düse zu der zu behandelnden Oberfläche im Bereich von 90 bis 150 mm und eine Bewegung der Düse über die behandelte Oberfläche hinweg mit einer Geschwindigkeit im Bereich von 0,5 bis 1 m/sec. Die Mikrooberfiächenrauheit Ra des auf diese Weise behandelten Grundkörpers liegt im Bereich von 5 bis 15 gemessen nach DIN 4768. Die Makrostruktur bleibt unverändert.According to an expedient embodiment of the method according to the invention, the surface of the pressure cylinder is first subjected to a roughening process. For this purpose, a roughening of the surface with sandblasting devices can preferably be provided, with mineral blasting material such as aluminum oxide, electro-corundum, silicon carbide, zirconium corundum, etc., being suitable as the abrasive. Preferred blasting conditions are a blasting pressure in the range from 2 to 6 bar, a grain size in the range from 0.1 to 1.5 mm, preferably 0.5 to 1.2 mm, a distance from the nozzle to the nozzle treating surface in the range of 90 to 150 mm and a movement of the nozzle across the treated surface at a speed in the range of 0.5 to 1 m / sec. The micro surface roughness R a of the base body treated in this way is in the range from 5 to 15 measured according to DIN 4768. The macro structure remains unchanged.
Zweckmäßigerweise folgt dem Aufrauhprozeß ein Reinigungsprozeß durch Druckluft oder in einem Reinigungsbad, gegebenenfalls mit Unterstützung durch Ultraschall. Durch den Reinigungsprozess wird im Rahmen der Erfindung sichergestellt, daß eventuell noch vorhandene Verunreinigungen an der Oberfläche wirksam entfernt werden.The roughening process is expediently followed by a cleaning process using compressed air or in a cleaning bath, if appropriate with the assistance of ultrasound. The cleaning process ensures within the scope of the invention that any contaminants still present on the surface are effectively removed.
Das Auftragen von Kupfer und Kupferlegierungen erfolgt erfindungsgemäß durch thermisches Spritzen von pulverförmigem, kugeligem, mikrofeinem Werkstoff mit einem Teilchendurchmesser DBQ von 6 bis 12 der nach der Analγsenmethode Laserbeugung Cilas bestimmt wird. Der Phosphorgehalt des Kupfers oder der Kupferlegierung liegt im Bereich von 0,08 bis 0,15 Gew.-% und wird fotometrisch bestimmt, während der Sauerstoffgehalt im Bereich von 0,2 bis 0,3 % liegt und durch Heißextraktion im Inertgasstrom bestimmt wird. Überraschend zeigte sich, daß ein Phosphorgehalt von vorzugsweise 0,10 bis 0,12 Gew.-% als Desoxidationsmittel positive Auswirkungen auf das Oxidationsverhalten der aufgetragenen Kupferschicht ausübt. Neben reinem Kupfer können auch Kupferlegierungen verwendet werden, wie z.B. Kupfer-Zink, Kupfer-Zinn, Kupfer-Aluminium, Kupfer-Nickel oder Kupfer-Nickel-Zink, die zusätzlich weitere Legierungsbestandteile wie z.B. Eisen, Mangan, Silizium oder Blei enthalten können.According to the invention, copper and copper alloys are applied by thermal spraying of powdery, spherical, microfine material with a particle diameter D BQ of 6 to 12 which is determined by the Cilas laser diffraction method. The phosphorus content of the copper or copper alloy is in the range from 0.08 to 0.15% by weight and is determined photometrically, while the oxygen content is in the range from 0.2 to 0.3% and is determined by hot extraction in an inert gas stream. Surprisingly, it was found that a phosphorus content of preferably 0.10 to 0.12% by weight as a deoxidizer has positive effects on the oxidation behavior of the applied copper layer. In addition to pure copper, copper alloys can also be used, such as copper-zinc, copper-tin, copper-aluminum, copper-nickel or copper-nickel-zinc, which can additionally contain further alloy components such as iron, manganese, silicon or lead.
