WO2007059545A1 - Outil comportant une couche de protection contre l'usure deposee par voie electrochimique - Google Patents

Outil comportant une couche de protection contre l'usure deposee par voie electrochimique Download PDF

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Publication number
WO2007059545A1
WO2007059545A1 PCT/AT2006/000475 AT2006000475W WO2007059545A1 WO 2007059545 A1 WO2007059545 A1 WO 2007059545A1 AT 2006000475 W AT2006000475 W AT 2006000475W WO 2007059545 A1 WO2007059545 A1 WO 2007059545A1
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WO
WIPO (PCT)
Prior art keywords
tool according
tool
substrate
convex
boride layer
Prior art date
Application number
PCT/AT2006/000475
Other languages
German (de)
English (en)
Inventor
Rafael Krendelsberger
Andres Pascual
Martin Kathrein
Hans-Peter Martinz
Gerhard Nauer
Georg Winkler
Original Assignee
Plansee Se
Echem Kompetenzzentrum Für Angewandte Elektrochemie
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Plansee Se, Echem Kompetenzzentrum Für Angewandte Elektrochemie filed Critical Plansee Se
Publication of WO2007059545A1 publication Critical patent/WO2007059545A1/fr

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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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
    • B23B2228/10—Coatings
    • B23B2228/105—Coatings with specified thickness

Definitions

  • the invention relates to a tool having at least one convex or pointed and at least one concave or plane-shaped region, which is a substrate and an electrochemically deposited thereon at least in some areas
  • Borid layer wherein the boride of one or more metals of the IV b , V b and V b elements is formed.
  • the transition elements of the IV b , V b and Vl b groups of the Periodic Table include the metals Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W. Borides of these metals are used on a laboratory scale or already on a large industrial scale as wear protection layers. In particular, TiB 2 hard material layers, which are deposited on carbide substrates, are used for the machining of non-ferrous metal alloys, for example aluminum alloys.
  • boride layers are currently mainly by PVD method. Boride coatings are very hard and brittle and provide good wear protection. For sharp-edged tools that are currently used in the machining of aluminum alloys and others
  • Non-ferrous metal alloys play a special role, it can lead to adhesive and cohesive layer failure at the sharp cutting edge, which on the one hand, the service life of the tool and on the other hand, the surface of the workpiece to be machined can be significantly affected.
  • boride coatings are also of interest for shaping tools in the field of melt metallurgy, and here again in special light metal melt metallurgy, as well as for glass production.
  • thin layers wear out very quickly. Thick layers are too expensive in low deposition rate processes. In addition, it can lead to Schichtabplatzept in areas with sharp or convex tool geometry. Electrochemical processes have a high deposition rate. It was therefore also attempted to deposit borides by electrochemical means. So is in the
  • an electrolyte which consists essentially of one or more metals of IV b , V b and VI b elements and an inorganic molten salt.
  • the molten salt comprises one or more chlorides and / or fluorides of the alkali metals, further KBF 4 and / or NaBF 4 and one or more compounds from the group Alkalihexafluorotitanat, Alkalihexafluorozirkonat, Alkalihexafluorochromat, Alkaliheptafluoroniobat Alkalihexafluorotitanat and / or one or more chlorides and / or fluorides of a or more metals of IV b , V b and Vl b elements.
  • This electrolyte is placed in a reaction vessel.
  • the metal of the IV b , V b and / or Vl b elements is lumpy, for example in the form of granules or wire sections introduced.
  • lower-valent ions of the metal to be deposited are stabilized, which facilitates the deposition of the boride.
  • the substrate In the heated to a temperature of 500 to 900 0 C electrolyte, the substrate is introduced and then the reaction vessel is evacuated. The substrate is optionally initially poled cathodically. Thereafter, it is charged with direct current of 0.001 to 0.5 A / cm 2 . Subsequently, the substrate is subjected to a current density of 0.1 to 1 A / cm 2 in pulse mode with interrupted (Pulsed Interrupted Current, abbreviated PIC) or reversal (Pulsed Reversed Current, abbreviated PRC) mode. In the PIC mode, the cathodic current is cycled on and off cyclically every about 2 to 50 ms, preferably 10 ms, with one cycle typically lasting about 5 to 50 ms. In the PRC, approximately every 2 to 10 cathodic current pulses are replaced by anodic.
  • PIC Pulsed Interrupted Current
  • PRC Pulsed Reversed Current
  • reaction upstream of the deposition is the rate-determining step, where due to the high current density, this can not run fast enough and does not provide enough product for deposition.
  • the lower layer thickness in the convex or pointed areas now leads to a significant improvement in the layer adhesion in these critical zones. Also, the probability of the occurrence of edge breakouts is significantly reduced.
  • the actually effective wear surfaces which are generally flat or concave, have a significantly improved wear resistance due to the greater layer thickness.
  • the deposition process according to the invention is characterized by very high deposition rates, which are about 100 times higher than in conventional PVD processes. In addition, it is possible to operate the coating process continuously, which enables automation.
  • the inscribed radius in the convex or pointed region is ⁇ 5 mm and again preferably ⁇ 1 mm, as is the case, for example Cutting edges is the case.
  • the y / x ratio is> 3, preferably> 10.
  • Preferred tools are therefore cutting tools, such as indexable inserts, drills, drill plates, cutters, cutting blades or saw teeth.
  • Further advantageous fields of application are light metal metallurgy (eg casting molds) and glass production (eg glass molds).
  • Advantageous boride layers are formed from the metals of the IV b group (TiB 2 , ZrB 2 and HfB 2 ).
  • the borides of the V b and V 1 b metals are characterized by NbB 2 and CrB.
  • Particularly suitable substrate materials are hard metals, cermets, refractory metals and refractory metal alloys.
  • the effect according to the invention can also be realized, for example, in steels.
  • an electrolyte consisting of Ti-NaCl-NaF-KCl-K 2 TiF 6 -KBF 4 has significant advantages in terms of handling and homogeneity of the layers deposited therefrom.
  • ZrB 2 this is Zr-NaCl-NaF-KCl-K 2 ZrF 6 -KBF 4 .
  • Further preferred parameters are an electrolyte temperature of 650 to 750 ° C, an initial loading of the substrate with DC of 0.01 to 0.1 A / cm 2 and then with a current density in pulsed mode (PIC) or reversal (PRC). Mode from 0.1 to 1 A / cm 2 .
  • PIC pulsed mode
  • PRC reversal
  • FIG. 1 shows a BE-SEM image of the cross section of sample 1 at 200 ⁇ magnification
  • Figure 2 is a BE-SEM image of the cross section of sample 1 at 500X magnification; 3 shows a BE-SEM image of the cross section of sample 2 at 500 ⁇ magnification.
  • TiB 2 Layer A solid mixture of NaCl, NaF, KCl, K 2 TiF 6 and KBF 4 was first prepared and dried in a glass tube for 12 hours at about 200 ° C. under a pre-vacuum. Thereafter, this mixture was transferred together with Ti wire sections in the glassy carbon crucible, introduced into the reaction vessel and finally melted at 700 ° C. Subsequently, a thin layer of TiB 2 was applied with direct current to two carbide substrates (samples 1 and 2). This process step serves to germinate the samples. The samples had a circular base and a trapezoidal cross-section with edge lengths of 16 mm and 13 mm, respectively.
  • Sample 1 was subjected to cathodic pulsing (10 ms 0.26 A / cm 2 , 10 ms without current) using PIC with cathodic (10 ms 0.4 A / cm 2 , 10 ms without current) and anodic pulses (9 ms 0.65 A / cm 2 , 10 ms without current) for 480 s.
  • the deposition parameters are shown in detail in Table 1.
  • FIGS. 1 to 3 show the layer geometry according to the invention.
  • the average boride layer thickness increases from the pointed area to the planar area.
  • the y / x ratio is greater than 10.
  • a determination of the hardness profile from the layer surface perpendicular to the substrate showed a hardening of the substrate at the interface to the boride. This hardening is due to boronation, as evidenced by microprobe analysis.
  • Zr-NaCl-NaF-KCl-K 2 ZrF 6 -KBF 4 melt coated at 700 ° C according to the PIC method with pre-peak, but without DC pretreatment.
  • Coating parameters for the preparation of sample 3 are shown in Table 2.
  • One cycle works as follows:
  • the average boride layer thickness increases from the pointed area to the planar area.
  • a layer thickness of 20 ⁇ m, in the edge region of about 2 ⁇ m, was measured (y / x 10).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne un outil comprenant au moins une zone convexe ou pointue et au moins une zone concave ou plane. Cet outil comporte un substrat, et une couche de borure qui est déposée par voie électrochimique au moins sur des zones partielles de ce substrat. Selon l'invention, le borure est constitué d'un ou de plusieurs métaux faisant partie des éléments IVb, Vb et Vlb. En outre, l'épaisseur moyenne de la couche de borure dans la zone convexe ou pointue est égale à x, tandis que l'épaisseur moyenne de la couche de borure dans la zone concave ou plane est égale à y, avec y/x > 1,3. Cette invention se rapporte en outre à un procédé pour produire ce type de couches.
PCT/AT2006/000475 2005-11-22 2006-11-20 Outil comportant une couche de protection contre l'usure deposee par voie electrochimique WO2007059545A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0079105U AT9144U1 (de) 2005-11-22 2005-11-22 Werkzeug mit elektrochemisch abgeschiedener verschleissschutzschicht
ATGM791/2005 2005-11-22

Publications (1)

Publication Number Publication Date
WO2007059545A1 true WO2007059545A1 (fr) 2007-05-31

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PCT/AT2006/000475 WO2007059545A1 (fr) 2005-11-22 2006-11-20 Outil comportant une couche de protection contre l'usure deposee par voie electrochimique

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AT (1) AT9144U1 (fr)
WO (1) WO2007059545A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009040250A2 (fr) * 2007-09-20 2009-04-02 Siemens Aktiengesellschaft Dispositif d'excitation par courant de source d'un réseau électrique d'installation de revêtement électrochimique
WO2011041809A1 (fr) * 2009-10-06 2011-04-14 Gerhard Nauer Procédé de production de couches de diborure de titane (tib2) à partir d'électrolytes fondus

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1007930A (en) * 1963-11-05 1965-10-22 Union Carbide Corp Electrodeposition of refractory metals
JP2004122263A (ja) * 2002-09-30 2004-04-22 Sumitomo Electric Ind Ltd 高精度加工用被覆切削工具
JP2004276178A (ja) * 2003-03-17 2004-10-07 Makino Fraes Seiki Kk 工具使用方法および該工具使用方法を利用する工作機械

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1007930A (en) * 1963-11-05 1965-10-22 Union Carbide Corp Electrodeposition of refractory metals
JP2004122263A (ja) * 2002-09-30 2004-04-22 Sumitomo Electric Ind Ltd 高精度加工用被覆切削工具
JP2004276178A (ja) * 2003-03-17 2004-10-07 Makino Fraes Seiki Kk 工具使用方法および該工具使用方法を利用する工作機械

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200434, Derwent World Patents Index; AN 2004-360471, XP002422372 *
ETT G ET AL: "Pulse current plating of TiB2 in molten fluoride", ELECTROCHIMICA ACTA, ELSEVIER SCIENCE PUBLISHERS, BARKING, GB, vol. 44, no. 17, 15 April 1999 (1999-04-15), pages 2859 - 2870, XP004161248, ISSN: 0013-4686 *
G. KAPTAY, S.A. KUZNETSOV: "ELECTROCHEMICAL SYSTHESIS OF REFRACTORY BORIDES FROM MOLTEN SALTS", PLASMAS & IONS, vol. 2, no. 2, 1999, pages 45 - 56, XP002422370 *
J.H. VON BARNER, P. NOYÉ, A. BARHOUN, F. LANTELME: "Influence of Oxide and Alloy Formation on the Electrochemistry of Ti Deposition from the NaCl-KCl-NaF-K2TiF6 Melt Reduced by Metallic Ti", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 152, no. 1, 1 December 2004 (2004-12-01), pages C20 - C26, XP002422375 *
LI ET AL: "Electrodeposition of [001] oriented TiB2 coatings", MATERIALS LETTERS, NORTH HOLLAND PUBLISHING COMPANY. AMSTERDAM, NL, vol. 59, no. 26, 16 June 2005 (2005-06-16), pages 3234 - 3237, XP005041638, ISSN: 0167-577X *
S.A.KUZNETSOV, S.V. KUZNETSOVA, S.V. DEVYATKIN, AND G. KAPTAY: "Electrodeposition of Niobium(V) Boride Coatings from Chloride-Fluoride Melts", RUSSIAN JOURNAL OF APPLIED CHEMISTRY, vol. 71, no. 1, 1998, pages 77 - 83, XP009079711 *
V.P. LUGOVOI ET AL.: "High temperature electrochemical systhesis of zirconium deboride from chloro-fluoride melts.", ELECTROCHEMICAL SOCIETY PROCEEDINGS, vol. 96-7, 1996, pages 303 - 311, XP001249301 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009040250A2 (fr) * 2007-09-20 2009-04-02 Siemens Aktiengesellschaft Dispositif d'excitation par courant de source d'un réseau électrique d'installation de revêtement électrochimique
WO2009040250A3 (fr) * 2007-09-20 2009-10-15 Siemens Aktiengesellschaft Dispositif d'excitation par courant de source d'un réseau électrique d'installation de revêtement électrochimique
WO2011041809A1 (fr) * 2009-10-06 2011-04-14 Gerhard Nauer Procédé de production de couches de diborure de titane (tib2) à partir d'électrolytes fondus

Also Published As

Publication number Publication date
AT9144U1 (de) 2007-05-15

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