EP1812607B1 - Fill fourré pour le traitement des métaux liquides - Google Patents
Fill fourré pour le traitement des métaux liquides Download PDFInfo
- Publication number
- EP1812607B1 EP1812607B1 EP05777175.0A EP05777175A EP1812607B1 EP 1812607 B1 EP1812607 B1 EP 1812607B1 EP 05777175 A EP05777175 A EP 05777175A EP 1812607 B1 EP1812607 B1 EP 1812607B1
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- EP
- European Patent Office
- Prior art keywords
- cored wire
- paper
- wire according
- pyrolizing
- bath
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
Definitions
- the invention relates to the technical field of tubular envelopes containing compacted powdered or granular materials, these core envelopes being used for the treatment of liquid metals, especially steels, and being conventionally referred to as "filled cores".
- cored son containing Mg and Ca C 2 or alternatively Na 2 CO 3, CaCO 3, CaO, MgO.
- Flux-cored wires are typically used in secondary metallurgy of steels, among other means such as pocket stirring, powder injection, CAS (Composition Adjustment Sealed), arc pocket furnace, RH (Ruhrstahl Heraeus), tank vacuum.
- the cored wires are used for the desulphurization of cast irons, for the production of GS cast irons, the inoculation of casting cast irons.
- the inoculation of cast irons consists in introducing into the cast irons elements which favor the germination of graphite to the detriment of cementite, these elements being, for example, alkalis, alkaline earths (Ca) or bismuth, alloyed with silicon. Generally, desulfurization, nodulisation and inoculation are performed in order. Magnesium and silicon carbide are often used and the bath temperatures are of the order of 1300 to 1400 ° C, ie lower than those of the liquid steel bags.
- flux cored wire The primary functions of flux cored wire are, for steels, deoxidation, desulfurization, inclusion control and shading.
- the deoxidation operation consists in combining the dissolved oxygen in the liquid steel from the converter or the electric furnace (content of about 500 ppm or more) with a deoxidizing agent, a part of which will remain dissolved in the metal. liquid.
- a deoxidizing agent a part of which will remain dissolved in the metal. liquid.
- the electric furnace flows into a pocket more or less decarburized metal, dephosphorized, but effervescent: given its dissolved oxygen content, the product% CO x% O is such that at the temperature considered, the reaction of formation of CO is spontaneous in the bath of liquid steel.
- Deoxidation is so called calming, by reference to this effervescence of the primary liquid steel bath.
- the deoxidizing agents contained in the cored wires are ferroalloys, most often (ferrosilicon, ferromanganese, aluminum). They lead to the formation of oxides (silica, manganese oxide, alumina) which, by moderate mixing of the pocket, decant in the slag.
- the cored wires also conventionally contain calcium for aluminum-killed steels.
- the addition of calcium alloys to a liquid steel killed with aluminum allows a modification of the inclusions of alumina, by partial reduction by calcium.
- Calcium aluminates are liquid at the temperature of liquid steels, close to 1600 ° C., and therefore globular on product when their CaO content is between 40% and 60%.
- the amount of calcium in solution needed to achieve the change in inclusions depends on the aluminum content of the metal bath. Most of the calcium introduced by cored wire is therefore in the liquid metal in the form of liquid inclusions of lime aluminates, and does not exceed a few ppm.
- Boiling is reduced by introducing the calcium, not unalloyed, but as CaSi, with the major drawback of introducing silicon into the liquid steel, which is unfavorable for some steels such as deep drawing.
- stirring or bubbling with argon through the porous plug of the pocket causes an intumescence of the slag surface, which further increases the calcium losses by evaporation or oxidation, during the simultaneous introduction of cored wire. intumescence causing direct contact of the liquid metal with the air.
- exogenous oxide inclusions resulting from the contact of calcium with the refractories or the powders of the distributor are in fact difficult to eliminate before the solidification of the metal.
- inclusions of alumina are solid and more harmful than the inclusions of calcium aluminate with regard to the capping of continuous casting nozzles, for example.
- Calcium-cored wire treatment of aluminum-killed liquid steel can also result in the formation of calcium sulphide deposited in continuous casting nozzles for steels with low aluminum content and high sulfur content.