Bei dem Plasmaspritzverfahren wird als Plasmagas ein Inertgas oder eine Inertgasmischung verwendet, vorzugsweise Argon in einer Menge im Bereich von 30 bis 60 l/min. Die Mikrokörnung des Auftragswerkstoffes bewirkt, daß der Plasmabrenner bei niedriger elektrischer Leistung betrieben werden kann. Die bevorzugte elektrische Leistung des Plasmabrenners beträgt 10 bis 15 kW, besonders bevorzugt 12 kW. Der Brenner wird an dem rotationssymmetrischen Grundkörper in einem Abstand im Bereich von 40 bis 100 mm, vorzugsweise von 40 bis 70 mm, mit einer Geschwindigkeit von 10 bis 100 mm/min vorbeibewegt. Unter derartigen Bedingungen wird eine Auftragsrate im Bereich von 2 bis 8 kg/h erreicht.In the plasma spraying process, an inert gas or an inert gas mixture is used as the plasma gas, preferably argon in an amount in the range from 30 to 60 l / min. The micro-grain of the application material means that the plasma torch can be operated at low electrical power. The preferred electrical power of the plasma torch is 10 to 15 kW, particularly preferably 12 kW. The burner is moved past the rotationally symmetrical base body at a distance in the range from 40 to 100 mm, preferably from 40 to 70 mm, at a speed of 10 to 100 mm / min. Under such conditions, an application rate in the range of 2 to 8 kg / h is achieved.
Die zur Beschichtung vorgesehenen Druckwalzen werden während des Beschichtungsvorgangs, um die Oxidbildung gering zu halten und um Eigenspannungen sowohl in der Beschichtung, als auch im Grundkörper vorzubeugen, vorzugweise gekühlt. Zu diesem Zweck wird bevorzugt CO2 in fein kristalliner Form bei einem hohen Druck von circa 40 bis 60 bar eingesetzt. Es ist zwar bekannt, daß CO2 zur Kühlung beim thermischen Spritzen Verwendung findet, jedoch ist es für den Fachmann überraschend, daß gleichzeitig ein Strahlen der Oberfläche durch die bei der Entspannung entstehenden feinen CO2-Partikel stattfindet, wodurch erreicht wird, daß eine Einbettung stark oxidierter, störender Kleinstpartikel in die Beschichtung unterbunden wird.The pressure rollers provided for the coating are preferably cooled during the coating process in order to keep the oxide formation low and to prevent residual stresses both in the coating and in the base body. For this purpose, CO 2 is preferably used in a finely crystalline form at a high pressure of approximately 40 to 60 bar. Although it is known that CO 2 is used for cooling in thermal spraying, it is surprising for the person skilled in the art that at the same time the surface is radiated by the fine CO 2 particles formed during the relaxation, whereby an embedding is achieved highly oxidized, disruptive small particles in the coating is prevented.
Nach dem erfindungsgemäßen Verfahren aufgetragene Schichtea können in einem einzigen Arbeitsgang eine Schichtdicke im Bereich von 50 bis 2000 μm aufweisen, vorzugsweise von 100 bis 1000 μm, wobei die Dickengleichmäßigkeit nur noch um 5 bis 10 % schwankt. Die Auftragung in einer Lage bewirkt, daß die Schicht keine oxidischen Zwischenlagen aufweist.Layers applied by the process according to the invention can have a layer thickness in the range from 50 to 2000 μm, preferably from 100 to 1000 μm, in a single operation, the thickness uniformity fluctuating only by 5 to 10%. The application in one layer means that the layer has no oxidic intermediate layers.
Die Figur 1 zeigt eine schematische Darstellung, nach der das erfindungsgemäße Beschichtungsverfahren durchgeführt werden kann. Im einzelnen sind mit Bezugszeichen der Plasmabrenner 1 dargestellt, in den das Plasmagas 2 eingeleitet wird. Das Kupferpulver 3 wird in einer Dosiervorrichtung 4 vorgelegt, mit einem Pulverträgergas 5 in den heißen Gasstrahl eingegeben und schlägt sich dann auf die metallische Oberfläche 6 nieder. Der rotationssymmetrische Körper wird durch eine Vorrichtung 7 in Rotation versetzt. Nach Beginn des Beschichtungsprozesses wird mit Kohlensäure 8 gekühlt und nichthaftende Partikel durch feine Kristalle abgestrahlt. Der Plasmabrenner 1 wird durch eine Bewegungseinrichtung 9 in einem Übergang bezogen auf die Längsachse an dem Beschichtungskörper entlang geführt. Der metallische Körper ist nach diesem Prozeß mit einer Kupferschicht 10 überzogen.FIG. 1 shows a schematic illustration according to which the coating method according to the invention can be carried out. The plasma torch 1, into which the plasma gas 2 is introduced, is shown in detail with reference numerals. The copper powder 3 is placed in a metering device 4, is introduced into the hot gas jet with a powder carrier gas 5 and is then deposited on the metallic surface 6. The rotationally symmetrical body is set in rotation by a device 7. After the start of the coating process, carbonic acid 8 is used for cooling and non-sticking Particles emitted through fine crystals. The plasma torch 1 is guided along the coating body by a moving device 9 in a transition with respect to the longitudinal axis. After this process, the metallic body is coated with a copper layer 10.
