KR100967708B1 - Method for producing metal oxide nanoparticles having a single particle size, and metal oxide nanoparticles prepared therefrom - Google Patents
Method for producing metal oxide nanoparticles having a single particle size, and metal oxide nanoparticles prepared therefrom Download PDFInfo
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- KR100967708B1 KR100967708B1 KR1020020075862A KR20020075862A KR100967708B1 KR 100967708 B1 KR100967708 B1 KR 100967708B1 KR 1020020075862 A KR1020020075862 A KR 1020020075862A KR 20020075862 A KR20020075862 A KR 20020075862A KR 100967708 B1 KR100967708 B1 KR 100967708B1
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- metal oxide
- oxide nanoparticles
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- iron
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 47
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000002245 particle Substances 0.000 title abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000003637 basic solution Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 19
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- 239000004094 surface-active agent Substances 0.000 claims description 34
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- 239000012266 salt solution Substances 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- FBELJLCOAHMRJK-UHFFFAOYSA-L disodium;2,2-bis(2-ethylhexyl)-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCC(CC)CC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CC(CC)CCCC FBELJLCOAHMRJK-UHFFFAOYSA-L 0.000 claims description 7
- 229960002089 ferrous chloride Drugs 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
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- 239000011734 sodium Substances 0.000 claims description 5
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- 229910052742 iron Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
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- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- -1 sodium alkylsulfonate Chemical class 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 2
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000012607 small angle X-ray scattering experiment Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229940031182 nanoparticles iron oxide Drugs 0.000 abstract description 32
- 238000009826 distribution Methods 0.000 abstract description 22
- 239000000693 micelle Substances 0.000 abstract description 12
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- 239000007858 starting material Substances 0.000 abstract description 2
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 20
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
본 발명은 초상자성을 가지며 입자 크기가 단일분포를 가지는 금속 산화물 나노입자의 제조방법에 관한 것이다. 본 발명에서는 유중수형계의 에멀젼을 이용하여 분산된 역미셀 수용액상의 물방울 안에서 금속염 출발물질을 염기성 용액과 반응시켜 입자 크기가 단일분포를 갖는 산화철 나노 입자를 제조한다. The present invention relates to a method for producing metal oxide nanoparticles having superparamagnetism and having a single particle size distribution. In the present invention, iron oxide nanoparticles having a single particle size are prepared by reacting a metal salt starting material with a basic solution in a water droplet of an inverted micelle aqueous solution dispersed using a water-in-oil emulsion.
역미셀, 단일분포, 산화철 나노입자, 금속 나노 산화물Reverse micelle, single distribution, iron oxide nanoparticles, metal nanooxide
Description
도 1은 역미셀(reverse micelle)에 의한 금속 산화물 나노입자 콜로이드 용액 제조 장치의 개략도이다.1 is a schematic diagram of an apparatus for preparing a metal oxide nanoparticle colloidal solution by reverse micelles.
도 2 내지 도 5는 실시예 1 내지 4의 산화철 나노입자의 X-선 소각 산란(small angle X-ray scattering) 실험의 기니에 도시법(Guinier plot)에 따른 결과를 보인 도면이다. 2 to 5 show the results according to the Guinea plot (Guinier plot) of the small angle X-ray scattering experiment of the iron oxide nanoparticles of Examples 1 to 4.
도 6은 실시예 1의 산화철 나노입자의 X-선 소각 산란실험의 간접 퓨리에 변환(Indirect Fourier transformation)과 로그노말 함수(Lognormal distribution)를 이용한 입자의 분포도를 나타낸 도면이다.FIG. 6 is a diagram showing the distribution of particles using indirect Fourier transformation and Lognormal distribution of X-ray incineration scattering experiments of iron oxide nanoparticles of Example 1. FIG.
도 7은 실시예 1에 따라 제조된 산화철 나노입자의 자기적 특성측정 (Vibrating Sample Magnetometer)을 나타낸 도면이다.FIG. 7 is a view showing a magnetic characteristic measurement (Vibrating Sample Magnetometer) of the iron oxide nanoparticles prepared according to Example 1.
도 8은 실시예 1에 따라 제조된 산화철 나노입자 콜로이드의 전자현미경 사진(transmittance electron microscope)이다. FIG. 8 is a transmission electron microscope of the iron oxide nanoparticle colloid prepared according to Example 1. FIG.
도 9는 실시예 1에 따라 제조된 산화철 나노입자 분말의 전자현미경 사진(transmittance electron microscope)이다. FIG. 9 is a transmission electron microscope of the iron oxide nanoparticle powder prepared according to Example 1. FIG.
[산업상 이용분야][Industrial use]
본 발명은 금속 산화물 나노입자의 제조방법 및 이로부터 제조되는 금속 산화물 나노입자에 관한 것으로서, 보다 구체적으로는, 입자 크기가 단일분포를 가지는 금속 산화물 나노입자의 제조방법 및 이로부터 제조되는 금속 산화물 나노입자에 관한 것이다. The present invention relates to a method for preparing metal oxide nanoparticles and metal oxide nanoparticles prepared therefrom, and more particularly, to a method for preparing metal oxide nanoparticles having a single particle size and metal oxide nanoparticles prepared therefrom. It is about particles.
