EP3831509A1 - Appareil et procédé métallurgique pour la préparation et l'alimentation des alliages semi-solides de magnésium dans un état quasi-liquide pour machines de coulée à injection - Google Patents

Appareil et procédé métallurgique pour la préparation et l'alimentation des alliages semi-solides de magnésium dans un état quasi-liquide pour machines de coulée à injection Download PDF

Info

Publication number
EP3831509A1
EP3831509A1 EP20211682.8A EP20211682A EP3831509A1 EP 3831509 A1 EP3831509 A1 EP 3831509A1 EP 20211682 A EP20211682 A EP 20211682A EP 3831509 A1 EP3831509 A1 EP 3831509A1
Authority
EP
European Patent Office
Prior art keywords
magnesium alloy
semi
chamber
quasi
liquid state
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.)
Granted
Application number
EP20211682.8A
Other languages
German (de)
English (en)
Other versions
EP3831509B1 (fr
Inventor
Fabrizio D'ERRICO
Marco ROMEO
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.)
Innsight Srl
Original Assignee
Innsight Srl
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 Innsight Srl filed Critical Innsight Srl
Publication of EP3831509A1 publication Critical patent/EP3831509A1/fr
Application granted granted Critical
Publication of EP3831509B1 publication Critical patent/EP3831509B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/002—Castings of light metals
    • B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
    • B22D1/002—Treatment with gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/007—Semi-solid pressure die casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/20—Accessories: Details
    • B22D17/28—Melting pots
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/20—Accessories: Details
    • B22D17/30—Accessories for supplying molten metal, e.g. in rations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D2/00—Arrangement of indicating or measuring devices, e.g. for temperature or viscosity of the fused mass
    • B22D2/006—Arrangement of indicating or measuring devices, e.g. for temperature or viscosity of the fused mass for the temperature of the molten metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D39/00—Equipment for supplying molten metal in rations
    • B22D39/003—Equipment for supplying molten metal in rations using electromagnetic field
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D39/00—Equipment for supplying molten metal in rations
    • B22D39/04—Equipment for supplying molten metal in rations having means for controlling the amount of molten metal by weight
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D39/00—Equipment for supplying molten metal in rations
    • B22D39/06—Equipment for supplying molten metal in rations having means for controlling the amount of molten metal by controlling the pressure above the molten metal
    • 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
    • C22B9/006—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with use of an inert protective material including the use of an inert gas
    • 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
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • C22C1/12—Making non-ferrous alloys by processing in a semi-solid state, e.g. holding the alloy in the solid-liquid phase
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium

Definitions

  • the present invention is in the metallurgic field of magnesium alloys, in particular, of apparatuses and processes for the preparation of semi-solid magnesium alloys in a quasi-liquid state for casting injection machines.
  • Mg magnesium alloys
  • the viscosity of magnesium (abbreviated Mg) at the molten state is lower than the viscosity of aluminum alloys, allowing an easier filling of the mold cavities, thus allowing to make castings of particular geometrical complexity, even with thin walls.
  • Mg magnesium in a liquid state also has reduced chemical compatibility with steel used for manufacturing shell casting molds; this property allows to markedly reduce the phenomena of gradual wear of steel molds due to liquid metal attack.
  • Mg alloys show significant problems due to the high reactivity of magnesium metal with oxygen.
  • the high affinity of magnesium for the atmosphere oxygen causes high flammability of Mg and alloys thereof which, once flame-triggered, proceed with an incessant exothermic process of self-combustion, fed by the presence of oxygen (abbreviated O 2 ) and supported by the flame temperature: once the flame is triggered, in the presence of oxygen, the combustion reaction proceeds forming the combustion product magnesium oxide (abbreviated MgO) and releasing heat.
  • the combustion flame rapidly reaches temperatures between 2,000 °K and 4,000 °K, therefore capable of perforating any crucible, even if made of refractory material.
  • Mg alloys require the use of special melting plants and trained personnel, increasing the production cost of Mg alloy castings despite the Mg raw material cost is actually similar to the cost of pure aluminum.
  • Mg foundries there are several techniques in Mg foundries, which are divided in: a) vacuum melting plants, b) melting plants provided with atmospheres being inert and protective of Mg bath.
  • the inert atmospheres usually used are those mixed SF 6 and CO 2 , those based on R-134a freon gas, and those based on SO 2 .
  • Both SF 6 R-134a freon gas are classified as very high GWP (global warming potential) greenhouse gases, while SO 2 gas, although being a valid alternative to greenhouse gases SF 6 and R-134a from an environmental point of view, requires stringent application protocols due to its high toxicity to the operators.
  • GWP global warming potential
  • the phenomenon regulating the higher protection provided by Ca, Be and Y elements present in the Mg bath against oxygen present in the atmosphere although little known, it is however known; the volume ratio between the volume of Mg oxide (abbreviated MgO) formed by spontaneous reaction of Mg of the bath with air O 2 and the volume of underlying melted Mg is lower than the unity.
  • MgO volume of Mg oxide
  • the result is the presence on the surface of the melted Mg of a film of porous oxide exposing the Mg bath underlying to the oxide film to the oxygen present in the atmosphere, activating the above-mentioned conditions of flame ignition and resulting reaction of exothermic combustion between liquid Mg and the oxygen in the atmosphere.
  • Sakamoto demonstrated that the structure of oxide film extending on the Ca-added Mg alloy added is characterized by a very thin and uniform oxide film, which is resistant although the long air expositions of the melted alloy at 973 °K for 60 minutes, confirming that the oxide film formed as Mg alloys with Ca acts as an effective barrier for preventing both oxygen diffusion from air to the melted metal and magnesium volatilization.
  • the present invention is directed to an apparatus for the preparation of semi-solid magnesium alloys in a quasi-liquid state, under safety conditions, avoiding the use of highly polluting protective gas.
  • the coupling of the apparatus according to the invention with the process involving the use thereof allows solving the limits related to magnesium melting and its alloys, thus reducing as much as possible the melting temperature and the temperature at which the product is poured. All of this is achieved through the apparatus of the invention and preparing a semi-solid magnesium alloy near to the alloy liquidus temperature, i.e. in a quasi-liquid state, using an oxygen-depleted atmosphere and a particular stirring system that, together with the above-mentioned conditions, allows to avoid the Mg flame ignition.
  • the process involves a step wherein, under isothermal conditions, the semi-solid magnesium alloy is subjected to stirring for a certain time, with particular stirring systems, which allow obtaining a highly-homogeneous alloy, a high-pourability globular equiaxed microstructure (see Fig. 4 ) and having a reduce volumetric contraction at the terminal stage of complete solidification, allowing to obtain complex-shape castings and in the absence of porosity and/or shrinkage cavities typical of solidified castings from liquid conditions.
  • Object of the present invention is an apparatus and a metallurgical process using the same for the preparation of a semi-solid magnesium alloy comprising calcium and/or calcium oxide (CaO) (hereinafter Mg alloy with Ca and/or CaO) semi-solid near to the liquidus temperature but within the range of solidification of the metal alloy, i.e., under conditions of quasi-liquid semi-solid mass.
  • CaO calcium and/or calcium oxide
  • An object of the invention is an apparatus (17) and a process for dosing the melted metal belonging to the magnesium alloy family, from a closed furnace achieving, inside, an inert atmosphere for Mg alloy casting.
  • the semi-solid magnesium alloy in a quasi-liquid state is prepared, it is directly dosed into the injection chamber of the pressure casting machine.
  • the above-mentioned three-chamber concept can be intended as one single chamber having three separated areas, for example, made by suitable separation elements, wherein the operations of described above points 1. to 4. are carried.
  • the apparatus (17) of the present invention for the preparation of a semi-solid magnesium alloy in a quasi-liquid state comprises three communicating chambers, where:
  • the apparatus (17) can also be named furnace, semisolid furnace, dosing furnace, melting furnace, etc..
