EP1999297B1 - Pistolet de projection a gaz froid - Google Patents

Pistolet de projection a gaz froid Download PDF

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Publication number
EP1999297B1
EP1999297B1 EP07723056.3A EP07723056A EP1999297B1 EP 1999297 B1 EP1999297 B1 EP 1999297B1 EP 07723056 A EP07723056 A EP 07723056A EP 1999297 B1 EP1999297 B1 EP 1999297B1
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EP
European Patent Office
Prior art keywords
spray gun
mixing chamber
gas
anyone
gun according
Prior art date
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Application number
EP07723056.3A
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German (de)
English (en)
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EP1999297A1 (fr
Inventor
Tobias Schmidt
Peter Heinrich
Heinrich Kreye
Peter Richter
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Oerlikon Metco AG
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Oerlikon Metco AG
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Publication of EP1999297A1 publication Critical patent/EP1999297A1/fr
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    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/14—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas designed for spraying particulate materials
    • B05B7/1481—Spray pistols or apparatus for discharging particulate material
    • B05B7/1486—Spray pistols or apparatus for discharging particulate material for spraying particulate material in dry state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/16—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
    • B05B7/1606—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed the spraying of the material involving the use of an atomising fluid, e.g. air
    • B05B7/1613—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed the spraying of the material involving the use of an atomising fluid, e.g. air comprising means for heating the atomising fluid before mixing with the material to be sprayed
    • B05B7/162—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed the spraying of the material involving the use of an atomising fluid, e.g. air comprising means for heating the atomising fluid before mixing with the material to be sprayed and heat being transferred from the atomising fluid to the material to be sprayed
    • B05B7/1626—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed the spraying of the material involving the use of an atomising fluid, e.g. air comprising means for heating the atomising fluid before mixing with the material to be sprayed and heat being transferred from the atomising fluid to the material to be sprayed at the moment of mixing

Definitions

  • the invention relates to a device for cold gas spraying.
  • the invention relates to a cold gas spray gun and a device with such a cold gas spray gun and a method that uses a cold gas spray gun according to the invention.
  • powder particles from 1 ⁇ m to 250 ⁇ m are accelerated in a gas stream to speeds of 200 m / s to 1600 m / s without melting or fusing, and sprayed onto the surface to be coated, the substrate. Only upon impact with the substrate does the temperature increase at the colliding interfaces due to plastic deformation under very high strain rates and leads to welding of the powder material to the substrate as well as to each other. For this, however, a minimum impact speed must be exceeded, the so-called critical speed.
  • the mechanism and quality of welding are comparable to explosive welding.
  • Laval nozzle i. an initially diverging up to a nozzle throat, then diverging nozzle to be accelerated to supersonic speed, wherein the powder material is injected before or after the nozzle throat in the gas jet and accelerated toward the substrate.
  • the particle temperature on impact increases with the process gas temperature. This leads to a thermal softening and ductilization of the powder material and lowers the critical velocity of the impacting particles. As the speed of sound also increases, raising the process gas temperature increases both particle velocity and particle temperature upon impact. Both have a positive effect on the order efficiency and coating quality.
  • the process gas temperature always remains below the melting temperature of the Spraying used powder material. In the cold gas spraying method, therefore, a "colder" gas is used in comparison to other spraying methods in which the powder particles are melted by the gas. As with injection molding, where filler metals are melted by hot gas, the gas must be heated in cold gas spraying as well.
  • gas at high pressure is necessary.
  • the components of a device for cold gas spraying must be designed to be pressure-resistant.
  • Most systems for stationary operation are designed for 30 bar, whereby the individual modules are designed for the necessary pre-pressure of approx. 35 bar.
  • Some plant types are even designed only for pressures up to 15 bar or for pressures up to 7 bar. If, as desired, the pressure is to be further increased and the high temperature can act directly on the material of the contact surfaces of the components, this leads to the fact that expensive and difficult to process high-temperature materials must be used or the component, in particular a spray gun, by his Size and the necessary wall thicknesses becomes relatively heavy.
  • the heat removal via the contact surface also leads to losses and an undesirable drop in the gas temperature, in particular in front of the nozzle throat of the Laval nozzle.
  • a spray gun with a Laval nozzle known, consisting of an input cone and an output cone, which abut one another at a nozzle neck.
  • the Laval nozzle is supplied with air under high pressure via an air heater and a mixing chamber in which an air powder is mixed. The powder is accelerated through the Laval nozzle as a supersonic nozzle and heated by the air heated in the air heater without it melts.
  • a disadvantage of this prior art is that the material strength and strength of the components of the spray gun must be designed very large in order to withstand the high pressure at high temperatures of the material can, as the material strength decreases sharply with temperature.
  • a spray gun with a nozzle and a mixing chamber is shown.
  • the gas is heated in a separate preheater and passed by a hose to the spray gun, the preheater is thus arranged independently of the spray gun.
  • a reheater is arranged on the spray gun.
  • a cold gas spray gun with a nozzle for accelerating gas jet and particles known to be in one converges converging nozzle portion and a nozzle outlet, which merge into one another at the nozzle neck, and a powder injection tube which ends more than 40 mm in front of the nozzle throat.
  • a device for cold gas spraying with a spray gun with a nozzle and a heater for gas heating is known, wherein the heating is divided into at least two heaters for gas heating and a post-heater is attached directly to the spray gun while a second, freestanding preheater via a line with the spray gun connected is.
  • the usable process gas pressure can be raised to well above 35 bar without excessively increasing the weight of the cold gas spray gun due to large material and wall thicknesses. Due to the internal insulation of the high-pressure gas heater and / or mixing chamber and the Laval nozzle, the components under pressure can be operated at significantly lower temperatures and thus higher material strength. The insulation further avoids unnecessary thermal losses to the environment and creates less Cost of gas heating. Finally, there is also a lower inertia of the cold gas spray gun when commissioning, since not the relatively large masses of wall material must be heated, and increased durability, due to the lower temperature stress of the materials.
  • the pressure vessel of the high-pressure gas heater and / or the mixing chamber are lined with an insulation consisting of solid or flexible ceramic insulating material.
  • the pressure vessel of the high pressure gasifier and / or the mixing chamber is isolated by a gas gap between an inner shell enclosing the gas and an outer shell.
  • high pressure gas heater, mixing chamber and Laval nozzle are linearly and concentrically aligned.
  • An angled gas guide in the available spray guns leads to an uneven thermal load, component distortion and thermally induced stresses, which would quickly lead to damage of the gun at the high gas temperatures required here. This is avoided by a straight gas flow.
  • the flow direction of the gas between high-pressure gas heater and mixing chamber can be deflected by an angle of up to 60 ° to each other.
  • the mixing chamber is at the same time the convergent section of the Laval nozzle.
  • the converging portion of the Laval nozzle has a length between 50 and 250 mm and has a conical or concave or convex inner contour.
  • the converging nozzle section is insulated from the inside or consists overall of an insulating material, in particular ceramic.
  • the pressure vessel and / or the mixing chamber and / or the convergent section and / or the divergent section may consist in whole or in part of titanium or aluminum and their alloys.
  • the spray gun can be made particularly easy, as well as by the use of aluminum.
  • the latter is particularly cost-effective as a construction material for the cold gas spray gun.
  • the distance between the particle feed in the mixing chamber and the nozzle throat 40 to 400 mm preferably 100 to 250 mm.
  • a sufficiently long residence time of the particles in the heated gas can be achieved by heating the particles.
  • the flow cross-section of the mixing chamber and / or the convergent section may be between 5 and 50 times the nozzle throat cross-sectional area, preferably between 8 and 30 times, more preferably between 10 and 25 times to at least 70% of the distance from the particle feed to the nozzle throat amount.
  • the flow velocity in the region between the particle feed and the nozzle throat is not too small, so that the two-phase flow of gas and particles is maintained. Particle agglomerations and deposits on walls, which can disturb the operation of the cold gas spray gun sensitive, such as in the case of a nozzle clogging, are prevented.
  • the nozzle throat has a diameter between 2 and 4 mm
  • the diverging portion has a length which corresponds to 30 to 90 times the diameter of the nozzle throat, and at the same time the area ratio of the cross section at the end of the diverging portion to that of the nozzle neck cross section 3 and 15 and the inner contour is conical, or convex or concave.
  • the gas is supplied under a pressure of 15 to 100 bar, preferably from 20 to 60 bar, more preferably from 25 to 45 bar and a flow rate of 30 and 600 m 3 / h.
  • the particle feed can consist of a tube supplied sideways at any angle or of one or more bores at the end of the high-pressure gas heater or in the mixing chamber.
  • the heating power of the heating element related to the flow cross section in the nozzle throat is advantageously 1.5 to 7.5 kW / mm 2 , preferably 2 to 4 kW / mm 2 .
  • the power volume of the heating element may be from 10 to 40 MW / m 3 , preferably from 20 to 30 MW / m 3 .
  • the spray gun the gas via a plastic tube, in particular Teflon, which is connected to a second high-pressure gas heater, preheated to up to 230 ° C, or via a H redesigngasmetallschlauch, preheated to up to 700 ° C, fed.
  • the total heat output of the high-pressure gas heater and the second high-pressure gas heater relating to the flow cross section in the nozzle throat is 4 to 16 kW / mm 2 , preferably 5 to 9 kW / mm 2 .
  • the gas can be supplied in a method according to the invention after the high-pressure gas heater in the mixing chamber with temperatures greater than 600 ° C, preferably greater than 800 ° C, more preferably greater than 1000 ° C.
  • more than 80 percent by weight of the particles fed into the mixing chamber in the nozzle throat reach 70% of the gas temperature in the nozzle throat, measured in Kelvin. This ensures a sufficient quality of the forming coating, since a sufficient proportion of the particles has the energy required for the formation of the layer upon impact.
  • a mixture of particles may be used whose mass is at least 80% of particles of grain size between 5 and 150 microns, preferably between 10 and 75 microns and more preferably between 15 and 50 microns.
  • the impact temperature of coarser particles can be significantly increased by efficient preheating of the particles in the hot process gas stream.
  • coarser particles lose in the expanding gas jet of the nozzle not so quickly back to temperature and the use of high quality and precisely specified powder of particles in coarser fractions (-38 + 11 microns, -45 + 15 microns, -75 + 25 microns; 105 + 45 microns) unproblematic and cheaper.
  • the handling and promotion of spraying is much easier than with conventional powder fractions with -22 microns and - 25 + 5 microns.
  • FIG. 1 schematically shows an advantageous embodiment of the cold gas spray gun according to the invention in longitudinal section.
  • a pressure vessel 1 has on its inside an insulation 2.
  • a heating element 3 is arranged, here in the form of a filament heater, which consists of a plurality of electrical heating wires.
  • the gas to be heated is supplied to the pressure vessel 1 via a gas supply line 4.
  • the pressure vessel 1 is a rotationally symmetrical body.
  • a gas outlet 5 directs the heated or further heated gas in a mixing chamber 6, to which the converging portion 7 of a Laval nozzle 8 connects.
  • the Laval nozzle 8 further consists of a nozzle throat 9 and a diverging section 10.
  • a particle tube 11 can supply particles to the mixing chamber 3. In this case, the mouth of the particle tube 11 is aligned with the forming gas stream.
  • the gas flows through the pressure vessel 1 and with this linearly aligned mixing chamber 6 and Laval nozzle 9 as indicated by the arrows, wherein it is distributed uniformly over the cross section of the heating element 3. Due to the internal insulation 2 is achieved that only a few heat energy reaches the wall of the pressure vessel 1 and the mixing chamber 6. Since the pressure vessel 1 and the mixing chamber 6 at the same time give off heat to the environment, the pressure vessel 1 and the mixing chamber 6 is a considerably lower temperature than the heated gas has. The pressure vessel 1 and the mixing chamber 6 can therefore be relatively thin-walled and lightweight.
  • the heated gas via the particle tube 11, the particles to be sprayed admixed. This is done by the particles are transported through the particle tube via a carrier gas stream.
  • the particles are heated, wherein more than 80 percent by weight of the particles in the nozzle throat reach 0.7 times the temperature of the gas jet in Kelvin at this location.
  • This distance has in the present embodiment, a length between 40 and 400 mm, preferably between 100 and 250 mm, depending on the particles and gases used.
  • the expanding gas is accelerated to speeds above the speed of sound.
  • the particles are strongly accelerated in this supersonic flow and reach speeds between 200 and 1500 m / s.
  • An extension of the diverging nozzle section 11 has a particularly strong effect together with an inventively possible temperature and pressure increase of the gas.
  • the effective use of elongate diverging nozzle sections 11 requires a high enthalpy of the gas.
  • Advantageous lengths of the diverging nozzle section 11 are 100 mm and more, preferably 100 to 300 mm, particularly preferably 150 to 250 mm.
  • a uniform flow through the heating element is ensured by the cross-sectional area of the heating cartridge is not greater than 1500 times, preferably not more than 1000 times the area of the flow cross-section in the nozzle throat 9.
  • Such a cold gas spray gun is characterized by a compact design and high power density.
  • the length to diameter ratio is between 3 and 6.
  • the power density of the cold gas spray gun, the quotient of heating power to total mass is between 1 and 8 kW / kg, with a well-realizable range between 2 and 4 kW / kg.
  • the heating element 3 used has a power volume of 10 to 40 MW / m 3 . This allows temperatures of the gas at the gas supply from 400 ° C to 700 ° C. This temperature can be achieved by a second stationary preheater, which is connected to the cold gas spray gun via a hose. If a metal hot gas hose is used, 700 ° C is possible.
  • Fig. 2 schematically shows a further embodiment of a cold gas spray gun according to the invention in longitudinal section. Identical components are provided with the same reference numerals.
  • the pressure vessel 1 and the mixing chamber 6 have on their inside an insulation 2. Inside the pressure vessel 1, the heating element 3 is arranged. Adjoining the mixing chamber 6 is a converging section 12 of the Laval nozzle 8, which further comprises the nozzle throat 9 and the diverging section 10.
  • the particle tube 11 can supply the mixing chamber 3 particles.
  • the converging section 12 also has an insulation 13. As a result, thermal stress on the nozzle and thermal losses are avoided.
  • Fig. 3 schematically shows a third embodiment of a cold gas spray gun according to the invention in longitudinal section. Identical components are again provided with the same reference numerals.
  • the pressure vessel 1 has on its inside an insulation 2 and in its interior, the heating element 3 is arranged.
  • a mixing chamber 14 is at the same time a converging section 15 of the Laval nozzle 8, which further comprises the nozzle throat 9 and the diverging section 10.
  • the particle tube 11 can supply 3 particles in the mixing chamber.
  • the converging section 15 or the mixing chamber 14 also has an insulation and has a length of between 50 to 250 mm. This results in a simpler construction of the cold gas spray gun.

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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)
  • Nozzles (AREA)

Claims (14)

  1. Un pistolet de projection à gaz froid avec un réchauffeur de gaz à haute pression, qui a un réservoir sous pression (1) traversé par du gaz et un élément chauffant (3) disposé dans le réservoir sous pression (1), et avec une chambre de mélange (6, 14), dans laquelle des particules peuvent être amenées au gaz par une alimentation en particules (11) et avec une buse de Laval (8) constituée d'une partie convergente (7, 12, 15), un col de buse (9) et une partie divergente (10), caractérisé en ce que le réchauffeur de gaz à haute pression est disposé à la chambre de mélange (6, 14) et la chambre de mélange (6, 14) est disposée à la buse de Laval (9) l'un après l'autre dans le sens de l'écoulement du gaz, et dans lequel le réchauffeur de gaz à haute pression et la chambre de mélange (6, 14) sont au moins partiellement isolés intérieurement sur les surfaces de contact avec le gaz et que le réservoir sous pression du réchauffeur de gaz à haute pression et / ou la chambre de mélange sont isolés par une fente de gaz entre une enveloppe intérieure enfermant le gaz et une enveloppe extérieure.
  2. Un pistolet de projection à gaz froid selon la revendication 1, caractérisé en ce que le réservoir sous pression du réchauffeur de gaz à haute pression et / ou la chambre de mélange (6, 14) sont revêtus d'une isolation constituée d'un matériau isolant céramique solide ou flexible.
  3. Un pistolet de projection à gaz froid selon l'une des revendications précédentes, caractérisé en ce que le réchauffeur de gaz à haute pression, la chambre de mélange (6, 14) et la buse de Laval (8) sont alignés de manière linéaire et concentrique l'un par rapport à l'autre.
  4. Un pistolet de projection à gaz froid selon l'une des revendications 1 à 3, caractérisé en ce que la direction d'écoulement du gaz entre le réchauffeur de gaz à haute pression et la chambre de mélange est déviée d'un angle pouvant atteindre 60° l'un par rapport à l'autre.
  5. Un pistolet de projection à gaz froid selon l'une des revendications précédentes, caractérisé en ce que la chambre de mélange est également la partie convergente (15) de la buse de Laval (8).
  6. Un pistolet de projection à gaz froid selon l'une des revendications précédentes, caractérisé en ce que la partie convergente (15) de la buse de Laval a une longueur comprise entre 50 et 250 mm et a un contour intérieur conique ou concave ou convexe.
  7. Un pistolet de projection à gaz froid selon l'une des revendications précédentes, caractérisé en ce que la partie de buse convergente (12, 15) est isolée de l'intérieur ou consiste entièrement en un matériau isolant, en particulier en céramique.
  8. Un pistolet de projection à gaz froid selon l'une des revendications précédentes, caractérisé en ce que le réservoir sous pression et / ou la chambre de mélange et / ou la partie convergente et / ou la partie divergente sont constitués entièrement ou partiellement de titane ou d'aluminium et de leurs alliages.
  9. Un pistolet de projection à gaz froid selon l'une des revendications précédentes, caractérisé en ce que la distance entre l'alimentation en particules (11) dans la chambre de mélange (6, 12, 15) et le col de buse (9) est de 40 à 400 mm, de préférence 100 à 250 mm.
  10. Un pistolet de projection à gaz froid selon l'une des revendications précédentes, caractérisé en ce que la section transversale d'écoulement de la chambre de mélange et / ou de la partie convergente sur au moins 70 % de la distance entre l'alimentation en particules et le col de buse est comprise entre 5 fois et 50 fois la surface de la section transversale du col de buse, de préférence entre 8 fois et 30 fois, particulièrement de préférence entre 10 fois et 25 fois.
  11. Un pistolet de projection à gaz froid selon l'une des revendications précédentes, caractérisé en ce que le col de buse a un diamètre compris entre 2 et 4 mm, la partie divergente a une longueur correspondant à 30 à 90 fois le diamètre du col de buse, et en même temps, le rapport de surface de la section transversale à l'extrémité de la partie divergente à celle du col de la buse est compris entre 3 et 15 et le contour intérieur est conique, convexe ou concave.
  12. Un pistolet de projection à gaz froid selon l'une des revendications précédentes, caractérisé en ce que l'alimentation en particules consiste en un tube (11) alimenté latéralement à n'importe quel angle ou en un ou plusieurs alésages à l'extrémité du réchauffeur de gaz à haute pression ou dans la chambre de mélange.
  13. Un pistolet de projection à gaz froid selon l'une des revendications précédentes, caractérisé en ce que la puissance de chauffage de l'élément chauffant (3), par rapport à la section transversale d'écoulement dans le col de buse, est de 1,5 à 7,5 kW/mm2, de préférence 2 à 4 kW/mm2.
  14. Un pistolet de projection à gaz froid selon l'une des revendications précédentes, caractérisé en ce que le volume de puissance de l'élément chauffant (3) est de 10 à 40 MW/m3, de préférence de 20 à 30 MW/m3.
EP07723056.3A 2006-03-24 2007-03-06 Pistolet de projection a gaz froid Active EP1999297B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006014124A DE102006014124A1 (de) 2006-03-24 2006-03-24 Kaltgasspritzpistole
PCT/EP2007/001911 WO2007110134A1 (fr) 2006-03-24 2007-03-06 Pistolet de projection à gaz froid

Publications (2)

Publication Number Publication Date
EP1999297A1 EP1999297A1 (fr) 2008-12-10
EP1999297B1 true EP1999297B1 (fr) 2019-03-06

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP07723056.3A Active EP1999297B1 (fr) 2006-03-24 2007-03-06 Pistolet de projection a gaz froid

Country Status (8)

Country Link
US (1) US7637441B2 (fr)
EP (1) EP1999297B1 (fr)
JP (1) JP5035929B2 (fr)
KR (1) KR101298162B1 (fr)
CN (1) CN101410551B (fr)
CA (1) CA2645846C (fr)
DE (1) DE102006014124A1 (fr)
WO (1) WO2007110134A1 (fr)

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US11662300B2 (en) 2019-09-19 2023-05-30 Westinghouse Electric Company Llc Apparatus for performing in-situ adhesion test of cold spray deposits and method of employing
US11898986B2 (en) 2012-10-10 2024-02-13 Westinghouse Electric Company Llc Systems and methods for steam generator tube analysis for detection of tube degradation
US11935662B2 (en) 2019-07-02 2024-03-19 Westinghouse Electric Company Llc Elongate SiC fuel elements

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JP2009531167A (ja) 2009-09-03
CA2645846A1 (fr) 2007-10-04
CA2645846C (fr) 2016-09-13
EP1999297A1 (fr) 2008-12-10
JP5035929B2 (ja) 2012-09-26
CN101410551B (zh) 2011-10-19
CN101410551A (zh) 2009-04-15
DE102006014124A1 (de) 2007-09-27
WO2007110134A1 (fr) 2007-10-04
KR20090006119A (ko) 2009-01-14
KR101298162B1 (ko) 2013-08-20
US20070221746A1 (en) 2007-09-27

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