KR101480169B1 - The Method for Preparation of Monodisperse Iron Oxide Nanoparticles Using High Pressure Homogenizer and Monodisperse Iron Oxide Nanoparticels Thereof - Google Patents
The Method for Preparation of Monodisperse Iron Oxide Nanoparticles Using High Pressure Homogenizer and Monodisperse Iron Oxide Nanoparticels Thereof Download PDFInfo
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- iron oxide
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- 229940031182 nanoparticles iron oxide Drugs 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 34
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims description 55
- 238000002360 preparation method Methods 0.000 title description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- 235000014413 iron hydroxide Nutrition 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 14
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 14
- 229960002089 ferrous chloride Drugs 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 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
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 26
- 239000002245 particle Substances 0.000 description 26
- 235000013980 iron oxide Nutrition 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910002588 FeOOH Inorganic materials 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000007348 radical reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 229960004887 ferric hydroxide Drugs 0.000 description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000002616 MRI contrast agent Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000012377 drug delivery Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- DEVYBOZJYUYBMC-KVVVOXFISA-N iron;(z)-octadec-9-enoic acid Chemical class [Fe].CCCCCCCC\C=C/CCCCCCCC(O)=O DEVYBOZJYUYBMC-KVVVOXFISA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002069 magnetite nanoparticle Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- -1 sodium hydroxide (tertiary octane) Chemical compound 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compounds Of Iron (AREA)
Abstract
본 발명은 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법 및 이에 의해 제조된 단분산 산화철 나노입자에 관한 것이다. 보다 구체적으로는, (a) 수산화철 용액을 제조하는 단계, (b) 상기 제조된 수산화철 용액을 시료의 주입구에 투입하고 압력펌프에 의해 초고압을 가하는 단계, (c) 상기 초고압 시킨 수산화철 용액을 미세 오리피스 노즐 챔버로 통과하여 침전물을 얻는 단계, 및 (d) 상기 (c)단계의 침전물을 세척하고 건조시키는 단계를 포함하는 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법 및 이에 의해 제조된 단분산 산화철 나노입자에 관한 것이다.The present invention relates to a process for producing monodisperse iron oxide nanoparticles using an ultra-high pressure homogenizer and monodisperse iron oxide nanoparticles produced thereby. (B) adding the produced iron hydroxide solution to an inlet of a sample and applying an ultrahigh pressure to the sample through a pressure pump; (c) applying the ultrahigh pressure iron hydroxide solution to the fine orifice And (d) washing and drying the precipitate of step (c). The method for producing monodisperse iron oxide nanoparticles using the ultra-high pressure homogenizer and the monodispersed iron oxide nanoparticles prepared by the method Nanoparticles.
Description
본 발명은 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법 및 이에 따라 제조된 단분산 산화철 나노입자에 관한 것이다. 보다 구체적으로는, 초고압 균질기를 이용한 입자크기가 10 ~ 30 ㎚인 단분산 산화철 나노입자의 제조방법 및 이에 따라 제조된 단분산 산화철 나노입자에 관한 것이며, 본 발명의 단분산 산화철 나노입자는 자기센서, 자기광학소자, 자성잉크, 중금속 폐수처리, MRI 조영제, 약물 전달시스템 및 온열치료 등의 산화철 나노입자 응용분야에 유용하게 이용할 수 있다.The present invention relates to a method for producing monodispersed iron oxide nanoparticles using an ultra-high pressure homogenizer and monodisperse iron oxide nanoparticles produced thereby. More particularly, the present invention relates to a method for producing monodisperse iron oxide nanoparticles having a particle size of 10 to 30 nm using an ultra-high pressure homogenizer and monodisperse iron oxide nanoparticles produced thereby. , Magnetic optical elements, magnetic ink, heavy metal wastewater treatment, MRI contrast agent, drug delivery system, and thermal therapy.