  • the apparatus (10) is composed of three communicating chambers, nominate X, Y, and Z, see scheme of Fig.1 .
  • the chamber X is related to the charge and melting of the material that can be already at liquid phase from a standing furnace with higher capacity, or, as in the example of Fig.1 , in solid phase as slabs or ingots.
  • the chamber X bearing a sluice-gate opening (1) or other types with similar function and objective which is, for its opening, protected by the inert gas flow to avoid the direct contact between the melting alloy in the chamber X and the new solid or liquid charge introduced.
  • the chamber X of charging and pre-heating is also provided, on the bottom, with a porous septum (2) made of graphite or in silicon carbide or other inert material, from which inert gas is insufflating, such as nitrogen or argon, for the optional degassing step.
  • a porous septum (2) made of graphite or in silicon carbide or other inert material, from which inert gas is insufflating, such as nitrogen or argon, for the optional degassing step.
  • the inductive coil plate (3), in a preferred low energy consumption form, of the present invention can be replaced by a rotating plate (10) or, alternatively, by adjacent multiple rotating plates (10), bearing permanent magnets (10bis) such as in the example of Fig.2 .
  • the permanent magnet plate (10bis) is also illustrated in the exemplified scheme of Fig.2bis .
  • the rotating plate (10) and related permanent magnets (10bis) can be replaced by permanent magnets (as a circumferential sector) represented in section from elements (10ter) in coaxial rotation with two main cylindrical section crucibles (13) and (14).
  • (13) is chamber Z, while (14) the two chambers Y and X separated by an inner wall almost diametral made in the same crucible (14).
  • the communicating crucibles (13) and (14) are preferably made of high electrical conductivity material and highly permeable to the variable magnetic flow generated by rotation ⁇ 1 and ⁇ 2 of the permanent magnets around axes (15) and (16).
  • the coaxial rotation of permanent magnets is carried out preferably by two independent constant torque electric motors of the brushless type connected preferably by two bevel gear groups (14).
  • the apparatus (17) can comprise one or more rotating plates (10) bearing permanent magnets (10bis). In the case of more than one rotating plate (10), and therefore in the case of multiple rotating plates 10) bearing permanent magnets (10bis), to put in rotation, they are adjacent to each other.
  • the rotating magnets (10bis) can be placed on different and smaller plates, which are adjacent to each other, instead of on a single plate (10) as shown in the scheme of Fig.2 .
  • inserts (4) made of highly conductive material preferably graphite or silicon carbide, i.e. highly conductive materials.
  • highly conductive material preferably graphite or silicon carbide, i.e. highly conductive materials.
  • electrical resistors (5) present in Fig.1 in chamber Y can be placed separately for each chamber to contribute through the submerging temperature auxiliary probes (5bis) to the thermoregulation of the mass present in chamber by suitably balancing the heat supply in order to obtain metal mass thermoregulation at a controlled temperature close to liquid-to-solid state passage.
  • the dosing chamber, or chamber Z of Fig. 1 is made such that channel (6), which connects it to the heating chamber Z can be closed through an electrovalve controlling a gate piston (7) in order to avoid the liquid mass back from chamber Z to chamber Y, as schematically shown in Fig.1 .
  • the electro-controlled piston(7) closes or opens the communication door between chamber Y and chamber Z.
  • a valve (8) located on the top of chamber Z is opened and pressurized inert gas is insufflated.
  • the pressurized gas forced metal returning in the dosing tube, allowing the magnesium alloy leaving from apparatus (17) through the connecting tube.
  • the alloy can optionally feed an injector through the dosing tube (9) connecting the apparatus (17) and the injector.
  • the apparatus (17) is, at least, completed with the following transducers:
  • the injector is, optionally, physically connected to the apparatus (17) and receives the metal, from this latter, in a dosed amount and under semisolid conditions.
  • the apparatus can be provided with, an immersion thermocouple to measure the magnesium alloy temperature, in each of the three chambers.
  • the heating elements (5) are, preferably, electrical resistors.
  • All the heating elements (5) are controlled by a PLC to thermoregulating the bath as a function of the instant temperature reading carried out by the auxiliary probe (5bis).
  • All the heating elements (5), preferably, the electrical resistors work independently. Therefore, they can provide different temperature values to the apparatus chambers.
  • the three heating elements are three electrical resistors operating independently.
  • each of the three chambers is provided with a pressure sensor.
  • the apparatus is made of refractory material.
  • the block plate with coil and/or turns for the electromagnetic induction (3) allows to carry out the electromagnetic stirring.
  • Said plate being optional, meaning that it can be integrated in the apparatus or, alternatively, the apparatus without such plate can be contacted, preferably above, to an outer electromagnetic induction block plate.
  • the electromagnetic induction block plate (3) is integrated in the apparatus (17).
  • the inductive coil plate (3) of the present invention, can be replaced by one or more rotating plates (10), adjacent to each other, bearing permanent magnets (10bis) such as in the example of Fig.2 .
  • the rotating plate (10) bearing permanent magnets (10bis) is optional, meaning that it can be integrated in the apparatus (17) or it can be independent and then external to the apparatus (17).
  • the apparatus (17), in such case, can be arranged adjacent to the rotating plate (10), or more adjacent rotating plates, bearing permanent magnets (10bis), preferably above and/or on the side.