- control of the inclusional state by the addition of chemical components housed in flux-cored wires mainly concerns oxides and sulphides.
- control of the inclusion cleanliness is very important for bearing steels, free cutting steels, reinforcing steels or valve spring steels.
- Irregular compaction of the material contained in the envelope results in an irregularity in the quantities of this material introduced, per unit time, in the bath of steel or liquid metal.
- Insufficient compaction of the material contained in the flux-cored wire thus reduces the amount, per unit of time, of the material that can be introduced into the liquid metal by dipping the flux-cored wire into the liquid metal bath.
- drum here is meant well so called dynamic packaging reels that the walls of so-called static packaging cages.
- Some cored wires especially of flattened section, have insufficient rigidity for their introduction deep into some high density metal baths, especially if these baths are covered by a high viscosity slag.
- the other techniques for closing the cored wire wrapping strips have other disadvantages: envelope thicknesses reducing the powder / sheath ratio, risk of deterioration of the powder during welding.
- the cored wire can lose its rigidity and gradually bend in the liquid metal bath so that its end rises to the surface before the wire content is released. This rise being due in particular to the ferrostatic thrust, the apparent density of the wire being generally lower than that of the metal bath.
- the cored wire contains Ca, Mg, a shallow release of these elements in the bath of liquid metal results in very high yield losses, for example for the desulphurization of cast irons.
- the depth L is low, for example 30 cm, there is a high risk that the product contained in the cored wire does not come into contact with the supernatant slag, and thus be lost.
- addition bodies of a treating agent similar to the wires are illustrated in FIG. FR2392126 and JP55-122834 .
- the document EP-B2-0.236.246 discloses a cored wire comprising a metal envelope stapled by a circumferentially connected fold, closed on itself and whose edge is engaged inside the compacted mass forming the core of the cored wire.
- the stapling is carried out along a generatrix of the envelope of the cored wire, possibly reinforced by crimping with transverse indentations over the entire width of the staple band.
- Compaction of the core of the cored wire is obtained by forming an open fold, opposite the staple zone, then closing this fold by radial pressure.
- the casing of the cored wire is made of steel or aluminum and contains, for example, a powdery CaSi alloy containing 30% Ca by mass.
- the document US 4163827 discloses a cored wire comprising a ferrosilicon core containing Ca, Al, powdered embedded in a resin or a polymeric binder such as polyurethane, this core being extruded before being wrapped by single or double winding, in a helix, d a thin strip of metal, plastic or paper with a thickness of 0.025 mm to 0.15 mm.
- a cored wire has many disadvantages. In the first place, the materials forming the resin are an unacceptable source of pollution for the liquid metal bath. Secondly, the mechanical strength and rigidity of the wire are very insufficient.
- the ferrosilicon powder is practically unprotected with respect to the high temperature of the liquid metal.
- the document EP-0032874 discloses a flux-cored wire comprising a metal thin-film sheath containing an additive at least partially surrounded by a casing of organic or metallic synthetic material in the form of a strip of thickness less than 100 microns.
- the wire has a flattened shape.
- the thin strip is made of polyethylene, polyester or polyvinyl chloride and form of sealing, possibly heat shrinkable. No manufacturing process is described for this flattened cored wire, whose design is more of a chimera than an industrial disclosure.
- the document FR-2610331 of the applicant describes a cored wire comprising an axial zone containing a first powdery material or granular, surrounded by an intermediate metal tubular wall, and an annular zone, between this intermediate wall and the envelope of the cored wire, this annular zone containing a second powdery or granular material.
- the axial zone advantageously contains the most reactive materials with respect to the bath to be treated.
- the document US 3921700 discloses a cored wire to be wrapped in steel, containing a magnesium axial wire and an iron powder, of low thermal conductivity and high heat capacity, thus forming thermal insulation protecting the magnesium from too rapid heating when the cored wire is immersed in liquid steel.
- graphite or carbon is mixed with the iron powder.
- a cored wire comprising a mild steel sheath (melting temperature 1538 ° C.) containing a ferrosilicon with 75% silicon (melt temperature 1300 ° C.) will melt around 1200 ° C. when immersed for example in a gray cast iron at 1400 ° C, this fusion from the inner part of the sheath, due to the diffusion of silicon in the sheath which lowers the melting temperature of mild steel.
- the document US 4297133 describes a paper tube wound in layers, this tube being closed by metal caps.
- the burning time of the paper is indicated as three seconds when the tube is placed in a bath of liquid steel at 1600-1700 ° C.
- the slow combustion of the so-called pyrotechnic paper does not cause the appearance of combustion residues affecting the composition of the liquid metal bath and does not produce inclusions modifying the behavior of the bath during casting.
- a metal protection is placed to prevent the layers of pyrotechnic paper from being damaged during winding on the drum of the cored wire or when the cored wire is unrolled from this drum.
- the applicant has endeavored to solve this technical problem, by providing, in addition, a cored wire whose life in the liquid metal bath is increased, compared to conventional son, so as to reach a predetermined depth in the bath of liquid metal.
- the invention therefore relates to a flux-cored wire as specified in claim 1. It comprises powdered or compacted grains or embedded in a resin, at least one material selected from the group consisting of Ca, Bi, Nb, Mg, CaSi , C, Mn, Si, Cr, Ti, B, S, Se, Te, Pb, CaC 2 , Na 2 CO 3 , CaCO 3 , CaO, MgO, land rats, and it comprises an outer thermal barrier layer, enveloping a metal sheath, said outer thermal barrier layer being made of a pyrolyzing material upon contact with a bath of liquid metal.
- the pyrolyzing material is loaded with water or with a chemical compound with latent heat of high vaporization, especially greater than 2MJ / kg.
- figure 1 is a representation of the principle of introduction of a cored wire into a ladle of liquid steel.
- the cored wire 1 is extracted from a cage 2 such as, for example, described in the document FR-2703334 of the applicant, or else extracted from a drum 3, and introduced into an injector 4.
- This injector 4 drives the wire in a bent guide tube 5, the cored wire coming out of this guide tube 5 at a height of the order of one meter to one meter and a half above the surface of the liquid steel bath 6 contained in a pocket 7.
- the Applicant wished, at first, to thermally simulate the path of the cored wire in order to limit the number of tests with instrumented cored wire.
- the form factors were calculated by the plane flow method, the transfer factors being calculated by the coating method taking into account diffuse multi-reflections.
- the flux received is supposed to radiate from the tube wrapping the cored wire with a form factor equal to 1.
- the transfer is considered as convective with an exchange coefficient of the order 50,000 W / m 2 K, the surface temperature being imposed.
- the total emissivity of the outer surface of the cored wire is considered equal to 0.8, that of the guide tube is equal to 1 while that of the bath is considered equal to 0.8.
- the figure 2 gives the variation of the transfer factor between the flux-cored wire and the bath of liquid metal ( ⁇ x F) as a function of the distance above this bath of liquid metal, the value zero on the x-axis corresponding to the surface of the bath of liquid metal.
- the cored wire is considered to comprise three concentric cylindrical layers, namely a steel sheathed calcium core, this steel sheath being covered with paper.
- the diameter of the core of calcium is 7.8 mm
- the thickness of the steel sheath is 0.6 mm
- the thickness of the paper can be set at different values, example 0.6 mm for eight layers of paper superimposed.
- the cored wire is considered to be formed of a solid core made of interlocked calcium and in contact with the steel sheath which is itself nested and in contact with the paper.
- the bath of liquid metal and the walls of the pocket 7 are represented in the numerical model by a volume of temperature equal to 1600 ° with radiation and convection to the cored wire depending on whether the wire is above the bath 6 or in this bath of liquid metal 6.
- the heat exchange is convective with a very high exchange coefficient (50,000 W / m 2 K) from the time T2 where the cored wire enters the liquid metal bath 6.
- T2 The 1 + The 2 / V or :
- L2 is the distance between the lower end of the guide tube 5 and the surface of the liquid metal bath 6.
- the speed of travel of the cored wire is equal to 2 m / s, the initial temperature of the cored wire being 50 ° C.
- the free path of the cored wire beyond the guide tube 5 and before introduction into the bath of liquid metal is considered to be 1.4 m in length.
- the yarn is considered destroyed when, by calculation, the surface of the calcium core has a temperature above 1400 ° C.
- the modeling indicates that, for a reference wire devoid of thermal protection, the surface temperature of the calcium core increases by 70 ° C only during the free path and reaches the threshold of 1400 ° C at 0, 15 s after a run inside the liquid metal bath of only 30 cm for a speed of 2m / s.
- the temperature gradient between the steel sheath and the calcium core does not exceed, by calculation, 65 ° C.
- an insulation thickness of 0.025 mm would be sufficient to protect the cored wire to the bottom of the bath of liquid metal.
- figure 5 is shown the evolution of the surface temperatures of the paper as a function of the conductivity of this paper, during the first second of free travel of the cored wire, the thickness of the paper being 0.6 mm, the running speed of the paper. cored wire being 2m / s.
- Curve 5a corresponds to a conductivity of 0.1 W / K.m
- curve 5b corresponds to a conductivity of 0.15 W / K.m
- curve 5c corresponds to a conductivity of 0.2 W / K.m.
- the figure 5 shows that the burning of paper is probable and the destruction of the paper in the free path of the cored wire is not excluded.
- the figure 6 represents the evolution of the temperature of the paper surface for a thermal conductivity of this paper of 0.15 W / Km, a injection speed of the cored wire of 2m / s, the paper thickness being in curve 6a of 0.6 mm, in curve 6b of 0.2 mm and in curve 6c of 0.1 mm.
- the surface of the bath of liquid metal such as steel is covered with a layer of slag which forms a heat shield
- the figure 7 shows that the temperature of the paper covering the cored wire is largely affected by the variation of the temperature of the radiation source.
- the curves 7a, 7b, 7c and 7d respectively correspond to emitting surface temperatures of 1500, 1400, 1300 and 1200 ° C.
- the injection speed of the cored wire was 2m / s and the thermal conductivity of the paper 0.15 W / Km
- the figure 8 gives the results of the numerical simulation for the surface temperature of the calcium contained in the flux-cored wire, the paper being supposed to be dissolved in the bath of liquid metal, just after its pyrolysis.
- Curve 8a corresponds to the conventional cored wire, without protective paper.
- Curve 8b corresponds to a cored wire provided with a protective paper having a thickness of 0.6 mm.
- Curve 8c corresponds to a cored wire provided with a protective paper to a thickness of 1.2 mm.
- the figure 8 suggests that if the paper disappears after pyrolysis, it is not possible to protect the cored wire so that it reaches the bottom of the liquid steel bath, even by doubling the thickness of the paper.
- Pyrolysis of Kraft paper was carried out by raising the temperature of the sheets of paper, protected from oxygen, to a temperature of about 600 ° C. and a measurement of the thermal conductivity of the paper was carried out before and after pyrolysis.
- the Applicant has conceived of absorbing the radiation or of reflecting it by moistening this paper or covering it with aluminum.
- the figure 10 shows the results of the numerical simulation for the variations of surface temperature of the paper as a function of time, the curves 10a, 10b, 10c, 10d respectively corresponding to humidity of 0%, 59%, 89% and 118%.
- the figure 11 gives the result of the radiative calculation carried out by adding a very thin layer of aluminum in coating of the paper enveloping the steel sheath of the cored wire.
- This figure 11 shows that the radiative transfer factor is reduced by a factor of 8 compared to that of paper whose emissivity is 0.8.
- the figure 12 allows the comparison of surface temperature changes of the paper as a function of time with and without aluminum coating, the injection speed of the cored wire remaining of 2m / s and the thermal conductivity of the paper being 0.15 W / Km
- the surface temperature of the paper increases very little, according to this numerical simulation, in the free path of the cored wire, the aluminum providing a very effective thermal protection for the paper of the cored wire.
- thermocouples The electrical connections and connection wires of the thermocouples are protected by steel tubes.
- the instrumented wire is introduced into a steel steel ladle and then reassembled after a predetermined downtime.
- point I corresponds to the entrance of the cored wire into the liquid steel ladle.
- the temperature drop at point D of the figure 13 is related to the destruction of thermo-couples.
- the figure 14 compares the results obtained with the reference wire (reference 14a) and a cored wire comprising a layer of Kraft paper placed between the calcium core and the steel sheath (reference 14b).
- the placement of Kraft paper inside the cored wire can delay the rise in temperature by 0.4 seconds or a total time of 0.7 seconds before destruction.
- the figure 15 compares the results obtained with the reference wire (curve 15a) and two instrumented son provided with two layers of external Kraft paper (curves 15b, 15c).
- the temperature rise delay obtained is 0.8 and 1.2 seconds allowing the cored wire to reach the bottom of the pocket.
- the abrupt rise in temperature of the curves 15b and 15c corresponds to the moment when the Kraft paper is totally degraded, the steel sheath of the cored wire coming into direct contact with the liquid steel bath.
- the figure 16 compares the results obtained with the reference wire (curve 16a) and a cored wire protected by two layers of Kraft paper and two layers of aluminized paper (two curved tests 16b and 16c).
- the curves of the figure 16 show that the presence of two layers of kraft paper and two layers of aluminized paper retard the rise in temperature by about 1 second, compared to a conventional reference wire.
- the figure 18 allows to compare the results obtained with six layers of kraft paper and two layers of aluminized paper (curves 18b and 18c), to be compared with the reference wire (curve 18a).
- the rise in temperature is here delayed by more than 1.2 seconds.
- Curve 19b of the figure 19 gives the results obtained for a cored wire protected with four layers of kraft paper and an aluminum layer, the delay of the rise in temperature being 0.6 seconds with respect to the reference wire, curve 19a.
- Curve 20b of the figure 20 gives the result obtained with a cored wire protected by eight layers of kraft paper and an aluminum layer, the delay of the rise in temperature being 0.8 seconds relative to the reference wire, curve 20a.
- Curve 20c corresponds to a test in which the cored wire dipped laterally into the slag and did not penetrate the molten steel, this test indirectly giving the temperature of the slag, ie 1200 ° C.
- Curves 21b and c of the figure 21 give the results obtained for filled son protected by two layers of aluminized paper, the delay of the rise in temperature being about 0.7 seconds with respect to the reference wire, curve 21a, these results are to be compared with those of the figure 18 .
- the risks of combustion can be limited by injecting argon above the liquid metal bag or by soaking the paper with water or covering the paper with a metal band.
- the document FR-2810919 of the applicant describes the establishment of thermal insulation paper between a steel outer casing and a steel sheath containing the powdery or granular additive.
- the outer steel sheath is designed to prevent the paper from being damaged during handling of the cored wire.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Insulated Conductors (AREA)
- Paper (AREA)
- Heat Treatment Of Strip Materials And Filament Materials (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Ropes Or Cables (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL05777175T PL1812607T3 (pl) | 2004-06-10 | 2005-06-10 | Drut rdzeniowy do obróbki metali ciekłych |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0406257A FR2871477B1 (fr) | 2004-06-10 | 2004-06-10 | Fil fourre |
PCT/FR2005/001447 WO2006000714A2 (fr) | 2004-06-10 | 2005-06-10 | Fil fourre |
Publications (2)
Publication Number | Publication Date |
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EP1812607A2 EP1812607A2 (fr) | 2007-08-01 |
EP1812607B1 true EP1812607B1 (fr) | 2018-12-26 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP05777175.0A Active EP1812607B1 (fr) | 2004-06-10 | 2005-06-10 | Fill fourré pour le traitement des métaux liquides |
Country Status (18)
Country | Link |
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US (1) | US7906747B2 (ko) |
EP (1) | EP1812607B1 (ko) |
JP (1) | JP5467721B2 (ko) |
KR (1) | KR101128598B1 (ko) |
CN (1) | CN1985012B (ko) |
AR (1) | AR049911A1 (ko) |
BR (1) | BRPI0511940A (ko) |
CA (1) | CA2569316C (ko) |
EG (1) | EG24787A (ko) |
FR (1) | FR2871477B1 (ko) |
MX (1) | MXPA06014310A (ko) |
MY (1) | MY155030A (ko) |
PL (1) | PL1812607T3 (ko) |
RU (1) | RU2381280C2 (ko) |
TW (1) | TWI365224B (ko) |
UA (1) | UA92322C2 (ko) |
WO (1) | WO2006000714A2 (ko) |
ZA (1) | ZA200610276B (ko) |
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FR2810919B1 (fr) | 2000-06-28 | 2002-09-13 | Affival Sa | Fil fourre pour l'introduction d'additifs dans un bain de metal en fusion |
KR20020051316A (ko) * | 2000-12-22 | 2002-06-29 | 이구택 | 아크 용접용 플럭스코드 와이어 |
-
2004
- 2004-06-10 FR FR0406257A patent/FR2871477B1/fr not_active Expired - Lifetime
- 2004-06-25 US US10/876,417 patent/US7906747B2/en not_active Expired - Lifetime
-
2005
- 2005-06-10 KR KR1020067025924A patent/KR101128598B1/ko active IP Right Grant
- 2005-06-10 PL PL05777175T patent/PL1812607T3/pl unknown
- 2005-06-10 RU RU2007100354/02A patent/RU2381280C2/ru active
- 2005-06-10 BR BRPI0511940-5A patent/BRPI0511940A/pt active IP Right Grant
- 2005-06-10 MY MYPI20052647A patent/MY155030A/en unknown
- 2005-06-10 JP JP2007526501A patent/JP5467721B2/ja active Active
- 2005-06-10 CA CA2569316A patent/CA2569316C/fr active Active
- 2005-06-10 WO PCT/FR2005/001447 patent/WO2006000714A2/fr active Application Filing
- 2005-06-10 CN CN2005800233388A patent/CN1985012B/zh not_active Expired - Fee Related
- 2005-06-10 TW TW094119551A patent/TWI365224B/zh active
- 2005-06-10 EP EP05777175.0A patent/EP1812607B1/fr active Active
- 2005-06-10 UA UAA200613012A patent/UA92322C2/ru unknown
- 2005-06-10 MX MXPA06014310A patent/MXPA06014310A/es active IP Right Grant
- 2005-06-13 AR ARP050102378A patent/AR049911A1/es active IP Right Grant
-
2006
- 2006-12-07 EG EGNA2006001179 patent/EG24787A/xx active
- 2006-12-08 ZA ZA2006/10276A patent/ZA200610276B/en unknown
Non-Patent Citations (1)
Title |
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None * |
Also Published As
Publication number | Publication date |
---|---|
CA2569316C (fr) | 2011-04-12 |
CN1985012A (zh) | 2007-06-20 |
KR20070033993A (ko) | 2007-03-27 |
EG24787A (en) | 2010-09-06 |
MXPA06014310A (es) | 2007-05-04 |
RU2007100354A (ru) | 2008-07-20 |
AR049911A1 (es) | 2006-09-13 |
UA92322C2 (en) | 2010-10-25 |
CA2569316A1 (fr) | 2006-01-05 |
WO2006000714A3 (fr) | 2006-06-15 |
PL1812607T3 (pl) | 2019-06-28 |
RU2381280C2 (ru) | 2010-02-10 |
TWI365224B (en) | 2012-06-01 |
JP5467721B2 (ja) | 2014-04-09 |
KR101128598B1 (ko) | 2012-06-12 |
US7906747B2 (en) | 2011-03-15 |
FR2871477B1 (fr) | 2006-09-29 |
CN1985012B (zh) | 2013-03-06 |
BRPI0511940A (pt) | 2008-01-22 |
FR2871477A1 (fr) | 2005-12-16 |
TW200611977A (en) | 2006-04-16 |
MY155030A (en) | 2015-08-28 |
US20050274773A1 (en) | 2005-12-15 |
WO2006000714A2 (fr) | 2006-01-05 |
ZA200610276B (en) | 2008-06-25 |
EP1812607A2 (fr) | 2007-08-01 |
JP2008501865A (ja) | 2008-01-24 |
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