EP1543172B1 - Reinigung von metallpartikeln durch hitzebehandlung - Google Patents

Reinigung von metallpartikeln durch hitzebehandlung Download PDF

Info

Publication number
EP1543172B1
EP1543172B1 EP03753690A EP03753690A EP1543172B1 EP 1543172 B1 EP1543172 B1 EP 1543172B1 EP 03753690 A EP03753690 A EP 03753690A EP 03753690 A EP03753690 A EP 03753690A EP 1543172 B1 EP1543172 B1 EP 1543172B1
Authority
EP
European Patent Office
Prior art keywords
particles
metal
impurities
pellets
heat source
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.)
Expired - Lifetime
Application number
EP03753690A
Other languages
English (en)
French (fr)
Other versions
EP1543172A2 (de
Inventor
Charles Malcolm QinetiQ Limited WARD-CLOSE
Alastair Bryan QinetiQ Limited GODFREY
Paul Stephen Casting Technology Int. GOODWIN
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.)
Metalysis Ltd
Original Assignee
Metalysis Ltd
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
Priority claimed from GB0222219A external-priority patent/GB0222219D0/en
Priority claimed from GB0222348A external-priority patent/GB2393450A/en
Priority claimed from GB0222358A external-priority patent/GB2393451A/en
Application filed by Metalysis Ltd filed Critical Metalysis Ltd
Publication of EP1543172A2 publication Critical patent/EP1543172A2/de
Application granted granted Critical
Publication of EP1543172B1 publication Critical patent/EP1543172B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1295—Refining, melting, remelting, working up of titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/14—Refining in the solid state