[종래기술][Private Technology]
최근 많은 주목을 받고 있는 나노기술 가운데 하나인 나노입자의 제조방법은 자기기록 매체, 프린트 잉크 토너, 의료용 진단시약, 대전 방지제, 전자파 차폐 및 흡수 등으로 응용하기 위해서 선진국을 비롯하여 많은 국가에서 연구가 시도되고 있는 첨단 분야이다. 특히 입자 크기가 단일분포를 가지는 산화철 나노입자는 전도성 고분자와 함께 복합체를 제조하는 데 이용 가능하거나 입자 크기가 단일분포로 인한 초상자성을 이용하여 자기 기록 매체 및 프린트 잉크 토너, 의료용 진단시약, 대전 방지제, 전자파 차폐 및 흡수체 등으로 응용 가능하여 전자, 의학, 전기 분야의 기초 소재로서 이용되고 있다. 일반적으로 자성 입자는 제조 조건이나 형성된 입자 크기에 따라서 여러 가지의 자성체의 특성을 갖는다. 더 나아가 단일분포를 가지는 산화철 나노입자는 단일 자성도메인을 가지고 높은 자화율을 가지는 초상자성을 나타낸다. The nanoparticle manufacturing method, which is one of the nano technologies recently attracting a lot of attention, has been attempted in many countries including developed countries for application to magnetic recording media, print ink toners, medical diagnostic reagents, antistatic agents, electromagnetic shielding and absorption, etc. It is a cutting edge field. In particular, iron oxide nanoparticles having a single particle size can be used to prepare composites with conductive polymers or by using superparamagnetism due to a single particle size, magnetic recording media and print ink toners, medical diagnostic reagents, and antistatic agents. It can be used as electromagnetic shielding and absorber, and is used as a basic material in the fields of electronics, medicine, and electricity. In general, the magnetic particles have various magnetic properties depending on the production conditions and the particle size formed. Furthermore, iron oxide nanoparticles with a single distribution exhibit superparamagnetism with a single magnetic domain and high susceptibility.
지금까지, 이러한 특성을 나타내는 산화철 나노입자를 제조하는 방법들 중 계면활성제를 이용한 역미셀에 의한 제조 방법은 몇 가지 제안들이 있었다. 예를 들어, 산화철 나노입자는 철염 용액을 염기성 용액에 벌크 상태로 침전시키고 이 침전된 나노입자를 생적합성(biocompatibility) 물질과 함께 계면활성제를 이용하여 마이크로 구형으로 제조하는 방법이 미국 특허 제4,206,094호 및 제4,219,411호에서 제안되었다. 이러한 제조방법들에 의해서 산화철 나노입자는 제조되었지만, 그 자성 입자가 수 나노미터 크기가 아니고, 입자가 단일분포를 나타내지 않았다. Until now, among the methods for producing iron oxide nanoparticles exhibiting these characteristics, there have been several proposals for the method of preparing reverse micelles using a surfactant. For example, iron oxide nanoparticles may be prepared by depositing an iron salt solution in a basic solution in a bulk state and preparing the precipitated nanoparticles in a microsphere using a surfactant together with a biocompatibility material. US Pat. No. 4,206,094 And 4,219,411. Iron oxide nanoparticles were produced by these preparation methods, but the magnetic particles were not several nanometers in size, and the particles did not exhibit a single distribution.
또한 미국 특허 제4,4454,234호, 제4,863,715호에서는 아크릴 고분자를 이용하여 강자성 및 준강자성을 가지는 자성입자를 코팅하거나 고분자를 포함하는 용액에 자성입자를 넣어 초음파 분해방법을 이용하여 제조하였다. 이들은 고분자를 이용하여 코팅함으로써 응집이 되지 않는 자성입자를 제조하였지만, 그 자성체의 특성은 초상자성을 나타내지는 않았다. In addition, US Pat. Nos. 4,4454,234, 4,863,715 were prepared using ultrasonic decomposition by coating magnetic particles having ferromagnetic and quasi-ferromagnetic properties using acrylic polymers or putting magnetic particles in a solution containing the polymers. They produced magnetic particles that were not aggregated by coating with a polymer, but the characteristics of the magnetic body did not show superparamagnetism.
WO 90/01295에서는 초상자성을 나타내는 산화철의 나노입자를 철염 수용액에 염기성 용액을 첨가시켜 침전법으로 제조하였지만, 그 나노입자의 크기가 균일하지 않았다. In WO 90/01295, nanoparticles of iron oxide showing superparamagnetism were prepared by adding a basic solution to an aqueous iron salt solution by precipitation, but the size of the nanoparticles was not uniform.
이와 같이 금속 산화물 나노입자의 활용 분야는 매우 넓고 다양하지만 아직도 다양한 제조방법의 개발이 미약한 실정이다.As such, the field of application of metal oxide nanoparticles is very wide and diverse, but development of various manufacturing methods is still weak.
본 발명은 상술한 특허들의 자성 특성과 입자분포의 다양성의 문제점을 해결하기 위하여 안출된 것으로서, 본 발명의 목적은 초상자성을 나타내는, 입자 크기 가 단일 분포를 가지는 금속 산화물 나노입자의 제조방법을 제공하기 위한 것이다.The present invention has been made to solve the problems of the magnetic properties and diversity of the particle distribution of the above-described patents, an object of the present invention is to provide a method for producing metal oxide nanoparticles having a single distribution of particle size exhibiting superparamagnetism. It is to.
본 발명의 다른 목적은 초상자성을 가지며, 입자 크기가 단일분포를 가지는 금속 산화물 나노입자를 제공하기 위한 것이다.Another object of the present invention is to provide a metal oxide nanoparticle having a superparamagnetism and having a single distribution of particle size.
본 발명의 또 다른 목적은 상기 금속 산화물 나노입자와 전도성 고분자를 포함하는 복합체를 제공하기 위한 것이다.Still another object of the present invention is to provide a composite including the metal oxide nanoparticles and the conductive polymer.
본 발명은 상기한 목적을 달성하기 위하여, 본 발명은The present invention to achieve the above object, the present invention
분산 유기용매에 계면활성제를 첨가 혼합하여 계면활성제 용액을 제조하는 단계;Adding a surfactant to a dispersed organic solvent to prepare a surfactant solution;
상기 계면활성제 용액과 금속염 수용액을 혼합하여 제1 유중수형계 에멀젼을 제조하는 단계;Preparing a water-in-oil emulsion by mixing the surfactant solution and an aqueous metal salt solution;
상기 계면활성제 용액과 염기성 용액을 혼합하여 제2 유중수형계 에멀젼을 제조하는 단계;Mixing the surfactant solution and the basic solution to prepare a second water-in-oil emulsion;
상기 제1 및 제2 유중수형계 에멀젼을 혼합하여 금속염과 염기성 용액을 반응시켜 금속 산화물 나노입자 콜로이드 용액을 제조하는 단계; 및Preparing a metal oxide nanoparticle colloidal solution by reacting a metal salt with a basic solution by mixing the first and second water-in-oil emulsions; And
상기 금속 산화물 나노입자 콜로이드 용액을 세척, 분리한 후 건조하여 금속 산화물 나노입자를 얻는 단계를 포함하는 금속 산화물 나노입자의 제조방법을 제공한다. It provides a method for producing a metal oxide nanoparticle comprising the step of obtaining a metal oxide nanoparticles by washing, separating and drying the metal oxide nanoparticle colloidal solution.