  • permanent magnets are optionally used (a circumferential sector) (10ter) or rotating permanent magnets or coaxial rotation permanent magnets.
  • said means generating the stirring are optional, meaning that they can be part of the apparatus (17) or external, and in such case, the apparatus (17) will be arranged adjacent to said means.
  • the electromagnetic induction block plate (3) and/or a rotating plate (10) bearing permanent magnets (10bis) and/or rotating permanent magnets (10ter) are an integral part of the apparatus (17).
  • the apparatus of the invention (17) is in fact possible the coexistence of various possible stirring modes, for example, the electromagnetic induction block plate (3) and a rotating plate (10) bearing permanent magnets (10bis) and rotating permanent magnets (10ter); alternatively the electromagnetic induction block plate (3) and one or more from rotating plate (10) bearing permanent magnets (10bis) or rotating permanent magnets (10ter) adjacent to each other; alternatively a rotating plate (10) bearing permanent magnets (10bis) and rotating permanent magnets (10ter); etcetera,.
  • various possible stirring modes for example, the electromagnetic induction block plate (3) and a rotating plate (10) bearing permanent magnets (10bis) and rotating permanent magnets (10ter); alternatively the electromagnetic induction block plate (3) and one or more from rotating plate (10) bearing permanent magnets (10bis) or rotating permanent magnets (10ter) adjacent to each other; alternatively a rotating plate (10) bearing permanent magnets (10bis) and rotating permanent magnets (10ter); etcetera,.
  • Said stirring means can be the same or different for each chamber, therefore a stirring mean can be present in a chamber, for example, the stirring in the electromagnetic induction block plate (3) and a different magnetic stirring mean can be present in another chamber, for example, a rotating plate (10) bearing permanent magnets (10bis) or rotating permanent magnets (10ter).
  • the electromagnetic induction block plate (3) and/or a rotating plate (10) bearing permanent magnets (10bis) is located on the bottom of the apparatus and/or outside the bottom.
  • the rotating permanent magnets (10ter) are positioned abreast and adjacent to the vertical walls of one or more chambers.
  • the apparatus optionally comprises a grounding for the electrostatic discharge.
  • Another object is the metallurgical process using the apparatus of the invention for the preparation of a semi-solid magnesium alloy in a quasi-liquid state comprising the following steps:
  • the magnesium alloy in step a') can be at the solid, semisolid, or molten state. Therefore, when solid or semisolid, it is brought to molten, or liquid state, in case it is already at the molten state, it is maintained at the molten state.
  • step a' one or more magnesium alloy ingots from the sluice-gate (1).
  • step a') is performed under an inert gas flow protective atmosphere; According to a preferred embodiment in step a') the ingot melting is carried out within chamber X through the presence of an already liquid mass.
  • step b' the stirring is carried out by electromagnetic stirring and/or magnetic stirring with permanent magnets and/or by bubbling nitrogen or argon gas.
  • step b' the stirring is carried out by electromagnetic and/or magnetic stirring.
  • step b' the melted material is constantly stirred by the block plate of the electromagnetic inductor (3) and/or a rotating plate (or plates) (10) bearing permanent magnets (10bis) and/or rotating permanent magnets (10ter), making the electromagnetic and/or magnetic stirring, respectively.
  • the induced currents allow to maintain the bath of magnesium alloy at the molten state under stirring, and, simultaneously, heat the inserts (4) due to the Joule effect.
  • the heat, produced in the insert by conduction, is transferred to chamber X. According to the same principle, heat is transferred in all three chambers.
  • the thermoregulation usually allows to suitably reduce the magnesium alloy temperature to bring and maintain it at the semisolid state.
  • the heating elements, preferably, the electrical resistors (5) allows to adjust the local temperature in chambers X, Y and Z.
  • the heating in the chambers is carried out by electromagnetic or magnetic stirring, depending on the variable source of the magnetic field, which causes the simultaneous heating of the container of one, two or three cambers, corroborated by the heating provided by the heating elements, preferably electrical resistors, thus allowing the fine and independent regulation of the temperatures in one, two or three chambers.
  • step e' the piston (7) is lifted controlled by an electrovalve to feed chamber Z with the metallostatic swing at the level of the chamber X (according to the communicating vessel principle);
  • step f' the piston (7) is lowered by closing chamber Z, hermetically.
  • step h' inert gas (for example, nitrogen or argon) is insufflated to exert pressure above the free surface of the quasi-liquid semisolid metal and pushing it within the dosing tube (9), from which the alloy comes out the apparatus (9).
  • inert gas for example, nitrogen or argon
  • the dosing tube (9) can optionally feed an injection group, or a container of the injection group, which then injects the alloy within the press.
  • Another object is a further metallurgical process using the apparatus of the invention for the preparation of a semi-solid magnesium alloy in a quasi-liquid state comprising the following steps:
  • the magnesium alloy in step a) can be at the solid, semisolid or molten state. Therefore, if solid or semisolid it is brought to the molten state, or liquid state, if already at the molten state, is maintained at the molten state.
  • the metallurgical process comprises the following steps:
  • Steps a) and b) are carried out in the chamber X of apparatus (17), steps c) and d) in the chamber Y, and step e) in the chamber Z).
  • the process can involve a variant wherein steps a) and b) are reversed.
