Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B32/00—Carbon; Compounds thereof
  • C01B32/90—Carbides
  • C01B32/914—Carbides of single elements
  • C01B32/949—Tungsten or molybdenum carbides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
  • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
  • B01J2/04—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
  • B01J2/18—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic using a vibrating apparatus
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/10—Solid density
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
  • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
  • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
  • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide

Definitions

• the present invention relates generally to preparation of a powder, by thermo-centrifugal atomization.
• the invention also relates to spherical tungsten carbide powder.
• the invention further relates to a device for implementing the method.
• SU 1 802466 discloses a method of preparation of powder of
• refractory material which includes processing of bars with bar supply to the melting zone with a pusher mechanism, melting of bars with plasma, teeming of a liquid-alloy with plasma stream of a second plasmatron, to pan nodulizer and centrifugal atomization.
• SU 503688 discloses an installation for preparation of spherical materials comprising a vacuum vessel with a rotary graphite crucible inside, with an inbuilt movable unmeltable tube wire which delivers powder.
• SU 503688 shows a method of preparation of spherical materials which includes an electrical discharge between a rotary graphite crucible being an anode and a tungsten unmeltable sleeve cathode which delivers the original substance to the crucible heated under the action of electric arc.
• a liquid alloy which rises under the influence of centrifugal force, and is pushed out of the crucible, where after it flies and solidifies to drops and crystallizes in flight.
• the process is to be carried out in an inert-gas medium - argon.
• RU 2301 1 33 discloses a method and a device for preparation of
• the device comprises a rotatable crucible in a chamber in which the material is melted. Nitrogen is used as inert gas. Droplets are formed when the crucible rotates. Heating is provided by plasma arc discharge. The formation of a "beard" is avoided by moving the plasma stream. The heat output distribution from plasma can be varied from the edge of the crucible to the internal surface of the crucible in order to avoid the formation of beard.
• a spherical tungsten carbide powder wherein the material has a microhardness higher than 3600 kgf/mm 2 , and that the powder has an apparent density from 9.80 to 1 1 .56 g/cm 3 .
• a method for the manufacture of a powder comprising the steps: a) providing a chamber comprising a rotatable crucible, b) adding material into said rotatable crucible, c) melting the material, wherein heating at least partially is conducted using a plasma arc discharge, d) rotating the crucible to atomize the molten material under centrifugal force to form liquid droplets, with subsequent cooling of the droplets to obtain a powder, wherein the material added into said rotatable crucible is heated to a temperature above 40% of the melting temperature of the material before it enters the crucible.
• a device suitable for manufacturing a powder comprising a chamber, a lid, a movable plasma torch, a cylindrical cooled crucible, a collecting device for the manufactured powder, wherein the device comprises a heating device for material to be added to the crucible.
• Advantages of the invention include that it is possible to reduce the current of the plasma discharge required for melting the stock, but also to securely keep the liquid-alloy temperature higher than its melting point. As a result the heat losses are decreased, the liquid-alloy becomes a homogenous composition, and the spherical powder obtained during atomization becomes homogeneous in its composition and structure.
• a further advantage is that the distribution of the particles size becomes narrower, so that the yield of a desired particle size increases.
• the energy consumption is more than 3.8 times lower compared to manufacture of spherical powder with induction heating.
• Fig. 1 presents an installation scheme for an embodiment of the preparation of refractory material powder.
• 15 denotes inlet and outlet of a cooling medium.
• Fig. 2 presents the scheme of an embodiment of the crucible of the
• breaking load is used in throughout the description and the claims denote the stress which, when steadily applied to an individual spherical powder particle is just sufficient to break or rupture it.
• the breaking load is measured by pressing a spherical powder particle between two flat surfaces with an increasing force until the spherical powder particle breaks or collapses.
• microhardness is used in throughout the description and the claims to denote the hardness testing of materials with low applied loads.
• microindentation hardness testing Another term is "microindentation hardness testing.” In microindentation hardness testing, a diamond indenter of specific geometry is impressed into the surface of the test specimen using a known applied force commonly called a test load. The microhardness is always measured using the Vickers hardness test HV 0.1 according to EN-ISO-6507 ( ISO 6507-1 :2005).
• spherical in connection with a powder does not mean that all powder particles are perfect spheres, it means that most particles, such as more than 90%, preferably 95%, most preferably 99% of the powder particles are essentially spherical.
• Spherical particles can deviate from a perfect geometric sphere but as long as they are essentially spherical they are denoted spheres.
• refractory materials which can be utilized include but are not limited to tungsten and molybdenum, carbides of refractory metals, mixtures of carbides of refractory metals, for example, an eutectic mixture of tungsten carbide (WC-W 2 C); borides, nitrides, and carbonitrides.
• An eutectic mixture of tungsten carbides (WC and W 2 C) with a content of carbon (C) of 3.8 - 4.2 wt% has high resistance against abrasive and chock wear. It is a part of compositions, used for manufacturing tools and abrasive resistant coatings within for instance building engineering, mining equipment, and chemical equipment, working in contact with hard materials.
• a spherical tungsten carbide powder wherein the material has a microhardness higher than 3600 kgf/mm 2 , and wherein the powder has an apparent density from 9.80 to 1 1 .56 g/cm 3 .
• the material has a microhardness from 3600 to 4200 kgf/mm 2 . In an alternative embodiment the material has a microhardness from 3600 to 4800 kgf/mm 2 .
• the powder comprises form 3.8 to 4.2 wt% of
• the powder contains less than 0.1 wt% iron (Fe).
• the tungsten carbide is an eutectic mixture of W 2 C and WC.
• the diameter of the spheres is from 20 to 1 800 ⁇ .
• a method for the manufacture of a powder comprising the steps: a) providing a chamber comprising a rotatable crucible, b) adding material into said rotatable crucible, c) melting the material, wherein heating at least partially is conducted using a plasma arc discharge, d) rotating the crucible to atomize the molten material under centrifugal force to form liquid droplets, with subsequent cooling of the droplets to obtain a powder, wherein the material added into said rotatable crucible is heated to a temperature above 40% of the melting temperature of the material before it enters the crucible.
• the material added into said rotatable crucible is heated to a temperature from 40% to 80% of the melting temperature of the material before it enters the crucible.
• the above described tungsten carbide powder is manufactured by the method.
• the material added to the crucible comprises
• the material added to the crucible comprises 3.7-3.9 wt% carbon (C).
• a gas comprising at least one gas selected from the group consisting of argon, helium, and nitrogen is used in said chamber.
• nitrogen is used in said chamber.
• the chamber is cleaned from detrimental oxygen by vacuum pumping the chamber and filling it with a gas.
• a gas mixture is used to fill the chamber, whereas another gas mixture is used as plasma generating gas. Both the gas in the chamber and the plasma generating gas are selected as described above.
• the plasma arc first is directed towards the centre of the crucible and thereafter is directed towards the edge of the crucible. In one embodiment the plasma arc alternating is directed towards the centre of the crucible and towards the edge of the crucible.
• the temperature of the molten material is kept above the melting temperature of the material. In one embodiment the temperature of the molten material is more than 20°C above the melting temperature of the material. In one embodiment the temperature of the molten material is from 20 to 1 00°C above the melting temperature of the material.
• the crucible rotates at a rotational speed of from 500 to 20000 rpm.
• said powder comprises tungsten carbide. In one embodiment said powder comprises an eutectic mixture of WC and W 2 C phases.
• said crucible is water cooled.
• powder includes delivery of material of the required composition to a rotary crucible located in the chamber, melting of the stock with plasma arc discharge between the crucible being an anode, through the material, and plasmatron cathode with the usage of nitrogen as a plasma-supporting gas, atomization of a liquid-alloy in gaseous atmosphere under the influence of centrifugal force forming liquid-alloy drops and drops crystallization at cooling.
• the anode and cathode are changed so that the crucible is the cathode and the plasmatron an anode.
• Melting of material in the device is made at least partially with plasma directly in the crucible. Direct heating of a hard stock to the temperature exceeding smelting point requires considerable power which leads to an increase of costs for conduction of the process and reduces productivity.
• Pre-heating of original stock in a heater above the temperature 0.4* Tmel before its delivery to the crucible makes it possible not only to reduce current intensity of plasma discharge required for melting the stock, but also to securely keep the liquid-alloy temperature higher than its melting point. As a result heat losses are decreased, the liquid-alloy becomes a homogenous composition, and the spherical powder obtained during atomization becomes homogeneous in its composition and structure. With the same current intensity of plasma discharge pre-heating of the stock provides increased productivity of the atomization process.
• Argon, helium, nitrogen or their mixture are in one embodiment used as a gas.
• the stock contains at least one refractory material.
• the crucible is to be rotated at the speed necessary for formation of drops of spherical granules of required particle composition at crystallization.
• Rotary speed of the crucible is in one embodiment from 500 to 20000 rpm.
• the heating device for delivery of original stock to the crucible is in one embodiment made as a tray with a tube heater around or made as a tube heater, for example from composite material carbon-carbon. Connection angle of the heated device for delivery of original stock to the crucible is more than the angle of natural slip of the stock.
• the crucible is in one embodiment made of copper, an insert located on the inside wall of the crucible is made, for instance, of composite material carbon-carbon.
• the material is added to said crucible by a vibrating feeder. In one embodiment the material is added to said crucible by a rotating feeder. Combinations of a vibrating feeder and a rotating feeder are
• the crucible vibrates.
• a first crucible vibrates.
• a third aspect there is provided device suitable for manufacturing a powder, comprising a chamber, a lid, a movable plasma torch, a cylindrical cooled crucible, a collecting device for the manufactured powder, wherein the device comprises a heating device for material to be added to the crucible.
• said heating device is a tray comprising a heater.
• said heating device is a tubular heater. In one embodiment said heating device is made of a carbon material.
• the device further comprises a feeding mechanism adapted to feed the material to said crucible by vibrations. In one embodiment the device further comprises a feeding mechanism adapted to feed the material to said crucible by rotation. Combinations of vibrations and rotation are also encompassed.
• the crucible is adapted to vibrate.
• powder contains cylindrical chamber with a cover where along the chamber axis a feed mechanism for delivery of original stock is located, with a bottom door having a device for powder unload, atomization device, located in line with the feed mechanism inside the chamber and made as cooled rotary current- conducting crucible, arc plasmatron fixed at an angle to the crucible's rotation axis with the possibility for its alternation.
• One embodiment of the device depicted in fig 1 comprises a cylindrical chamber (1 3) with a sloped bottom and a cover.
• Plasmatron (5) and feed mechanism (1 0) are mounted into the cover in different directions of the axis.
• the plasmatron (5) is connected to the mover (4).
• the feed mechanism is connected to the storage hopper (8) with original stock (7) outside the chamber having a dosing mechanism (9).
• a spaying crucible (2) fixed on a rotary mechanism (1 ) is located in the chamber in line with it a spaying crucible (2) fixed on a rotary mechanism (1 ) is located.
• Heated device for delivery of original stock (1 2) to the crucible (2) located in the chamber (1 3) is connected to the feed mechanism (1 0).
• Heating device may comprise a tray with tube heater (6) around.
• the tube heater (6) is in one embodiment made of a composite material carbon-carbon, and serves in one embodiment as a heating device for delivery of powder in case of absence of a tray (1 1 ).
• a hopper (1 4) In the lower part of the sloped bottom of the camera (1 3) there is located a hopper (1 4) connected to it for collecting powder.
• the device is operated according to the following.
• Original stock (7) in the form of grit from the storage (8) is loaded to the dosing mechanism (9).
• the installation is pressurized, vacuumed and filled with the required gas to the atmospheric pressure or the pressure necessary for preparation of powder of required refractory material.
• rotary mechanism (1 ) With the help of rotary mechanism (1 ) the required speed of crucible (2) rotation is set.
• the plasma arc is started.
• Anode spot of the arc is concentrated on the bottom of the crucible (2) .
• the delivery of the powder is turned on.
• the grit from the dosing mechanism (9) through feed mechanism (1 0) goes to the tray ( 1 1 ) heated with the help of tube heater (6) made of, for instance, carbon-carbon material, up to 3000°C. Passing the tray particles of grit are heated above 0.4*Tmel and poured to the rotating crucible (2) where they melt under the influence of plasma arc. Tmel denotes the melting temperature.
• the liquid-alloy under the influence of centrifugal force is forced to the side face of the crucible (2) covered with heat-insulating insertion (1 6). As new portions of grit are being delivered the amount of liquid-alloy increases and it rises along the side face.
• Anode spot of plasma arc is risen after the liquid-alloy with plasmatron mover (4) and concentrated on the edge of the crucible (2).
• the liquid-alloy is drawn out over the edge of the crucible by the centrifugal force and falls through the gas of the chamber where is solidifies during the fall and falls down from on the bottom of the chamber in the form of small spheres.
• Prepared powder is poured to the storage hopper (1 4) located in the lower part of the chamber. 66]
• the placement of a conductive material at the bottom of the crucible protects the crucible from burn-through.
• Placement of heat-insulating insertions of material inactive to melting on face sides of the crucible not only considerably reduces electro thermal loads on the crucible, but also considerably reduces total heat losses of material melting process. As a result, operational life of the crucible is prolonged and energy costs of the process are reduced. [0067] Placement of the plasmatron and storage hopper with dosing mechanism at different directions of the cylindrical chamber axis makes it possible to promptly and accurately move the anode spot along the side face of the crucible after the rising liquid-alloy and to eliminate formation of hardened liquid-alloy on the edge (beard) of the crucible which leads to stabilization and homogenization of liquid-alloy and improvement of properties of the powder prepared.
• refractory metals such as tungsten and molybdenum
• carbides of refractory metals such as tungsten and molybdenum
• mixture of carbides of refractory metals for instance, cast tungsten carbides (WC-W 2 C)
• borides, nitrides and carbonitrides, carbonitroborides and other refractory metals compounds such as tungsten and molybdenum
• the breaking load of a spherical tungsten carbide alloy particle according to the invention is larger than 20 kgf. In one
• the breaking load of a spherical tungsten carbide alloy particle according to the invention of from about 20 to about 27 kgf.
• the breaking load of a spherical tungsten carbide alloy particle according to the invention of from 20.8 to 27.2 kgf. The measurements of the breaking load is repeated 20-30 times and an average value is calculated.
• the hardness of spherical tungsten carbide alloy is the highest of all achieved for carbides of metals and concedes only to hardness of a diamond and the boron carbide.
• Spherical tungsten carbide alloy present product 3600 - 4800
• Atomization of tungsten with melting point 3380°C was carried out on an installation for centrifugal atomization equipped with the mechanisms of suggested invention and without them. Atomization was carried out in a pure nitrogen atmosphere.
• the crucible was used with the insertions suggested in the invention and without them. Diameter of an open edge of the crucible was 60mm.
• the crucible rotary sped was 5000 rpm.
• the current of the plasma arc was alternated within the limits from 800 to 1500 A, voltage on the arc was 70- 85 V.
• Preliminary heating of grit was carried out by means of contact of moving original grit with the trough surface of tungsten with a tube neater around.
• the heater is made of composite material carbon-carbon and it was heated up to 2500°C with passing current from an autonomic electrical power source. Outlet temperature of the grit from the heater was 1 850 - 1 950°C.
• Table 1 The results of atomization are given in Table 1 . Atomization of tungsten with the suggested method on the suggested device provides increase of process productivity, stabilization of properties of spherical powder obtained and considerable reduction of current and thermal loads on the crucible which prolongs its operation life.
• Cast tungsten carbides (eutectic mixture of tungsten carbides WC-W 2 C) was atomized at centrifugal atomization installation at the crucible rotary speed 2850 rpm.
• a grit of crushed cast tungsten carbide with particles size less than 1 mm was used.
• Content of carbon in original grit was 4,0 % of its mass, average microhardness of crushed cast tungsten carbide ⁇ - 1 800 HV.
• the current of the plasma arc was alternated within the limits from 800 to 1 500 A, the voltage on the arc was 70-85 V.
• Preliminary heating of cast tungsten carbide grit was carried out by means of contact of moving original grit with inner surface of tube heater.
• the heater is made of composite material carbon- carbon and it was heated up to 2200°C with passing current from an autonomic electrical power source. Outlet temperature of the grit from the heater was 1 850 - 1 900°C. Atomization was carried out in pure nitrogen atmosphere with open edge diameter 62mm. Also comparative atomization of cast tungsten carbide grit by the known method was carried out. Atomization results are given in Table 2.
• Atomization of cast tungsten carbide with the suggested method on the suggested device provides increase of process productivity, stabilization of properties of spherical powder obtained and considerable reduction of current and thermal loads on the crucible which prolongs its operation life.
• Micro hardness of cast tungsten carbide powder prepared by the declared method is within the range 3600-4200 HV, which is 1 .2-1 .3 times as higher than microhardness values of cast tungsten carbide powder prepared by the known method.
• the resulting powder had a particle size ranging from 50 microns to 800 microns.
• Micro-hardness of fused tungsten carbide powder produced by the method was in the range of 3400-3550 kgf/mm 2 . That is 1 .25-1 .27 times the value of the micro-hardness of tungsten carbide powder produced in an argon atmosphere. Increase in micro-hardness significantly increases the material resistance to abrasion.
• Atomization in a helium atmosphere As plasma gas mixture helium and nitrogen in a ratio of 1 : 1 was used. Input raw material had a carbon (C) content of 3.90 - 3.92 wt%. The raw material was heated to 1 050 - 2000°C before entered to the rotating crucible. Atomization was performed at the same rotational speed, as in Example 3. Atomization was performed at the maximum value of electric current plasma arc i.e. no more than 1 200 A.
• the resulting powder particles were spherical in shape with virtually no internal porosity.
• Anode arc spot was raised after the melt and focused on the inner edge of the crucible, which provided a complete absence of uncontrolled formation of solid carbide - "beard" - on the edge of the crucible.
• the apparent density of the powder was 9.80-1 1 .5 g/cm 3 , which confirms the substantial decrease in the level of porosity and impurity content in the resulting material compared with material from example 3.
• claimed method in a helium atmosphere using plasma gas helium-nitrogen resulted in the range of 3600-4800 kgf/mm 2 . That is 1 .20-1 .27 times the micro hardness of tungsten carbide powder produced in a nitrogen atmosphere.
• the increase of the micro hardness significantly increases the material resistance to abrasion and is a determining parameter in the choice of powder as a filler for wear-resistant coatings.
• Atomization was performed of crushed nibs (grains) of raw material containing 3.8 - 3.9 wt% fixed carbon, 0.09 - 0.1 0 wt% free carbon and 1 .1 - 1 .2 wt% of other impurities (chromium, vanadium, niobium, cobalt, etc.) and 0.5, 0.3; 0.15 and 0.1 wt% iron content and other impurities. Atomization regimes was maintained as in Example 4. The grit were preheated to 1 050- 2000°C.
• the purity of the raw material define the properties of the manufactured powder and may give additionally increased microhardness to the material.
• the micro hardness of the produced spherical powder varied from 3600 kgf/mm 2 , (for iron content less than 0.1 0 wt%, free carbon less than 0.05 wt%, other impurities not exceeding 1 .0 wt%) up to 4800 kgf/mm 2 (for iron content less than 0.06 wt%, free carbon less than 0.02 wt%) and the content of other impurities less than 0.50 wt%.
• the apparent density ranged from 9.80 to 1 1 .5 g/cm 3 .
• a critical value, which determines the characteristics of the material is that the iron content is less than 0.1 wt%.
• the apparent density of the powder, with iron content over 0.1 wt% is 0.3 to 0.1 units (g/cm 3 ) lower than the apparent density of powder with an content less than 0.1 wt%.
• the claimed set of essential features provides fused tungsten carbide, a spherical particle with a high micro hardness, high resistance to crushing forces and high apparent density of the powder.
• the above properties of the powder produced contribute to high a resistance to abrasion and impact wear.
• Atomization using carboboride tungsten nibs (grain). This is a mixture of carbide and boride of tungsten. I.e. it comprises W 2 C, WC, and W 2 B 5 . 50% of W 2 C + WC, and 50% of W 2 B 5 .
• the rotational speed of the crucible was about 5000 rpm.
• the grit was pre-heated to 1 800°C.
• the arc current was 1 000 A.
• the atomization was performed on a device according to the description. Helium was used to fill the device, and a mixture of 50% argon + 50% helium was used as plasma generating gas. The plasma was directed towards the inside of the crucible and towards the edge of the crucible in order to minimize the formation of beard.
• the size of the particles are from 20-1 200 ⁇ .
• the particles were porous
• the porosity was determined by hydrostatic weighing.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Carbon And Carbon Compounds (AREA)
• Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Priority Applications (9)

Applications Claiming Priority (4)

Publications (1)

Family

ID=44119109

Family Applications (1)

Country Status (11)

Cited By (3)

Families Citing this family (26)

Citations (7)

Family Cites Families (5)

• 2011
  • 2011-05-18 CA CA2918127A patent/CA2918127C/en active Active
  • 2011-05-18 CA CA2799342A patent/CA2799342C/en active Active
  • 2011-05-18 EP EP16151793.3A patent/EP3090985B1/en active Active
  • 2011-05-18 DK DK11721505.3T patent/DK2571807T3/en active
  • 2011-05-18 EP EP11721505.3A patent/EP2571807B1/en not_active Not-in-force
  • 2011-05-18 CN CN2011800249127A patent/CN103068731A/zh active Pending
  • 2011-05-18 ES ES16151793T patent/ES2925034T3/es active Active
  • 2011-05-18 WO PCT/EP2011/058073 patent/WO2011144668A1/en not_active Ceased
  • 2011-05-18 JP JP2013510620A patent/JP5815684B2/ja not_active Expired - Fee Related
  • 2011-05-18 CN CN201610055670.2A patent/CN105731462B/zh not_active Expired - Fee Related
  • 2011-05-18 ES ES11721505.3T patent/ES2599369T3/es active Active
  • 2011-05-18 AU AU2011254574A patent/AU2011254574B2/en not_active Ceased
  • 2011-05-18 US US13/697,535 patent/US8784706B2/en active Active
  • 2011-05-18 PL PL11721505T patent/PL2571807T3/pl unknown
  • 2011-05-18 PT PT117215053T patent/PT2571807T/pt unknown

Patent Citations (7)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events