본 발명은 또한 초상자성과 단일분포의 입자 크기를 가지는 금속 산화물 나노입자를 제공한다. The present invention also provides metal oxide nanoparticles having superparamagnetic and monodisperse particle sizes.
본 발명은 또한 금속 산화물 나노입자와 전도성 고분자를 포함하는 복합체를 제공한다.The invention also provides a composite comprising a metal oxide nanoparticle and a conductive polymer.
이하 본 발명을 보다 상세히 설명한다. Hereinafter, the present invention will be described in more detail.
본 발명의 초상자성을 나타내는, 입자 크기가 단일 분포를 가지는 금속 산화물 나노입자는 유중수형계의 역미셀을 포함하는 금속 산화물 나노입자 콜로이드 용액을 이용하여 제조된다.Metal oxide nanoparticles having a single distribution of particle size, which exhibits superparamagnetism of the present invention, are prepared using a colloidal solution of metal oxide nanoparticles containing reverse micelles of water-in-oil type.
우선 분산 유기용매에 계면활성제를 첨가한 후 혼합하여 계면활성제 용액(저장 용액)을 제조한다. 상기 분산 유기용매로는 핵산, 헵탄, 옥탄, 데칸, 도데칸 등과 같은 포화된 선형 탄화수소류, 사이클로헥산, 사이클로헵탄 등의 포화된 고리화 탄화수소류, 벤젠, 톨루엔, 부틸벤젠 등의 방향족 탄화수소류가 사용되며, 바람직하게는 헵탄을 사용한다. 상기 계면활성제로는 음이온 계면활성제가 바람직하게 사용될 수 있으며, 이의 구체적인 예로는 소듐 도데실술페이트, 소듐 비스(2-에틸헥실)술포숙시네이트(AOT), 도데실벤젠술폰닉산, 소듐 디옥틸술포숙시네이트, 소듐 알킬페놀 에테르 술포네이트, 소듐 알킬술포네이트 등이 있으며, 이중에서 소듐 비스(2-에틸헥실)술포숙시네이트가 바람직하다. First, a surfactant is added to the dispersed organic solvent, followed by mixing to prepare a surfactant solution (stock solution). The dispersed organic solvents include saturated linear hydrocarbons such as nucleic acid, heptane, octane, decane and dodecane, saturated cyclic hydrocarbons such as cyclohexane and cycloheptane, and aromatic hydrocarbons such as benzene, toluene and butylbenzene. Is used, preferably heptane is used. Anionic surfactant may be preferably used as the surfactant, and specific examples thereof include sodium dodecyl sulfate, sodium bis (2-ethylhexyl) sulfosuccinate (AOT), dodecylbenzenesulfonic acid, and sodium dioctylsulfosuccinate. Cyanate, sodium alkylphenol ether sulfonate, sodium alkylsulfonate, and the like, of which sodium bis (2-ethylhexyl) sulfosuccinate is preferred.
분산 유기용매와 계면활성제는 초음파 분해하여 혼합하는 것이 바람직하고, 초음파 분해시간은 10 내지 30 분간 실시하는 것이 바람직하다. 상기에서와 같이 제조된 계면활성제는 0.1 내지 1.0 몰의 양으로 분산 유기용매에 첨가되는 것이 바람직하다.The dispersed organic solvent and the surfactant are preferably ultrasonically decomposed and mixed, and the ultrasonic decomposition time is preferably performed for 10 to 30 minutes. The surfactant prepared as above is preferably added to the dispersed organic solvent in an amount of 0.1 to 1.0 mole.
그런 다음 상기 계면활성제 용액과 금속염 수용액을 혼합하여 제1 유중수형 계 에멀젼을 제조한다. Then, the first water-in-oil emulsion is prepared by mixing the surfactant solution and the aqueous metal salt solution.
상기 금속염 수용액은 금속염을 증류수에 첨가하여 제조하는 것으로 상기 증류수는 이차 증류한 것으로 질소가스로 약 30분 정도 기포화하여 탈이온화된 것을 사용한다. 상기 금속염으로는 철, 코발트, 니켈 또는 크롬의 금속염이 바람직하게 사용될 수 있다. 염의 형태는 특별히 제한되지는 않으며, 특히 자기 특성의 산화철 나노입자 제조시에 모든 철염이 사용될 수 있다. 바람직한 금속염 형태로는 염화물, 황산염, 질산염, 아세트산염, 옥살산염, 카보닐염 등이 사용되는 것이 바람직하다. 바람직한 구체적인 예로는 황산철, 염화제일철, 염화제이철, 질산철, 펜타카보닐철, 아세트산철, 옥살산철, 또는 이들의 혼합물이 있으며, 철염으로는 염화제일철과 염화제이철이 바람직하게 사용될 수 있다. 염화제일철과 염화제이철은 1:2의 몰비로 사용되는 것이 바람직하다. The aqueous metal salt solution is prepared by adding a metal salt to distilled water, and the distilled water is secondary distilled, and deionized by bubbling with nitrogen gas for about 30 minutes. As the metal salt, a metal salt of iron, cobalt, nickel or chromium may be preferably used. The form of the salt is not particularly limited, and in particular, all iron salts may be used in the production of magnetic iron oxide nanoparticles. Preferred metal salt forms are chlorides, sulfates, nitrates, acetates, oxalates, carbonyl salts and the like. Preferred specific examples include iron sulfate, ferrous chloride, ferric chloride, iron nitrate, pentacarbonyl iron, iron acetate, iron oxalate, or mixtures thereof, and ferrous chloride and ferric chloride may be preferably used as the iron salt. Ferrous chloride and ferric chloride are preferably used in a molar ratio of 1: 2.
