EP2038441B1 - Verfahren zur herstellung von refraktärmetallformkörpern - Google Patents

Verfahren zur herstellung von refraktärmetallformkörpern Download PDF

Info

Publication number
EP2038441B1
EP2038441B1 EP07765458.0A EP07765458A EP2038441B1 EP 2038441 B1 EP2038441 B1 EP 2038441B1 EP 07765458 A EP07765458 A EP 07765458A EP 2038441 B1 EP2038441 B1 EP 2038441B1
Authority
EP
European Patent Office
Prior art keywords
weight
tungsten
molybdenum
heavy metal
alloy
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.)
Not-in-force
Application number
EP07765458.0A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2038441A1 (de
Inventor
Henning Uhlenhut
Uwe BLÜMLING
Klaus Andersson
Bernd DÖBLING
Michael Svec
Karl-Hermann Buchner
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.)
QSIL Metals Hermsdorf GmbH
Original Assignee
HC Starck GmbH
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 HC Starck GmbH filed Critical HC Starck GmbH
Priority to PL07765458T priority Critical patent/PL2038441T3/pl
Publication of EP2038441A1 publication Critical patent/EP2038441A1/de
Application granted granted Critical
Publication of EP2038441B1 publication Critical patent/EP2038441B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/20—Refractory metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]