Definitions

  • This invention relates to a method for the purification of metal particles, for example, metal powders and other finely sized metal samples, and, in particular, to ones that have been produced by the process of electrochemical reduction of metal compounds.
  • the invention is particularly suited to the purification of titanium powder formed from the electrolytic reduction of titanium oxide TiO 2 .
  • WO 99/64638 describes methods for the electrolytic reduction (or "electro-reduction") of metal compounds. Certain embodiments of those methods involve the electrolysis of metal oxides or other compounds in a cell containing a liquid (fused salt) electrolyte and an anode, the metal oxide forming or contacting the cathode. Conditions are controlled so as to bring about the selective dissolution of the oxygen of the cathode in preference to deposition of the metal cation of the fused electrolyte. The metals extracted by such methods, however, often require further purification.
  • GB2359564 is directed to improved methods for carrying out such processes, particularly to produce powdered titanium, and some of those methods are summarised below:-
  • Sintered granules or powders of metal oxide can be used as the feedstock for the electrolysis described in the above referenced method, as long as appropriate conditions are present.
  • powdered titanium dioxide in the form of granules or a powder is used, the powdered particles preferably having a size in the region of 200 ⁇ m.
  • the granules of titanium dioxide 1 are held in a basket 2 below a carbon anode 3 located in a crucible 4 having a molten salt 5 therein. These are prevented from sintering together by maintaining particle motion by any appropriate method e.g. in a fluidised bed arrangement.
  • Agitation is provided either by mechanical vibration or by the injection of gas underneath the basket. Mechanical vibration can, for example, be provided by ultrasonic transducers mounted on the outside of the crucible or on control rods.
  • the key variables to be adjusted are the frequency and amplitude of the vibrations in order to get an average particle contact time which is long enough to get reduction, but short enough to prevent diffusion bonding of the particles into a solid mass. Similar principles would apply to agitation by the injection of gas, except here the flow rate of the gas and size of the gas bubbles would be the variables controlling particle contact time.
  • a metal is deposited onto a cathode (based on the electrolytic process previously described) from a second source of the metal at a more positive potential, the resulting metal deposited thereon is dendritic in structure. This is particularly so where the metal is titanium.
  • This form of titanium is easy to break up in to a powder as individual particles are connected together only by a small surface area.
  • This method can be used to produce titanium powder from titania. In this method, illustrated in Figure 2 , a second cathode 6 is provided which is maintained at a potential that is more negative than the first cathode 7.
  • Continuously feeding a fine powder of metal oxide into the electrochemical cell allows for a constant current and a higher reaction rate.
  • a carbon electrode is preferred for this method. This method permits the use of cheaper feedstock as a sintering and/or forming stage is no longer needed.
  • FIG. 3 shows a conducting crucible 1 which is made the cathode containing a molten salt 2 and inserted therein is an anode 3. Titanium dioxide powder 4 is fed into the crucible where it undergoes reduction and is deposited at the base of the crucible.
  • the thick arrow shows the increasing thickness of the reduced feedstock 5.
  • the purity of the metal powder may be affected by the starting materials and processing parameters used. For example, it has been found that some variations of the method when used to produce titanium powder result in powder that contains "contaminating impurities" resulting wherefrom, including light metals such as magnesium or calcium, as well as salts such as calcium chloride (the latter being a preferred electrolyte). Such impurities are known to affect the mechanical properties of alloyed metal components, for example, salt inclusions are known to affect the fatigue performance and weldability of titanium alloys.
  • a method for purifying metal M 1 particles manufactured by an electrochemical reduction process comprising the steps of:
  • the present invention thus provides a method for purifying electrochemically reduced metal particles so as to reduce or remove the aforementioned "contaminating impurities" introduced by the reduction process, so as to enable, for example, direct use of the electrolytically reduced metals in lower temperature powder metallurgy processes.
  • the kinds of impurities introduced by such electro-reduction processes are usually more volatile than the metal M 1 and may be conveniently removed by the present process.
  • Such impurities may comprise light metals, for example, calcium and magnesium, as well as salts from the electrolyte, such as calcium chloride.
  • the impurities should preferably be more volatile than the metal M 1 by at least a factor of ten, or preferably 20, in terms of their respective vapour pressures at the processing temperature.
  • the processing temperature and/or heating time should be sufficient to remove substantially all the contaminating impurities, for example, so as to reduce their total level to less than 50 ppm, or less than 10% their initial total concentration.
  • the process is conducted so that there is little or no evaporation (for example, less than 5%) of the metal M 1 .
  • metal powders produced by electrolytic reduction of oxide or oxides are desirable, and a fully dense spherical particle morphology is preferred, for example in order to impart good flowability.
  • the particles may only be partially melted in order to remove said impurities, in most cases the particles need to be fully melted to achieve dense, spherical particles.
  • the heat source is arranged such that the metal particles may be allowed to free fall through the heat source.
  • Suitable heat sources include but are not strictly limited to a hot plasma torch, a hot gas flame, a tube furnace, an induction coil, electric arcs and lasers.
  • the particles may be blown through a plasma torch into the flame and allowed to free fall into a collecting vessel.
  • the torch is preferably arranged at a sufficient height above the vessel such that any portion of the particles that is melted by the heat source is substantially solidified before collection. This prevents distortion of the shape of the particles.
  • the established method of levitation melting may be used to hold particles of powder in a surrounding heat source for a period sufficient to vaporise the impurities.
  • zero gravity processing may be used. The common purpose of these embodiments is to suspend the particles individually in mid-air, out of contact with any surfaces, so as to enable particles to be heated and melted and resolidified individually, without contact with each other, or a container.