계면활성제 용액과 금속염 수용액의 혼합공정은 10:1 내지 20:1의 부피 비로 질소 분위기 하에서 실시하는 것이 바람직하다. 계면활성제 용액과 금속염 수용액은 초음파 분해하여 혼합하는 것이 바람직하고, 초음파 분해시간은 10 내지 30 분간 실시하는 것이 바람직하다. The mixing step of the surfactant solution and the aqueous metal salt solution is preferably carried out in a nitrogen atmosphere at a volume ratio of 10: 1 to 20: 1. The surfactant solution and the metal salt aqueous solution are preferably ultrasonically decomposed and mixed, and the ultrasonic decomposition time is preferably performed for 10 to 30 minutes.
별도의 공정으로 상기 계면활성제 용액과 염기성 용액을 혼합하여 제2 유중수형계 에멀젼을 제조한다. 상기 염기성 용액은 모든 무기성 및 유기성 염기 화합물을 사용하여 제조될 수 있으며, 이 용액의 pH는 7.01 내지 14.00 범위, 바람직하게는 12.00 내지 13.00 범위에 있다. 염기성 용액의 구체적인 예로는 수산화 나트륨, 수산화 칼륨, 수산화 리튬, 테트라메틸암모니아수, 암모니아수 및 탄산나트륨 으로 이루어진 군에서 선택되며, 이중에서 암모니아수가 바람직하다.In a separate process, the surfactant solution and the basic solution are mixed to prepare a second water-in-oil emulsion. The basic solution can be prepared using all inorganic and organic base compounds, the pH of this solution being in the range of 7.01 to 14.00, preferably in the range of 12.00 to 13.00. Specific examples of the basic solution are selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, tetramethylammonium water, ammonia water and sodium carbonate, of which ammonia water is preferable.
계면활성제 용액과 염기성 용액은 질소 분위기 하에서 초음파 분해하여 혼합하는 것이 바람직하고, 초음파 분해시간은 10 내지 30 분간 실시하는 것이 바람직하다. The surfactant solution and the basic solution are preferably ultrasonically decomposed and mixed in a nitrogen atmosphere, and the ultrasonic decomposition time is preferably performed for 10 to 30 minutes.
상기 제1 및 제2 유중수형계 에멀젼을 혼합하여 금속염과 염기성 용액을 반응시킴으로써 금속 산화물 나노입자 콜로이드 용액을 제조한다. 상기 유중수형계 역미셀에서 계면활성제에 둘러 싸여있는 나노 물방울이 나노 반응기로 작용하며, 그 나노 물방울 안에서 금속염과 염기성 용액의 반응으로 금속산화물 나노입자가 형성되며, 그 입자의 크기는 나노 물방울의 크기, 혼합속도, 반응온도, 계면활성제와 물의 농도 및 분산 유기용매에 의해서 조절된다. 바람직한 나노 물방울의 크기는 0.5 내지 5.0 나노 미터이고, 혼합속도는 5,000 내지 30,000 rpm, 바람직하게는 25,000 내지 30,000 rpm의 속도로 조절한다. 반응온도는 25 내지 70℃, 바람직하게는 50 내지 70℃에서 수행하고, 반응시간은 2 내지 24시간, 바람직하게는 2 내지 5시간 수행한다. 계면활성제는 0.1 내지 1.0몰, 바람직하게는 0.5 내지 1.0몰 농도로 한다. 용액의 pH는 7.01 내지 14.00 범위, 바람직하게는 12.00 내지 13.00 범위로 사용한다. 여기서 물은 극성 친수성을 나타내며, 분산 유기용매는 비극성 소수성을 띤다. The metal oxide nanoparticle colloidal solution is prepared by mixing the first and second water-in-oil emulsion and reacting the metal salt with the basic solution. In the water-in-oil type reverse micelle, nano water droplets surrounded by a surfactant act as a nano reactor, and metal oxide nanoparticles are formed by reaction of a metal salt and a basic solution in the nano water droplets, and the size of the particles is the size of the nano water droplets. It is controlled by the mixing speed, the reaction temperature, the concentration of the surfactant and water, and the dispersed organic solvent. Preferred nanodroplets have a size of 0.5 to 5.0 nanometers and the mixing speed is controlled at a speed of 5,000 to 30,000 rpm, preferably 25,000 to 30,000 rpm. The reaction temperature is carried out at 25 to 70 ℃, preferably 50 to 70 ℃, the reaction time is carried out for 2 to 24 hours, preferably 2 to 5 hours. Surfactant is 0.1-1.0 mol, Preferably it is 0.5-1.0 mol concentration. The pH of the solution is used in the range of 7.01 to 14.00, preferably in the range of 12.00 to 13.00. Here, water represents polar hydrophilicity, and the dispersed organic solvent has nonpolar hydrophobicity.
본 발명의 금속 산화물 나노입자의 제조방법은 종래의 이온 교환수지의 다공성 망상구조 이용법, 산소를 포함하는 산화제 첨가법 및 고분자 마이크로구형을 이용하여 캡슐화 하는 방법과는 달리 유중수형계의 에멀젼을 이용하여 분산된 역미셀 수용액상의 물방울 안에서 금속염 출발물질을 염기성 용액과 반응시켜 입자 크기가 단일분포를 갖는 산화철 나노입자를 제조하는 것이다. The method of preparing the metal oxide nanoparticles of the present invention is different from the method of encapsulating using a porous network structure of an ion exchange resin, an oxidizing agent containing oxygen, and a polymer microsphere, using an oil-in-water emulsion. The metal salt starting material is reacted with the basic solution in the water droplets of the dispersed reverse micelle solution to prepare iron oxide nanoparticles having a single distribution of particle size.
제1 및 제2 유중수형계 에멀젼은 질소 분위기 하에서 도 1과 같은 균질화기를 이용하여 초음파 분해하면서 격렬히 혼합되는 것이 바람직하다. 또한 균질화기는 5,000내지 30,000 rpm의 속도로 조절되는 것이 바람직하다.It is preferable that the first and second water-in-oil emulsions are mixed vigorously while ultrasonically decomposing using a homogenizer as shown in FIG. 1 under a nitrogen atmosphere. In addition, the homogenizer is preferably controlled at a speed of 5,000 to 30,000 rpm.
