WO2011071225A1 - 열플라즈마를 이용한 고순도 구리분말의 제조방법 - Google Patents
열플라즈마를 이용한 고순도 구리분말의 제조방법 Download PDFInfo
- Publication number
- WO2011071225A1 WO2011071225A1 PCT/KR2010/004734 KR2010004734W WO2011071225A1 WO 2011071225 A1 WO2011071225 A1 WO 2011071225A1 KR 2010004734 W KR2010004734 W KR 2010004734W WO 2011071225 A1 WO2011071225 A1 WO 2011071225A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- powder
- purity
- high purity
- thermal plasma
- copper
- Prior art date
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 65
- 239000010949 copper Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 10
- 238000002347 injection Methods 0.000 abstract description 7
- 239000007924 injection Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 2
- 238000005477 sputtering target Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 230000008018 melting Effects 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000009832 plasma treatment Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 241000380131 Ammophila arenaria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 tungstian (W) Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/12—Making metallic powder or suspensions thereof using physical processes starting from gaseous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Definitions
- the production method of high purity copper powder is generally known to process chemical wet separation and purification from ore, and to produce metal powder by decomposing and hydrogen-reducing the oxide or compound wool obtained by producing intermediate oxide or compound wool of high purity. have.
- the oxygen content of the wet powder is more than 2000 ppm, and there is a limit to high purity due to the residue of impurities in the oxide, and there is a problem of high environmental pollution by various solutions. , There is considerable difficulty in handling the particle size of the powder produced to 1 or less.
- Korean Patent Publication No. 10-2005 -0033721 introduces carbon nanotube manufacturing method by ultra high silver by using DC thermal plasma, and the DC plasma method has difficulty in producing high purity metal powder due to the inevitable contamination of impurities caused by electrode erosion. .
- Prior art A obtains a high-purity metal powder such as tungstian (W), molybdenum (Mo), tantalum (Ta), lute s (Ru), etc. using a thermal plasma from a powder obtained by pulverizing a metal block.
- High purity metal powders such as Ta) and Ru Ib (Ru) have been obtained.
- the high melting point metal is not melted and vaporized in the process of passing the high melting point metal through the heat plasma, and the impurities have a high purity through a process in which impurities having low melting points are vaporized to fly to a cyclone. Since this relatively low copper (Cu) is evaporated and blown away with impurities to the raw material powder by a method such as a high melting point metal, it is impossible to high-purify the copper powder by the method as described above.
- the present invention is to improve the conventional problems and to use a thermal plasma as in the prior art, to obtain a copper powder having a relatively low melting point
- the purpose of the present invention is to obtain a high-purity copper powder different from the prior art by appropriately applying the injection rate injected into the thermal plasma torch of the raw material powder and the reaction passage section in the reaction vessel.
- the present invention for achieving the above object in the method for producing a metal powder using a heat plasma torch, the copper (Cu) powder having an average particle diameter of 30 ⁇ 450 by passing the thermal plasma torch at a rate of 2 ⁇ 30kg / hr It consists of a manufacturing method of obtaining a high purity copper powder having an average particle diameter of 5 to 300 ⁇ .
- the copper (Cu) powder introduced into the thermal plasma torch is preferably 95 99% pure, and the final high purity copper powder obtained through the thermal plasma torch is preferably 4N class (99.99%) or more. .
- the present invention provides relatively low melting points such as aluminium (AI), silver (Ag), nickel (Ni), tungsten (W), molybdenum (Mo), and ruthenium (Ru).
- high melting point metal powder such as tantalum (Ta) can be applied.
- the raw powder used was an average particle diameter of 30 450 f ⁇ copper powder.
- the reason is that when the raw material powder becomes fine below 30 m, the average particle diameter of the powder becomes 5 / or less after the plasma reaction, so that coagulation occurs between the powders, and when the raw material powder reaches 450 ⁇ or more, the plasma treatment effect rapidly decreases. to be.
- the present invention can be distinguished from the prior art by using a metal powder through a thermal plasma torch at an injection speed of 2 to 30 kg / hr and designing the length of the reaction vessel in a range of at least 1.4 m to 2.5 m. .
- Operating gases generating heat plasma include argon (Ar), hydrogen (H2), Helm (He), and because the H purifying effect tends to increase due to the increase in the amount of hydrogen clearing, 5 to 50 vol% hydrogen is added to argon (Ar).
- the effect is sharply increased from 5vol% or more, 5-50 %% of the Qinggae is preferable because the high purity effect is sharply lowered to 50vol% or more.
- FIG. 1 shows a schematic diagram of a thermal plasma apparatus used in the present invention, in which a coil 2 is wound around an outer shaft of a water-cooled insulation tube at a lower end of a supply part 2 to which powder raw material is supplied, and a high frequency electric field is applied to the coil.
