EP2438218B1 - Pièce présentant deux couches à base de nickel - Google Patents

Pièce présentant deux couches à base de nickel Download PDF

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Publication number
EP2438218B1
EP2438218B1 EP10709166.2A EP10709166A EP2438218B1 EP 2438218 B1 EP2438218 B1 EP 2438218B1 EP 10709166 A EP10709166 A EP 10709166A EP 2438218 B1 EP2438218 B1 EP 2438218B1
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EP
European Patent Office
Prior art keywords
layer
gravure cylinder
nickel
cylinder according
mass fraction
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EP10709166.2A
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German (de)
English (en)
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EP2438218A2 (fr
Inventor
Matthias Kurrle
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.)
Stohrer Ipt AG
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Stohrer Ipt AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex 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
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • 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
    • B41N1/04—Printing plates or foils; Materials therefor metallic
    • B41N1/06—Printing plates or foils; Materials therefor metallic for relief printing or intaglio printing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • C25D3/18—Heterocyclic compounds

Definitions

  • the invention relates to a gravure cylinder with at least one nickel-containing layer.
  • the DE 102 14 989 A1 shows a printing cylinder with an intended for engraving surface coating.
  • a pure copper layer with a microhardness of about 200 HV either a surface coating of pure nickel and / or mixed crystal alloys and / or composite layers is proposed which have copper or nickel as Hauptkompönente.
  • the EP 0 545 468 A1 shows a metal plate for a gravure sleeve, which is clamped on a support and is suitable for mechanical engraving.
  • a engravable metal layer has a thickness of 25 microns, 50 microns or 100 microns, and an outermost layer has a thickness of less than 10 microns.
  • the engravable metal layer usually has a hardness of 80 to 350 HV, and the outermost layer preferably has a hardness of 450 to 750 HV.
  • engravable metal layer a group of materials is given, which are soft nickel, hard copper; Aluminum, zinc, iron, alloys and special plastics.
  • a group of materials comprising metals, in particular chromium, alloys and ceramic material from the subgroup of titanium nitride, boron nitride and chromium carbide. Chemically deposited phosphorus-nickel, boron-nickel, tin-nickel, nickel and nickel-cobalt are also mentioned.
  • the object is achieved by a gravure cylinder according to claim 1.
  • a gravure cylinder according to claim 1.
  • the recycling of the first and second layer is facilitated because both layers have nickel as the main component.
  • the gravure cylinder is also suitable for laser engraving.
  • a layer containing nickel and hexagonal boron nitride has advantageous properties and can also serve as a wear protection layer in particular.
  • Fig. 1 shows a gravure cylinder (generally: workpiece) 10 having a core (in general: base body) 12, a first layer 14, which is applied to the core, and a second layer 16, which is applied to the first layer 14.
  • the longitudinal axis 18 of the gravure cylinder 10 is indicated schematically.
  • the core 12 for example, a cylinder made of steel, copper or zinc is used.
  • the first layer 14 is preferably made of pure nickel
  • the second layer 16 is preferably made of a composition NiX, where X is e.g. Silicon carbide (SiC), phosphorus (P), hexagonal boron nitride (h-BN) and / or another, preferably non-metallic component (additive), which together with the nickel has better anti-wear properties than pure nickel.
  • the mass fraction of the non-metallic constituent in the second layer 16, ie the relative mass of the non-metallic constituent to the total mass of the substance mixture, is preferably between 0.001 and 0.15, more preferably between 0.003 and 0.12, more preferably between 0.01 and 0.10, more preferably between 0.03 and 0.09.
  • the wear ie the continuous loss of material from the surface of a solid body, caused by mechanical causes, depends on a variety of material properties. In general, a high hardness, anti-adhesive properties and a low coefficient of friction are advantageous.
  • Pure, electrodeposited nickel has a hardness in the range of 350 to 550 HV 0.05, depending on the galvanic bath used, and the second Layer preferably has a hardness of at least 450 HV 0.05, for example between 450 and 750 HV 0.05.
