EP4180879A1 - Module micromécanique, son procédé de fabrication et son utilisation - Google Patents

Module micromécanique, son procédé de fabrication et son utilisation Download PDF

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Publication number
EP4180879A1
EP4180879A1 EP21207650.9A EP21207650A EP4180879A1 EP 4180879 A1 EP4180879 A1 EP 4180879A1 EP 21207650 A EP21207650 A EP 21207650A EP 4180879 A1 EP4180879 A1 EP 4180879A1
Authority
EP
European Patent Office
Prior art keywords
functional component
axle
shaft
recess
assembly
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21207650.9A
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German (de)
English (en)
Inventor
Peter Gluche
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.)
GFD Gesellschaft fuer Diamantprodukte mbH
Original Assignee
GFD Gesellschaft fuer Diamantprodukte mbH
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 GFD Gesellschaft fuer Diamantprodukte mbH filed Critical GFD Gesellschaft fuer Diamantprodukte mbH
Priority to EP21207650.9A priority Critical patent/EP4180879A1/fr
Publication of EP4180879A1 publication Critical patent/EP4180879A1/fr
Pending legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B13/00—Gearwork
    • G04B13/02—Wheels; Pinions; Spindles; Pivots
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B13/00—Gearwork
    • G04B13/02—Wheels; Pinions; Spindles; Pivots
    • G04B13/021—Wheels; Pinions; Spindles; Pivots elastic fitting with a spindle, axis or shaft
    • G04B13/022—Wheels; Pinions; Spindles; Pivots elastic fitting with a spindle, axis or shaft with parts made of hard material, e.g. silicon, diamond, sapphire, quartz and the like
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B15/00—Escapements
    • G04B15/14—Component parts or constructional details, e.g. construction of the lever or the escape wheel
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B17/00—Mechanisms for stabilising frequency
    • G04B17/32—Component parts or constructional details, e.g. collet, stud, virole or piton