- a plasma torch section 1 having a thermal plasma high temperature zone 6 in the torch.
- the reaction raw material is composed of a reaction vessel (3) in which the injected raw powder is highly purified by thermal plasma, a ' cyclone (4) for collecting the removed impurities, and a bag filter (5) for collecting the manufactured high purity metal powder. have.
- the thermal plasma generated by such a high frequency power supply is called RF thermal plasma (or high frequency plasma).
- the generation of RF thermal plasma does not require an electrode, and contamination by the evaporation of the cathode material can be avoided.
- the frequency of the high frequency power source used to generate the RF thermal plasma can be 4 ⁇ 13.5MHz, but 4MHz is used to widen the high temperature range.
- the present invention is similar in terms of applying through the thermal plasma torch of the prior art described above, the method applied in the prior art is a high purity in the present invention because the raw material powder is vaporized with impurities and fly away The copper powder to be applied is not applicable.
- the present invention is preferably implemented to limit the range of the raw material powder injection speed to 2 ⁇ 30kg / hr.
- the present invention is more preferable to design the length of the reaction vessel (3) in the range of 1.4m ⁇ 2.5m in the apparatus. The length of the reaction vessel of the present invention is 2m or more different from the prior art, and when the length of the reaction vessel is 1.4m or less, the above raw material powder cannot be treated.
- the injection speed (2 to 30 kg / hr) and the length of the reaction vessel (1.4 to 2.5 m) when the plasma torch passes through the raw material powder are appropriately applied. It is possible to obtain a high-purity metal powder having an effect of improving the problem of evaporating and flying with impurities.
- Figure 2 is a micrograph of the raw material powder (Cu) before the plasma treatment
- Cu powder having an average particle diameter of 20 ps ⁇ and a purity of 96% was used as a raw material, and RF thermal plasma treatment shown in FIG.
- the high frequency power supply frequency is 4MHz
- Cu powder is supplied to the plasma high temperature region through the raw material supply unit, and the raw powder is melted by heat plasma, and spheroidized and high purity.
- the injection speed of the raw material powder was 5kg / hr and 30kg / hr, respectively.
- Example 2 A high-purity Cu powder having a purity of 99.999% and an average particle diameter of 11.88 spherical shape was prepared in the same manner as in Example 1 except for using Cu powder having an average particle diameter of 33 and a purity of 96%.
- a high-purity Cu powder having a purity of 99.99% and an average particle diameter of 19.8 spherical shape was prepared in the same manner as in Example 1 except for using Cu powder having an average particle size of 48 and a purity of 97%.
- a high-purity Cu powder having a purity of 99.99% purity and an average particle diameter of 35.3 spherical shape was prepared in the same manner as in Example 1, except that Cu powder having an average particle diameter of 86% purity was used.
- a high-purity Cu powder having a purity of 99.99% purity and an average particle diameter of 48.1 spherical shape was prepared in the same manner as in Example 1 except that Cu powder having an average particle diameter of 103 / M and a purity of 96% was used.
- a high-purity Cu powder having a purity of 99.99% purity and an average particle diameter of 110.5 was prepared in the same manner as in Example 1, except that Cu powder having an average particle diameter of 233 / M and a purity of 96% was used.
- a high-purity Cu powder having a purity of 99.45% and an average particle diameter of 259.8 was prepared in the same manner as in Example 1 except for using Cu powder having an average particle diameter of 588 and a purity of 97%.
- FIGS. 1 and 2 show micrographs of the metal powder
- Figure 1 shows the raw powder (Cu) state before the plasma treatment
- Figure 2 is a metal powder (Cu) prepared by the above embodiment It is shown.
- the metal powder after the plasma treatment is particulate and spherical in shape.