입자가 나노미터 크기로 감소하면 덩어리(Bulk) 크기에서 나타나지 않던 새로운 전기적, 광학적 또는 자기적 특성을 보인다. 나노 입자에서는 덩어리와 달리 표면의 비율이 크기 때문이며, 표면비는 입자의 크기에 의존하게 되므로 결국 나노 입자의 크기가 물리, 화학적인 성질을 결정하는데 가장 중요한 요소가 된다.As the particles decrease in nanometer size, they exhibit new electrical, optical, or magnetic properties that did not appear at bulk size. In nanoparticles, unlike lumps, the ratio of the surface is large. Since the surface ratio depends on the size of the particles, the size of the nanoparticles is the most important factor in determining the physical and chemical properties.
산화철 나노입자의 경우, 그 입자의 크기가 어떤 임계 크기 이하로 되면 단일 자기구역(Single magnetic domain)화 되는데, 이때 산화철 입자는 초상자성(Superparamagnetism)을 띠게 되고, 입자들 사이의 인력보다는 운동 에너지가 증가하여 적절한 용매 안에서 분산되어 안정한 콜로이드 상태가 된다. 하지만 졸겔법, 공침법, 유기금속 전구체의 열분해, 금속 이온들의 고온 산화·환원 및 역마이셀 내에서의 침전·산화·환원 등 종래의 나노입자의 제조방법으로는 산화철 나노입자의 크기 조절이 쉽지 않으며, 입도 분포도 수 ㎚에서 수백 ㎚까지 너무 넓어 산화철 크기에 따른 자기적 특성 및 구조 연구는 최근까지 정확한 결과가 많지 않다.In the case of iron oxide nanoparticles, when the particle size is below a certain critical size, a single magnetic domain is formed. In this case, the iron oxide particles are superparamagnetized and the kinetic energy And dispersed in an appropriate solvent to give a stable colloidal state. However, conventional methods for preparing nanoparticles such as sol-gel method, coprecipitation method, pyrolysis of an organic metal precursor, high-temperature oxidation and reduction of metal ions, and precipitation, oxidation and reduction in reverse micelle are not easy to control the size of iron oxide nanoparticles , The particle size distribution is too wide from several nanometers to several hundred nanometers, and the study of magnetic properties and structures according to the size of iron oxide has not been accurate until recently.
또한, 유기금속 전구체의 열분해, 금속 이온들의 고온 산화·환원 등의 방법은 고온에서 반응이 일어나고 공정이 복잡하기 때문에 보다 효율적이고 균일한 산화철 나노입자의 합성방법이 필요하다.In addition, pyrolysis of the organometallic precursor, high temperature oxidation and reduction of the metal ions, etc., require a more efficient and uniform synthesis method of iron oxide nanoparticles because the reaction takes place at a high temperature and the process is complicated.
먼저 J. AM. Chem. Soc. 2001, 123, 12798에서는 펜타카르보닐 철과 올레인산의 반응으로부터 만들어진 철-올레인산 착화합물의 열분해로부터, 크기 선택 과정 없이, 균일한 자성 철산화물 나노입자들의 합성방법을 개시하였다. 그러나 산화철 제조 온도가 100℃ 이상이고, 반응이 두 단계로 총 3시간 이상 걸리는 등 제조 온도가 높고 제조 시간이 길다는 문제점이 있었다. 또한, 산화철 제조 원료로 사용된 Fe(CO)5는 매우 유독하고 고가이면서 보관이 어렵기 때문에 상기 방법은 산화철 나노입자 제조에 적합하지 않는다.First, J. AM. Chem. Soc. 2001, 123, 12798 discloses a method for the synthesis of uniform magnetic iron oxide nanoparticles from pyrolysis of iron-oleic acid complexes made from the reaction of pentacarbonyl iron with oleic acid without size selection. However, there is a problem that the production temperature is high and the production time is long, for example, the production temperature of iron oxide is 100 ° C or more and the reaction takes two hours in total for 3 hours or more. Also, since Fe (CO) 5 used as a raw material for producing iron oxide is very toxic, expensive, and difficult to store, the method is not suitable for manufacturing iron oxide nanoparticles.