이때 금속염과 염기성 용액의 반응으로 금속 산화물 나노입자 콜로이드 용액이 형성되는데, 이때의 반응온도는 25 내지 70℃, 반응압력은 0.5 내지 10기압, 반응시간은 2 내지 24시간인 것이 바람직하다. In this case, the metal oxide nanoparticle colloidal solution is formed by the reaction of the metal salt and the basic solution. At this time, the reaction temperature is 25 to 70 ° C, the reaction pressure is 0.5 to 10 atm, and the reaction time is preferably 2 to 24 hours.
상기와 같이 제조된 산화철 나노입자 콜로이드 용액을 아세톤, 헵탄, 메탄올, 증류수로 씻어주고 원심분리와 자기장을 이용하여 산화철 나노입자를 분리한 후 50 내지 100℃의 진공오븐에서 12 내지 24시간 건조함으로써 분산 유기용매와 계면활성제를 제거하여 분말의 금속 나노입자를 얻는다. The iron oxide nanoparticle colloidal solution prepared as described above was washed with acetone, heptane, methanol and distilled water and separated by centrifugation and magnetic field to separate the iron oxide nanoparticles, and then dispersed by drying in a vacuum oven at 50 to 100 ° C for 12 to 24 hours. The organic solvent and the surfactant are removed to obtain powdered metal nanoparticles.
본 발명의 바람직한 실시예에 따르면 금속염으로 염화제일철과 염화제이철을 이용하고, 염기성 용액으로 암모니아수를 이용하여 pH, 계면활성제, 및 물의 농도를 조절하여 입자 크기가 균일한 산화철 나노입자의 제조방법을 제공한다. According to a preferred embodiment of the present invention using ferrous chloride and ferric chloride as a metal salt, using ammonia water as a basic solution by adjusting the concentration of pH, surfactant, and water to provide a method for producing iron oxide nanoparticles of uniform particle size do.
본 발명의 방법에 의해서 제조된 금속 산화물 나노입자는 0.5 내지 1,000 나노미터 크기의 입경을 가지며, 바람직하게는 0.5 내지 5.0 나노미터 크기의 입경을 가진다.The metal oxide nanoparticles prepared by the method of the present invention have a particle size of 0.5 to 1,000 nanometers, and preferably have a particle size of 0.5 to 5.0 nanometers.
본 발명에 따라 제조되는 금속 산화물 나노입자의 반경은 X-선 소각 산란 실험(small angle X-ray scattering)을 통해서 얻을 수 있다. X-선 소각 산란 실험 에 따르면, 역미셀에 의한 금속산화물 나노입자를 포함하는 유체를 분산 유기용매를 이용하여 농도를 묽혀서 측정하고, 백그라운드(background)를 보정해서 얻어진 데이터로부터 기니에 도시법을 통해서 입자의 크기를 구한다. 본 발명에 따라 제조된 금속 산화물 나노입자는 X-선 소각 산란실험으로 측정한 결과 평균 반경이 1.0 내지 3.0 나노미터, 바람직하게는 1.3 내지 2.4 나노미터이다.The radius of the metal oxide nanoparticles prepared according to the present invention can be obtained through X-ray scattering experiments (small angle X-ray scattering). According to the X-ray incineration scattering experiment, the fluid containing metal oxide nanoparticles by reverse micelles was measured by diluting the concentration using a dispersed organic solvent, and the Guinea method was performed from data obtained by correcting the background. Find the size of the particles through The metal oxide nanoparticles prepared according to the present invention have an average radius of 1.0 to 3.0 nanometers, preferably 1.3 to 2.4 nanometers, as measured by X-ray incineration scattering experiments.
또한 입자의 분포를 구하기 위한 방법으로는 분석(analytical) 방법과 통계(numerical) 방법이 있다. 두 가지 방법중 보다 적용이 용이한 통계 방법은 임의의 분포함수를 가정하는 방법과 분포함수를 가정하지 않는 방법이 있다. 본 발명에서는 로그노말 분포함수를 가정하여 데이터를 분석(fitting)하였으며, 구해진 분포함수로부터 관성반경과 입자의 분포도를 구할 수 있다. 본 발명에 따라 제조된 금속 산화물 나노입자의 관성반경은 1.5 내지 3.5 나노미터의 범위에 있으며, 바람직하게는 1.8 내지 3.0 나노미터의 범위에 있다. 로그노말 분포함수로 구한 부피 분포와 간접 퓨리에 변환 방법으로 구한 수 크기 분포의 결과를 부피 분포로 변화하여 도시한 결과 비슷한 결과를 얻을 수 있다.In addition, there are analytical methods and numerical methods for obtaining particle distribution. Statistical methods that are easier to apply are the ones that assume arbitrary distribution functions and those that do not assume distribution functions. In the present invention, the data are analyzed by assuming a lognormal distribution function, and the distribution of inertia radius and particle distribution can be obtained from the obtained distribution function. The inertial radius of the metal oxide nanoparticles prepared according to the present invention is in the range of 1.5 to 3.5 nanometers, preferably in the range of 1.8 to 3.0 nanometers. A similar result can be obtained by converting the volume distribution obtained by the lognormal distribution function and the number size distribution obtained by the indirect Fourier transform method into the volume distribution.
또한 자기적 성질을 측정하기 위해서 자기적 특성측정(Vibrating Sample Magnetometer)를 이용하여 20.2 ℃의 조건에서 포화 자화율을 얻을 수 있다. 그리고 산화철 입자의 형태와 크기를 JEOL회사의 JEM 3000F 모델의 전자현미경(transmittance electron microscope)을 이용하여 분산 유기용매를 이용하여 농도를 묽혀서 400 mesh의 탄소 코팅된 그리드(carbon-coated grid)위에 한 두 방울 떨어뜨려서 상온에서 건조시켜서 측정한다. 이와 같이 측정된 금속 산화 물 나노입자의 포화 자화율은 8.00내지 20.00 emu/g 인 것을 특징으로 한다.In addition, the saturation susceptibility can be obtained under the condition of 20.2 ℃ by using the Vibrating Sample Magnetometer to measure the magnetic properties. The shape and size of the iron oxide particles were measured on a 400 mesh carbon-coated grid by diluting the concentration using a dispersed organic solvent using a transmission electron microscope of JEOL's JEM 3000F model. Measure by dropping two drops and drying at room temperature. The saturation susceptibility of the metal oxide nanoparticles measured as described above is characterized in that 8.00 to 20.00 emu / g.