Definitions

  • the present invention relates to a method for the production of sheets of tungsten heavy metal or molybdenum alloy and their use. Due to their high density of 17 to 18.6 g / cm 3 , tungsten heavy metal alloys are suitable for shielding short-wave electromagnetic radiation, for example. They are therefore often used for radiation protection or beam guidance in X-ray equipment. Other applications include balancing weights in the aerospace and automotive industries or molded components for aluminum die casting molds. Tungsten heavy metal alloys consist of about 90% to about 97% by weight tungsten. The remainder is binder metal. Such sheets are commercially available in thicknesses of about 0.4 mm to about 1.2 mm, but have by rolling anisotropic material properties and an anisotropic microstructure (based on tungsten) on. Tungsten heavy metal components are usually sintered close to the final shape and then machined or, in the case of flat components, produced from sheet metal.
  • US 3,155,502 discloses a method for producing shaped articles, wherein first a refractory metal powder with water-soluble organic binders . Lubricants and a small amount of water is mixed. The mixture is extruded into a green body and can be further compacted in a cold rolling step and then sintered in an inert atmosphere.
  • EP 0 325 179 describes a process for the production of sheets from a tungsten heavy metal alloy, in which the constituents of the alloy are mixed in a liquid medium to a slurry in which the liquid constituents are sucked off. From the dried slurry, a planar shaped body is prepared, which is dried and sintered to a density of at least 90% of the theoretical density of the alloy. The sintered shaped body is then rolled in further steps to the desired final thickness.
  • This object is achieved by a method for the production of shaped articles from a tungsten heavy metal alloy and from molybdenum alloys, wherein a slurry for film casting is produced from a tungsten heavy metal alloy or molybdenum alloy, a film is poured from the slurry and the film is debinded and sintered after drying, to get a sheet.
  • the molded article according to the invention is generally available as a sheet or as a sheet metal by, for example, stamping, stamping or forming. Other suitable forming methods for obtaining the molded article include, for example, bending, water jet or laser cutting, spark erosion, and machining.
  • tungsten heavy metal alloy or molybdenum alloy means materials selected from the group consisting of tungsten heavy metal alloys, tungsten, tungsten alloys, molybdenum and molybdenum alloys. The method according to the invention can thus be used advantageously for many materials.
  • the objects obtained by the process according to the invention have these features and thus solve this task.
  • Film casting is a cost effective process for producing planar components for a variety of applications in the electrical industry, such. As chip substrates, piezo actuators and multilayer capacitors. In recent years, however, interest in film casting has grown significantly for other, new product areas. With conventional methods for the production of ceramic components, such as dry pressing, slip casting or extrusion, the economic production of large-area, flat, thin, defect-free and homogeneous substrates, which have sufficient green strength, tight dimensional tolerances and a smooth surface is extremely difficult or even impossible ,
  • Suitable shaping methods include, for example, bending, water jet or laser cutting, spark erosion and machining.
  • An object of the invention is a method as defined in claims 1 to 5.
  • Another object is the use as defined in any one of claims 6 to 11.
  • a slurry for film casting is prepared from a tungsten heavy metal alloy or molybdenum alloy, cast from the slurry a film on a substrate and the film is debind after drying and sintered to obtain the sheet, the film by pulling the pad is brought in the drawing direction by pouring cut to the desired thickness.
  • tungsten metal powder or molybdenum metal powder is first mixed with a metal binder, also in the form of a metal powder.
  • the metallic binder is usually an alloy containing metals selected from the group consisting of nickel, iron, copper with each other or with other metals.
  • an alloy of tungsten or molybdenum may be used with the metallic binder in the form of a metal powder.
  • metal binder can be used advantageously nickel / iron and nickel / copper alloys.
  • the metallic binder is usually made of nickel, iron, copper, cobalt, manganese, molybdenum and / or aluminum.
  • the tungsten or molybdenum content is from 60% by weight to 98% by weight, advantageously from 78% by weight to 97% by weight, in particular from 90% by weight to 95% by weight, or 90.2% by weight .-% to 95.5 wt .-%.