  • the specification 350 HV 0.05 indicates, for example, that the hardness test according to Vickers with a test force of 0.05 kp a hardness value of 350 was measured.
  • the first layer 14 preferably has a layer thickness of 20 to 210 ⁇ m, more preferably 30 to 200 ⁇ m, more preferably 30 to 80 ⁇ m
  • the second layer 16 preferably has a layer thickness of 1 to 20 ⁇ m, more preferably 3 to 15 ⁇ m, more preferably from 5 to 15 ⁇ m.
  • the main body 12 may also be formed in multiple layers and have different shapes. In particular, it may have an additional stop layer / base layer of nickel or copper.
  • the first layer 14 has a thickness of 30 microns and consists of pure nickel with a mass fraction of 1.00
  • the second layer 16 has a thickness of 5 microns and consists from a composition of nickel with a mass fraction of 0.96 and phosphorus with a mass fraction of 0.04.
  • the first layer 14 has a thickness of 35 ⁇ m and consists of a composition (alloy) of nickel with a mass fraction of 0.96 and chromium with a mass fraction of 0, 04
  • the second layer 16 has a thickness of 5 microns and consists of a composition of nickel with a mass fraction of 0.911, chromium with a mass fraction of 0.039, and hexagonal boron nitride with a mass fraction of 0.05.
  • the mass ratio of chromium to nickel in the second Layer at 0.0428 substantially the same as in the first layer at 0.042 (calculated by 0.04 / 0.96).
  • Fig . 2 shows an enlarged view of the printing cylinder 10 with a cup 22 which extends through the second layer 16 into the first layer 14 and filled with ink 20.
  • the second layer (NiX layer) 16 also has the advantage of poorer wetting compared to pure nickel in addition to the better anti-wear properties, so that the printing ink 20 does not get stuck in the wells 22.
  • the cups 22 can be produced by engraving, in particular laser engraving and - if not too high hardness of the second layer 16 and / or a thin second layer 16 - by electromechanical engraving.
  • a great advantage of the second layer (NiX layer) 16 and also the first layer 14 is the good suitability for laser engraving. Especially with respect to the chromium and copper layers which are customary today, better results can be achieved in laser engraving in nickel.
  • Fig . 3 1 shows a galvanizing plant 50 with an upper trough 52, in which the gravure cylinder 10 is rotatably mounted, a first lower trough 54 with a galvanic nickel bath 55, and a second lower trough 56 with a galvanic NiX bath 57.
  • An anode cage 60 is partially disposed about the gravure cylinder 10 and connected to a voltage or current source 62, which is also connected to the gravure cylinder 10.
  • a pumping device 70 allows the bath 55 to be pumped into the upper trough 52, and a valve 72 allows the bath to be drained from the upper trough 52 into the first lower trough 54.
  • a pumping device 80 allows the bath 57 to be pumped into the first trough 54 Upper trough 52, and a valve 82 allows draining the bath from the upper trough 52 into the second lower trough 56th
  • the nickel bath is pumped in the circuit via the pumping device 70 into the upper trough 52 and then discharged via the valve 72 back into the first lower trough 54.
  • the electroplating of the gravure cylinder 10 with the first layer 14 of nickel e.g. with a relatively high deposition rate of, for example, up to 10 microns / min is possible, so that a layer thickness of 50 microns requires about 5 minutes.
  • the nickel bath is completely discharged via the valve 72 into the first lower trough 54, and then the NiX bath from the second lower trough 56 is likewise pumped into the upper trough 52 in the same way, and the coating of the gravure cylinder 10 with the second layer 16 of NiX takes place.
  • the deposition rate is lower, for example, up to 5 ⁇ m / min, but the second layer 16 is thinner than the first layer 14, so that the entire coating of the gravure cylinder 10 with the first and second layers can take about 7 to 30 minutes.
  • a speed advantage is also achieved in that the same upper tray 52 can be used for both layers, since in both process steps a galvanic bath 55, 57 is used with the metal nickel and so impurity of the baths with foreign metals is excluded, which would normally require the use of two separate upper trays and a transport of the gravure cylinder 10.
  • the gravure cylinder is usually polished before the engraving is subsequently performed.
  • the second layer 16 is completely turned off and the first layer 14 is partially turned off or milled on a lathe, and then a new coating can take place.