본 발명의 금속 산화물 나노입자는 전도성 고분자와 복합체를 형성하여 다양한 분야에 적용될 수 있다. 복합체의 형성은 이 분야의 통상의 지식에 의하여 실시될 수 있다.The metal oxide nanoparticles of the present invention may be applied to various fields by forming a composite with a conductive polymer. Formation of the complex can be carried out by common knowledge in the art.
실시예Example
이하, 본 발명의 바람직한 실시예를 제시한다. 다만, 하기 실시예는 본 발명의 이해를 돕기 위하여 제시되는 것일 뿐 본 발명이 하기 실시예에 한정되는 것은 아니다.Hereinafter, a preferred embodiment of the present invention. However, the following examples are only presented to aid the understanding of the present invention, and the present invention is not limited to the following examples.
<실시예 1>≪ Example 1 >
헵탄 용매에 소듐 비스(2-에틸헥실)술포숙시네이트(AOT)을 첨가하여 20분간 초음파 분해를 하여 0.3몰의 계면활성제 용액(저장용액)을 제조하였다. Sodium bis (2-ethylhexyl) sulfosuccinate (AOT) was added to the heptane solvent and sonicated for 20 minutes to prepare 0.3 mole of a surfactant solution (stock solution).
염화제일철 0.1몰과 염화제이철 0.2몰을 증류수 2ml에 첨가하여 철염 수용액을 제조하였다. 여기서 사용되는 증류수는 이차 증류한 것으로 질소가스로 30분 정도 기포화하여 탈이온화된 것을 사용하였다. 이 철염 수용액과 상기 계면활성제 용액을 2:22의 부피 비로 질소 분위기 하에서 20분간 초음파 분해하여 제1 수중유형계 에멀젼을 제조하였다.0.1 mol of ferrous chloride and 0.2 mol of ferric chloride were added to 2 ml of distilled water to prepare an aqueous iron salt solution. The distilled water used here was secondary distilled and deionized by bubbling with nitrogen gas for about 30 minutes. The aqueous iron salt solution and the surfactant solution were ultrasonically decomposed in a nitrogen atmosphere at a volume ratio of 2:22 for 20 minutes to prepare a first oil-in-water emulsion.
28 중량%의 암모니아수와 상기 계면활성제 용액을 2:16의 부피 비로 질소 분위기 하에서 10 내지 30분간 초음파 분해하여 제2 수중유형계 에멀젼을 제조하였다.A second oil-in-water emulsion was prepared by sonicating 28% by weight of ammonia water and the surfactant solution at a volume ratio of 2:16 under a nitrogen atmosphere for 10 to 30 minutes.
상기에서 제조한 제1 및 제2 수중유형계 에멀젼을 질소 분위기 하에서 도 1 의 균질화기를 이용하여 초음파 분해하면서 격렬히 혼합하여 철염과 염기성 용액의 반응을 유도하였다. 반응시 반응온도는 50 ℃, 반응압력 1.0기압, 반응시간 2시간으로 조절하였다. 이때 혼합용액은 혼합한 후 즉시 푸른빛의 녹색을 나타내고 수 분 안에 붉은빛의 진한 갈색을 나타냈다. The first and second oil-in-water emulsions prepared above were mixed vigorously by ultrasonic decomposition using a homogenizer of FIG. 1 under a nitrogen atmosphere to induce a reaction between the iron salt and the basic solution. The reaction temperature was adjusted to 50 ° C., a reaction pressure of 1.0 atm, and a reaction time of 2 hours. At this time, the mixed solution appeared blue green immediately after mixing and dark reddish brown in several minutes.
상기와 같이 제조된 산화철 나노입자 콜로이드 용액은 아세톤, 헵탄, 메탄올, 증류수로 씻어주고 원심분리와 자기장을 이용하여 산화철 나노입자를 분리한 후 70℃의 진공오븐에서 24시간 건조함으로써 남아있는 헵탄과 소듐 비스(2-에틸헥실)술포숙시네이트(AOT)를 제거하여 분말의 산화철 나노입자를 얻었다. The iron oxide nanoparticle colloidal solution prepared as above was washed with acetone, heptane, methanol and distilled water, and the iron oxide nanoparticles were separated by centrifugation and magnetic field, and then heptane and sodium remained by drying in a vacuum oven at 70 ° C. for 24 hours. Bis (2-ethylhexyl) sulfosuccinate (AOT) was removed to obtain powdered iron oxide nanoparticles.
상기 산화철 나노입자의 반경은 X-선 소각 산란 실험을 통해서 측정하였다. X-선 소각 산란 실험은 역미셀에 의한 산화철 나노입자를 포함하는 유체를 분산 유기용매인 헵탄을 이용하여 농도를 묽혀서 측정하고 얻어진 데이터는 도 2의 기니에 도시법을 통해서 입자의 반경이 1.3 나노미터를 가지는 것을 알 수 있었다. 이때 계산은 기니에 법칙에 의해서 관성반경을 구할 수 있고, 식은 다음과 같다. The radius of the iron oxide nanoparticles was measured through X-ray incineration scattering experiment. X-ray incineration scattering experiment was measured by diluting the concentration of the fluid containing iron oxide nanoparticles by reverse micelles using heptane, a dispersed organic solvent, and the data obtained is 1.3 by the Guinea method shown in FIG. It was found to have nanometers. At this time, the inertia radius can be calculated by Guinea's law.