  • the nickel content is 1 wt .-% to 30 wt .-%, advantageously 2 wt .-% to 15 wt .-%, or 2.6 wt .-% to 6 wt .-%, or 3 wt .-% to 5.5% by weight.
  • the iron content is 0 wt .-% to 15 wt .-%, advantageously 0.1 wt .-% to 7 wt .-%, in particular 0.2 wt .-% to 5.25 wt .-% or 0.67 Wt .-% to 4.8 wt .-%.
  • the copper content is 0 wt .-% to 5 wt .-%, advantageously 0.08 wt .-% to 4 wt .-%, in particular 0.5 wt .-% to 3 wt .-% or 0.95 wt. % to 2.1% by weight.
  • the cobalt content is 0 wt .-% to 2 wt .-%, advantageously 0.1 wt .-% to 0.25 wt .-% or 0.1 wt .-% to 0.2 wt .-%.
  • the manganese content is 0 wt.% To 0.15 wt.%, Preferably 0.05 wt .-% to 0.1 wt .-%.
  • the aluminum content is 0 to 0.2 wt .-%, preferably 0.05 to 0.15 Wt .-%, or 0.1 wt .-%.
  • the tungsten content is from 60 1 wt .-% to 30 wt .-% to 80 wt .-% to 30 wt .-%, if only iron and nickel are used as a metallic binder. In this case, optionally 0 to 0.2% by weight of aluminum may be advantageous.
  • the tungsten or molybdenum powder or alloy powder advantageously has a specific surface area of about 0.1 m 2 / g to about 2 m 2 / g, the particle size is usually less than 100 .mu.m, in particular less than 63 .mu.m.
  • This mixture is then introduced into a solvent which preferably contains a dispersant and then deagglomerated, for example in a ball mill or other suitable device.
  • the dispersant prevents agglomeration of the powder particles, lowers the viscosity of the slurry and results in a higher green density of the cast film.
  • Polyester / polyamine condensation polymers such as Hypermer KD1 from Uniqema are advantageously used as the dispersant; however, those skilled in the art will be aware of other suitable materials such as fish oil (Menhaden Fish Oil Z3) or alkyl phosphate compounds (ZSCHIMMER & SCHWARZ KF 1001).
  • solvents it is possible to use polar organic solvents, for example esters, ethers, alcohols or ketones, such as methanol, ethanol, n-propanol, n-butanol, diethyl ether, tert-butyl methyl ether, methyl acetate, ethyl acetate, acetone, ethyl methyl ketone or mixtures thereof ,
  • the solvent used is an azeotropic mixture of two solvents, for example a mixture of ethanol and ethyl methyl ketone in a ratio of 31.8 to 68.2 percent by volume.
  • This mixture is ground, for example, in a ball mill or other suitable mixing unit and thereby homogenized. This process is generally carried out for about 24 hours to obtain the first mixture.
  • the polymeric binder may be added in the preparation of the first mixture, optionally with additional solvent and optionally a plasticizer.
  • the polymeric binder can also be added in the preparation of the second mixture.
  • the polymeric binder may be added in part both in the preparation of the first mixture and in part in the preparation of the second mixture.
  • a solvent or solvent mixture may be used and the polymeric binder added with another solvent or solvent mixture such that a desired solvent mixture (e.g., an azeotropic mixture) does not set until after the addition of the polymeric binder.
  • a desired solvent mixture e.g., an azeotropic mixture
  • the polymeric binder must meet many requirements. It serves primarily to combine individual powder particles when drying together, should be soluble in the solvent and be well compatible with the dispersant.
  • the addition of the polymeric binder greatly influences the viscosity of the slurry. Advantageously, it causes only a slight increase in viscosity and at the same time has a stabilizing effect on the dispersion.
  • the polymeric binder must burn out without residue.
  • the polymeric binder provides good strength and handleability of the green sheet. An optimal polymeric binder reduces the tendency of drying cracks in the green sheet and does not hinder solvent evaporation by forming a dense surface layer.
  • polymeric binder it is generally possible to use polymers or polymer formulations having a low ceiling temperature, such as polyacetal, polyacrylates or methacrylates or its copolymers (acrylic resins such as ZSCHIMMER & SCHWARZ KF 3003 and KF 3004), as well as polyvinyl alcohol or its derivatives such as polyvinyl acetate or Polyvinyl butyral (KURARAY Mowital SB 45 H, FERRO Butvar B-98, and B-76, KURARAY Mowital SB 60 H).
  • polyacetal polyacrylates or methacrylates or its copolymers
  • polyvinyl alcohol or its derivatives such as polyvinyl acetate or Polyvinyl butyral (KURARAY Mowital SB 45 H, FERRO Butvar B-98, and B-76, KURARAY Mowital SB 60 H).
  • plasticizer plasticizer additives
  • plasticizer additives which cause by lowering the glass transition temperature of the polymeric binder, a higher flexibility of the green sheet.