Definitions

  • the present invention relates to micromechanical assemblies that have at least one functional component and at least one axis and/or shaft, these being non-positively connected by means of press joining.
  • the invention also relates to a method for producing such micromechanical assemblies and their use in watch movements.
  • the escapement of a watch is an escape wheel with Axle and/or integrated drive (on the axle) and an armature with an armature shaft.
  • the components of the assemblies are usually made of metallic materials in a conventional design.
  • the axles are typically turned from steel and, if necessary, integrated gearing for the drive.
  • the axes are hardened after machining.
  • the pin diameters are usually rolled on high-quality shafts, on the one hand to set a micrometer-precise diameter of the pin and on the other hand to compact and harden the surface of the pin and, if necessary, to additionally smooth the friction contact surfaces. In order to further minimize friction, additional polishing steps can also be carried out.
  • the escape wheel or the anchor (hereafter: functional component) have so far been manufactured separately. Stamping, milling, turning, toothing or laser cutting processes are used for this.
  • metallic materials are also used, eg steel in different alloys such as 20AP ® or non-magnetic metallic alloys such as Phynox ® (cobalt alloy).
  • a press connection is usually used, which can optionally be reinforced by a joint connection (e.g. riveting the escapement wheel seat).
  • a rivet structure is already provided on the axle, which is plastically deformed after the wheel is pressed on so that the wheel sits frictionally on the axle.
  • the object of the present invention is therefore to put a non-ductile material on a conventionally manufactured axle made of a ductile material to be mounted force-fit and at the same time to completely dispense with gluing processes and intermediate pieces.
  • the at least one functional component has at least one essentially cylindrical recess for receiving the axle.
  • the axle or shaft is formed from a ductile material and the at least one functional component has a plurality of tooth-shaped structures or teeth on the inner circumference of the recess. At least the areas of the tooth-shaped structures that come into contact with the axle or shaft are formed from a brittle and hard material.
  • ductile material is to be understood as meaning a material which has a range of plastic deformation, the beginning of which lies in the stress-strain diagram of 40-1700 MPa due to the elastic limit R p0.2 .
  • the elastic limit R p0.2 also often referred to as the 0.2% yield strength, is the (uniaxial) mechanical stress at which the permanent elongation related to the initial length of the sample (ie plastic elongation after relief) is 0.2% amounts to.
  • brittle-hard material is to be understood as meaning a material which is advantageously from the material class of semiconductors (4th main group of the periodic table (in particular silicon, germanium, diamond) or ceramics (in particular silicon, aluminum zirconium and yttrium based ceramics) is selected. It has no region of plastic deformation and a transverse rupture stress greater than 1 GPa, preferably more than 2 GPa.
  • the at least one functional component and the at least one axle or shaft are non-positively connected in the area of the recess by press joining.
  • the invention is based on the fact that the tooth-like structures are formed at least in regions, preferably completely, from the brittle material.
  • the tooth-like structures have a sufficiently high mechanical stability, as a result of which the tooth-like structures can be prevented from breaking out during press joining. Due to the high mechanical stability, the tooth-like structures dig into the ductile material of the axle or shaft during press joining and thus ensure a particularly stable fixing of the axle or shaft to the functional component.
  • the hard, brittle material of the functional component has a high hardness of more than 50 GPa, preferably from 60 to 110 GPa (the hardness is determined using the HIT nanoindention method). This prevents the tooth structures, in particular the sensitive tooth tip, from changing their shape due to wear during the pressing-in process.
  • the at least one functional component preferably has from 3 to 21 tooth-like structures, preferably from 5 to 19 tooth-like structures and particularly preferably from 7 to 11 tooth-like structures. It is advantageous here that the number of tooth-like structures is odd, since this leads to a smaller concentricity error.
  • the tooth-like structures preferably have an opening angle ⁇ in the range from 10° to 120°, preferably from 20° to 60° and particularly preferably from 20° to 50° and in particular from 45°.
  • tooth-like structures are at least partially chamfered from the top and/or bottom. All tooth-like structures are particularly preferably bevelled from the top and/or bottom. In this case, at least the tooth-like structures have chamfers on the structure edges.
  • the ductile material preferably has a Vickers hardness of 350 to 920 HV, particularly preferably 400 to 800 HV, very particularly preferably 550 to 700 HV.
  • the brittle material is selected from the group consisting of single crystal diamond, polycrystalline diamond, nanocrystalline diamond, diamond-like amorphous carbon (DLC), and combinations thereof.
