US20070074846A1 - Continuous casting method - Google Patents
Continuous casting method Download PDFInfo
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- US20070074846A1 US20070074846A1 US10/547,607 US54760704A US2007074846A1 US 20070074846 A1 US20070074846 A1 US 20070074846A1 US 54760704 A US54760704 A US 54760704A US 2007074846 A1 US2007074846 A1 US 2007074846A1
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- strand
- coolant
- cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/12—Accessories for subsequent treating or working cast stock in situ
- B22D11/124—Accessories for subsequent treating or working cast stock in situ for cooling
- B22D11/1241—Accessories for subsequent treating or working cast stock in situ for cooling by transporting the cast stock through a liquid medium bath or a fluidized bed
Definitions
- the invention concerns the continuous casting of metals of all kinds where liquid metal is used as coolant for directly cooling the strand and a device for such a cooling method according to the introducing parts of claims 1 and 9 , respectively.
- the U.S. Pat. No. 3,430,680 A discloses a cooling method, with a vertically oriented pipe, through which the coolant flows due to gravity.
- a nozzle is centrally inserted into this pipe, the metal to cast runs through this nozzle in a liquid state and the same velocity as the coolant, in order to avoid any shear forces or other disturbances of the liquid-liquid contact surface.
- the metal to cast solidifies from this contact surface towards the centre of the strand and is finally hard and tough enough to be separated from the coolant. Beside the enormous difficulties to come to identical velocities for two separate liquids in a stream consisting of two components flowing in purely a laminar state, the cooling efficiency is rather poor for exactly this reasons!
- the U.S. Pat. No. 3,874,438 A discloses a cooling bath of liquid metal which has its surface underneath the (shape providing) crucible outlet.
- the temperature situation is very tricky, the melt reaches its solidification point at the area of the outlet, shortly before entering the cooling bath.
- the cooling bath is provided in a cylinder and cooled by heat transfer through the side walls of the cylinder.
- Special provisions, namely an additional recipient for cooling liquid are provided for keeping the surface of the coolant at the chosen height. It is extremely difficult to keep the solidification temperature within the outlet, one has to take into account that the strand is still liquid over the greatest part of its cross section, that thermal energy is set free by the solidification and that the cooling process along the strand is changing during the cast, because the coolant gets warmer and warmer.
- the U.S. Pat. No. 5,344,597 A discloses a very sophisticated process for the manufacturing of thin sheets of steel out of the liquid state: A thin layer of molten cast is brought to the surface of a coolant consisting of molten metal (e.g. led) and swims on it to a roller bed where it is kept, guided and moved away. The coolant comes into contact with the lower side of the cast only. The coolant is transferred from the surface region of the bath to a cooler and brought back to the bottom area of the bath by a pump. Due to the one-side-only cooling, due to the fact that the coolant is underneath the cast and due to the parallel movement of the sheet to the surface, the heat transport and therefore the cooling is rather poor and asymmetrical, leading to stress and distortions of the product.
- a coolant consisting of molten metal (e.g. led) and swims on it to a roller bed where it is kept, guided and moved away.
- the coolant comes into contact with the lower side of the cast only.
- U.S. Pat. No. 2,363,695 A shows an interesting idea: Molten material, in most cases steel is fed through an thermally insulated pipe with U-shape to a nozzle which is directed upwards in a vessel filled with liquid led as coolant and then drawn vertically upwards.
- the coolant is kept in the vessel without stirring or agitating, therefore only moved by the strand and the convection movement due to temperature differences, meaning without remarkably movement. This, and the co-movement of the strand and the led raising due to its warming brings problems with uniform cooling and long lasting operation cycles.
- SU 863 161 A discloses the casting of a pipe in two steps: In the first step, a water cooled mould is used to produce a thin layer of solidified metal on the surface of the strand, in the second step, the strand is, along a curved path, further cooled by direct contact with liquid metal. The liquid metal is kept in a ring-like slit around the cast and is cooled indirectly with water. Beside problems with the toroidal form of the mould, problems with the uniformity of complicated heat transfer exist: The heat goes from the molten core through the solidified surface area to the liquid metal which is used as coolant, further into the wall of the mould and into the water which circulates in channels in this wall. It is nearly impossible to come to a defined and uniform cooling scheme with such an arrangement.