  • a major advantage of using the same metal or the same metal combination for the first and second layers 14, 16 is that the separated material - possibly after a cleaning process - can be used again for coating and no consuming or in part impossible separation of different metals must be done.
  • Fig. 4 shows a cross section through a gravure cylinder 10, in which between the base body 12 and the first layer 14, a release layer 13 is arranged.
  • the separating layer 13 serves to prevent a firmly adhering connection between the first layer 14 and the main body 12, so as to allow mechanical breaking and subsequent stripping of the first layer 14 and second layer 16 in the manner of a ballard skin.
  • a separation layer 13 for example, a silver layer can be applied, which oxidizes, or an organic layer (eg, protein) can be used.
  • Fig. 5 shows a transverse section through a workpiece 10 with a base body 12 made of copper (copper bolt), on the surface 15 an outer, 60 micron thick layer (wear protection layer) 16 is applied, which consists of a composition of nickel and hexagonal boron nitride (h-BN) , The hexagonal boron nitride is visible in the form of dots 17, which are darker than the nickel. By contrast, the larger, very dark dots 24 are superficial deposits that have been added in connection with the creation of the cross section.
  • h-BN hexagonal boron nitride
  • a protective layer 19 of a potting agent (e.g., plastic) is applied, which is provided only to prevent destruction of the outer layer 16 in cross-section.
  • the protective layer 19 and the main body 12 have been lightened by image processing for better reproduction.
  • Fig. 6 shows a cross-section through a Ni h-BN layer 16, the opposite to the layer 16 of Fig. 5 has a higher mass fraction of hexagonal boron nitride 17, recognizable as darker spots.
  • the grooves 25 come from the cross section. Image editing has increased brightness and contrast. A scale is not available.
  • Fig. 7 shows the cross section Fig. 5 in the original.
  • Ni h-BN layer has very good anti-wear properties and therefore can be used in the coating of gravure cylinders as a replacement for a wear protection layer of hard chrome.
  • the hardness is approximately 450 to 600 HV 0.05, similar to a NiP layer, but less than that of hard chrome (up to 1200 HV 0.05).
  • a major advantage of the Ni h-BN layer is a large reduction in friction coefficient (friction coefficient reduction, friction coefficient reduction), in particular in the reduction of dry friction, wherein the friction coefficient reduction leads to Reduction of dry friction, whereby the friction coefficient reduction leads to the fact that the wear protection properties - depending on the application - are similar to hard chrome.
  • the advantage of good coefficient of friction reduction is more important in terms of scuffing than the disadvantage of lower hardness. It is advantageous to add further particles such as SiC.
  • the mass fraction of the hexagonal boron nitride 17 in the layer 16 is preferably between 0.001 and 0.08, more preferably between 0.002 and 0.07, and more preferably between 0.01 and 0.05.
  • the hexagonal boron nitride does not dissolve in the bath, it is advantageous to use a ready-to-use aqueous h-BN suspension with a wetting agent, as it is commercially available, in the manufacture of the plating solution, and the plating bath must be present during the plating process Movement be offset.
  • a nickel content in the electrolytic bath of about 110 g / l and a pH in the range of 1.7 to 4.5 has proved to be advantageous.
  • the specified bath batch can also be used for the other mentioned NiX layers, the respective X content being added as an additive at the desired concentration.
  • the stated solids were dissolved in water.
  • the temperature was 60 ° C. and the pH was 2.
  • the electroplating program for 2 minutes was 2.5 A / dm 2 for a smooth layer and then 10 minutes at 30 A / dm 2 (depending on the desired layer thickness).
  • a gravure cylinder preferably has an outer layer 16, in which nickel with a mass fraction of at least 0.85 and hexagonal boron nitride 17 are provided.
  • the outer layer 16 comprises nickel with a mass fraction of at least 0.95.
  • the outer layer 16 serves as a wear protection layer
  • the outer layer 16 is electrodeposited.
  • the outer layer 16 is deposited from an aqueous dispersion.
  • the outer layer 16 contains silicon carbide.
  • the outer layer 16 contains phosphorus.
  • the outer layer 16 preferably contains hexagonal boron nitride 17 with a mass fraction of between 0.001 and 0.08, preferably between 0.002 and 0.07, more preferably between 0.01 and 0.05.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)