  • the temperature of the heat source should be at or above the melting point of the metal M 1 .
  • the desired point is about 1680°C and for titanium alloys approximately 1500-1800°C.
  • an argon or helium arc plasma torch can achieve temperatures sufficient to melt titanium powder particles entrained in the flame.
  • the process is conducted in a controlled atmosphere, for example, at low pressure/vacuum and/or in an inert atmosphere.
  • the powder particles are kept separate from oxygen or nitrogen while above a temperature of about 500°C. This is achieved in practice either by processing in a vacuum or in an atmosphere of Ar.
  • the method is applicable to all metals and alloys provided a temperature sufficient to melt the particles and volatise the contaminants can be achieved.
  • the step of removing the impurities may simply involve allowing them to be swept away by the gas flow from the flame of the heat source.
  • the step of removing the impurities involves condensing the vaporised impurities on cold collector plates positioned adjacent the hot gas flame and disposing of the condensed impurities. Additionally, if the contaminants re-condense onto the surfaces of the powder particles M 1 , then they can be removed easily with a water or dilute acid wash.
  • the inventors have appreciated that by exposing small particles of a metal M 1 to a heat source at around or above the melting point, but below the boiling point of M 1 , and allowing them to fall freely through the heat source, the shape of the particles can be altered to a near spherical shape. Spherical particles provide improved bonding in powder metallurgy processes.
  • the temperature of the heat source used in the purification process of the method is substantially equal to or higher than the melting point of M 1 but lower than the boiling point of M 1 .
  • Powdered particles purified in accordance with the method of the invention may be used in the formation of alloy metal articles made by various powder metallurgy methods and will provide improved particle bonding and mechanical properties in the alloyed article.
  • the invention provides a method for the manufacture of a metal article containing a metal M 1 , by purifying metal M 1 particles as set out in the first aspect of the invention above and performing a powder metallurgy process on the particles to form the article.
  • the temperature of the heat source will be substantially equal to or above the melting point of the metal M 1 .
  • the electrochemical reduction method may comprise any suitable electro-reduction method for the production of metal particles, and includes the methods described herein or as described in WO 99/64638 .
  • the powder metallurgy process used may be any conventional powder metallurgy process including but not limited to powder sintering and/or forging.
  • powder sintering and/or forging One example of such a process is hot isostatic pressing.
  • Purified powders made according to the first aspect of the invention may be used in various other processes for the manufacture of metal articles where powdered starting materials are desirable.
  • M 1 may be construed to mean a single metal or a combination of different metals formed in a single method.
  • References to particles may be construed to mean a powder or other finely sized metal samples, for example, granules or pellets, that could be purified by the present method.
  • a powder may be construed to comprise small particles up to about 1mm in diameter.
  • Figures 1 to 3 show, by way of example, three suitable prior art arrangements for producing metal powders by electrolytic reduction, and are discussed in more detail above.
  • FIG 4 shows a preferred arrangement for purifying a powder in which the particles are blown through a plasma torch into a flame and allowed to free fall into a collecting means.
  • the reactor 10 comprises a large metal vessel 11, provided with an inert atmosphere 12, which is preferably argon dispensed from jets 9.
  • an inert atmosphere 12 which is preferably argon dispensed from jets 9.
  • the metal particles (M 1 ) enter the vessel from a supply hopper 14 through the plasma torch 13, which is attached and sealed to the top of the vessel 11 so that it points downwards, and provides sufficient heat to melt and vaporise the metal particles and contaminants, respectively, as they pass through the upper section of the vessel 11.
  • the torch 13 is preferably arranged at a sufficient height above the collecting means that any portion of the particles that is melted by the heat source is substantially solidified before collection. This prevents distortion of the shape of the particles.
  • the re-solidified powder is collected and sealed into a metal collection hopper 15 via a funnel cyclone collector 16.
  • levitation melting is used to hold particles of powder in a surrounding heat source for a period sufficient to vaporise the impurities.
  • the apparatus comprises a supply hopper 14 through which metal particles (M 1 ) enter via a valve 24 into a large ceramic tube-like chamber 23.
  • the powder is allowed to fall through the ceramic tube under its own weight.
  • an external concentric electromagnetic induction coil 22 Around the mid-section of the chamber 23 is an external concentric electromagnetic induction coil 22, which both heats and levitates the metal powder particles such that they spend sufficient time at a suitable temperature for volatile contamination removal and spheroidisation to take place.
  • the purified powder then falls to the bottom of the chamber 23, cooling sufficiently to solidify, before exiting via valve 25 and being collected and sealed into a metal canister 15.
  • an inert gas flow is introduced counter to the direction of the metal powder flow via inlet 21 and outlet 20, and this both enhances the cooling of the powder particles at the lower end of the tube, and also helps to carry away volatile species.
  • An electro-reduction process also known as an electro-deoxidation (EDO) process, is less expensive and easier to perform than conventional metal extraction methods.
  • Metal particles produced by an EDO process may advantageously be used directly as feedstocks in manufacturing processes that incorporate the present purification process as an integral stage.
  • Such a manufacturing process has, in particular, significant benefits over conventional processes for the production of titanium articles.
  • Conventional methods for the manufacture of titanium and titanium alloy stock involve hot working of large titanium alloy ingots. The high temperatures and pressures required for these processes contribute to the high cost of this stock compared to other metal products such as steel and aluminium alloys.
  • Titanium is conventionally obtained from its ore by the Kroll route, a complex chlorination and magnesium reduction method.
  • the purified metal granules, called sponge are then melted with the alloying additions and cast into large titanium alloy ingots.
  • the metal is melted at least twice and sometimes more, in order to ensure chemical homogeneity and freedom from defects.