- U.S. Pat. No. 3,128,513 A discloses a casting process where molten salt is used as coolant. Therefore, the strand has a higher density than the coolant and sinks to the bottom of the vessel. The pressure of the liquid interior of the strand is used to form the cross section of the strand, but this also brings a lot of problems and even dangerous risks (outbreak of molten metal, etc.). The coolant is simply kept in the vessel without any agitating, in some embodiments, where movable moulds for the strand are used, the contact between the surface of the strand and the coolant is hampered.
- JP 62101353 A discloses a conventional casting process for pipes.
- a hollow core is inserted at the nozzle.
- the hollow core is cooled on its inside with molten metal instead of water, in order to prevent any danger of direct contact of water and molten metal (steam explosion) in case of an accident. There is no direct contact between the strand and the liquid metal.
- the casting melt is cooled indirect by a mould as far as it is necessary to solidify a shell strong enough to carry the stresses at the mould exit and to resist a breakout of liquid casting melt.
- the strand is cooled directly by water realised as film cooling or as spray cooling or a two phase cooling with water and air.
- the direct cooling stage ensures the solidification of the liquid core of the strand.
- the second cooling stage is followed by a third one, a submerging in a water bath or a soft cooling stage by a flow of air.
- a heated mould is used in the so called Ohno continuous casting process (OCC), the mould temperatures are higher than the melting point of the cast material in order to prevent nucleation at the mould wall and to ensure axial directional solidification.
- OCC Ohno continuous casting process
- the necessary heat removal for this process is realised by direct cooling at only one position at a defined distance from the mould exit.
- Strands produced in this process are always single crystals with a very smooth surface. But the production of single crystals is not the aim of usual continuous casting, as the produced strands should be formable by rolling, extruding or forging or other cold or hot working process with isotropic properties.
- the EP 063 832 discloses a concept for the “casting” of a probe which gets solidified in its mould and is therefore no real casting process, even less a continuous casting process.
- the DE 41 27 792 discloses to cast a problematic probe into a pre-heated mould with special geometric properties, where a special form of solidification takes place. This is a casting process, but has nothing to do with a continuous casting process.
- the invention proposes to use one or more jets or streams of liquified metal or ionic liquids as cooling medium with turbulent flow and, advantageously, an insulated mould. This makes sure that no water steam film exists at the surface of the strand and that the coolant hits the strand in a defined way after a defined treatment. This guarantees that the cooling properties and characteristics are well defined and controllable.
- Ionic liquids or designer liquids is the name for a group of salts composed of organic kations and mostly inorganic anions which have a melting point below 100° C. They may be used with the invention as long they do not decompose at the maximal working temperature of the process or react with the strand under the given circumstances. In the following description, they are in most cases not mentioned expressively, but always included when the term “molten metal” or “coolant” or the like is used.
- the mould consists preferably of an insulating mould, which enables a solidification of the strand shell in the near vicinity of the mould exit. This is responsible for the prevention of many surface defects and the prevention of an unwanted subsurface layer. Solidification occurs by the influence of the direct cooling.
- the direct cooling uses a liquid metal like lead, tin, bismuth, gallium, indium or alloys of them as well as other liquid metals or alloys being liquid below the solidification temperature of the cast metal or alloy.
- the feature of direct cooling in continuous casting with liquid metal ensures a very constant cooling behaviour, prevents, it this is wanted, oxidation of the new formed strand surface and eliminates the danger of explosions as a consequence of the use of water as coolant fully. Furthermore the hot tearing and cold tearing may be eliminated by the choice of the cooling metal and cooling metal temperature at the cooler entry and cooler exit.
- the produced strand is substantially free of the well known subsurface layer usually found in conventional continuous casting processes.
- the grain structure of the produced strands can be controlled by adjusting the coolant temperature.
- oxidation of the surface may be advantageous, because it gives a very well defined border to the coolant with respect to reactions and interactions between the coolant and the strand.
- air or oxygen may be inserted at the downstream end of the mould, the mould exit (coquille), but upstream of the place(s) where the jet(s) hit the surface of the strand.
- a very simple way to achieve this is (when vertically casting occurs) to let a small annular slot between the coquille and the coolant distribution unit which slot has a connection to the ambient air. If necessary, more sophisticated supplies may be used.
- the liquid metal as coolant can be directed onto the hot strand surface as continuous film or jet or as drops.
- the coolant distribution unit can be realised by a continuous slot around the strand perimeter but also may consist of slotted segments at different angles to the strand withdrawal direction.
- the mould itself can have any cross section and be cylindrical or conical getting wider in casting direction. For lower casting rates it is also possible to realise the direct cooling step by submerging the coolant distribution unit and the hot strand into a bath of liquid cooling metal.
- the invention was successful applied for casting of copper, magnesium and aluminium showing that it can applied for all non-ferrous metals and alloys as well as for steel.
- FIG. 1 a mould according to the invention in a vertical cross section
- FIG. 2 an other embodiment of the invention in a similar view
- FIG. 3 a third embodiment of the invention in a similar view
- FIG. 4 a fourth embodiment of the invention in a similar view
- FIG. 5 a fifth embodiment of the invention in a similar view
- FIG. 6 a sixth embodiment of the invention in a similar view
- FIG. 7 a principal view of the cooling system
- FIG. 8 a principal view of an strand cooler.
- FIG. 1 shows a strand with vertical withdrawal direction.
- the cooling is done in a totally new way, using a complete filled strand cooler which is, in some ways, operated similar to heat exchanger known from chemical industry.
- the melt 1 is sucked from the tundish 2 (which can be heated) into the mould 3 and solidifies at the mould exit since the strand 4 is cooled by a liquid metal coolant 8 over the entire length of a cooling unit.
- the coolant 8 fills the entire gap-like room 11 between the surface of the strand 4 and the inner surface of a pipe 12 which surrounds the strand.
- the temperature of the strand 4 decreases during its movement through the strand cooler until its end is reached.
- a strand cleaning unit 7 ensures the slip off of the coolant from the strand 4 .
- the cold coolant is fed into the strand cooler 5 and is distributed as it is required for the cast shape by a coolant distribution unit 6 .
- the coolant 8 leaves the coolant distribution unit 6 either through a slit which has the form of a ring (depending on the cast shape) and is directed to the surface of the strand 4 or through a plurality of openings or nozzles which are arranged along a closed line and are directed to the surface of the strand too.
- the variant with the slit forms a closed, conical “wall” of flowing coolant 8 , the variant with the openings a plurality of jets 10 of coolant 8 .
- the coolant 8 takes up heat from the hot strand 4 , thereby heating up.
- the coolant collecting unit 9 ensures the required coolant distribution along the strand perimeter. This process type enables highest cooling rates but needs an accurate pressure control in the coolant feed.
- the hydraulic diameter “D H ” of an annulus and of noncircular channels is equivalent to the diameter of a circle with the same cross section. Hydraulic diameters for different shapes of the cross section are listed for example in Robert H. Perry (Ed.): “Perry's Chemical Engineers' Handbook” (Sixth Edition 1984). Pages 5-25 and 5-26 of this publication are hereby incorporated by reference.
- the point, where laminar flow turns over to turbulent flow is not only dependent on the cross-section of the channel but also on the shape of the cross sectional area.
- Reynolds numbers which have, by definition, no dimension
- the flow is usually turbulent.
- the Reynolds number in case of a “wall jet” should be at least 15 000 and preferably over 25 000. It has to be mentioned, that the slit in the coolant distribution unit 6 is not cylindrical, but conical, but the differences are small enough to be disregarded.
- the coolant distribution unit 6 comprises several individual parts, which can be adjusted against each other preferably by means of a thread, in order to change the width of the conical slits in the coolant distribution unit 6 . This enables the operator to change easily the width of the slits, and thus the Reynolds number, even during operation.
- the change from laminar to turbulent flow occurs with such a geometry at a point between 2 600 ⁇ Re ⁇ 4000, depending of hard to define second order effects.
- the Reynolds number in case of such individual jets should be therefore at least 5 000, preferably over 7500.
- the kinematic viscosity may be found in the data sheets or chemical or metallurgical textbooks, the velocity is given by the known cross section area (in m 2 ) of the slit and the volume of coolant (in m 3 ) passing per second, the width of the slit (which is half its hydraulic diameter) is known from the construction, therefore, with this description at hand, there exists no problem for the man skilled in the art to come to the turbulent flow which is used by the invention.
- FIG. 2 represents a process type, in which the cast strand 4 may be cooled softer than in the process type of FIG. 1 .
- the casting melt 1 is sucked from the tundish 2 (which can be heated) into the mould 3 and solidifies at the mould exit as the heat is withdrawn by the coolant in direct contact with the strand 4 .
- a cooling box 13 is provided around the area where the strand 4 solidifies during its movement. The cooling box 13 serves to collect the hot coolant.
- a strand cleaning unit 7 is fixed, it ensures that no coolant (in a technical sense) is remaining on the strand surface.
- the “cold” coolant is distributed along the strand perimeter as required for the cast strand shape by a coolant distribution unit 6 . After getting in contact with the strand 4 , the now hot coolant flows down to the bottom of the cooling box 13 and then leaves it through the coolant outlet.
- FIG. 3 represents a casting process according to the invention, and mould, respectively, with a heat withdrawal rate, which is substantially higher than that of the aforementioned casting processes shown in FIG. 2 . Due to two consecutive cooling steps a high rate of heat flow away from the strand 4 to the coolant 9 is achieved. Thereby separate coolant feeds are provided for each cooling step.
- the casting melt 1 in the tundish 2 (which can be heated) is sucked into the mould 3 and solidifies at the mould exit.
- the axial heat removal in the strand 4 is, in a first cooling stage, similar to that according to FIG. 2 but gets increased by a second cooling stage in an additional cooling unit, which is similar to the cooling unit shown in FIG. 1 .
- the device for the first cooling stage consists of a coolant distributor 6 which produces a coolant film 14 .
- the device for the second cooling stage consists of a coolant distribution unit 6 ′ and an attached pipe 12 , acting as a heat exchanger tube, which ensures a higher heat removal than cooling stage one.
- the strand 4 is cleaned (technical clean) from the remaining coolant 8 on the surface by the cleaning unit 7 .
- a cooling or collecting box 15 encloses the whole cooling unit.
- FIGS. 4, 5 and 6 show devices similar to those shown in FIGS. 1, 2 and 3 , respectively, but with horizontal withdrawal of the strand.
- Continuous casting with horizontal withdrawal is well known in the art, for the person skilled in the art, there is no problem to adapt the invention to this version of casting.
- the only difference that should be mentioned is, that the liquid metal has a much higher density than the water which has mostly been used in the prior art. Therefore, the free applied coolant in the devices according to FIG. 5 and the first cooling stage of FIG. 6 must be differently pressurised on the top-side and the down-side of the strand 4 .
- FIG. 7 shows the flow sheet for the whole casting plant:
- the liquid metal used as coolant is stored in a tank 16 , which needs to be heated by a heating unit 17 before starting the casting process.
- the liquid coolant is pumped by the pump 18 into the cooling unit 5 .
- the cooling unit 5 it picks up heat from the hot strand 4 , then the hot coolant leaves the cooling unit and gives up this heat in the heat exchanger 19 .
- the cold coolant flows back into the coolant tank 16 .
- the heat withdrawn in heat exchanger 19 can be used for different things in any case it may help to safe costs for energy in a firm.
- the coolant tank 16 as well as the whole cooling system needs to be free from air and especially from oxygen, this is ensured by flushing the coolant tank 16 and the cooling unit 5 with inert-gas 20 .
- inert-gas 20 all such gases known in the art are usable, they have to stay inert at the given temperatures at contact with the coolant and the material of the strand. It is, of course, advantageous to use the same inert-gas in the storage tank 16 and the cooling unit 5 .
- the whole casting plant can further comprise a strand withdrawal unit 25 and a Flying saw 26 for cutting the strand 4 in pieces of certain length.
- sensors for the temperature (TIC) 21 , 22 , sensors for the flow rate (FIC) 23 and sensors for the pressure (PIC) 24 are preferred to have further measuring points within this system.
- Coolant can be a liquid metal like lead, tin, bismuth, gallium, indium or alloys of them as well as metals or alloys, which are having a melting point lower equal 60% of the melting point of the casting material. Further, it is possible to use non-metallic liquids, namely any liquid medium, which does not react with the material of the strand at the relevant temperatures and which stays in a liquid state at all temperatures involved in the cooling process. This may be some organic compounds, especially for strands of low-melting alloys.
- the storage tank 16 is arranged at lower level than the mould 3 , but for safety reasons, this arrangement is preferred. If an other arrangement is provided, the pump 18 and other armatures have to be put to other positions, but this brings no problem to the man skilled in the art.
- the pipes, the pump 18 , the armatures, the sensors 21 , 22 , 23 , 24 , the cooling device 5 , the pipe-like heat exchanger and other equipment for the coolant are, given the disclosure of the invention, readily available for the man skilled in the art of casting metal, may it be ferrous or not.
- the casting process can apply one or more direct cooling steps.
- the use of liquid metal as coolant prevents, if this is wanted, the formation of oxide layers on the strand surface.
- the adjustment of the coolant feed temperature and coolant flow rate allows good control of the cooling rate and hence the formation of grain structure.
- the use of an insulating mould or, more precisely, a low heat removal in the mould prevents the formation of surface defects and inhomo- geneous subsurface layers.
- the use of liquid metal for the direct cooling in continuous casting eliminates the danger of explosions known from the conventional process using water as coolant. This increases the safety in cast shops enormous. For this continuous casting process no lubricant is necessary.
- the existing plants may easily be adapted to the invention, existing cooling systems using water my be stripped and replaced by the new system.
- the mould itself hardly needs any adaptation, it is only necessary to have the freezing area at the end of the mould, therefore, insulated moulds or very short cooled moulds may be best used.
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- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Centrifugal Separators (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
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- Treatment Of Steel In Its Molten State (AREA)
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03450060A EP1452252A1 (en) | 2003-02-28 | 2003-02-28 | Continuous casting method |
EP03450060.3 | 2003-02-28 | ||
PCT/EP2004/001794 WO2004076096A1 (en) | 2003-02-28 | 2004-02-24 | Continuous casting method |
Publications (1)
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US20070074846A1 true US20070074846A1 (en) | 2007-04-05 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US10/547,607 Abandoned US20070074846A1 (en) | 2003-02-28 | 2004-02-24 | Continuous casting method |
Country Status (18)
Country | Link |
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US (1) | US20070074846A1 (es) |
EP (2) | EP1452252A1 (es) |
JP (1) | JP2007523745A (es) |
CN (1) | CN100342996C (es) |
AT (1) | ATE367228T1 (es) |
AU (1) | AU2004216532B2 (es) |
BR (1) | BRPI0407886B1 (es) |
CA (1) | CA2516038C (es) |
DE (1) | DE602004007628T2 (es) |
ES (1) | ES2290675T3 (es) |
IL (1) | IL170168A (es) |
IS (1) | IS2493B (es) |
MX (1) | MXPA05009163A (es) |
NO (1) | NO20054099L (es) |
PL (1) | PL206578B1 (es) |
SI (1) | SI1599300T1 (es) |
WO (1) | WO2004076096A1 (es) |
ZA (1) | ZA200506448B (es) |
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- 2004-02-24 AT AT04713860T patent/ATE367228T1/de active
- 2004-02-24 ES ES04713860T patent/ES2290675T3/es not_active Expired - Lifetime
- 2004-02-24 CN CNB200480005192XA patent/CN100342996C/zh not_active Expired - Fee Related
- 2004-02-24 WO PCT/EP2004/001794 patent/WO2004076096A1/en active IP Right Grant
- 2004-02-24 AU AU2004216532A patent/AU2004216532B2/en not_active Ceased
- 2004-02-24 CA CA2516038A patent/CA2516038C/en not_active Expired - Fee Related
- 2004-02-24 SI SI200430459T patent/SI1599300T1/sl unknown
- 2004-02-24 MX MXPA05009163A patent/MXPA05009163A/es active IP Right Grant
- 2004-02-24 EP EP04713860A patent/EP1599300B1/en not_active Expired - Lifetime
- 2004-02-24 JP JP2006501935A patent/JP2007523745A/ja active Pending
- 2004-02-24 PL PL378634A patent/PL206578B1/pl unknown
- 2004-02-24 BR BRPI0407886-1A patent/BRPI0407886B1/pt not_active IP Right Cessation
- 2004-02-24 US US10/547,607 patent/US20070074846A1/en not_active Abandoned
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2005
- 2005-08-09 IL IL170168A patent/IL170168A/en not_active IP Right Cessation
- 2005-08-12 ZA ZA200506448A patent/ZA200506448B/en unknown
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US20120085021A1 (en) * | 2006-05-12 | 2012-04-12 | Woodall Jerry M | Power generation from solid aluminum |
US10646919B2 (en) | 2012-05-17 | 2020-05-12 | Almex USA, Inc. | Process and apparatus for direct chill casting |
US8479802B1 (en) * | 2012-05-17 | 2013-07-09 | Almex USA, Inc. | Apparatus for casting aluminum lithium alloys |
US10946440B2 (en) | 2012-05-17 | 2021-03-16 | Almex USA, Inc. | Process and apparatus for minimizing the potential for explosions in the direct chill casting aluminum alloys |
US9849507B2 (en) | 2012-05-17 | 2017-12-26 | Almex USA, Inc. | Process and apparatus for minimizing the potential for explosions in the direct chill casting of aluminum lithium alloys |
US9895744B2 (en) | 2012-05-17 | 2018-02-20 | Almex USA, Inc. | Process and apparatus for direct chill casting |
US10864576B2 (en) | 2013-02-04 | 2020-12-15 | Almex USA, Inc. | Process and apparatus for minimizing the potential for explosions in the direct chill casting of lithium alloys |
US9950360B2 (en) | 2013-02-04 | 2018-04-24 | Almex USA, Inc. | Process and apparatus for minimizing the potential for explosions in the direct chill casting of lithium alloys |
US9764380B2 (en) | 2013-02-04 | 2017-09-19 | Almex USA, Inc. | Process and apparatus for direct chill casting |
US9616493B2 (en) | 2013-02-04 | 2017-04-11 | Almex USA, Inc. | Process and apparatus for minimizing the potential for explosions in the direct chill casting of aluminum lithium alloys |
US9936541B2 (en) | 2013-11-23 | 2018-04-03 | Almex USA, Inc. | Alloy melting and holding furnace |
US10932333B2 (en) | 2013-11-23 | 2021-02-23 | Almex USA, Inc. | Alloy melting and holding furnace |
US10835954B2 (en) | 2014-05-21 | 2020-11-17 | Novelis Inc. | Mixing eductor nozzle and flow control device |
US11383296B2 (en) | 2014-05-21 | 2022-07-12 | Novelis, Inc. | Non-contacting molten metal flow control |
US11272584B2 (en) | 2015-02-18 | 2022-03-08 | Inductotherm Corp. | Electric induction melting and holding furnaces for reactive metals and alloys |
EP3599037A1 (de) | 2018-07-25 | 2020-01-29 | Primetals Technologies Germany GmbH | Kühlstrecke mit einstellung der kühlmittelströme durch pumpen |
WO2020020868A1 (de) | 2018-07-25 | 2020-01-30 | Primetals Technologies Germany Gmbh | Kühlstrecke mit einstellung der kühlmittelströme durch pumpen |
US11167332B2 (en) * | 2018-07-25 | 2021-11-09 | Primetals Technologies Germany Gmbh | Cooling section with coolant flows which can be adjusted using pumps |
Also Published As
Publication number | Publication date |
---|---|
NO20054099L (no) | 2005-09-20 |
CA2516038A1 (en) | 2004-09-10 |
IS8046A (is) | 2005-09-26 |
AU2004216532A1 (en) | 2004-09-10 |
BRPI0407886A (pt) | 2006-03-01 |
EP1452252A1 (en) | 2004-09-01 |
CN100342996C (zh) | 2007-10-17 |
ATE367228T1 (de) | 2007-08-15 |
ES2290675T3 (es) | 2008-02-16 |
IS2493B (is) | 2009-02-15 |
BRPI0407886B1 (pt) | 2012-09-04 |
AU2004216532B2 (en) | 2009-05-07 |
NO20054099D0 (no) | 2005-09-02 |
EP1599300A1 (en) | 2005-11-30 |
WO2004076096A1 (en) | 2004-09-10 |
PL378634A1 (pl) | 2006-05-15 |
MXPA05009163A (es) | 2006-01-27 |
EP1599300B1 (en) | 2007-07-18 |
DE602004007628T2 (de) | 2008-06-05 |
ZA200506448B (en) | 2006-04-26 |
IL170168A (en) | 2010-11-30 |
JP2007523745A (ja) | 2007-08-23 |
CN1753743A (zh) | 2006-03-29 |
SI1599300T1 (sl) | 2007-12-31 |
DE602004007628D1 (de) | 2007-08-30 |
PL206578B1 (pl) | 2010-08-31 |
CA2516038C (en) | 2011-05-03 |
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