  • the at least one functional component consists of the brittle-hard material, i.e. the functional component is a full diamond component, for example.
  • the functional component is a substrate made of a material selected from the group consisting of silicon, hard metal, steel, ceramic materials, in particular Si 3 N 4 and SiC, , SiO 2 , Si x O y , SiO x N y (where x, y are natural numbers) and combinations thereof, or consists of them, and has an at least regional coating of the hard and brittle material.
  • This coating is then applied in particular to the surfaces of the functional component that are in contact with the axle or the shaft.
  • the coating preferably has a layer thickness in the range from 1 to 100 ⁇ m, preferably from 2 to 50 ⁇ m and particularly preferably from 4 to 10 ⁇ m.
  • the coating is preferably a coating applied isotropically, for example by means of chemical vapor deposition (CVD).
  • the hard material coating preferably consists of diamond.
  • the bending stress is determined by statistical evaluation of fracture tests, e.g. in the B3B load test according to the literature references above. It is defined as the breaking stress at which there is a 63% probability of breaking.
  • the modulus of elasticity or Young's modulus is determined according to the method according to " Young's modulus, fracture strength, and Poisson's ratio of nanocrystalline diamond films", J. Appl. Phys. 116, 124308 (2014 ), in particular paragraph III.
  • the surface roughness R RMS is determined according to DIN EN ISO 25178. The mentioned surface roughness makes an additional mechanical polishing of the grown material superfluous.
  • the hardness is determined using the nanoindention method HIT.
  • the at least one functional component contains or consists of silicon and the coating consists of nanocrystalline diamond.
  • the at least one functional component preferably has a thickness in the range from 10 ⁇ m to 2 mm, preferably from 50 ⁇ m to 1 mm and particularly preferably from 100 ⁇ m to 500 ⁇ m.
  • the recess in the at least one functional component preferably has a diameter in the range from 0.1 to 1 mm, preferably from 0.2 to 0.5 mm and particularly preferably from 0.3 to 0.4 mm.
  • the recess and/or the axis or shaft has a taper of ⁇ 1° to 3°, particularly preferably of 0° to 2.5° and very particularly preferably of 0.5° to 2°. This taper makes it easier to insert the axle or shaft into the recess of the functional component. At the same time, the formation of chips when pressing into the ductile material of the axle or shaft is prevented.
  • a variant according to the invention provides that the press fit area is conically shaped in the direction of the axis, ie the diameter d p of the axis decreases down towards, is therefore not constant.
  • the adhesion of the components is largely defined by the overlap Ü in the press fit area. The larger the overlap, the greater the frictional connection, anti-twist security and press-out force.
  • the conicity can also be achieved by a conical design of the press fit area in the ductile material of the shaft/axle.
  • the press-fit area is conical, i.e. with an increasing diameter in the direction of the pressing direction of the functional component. This is particularly important when a corresponding conical design of the recess in the functional component is not possible due to the microtechnical processing.
  • the at least one functional component has at least one further recess, e.g. in the radial direction, running from the recess to the outer edge of the functional component, which enables elastic deformation of the functional component in the area of the axle plate and thus the functional component the axle or encloses the shaft in a press fit. This is particularly advantageous if the component is subsequently to be moved again in position.
  • An alternative embodiment provides for the functional component and the axle or shaft to be provided with an additional fixation in the area of the contact surfaces for the assembly group connected by press joining.
  • This can be rivets or an adhesive. This is particularly necessary in the event that particularly high axial extrusion forces are required.
  • the micromechanical assembly is a clockwork assembly with an axis or a shaft and a functional component, wherein the functional component is selected in particular from the group consisting of gear, escapement wheel, anchor, pinion, double roller, safety knife, lever stone, lifting stone, safety roller, journals and combinations thereof.
  • the recess of the functional component is conical and the axis is inserted at the larger opening of the recess. This eases insertion, prevents chip formation in the ductile material, and allows for a larger contact area between the axle and the teeth of the press fit (recess). It is particularly preferred that the larger recess of the functional component has an inscribed circle diameter that is larger than the diameter of the axle in the area of the press fit. It is also necessary for the smaller area of the recess to have a smaller inscribed circle diameter than the diameter of the axle in the area of the press fit.
  • a preferred embodiment provides that the axle or shaft is processed in the later contact area with the functional component using a rolling process. This ensures that the narrow diameter specifications are achieved and the surface of the axle has a sufficiently smooth surface quality. Rough surfaces increase the risk of undesirable chip formation during the pressing process and lead to an increase in the press-in force.