  • the large titanium alloy ingots are then hot forged repeatedly to produce the semi-finished alloy stock shapes, such as bar, plate, sheet and wire, required for the manufacture of articles.
  • the present invention aims to provide novel methods for the manufacture of titanium or other metal alloy stock, which are less expensive and easier to perform.
  • the above-mentioned manufacturing process incorporating the purification stage may involve:
  • pellets should be heated sufficiently to allow them to coalesce to form a sheet when subjected to the pressure of the nip, and may be heated so that they soften, or, at least partly melt, or even fully melt.
  • pellet covers particles ranging from powders to granules.
  • either or both of the feed rollers are water cooled by passing a coolant through their centres.
  • a coolant is water, other suitable fluids will no doubt occur to the skilled addressee.
  • the above-mentioned manufacturing process incorporating the purification stage may involve:
  • the sheet or cast stock may be allowed to cool or may be actively cooled.
  • the alloy pellets may be obtained by an electro-deoxidation process such as that described in WO 99/64638 , or, in the Applicant's co-pending applications GB2359564 or GB2362164 . As is described in the above specifications, electrochemical reduction may be used to provide small pellets of alloy having high purity and good grain structure. Thus, heating and purification involving softening or partially melting the pellets is sufficient to bond the pellets and obtain a mass of alloy having good mechanical properties.
  • the step of heating the pellets is preferably carried out by means of an energy beam.
  • the energy beam may, optionally, be selected from an electron beam, a laser or a plasma torch.
  • the processing temperature and/or heating time should be sufficient to remove substantially all the contaminating impurities, for example, so as to reduce their total level to less than 50 ppm, or less than 10% their initial total concentration.
  • the process is conducted so that there is little or no evaporation (for example, less than 5%) of the metal.
  • the process is conducted in a controlled atmosphere, for example, at low pressure/vacuum and/or in an inert atmosphere.
  • a controlled atmosphere for example, at low pressure/vacuum and/or in an inert atmosphere.
  • Ti it is important that the powder particles are kept separate from oxygen or nitrogen while above a temperature of about 500°C. This is achieved in practice either by processing in a vacuum or in an atmosphere of Ar.
  • the use of argon or helium arc torches is particularly preferred.
  • the rolled or cast stock may be further processed, for example, by one or more additional intermediate steps such as further working or heat treatments of the stock, prior to final cooling.
  • Products of the methods are comprised of fully dense metal alloy.
  • the homogeneity of the final metal is improved considerably because the pellets are provided via an electrochemical reduction method, as compared to the alternative of using Kroll sponge and powder or particles of the alloy additions.
  • the present methods require considerably less cumbersome and costly apparatus compared to conventional methods where the starting materials are introduced to the casting or rolling apparatus fully molten and are particularly suited to the production of small quantities of stock where mechanical properties and metal homogeneity are of importance.
  • the present methods are particularly suited to the manufacture of low volume or small size products, which could be prohibitively costly to produce by conventional methods.
  • pellets of titanium metal or alloy 31 are delivered through a hopper 32 to a pair of counter-rotating feed rollers 33a, 33b.
  • the rollers are cooled by a water-cooling system (not shown).
  • An energy beam 34 is arranged to concentrate a beam of energy along a line just above the nip of rollers 33a, 33b and causes at least partial melting of the pellets seated on and between the rollers.
  • the rollers 33a, 33b rotate, the at least partially melted pellets are drawn into the nip and are squeezed together to form a solid mass of the titanium or titanium alloy in the form of a sheet 35.
  • the hot sheet falls to a conveyor 36 and is carried away for further processing and/or cooling.
  • Figure 7 illustrates a similar arrangement for the production of bar stock having a square cross-section.
  • a source of pellets 41 is delivered through a hopper 42 to a shallow crucible 47.
  • a laser 44 is mounted on a track 48 along which the energy beam sweeps back and forth.
  • the energy beam is aimed at the top surface of the crucible 47 and causes at least partial melting of the pellets 41 delivered thereto.
  • the metal is drawn through a square shaped die 49 communicating with a lower surface of the crucible 47 and bar stock 45 of the titanium or titanium alloy emerges.
  • the bar stock may be cut to length by a cutter (not shown).
  • the bar stock is collected by a conveyor system 46 and removed for cooling and/or further processing.
  • the feedstock in the form of pellets is stored inside a hopper that is an integral part of a vacuum chamber housing the roller and for example, E-beam (electron-beam) or a laser beam melting assembly.
  • E-beam electron-beam
  • the vacuum chamber is desirably at a pressure ranging from 1 x 10 -6 to 1 x 10 -5 mBar during the operation.
  • the energy beam directed at the pellets heats and at least partially melts the titanium feedstock between the roller gap, which either softens it sufficiently for it to be deformed and consolidated as it passes through the roll gap, or melts it then solidifies it instantaneously on contacting the rollers and also gets deformed into a strip subsequently.
  • the temperature of the solid strip coming out of the rollers is in the region of 600°C.
  • This method is not specific only to titanium feedstock, it has potential application for direct production of strips of any metallic powder, and especially those that are very sensitive to the absorption of impurities such as oxygen or nitrogen.
  • the method of manufacture of strip described above is ideally suited to feed stock of uniformly sized granules of less than about 1 mm dimensions. Larger granules may be optimal for production of thicker sheets by this method.
  • Rollers are desirably cooled through the centre.
  • the primary requirement is that the chamber housing the rollers should be in a vacuum (or very low pressure environment) to stop the molten titanium from picking up oxygen.
  • a water-cooled roller assembly has been developed by the applicants that lets the water flow through the rollers and bearings, while maintaining good vacuum tightness.
  • the heating is conducted so as simultaneously to remove all or part of any volatile contamination that may be present in the feed material, for example, EDO granules may contain contaminants such as calcium chloride, calcium oxide or calcium metal.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Powder Metallurgy (AREA)