Überraschend zeigte sich, daß sich die nach dem erfindungsgemäßen Herstellverfahren erhaltenen beschichteten metallischen Zylinder besonders gut zur mechanischen Bearbeitung für die Verwendung als gravierte Druckwalzen eignen, wobei insbesondere die nicht gravierte, polierte, schattenfreie Oberfläche eine Rauheit Ra < 0,1 mm (DIN 4768) aufweist.Surprisingly, it was found that the coated metallic cylinders obtained by the production process according to the invention are particularly well suited for mechanical processing for use as engraved printing rollers, in particular the non-engraved, polished, shadow-free surface having a roughness R a <0.1 mm (DIN 4768 ) having.
Die geschlossene Oberfläche läßt sich galvanisch oder chemisch mit Metallen wie z.B. Nickel, Chrom, Kupfer u.a. sowie mit Metallegierungen versehen.The closed surface can be galvanically or chemically coated with metals such as Nickel, chrome, copper, etc. and provided with metal alloys.
Die Erfindung soll nachfolgend anhand eines Ausführungsbeispiels näher beschrieben werden, ohne aber auf die konkret beschriebene Ausführungsform beschränkt zu sein.The invention will be described in more detail below with the aid of an exemplary embodiment, but without being restricted to the specifically described embodiment.
Beispiel 1example 1
Die Oberfläche eines Druckzγlinders aus Stahl mit einem Durchmesser von 1 13,2 mm und einer Länge von 375 mm wurde zur Auftragung der Kupferschicht durch Sandstrahlen aufgerauht. Als Strahimittel wurde Elektrokorund verwendet, ein Aluminiumoxidpulver mit einem Anteil von 3 % Titandioxid und einer Korngröße im Bereich von 1 bis 1 ,2 mm. Der Strahldruck betrug 2,5 bar bei einem Strahlabstand von 120 mm und bei einem Strahldüsendurchmesser von 8 mm. Nach dem Aufrauhen wurde die Oberfläche mit gereinigter Druckluft gereinigt.The surface of a steel pressure cylinder with a diameter of 1 13.2 mm and a length of 375 mm was roughened by sandblasting to apply the copper layer. Electro-corundum was used as the blasting agent, an aluminum oxide powder with a content of 3% titanium dioxide and a grain size in the range from 1 to 1.2 mm. The jet pressure was 2.5 bar with a jet spacing of 120 mm and with a jet nozzle diameter of 8 mm. After roughening, the surface was cleaned with cleaned compressed air.
Die so behandelte Oberfläche des Grundkörpers wurde durch Plasmaspritzen mit einem Kupferpulver mit einer Korngröße D^, im Bereich von 8 bis 10 μm beschichtet. Als Plasmagas wurde Argon verwendet. Die Brennerleistung betrug 12 kW und der Brenner wurde in einem Abstand von 60 mm mit einer Ge- schwindigkeit von 22 mm/min über den mit einer Drehzahl von 320 U/min rotierenden Grundkörper hinwegbewegt. Die Oberfläche des Grundkörpers wurde dabei im Bereich der Plasmaflamme mit C02 unter einem Druck von 60 bar gekühlt und nicht haftendes Material durch Strahlen mit CO2-Partikeln entfernt.The surface of the base body treated in this way was coated by plasma spraying with a copper powder with a grain size D 1 in the range from 8 to 10 μm. Argon was used as the plasma gas. The burner output was 12 kW and the burner was placed at a distance of 60 mm with a speed of 22 mm / min moved over the rotating base body at a speed of 320 rpm. The surface of the base body was cooled in the C0 2 under a pressure of 60 bar in the area of the plasma flame and non-adhesive material is removed by blasting with CO 2 particles.