관성반경= 
도 2의 데이터를 간접 퓨리에 변환방법과 로그노말 함수를 사용하여 얻은 결과를 도 6에 도시하였다. 도 6으로부터 관성반경이 1.8나노미터이고 입자 크기가 단일분포를 가짐을 알 수 있다. The results obtained using the indirect Fourier transform method and the lognormal function are shown in FIG. 6. It can be seen from FIG. 6 that the inertia radius is 1.8 nanometers and the particle size has a single distribution.
20.2 ℃의 조건에서 산화철 나노입자의 자기적 특성(Vibrating Sample Magnetometer)을 측정한 결과를 도 7에 도시하였다. 도 7에서 포화 자화율은 9.48 emu/g인 것을 알 수 있다. 7 shows the results of measuring the magnetic properties (Vibrating Sample Magnetometer) of the iron oxide nanoparticles at 20.2 ℃. In Figure 7, it can be seen that the saturation susceptibility is 9.48 emu / g.
산화철의 입자 형태와 크기는 전자현미경을 통해서 관찰하였다. 도 8는 산화철 콜로이드 상태의 입자의 전자 현미경 사진이다. 도 8에서 보는 바와 같이 입자의 크기가 2 나노미터로 X-선 소각 산란 실험을 통해서 얻은 결과와 비슷한 결과를 보였다. 도 8에서 계면활성제에 둘러싸인 산화철 산화철 나노 입자가 분산되어 있는 것을 볼 수 있다. The particle shape and size of iron oxide was observed by electron microscopy. 8 is an electron micrograph of particles in the state of iron oxide colloid. As shown in FIG. 8, the particle size was 2 nanometers, and similar results were obtained through X-ray incineration scattering experiments. In Figure 8 it can be seen that the iron oxide oxide nanoparticles surrounded by the surfactant is dispersed.
도 9는 산화철 분말을 에탄올 용매에 분산시켰을 경우의 전자 현미경의 사진이다. 도 9에서 2 나노미터 내외의 입자들이 일정한 크기를 가지면서 분포되어 있는 것을 알 수 있다.9 is a photograph of an electron microscope when the iron oxide powder is dispersed in an ethanol solvent. In Figure 9 it can be seen that particles of about 2 nanometers are distributed with a certain size.
<실시예 2> <Example 2>
헵탄 용매에 소듐 비스(2-에틸헥실)술포숙시네이트(AOT)를 첨가하여 20분간 초음파 분해를 하여 0.5 몰의 계면활성제 용액(저장용액)을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 산화철 나노입자를 제조하였다. The same procedure as in Example 1 was conducted except that 0.5 mole of a surfactant solution (stock solution) was prepared by sonication for 20 minutes by adding sodium bis (2-ethylhexyl) sulfosuccinate (AOT) to a heptane solvent. The iron oxide nanoparticles were prepared by the method.
제조된 산화철 나노입자의 반경은 X-선 소각 산란 실험을 통해서 얻었다. X-선 소각 산란 실험은 역미셀에 의한 산화철 나노입자를 포함하는 유체를 분산 유기용매인 헵탄을 이용하여 농도를 묽혀서 측정하고 얻어진 데이터는 도 3의 기니에 도시법을 이용해서 입자의 반경이 1.9 나노미터를 가지는 것을 알 수 있었다. 상기의 데이터를 간접 퓨리에 변환방법과 로그노말 함수를 사용하여 얻은 결과, 관성반경이 2.3 나노미터이고 입자 크기가 단일분포를 가짐을 알 수 있었다. The radius of the prepared iron oxide nanoparticles was obtained through X-ray incineration scattering experiment. X-ray incineration scattering experiment was measured by diluting the concentration of the fluid containing iron oxide nanoparticles by reverse micelles using heptane, a dispersed organic solvent, and the obtained data was obtained using the method shown in FIG. It was found that it has 1.9 nanometers. The above data were obtained by using the indirect Fourier transform method and the lognormal function. The inertia radius was 2.3 nanometers and the particle size had a single distribution.
20.2 ℃의 조건에서 산화철 나노입자의 자기적 특성을 측정한 결과를 포화 자화율은 9.94 emu/g으로 나타났다. The magnetic susceptibility of the iron oxide nanoparticles was measured at 20.2 ° C. The saturation susceptibility was 9.94 emu / g.
<실시예 3> <Example 3>
헵탄 용매에 소듐 비스(2-에틸헥실)술포숙시네이트(AOT)를 첨가하여 20분간 초음파 분해를 하여 0.7 몰의 계면활성제 용액(저장용액)을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 산화철 나노입자를 제조하였다. The same procedure as in Example 1 was performed except that 0.7 moles of a surfactant solution (stock solution) was prepared by adding sodium bis (2-ethylhexyl) sulfosuccinate (AOT) to a heptane solvent and performing sonication for 20 minutes. The iron oxide nanoparticles were prepared by the method.
제조된 산화철 나노입자의 반경은 X-선 소각 산란 실험을 통해서 얻었다. X-선 소각 산란 실험은 역미셀에 의한 산화철 나노입자를 포함하는 유체를 분산 유기용매인 헵탄을 이용하여 농도를 묽혀서 측정하고 얻어진 데이터는 도 4의 기니에 도시법을 이용해서 입자의 반경이 2.1 나노미터를 가지는 것을 알 수 있었다. 상기의 데이터를 간접 퓨리에 변환방법과 로그노말 함수를 사용하여 얻은 결과, 관성반경이 2.6 나노미터이고 입자 크기가 단일분포를 가짐을 알 수 있었다. The radius of the prepared iron oxide nanoparticles was obtained through X-ray incineration scattering experiment. X-ray incineration scattering experiments were measured by diluting the concentration of the fluid containing iron oxide nanoparticles by reverse micelles with heptane, a dispersed organic solvent, and the data obtained by using the Guinea method shown in FIG. It was found to have 2.1 nanometers. As a result of using the indirect Fourier transform method and the lognormal function, the inertial radius was 2.6 nanometers and the particle size was a single distribution.
20.2 ℃의 조건에서 산화철 나노입자의 자기적 특성을 측정한 결과를 포화 자화율은 10.32 emu/g으로 나타났다. The magnetic properties of the iron oxide nanoparticles were measured at 20.2 ° C. The saturation susceptibility was 10.32 emu / g.