Claims (26)

  1. Verfahren zum Reinigen von Partikeln eines Metalls M1, die mit einem elektrochemischen Reduktionsverfahren hergestellt wurden, wobei das Verfahren die folgenden Schritte beinhaltet:
    Einleiten der Partikel des Metalls M1 in eine Wärmequelle, so dass die Partikel mit keinen Flächen in Kontakt sind, bei einer Temperatur, die im Wesentlichen gleich oder höher als der Schmelzpunkt von M1 ist, um zu bewirken, dass die vorhandenen kontaminierenden Verunreinigungen teilweise oder im Wesentlichen ganz verdampfen;
    Beseitigen der verdampften Verunreinigungen aus der Nähe der Partikel;
    und Kühlen der gereinigten Partikel des Metalls M1, um sie in fester Form aufzufangen.
  2. Verfahren zur Herstellung eines Metalllegierungsartikels, der ein Metall M1 enthält, durch Reinigen der Partikel des Metalls M1 mit dem Verfahren von Anspruch 1 und Ausführen eines Pulvermetallurgieverfahrens an den Partikeln zum Bilden des Artikels.
  3. Verfahren nach Anspruch 2, wobei der Artikel ein Metalllegierungsartikel ist und wobei die gereinigten M1-Partikel mit Partikeln anderer Legierungskomponenten gemischt werden und das Pulvermetallurgieverfahren an dem Gemisch zum Bilden des legierten Artikels ausgeführt wird.
  4. Verfahren nach Anspruch 1, 2 oder 3, wobei die Partikel in Form eines Pulvers vorliegen.
  5. Verfahren nach Anspruch 4, wobei das Pulver Partikel mit einem Durchmesser von bis zu etwa 1 mm umfasst.
  6. Verfahren nach Anspruch 1, 2 oder 3, wobei die Partikel in Form von fein bemessenen Metallproben, Körnern oder Pellets vorliegen.
  7. Verfahren nach einem der vorherigen Ansprüche, wobei die Partikel, wenn sie mit keinen Flächen in Kontakt sind, in der Luft suspendiert und/oder frei an der Wärmequelle vorbei oder darin fallen gelassen werden.
  8. Verfahren nach einem der Ansprüche 1 bis 6, wobei die Partikel, wenn sie mit keinen Flächen in Kontakt sind, in einer Flamme mitgeführt oder durch einen Plasmabrenner geblasen werden oder sich innerhalb einer Induktionsspule befinden.
  9. Verfahren nach einem der vorherigen Ansprüche, wobei die Partikel erhitzt, geschmolzen und im Wesentlichen ohne Kontakt mit Flächen wieder verfestigt werden.
  10. Verfahren nach einem der vorherigen Ansprüche, wobei die Freifalldistanz von der Wärmequelle ausreicht, damit von der Wärmequelle geschmolzenes Metall M1 vor dem Auffangen erneut verfestigen kann.
  11. Verfahren nach einem der vorherigen Ansprüche, wobei die Wärmequelle ausgewählt wird aus der Gruppe bestehend aus einem Plasmabrenner, einem Laser, einem Lichtbogen, einer Induktionsspule oder einem Rohrofen.
  12. Verfahren nach einem der vorherigen Ansprüche, wobei das Verfahren in einer geregelten Atmosphäre ausgeführt wird.
  13. Verfahren nach einem der vorherigen Ansprüche, das in einer Vorrichtung ausgeführt wird, die eine Wärmequelle, ein Auffangmittel zum Auffangen der gereinigten Partikel und ein separates Auffangmittel zum Auffangen der Verunreinigungen beinhaltet.
  14. Verfahren nach einem der vorherigen Ansprüche, wobei die Wärmequelle ein Plasmabrenner ist und der Schritt des Entfernens der verdampften Verunreinigungen das Wegreißenlassen der Verunreinigungen durch den Heißgasfluss von dem Brenner beinhaltet.
  15. Verfahren nach einem der vorherigen Ansprüche, wobei die Temperatur der Wärmequelle um oder über dem Schmelzpunkt, aber unter dem Siedepunkt von M1 liegt.
  16. Verfahren nach einem der vorherigen Ansprüche, wobei die Partikel von Metall M1 zur Reinigung durch ein elektrochemisches Reduktionsverfahren hergestellt werden.
  17. Verfahren nach einem der vorherigen Ansprüche, wobei M1 Titan umfasst.