  • the plasticizer penetrates into the network structure of the polymeric binder, which causes the intermolecular frictional resistance and thus the viscosity of the slurry to be reduced.
  • the plasticizer used is advantageously a benzyl phthalate (FERRO Santicizer 261A).
  • Binders and plasticizers can be added as binder suspension or binder solution.
  • the binder suspension is advantageously composed of polyvinyl butyral and benzyl phthalate at a ratio of 1: 1, by weight.
  • the second mixture is obtained.
  • the second mixture has a solids content of about 30 to 60 percent by volume.
  • the solvent content is usually less than 45 percent by volume.
  • the proportion of organic compounds other than the solvent, such as polymeric binder, dispersant and plasticizer, is generally 5 to 15% by volume in total.
  • the second mixture has a specific viscosity which is in the range from 1 Pa ⁇ s to 7 Pa ⁇ s.
  • the second mixture After homogenizing the second mixture, it is conditioned in casting charges and degassed.
  • the conditioned slurry is slowly stirred in a special pressure vessel and evacuated at reduced pressure. This is a common process step, which is known in principle to the person skilled in the art, so that the optimal conditions can be found with a small number of experiments.
  • the slurry thus obtained, or the homogenized, conditioned and degassed second mixture is then used for film casting.
  • the slip is poured onto a base and brought to a certain thickness with a squeegee.
  • a film casting installation is also used which has an in FIG. 1 having pictured casting shoe.
  • the slip 4 is filled and is brought by pulling the pad 5 in the drawing direction 6 by the Gellozier 3 to the desired thickness.
  • a base can advantageously be used on one side silicone coated plastic film, which consists for example of PET (polyethylene terephthalate); in principle, however, other films are also suitable, which can withstand the forces occurring during pulling and have low adhesion to the dried slip.
  • the surface of the film may also be patterned to impart a surface texture to the finished sheet.
  • silicone-coated PET films having a thickness of about 100 ⁇ m are suitable.
  • the thickness of the cast film depends on the cutting height, the hydrostatic pressure in the casting shoe, and the pulling rate.
  • the slip height In order to achieve a constant hydrostatic pressure, the slip height must be kept constant via a corresponding filling and level control.
  • the in FIG. 1 Shown Doppelschg hassleschuh improves compliance with a constant hydrostatic pressure in the second chamber, which is formed by the cutting 1 and 2 and allows very accurate compliance with a desired film thickness.
  • foils up to 40 cm wide can be easily cast.
  • the belt speed varies between 15 m / h (meters per hour) and 30 m / h.
  • the set cutting heights depend on the desired film thickness and are between 50 .mu.m and 2000 .mu.m, in particular between 500 .mu.m and 2000 .mu.m.
  • the film thickness after drying is about 30% of the cutting height.
  • the thickness of the sintered sheets depends on the z-shrinkage during sintering.
  • the shrinkage of the dried film is about 20% during sintering.
  • the cast metal powder films dry continuously in the drying channel of the casting plant in a temperature range of 25 - 70 ° C.
  • the drying channel is flowed through in countercurrent with air.
  • the high solvent vapor concentrations during drying necessitate a drying channel that complies with the explosion protection guidelines.
  • the film can be processed for example by cutting, punching or machining.
  • thin welding rods, rings, crucibles, boats or isotope containers can be obtained.
  • film parts are folded or assembled, for example, to pipes, boats or larger crucibles, wherein the film can also be glued.
  • an adhesive for example, unconsumed slip or unconsumed binder suspension can be used.
  • the article obtained from the film can be subjected to the further process steps.
  • Debinding means removing as far as possible residue-free organic constituents required for film casting, such as polymeric binders and plasticizers from the material. If residues remain in the form of carbon, this leads to the formation of carbides, such as tungsten carbide, in the subsequent sintering process.
  • Debindering takes place in a thermal process.
  • the films are heated with a suitable temperature profile.
  • FIG. 2 shows an example of a suitable temperature profile.
  • the organic components are first softened and possibly liquid.
  • Polymeric components such as the polymeric binder or dispersant are advantageously depolymerized, therefore, as mentioned above, a low ceiling temperature of these components is advantageous.