  • a support plate (so-called plateau) is preferably implemented in step a) in order to ensure the correct height level of the functional component on the axis, the support plate preferably having a cavity for receiving any chips that may occur during press joining. To do this, the support plate can be screwed directly onto the axle.
  • the functional component lies flat on the plateau. This also ensures flat running. In this case, the larger the diameter of the support plate, the more precise the flat run. However, in the case of rotating components, the moment of inertia of the axis must be taken into account, which also increases with increasing diameter of the plateau.
  • step d) the non-positive connection is realized by additional rivets or an adhesive
  • shoots can also be produced and pressed onto the axle.
  • the drive/wheel contact can also be made of diamond for the first time in the gear train.
  • these components are then lubrication-free, have a low coefficient of friction, low mass inertia and are low-wear.
  • a lubrication-free operation of the gearing can be achieved because, for example, diamond has a very low coefficient of sliding friction. This is a significant advantage, especially for future applications in the micro-drive area, since high speeds of the drive motor are required here, which are then reduced to the application speed/torque range via multi-stage reductions of a micro-gear.
  • the low moment of inertia, the low coefficient of sliding friction and the wear resistance of the functional components play an important role here.
  • the micromechanical assembly is used as a clockwork assembly, particularly as a gear, escapement wheel, anchor, pinion, double roller of a balance wheel, lever jewel of a double roller, lever jewel, bearing journal, and combinations thereof.
  • 1 1 shows a functional component 2 in the form of an escapement wheel with a recess 4.
  • the recess 4 has a plurality of tooth-shaped structures 5, 5′, which implements a press fit of the axle inserted into the recess 4 (not shown here).
  • figure 1 also shows a sectional representation of the partial section AA, which represents the interface between the escapement wheel 2 and the recess 4.
  • the detail view of the partial section AA shows that the inscribed circle diameter d i of the surface side O of the functional component 2 is smaller than the inscribed circle diameter d a on the underside U of the functional component 2 .
  • the axis or shaft 3 (not shown here) is inserted from the underside U into the recess 4 of the functional component 2 .
  • the functional component 2 thus has an inscribed circle diameter that increases over the thickness t, which leads to a conicity (characterized by the flank angle ⁇ ) of the functional component 2 at the interface to the recess 4 .
  • the 2 shows a functional component 2 and here in particular the area of the axle plate 12, which has a recess 4 in the form of an axle hole.
  • the axle plate 12 has an outside diameter d AP and in the center of the axle plate 12 there is the recess 4 with the inscribed circle diameter d i .
  • the detailed view shows that several tooth-shaped structures 5, 5', 5", 5′′′ are arranged on the recess 4, with the inscribed circle diameter d i being defined by the tips of these tooth-shaped structures.
  • the tooth-shaped structures 5, 5', 5 ", 5′′′ have a rounding radius r Z at the tip, which is usually in the range of 5 to 10 ⁇ m. In the case of a diamond-coated functional component, this rounding radius rz usually corresponds to the layer thickness applied.
  • Each tooth has an opening angle ⁇ , which is preferably in the range of 45°.
  • the axis 3 shows an axis or shaft 3, which can be pressed into a recess 4 of a functional component 2, in plan view.
  • the structure of the axis 3 is explained in more detail using a sectional view of the partial section AA.
  • the axis 3 has a pin 13 for storage.
  • the cross section shows that this is followed by a tapered area 14 and a press fit area 15 with a radius r p corresponding to a diameter d p .
  • the tapered area 14 makes it possible to prevent chip formation during the pressing process and to avoid scoring in this area that is undesirable for optical reasons.
  • the press-fit area 15 has a diameter d p that is larger than the inscribed circle diameter d i of the functional component 2, as shown in FIG 1 is shown.
  • the press-fit region 15 it is also possible here for the press-fit region 15 to be conically shaped in the axial direction, ie the diameter d p of the axis increases downwards, so it is not constant.
  • the maximum diameter dp in the press-fit area of the axle is dpmax in this case.
  • This results in an overlap of Ü d pmax -d i .
  • the adhesion of the components is largely defined by the overlap Ü in the press fit area. The larger the overlap, the greater the frictional connection, anti-twist security and press-out force.
  • Such a configuration enables in particular the reliable press connection of a non-conical recess 4 of the functional component.
  • a plateau 16 is also shown in partial section A-A, with which the height level of the functional component 2 is defined and, in addition, a sufficiently good axial run-out of the functional component 2 is made possible.
  • the plateau 16 has an undercut 17 adjoining the press-fit region 15, through which a planar support of the functional component 2 on the plateau 16 is made possible and any chips produced by the pressing process can be absorbed.
  • figure 5 shows an axis or shaft 3, which can be pressed in a recess 4 on the functional component 2, in plan view.
