WO2012130464A1 - Procédé permettant de revêtir une bande d'acier mobile avec un revêtement métallique ou en alliage métallique - Google Patents

Procédé permettant de revêtir une bande d'acier mobile avec un revêtement métallique ou en alliage métallique Download PDF

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Publication number
WO2012130464A1
WO2012130464A1 PCT/EP2012/001401 EP2012001401W WO2012130464A1 WO 2012130464 A1 WO2012130464 A1 WO 2012130464A1 EP 2012001401 W EP2012001401 W EP 2012001401W WO 2012130464 A1 WO2012130464 A1 WO 2012130464A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
steel strip
bath
coating
metal alloy
Prior art date
Application number
PCT/EP2012/001401
Other languages
English (en)
Inventor
Willem VAN RIJSWIJK
Hendrik Bart Van Veldhuizen
Nicolaas Noort
Original Assignee
Tata Steel Nederland Technology B.V.
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 Tata Steel Nederland Technology B.V. filed Critical Tata Steel Nederland Technology B.V.
Priority to EP12711577.2A priority Critical patent/EP2691552A1/fr
Priority to US14/008,545 priority patent/US20140023797A1/en
Priority to KR1020137027911A priority patent/KR20140014247A/ko
Priority to JP2014501482A priority patent/JP2014509693A/ja
Priority to CA2831178A priority patent/CA2831178A1/fr
Priority to CN2012800166970A priority patent/CN103459649A/zh
Priority to AU2012237449A priority patent/AU2012237449A1/en
Publication of WO2012130464A1 publication Critical patent/WO2012130464A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/22—Removing excess of molten coatings; Controlling or regulating the coating thickness by rubbing, e.g. using knives, e.g. rubbing solids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/003—Apparatus
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C23C2/18—Removing excess of molten coatings from elongated material
    • C23C2/20—Strips; Plates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips

Definitions

  • the invention relates to a method for coating a moving steel strip with a metal or metal alloy coating, wherein the steel strip runs through a bath of molten metal or metal alloy to coat the steel strip, and the coated steel strip is wiped to control the thickness of the coating.
  • hot dip coating Such a method is well known in the art and is called hot dip coating.
  • hot dip coating is performed using a container with a molten metal bath, through which the steel strip is guided using a submerged guiding roll.
  • the strip is forwarded from an annealing line and enters the metal bath through a snout under an angle at an elevated temperature.
  • the steel strip leaves the metal bath in a vertical direction, on both sides coated with a metal layer.
  • this metal coating is too thick, and a wiping device is present not far above the metal bath to wipe off the surplus of metal.
  • the metal normally is zinc, a zinc alloy, aluminum or an aluminum alloy, but the use of other metals is also possible.
  • air knives are used to wipe the metal from the steel strip. Since the steel strip can be up to 2 meters in width, the metal bath often has a volume of about 24 cubic meters.
  • This wiping device mainly consists of two foils or sheets which are pressed towards the steel strip using a number of springs.
  • This wiping device is placed above for instance a zinc bath as described hereinabove in the place of the usual air knives.
  • the foils are more or less planing, floating or gliding on the liquid zinc on the steel strip, similar to the well-known aquaplaning effect.
  • the pressure exerted by the springs in relation to the speed of the strip, the thickness of the zinc coating leaving the wiping device can be controlled. In this way coatings with a reduced thickness as compared to coatings formed using air knives can be produced.
  • the foil wiping device of BE 1018202 can not be used in practice because zinc dross particles that are formed in and on the zinc bath are entrained with the zinc that forms the coating on the steel strip.
  • Zinc dross particles contain iron and aluminum and are quite hard. The zinc dross particles get stuck between the foil of the wiping device and the steel strip and cause scratches on the steel strip. For this reason, the wiping device of BE 1018202 is not used in practice. It is an object of the invention to provide a method for coating moving steel strip material with a metal or metal alloy coating by which can coat strip material with a higher velocity of the strip.
  • d the thickness of the coating in meters
  • s the velocity of the strip in meters per second.
  • the dross particles that grow in the bath can remain small enough not to stick between the steel strip and the foils or sheets of the wiping device.
  • the volume of the bath to be used will at least depend on the coating metal or metal alloy, the growing rate of the dross particles, the coating thickness on the steel sheet and the velocity of the steel strip. For this reason, the volume of the bath is dependant on these last parameters. In this way, the known foil wiper as discussed above can be used, which provides the possibility of a high strip velocity and thin coatings.
  • a relatively small bath has also the advantage that the coating system using the bath according to the invention is much more flexible than the known hot dip coating, because it is not necessary to keep a large volume of metal at a high temperature anymore, and because there are less or no metal losses due to the forming of metallic dross on the surface of the metal bath.
  • the bath of molten metal has a volume that is at most 2000 times the volume V of the coating on the steel strip per second, preferably a volume that is at most 500 times the volume of the coating on the steel strip per second, more preferably a volume that is at most 100 times the volume of the coating on the steel strip per second.
  • the smaller the volume of the bath the easier it is to keep the oxidic or metallic dross particles at a size such that they do not stick between the steel strip and the foils or sheets of the wiping device.
  • a smaller bath also has the advantage that a change of coating material on the steel strip can be executed faster.
  • the bath of molten metal has a volume such that metallic dross particles formed in the bath of molten metal or metal alloy on average are smaller than the thickness of the metal or metal alloy coating on the steel strip after wiping using foils or sheets. Since the bath of molten metal or metal alloy thus should contain only small metallic dross particles, in the range of a few micrometers, the bath will have a preferred volume in the order of a few liters. The small metallic dross particles cannot be entrapped between the steel strip and a foil or sheet for wiping the metal or metal alloy coated steel, nor cause scratches.
  • the wiping of the molten metal or metal alloy is performed using foils or sheets which are pressed towards the moving steel strip, wherein the moving of the steel strip causes a hydrodynamic lifting force by the coating which is in equilibrium with the pressure exerted on the foils or sheets.
  • the foils or sheets provide the coating according to BE 1018202.
  • the bath of molten metal or metal alloy is positioned under the foils or sheets.
  • the steel sheet thus enters the bath from below, which means that for instance in case of emergency the foil wiping device can be opened and the bath can be emptied, without contaminating the steel strip.
  • a change of width or thickness of the steel strip, for which the foil wiping device has to be opened, can be performed without emptying the bath. It is also possible to have the steel strip enter the bath from above, but this does not give this advantage.
  • the steel strip is moved vertical or under an angle of at most 45 degrees with the vertical first through the bath of molten metal or metal alloy and than in between the foils or sheets. In this way it is easy to guide the strip.
  • the bath of molten metal or metal alloy is in fluid connection with the metal or metal alloy layers between the steel strip and the foils or sheets. This means that the metal or metallic alloy in the bath is in direct contact with the metal or metal alloy layers between the foils or sheets and the steel strip, and thus that no un-wiped coatings are formed before a foil wiping device forms the coatings as these are desired.
  • a replenishing bath with metal or metal alloy is used to refill the bath of molten metal or metal alloy. Since the bath through which the steel strip runs is small, this bath should preferably be refilled using a replenishing bath.
  • electromagnetic induction is used to retain the molten metal or metal alloy in a container for the bath of molten metal or metal alloy. This is especially important in the situation that the bath is situated under the foils or sheets, but such electromagnetic induction is also useful when the bath is situated above the foils or sheets.
  • the metal or metal alloy in the bath is protected from oxygen in the surrounding air.
  • oxygen in the surrounding air.
  • a shielding gas is used to protect the molten metal or metal alloy in the bath from outside air.
  • the foils or sheets are pressed towards the strip to control the thickness of the metal or metal alloy coating.
  • the pressing can be executed using any one of the usual physical possibilities, such as hydraulically, by using springs, by using pies elements, et cetera.
  • the steel strip is annealed before entering the bath of metal or metal alloy.
  • Annealing usually has to be performed after a steel strip is cold rolled, and the annealing also provides a desired surface quality for hot dip coating with a metal or metal alloy coating.
  • the steel strip is heated to a predetermined temperature before entering the bath of metal or metal alloy.
  • a predetermined temperature Especially for third generation high strength steel types it is often necessary to perform an additional heating step just before the steel strip enters the bath with metal or metal alloy coating material.
  • the temperature of the bath of metal or metal alloy is higher than the temperature of the steel strip when entering the bath, preferably the temperature of the bath being 0 - 30 °C higher than the temperature of the steel strip, more preferably 10 - 20 °C.
  • the strip entry temperature SET
  • the temperature of the bath is SET plus C2, wherein C2 is between 0 and 30 °C, and preferably C2 is between 10 and 20 °C. In this way the temperature of the steel strip is lower than the temperature of the bath and therefore the forming of dross particles in the bath is retarded.
  • the metal or metal alloy coated steel strip is cooled after leaving the bath of metal or metal alloy. Cooling, especially fast cooling, is necessary for third generation high strength steel types, but other steel type must usually be cooled as well after leaving the metal or metal alloy bath.
  • the steel strip has a width of 0.75 to 2.25 meters. These widths are economical to coat using the method according to the invention.
  • the steel strip has a velocity of 2 to 10 m/s. This velocity is at the high end and higher than the speed that can be used to hot dip coat using air knives.
  • the metal or metal alloy coating has a thickness of 1 to 30 ⁇ on each side of the steel strip.
  • the metal is zinc, magnesium, aluminum or tin, or an alloy of one of these metals.
  • zinc, magnesium or aluminum are used for hot dip coating, but also alloys thereof such as an alloy of zinc and aluminum or an alloy of zinc and aluminum and magnesium.
  • Tin can also be used, often for very thin coatings.
  • a steel strip with is moved in a downward direction through a zinc bath and subsequently through a foil wiping device.
  • the zinc bath is contained in a container which forms one apparatus with the foil wiping device, such that the zinc in the zinc bath is directly fed into the zinc layers between the foils and the steel strip.
  • the foils are pressed towards the steel strip such that a coating is formed on the steel strip.
  • a replenishing bath is used to fill the bath with molten zinc, such that the volume in the zinc bath remains substantially constant.
  • the zinc bath will be protected by a shielding gas, such that no oxidation by the outside air takes place.
  • the zinc layers between the strip and the foils have a velocity zero at the surface of the foils and the velocity of the steel strip at the surface of the steel strip.
  • the zinc coating formed at the surface of the strip has approximately half the thickness of the zinc layer between a foil and the steel strip.
  • Dross particles are formed in the zinc bath due to the iron in the steel strip. These dross particles are taken along from the zinc bath with the zinc that is used for coating the steel strip. These dross particles should all be small enough to pass in between the foils and the steel strip. When a dross particle has become too large, it will get stuck between a foil and the steel strip, and cause scratches on the steel strip.
  • the zinc dross particles should have an average size that is smaller than half the thickness of the zinc layer between the foils and the steel strip, which is the same as being smaller than the thickness of the zinc coating leaving the foil wiping device.
  • the volume V of the coating on the steel strip per second is 2 x d x w x s.
  • the width is for instance 1 meter
  • the velocity of the strip is 2 meter per second.
  • the bath will thus have a volume of 2 liters.
  • the average residence time of dross particles for a zinc coating thickness of 10 ⁇ then drops from 400.000 seconds in a traditional bath to 125 seconds in the bath having a volume of 0,005 m3.
  • a dross growth rate of 0,05 pm/s thermodynamics and kinetics of alloy formation in galvanized coating, Nai-yong Tang, Zinc Based Steel coating systems production and performance, February 1998, Texas
  • the dross particle size will be about 6 pm.
  • the average zinc dross particle size is smaller than the thickness of the zinc coating of 10 pm.
  • the reduced bath volume makes online bath changes possible.
  • the reduced submerging time enables production of a new class of high strength steel.
  • metal coating can also be used, such as aluminium or tin, or an alloy of zinc, aluminium or tin, respectively.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)

Abstract

L'invention se rapporte à un procédé permettant de revêtir une bande d'acier mobile avec un revêtement métallique ou en alliage métallique, la bande d'acier se déplaçant à travers un bain de métal liquide ou d'alliage métallique liquide pour revêtir la bande d'acier, et la bande d'acier recouverte étant essuyée afin de réguler l'épaisseur du revêtement à l'aide de feuilles ou de plaques. Selon l'invention, le bain de métal liquide présente un volume qui fait au moins 10 000 fois le volume (V) du revêtement sur la bande d'acier par seconde, le volume (V) en m3 étant donné par la formule V = 2 x d x w x s, d étant l'épaisseur du revêtement en mètres, w étant la largeur de la bande en mètres et s étant la vitesse de la bande en mètres par seconde.
PCT/EP2012/001401 2011-03-30 2012-03-30 Procédé permettant de revêtir une bande d'acier mobile avec un revêtement métallique ou en alliage métallique WO2012130464A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP12711577.2A EP2691552A1 (fr) 2011-03-30 2012-03-30 Procédé permettant de revêtir une bande d'acier mobile avec un revêtement métallique ou en alliage métallique
US14/008,545 US20140023797A1 (en) 2011-03-30 2012-03-30 Method for coating a moving steel strip with a metal or metal alloy coating
KR1020137027911A KR20140014247A (ko) 2011-03-30 2012-03-30 금속 또는 금속 합금 코팅 재료를 이동하는 강 스트립에 코팅하기 위한 방법
JP2014501482A JP2014509693A (ja) 2011-03-30 2012-03-30 移動する鋼ストリップを金属または金属合金塗料で被覆する方法
CA2831178A CA2831178A1 (fr) 2011-03-30 2012-03-30 Procede permettant de revetir une bande d'acier mobile avec un revetement metallique ou en alliage metallique
CN2012800166970A CN103459649A (zh) 2011-03-30 2012-03-30 用金属或金属合金涂层涂覆移动的钢带的方法
AU2012237449A AU2012237449A1 (en) 2011-03-30 2012-03-30 Method for coating a moving steel strip with a metal or metal alloy coating

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11002610 2011-03-30
EP11002610.1 2011-03-30

Publications (1)

Publication Number Publication Date
WO2012130464A1 true WO2012130464A1 (fr) 2012-10-04

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PCT/EP2012/001401 WO2012130464A1 (fr) 2011-03-30 2012-03-30 Procédé permettant de revêtir une bande d'acier mobile avec un revêtement métallique ou en alliage métallique

Country Status (8)

Country Link
US (1) US20140023797A1 (fr)
EP (1) EP2691552A1 (fr)
JP (1) JP2014509693A (fr)
KR (1) KR20140014247A (fr)
CN (1) CN103459649A (fr)
AU (1) AU2012237449A1 (fr)
CA (1) CA2831178A1 (fr)
WO (1) WO2012130464A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9469894B2 (en) 2011-03-30 2016-10-18 Tata Steel Nederland Technology B.V. Apparatus for coating a moving strip material with a metallic coating material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105132846A (zh) * 2015-10-14 2015-12-09 江苏中远稀土新材料有限公司 一种工民用薄型钢材构件的不变形热镀锌工艺方法
CN105839041B (zh) * 2016-04-14 2018-08-07 上海大学 一种制备成分渐变合金材料的热浸镀工艺方法及其设备

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JPS589964A (ja) * 1981-07-10 1983-01-20 Nisshin Steel Co Ltd 鋼帯の連続溶融めつきにおけるめつき厚み制御法およびその装置
FR2798937A3 (fr) * 1999-09-24 2001-03-30 Lorraine Laminage Installation de revetement par immersion d'une bande metallique en defilement rectiligne
BE1018202A3 (fr) 2008-06-27 2010-07-06 Ct Rech Metallurgiques Asbl Dispositif pour l'essorage hydrodynamique d'une bande metallique en defilement contunu.
FR2945823A1 (fr) * 2009-05-25 2010-11-26 Snecma Procede et dispositif d'enduction metallique par voie liquide de fibres en materiau ceramique

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US3962501A (en) * 1972-12-15 1976-06-08 Nippon Steel Corporation Method for coating of corrosion-resistant molten alloy
US4082864A (en) * 1974-06-17 1978-04-04 Fiber Materials, Inc. Reinforced metal matrix composite
US4024309A (en) * 1975-03-17 1977-05-17 Ronald P. Wilder Foam glass structural element and method of producing
US4153006A (en) * 1975-04-17 1979-05-08 Armco Steel Corporation Apparatus for finishing molten metallic coatings
US4029478A (en) * 1976-01-05 1977-06-14 Inland Steel Company Zn-Al hot-dip coated ferrous sheet
CA1306614C (fr) * 1987-06-08 1992-08-25 Ralph Harris Production de metaux volatils
CA2225537C (fr) * 1996-12-27 2001-05-15 Mitsubishi Heavy Industries, Ltd. Dispositif et methode de revetement metallique a chaud
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JPS589964A (ja) * 1981-07-10 1983-01-20 Nisshin Steel Co Ltd 鋼帯の連続溶融めつきにおけるめつき厚み制御法およびその装置
FR2798937A3 (fr) * 1999-09-24 2001-03-30 Lorraine Laminage Installation de revetement par immersion d'une bande metallique en defilement rectiligne
BE1018202A3 (fr) 2008-06-27 2010-07-06 Ct Rech Metallurgiques Asbl Dispositif pour l'essorage hydrodynamique d'une bande metallique en defilement contunu.
FR2945823A1 (fr) * 2009-05-25 2010-11-26 Snecma Procede et dispositif d'enduction metallique par voie liquide de fibres en materiau ceramique

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9469894B2 (en) 2011-03-30 2016-10-18 Tata Steel Nederland Technology B.V. Apparatus for coating a moving strip material with a metallic coating material

Also Published As

Publication number Publication date
AU2012237449A1 (en) 2013-10-17
KR20140014247A (ko) 2014-02-05
EP2691552A1 (fr) 2014-02-05
JP2014509693A (ja) 2014-04-21
CN103459649A (zh) 2013-12-18
CA2831178A1 (fr) 2012-10-04
US20140023797A1 (en) 2014-01-23

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