  • the process of the present invention which is carried out in the apparatus (17), allows the preparation of magnesium alloys comprising Ca and/or CaO under semi-solid conditions avoiding the adoption of conventional highly polluting protective gases (such as SF 6 , SO 2 , R134a) which, in the conventional processes, on a precautionary basis, however, are necessary although the alloys are Ca- or CaO-added since, during the stirring step, the oxide film stabilized in a static melting stage would continuously removed thus causing the trigger of incipient flame also on the Mg alloys containing Ca/CaO, thus making the preparation of the semi-solid mass unfeasible even for these alloys in a free atmosphere.
  • conventional highly polluting protective gases such as SF 6 , SO 2 , R134a
  • the semi-solid magnesium alloy in a quasi-liquid state can have preferably a solid fraction content between about 0% and about 20%.
  • the quasi-liquid semi-solid magnesium alloy is a magnesium alloy non-flammable under certain conditions, i.e. a magnesium alloy known to be non-flammable, such as Mg-alloys comprising Ca and/or CaO (and, in substitution or in addition to Ca as anti-flammability, also Be and/or Y elements) and it can further comprise other elements usually used in foundry Mg-alloys.
  • a magnesium alloy known to be non-flammable such as Mg-alloys comprising Ca and/or CaO (and, in substitution or in addition to Ca as anti-flammability, also Be and/or Y elements) and it can further comprise other elements usually used in foundry Mg-alloys.
  • the quasi-liquid semi-solid magnesium alloy must comprise, as well as the typical alloy elements present in the magnesium alloys, Ca and/or calcium oxide such as elements increasing the flammability temperature of conventional magnesium alloys; it can optionally comprise other elements, such as Be, Y together with or alternatively to Ca and/or CaO and/or Aluminum.
  • the semi-solid magnesium alloy in a quasi-liquid state comprises calcium and/or calcium oxide, and according to a preferred embodiment, the semi-solid magnesium alloy in a quasi-liquid state can further comprise aluminum.
  • the aluminum improves the mechanical properties in the aluminum alloys, but reducing the time of alloy self-combustion trigger in air.
  • the semi-solid magnesium alloy in a quasi-liquid state comprises calcium and/or calcium oxide in an amount ranging between 1% and 2 % by weight, i.e. weight-on-weight, and aluminum ranging between 2% and 9% by weight.
  • step b) an atmosphere with an oxygen content lower than 10% mol. is achieved inside the apparatus.
  • the apparatus is hermetically sealed and provided with a closed heated thermoregulation chamber, closed provided with the porous septum inlet channel (2) to insufflate inert gas such as, for example, nitrogen or argon, and with an outlet channel to remove the air of the atmosphere containing oxygen to reduce O 2 concentration in the apparatus atmosphere below 10% mol. before the beginning of the semi-solid mass stirring.
  • insufflate inert gas such as, for example, nitrogen or argon
  • 10% mol. means the oxygen content in dry atmosphere as oxygen moles with respect to the total moles.
  • the oxygen content in dry atmosphere means a water-free atmosphere, steam or moisture.
  • the atmosphere has an oxygen content ranging between 0.1 and 10% mol., more preferably between 0.1% and 5% mol..
  • the outlet channel can be connected with a vacuum pump to accelerate oxygen evacuation from the apparatus.
  • the quantification of the maximum oxygen content, into the atmosphere of the closed apparatus must be lower than 10% mol. can be carried out on the leaving gas effluent by the conventional oxygen-content detectors currently available on the market.
  • Step a) of loading the apparatus with melted magnesium alloy can be carried out by simple pouring of the melted Ca and/or CaO-added magnesium alloy prepared in another furnace through an opening, closeable, of the apparatus.
  • the loading is carried out by a closable inlet mouth, maintaining open the inert gas inlet inside the apparatus chamber, such that the loading occurs under a protective atmosphere, and in countercurrent.
  • the apparatus chamber is thermoregulated to get the temperature of the melted Ca and/or CaO-added magnesium alloy to a value such that a semi-solid magnesium alloy in a quasi-liquid state is made.
  • the temperature at which the apparatus is set is a temperature below the one at which the alloy passes into a liquid state, but above the minimum temperature wherein the chemical composition of the alloy can locally vary due to the solidification, even partial, of one or more of its constituents; said minimum temperature depends on the composition of the magnesium alloy considered and it must be set such not more than 20% of solid fraction is present in the semi-solid magnesium alloy in a quasi-liquid state.
  • the temperature of the magnesium alloy can be controlled by a thermocouple submersed in the alloy itself.
  • step c) the melted magnesium alloy is cooled until a temperature within a ranged between 5°C and 15°C, preferably between 5°C and 10°C, below the liquidus temperature (i.e. specific temperature of solidification beginning during the cooling of the overheated liquid) so as to make a semi-solid Ca and/or CaO-added magnesium alloy in a quasi-liquid state.
  • the liquidus temperature i.e. specific temperature of solidification beginning during the cooling of the overheated liquid
  • step c) the melted magnesium alloy is cooled until a temperature ranging between 570 °C and 610°C, even more preferably 580-595 °C.
  • step c) the apparatus chamber is thermoregulated to maintain the magnesium alloy in such an isothermal temperature condition, below the temperature wherein the alloy passes into a liquid state, but above the minimum temperature for which the subsequent and essential step of isothermal stirring described at point d) makes the nucleation conditions of solid germs and the equiaxed growth thereof without the need of mechanically breaking of dendrites, which are conventional solidification structures.
  • step d) The temperature of step d) is the same with respect to the temperature obtained at the end of step c).