  • the axis or shaft 3 shown here can be fixed with an additional rivet connection. This can be of particular advantage when high axial strength, ie high extrusion forces, are required.
  • the rivet lug 19 can be plastically deformed in the later course of the fixation, so that there is an additional rivet connection between the functional component 2 and the axle or shaft 3 .
  • the further details in figure 5 correspond to the variant 4 .
  • an assembly 1 according to the invention which consists of a functional component 2 in the form of an escapement wheel and an axle 3 .
  • the assembly is first shown in the top view and details can be found in the sectional view according to part section AA.
  • section AA in this case, the axis 3 is in direct contact with the functional component 2 , the height level of the functional component 2 being defined by the plateau 16 .
  • the free seat 17 enables the functional component 2 to rest flat on the plateau 16 and can possibly accommodate any chips that may arise during the pressing process.
  • Figure 6c Another variant is shown, which is essentially the structure of Figure 6b is equivalent to.
  • the functional component is made up of a substrate 6 (eg made of silicon) with a coating 7, preferably a hard material coating.
  • a diamond coating is particularly suitable as a hard material coating. Due to its high breaking stress, the diamond coating also enables filigree tooth shapes with a small included angle ⁇ to be pressed without damage.
  • the axle plate is additionally mechanically reinforced by the diamond layer and a failure fracture in the radial direction only occurs at significantly higher press-in forces than with an uncoated axle plate.
  • Figure 7a shows a further variant of an assembly 1 according to the invention in plan view.
  • This consists of the functional component 2 and the axle 3 .
  • a sectional view that clarifies the structure of the functional component 2 results from the partial section AA.
  • This is in particular from the detail view in Figure 7b to be taken, which shows that in contrast to Figure 6b here there is no conicity of the functional component 2 nor of the axis 3. Rather is here provide the functional component with a cylindrical recess which is in planar contact with the axis 3. This achieves a maximum contact length L in the press fit area and thus a maximum frictional connection.
  • chip formation can be avoided in that the functional component 2 has a chamfer 21 at the lower end.
  • FIG. 8 shows a plan view of an assembly 1 according to the invention with a functional component 2 in the form of an anchor wheel, the area of the anchor plate 12 being shown here essentially.
  • a functional component 2 in the form of an anchor wheel, the area of the anchor plate 12 being shown here essentially.
  • the tooth-shaped structures engage in the more ductile material of the axis 3 This is illustrated again in the second detailed view, in which the tooth-shaped structure has dug into the material of the axle as a result of the press-joining process of the tooth structure 5 in the material of the axis 3 allows security against twisting and a non-positive connection, which ensures that the axis 3 is securely fixed in the recess 4 of the functional component 2 .
  • Figure 9a is the top view of a variant of an assembly 1 according to the invention with a functional component 2 in the form of an escapement wheel, in whose central recess an axle 3 is inserted.
  • the arrangement of the axis 3 in the functional component 2 is illustrated using a sectional view according to the partial section AA.
  • the functional component 2 has a conical flank, which enables simple assembly and avoids the formation of chips.
  • the plastically deformable rivet flag 19 (as shown in figure 5 shown) was formed in such a way that it is pressed onto the functional component 2 from the top. It is advantageous here if the functional component has a chamfer 24 on the upper side.
  • FIG. 10 shows a top view of a variant of an assembly 1 according to the invention with a functional component 2 in the form of an armature, the axle plate 12 being shown essentially.
  • the axle plate has a central recess 4 according to the invention with tooth-shaped structures.
  • the anchor plate 12 has a recess 25 running from the recess 4 to the outer edge 26 of the functional component. This enables an elastic deformation of the functional component, as a result of which the functional component 2 can enclose the axle or shaft 3 (not shown here) with a press fit.
  • a similar variant is shown 11 for an escapement wheel, with the axle plate 12 having four recesses 25, 25', 25", 25′′′ running from the recess 4 to the outer edges 26, 26', 26", 26" of the functional component.
  • the recesses are to be made in this way that the effects on the functional zones, ie above all the effect of elastic deformation and the associated change in geometry of the component are minimized.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Gears, Cams (AREA)
EP21207650.9A 2021-11-10 2021-11-10 Module micromécanique, son procédé de fabrication et son utilisation Pending EP4180879A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP21207650.9A EP4180879A1 (fr) 2021-11-10 2021-11-10 Module micromécanique, son procédé de fabrication et son utilisation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21207650.9A EP4180879A1 (fr) 2021-11-10 2021-11-10 Module micromécanique, son procédé de fabrication et son utilisation