- the present invention is widely used in the manufacture of spi S ring target materials in the electronics industry, high purity copper powder materials used in conductive pastes, penetrator liners, and the like.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/513,712 US9061353B2 (en) | 2009-12-07 | 2010-07-20 | Production method for high purity copper powder using a thermal plasma |
JP2012543006A JP5746207B2 (ja) | 2009-12-07 | 2010-07-20 | 熱プラズマを用いた高純度銅粉の製造方法 |
EP10836122.1A EP2511032A4 (en) | 2009-12-07 | 2010-07-20 | PROCESS FOR THE PRODUCTION OF HIGH-DEGREASED POWDER COPPER USING THERMAL PLASMA |
CN201080055710.4A CN102665972B (zh) | 2009-12-07 | 2010-07-20 | 借助热等离子体生产高纯度铜粉末的方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020090120452A KR101134501B1 (ko) | 2009-12-07 | 2009-12-07 | 열플라즈마를 이용한 고순도 구리분말의 제조방법 |
KR10-2009-0120452 | 2009-12-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011071225A1 true WO2011071225A1 (ko) | 2011-06-16 |
Family
ID=44145751
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2010/004734 WO2011071225A1 (ko) | 2009-12-07 | 2010-07-20 | 열플라즈마를 이용한 고순도 구리분말의 제조방법 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9061353B2 (zh) |
EP (1) | EP2511032A4 (zh) |
JP (1) | JP5746207B2 (zh) |
KR (1) | KR101134501B1 (zh) |
CN (1) | CN102665972B (zh) |
WO (1) | WO2011071225A1 (zh) |
Families Citing this family (19)
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EP2923781A4 (en) * | 2012-11-26 | 2016-07-13 | Mitsui Mining & Smelting Co | COPPER POWDER AND PROCESS FOR PRODUCING THE SAME |
KR101510852B1 (ko) * | 2013-09-16 | 2015-04-10 | 한국생산기술연구원 | Rf 플라즈마 처리를 이용한 루테늄-크롬 합금 분말의 제조방법 |
KR101647997B1 (ko) * | 2014-09-15 | 2016-08-12 | 한국생산기술연구원 | 밀도와 구형도가 향상된 루테늄-크롬 합금 및 그 제조방법 |
CN106257978B (zh) * | 2015-04-22 | 2019-09-24 | 日立金属株式会社 | 金属颗粒以及它的制造方法、包覆金属颗粒、金属粉体 |
EP4324577A1 (en) | 2015-12-16 | 2024-02-21 | 6K Inc. | Method of producing spheroidal dehydrogenated titanium alloy particles |
KR101777308B1 (ko) * | 2016-01-13 | 2017-09-12 | 주식회사 풍산홀딩스 | 열플라즈마를 이용한 균일한 산소 패시베이션 층을 갖는 구리 나노 금속분말의 제조방법 및 이를 제조하기 위한 장치 |
KR102343903B1 (ko) * | 2016-04-14 | 2021-12-30 | 주식회사 풍산홀딩스 | 열플라즈마를 이용한 균일한 산소 패시베이션 층을 갖는 은나노 금속분말의 제조방법 및 이를 제조하기 위한 장치 |
KR20170118290A (ko) * | 2016-04-14 | 2017-10-25 | 주식회사 풍산홀딩스 | 열플라즈마를 이용한 균일한 산소 패시베이션 층을 갖는 은나노 금속분말의 제조방법 및 이를 제조하기 위한 장치 |
CN107931626A (zh) * | 2017-12-18 | 2018-04-20 | 南通金源智能技术有限公司 | 一种新型3d打印铝合金粉末的成分及制备方法 |
EP3810358A1 (en) * | 2018-06-19 | 2021-04-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
US11312638B2 (en) * | 2019-03-14 | 2022-04-26 | Kolon Glotech, Inc. | Method for synthesizing copper sulfide nano powder using plasma synthesis |
CN110039062B (zh) * | 2019-04-18 | 2020-11-10 | 北京科技大学 | 一种制备球形镍基粉末的方法 |
WO2020223374A1 (en) | 2019-04-30 | 2020-11-05 | 6K Inc. | Lithium lanthanum zirconium oxide (llzo) powder |
US11311938B2 (en) | 2019-04-30 | 2022-04-26 | 6K Inc. | Mechanically alloyed powder feedstock |
EP4061787B1 (en) | 2019-11-18 | 2024-05-01 | 6K Inc. | Unique feedstocks for spherical powders and methods of manufacturing |
US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
EP4173060A1 (en) | 2020-06-25 | 2023-05-03 | 6K Inc. | Microcomposite alloy structure |
CA3186082A1 (en) | 2020-09-24 | 2022-03-31 | 6K Inc. | Systems, devices, and methods for starting plasma |
KR20230095080A (ko) | 2020-10-30 | 2023-06-28 | 6케이 인크. | 구상화 금속 분말을 합성하는 시스템 및 방법 |
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2009
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2010
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- 2010-07-20 JP JP2012543006A patent/JP5746207B2/ja not_active Expired - Fee Related
- 2010-07-20 US US13/513,712 patent/US9061353B2/en not_active Expired - Fee Related
- 2010-07-20 EP EP10836122.1A patent/EP2511032A4/en not_active Withdrawn
- 2010-07-20 WO PCT/KR2010/004734 patent/WO2011071225A1/ko active Application Filing
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Also Published As
Publication number | Publication date |
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JP5746207B2 (ja) | 2015-07-08 |
KR101134501B1 (ko) | 2012-04-13 |
US9061353B2 (en) | 2015-06-23 |
KR20110064036A (ko) | 2011-06-15 |
JP2013513032A (ja) | 2013-04-18 |
US20120240726A1 (en) | 2012-09-27 |
EP2511032A1 (en) | 2012-10-17 |
EP2511032A4 (en) | 2013-10-30 |
CN102665972B (zh) | 2015-09-23 |
CN102665972A (zh) | 2012-09-12 |
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