<실시예 4> <Example 4>
헵탄 용매에 소듐 비스(2-에틸헥실)술포숙시네이트(AOT)를 첨가하여 20분간 초음파 분해를 하여 1.0 몰의 계면활성제 용액(저장용액)을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 산화철 나노입자를 제조하였다. Example 1 Except that sodium bis (2-ethylhexyl) sulfosuccinate (AOT) was added to the heptane solvent and sonicated for 20 minutes to prepare 1.0 mole of a surfactant solution (stock solution). The iron oxide nanoparticles were prepared by the method.
제조된 산화철 나노입자의 반경은 X-선 소각 산란 실험을 통해서 얻었다. X-선 소각 산란 실험은 역미셀에 의한 산화철 나노입자를 포함하는 유체를 분산 유 기용매인 헵탄을 이용하여 농도를 묽혀서 측정하고 얻어진 데이터는 도 5의 기니에 도시법을 이용해서 입자의 반경이 2.4 나노미터를 가지는 것을 알 수 있었다. 상기의 데이터를 간접 퓨리에 변환방법과 로그노말 함수를 사용하여 얻은 결과, 관성반경이 3.0 나노미터이고 입자 크기가 단일분포를 가짐을 알 수 있다. The radius of the prepared iron oxide nanoparticles was obtained through X-ray incineration scattering experiment. X-ray incineration scattering experiment was measured by diluting the concentration of the fluid containing iron oxide nanoparticles by reverse micelles using heptane, a dispersed organic solvent, and the obtained data was measured using the Guinea method shown in FIG. It was found to have 2.4 nanometers. As a result of using the indirect Fourier transform method and the lognormal function, the above data shows that the inertia radius is 3.0 nanometers and the particle size has a single distribution.
20.2 ℃의 조건에서 산화철 나노입자의 자기적 특성을 측정한 결과를 포화 자화율은 10.73 emu/g으로 나타났다. The magnetic properties of the iron oxide nanoparticles were measured at 20.2 ° C. The saturation susceptibility was 10.73 emu / g.
본 발명의 산화철 나노입자의 제조방법에 따라 제조된 금속 산화물 나노입자는 초상자성을 가지며 입자 크기가 단일분포를 가진다. 따라서 본 발명에 따른 금속 산화물 나노입자는 전기, 전자 디바이스 분야, 자기 기록 매체 및 프린트 잉크 토너, 의료용 진단시약, 대전 방지제, 전자파 차폐 및 흡수체 등의 응용분야에 널리 응용이 가능하다. Metal oxide nanoparticles prepared according to the method for producing iron oxide nanoparticles of the present invention has a superparamagnetic and particle size has a single distribution. Therefore, the metal oxide nanoparticles according to the present invention can be widely applied to applications such as electric, electronic device fields, magnetic recording media and print ink toners, medical diagnostic reagents, antistatic agents, electromagnetic shielding and absorbers.
본 발명의 단순한 변형 또는 변경은 모두 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다. All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
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| KR100861355B1 (en) * | 2007-06-27 | 2008-10-01 | 성균관대학교산학협력단 | Apparatus for producing metal nanoparticles using an electroless plating solution and a method for producing metal nanoparticles using the same |
| KR101421619B1 (en) | 2008-05-30 | 2014-07-22 | 삼성전자 주식회사 | Nanocrystalline-metal oxide-polymer composites and methods for making same |
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| KR101356990B1 (en) | 2013-09-25 | 2014-02-03 | 한국에너지기술연구원 | Iron oxalate hydrate particles with controlled shapes and manufacturing method thereof, iron oxide/carbon composites manufactured by using the iron oxalate hydrate particles and manufacturing method thereof |
| KR101393413B1 (en) * | 2013-10-04 | 2014-05-12 | 한국에너지기술연구원 | Manufacturing method of fe5c2/c nano composite catalysts for high temperature fischer-tropsch synthesis reaction and fe5c2/c nano composite catalysts thereof, manufacturing method of liquid hydrocarbon using the same and liquid hydrocarbon thereof |
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| KR101480169B1 (en) * | 2014-05-30 | 2015-01-08 | (주)일신오토클레이브 | The Method for Preparation of Monodisperse Iron Oxide Nanoparticles Using High Pressure Homogenizer and Monodisperse Iron Oxide Nanoparticels Thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63185802A (en) * | 1986-09-30 | 1988-08-01 | Ricoh Co Ltd | Ultrafine oxide powder |
| JPH03253506A (en) * | 1990-03-01 | 1991-11-12 | Titan Kogyo Kk | Production of noble metal fine particles using emulsion type liquid film method |
| JPH08143916A (en) * | 1994-11-24 | 1996-06-04 | Nok Corp | Production of fine iron particles |
| JP2001172705A (en) * | 1999-12-16 | 2001-06-26 | Murata Mfg Co Ltd | Method for producing metal powder, electrically conductive paste and ceramic electronic parts |
| WO2003037788A1 (en) * | 2001-11-01 | 2003-05-08 | Oxonica Limited | Water soluble luminescent nanoparticles |
-
2002
- 2002-12-02 KR KR1020020075862A patent/KR100967708B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63185802A (en) * | 1986-09-30 | 1988-08-01 | Ricoh Co Ltd | Ultrafine oxide powder |
| JPH03253506A (en) * | 1990-03-01 | 1991-11-12 | Titan Kogyo Kk | Production of noble metal fine particles using emulsion type liquid film method |
| JPH08143916A (en) * | 1994-11-24 | 1996-06-04 | Nok Corp | Production of fine iron particles |
| JP2001172705A (en) * | 1999-12-16 | 2001-06-26 | Murata Mfg Co Ltd | Method for producing metal powder, electrically conductive paste and ceramic electronic parts |
| WO2003037788A1 (en) * | 2001-11-01 | 2003-05-08 | Oxonica Limited | Water soluble luminescent nanoparticles |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021124029A1 (en) * | 2019-12-19 | 2021-06-24 | Universidad De Guadalajara | Method for synthesising magnetite nanoparticles |
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