  • step d) the isothermal condition is obtained by a constant temperature which is comprised in a temperature range set between 5° and 15°C below the temperature of liquidus of the specific alloy treated.
  • step d) the isothermal condition is carried out by a constant temperature ranging between 570°C and 610°C, more preferably between 580 °C and 600 °C, even more preferably between 580-595 °C.
  • step d) the stirring under isothermal conditions is carried out for at least 20 seconds, preferably for a time ranging between 20 seconds and 30 minutes, more preferably between 60 seconds and 20 minutes, even more preferably between 60 seconds and 500 seconds.
  • step d) the stirring can be carried out by electromagnetic stirring and/or by magnetic stirring with permanent magnets.
  • step d) the stirring can be carried out by magnetic stirring with rotating permanent magnets.
  • the magnetic stirring with rotating permanent magnets can be carried out by a rotating plate (10) bearing permanent magnets (10bis) and/or by rotating permanent magnets (10ter) (see Fig. 2 + Fig. 2bis and/or Fig. 3 , respectively).
  • step d) the stirring can be carried out by magnetic stirring with rotating permanent magnets such as in the example of Fig.2 and Fig.3 .
  • rotating permanent magnets such as in the example of Fig.2 and Fig.3 .
  • pushing effects of electromotive forces developed in the liquid or semisolid mass are developed, which are capable of giving an effect of "lifting" in the liquid mass which tends to separate the metal mass from crucible walls, thus reducing also the physiological phenomena of wear if the construction material of crucible is refractory.
  • the electromagnetic stirring and, more efficiently, the magnetic stirring allow to carry out the stirring action under isothermal conditions thus avoiding the use of mechanical stirrers whose integration inside the apparatus would cause several mechanical problems on one side, and subjecting the semi-solid magnesium alloy to shearing, which provides, as already said, worse results in terms of magnesium alloy homogeneity, on the other side.
  • the stirring system through which carrying out step d) allows to avoid the use of complex mechanical architecture of the apparatus for the preparation of semi-solid magnesium alloys and provide a product with the best homogeneity, or minor defects.
  • the step e) of discharging the semi-solid alloy in a quasi-liquid state from the apparatus can be carried out by pouring the content of the apparatus into another apparatus, for example in an injector or in a press.
  • Another object is a process for the preparation of objects or articles consisting of magnesium alloy comprising the following steps:
  • the object or article is then discharged from the press.
  • the present process provides objects with high shapes definition and, then consequently, of the shapes details.
  • step 3 the filling of the injector with the semi-solid magnesium alloy in a quasi-liquid state is performed under an atmosphere with an oxygen content not higher than 10% mol..
  • the apparatus (17) and the metallurgical processes of the present invention was developed for treating magnesium alloys comprising calcium and/or calcium oxide (CaO) affected by the problem of easy inflammability, in the absence of polluting protective gases. Furthermore, the apparatus and the processes allow the manufacturing of more homogeneous alloys and therefore products having minor micro-defects or more defined. However, it is evident that metals or metal alloys having minor problems of inflammability such as, for example, aluminum alloys, can be, equivalently, manufactured through the apparatus and the processes of the present invention.
  • An apparatus (17) as reported in Fig.1 is filled with 2000 g of alloy of the AZ91D series added with 1.5% of CaO.
  • the cited alloy is a commercially available alloy.
  • the apparatus was fed through a feeding control unit (not shown in the scheme).
  • the feeding control unit provided the conductive coil (3ter) with alternating current between 1000 and 3000 A with a variable frequency con in the range 300-1000Hz.
  • the apparatus (17) was closed through the door (1) and then the valve for nitrogen-type inert gas insufflation were opened, and simultaneously the seal valve is opened (not shown in the scheme) to promote atmosphere turnover within the furnace through the progressive evacuation of an oxygen-rich atmosphere.
  • a temperature of chamber of 680°-700°C was then reached within the apparatus (17), in order to promote the complete melting of the mass.
  • the complete melting of the mass occurred in about 40 minutes.
  • the furnace temperature was brought to the temperature of 580 °C and thermoregulated through auxiliary submerging probes (7) and auxiliary resistors of nominal power equal to 3kW, at the target temperature of 590 °C.
  • the sluice-gate (7) is closed through the control of the operating electrovalve. Therefore, the set-point temperature stabilization equal to 595 °C was reached.
  • valve was opened by nitrogen inert gas flushing (a pressure of 1,5-3 bar was reached in the chamber Z) in order to promote metal outflow from the nozzle (9).
  • the liquid mass was therefore cast into a pre-heated graphite ingot mold at 150°C for the examination of the final structure obtained.
  • the casting specimens are sectioned by a metallographic blanking machine, smoothed, and polished for the optical microscope examination.
  • a globular equiaxed structure was observed, as shown in Fig.4 .
  • Fig.5 the microstructure obtained for the same alloy by conventional melting, without using the device (17), and casting in the same graphite ingot mold by gravity, is reported.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP20211682.8A 2019-12-05 2020-12-03 Appareil et procédé métallurgique pour la préparation et l'alimentation des alliages semi-solides de magnésium dans un état quasi-liquide pour machines de coulée à injection Active EP3831509B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT102019000023061A IT201900023061A1 (it) 2019-12-05 2019-12-05 Apparato e processo metallurgico per la preparazione e l’alimentazione di leghe di magnesio semisolide in stato quasi-liquido per macchine di iniezione di colata.