  18. Verfahren nach einem der vorherigen Ansprüche, wobei die Verunreinigungen Magnesium, Calcium und/oder Calciumchlorid beinhalten.
  19. Verfahren zur Herstellung eines Metalllegierungsartikels mit gleichförmigem Querschnitt, das die folgenden Schritte beinhaltet:
    Zuführen eines kontinuierlichen Vorrats von Pellets aus einer Metalllegierung M1, die kontaminierende Verunreinigungen enthalten, die flüchtiger sind als M1, zu einem Verarbeitungsmittel;
    Erhitzen der Pellets bei ihrer Annäherung an das Verarbeitungsmittel durch freien Fall durch eine Wärmequelle bis auf eine Temperatur, die im Wesentlichen gleich oder höher als der Schmelzpunkt von M1 ist, um eine Verdampfung von einigen oder im Wesentlichen allen der vorhandenen kontaminierenden Verunreinigungen zu bewirken;
    Entfernen der verdampften Verunreinigungen aus der Nähe der Pellets;
    Ziehen des Metalls durch das Verarbeitungsmittel, um die Pellets zu dem gewünschten Artikel zu koaleszieren; und
    Kühlen des gegossenen Produkts.
  20. Verfahren nach Anspruch 19 zur Herstellung eines Metalllegierungsblechs, das die folgenden Schritte beinhaltet:
    Zuführen des kontinuierlichen Pelletvorrats zu einem Paar gekühlten Zuführungswalzen;
    Erhitzen der Pellets gemäß Anspruch 19 bei ihrer Annäherung an den Walzenspalt des Zuführungswalzenpaares;
    Ziehen des Metalls durch den Spalt der Walzen, um ein Metalllegierungsblech zu bilden; und
    Kühlen des Blechs.
  21. Verfahren nach Anspruch 19 zur Herstellung eines Metalllegierungsmaterials mit gleichförmigem Querschnitt, das die folgenden Schritte beinhaltet:
    Zuführen des kontinuierlichen Pelletvorrats aus der Metalllegierung zu einem gestalteten Schmelztiegel;
    Erhitzen der Pellets nach Anspruch 19 bei ihrer Annäherung an die exponierte Oberfläche des Schmelztiegels;
    Ziehen des wenigstens teilweise geschmolzenen Metalls von einer gegenüberliegenden Fläche des Schmelztiegels durch eine Düse, wobei die Nettoform und die Nettoabmessungen des Querschnitts der Düse nahezu der/den gewünschten Nettoform und -abmessungen des gewünschten Materials entsprechen; und
    Kühlen des Gussteils.
  22. Verfahren nach einem der Ansprüche 19 bis 21, wobei der Schritt des Erhitzens der Pellets mit einem Energiestrahl ausgeführt wird, der aus einem Elektronenstrahl, einem Laser oder einem Plasmabrenner ausgewählt wird.
  23. Verfahren nach einem der Ansprüche 19 bis 21, wobei die Legierung im Wesentlichen Titan umfasst.
  24. Verfahren zur Herstellung von gereinigten Metallpartikeln, die sphärische Partikel mit einer reduzierten Konzentration der flüchtigen Verunreinigungen unter Anwendung eines Verfahrens nach einem der Ansprüche 1 bis 18 beinhaltet.
  25. Verfahren nach Anspruch 24, wobei die Konzentration der flüchtigen Verunreinigungen weniger als 50 ppm beträgt.
  26. Verfahren nach Anspruch 24 oder 25, wobei die Konzentration der flüchtigen Verunreinigungen weniger als 10% der Konzentration vor dem Reinigen ausmacht.
EP03753690A 2002-09-25 2003-09-24 Reinigung von metallpartikeln durch hitzebehandlung Expired - Lifetime EP1543172B1 (de)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
GB0222219A GB0222219D0 (en) 2002-09-25 2002-09-25 Purification process
GB0222219 2002-09-25
GB0222358 2002-09-26
GB0222348A GB2393450A (en) 2002-09-26 2002-09-26 Method of Manufacture of Metal Alloy Stock
GB0222348 2002-09-26
GB0222358A GB2393451A (en) 2002-09-26 2002-09-26 A Method of Manufacture of Metal Alloy Sheet
PCT/GB2003/004093 WO2004029332A2 (en) 2002-09-25 2003-09-24 Purification of electrochemically deoxidised refractory metal particles by heat processing

Publications (2)

Publication Number Publication Date
EP1543172A2 EP1543172A2 (de) 2005-06-22
EP1543172B1 true EP1543172B1 (de) 2009-12-16

Family

ID=32045677

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03753690A Expired - Lifetime EP1543172B1 (de) 2002-09-25 2003-09-24 Reinigung von metallpartikeln durch hitzebehandlung

Country Status (6)

Country Link
US (2) US20060130610A1 (de)
EP (1) EP1543172B1 (de)
AT (1) ATE452214T1 (de)
AU (1) AU2003271852B2 (de)
DE (1) DE60330577D1 (de)
WO (1) WO2004029332A2 (de)

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4754488B2 (ja) * 2003-08-28 2011-08-24 テクナ・プラズマ・システムズ・インコーポレーテッド 粉末材料の合成や分離や精製のための方法
EP1671711A1 (de) * 2003-10-09 2006-06-21 Ebara Corporation Verfahren zur reinigung von durch schwermetall verunreinigtem material und vorrichtung dafür
RU2370559C1 (ru) * 2008-06-26 2009-10-20 Вадим Георгиевич Глебовский Способ получения высокочистого титана для распыляемых мишеней
KR102322229B1 (ko) 2014-05-13 2021-11-05 더 유니버시티 오브 유타 리서치 파운데이션 실질적으로 구형인 금속 분말의 제조
KR20170101927A (ko) 2014-12-02 2017-09-06 더 유니버시티 오브 유타 리서치 파운데이션 금속 분말의 용융 염 탈산소화
CN107208978B (zh) * 2015-10-22 2019-08-23 株式会社Posco 原料装载设备、冷却辊及防止粘附矿石产生的方法
HUE065423T2 (hu) 2015-12-16 2024-05-28 6K Inc Eljárás szferoidális dehidrogénezett titánötvözet részecskék elõállítására
US10987735B2 (en) 2015-12-16 2021-04-27 6K Inc. Spheroidal titanium metallic powders with custom microstructures
US11077497B2 (en) 2017-06-07 2021-08-03 Global Titanium Inc. Deoxidation of metal powders
AU2019290663B2 (en) 2018-06-19 2023-05-04 6K Inc. Process for producing spheroidized powder from feedstock materials
KR20240036705A (ko) 2019-04-30 2024-03-20 6케이 인크. 리튬 란타넘 지르코늄 산화물(llzo) 분말
CA3134573A1 (en) 2019-04-30 2020-11-05 Sunil Bhalchandra BADWE Mechanically alloyed powder feedstock
WO2021118762A1 (en) 2019-11-18 2021-06-17 6K Inc. Unique feedstocks for spherical powders and methods of manufacturing
US11590568B2 (en) 2019-12-19 2023-02-28 6K Inc. Process for producing spheroidized powder from feedstock materials
US11181325B2 (en) * 2019-12-23 2021-11-23 Valgroup S.A. System for the production of molten salt used as a heat transfer medium for a pyrolysis system
AU2021297476A1 (en) 2020-06-25 2022-12-15 6K Inc. Microcomposite alloy structure
AU2021349358A1 (en) 2020-09-24 2023-02-09 6K Inc. Systems, devices, and methods for starting plasma
EP4237174A1 (de) 2020-10-30 2023-09-06 6K Inc. Systeme und verfahren zur synthese von sphäroidisierten metallpulvern
EP4275239A4 (de) 2021-01-11 2024-12-18 6K Inc. Verfahren und systeme zur rückgewinnung von li-ionen-kathodenmaterialien mittels mikrowellenplasmaverarbeitung
WO2022192394A1 (en) * 2021-03-10 2022-09-15 The Regents Of The University Of California Gas-phase production of aligned metal nanoparticles using external magnetic fields
US20220324022A1 (en) * 2021-03-31 2022-10-13 6K Inc. Microwave plasma processing of spheroidized copper or other metallic powders
AU2022246797A1 (en) 2021-03-31 2023-10-05 6K Inc. Systems and methods for additive manufacturing of metal nitride ceramics
CN113999981A (zh) * 2021-11-02 2022-02-01 广东先导微电子科技有限公司 一种高纯金属真空升华的除杂方法
WO2023229928A1 (en) 2022-05-23 2023-11-30 6K Inc. Microwave plasma apparatus and methods for processing materials using an interior liner
US12040162B2 (en) 2022-06-09 2024-07-16 6K Inc. Plasma apparatus and methods for processing feed material utilizing an upstream swirl module and composite gas flows
WO2024044498A1 (en) 2022-08-25 2024-02-29 6K Inc. Plasma apparatus and methods for processing feed material utilizing a powder ingress preventor (pip)
US12195338B2 (en) 2022-12-15 2025-01-14 6K Inc. Systems, methods, and device for pyrolysis of methane in a microwave plasma for hydrogen and structured carbon powder production
CN115846649B (zh) * 2022-12-20 2024-08-16 江苏宇钛新材料有限公司 一种低熔点球形金属粉末的制备方法

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2943032A (en) * 1951-06-23 1960-06-28 Nat Res Corp Electrolytic production of titanium
US2876094A (en) * 1956-02-17 1959-03-03 Du Pont Production of refractory metals
US3343944A (en) * 1963-09-06 1967-09-26 Pechiney Prod Chimiques Sa Electrolytic beryllium granules and method for manufacturing same
FR1445684A (fr) * 1965-06-03 1966-07-15 Commissariat Energie Atomique Dispositif de coulée continue de matériaux réfractaires
US3690635A (en) * 1969-05-16 1972-09-12 Air Reduction Condensate collection means
US4114251A (en) * 1975-09-22 1978-09-19 Allegheny Ludlum Industries, Inc. Process for producing elongated metal articles
CA1163800A (en) * 1980-09-08 1984-03-20 Westinghouse Electric Corporation Metal distillation apparatus
US4390368A (en) * 1981-04-01 1983-06-28 Gte Products Corporation Flame spray powder
AT380491B (de) * 1984-02-03 1986-05-26 Kos Bernd Verfahren und vorrichtung zum aufbereiten von spaenen aus der bearbeitung von titanwerkstuecken
US4602947A (en) * 1984-11-01 1986-07-29 Alti Corporation Process for producing titanium metal and titanium metal alloys
US4612179A (en) * 1985-03-13 1986-09-16 Sri International Process for purification of solid silicon
LU86090A1 (fr) * 1985-09-23 1987-04-02 Metallurgie Hoboken Procede pour preparer du tantale ou du niobium affins
JPS63183145A (ja) * 1987-01-22 1988-07-28 Sumitomo Electric Ind Ltd 高硬度チタン−アルミニウム−バナジウム系合金およびその製造方法
US5336378A (en) * 1989-02-15 1994-08-09 Japan Energy Corporation Method and apparatus for producing a high-purity titanium
EP0476651B1 (de) * 1990-09-20 1996-03-20 Fujitsu Limited Josephson-Einrichtung mit einer Überlagenstruktur von verbesserter thermischer Stabilität
US5147451A (en) * 1991-05-14 1992-09-15 Teledyne Industries, Inc. Method for refining reactive and refractory metals
US6024847A (en) * 1997-04-30 2000-02-15 The Alta Group, Inc. Apparatus for producing titanium crystal and titanium
US6309595B1 (en) * 1997-04-30 2001-10-30 The Altalgroup, Inc Titanium crystal and titanium
GB9812169D0 (en) * 1998-06-05 1998-08-05 Univ Cambridge Tech Purification method
JP2001020065A (ja) * 1999-07-07 2001-01-23 Hitachi Metals Ltd スパッタリング用ターゲット及びその製造方法ならびに高融点金属粉末材料
JP3053183B1 (ja) * 1999-08-27 2000-06-19 科学技術振興事業団 磁気力による擬似微小重力場を利用した浮遊溶融
GB2359564B (en) * 2000-02-22 2004-09-29 Secr Defence Improvements in the electrolytic reduction of metal oxides

Also Published As

Publication number Publication date
ATE452214T1 (de) 2010-01-15
DE60330577D1 (de) 2010-01-28
US20060130610A1 (en) 2006-06-22
WO2004029332A3 (en) 2004-10-21
EP1543172A2 (de) 2005-06-22
AU2003271852A1 (en) 2004-04-19
US20120230860A1 (en) 2012-09-13
WO2004029332A2 (en) 2004-04-08
AU2003271852B2 (en) 2010-03-11

Similar Documents

Publication Publication Date Title
EP1543172B1 (de) Reinigung von metallpartikeln durch hitzebehandlung
EP1445350B1 (de) Verfahren und vorrichtung zum schmelzen von titanmetall
US8092570B2 (en) Method for producing titanium metal
US7300491B2 (en) Method and apparatus for the production of metal powder
CA2834328A1 (en) Low cost processing to produce spherical titanium and titanium alloy powder
US20080187455A1 (en) Titanium and titanium alloys
US6368375B1 (en) Processing of electroslag refined metal
US4108644A (en) Manufacture of reactive metals and alloys
JPH09104931A (ja) 高純度チタン材の製造方法
CN119876619A (zh) 一种高回收比高均匀性tc4钛合金铸锭制备方法
US4595413A (en) Group IVb transition metal based metal and processes for the production thereof
US4655825A (en) Metal powder and sponge and processes for the production thereof
US7445658B2 (en) Titanium and titanium alloys
JP7471946B2 (ja) チタン系インゴットの製造方法
JP3981601B2 (ja) 金属チタンの精錬方法及びその精錬装置
JP3195156B2 (ja) チタンの製造方法
JP2784324B2 (ja) チタンの製造方法
GB2393450A (en) Method of Manufacture of Metal Alloy Stock
EP0187741A1 (de) Auf gruppe iv-b-übergangsmetall basierendes metall und deren herstellung
GB2393451A (en) A Method of Manufacture of Metal Alloy Sheet
JP2002275551A (ja) バナジウム合金の製造方法
CA1238803A (en) Group ivb transition metal based metal and processes for the production thereof
Tripp Electron Beam Melting
JPH0867921A (ja) 高融点活性金属の消耗電極式真空アーク溶解法
Lochbichler et al. Cost Reduction of TiAl by Alternative Production and Integration of TiAl Scrap Recycling--Concepts and Vacuum-Metallurgical Equipment

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: 20050321

AK Designated contracting states

Kind code of ref document: A2

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

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: METALYSIS LIMITED

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: METALYSIS LIMITED

17Q First examination report despatched

Effective date: 20051010

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: PURIFICATION OF METAL PARTICLES BY HEAT PROCESSING

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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 IT LI LU MC NL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60330577

Country of ref document: DE

Date of ref document: 20100128

Kind code of ref document: P

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20091216

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

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: 20091216

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: 20091216

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091216

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: 20100416

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: 20100316

Ref country code: ES

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: 20100327

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: 20091216

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: 20091216

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

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: 20091216

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

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

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: 20100317

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: 20091216

26N No opposition filed

Effective date: 20100917

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091216

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 NON-PAYMENT OF DUE FEES

Effective date: 20100930

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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: 20100924

Ref country code: CH

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

Effective date: 20100930

Ref country code: LI

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

Effective date: 20100930

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: 20100924

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

Effective date: 20100617

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

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: 20091216

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

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

Ref country code: IT

Payment date: 20180921

Year of fee payment: 16

Ref country code: FR

Payment date: 20180921

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: 20180918

Year of fee payment: 16

Ref country code: CZ

Payment date: 20180918

Year of fee payment: 16

Ref country code: BE

Payment date: 20180913

Year of fee payment: 16

Ref country code: SE

Payment date: 20180919

Year of fee payment: 16

Ref country code: GB

Payment date: 20180924

Year of fee payment: 16

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

Ref country code: DE

Payment date: 20180926

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60330577

Country of ref document: DE

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: 20190925

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: 20190924

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: 20200401

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190930

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 452214

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190924

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

Ref country code: IT

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

Effective date: 20190924

Ref country code: BE

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

Effective date: 20190930

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

Effective date: 20190924

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

Ref country code: FR

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

Effective date: 20190930

Ref country code: GB

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

Effective date: 20190924

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: 20190924

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230523