Claims (14)

  1. Cylindre d'impression en creux (10), lequel présente :
    un corps de base (12),
    une première couche (14), laquelle est disposée au moins partiellement sur le corps de base (12) et contient du nickel dans une fraction massique d'au moins 0,80, en particulier d'au moins 0,95,
    et une seconde couche (16), laquelle est disposée au moins partiellement du côté de la première couche (14) opposé au corps de base (12), laquelle contient du nickel dans une fraction massique d'au moins 0,70, en particulier d'au moins 0,85, et au moins un composant non métallique,
    l'épaisseur de la première couche (14) se situant entre 30 µm et 200 µm,
    l'épaisseur de la seconde couche (16) se situant entre 1 µm et 20 µm, et
    la seconde couche (16) étant plus dure que la première couche (14),
    le composant non métallique total de la seconde couche (16) ayant une fraction massique compris entre 0,001 et 0,15,
    et le cylindre d'impression en creux (10) présentant au moins dans la seconde couche (16) des alvéoles (22) qui sont réalisées par gravure au laser.
  2. Cylindre d'impression en creux selon la revendication 1, dans lequel le composant non métallique présente du phosphore (P).
  3. Cylindre d'impression en creux selon la revendication 1 ou 2, dans lequel la première couche (14) est plus épaisse que la seconde couche (16).
  4. Cylindre d'impression en creux selon l'une des revendications précédentes, lequel présente des alvéoles (22) qui s'étendent dans la première couche (14) à travers la seconde couche (16).
  5. Cylindre d'impression en creux selon l'une des revendications précédentes, dans lequel l'épaisseur de la seconde couche (16) est comprise entre 3 et 15 µm.
  6. Cylindre d'impression en creux selon l'une des revendications précédentes, dans lequel le composant métallique de la première couche (14) et de la seconde couche (16) présente chaque fois du nickel dans un pourcentage en masse d'au moins 0,95, en particulier d'au moins 0,98.
  7. Cylindre d'impression en creux selon l'une des revendications précédentes, dans lequel le composant métallique de la première couche (14) et de la seconde couche (16) présente, en plus du nickel, au moins un autre métal identique.
  8. Cylindre d'impression en creux selon la revendication 7, dans lequel le rapport massique relatif entre la masse dudit au moins un autre métal identique et la masse du nickel est sensiblement égal dans les deux couches.
  9. Cylindre d'impression en creux selon l'une des revendications précédentes, dans lequel la première couche et la seconde couche sont déposées par électrolyse.
  10. Cylindre d'impression en creux selon l'une des revendications précédentes, dans lequel le composant non métallique total de la seconde couche a une fraction massique comprise entre 0,003 et 0,12, de préférence entre 0,01 et 0,10.
  11. Cylindre d'impression en creux selon l'une des revendications précédentes, dans lequel une couche de séparation (13) est disposée entre le corps de base (12) et la première couche (14), laquelle s'oppose à une liaison adhésive entre la première couche (14) et le corps de base (12).
  12. Cylindre d'impression en creux selon l'une des revendications 1 à 10, dans lequel la première couche (14) et la seconde couche (16) sont reliées de façon adhésive au corps de base (12).
  13. Cylindre d'impression en creux selon l'une des revendications précédentes, dans lequel le composant non métallique présente du carbure de silicium (SiC).
  14. Cylindre d'impression en creux selon l'une des revendications précédentes, dans lequel le composant non métallique présente du nitrure de bore hexagonal (h-BN).
EP10709166.2A 2009-03-13 2010-03-11 Pièce présentant deux couches à base de nickel Active EP2438218B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009014522 2009-03-13
PCT/EP2010/001505 WO2010102808A2 (fr) 2009-03-13 2010-03-11 Pièce présentant au moins une couche à base de nickel

Publications (2)

Publication Number Publication Date
EP2438218A2 EP2438218A2 (fr) 2012-04-11
EP2438218B1 true EP2438218B1 (fr) 2015-09-30

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Application Number Title Priority Date Filing Date
EP10709166.2A Active EP2438218B1 (fr) 2009-03-13 2010-03-11 Pièce présentant deux couches à base de nickel

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EP (1) EP2438218B1 (fr)
DE (1) DE102010012004A1 (fr)
WO (1) WO2010102808A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010047574A1 (de) * 2010-10-07 2012-04-12 Tenneco Gmbh Zylinderkopf-integrierter Krümmer
FR3032725B1 (fr) * 2015-02-12 2019-04-12 Safran Aircraft Engines Procede de depot d'un revetement de protection contre l'erosion sur une piece metallique

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0545468A1 (fr) * 1991-11-25 1993-06-09 Stork Screens B.V. Plaque métallique pour la fabrication d'un manchon pour l'impression en creux, procédé de fabrication et rouleau pourvu d'un motif

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0355430A3 (fr) * 1988-08-23 1991-06-12 Bayerische Motoren Werke Aktiengesellschaft Elément de construction en aluminium soumixe à la friction
EP0473973B1 (fr) * 1990-09-04 1995-11-29 MDC Max Dätwyler Bleienbach AG Procédé pour le traitement de plaques d'impression intaglio
JP3561929B2 (ja) * 1993-08-23 2004-09-08 株式会社豊田自動織機 スクロール型圧縮機
EP1461478B1 (fr) * 2000-12-20 2011-02-09 Honda Giken Kogyo Kabushiki Kaisha Film de placage composite et son procede de formation
DE10214989A1 (de) * 2002-04-04 2003-10-30 Georg Frommeyer Druckzylinder zur Verwendung in einer Tiefdruckmaschine, sowie Verfahren zur Herstellung einer Oberflächenbeschichtung eines Druckzylinders

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0545468A1 (fr) * 1991-11-25 1993-06-09 Stork Screens B.V. Plaque métallique pour la fabrication d'un manchon pour l'impression en creux, procédé de fabrication et rouleau pourvu d'un motif

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DE102010012004A1 (de) 2010-09-16
EP2438218A2 (fr) 2012-04-11
WO2010102808A2 (fr) 2010-09-16
WO2010102808A3 (fr) 2010-11-25

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