  • these liquid phases should evaporate and be removed via the atmosphere. The temperature is expected to rise so fast that no low-volatile cracking products.
  • These lead to carbon deposits in the form of soot To increase the vapor pressure is heated to 600 ° C under a vacuum of 50 - 150 mbar absolute, whereby a better evaporation of the liquid phase is achieved.
  • the atmosphere in the furnace chamber must be rinsed.
  • nitrogen is used in a proportion of about 2% by volume of hydrogen or less.
  • the hydrogen content advantageously has the effect that the furnace atmosphere is free of oxygen and oxidation of the metal powders is avoided.
  • Debinding is completed up to about 600 ° C.
  • the components at this stage are a weakly bound powder packing.
  • the thermal process is increased to about 800 ° C. There arise manageable, very brittle components that can be subjected to the following sintering step.
  • the film is sintered.
  • the sintering temperature is between about 1300 ° C and about 1600 ° C, especially 1400 ° C and 1550 ° C. Typically, the sintering times are about 2 hours to 8 hours. It is preferably sintered in a hydrogen atmosphere, in a vacuum or under an inert gas such as nitrogen or a noble gas such as argon with the addition of hydrogen. After sintering, there is a dense sheet with up to 100% of the theoretical density. The sintering can take place in batch or push furnaces.
  • the debindered and sintered foils are to be sintered on suitable sintered bases.
  • the films to be sintered with a smooth, flat cover, so that discarding of the film is avoided during the sintering process.
  • several films can be superimposed, which additionally increases the sintering capacity.
  • the stacked films are preferably separated from each other by sintering pads.
  • As sintering substrate are preferably ceramic plates or films which do not react with the tungsten heavy metal alloy under the sintering conditions. There are, for example, in question: alumina, aluminum nitride, boron nitride, silicon carbide or zirconium oxide. Furthermore, the surface quality of the sintered substrate is decisive for the surface quality of the film to be sintered.
  • the sheet may be rolled under conditions known in the art. It is rolled depending on the thickness of the sheet between about 1100 ° C and room temperature. Sheets approximately 2 mm thick are rolled at high temperatures, while foils can be rolled at room temperature.
  • rolling in the method according to the invention unlike the prior art, serves less to reduce the thickness, but it is intended Above all, the rippling of the sheet eliminated and the surface quality can be improved.
  • annealing to reduce internal stresses can be performed.
  • the annealing is generally carried out at temperatures of 600 ° C to 1000 ° C in a vacuum or under protective gas or reducing atmosphere. If necessary, the steps of rolling and annealing may be repeated until the desired surface quality and, if necessary, thickness have been achieved.
  • the method according to the invention allows the production of sheets of a tungsten heavy metal alloy or molybdenum alloy which have a thickness of less than 0.4 mm.
  • the density of the sheet is 17 g / cm 3 to 18.6 g / cm 3 , preferably 17.3 g / cm 3 to 18.3 g / cm 3 .
  • the method according to the invention allows the production of sheets from a tungsten heavy metal alloy or molybdenum alloy, which has an isotropic microstructure based on tungsten or molybdenum.
  • an isotropic microstructure is understood to mean a uniform mixture of the crystallographic orientations without a preferred orientation, as well as an approximately round grain shape of the tungsten phase or molybdenum phase.
  • Sheets and films produced by rolling in accordance with the prior art preferably have ⁇ 100> and ⁇ 110> orientations parallel to the normal direction of the sheet (see FIG. 11 ). These preferred orientations are part of a typical rolling texture as seen from the pole figures (see FIG. 12 ) can be read.
  • This formation of the crystallographic texture is accompanied by the oblong expression of the grain shape along the rolling direction (cf. Fig. 3 and Fig. 9 ).
  • FIG. 7 no crystallographic preferred direction along the standard of brass read (see. Fig. 7 and Fig. 11 ).
  • the pole pieces ( FIG. 8 ) have an intensity maximum of 2.0, but this is compared to the maximum intensity of 4.7 in the pole pieces for the rolled sheet ( FIG.
  • the thickness of the sheets described is advantageously less than 1.5 mm, in particular less than 0.5 mm, especially less than 0.4 mm.
  • the sheets of the invention have as another property that the strength and bendability are independent of direction.
  • the open porosity of the sheets of the invention is low and is 20 percent or less.
  • the sheets contain the materials described above. Iron should not be used if the material is to be non-magnetic.
  • an alloy powder of the composition W-0.2% Fe-5.3% Ni-2.1% Cu-0.2% Fe was used to produce a tungsten heavy metal sheet.
  • the powder had a specific surface area of 0.6 m 2 / g and a particle size of less than 63 ⁇ m.
  • the alloy powder was in a ball mill with 0.3 kg of polyester / polyamine condensation polymer (UNIQEMA Hypermer KD1) and 2.3 l of a mixture of 31.8 vol .-% ethanol and 68.2 vol .-% ethyl methyl ketone for 24 hours in ground and homogenized in a ball mill.
  • FIG. 3 shows the microstructure of the obtained tungsten heavy metal sheet, the image vertical is parallel to the lead normal, the image horizontal parallel to the drawing direction.
  • FIGS. 5 and 6 show pictures of the microstructure of the obtained tungsten heavy metal sheet, FIG. 5 with the image vertical parallel to the sheet normal and the image horizontal parallel to the rolling direction, FIG. 5 with the image vertical parallel to the lead normals and the image horizontals parallel to the transverse direction. In FIG. 5 is a slight stretch to see in FIG. 6 is a flattening of the particles recognizable.
  • FIG. 7 represents the microstructure (cf. FIG. 3 ), in which the color of the tungsten particles indicates the crystal direction of the grain, which is parallel to the normal direction of the sheet (compare to Figure 7a: color code).
  • FIG. 7 shows a uniform distribution of all colors, so that no crystallographic preferred direction with respect to the sheet normal is recognizable.
  • the texture is represented in the form of pole figures.
  • FIG. 8 shows a relatively restless texture with no apparent rolling texture.
  • a tungsten heavy metal sheet with a density of 17.5 g / cm 3 which was obtained by rolling and contained an amount of 92.4% tungsten and 7.6% metallic binder, was investigated analogously.
  • element powders in the composition W-0.2% Fe-5.3% Ni-2.1% Cu-0.2% Fe were mixed in a ball mill and ground.
  • the powder mixture was isostatically pressed at 1500 bar and then sintered at 1450 ° C in a hydrogen atmosphere.
  • An approximately 10 mm thick plate of the sintered material was brought by multiple hot / hot rolling by about 20% each with subsequent annealing to a thickness of about 1 mm.
  • the preheating temperature of about 1300 ° C is reduced at 10 mm thickness with decreasing thickness. In the last rolling step is preheated only at about 300 ° C.
  • FIG. 9 shows the microstructure of the obtained tungsten heavy metal sheet, the image vertical is parallel to the lead normal, the image horizontal parallel to the rolling direction.
  • FIG. 10 shows the microstructure of the obtained Tungsten heavy metal sheet, the image vertical is parallel to the metal standard, the image horizontal is parallel to the transverse direction. In both pictures it can be clearly seen that the tungsten particles were stretched in the rolling direction by the rolling process.
  • FIG. 10 shows the microstructure across the rolling direction. The tungsten particles are slightly flattened.
  • FIG. 8 represents the microstructure (cf. FIG. 9 ), wherein the color of the tungsten particles indicates the crystal direction of the grain, which is parallel to the normal direction of the sheet (cf. Figure 7a : Color code). In contrast to FIG. 7 dominate in FIG. 11 red and blue colors. It can It can be read that the stretched tungsten particles have aligned preferably ⁇ 100> and ⁇ 110> directions parallel to the sheet normal.
  • FIG. 12 the texture is represented in the form of pole figures. In FIG. 12 is contrary to FIG. 8 to recognize a clear difference between the transverse and rolling direction. Therefore, due to the orientation of the tungsten particles, the sheet has anisotropic material properties within the sheet plane.
  • Table 1 are further examples of compositions which are processed as in Example 1 into sheets. Tungsten is filled in wt .-% to a total of 100 wt .-% (identified by "ad 100").
  • Table 2 consists of 136 sheets using molybdenum instead of tungsten and the content of the metal binder components nickel, iron, copper, cobalt, manganese or aluminum as shown in Table 1 in weight percent. No.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Compositions Of Oxide Ceramics (AREA)
EP07765458.0A 2006-06-22 2007-06-18 Verfahren zur herstellung von refraktärmetallformkörpern Not-in-force EP2038441B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL07765458T PL2038441T3 (pl) 2006-06-22 2007-06-18 Sposób wytwarzania refrakcyjnych kształtek metalowych

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006029101 2006-06-22
PCT/EP2007/055986 WO2007147792A1 (de) 2006-06-22 2007-06-18 Verfahren zur herstellung von refraktärmetallformkörpern

Publications (2)

Publication Number Publication Date
EP2038441A1 EP2038441A1 (de) 2009-03-25
EP2038441B1 true EP2038441B1 (de) 2015-10-28

Family

ID=38421170

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07765458.0A Not-in-force EP2038441B1 (de) 2006-06-22 2007-06-18 Verfahren zur herstellung von refraktärmetallformkörpern

Country Status (9)

Country Link
US (2) US20110206944A1 (ja)
EP (1) EP2038441B1 (ja)
JP (2) JP5661278B2 (ja)
CN (1) CN101473054B (ja)
DK (1) DK2038441T3 (ja)
ES (1) ES2558877T3 (ja)
HK (1) HK1132017A1 (ja)
PL (1) PL2038441T3 (ja)
WO (1) WO2007147792A1 (ja)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011115866A1 (de) * 2011-10-13 2013-04-18 Karlsruher Institut für Technologie Metallrohr; Verwendung eines Metallrohrs als Strukturbauteil; Verfahren zum Herstellen eines Metallrohrs; metallisches Strukturbauteil; Divertor
US20140308536A1 (en) * 2011-12-07 2014-10-16 A.L.M.T. Corp Sintered tungsten alloy
DE102012006998A1 (de) 2012-04-10 2013-12-12 H.C. Starck Ceramics Gmbh Herstellung hartstoffhaltiger Schichten
DE102012217191A1 (de) 2012-09-24 2014-03-27 Siemens Aktiengesellschaft Herstellen eines Refraktärmetall-Bauteils
DE102012217182A1 (de) 2012-09-24 2014-03-27 Siemens Aktiengesellschaft Herstellen eines Refraktärmetall-Bauteils
DE102012217188A1 (de) 2012-09-24 2014-03-27 Siemens Aktiengesellschaft Herstellen eines Refraktärmetall-Bauteils
DE102012109782A1 (de) 2012-10-15 2014-04-17 Karlsruher Institut für Technologie Schichtverbund
CN105263655A (zh) * 2013-06-04 2016-01-20 H·C·施塔克公司 难熔金属体的粉浆和压力铸造
CN104588651A (zh) * 2014-10-31 2015-05-06 成都易态科技有限公司 柔性多孔金属箔及其制备方法
DE102015218408A1 (de) 2015-09-24 2017-03-30 Siemens Aktiengesellschaft Bauteil und/oder Oberfläche aus einem Refraktärmetall oder einer Refraktärmetalllegierung für thermozyklische Belastungen und Herstellungsverfahren dazu
CN106141507B (zh) * 2016-07-01 2018-08-24 中国科学院上海硅酸盐研究所 一种低有机物含量的陶瓷颗粒增强复合钎料膜的制备方法
CN106756379B (zh) * 2017-01-10 2019-01-25 广州市华司特合金制品有限公司 钨合金屏蔽板及设置有钨合金屏蔽板的电子信息卡
JP7174476B2 (ja) * 2017-03-31 2022-11-17 Ｊｘ金属株式会社 タングステンターゲット
KR102267505B1 (ko) * 2017-05-16 2021-06-22 주식회사 엘지화학 금속폼의 제조 방법
CN109518054A (zh) * 2019-01-15 2019-03-26 株洲市美力迪实业有限公司 一种拉刀材料及其制备方法和拉刀
CN110903020A (zh) * 2019-11-27 2020-03-24 株洲硬质合金集团有限公司 一种3d玻璃热弯机用均温板及其制备方法和应用
CN113462942A (zh) * 2021-07-02 2021-10-01 西安华力装备科技有限公司 一种高屈服钨合金材料的制备方法
CN114480935B (zh) * 2022-01-20 2022-11-29 广东工业大学 一种晶粒尺寸具有梯度效应的钨基合金及其制备方法
CN115029597A (zh) * 2022-06-02 2022-09-09 安泰天龙钨钼科技有限公司 一种制备钨及钨合金薄片的方法
CN114769593A (zh) * 2022-06-02 2022-07-22 安泰科技股份有限公司 一种制备钼及钼合金箔材的方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3155502A (en) 1960-08-12 1964-11-03 Union Carbide Corp Powder metallurgy
US3403009A (en) * 1964-08-10 1968-09-24 Minnesota Mining & Mfg Refractory metal structures
GB1121646A (en) * 1964-08-10 1968-07-31 Minnesota Mining & Mfg Sintered metal articles
US3324699A (en) * 1965-01-04 1967-06-13 Gen Electric Production of non-earing molybdenum sheet
US4491559A (en) * 1979-12-31 1985-01-01 Kennametal Inc. Flowable composition adapted for sintering and method of making
US4777015A (en) * 1988-01-14 1988-10-11 Gte Products Corporation Process for producing tungsten heavy alloy sheet using a metallic salt binder system
EP0325179A1 (en) * 1988-01-14 1989-07-26 GTE Products Corporation Process for producing tungsten heavy alloy sheet
JPH09235641A (ja) * 1996-02-28 1997-09-09 Toho Kinzoku Kk タングステン重合金板及びその製法
US6447715B1 (en) * 2000-01-14 2002-09-10 Darryl D. Amick Methods for producing medium-density articles from high-density tungsten alloys
JP2002030372A (ja) * 2000-07-12 2002-01-31 Allied Material Corp 薄物・異形状超重合金板及びその製造方法
US20070172378A1 (en) * 2004-01-30 2007-07-26 Nippon Tungsten Co., Ltd. Tungsten based sintered compact and method for production thereof

Also Published As

Publication number Publication date
JP5661278B2 (ja) 2015-01-28
JP2009541584A (ja) 2009-11-26
ES2558877T3 (es) 2016-02-09
EP2038441A1 (de) 2009-03-25
US20110206944A1 (en) 2011-08-25
CN101473054A (zh) 2009-07-01
JP2014098209A (ja) 2014-05-29
CN101473054B (zh) 2012-07-04
US20170050244A1 (en) 2017-02-23
PL2038441T3 (pl) 2016-04-29
DK2038441T3 (en) 2016-02-01
HK1132017A1 (en) 2010-02-12
US10549350B2 (en) 2020-02-04
WO2007147792A1 (de) 2007-12-27

Similar Documents

Publication Publication Date Title
EP2038441B1 (de) Verfahren zur herstellung von refraktärmetallformkörpern
US5846664A (en) Porous metal structures and processes for their production
DE69920621T2 (de) Verfahren zur herstellung von sinterteilen
EP3468939B1 (de) Zirkonoxid-keramik, zellularer werkstoff daraus und verfahren zur herstellung der zirkonoxid-keramik
WO2014044429A1 (de) Herstellen eines refraktärmetall-bauteils
DE2232884A1 (de) Verfahren zum herstellen von pulver aus verbundteilchen
DE112015001562B4 (de) Verfahren zur Herstellung eines Siliciumnitrid-Substrates
WO2005080618A1 (de) Verfahren zur herstellung einer molybdän-legierung
DD249006A5 (de) Homogene masse, enthaltend teilchenfoermiges keramisches material
DE102020109047A1 (de) Sintercarbidpulver für additive fertigung
DE4320102A1 (de) Verfahren zur Herstellung von polykristallinen dichten Formkörpern auf der Basis von Borcarbid durch drucklose Sinterung
EP1801247B1 (de) Verfahren zur Herstellung eines hochdichten Halbzeugs oder Bauteils
WO2012045106A1 (de) Kollimator für röntgen-, gamma- oder teilchenstrahlung
WO2014044433A1 (de) Herstellen eines refraktärmetall-bauteils
WO1994018140A1 (de) VERFAHREN ZUR HERSTELLUNG VON FEINKÖRNIGEN Al2O3 ENTHALTENDEN KERAMISCHEN FORMKÖRPERN UNTER VERWENDUNG VON PULVERFÖRMIGEM ALUMINIUMMETALL
DE10008162A1 (de) Einstellelement zum Entfetten und/oder Brennen und Verfahren zu dessen Herstellung
DE102012015127B4 (de) Sinterunterlage
DE102010019255B4 (de) Substratkörper auf der Basis von Siliziumnitrid
WO2014044432A1 (de) Herstellen eines refraktärmetall-bauteils
DE102012020829B4 (de) Verfahren zur Herstellung von Verbundbauteilen
DE2255975C2 (de) Anwendung des Verfahrens der Nitridierung von Eisen-Legierungsteilchen auf bestimmte Legierungspulver für die Herstellung von Polhörnern von Magnetköpfen
EP2425885B1 (de) Keramischer Filter sowie Verfahren zur Erstellung eines keramischen Filters
DE10335167B4 (de) Verfahren zur Herstellung eines keramischen Leuchtstoffs
DE19845532A1 (de) Verfahren zur Herstellung von Kompositwerkstoffen und Vertreter solcher Kompositwerkstoffe
DE19758454A1 (de) Dünne, feinporige Metallschicht

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090122

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

RIN1 Information on inventor provided before grant (corrected)

Inventor name: SVEC, MICHAEL

Inventor name: ANDERSSON, KLAUS

Inventor name: BLUEMLING, UWE

Inventor name: UHLENHUT, HENNING

Inventor name: BUCHNER, KARL-HERMANN

Inventor name: DOEBLING, BERND

17Q First examination report despatched

Effective date: 20090813

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150625

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 757982

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502007014356

Country of ref document: DE

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: H.C. STARCK HERMSDORF GMBH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 502007014356

Country of ref document: DE

Owner name: H.C. STARCK HERMSDORF GMBH, DE

Free format text: FORMER OWNER: H.C. STARCK GMBH, 38642 GOSLAR, DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Effective date: 20160129

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2558877

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20160209

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151028

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160228

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151028

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160129

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151028

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160229

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20160613

Year of fee payment: 10

Ref country code: GB

Payment date: 20160615

Year of fee payment: 10

Ref country code: CZ

Payment date: 20160607

Year of fee payment: 10

Ref country code: ES

Payment date: 20160510

Year of fee payment: 10

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502007014356

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151028

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151028

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151028

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20160425

Year of fee payment: 10

Ref country code: NL

Payment date: 20160610

Year of fee payment: 10

Ref country code: DK

Payment date: 20160610

Year of fee payment: 10

Ref country code: FR

Payment date: 20160516

Year of fee payment: 10

Ref country code: PL

Payment date: 20160421

Year of fee payment: 10

Ref country code: SE

Payment date: 20160613

Year of fee payment: 10

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20160729

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20160621

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151028

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151028

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160618

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Effective date: 20170630

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170618

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20170701

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20170618

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20180228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170630

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170630

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170618

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20070618

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151028

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170618

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170630

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20170630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160618

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151028

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151028

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170630

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151028

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170630

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20181114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170618

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170619

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20220427

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20220525

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502007014356

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 757982

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230618

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230618

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240103

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230618