Publications (1)

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EP4180879A1 true EP4180879A1 (fr) 2023-05-17

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EP21207650.9A Pending EP4180879A1 (fr) 2021-11-10 2021-11-10 Module micromécanique, son procédé de fabrication et son utilisation

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2230570A2 (fr) * 2009-03-19 2010-09-22 MHVJ Manufacture Horlogère Vallée de Joux Composant d'une pièce d'horlogerie allégé et renforcé
US20120159766A1 (en) * 2010-12-22 2012-06-28 Nivarox-Far S.A. Assembly of a part that has no plastic domain
EP2637066A2 (fr) 2012-03-06 2013-09-11 Sigatec SA Procédé d'assemblage de composants fragiles et les composantes assemblées selon ce procédé
EP2727880A1 (fr) * 2012-11-05 2014-05-07 GFD Gesellschaft für Diamantprodukte mbH Composant micromécanique tridimensionnel chanfreiné et son procédé de fabrication
EP3413143A2 (fr) * 2017-06-07 2018-12-12 Seiko Epson Corporation Composant mécanique, pièce d'horlogerie, procédé de fabrication du composant mécanique
EP3627238A1 (fr) * 2018-09-21 2020-03-25 Nivarox-FAR S.A. Organe de maintien élastique pour la fixation d'un composant d'horlogerie sur un élément de support
EP3644128A1 (fr) * 2018-10-24 2020-04-29 Seiko Epson Corporation Pièce d'horloge et horloge

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2230570A2 (fr) * 2009-03-19 2010-09-22 MHVJ Manufacture Horlogère Vallée de Joux Composant d'une pièce d'horlogerie allégé et renforcé
US20120159766A1 (en) * 2010-12-22 2012-06-28 Nivarox-Far S.A. Assembly of a part that has no plastic domain
EP2637066A2 (fr) 2012-03-06 2013-09-11 Sigatec SA Procédé d'assemblage de composants fragiles et les composantes assemblées selon ce procédé
EP2727880A1 (fr) * 2012-11-05 2014-05-07 GFD Gesellschaft für Diamantprodukte mbH Composant micromécanique tridimensionnel chanfreiné et son procédé de fabrication
EP3413143A2 (fr) * 2017-06-07 2018-12-12 Seiko Epson Corporation Composant mécanique, pièce d'horlogerie, procédé de fabrication du composant mécanique
EP3627238A1 (fr) * 2018-09-21 2020-03-25 Nivarox-FAR S.A. Organe de maintien élastique pour la fixation d'un composant d'horlogerie sur un élément de support
EP3644128A1 (fr) * 2018-10-24 2020-04-29 Seiko Epson Corporation Pièce d'horloge et horloge

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Youngs modulus, fracture strength, and Poisson's ratio of nanocrystalline diamond films", J. APPL. PHYS., vol. 116, 2014, pages 124308
R. DANZER ET AL.: "Technische keramische Werkstoffe", HVB VERLAG, article "Der 4-Kugelversuch zur Ermittlung der biaxialen Biegefestigkeit spröder Werkstoffe"
R. MORRELL ET AL., INT. JOURNAL OF REFRACTORY METALS & HARD MATERIALS, vol. 28, 2010, pages 508 - 515

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RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR