WO2005078150A1 - Porous coated member and manufacturing method thereof using cold spray - Google Patents

Porous coated member and manufacturing method thereof using cold spray Download PDF

Info

Publication number
WO2005078150A1
WO2005078150A1 PCT/KR2005/000387 KR2005000387W WO2005078150A1 WO 2005078150 A1 WO2005078150 A1 WO 2005078150A1 KR 2005000387 W KR2005000387 W KR 2005000387W WO 2005078150 A1 WO2005078150 A1 WO 2005078150A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating layer
metal
powder
mother material
set forth
Prior art date
Application number
PCT/KR2005/000387
Other languages
English (en)
French (fr)
Inventor
Kyung Hyun Ko
Ha Yong Lee
Original Assignee
Kyung Hyun Ko
Ha Yong Lee
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 Kyung Hyun Ko, Ha Yong Lee filed Critical Kyung Hyun Ko
Priority to US10/589,184 priority Critical patent/US20070240603A1/en
Priority to JP2006553054A priority patent/JP2007522346A/ja
Priority to EP05721848A priority patent/EP1718781A4/en
Publication of WO2005078150A1 publication Critical patent/WO2005078150A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62BDEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B7/00Respiratory apparatus
    • A62B7/02Respiratory apparatus with compressed oxygen or air
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62BDEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B7/00Respiratory apparatus
    • A62B7/10Respiratory apparatus with filter elements
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C24/00Coating starting from inorganic powder
    • C23C24/02Coating starting from inorganic powder by application of pressure only
    • C23C24/04Impact or kinetic deposition of particles
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/028Including graded layers in composition or in physical properties, e.g. density, porosity, grain size
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18After-treatment
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21VFUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V33/00Structural combinations of lighting devices with other articles, not otherwise provided for
    • F21V33/0064Health, life-saving or fire-fighting equipment
    • F21V33/0068Medical equipment

Definitions

  • the present invention relates, in general, to a coated member on which a porous coating layer is formed and a method of producing the same and, more particularly, to a method of forming a porous coating layer on a surface of mother material using a low temperature spraying process and a coated member in which a pore distribution and a size of the coating layer are controlled.
  • a porous coating layer improves thermal and mechanical properties of the member .
  • a porous coating layer which includes open pores communicating with each other is formed on the surface of a heat exchanger, the heat exchanger has an increased area of contact with surrounding air, thereby assuring efficient heat exchanging performance.
  • the porous coating layer can satisfy this requirement.
  • stress may occur due to lattice misalignment at an interface.
  • the porous coating layer can act as a buffer layer for avoiding stress during the joining.
  • various coating methods have been employed as a method of forming a metal coating layer on the surface of a member for thermal and mechanical applications.
  • the method may be exemplified by an electro-plating process, a hot dip plating process, or thermal spraying process.
  • these processes have limits in terms of application, or may cause thermal impact to the mother material or thermal deformation of the mother material.
  • it is difficult to artificially control the porosity and pore distribution of the coating layer using the above processes .
  • the thermal conductive metal coating layer which is applied to pipes of the conventional heat exchanger corrodes or is mossy on a surface thereof in a corrosive environment, such as waste water or sea water, thus it does not perform its function.
  • An object of the present invention is to provide a member for thermal and mechanical applications, which does not cause thermal deformation of mother material or damage to the mother material due to thermal impact and which is capable of being applied to various fields, and a method of forming a porous coating layer used in the member.
  • Another object of the present invention is to provide a member for thermal and mechanical applications, in which porosity, a pore size, and a pore distribution of a surface coating layer are capable of being controlled, a method of forming a porous coating layer used in the member, and a porous coated member produced using the method.
  • a further object of the present invention is to provide a method of forming a porous coating layer having high thermal conductivity, which is capable of being used in an external corrosive environment for a long time.
  • the present invention provides a method of forming a porous coating layer on mother material.
  • the method comprises providing the mother material, feeding powder having a metal composition, which includes at least two different metals selected from the group consisting of Al, Mg, Zn, and Sn and which is expressed by xA-(l-x)B (0 ⁇ x ⁇ l, x is a weight ratio of A and B) , onto the mother material, supplying high pressure gas to the powder, applying the metal powder on the mother material by spraying the metal powder using the high pressure gas through an supersonic nozzle, and heat- treating the coated mother material to form the porous coating layer.
  • A is Al
  • B includes a metal element selected from the group consisting of Mg, Zn, ' and Sn.
  • the heat- treatment of the coated mother material be conducted at a temperature between a eutectic temperature of A and B and a melting point of a metal having the higher melting point of A and B.
  • the heat-treatment is conducted at about 200 - 650 ° C.
  • the feeding of the powder may further comprise changing x to change the composition of the powder.
  • the present invention provides a metal coated member.
  • the metal coated member comprises metal mother material, and a coating layer formed on the metal mother material, which includes at least two metal elements and is expressed by xA-(l-x)B (x is a weight ratio of A and B) .
  • a and B are different metals selected from the group consisting of Al, Mg, Zn, and Sn, x changes when moving in a thickness direction of the coating layer within a range of 0 ⁇ x ⁇ 1, and porosity of the coating layer is changed depending on a change in x.
  • x increases or decreases moving in a thickness direction of the coating layer, and the porosity of the coating layer is increased or decreased as x is increased or decreased.
  • A is Al
  • B is any one metal selected from the group consisting of Mg, Zn, and Sn, and x is decreased and the porosity of the coating layer is increased moving from an interface of the metal mother material and the coating layer to a surface of the coating layer.
  • the present invention provides a metal coated member.
  • the metal coated member comprises metal mother material, and a coating layer formed on the metal mother material, which includes at least two metal elements and is expressed by A-B.
  • a and B are different metals selected from the group consisting of Al, Mg, Zn, and Sn, A or B selected from the above group changes when moving in a thickness direction of the coating layer, and porosity of the coating layer is changed depending on a change in A or B.
  • the coating layer may include open pores which are at least partially interconnected with each other, and it is preferable that the open pores exist in an upper part of the coating layer in specific application fields. Additionally, the present invention provides a method of forming a porous carbon coating layer on mother material.
  • the method comprises providing the mother material, feeding carbon powder which is conglomerated by an organic binder, supplying high pressure gas to the carbon powder, and applying the carbon powder on the mother material by spraying the carbon powder using the high pressure gas through a supersonic nozzle.
  • the organic binder which is used to make the carbon powder coarse may be at least one selected from the group consisting of polyvinyl alcohol (PVA), rosin, resin, polyvinyl butyral (PVB) , and polyethylene glycol (PEG) . It is preferable that the organic binder be contained in a content of 10 - 30 wt% based on carbon.
  • the coating layer may be additionally subjected to a step of burning out the organic binder at 400 - 500 ° C.
  • FIG. 1 schematically illustrates a low temperature spraying system 100 used to form a coating layer in the present invention
  • FIGS. 2a and 2b are flow charts showing the formation of the porous coating layer, according to an embodiment of the present invention
  • FIG. 3 is a sectional view of a coated member 200 which includes a coating layer having a variable composition, according to the embodiment of the present invention
  • FIG. 4 is an optical microscope picture of a section of a coating layer having a composition of 0.5A1-0.5AlMg after heat treatment, according to the embodiment of the present invention
  • FIG. 1 schematically illustrates a low temperature spraying system 100 used to form a coating layer in the present invention
  • FIGS. 2a and 2b are flow charts showing the formation of the porous coating layer, according to an embodiment of the present invention
  • FIG. 3 is a sectional view of a coated member 200 which includes a coating layer having a variable composition, according to the embodiment of the present invention
  • FIG. 4 is an optical microscope picture of a section of a coating
  • FIG. 5 is an optical microscope picture of a section of a coating layer having a composition of 0.3A1-0.7AlMg after heat treatment, according to the embodiment of the present invention
  • FIG. 6 is an optical microscope picture of a section of a coating layer in which Al/AlMg/Al/AlMg/Al components are sequentially layered after heat treatment, according to the embodiment of the present invention
  • FIG. 7 is an optical microscope picture of a section of a coating layer in which 0.667A1-0.333Mg/0.5A1-0.5Mg components are sequentially layered after heat treatment, according to the embodiment of the present invention
  • FIG. 6 is an optical microscope picture of a section of a coating layer in which Al/AlMg/Al/AlMg/Al components are sequentially layered after heat treatment, according to the embodiment of the present invention
  • FIG. 7 is an optical microscope picture of a section of a coating layer in which 0.667A1-0.333Mg/0.5A1-0.5Mg components are sequentially
  • FIG. 8 is an optical microscope picture of a section of a coating layer having a composition of 0.5Al-0.5Sn after heat treatment, according to the embodiment of the present invention
  • FIG. 9 is an optical microscope picture of a section of a coating layer in which 0.667Al-0.333Sn/0.5Al-0.5Sn components are sequentially layered after heat treatment, according to the embodiment of the present invention
  • FIG. 10 is an optical microscope picture of a section of a coating layer in which 0.667A1-0.333Zn/0.5A1-0.5Zn components are sequentially layered after heat treatment, according to the embodiment of the present invention
  • FIG. 11 is a flow chart showing the formation of a porous carbon coating layer, according to another embodiment of the present invention
  • FIGS. 12a and 12b are electron microscope pictures of a section and a surface of the carbon coating layer formed through the procedure of FIG. 11.
  • FIG. 1 schematically illustrates a low temperature spraying device 100 which accelerates powder to form a coating layer on a substrate (S) in the present invention.
  • the spraying device 100 accelerates the powder for forming the coating layer at subsonic or supersonic speed to apply it to the substrate (S) .
  • the spraying device 100 comprises a gas compressor 110, a gas heater 120, a powder feeder 130, and a spraying nozzle 140.
  • the powder of about 1 - 50 m fed from the powder feeder 130 is sprayed using compressed gas of about 5 - 20 atm supplied from the gas compressor 110 through the spraying nozzle 140 at a rate of about 300 - 1200 mm/s.
  • the powder sprayed in conjunction with the gas collides with the substrate (S) .
  • kinetic energy of the powder plastically deforms the powder when the powder collides against the substrate (S) , and provides bonding strength to the substrate, thereby forming the coating layer having very high density.
  • the gas heater 120 which is positioned in a path for feeding the compressed gas is a supplementary unit for heating the compressed gas to increase the kinetic energy of the compressed gas so as to increase the spraying speed of the spraying nozzle.
  • FIG. 2a is a flow chart showing the formation of the coating layer on the mother material or the substrate using the spraying device described referring to FIG.
  • the method of the present invention starts from the step (S210) of feeding metal powder containing two or more metals from the powder feeder 130 of the spraying device 100 and the step (S220) of feeding compressed gas at high pressure from the gas compressor 110.
  • the powder containing two or more metals includes a mixture or a solid solution of at least two metals selected from the group consisting of Al, Mg, Zn, and Sn, or a mixture of both.
  • the metals selected in the present invention are different from each other.
  • a composition of the metal powder may be a binary system, such as Al-Mg, Al- Zn, or Al-Sn, a ternary system, such as Al-Mg-Zn, or a system having more than three metals.
  • Ti, Si, Mn, Cr, Fe, Co, Ni, or Cu may be also used without departing from the spirit of the present invention.
  • the powder having the metal components may be provided in the form of solid solution.
  • the metal powder containing Al-Mg may be provided in the form of AlMg solid solution which is so- called Magal .
  • the powder having the metal components may be provided in a mixture of the solid solution powder and the monolith powder.
  • the metal powder may be a mixture of Al powder and AlMg powder. Since the metal powder containing Mg is dangerous to handle, for example, it may cause explosions, it is provided as a solid solution to assure ease of handling.
  • the coating layer of the present invention is used in members having thermal and mechanical applications, since the metal powder has relatively good thermal and mechanical properties, such as thermal conductivity or strength, compared to its specific gravity, it is preferable that it contain Al or an Al alloy extensively used in machine members .
  • the gas may be exemplified by helium, nitrogen, argon, or air as described above.
  • the gas is compressed by the gas compressor to pressure of about 5 - 20 atm and is then provided. If necessary, the compressed gas may be provided while being heated to about 200 - 500 ° C using a heating unit, such as the gas heater 120 of FIG. 1. However, even though the compressed gas is heated according to the embodiment, the temperature change of the metal powder is insignificant due to the very low specific gravity of the gas. Accordingly, the spraying step of the present invention is different from a conventional spraying process, in which the powder is heated and coated at a melting point or higher, in that the spraying is conducted at low temperatures . Meanwhile, as described above, a portion of the compressed gas used in the step (S220) of feeding the compressed gas may be used as carrier gas for continuously and stably feeding the metal powder.
  • a mixture of the compressed gas and the metal powder is sprayed using the supersonic spraying nozzle (S230) .
  • the flow rate of the gas-powder mixture sprayed through the nozzle depends on the temperature and pressure of the gas and the particle size and specific gravity of the powder.
  • the gas-powder mixture having the particle size of about 1 - 50 [M is sprayed at the rate of about 300 - 1200 m/s under the pressure and temperature conditions of the fed gas .
  • the metal powder which is sprayed at the high rate collides against the mother material to form the high density coating layer.
  • the spraying step (S230) is conducted until the coating layer having a desired thickness is formed, and the coating layer thus formed is then heat treated (S240) .
  • the heat treatment temperature be about 200 - 650 ° C .
  • the heat treatment temperature of 650 ° C or higher causes complete melting of the metal coat, and the coat is barely melted at the temperature of 200 ° C or lower, resulting in a negligible heat treatment effect.
  • the high density coating layer formed on the mother material is subjected to the heat treatment step (S240) to acquire porosity.
  • porosity and the pore size of the porous coating layer depend on the change in composition of the applied metal powder.
  • the "change in composition" as used herein is intended to include a change in quantity as well as metals used.
  • 2b shows the method of forming the porous coating layer, which comprises the step (S250) of changing the composition of the metal powder so as to control a pore distribution of the coating layer, with respect to the coating method of the present invention described referring to FIG. 2a.
  • the composition of the powder is changed in the course of forming the coating layer during the step of spraying using the nozzle (S240) .
  • the ratio is controlled to 1:2, or the powder having Al-Zn instead of Al-Mg, in which a ratio of Al : Zn is 1:1, is fed, thereby forming the coating layer which has a vertical composition gradient or contains different components.
  • the change in composition of the powder may be achieved through a typical procedure well known to those skilled in the art.
  • powders having different compositions may be sequentially fed into one powder feeder, or, after a plurality of powder feeders for storing the powders having the different compositions are prepared, the powder feeder containing the powder having the desired composition may be selected using valves.
  • FIG. 3 is a sectional view of a coated member 200 which includes the coating layer formed through the procedure .
  • an Al-Zn layer 210 having a weight ratio of 2:1, an Al-Zn layer 220 having a weight ratio of 1:1, and an Al-Zn layer 230 having a weight ratio of 1:2 are formed on the mother material (S) , such as Al .
  • the mother material (S) such as Al .
  • the coating layer is heat treated, the Zn content increases, thus increasing the pore size and porosity.
  • the member which is coated with the powder having the composition shown in FIG. 3 is heat treated, it is possible to form the coated member in which porosity and/or a pore volume increase moving away from the mother material.
  • the pore distribution as described above is desirable because it contributes to the stable coating at an interface between the coating layer and the mother material. Furthermore, in the structure as describe above, since porosity and the pore volume increase, the pores formed at an outermost surface of the coating layer may be open pores communicating with each other. Particularly, the open pores play an important role in improving a heat exchanging property of the mother material . As described above, the change in pore distribution of the coating layer, which is described referring to FIG. 3, may be obtained by changing the quantities of the components or by changing the types of components .
  • FIG. 11 is a flow chart showing the formation of a porous carbon coating layer, according to another embodiment of the present invention.
  • carbon powder having an average particle size of 10 ⁇ m or less is mixed with at least one binder selected from the group consisting of PVA, PVB, PEG, resin, and rosin (S310) .
  • a suitable solvent that is, an organic solvent, such as water or alcohol, depending on the type of binder.
  • the resultant slurry is dried to produce a carbon powder cake, and the cake is pulverized and sorted, thereby producing carbon powder having a particle size that is suitable to the nozzle spraying, for example, an average particle size of 50 - 200 m (S320 to S340) .
  • the carbon powder is conglomerated using the organic binder to be made coarse in comparison with the original size of the powder.
  • the resulting carbon powder is sprayed in conjunction with high pressure gas of about 4 - 7 kgf/cm 2 (S350) using a low temperature spraying device described referring to FIG. 1 through the nozzle so as to form the coating layer on the mother material (S350) .
  • a burn out process may be conducted at about 400 - 500 ° C to remove the organic binder from the coating layer.
  • a better understanding of the present invention may be obtained through the following preferred examples . Physical properties of metals used in the following examples 1 to 7 are described in Table 1.
  • Spraying conditions of a nozzle in examples 1 to 7 are as follows.
  • - Nozzle standard laval type aperture : 4 X 6 mm throat gap : 1 mm
  • Compressed gas type : air pressure : 7 atm temperature : 330 ° C
  • Size of powder fed : ⁇ 44 ⁇ m (325 mesh)
  • EXAMPLE 1 Mixture powder which includes Al powder and AlMg powder (eutectic temperature of about 400 ° C) in a weight ratio of 50:50 (i.e. 0.5A1-0.5AlMg) and air at 7 atm were fed into a spraying nozzle to be applied on an aluminum substrate.
  • the resulting coating was heat treated at about 620 ° C for 1 hour.
  • the heat treated substrate was cut and polished, and cross section was observed using an optical microscope.
  • FIG. 4 illustrates a picture of the cut surface of the resultant substrate. From FIG. 4, it can be seen that the coating layer is nicely attached to the Al substrate. An interface between the Al substrate and the coating layer is apparent due to pores (black portions) trapped in the coating layer. The pores were not observed during the coating, but were generated after the heat treatment.
  • a coating layer was produced under the same conditions as example 1 except that the weight of AlMg increased in the mixture powder so that the metal powder had a composition of 0.3A1-0.7AlMg.
  • the coating layer was heat treated, a section was observed using an optical microscope, and the results are shown in FIG. 5. In comparison with FIG. 4, from FIG. 5, it can be seen that the size of the pore is increased, and an increase in porosity can be confirmed even with the naked eye.
  • FIG. 6 is an optical microscope picture showing a section of a heat treated substrate. As shown in the drawing, pores were scarcely observed in the Al layer, but frequently observed in the AlMg layer.
  • FIG. 7 is an optical microscope picture of the section. From FIG. 7, it can be seen that the porosity of a coating portion (an outermost surface) having the composition of 0.5Al-0.5Mg is higher than that of a coating portion (an interface) having the composition of 0.667A1- 0.333Mg. Accordingly, it can be seen that the porosity of the coating layer increases as the Mg content increases.
  • the pores at the outermost surface are open pores communicating with each other.
  • the pores which are interconnected with each other and are distributed from the outermost surface of the coating layer to the inside thereof, increase the area of contact with surrounding air. Thus, particularly, it is available to applications requiring excellent heat exchanging or heat radiation properties .
  • An Al substrate was coated with mixture powder of Al and Sn, which had a composition of 0.5Al-0.5Sn.
  • the remaining coating conditions were the same as in example 1.
  • the resulting coating layer was heat treated at about 650 ° C for 1 hour, and a section was observed using an optical microscope after it was polished.
  • FIG. 8 is an optical microscope picture of the section. As shown in FIG. 7, very many pores were observed in the coating layer. Judging from the shape of the pores and the porosity, the pores seem to be interconnected with each other.
  • FIG. 9 is a picture of the section. From comparison of an interface portion coated with 0.667A1-0.333Sn with an outermost surface portion coated with 0.5Al-0.5Sn, it can be seen that the pore size is significantly higher and porosity is higher at the outermost surface portion. Accordingly, it can be seen that an increase in the Sn content promotes the generation of pores .
  • Mg, Zn, and Sn which are added to the coating layer in conjunction with Al contribute to the formation of pores in the coating layer after heat treatment.
  • the pore size and porosity increase as the added amount increases.
  • the pores are interconnected with each other and thus become open pores when the content of Mg, Zn, and Sn increases.
  • the inventors of the present invention presume that the reason for this is as follows. However, the following description is referentially provided for purposes of understanding of the present invention but is not intended to be a basis for limitation of the scope of the present invention .
  • Mg, Zn, and Sn which are added with Al form a eutectic liquid phase in conjunction with Al at a heat treatment temperature, and Al is partially melted.
  • the heat treatment temperature must be at least higher than the eutectic temperature of two metals to be mixed with each other.
  • the term "eutectic temperature" as used herein is intended to include a peritectic temperature.
  • the metal powder may contain a small amount of impurities, partial melting may occur at the eutectic temperature or less.
  • the heat treatment temperature must not be higher than the melting point of pure Al, which has the highest melting point. The reason is that the coating will lose structural stability in this case.
  • a carbon coating layer was formed on a copper (Cu) plate. After carbon powder having an average particle size of 5 - 10 m was mixed with about 15 wt% PVA and dried to produce a carbon cake, it was pulverized in a mortar and carbon particles having a particle size of 150 ⁇ m or less were sorted. The sorted carbon powder was sprayed onto the copper plate at the same temperature and pressure as in the above examples, thereby forming a carbon coating layer.
  • FIGS. 12a and 12b are electron microscope pictures of a section and a surface of the carbon coating layer formed on the copper plate. From the drawings, it can be seen that the porous carbon coating layer having excellent adhesion strength was formed on the copper plate.
  • a method of the present invention has the existing advantages of a low temperature spraying process .
  • high temperature treatment since high temperature treatment is not conducted, oxidation of mother material or of a coating layer is maximally suppressed, and damage to the mother material due to heat impact does not occur. Furthermore, a very high coating speed can be assured and it is very easy to control the thickness of the coating layer.
  • Mg, Sn, and Zn which are used in conjunction with Al in the coating method of the present invention, have a melting point lower than Al. Accordingly, since heat treatment is conducted at a melting point of Al or less, the present invention can be applied to most members for thermal and mechanical applications, which include Al or an Al alloy as a mother material, without damage to the mother material .
  • the coating composition is changed to change the porosity of the coating layer.
  • porous coating layers needed in various industrial fields through the above method.
  • a coated member produced according to the method of the present invention it is possible to freely control pore size and porosity. Therefore, it can be used in various members for thermal and mechanical applications .
  • a carbon coating layer produced according to the method of the present invention high thermal conductivity is assured due to a porous structure having many pores, and carbon is much more stable in a corrosive environment, such as sea water or waste water, than metal, thus it is suitable to be used as a member for thermal applications in corrosive environments.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Emergency Management (AREA)
  • Pulmonology (AREA)
  • General Health & Medical Sciences (AREA)
  • Business, Economics & Management (AREA)
  • General Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Emergency Medicine (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Powder Metallurgy (AREA)
PCT/KR2005/000387 2004-02-13 2005-02-11 Porous coated member and manufacturing method thereof using cold spray WO2005078150A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US10/589,184 US20070240603A1 (en) 2004-02-13 2005-02-11 Porous Coated Member and Manufacturing Method Thereof Using Cold Spray
JP2006553054A JP2007522346A (ja) 2004-02-13 2005-02-11 多孔性コーティング部材及び低温噴射法を利用したその製造方法
EP05721848A EP1718781A4 (en) 2004-02-13 2005-02-11 POROUS COATED ELEMENT AND MANUFACTURING METHOD THEREFORE USING COLD SPRAY

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020040009441A KR20050081252A (ko) 2004-02-13 2004-02-13 다공성 금속 코팅 부재 및 저온 분사법을 이용한 그의제조 방법
KR10-2004-0009441 2004-02-13

Publications (1)

Publication Number Publication Date
WO2005078150A1 true WO2005078150A1 (en) 2005-08-25

Family

ID=34858707

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2005/000387 WO2005078150A1 (en) 2004-02-13 2005-02-11 Porous coated member and manufacturing method thereof using cold spray

Country Status (6)

Country Link
US (1) US20070240603A1 (ko)
EP (1) EP1718781A4 (ko)
JP (1) JP2007522346A (ko)
KR (2) KR20050081252A (ko)
CN (1) CN100582284C (ko)
WO (1) WO2005078150A1 (ko)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2072634A3 (en) * 2007-12-19 2011-03-16 United Technologies Corporation Porous protective clothing for turbine engine components
US8642132B2 (en) 2009-05-19 2014-02-04 Toyota Jidosha Kabushiki Kaisha Method of forming carbon particle-containing film, heat transfer member, power module, and vehicle inverter
DE102007017762B4 (de) * 2007-04-16 2016-12-29 Hermle Maschinenbau Gmbh Verfahren zur Herstellung eines Werkstücks mit mindestens einem Freiraum
DE102007017754B4 (de) * 2007-04-16 2016-12-29 Hermle Maschinenbau Gmbh Verfahren zur Herstellung eines Werkstücks mit mindestens einem Freiraum
WO2019008503A1 (en) * 2017-07-04 2019-01-10 Arcelormittal METALLIC SUBSTRATE WITH COLD SPRAY COATING

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100794294B1 (ko) * 2004-03-04 2008-01-14 고경현 내마모성 금속-세라믹 복합체 코팅 형성 방법
KR100554955B1 (ko) * 2004-04-09 2006-03-03 양정인 강구조물 보강방법
KR100802328B1 (ko) * 2005-04-07 2008-02-13 주식회사 솔믹스 내마모성 금속기지 복합체 코팅층 형성방법 및 이를이용하여 제조된 코팅층
KR101118303B1 (ko) * 2005-12-26 2012-03-20 재단법인 포항산업과학연구원 전착 다이아몬드 휠과 그 제조 방법
JP4765103B2 (ja) * 2006-09-29 2011-09-07 日本ケミコン株式会社 コンデンサ
KR101142498B1 (ko) * 2006-12-19 2012-05-07 재단법인 포항산업과학연구원 메탈 베어링 및 그 제조방법
EP2103706A1 (fr) * 2008-03-17 2009-09-23 CENTRE DE RECHERCHES METALLURGIQUES a.s.b.l., CENTRUM VOOR RESEARCH IN DE METALLURGIE v.z.w. Alliage de revêtement obtenu par projection de poudre
KR100974452B1 (ko) * 2008-04-16 2010-08-06 한국에너지기술연구원 고열유속 마이크로다공성 전열표면의 제조방법 및마이크로다공성 전열관.
US20100080921A1 (en) * 2008-09-30 2010-04-01 Beardsley M Brad Thermal spray coatings for reduced hexavalent and leachable chromuim byproducts
KR101145514B1 (ko) * 2009-06-25 2012-05-15 아주대학교산학협력단 콜드 스프레이방법을 이용한 도금층의 형성방법
EP2316374A1 (en) * 2009-11-02 2011-05-04 Straumann Holding AG Process for preparing a ceramic body having a surface roughness
KR101145827B1 (ko) * 2010-04-05 2012-05-17 재단법인 포항산업과학연구원 구리 다공체 제조방법
KR101171682B1 (ko) 2010-04-19 2012-08-07 아주대학교산학협력단 저온 분사 방법을 이용한 알루미늄 또는 알루미늄 합금 표면의 질화처리방법
JP5666167B2 (ja) 2010-05-07 2015-02-12 日本発條株式会社 ステージヒータ及びシャフトの製造方法
DE102010022597A1 (de) * 2010-05-31 2011-12-01 Siemens Aktiengesellschaft Verfahren zum Herstellen einer Schicht mittels Kaltgasspritzen und Verwendung einer solchen Schicht
KR101171535B1 (ko) * 2010-07-09 2012-08-07 아주대학교산학협력단 박막의 부착력 향상을 위한 전처리 장치 및 전처리 방법
CN102059218B (zh) * 2010-12-14 2013-01-30 北京科技大学 一种聚合物基复合材料表面金属化涂层的制备方法及装置
JP5745315B2 (ja) 2011-04-06 2015-07-08 日本発條株式会社 積層体および積層体の製造方法
DE102011102602A1 (de) * 2011-05-27 2012-11-29 Mtu Aero Engines Gmbh Kaltgasspritzverfahren mit verbesserter Haftung und verringerter Schichtporosität
US8974588B2 (en) 2011-09-29 2015-03-10 General Electric Company Coating composition, a process of applying a coating, and a process of forming a coating composition
US20130089726A1 (en) * 2011-10-11 2013-04-11 General Electric Company Process of applying porous metallic structure and cold-sprayed article
US8475882B2 (en) 2011-10-19 2013-07-02 General Electric Company Titanium aluminide application process and article with titanium aluminide surface
KR101657643B1 (ko) * 2014-03-14 2016-09-19 주식회사 알란텀 정전식 금속 다공체 형성장치 및 이를 이용한 정전식 금속 다공체 형성방법
CN104046939B (zh) * 2014-06-25 2017-02-22 中国船舶重工集团公司第七二五研究所 一种用于lng气化器表面防腐复合涂层的制备方法
CN104325148B (zh) * 2014-12-01 2017-02-08 北京矿冶研究总院 一种冷喷涂用低阻力球形金属粉末的制备方法及球形金属粉末
US10047880B2 (en) 2015-10-15 2018-08-14 Praxair Technology, Inc. Porous coatings
US10265810B2 (en) * 2015-12-03 2019-04-23 General Electric Company System and method for performing an in situ repair of an internal component of a gas turbine engine
GB2551191B (en) * 2016-06-10 2020-01-15 Imperial Innovations Ltd Electrically conductive composite coating with azole corrosion inhibitor
CN108720545A (zh) * 2017-04-24 2018-11-02 佛山市顺德区美的电热电器制造有限公司 一种烹饪器具及其制备方法
CN108500444A (zh) * 2018-04-09 2018-09-07 北京石油化工学院 一种提高轻质合金搅拌摩擦焊接接头表面腐蚀性能的方法
EP3835454A4 (en) * 2018-08-10 2022-04-27 NHK Spring Co., Ltd. PROCESS FOR MAKING A MULTI-LAYER BODY
CN115537710A (zh) * 2022-10-11 2022-12-30 江苏智慧光彩光电科技有限公司 Led灯用铝合金表面防腐工艺

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5302414A (en) * 1990-05-19 1994-04-12 Anatoly Nikiforovich Papyrin Gas-dynamic spraying method for applying a coating
JPH09296264A (ja) * 1996-05-08 1997-11-18 Nakabootec:Kk 防汚用常温亜鉛溶射被覆および該溶射被覆の防汚管理方法
WO2002061177A2 (en) * 2001-01-30 2002-08-08 Siemens Westinghouse Power Corporation Thermal barrier coating applied with cold spray technique

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60106975A (ja) * 1983-11-12 1985-06-12 Res Dev Corp Of Japan 加熱ガスによる金属又は合金の超微粒子膜形成法並に装置
JPH02175881A (ja) * 1988-12-27 1990-07-09 Hitachi Cable Ltd 内面多孔質管の製造方法
JP2818226B2 (ja) * 1989-11-22 1998-10-30 株式会社川邑研究所 固体潤滑皮膜を形成する方法
US5305414A (en) * 1992-08-03 1994-04-19 The United States Of America As Represented By The Secretary Of The Navy Low loss glass and optical fibers therefrom
JP3332829B2 (ja) * 1993-12-29 2002-10-07 株式会社東芝 複合金属材料とその製造方法
JPH0978258A (ja) * 1995-09-20 1997-03-25 Toshiba Corp 遮熱コーティングを有する高温部材およびその製造方法
JP4248037B2 (ja) * 1997-02-04 2009-04-02 株式会社不二機販 金属被膜の形成方法
JPH1190579A (ja) * 1997-09-18 1999-04-06 Nippon Karu Kk 耐熱衝撃性黒鉛型およびその製造方法
DE69902449T2 (de) * 1998-03-14 2002-12-12 Dana Corp., Toledo Verfahren zur herstellung einer gleitlagerbeschichtung
US6139913A (en) * 1999-06-29 2000-10-31 National Center For Manufacturing Sciences Kinetic spray coating method and apparatus
US6372299B1 (en) * 1999-09-28 2002-04-16 General Electric Company Method for improving the oxidation-resistance of metal substrates coated with thermal barrier coatings
RU2183695C2 (ru) * 2000-08-25 2002-06-20 Общество С Ограниченной Ответственностью Обнинский Центр Порошкового Напыления Способ получения покрытий
JP2003082476A (ja) * 2001-06-26 2003-03-19 Toshiba Corp 耐食・耐摩耗タービン部材および製造方法
US20030039856A1 (en) * 2001-08-15 2003-02-27 Gillispie Bryan A. Product and method of brazing using kinetic sprayed coatings
RU2205897C1 (ru) 2001-12-26 2003-06-10 Общество С Ограниченной Ответственностью Обнинский Центр Порошкового Напыления Способ нанесения покрытий
JP3613255B2 (ja) * 2002-03-22 2005-01-26 独立行政法人産業技術総合研究所 成膜装置
US6592947B1 (en) * 2002-04-12 2003-07-15 Ford Global Technologies, Llc Method for selective control of corrosion using kinetic spraying

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5302414A (en) * 1990-05-19 1994-04-12 Anatoly Nikiforovich Papyrin Gas-dynamic spraying method for applying a coating
US5302414B1 (en) * 1990-05-19 1997-02-25 Anatoly N Papyrin Gas-dynamic spraying method for applying a coating
JPH09296264A (ja) * 1996-05-08 1997-11-18 Nakabootec:Kk 防汚用常温亜鉛溶射被覆および該溶射被覆の防汚管理方法
WO2002061177A2 (en) * 2001-01-30 2002-08-08 Siemens Westinghouse Power Corporation Thermal barrier coating applied with cold spray technique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1718781A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007017762B4 (de) * 2007-04-16 2016-12-29 Hermle Maschinenbau Gmbh Verfahren zur Herstellung eines Werkstücks mit mindestens einem Freiraum
DE102007017754B4 (de) * 2007-04-16 2016-12-29 Hermle Maschinenbau Gmbh Verfahren zur Herstellung eines Werkstücks mit mindestens einem Freiraum
EP2072634A3 (en) * 2007-12-19 2011-03-16 United Technologies Corporation Porous protective clothing for turbine engine components
US8147982B2 (en) 2007-12-19 2012-04-03 United Technologies Corporation Porous protective coating for turbine engine components
US8642132B2 (en) 2009-05-19 2014-02-04 Toyota Jidosha Kabushiki Kaisha Method of forming carbon particle-containing film, heat transfer member, power module, and vehicle inverter
WO2019008503A1 (en) * 2017-07-04 2019-01-10 Arcelormittal METALLIC SUBSTRATE WITH COLD SPRAY COATING
WO2019008404A1 (en) * 2017-07-04 2019-01-10 Arcelormittal METALLIC SUBSTRATE CARRYING COLD SPRAY COATING

Also Published As

Publication number Publication date
KR100794295B1 (ko) 2008-01-14
KR20050081252A (ko) 2005-08-18
EP1718781A1 (en) 2006-11-08
KR20060114363A (ko) 2006-11-06
CN1918316A (zh) 2007-02-21
US20070240603A1 (en) 2007-10-18
EP1718781A4 (en) 2009-03-18
JP2007522346A (ja) 2007-08-09
CN100582284C (zh) 2010-01-20

Similar Documents

Publication Publication Date Title
US20070240603A1 (en) Porous Coated Member and Manufacturing Method Thereof Using Cold Spray
CN107761035B (zh) 一种耐腐蚀的完全致密热喷涂金属合金涂层及其制备方法
EP0771884B1 (en) Boron nitride and aluminum thermal spray powder
EP1756330B1 (en) Method for reducing metal oxide powder and attaching it to a heat transfer surface and the heat transfer surface
CA1103529A (en) Slurry coating process
Takaku et al. Development of Bi-base high-temperature Pb-free solders with second-phase dispersion: Thermodynamic calculation, microstructure, and interfacial reaction
KR20080096576A (ko) 저온 분무 기법에 의한 금속 발포체의 형성방법
CN101730757A (zh) 涂覆基材表面的方法和经过涂覆的产品
US20240247359A1 (en) Pristine graphene disposed in a metal matrix
WO2015174541A1 (ja) 多孔質アルミニウム焼結体及び多孔質アルミニウム焼結体の製造方法
CN114226722A (zh) 防腐蚀材料、由其制备的防腐蚀层和包括防腐蚀层的炊具
JP2015137384A (ja) 金属皮膜およびその成膜方法
JP6855891B2 (ja) 溶射用粉末およびこれを用いた溶射皮膜の成膜方法
KR20080065480A (ko) 저온분사공정을 이용한 텅스텐/구리 복합재료의 코팅방법
KR100723538B1 (ko) 분산강화 합금 형성방법 및 이에 의해 제조된 분산강화합금
Khan et al. Evaluation of die-soldering and erosion resistance of high velocity oxy-fuel sprayed MoB-based cermet coatings
CN101545087A (zh) 微复合Fe-Al/Al2O3陶瓷涂层及其制备方法
CA2177921C (en) Method for producing a tib 2-based coating and the coated article so produced
Gale et al. Microstructure and mechanical properties of titanium aluminide wide-gap, transient liquid-phase bonds prepared using a slurry-deposited composite interlayer
CN114507827B (zh) 一种铝基非晶复合材料的制备方法及铝基非晶复合材料
CN111690892B (zh) 一种max相基涂层的制备方法
CN115283664A (zh) Cu-Al2O3冷喷涂复合粉末及其制备方法和应用
CN1052473A (zh) 陶瓷-金属粘接
JP3288567B2 (ja) 複合熱溶射粉末
WO2006088233A1 (en) Heat exchanger member and production method thereof

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200580004854.6

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1020067013942

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2006553054

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Ref document number: DE

WWE Wipo information: entry into national phase

Ref document number: 2005721848

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020067013942

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2005721848

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 10589184

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 10589184

Country of ref document: US