Die so hergestellte Kupferschicht hatte eine Schichtdicke von 1 mm. Die Kupferoberfläche ließ sich mechanisch sehr gut mit polykristallinem Diamant bearbeiten. Nach einer Durchmesserverringerung von 0,15 mm wurde eine porenfreie Oberfläche mit einer Rauheit Ra von 0,3 mm erreicht. Die Oberflächengüte der anschließenden Endbearbeitung durch Diamantfilm-Läppen betrug Ra < 0,04 mm. Die Rauheiten wurden gemessen nach DIN 4768. Die Formabweichung des fertigen Zylinders betrug 0,01 mm, während seine Lageabweichung 0,01 mm betrug, jeweils im Einklang mit DIN ISO 1 101. The copper layer produced in this way had a layer thickness of 1 mm. The copper surface could be machined very well with polycrystalline diamond. After a reduction in diameter of 0.15 mm, a pore-free surface having a roughness R a was achieved of 0.3 mm. The surface quality of the subsequent finishing by diamond film lapping was R a <0.04 mm. The roughness was measured according to DIN 4768. The shape deviation of the finished cylinder was 0.01 mm, while its position deviation was 0.01 mm, in each case in accordance with DIN ISO 1 101.

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung von Druckwalzen aus einem metallischen Kernzylinder und einer plasmagespritzten Auflage aus elementarem Kupfer oder einer Kupferlegierung, die sich mechanisch zu einer homogenen geschlossenen Oberfläche mit geringer Rauheit bearbeiten läßt und in die sich dann Gravuren mit hoher Güte einbringen lassen, dadurch gekennzeichnet, daß feinkörniges Kupfer oder Kupferlegierungspulver mit einem mittleren Teilchendurchmesser1. A process for the production of printing rollers from a metallic core cylinder and a plasma-sprayed overlay made of elemental copper or a copper alloy, which can be machined mechanically to form a homogeneous, closed surface with low roughness and into which engravings with high quality can then be introduced, characterized in that that fine-grain copper or copper alloy powder with an average particle diameter
---- 12 μm durch Plasmaspritzen bei niedriger Energie des Plasmabrenners ohne oxidische Zwischenlagen auf die Oberfläche des Zylinders aufgebracht wird.---- 12 μm is applied to the surface of the cylinder by plasma spraying at low energy of the plasma torch without oxidic intermediate layers.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß als Kernzylinder ein metallischer Körper aus Stahl, hochfesten Aluminiumlegierungen oder anderen Metallen oder Legierungen verwendet wird.2. The method according to claim 1, characterized in that a metallic body made of steel, high-strength aluminum alloys or other metals or alloys is used as the core cylinder.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Kernzylinder vor dem Plasmaspritzen mit einer galvanischen oder chemischen Beschichtung, vorzugsweise aus Nickel, Kupfer oder einer Kupferlegierung, überzogen wird.3. The method according to claim 1 or 2, characterized in that the core cylinder is coated with a galvanic or chemical coating, preferably made of nickel, copper or a copper alloy, before plasma spraying.
4. Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß die metallische Oberfläche vor dem Plasmaspritzen einem Aufrauhprozeß durch Sandstrahlen mit mineralischem Strahlgut wie Aluminiumoxid, Elektrokorund, Siliciumcarbid oder Zirkonkorund unterzogen und anschließend mit gereinigter Druckluft oder in einem wäßrigen Reinigungsbad, gegebenenfalls mit Unter¬ stützung von Ultraschall, gereinigt wird.4. The method according to claim 1 to 3, characterized in that the metallic surface before the plasma spraying is subjected to a roughening process by sandblasting with mineral blasting material such as aluminum oxide, electro-corundum, silicon carbide or zirconium corundum and then with cleaned compressed air or in an aqueous cleaning bath, optionally with Unter¬ support of ultrasound, is cleaned.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Pulver aus Kupfer oder einer Kupferlegierung eine kugelige Form und eine Korngröße DM im Bereich von 8 bis 12 μm besitzt, wobei dem Kupfer als Legierungsbestandteile ein oder mehrere Elemente der Metalle Zink, Zinn, Nickel, Mangan, Silizium, Aluminium, Blei oder andere zulegiert sein können.5. The method according to any one of claims 1 to 4, characterized in that the powder of copper or a copper alloy has a spherical shape and a grain size D M in the range of 8 to 12 microns, the copper as alloy components one or more elements of the metals Zinc, tin, nickel, Manganese, silicon, aluminum, lead or others can be alloyed.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß Kupfer- oder Kupferlegierungspulver mit desoxidierenden Zusätzen, vorzugsweise Phosphor, in einer Menge im Bereich von 0,08 bis 0,15 Gew.-%, bezogen auf das Gesamtgewicht des Pulvers, verwendet wird.6. The method according to any one of claims 1 to 5, characterized in that copper or copper alloy powder with deoxidizing additives, preferably phosphorus, in an amount in the range of 0.08 to 0.15 wt .-%, based on the total weight of the powder , is used.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Zylinder während des Plasmaspritzens gekühlt und daß gleichzeitig Metalldämpfe und nicht aufgeschmolzene Partikel von der Oberfläche des Zylinders entfernt werden.7. The method according to any one of claims 1 to 6, characterized in that the cylinder is cooled during plasma spraying and that at the same time metal vapors and unmelted particles are removed from the surface of the cylinder.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß zur Kühlung und Entfernung der Metalldämpfe und nicht aufgeschmolzenen Partikel CO2 in fein kristalliner oder gasförmiger Form bei einem Druck im Bereich von 40 bis 60 bar eingesetzt wird.8. The method according to claim 7, characterized in that for cooling and removal of the metal vapors and unmelted particles CO 2 is used in a finely crystalline or gaseous form at a pressure in the range from 40 to 60 bar.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Kupfer- oder Kupferlegierungsbeschichtung in einem Arbeitsgang mit einer Schichtdicke im Bereich von 50 bis 2000 μm ohne oxidische Zwischenlagen aufgetragen wird.9. The method according to any one of claims 1 to 8, characterized in that the copper or copper alloy coating is applied in one operation with a layer thickness in the range of 50 to 2000 microns without oxidic intermediate layers.
10. Mit Kupfer oder einer Kupferlegierung beschichteter Metalizylinder hergestellt nach einem Verfahren gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß seine äußere Oberfläche mechanisch durch Drehen und Polieren bearbeitet ist und eine homogene, geschlossene Oberfläche mit einer Oberfiächenrauheit Ra im Bereich < 0,04 mm darstellt.10. Copper or a copper alloy coated metal cylinder produced by a method according to any one of claims 1 to 9, characterized in that its outer surface is machined by turning and polishing and a homogeneous, closed surface with a surface roughness R a in the range <0 , 04 mm.
1 1. Zylinders nach Anspruch 10, dadurch gekennzeichnet, daß seine äußere Oberfläche Gravuren trägt, die mit Hilfe der Lasertechnik oder auf chemischem oder mechanischem Wege aufgebracht sind. 1 1. Cylinder according to claim 10, characterized in that its outer surface bears engravings which are applied with the aid of laser technology or by chemical or mechanical means.
12. Verwendung eines mit Kupfer oder mit Kupferlegierung beschichteten Metalizylinders nach Anspruch 10 oder 11 als Druckzγlinder für das Tiefdruckverfahren oder als Auftragswalze für Farben, Leime und andere Zubereitungen in der Druck-, Papier-, Folien- oder sonstigen Industrie. 12. Use of a metal cylinder coated with copper or with copper alloy according to claim 10 or 11 as a printing cylinder for the gravure printing process or as an application roller for inks, glues and other preparations in the printing, paper, film or other industries.
EP94915549A 1993-05-12 1994-04-27 Process for producing print rolls made of a metallic core cylinder and a plasma-sprayed copper or copper alloy coating Expired - Lifetime EP0700340B1 (en)

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DE4315813 1993-05-12
DE4315813A DE4315813A1 (en) 1993-05-12 1993-05-12 Process for the production of printing rollers from a metallic core cylinder and a copper or copper alloy coating
PCT/EP1994/001322 WO1994026534A1 (en) 1993-05-12 1994-04-27 Process for producing print rolls made of a metallic core cylinder and a plasma-sprayed copper or copper alloy coating

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