Publications (2)

Publication Number Publication Date
EP3831509A1 true EP3831509A1 (fr) 2021-06-09
EP3831509B1 EP3831509B1 (fr) 2022-07-20

Family

ID=70009247

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20211682.8A Active EP3831509B1 (fr) 2019-12-05 2020-12-03 Appareil et procédé métallurgique pour la préparation et l'alimentation des alliages semi-solides de magnésium dans un état quasi-liquide pour machines de coulée à injection

Country Status (2)

Country Link
EP (1) EP3831509B1 (fr)
IT (1) IT201900023061A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113953498A (zh) * 2021-10-11 2022-01-21 中北大学 两级电磁驱动定量浇注的铸造方法
CN118308618A (zh) * 2024-06-07 2024-07-09 中北大学 一种颗粒增强铝基复合材料反射镜及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113842964B (zh) * 2021-09-18 2023-10-20 蚌埠学院 一种二元合金共晶熔化坩埚

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992015412A1 (fr) * 1991-03-11 1992-09-17 Alcan International Limited Appareil permettant de preparer une matiere composite coulable a matrice metallique
WO2002018072A1 (fr) * 2000-09-01 2002-03-07 Showa Denko K.K. Procede et appareil de coulee de metal, systeme de coulee et systeme de forgeage de pieces coulees
US20040129402A1 (en) * 2002-11-13 2004-07-08 Boulet Alain Renaud Magnesium die casting system
CN109666818A (zh) * 2018-12-06 2019-04-23 中北大学 一种碳材料与铝合金复合集成的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992015412A1 (fr) * 1991-03-11 1992-09-17 Alcan International Limited Appareil permettant de preparer une matiere composite coulable a matrice metallique
WO2002018072A1 (fr) * 2000-09-01 2002-03-07 Showa Denko K.K. Procede et appareil de coulee de metal, systeme de coulee et systeme de forgeage de pieces coulees
US20040129402A1 (en) * 2002-11-13 2004-07-08 Boulet Alain Renaud Magnesium die casting system
CN109666818A (zh) * 2018-12-06 2019-04-23 中北大学 一种碳材料与铝合金复合集成的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MITSURU ET AL.: "Suppression of ignition and burning of melted Mg alloys by Ca bearing stable oxide film", JOURNAL OF MATERIALS SCIENCE LETTERS, vol. 16, 1997, pages 1048 - 1050

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113953498A (zh) * 2021-10-11 2022-01-21 中北大学 两级电磁驱动定量浇注的铸造方法
CN113953498B (zh) * 2021-10-11 2023-02-10 中北大学 两级电磁驱动定量浇注的铸造方法
CN118308618A (zh) * 2024-06-07 2024-07-09 中北大学 一种颗粒增强铝基复合材料反射镜及其制备方法

Also Published As

Publication number Publication date
IT201900023061A1 (it) 2021-06-05
EP3831509B1 (fr) 2022-07-20

Similar Documents

Publication Publication Date Title
EP3831509B1 (fr) Appareil et procédé métallurgique pour la préparation et l'alimentation des alliages semi-solides de magnésium dans un état quasi-liquide pour machines de coulée à injection
EP2067547A1 (fr) Procédés pour mouler de manière centrifuge des métaux en titane hautement réactif
EP2207638B1 (fr) Dispositif de détection et de traitement de métal semi-liquide et son procédé d'utilisation
US20090133850A1 (en) Systems for centrifugally casting highly reactive titanium metals
US9839958B2 (en) Method for induction stirred, ultrasonically modified investment castings
JP2731787B2 (ja) 誘導加熱装置及び方法
US5819837A (en) Process and apparatus for melting and casting of metals in a mold
US3650311A (en) Method for homogeneous refining and continuously casting metals and alloys
JPH11156517A (ja) 高度の減圧状態のダイカスト鋳造装置及び鋳造方法
US3268958A (en) Slow pouring and casting system for ferrous and other metals
JPH08120357A (ja) 活性金属を含有する銅合金の製造方法
EP1292411B1 (fr) Production de materiau semi-solide a la demande pour pieces de fonderie
US20160312322A1 (en) Device and method for treating metallic materials
US3752216A (en) Apparatus for homogeneous refining and continuously casting metals and alloys
CN104878232A (zh) 一种铝铜铁准晶与碳化硅混合增强型铝基复合材料的制备方法
US20140083250A1 (en) Crucible and dual frequency control method for semi-liquid metal processing
US3273212A (en) Method of operating an electric furnace
CN117259739A (zh) 一种金属材料的真空感应熔炼浇注装置及成形方法
EP3822377A1 (fr) Procédé métallurgique pour la préparation d'alliages semi-solides de magnesium dans un état quasi liquide
Beall et al. Production of Titanium Castings
EP0293960A1 (fr) Procédé et dispositif pour la coulée du métal
US3470936A (en) Method for producing high purity copper castings
Eremin et al. Promising method of producing cast billets from superalloys
CN102398005B (zh) 一种内置式电磁搅拌装置及其使用方法
US4971294A (en) Induction heated sliding gate valve for vacuum melting furnace

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20201203

AK Designated contracting states

Kind code of ref document: A1

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

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 23/00 20060101ALI20220120BHEP

Ipc: C22C 1/02 20060101ALI20220120BHEP

Ipc: B22D 17/28 20060101ALI20220120BHEP

Ipc: C22C 1/00 20060101ALI20220120BHEP

Ipc: C22B 9/00 20060101ALI20220120BHEP

Ipc: B22D 39/06 20060101ALI20220120BHEP

Ipc: B22D 39/04 20060101ALI20220120BHEP

Ipc: B22D 39/00 20060101ALI20220120BHEP

Ipc: B22D 21/00 20060101ALI20220120BHEP

Ipc: B22D 17/30 20060101ALI20220120BHEP

Ipc: B22D 17/00 20060101ALI20220120BHEP

Ipc: B22D 2/00 20060101ALI20220120BHEP

Ipc: B22D 1/00 20060101AFI20220120BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20220315

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

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

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602020004098

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1505207

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220815

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20220720

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

Effective date: 20220720

Ref country code: RS

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: 20220720

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: 20221121

Ref country code: NO

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: 20221020

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: 20220720

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: 20220720

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: 20220720

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: 20220720

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: 20220720

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1505207

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220720

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

Effective date: 20220720

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: 20221120

Ref country code: HR

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: 20220720

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: 20221021

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602020004098

Country of ref document: DE

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

Ref country code: SM

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: 20220720

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: 20220720

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: 20220720

Ref country code: CZ

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: 20220720

Ref country code: AT

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: 20220720

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: 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: 20220720

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: 20220720

26N No opposition filed

Effective date: 20230421

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

Ref country code: AL

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: 20220720

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20221231

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: 20220720

Ref country code: LU

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

Effective date: 20221203

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: 20221203

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: 20221231

Ref country code: BE

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

Effective date: 20221231

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

Ref country code: DE

Payment date: 20231010

Year of fee payment: 4

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

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: 20220720

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

Ref country code: MK

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: 20220720

Ref country code: IT

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: 20220720

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: 20220720

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: 20220720

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: 20220720

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

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: 20220720

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: 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: 20220720