두 번째로 대한민국 공개특허공보 제10-2006-0012346호(2006.02.08.)에서는 염화제일철과 소듐올레이트의 반응으로부터 만들어진 철-올레이트 착화합물의 열분해로부터, 균일한 크기의 나노자성체 입자의 합성방법을 개시하였다. 그러나 산화철 제조 온도가 300℃ 이상이고, 0.3 Torr로 감압을 해야 하는 등 제조 온도가 높고 공정이 복합한 문제점이 있었다. Secondly, Korean Patent Laid-Open Publication No. 10-2006-0012346 (Mar. 2, 2006) discloses a method for synthesizing nano-sized magnetic particles of uniform size from pyrolysis of a ferroallate complex formed from the reaction of ferric chloride and sodium oleate Lt; / RTI > However, there is a problem that the production temperature is high and the process is complicated, for example, the iron oxide production temperature is 300 ° C or higher and the pressure is reduced to 0.3 Torr.
세 번째로 Journal of Alloys and Compouns, 2009, 475, 898에서는 황산제일철 용액에 암모니아수를 첨가하여 만들어진 수산화제일철(Fe(OH)2)에 산화제로 과산화수소를 첨가하여 수열합성으로부터 마그네타이트 나노입자의 합성방법을 개시하였다. 그러나 분산제로 폴리에틸렌글리콜 고분자를 첨가하여 수산화제일철 용액을 제조하고 산화제로 과산화수소를 첨가하여 160℃에서 5 ~ 8시간 수열합성과정을 거치는 등 제조 온도가 높고 장시간의 제조시간을 필요로 하기 때문에 산업적으로 대량생산에 효과적이지 않았다.
Third, in Journal of Alloys and Compouns, 2009, 475, and 898, the method of synthesizing magnetite nanoparticles from hydrothermal synthesis by adding hydrogen peroxide as an oxidizing agent to ferrous hydroxide (Fe (OH) 2 ) produced by adding ammonia water to a ferrous sulfate solution . However, since a ferric hydroxide solution is prepared by adding a polyethylene glycol polymer as a dispersant and hydrogen peroxide is added as an oxidizing agent, a hydrothermal synthesis process is carried out at 160 ° C. for 5 to 8 hours, and a long manufacturing time is required. It was not effective in production.
이에, 본 발명자들은 종래 산화철 나노입자 제조방법의 단점인 고온에서의 복잡한 공정, 장시간의 제조시간, 입자의 넓은 입도 분포, 독성이 있는 계면활성제 및 산화제 사용 등의 문제점을 해결하기 위해 연구하던 중 초고압 균질기를 통한 합성법에 의해 상온에서 간단한 공정으로 결정성이 우수하고 균일한 크기의 산화철 나노입자를 경제적으로 제조할 수 있는 단분산 산화철 나노입자 제조방법을 개발하고, 본 발명을 완성하였다.Accordingly, the present inventors have conducted studies to solve problems such as complicated processes at high temperatures, long production time, wide particle size distribution of particles, toxic surfactants and oxidizing agents, which are disadvantages of conventional iron oxide nanoparticle production methods, The present invention has been accomplished based on the synthesis of monodisperse iron oxide nanoparticles which can economically produce iron oxide nanoparticles having excellent crystallinity and uniform size by a simple process at room temperature by a synthesis method using a homogenizer.
본 발명의 목적은 상기의 문제점을 해결하기 위한 것으로, 수산화철 용액을 초고압 균질기에 통과시킴으로써, 산화철 나노입자 분리 과정이 필요하지 않고, 공정이 단순화되며, 공정시간이 단축됨과 동시에 친환경적인 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법 및 이에 따라 제조된 단분산 산화철 나노입자를 제공하는 것이다.The object of the present invention is to solve the above-mentioned problems, and it is an object of the present invention to provide a method for producing a ferrofluidic iron oxide nanoparticle by passing a ferrohydroxide solution through an ultra-high pressure homogenizer, To provide a method for producing monodispersed iron oxide nanoparticles and monodisperse iron oxide nanoparticles produced thereby.
본 발명의 다른 목적은, 결정성이 우수하고 균일한 크기의 산화철 나노입자를 경제적으로 제조할 수 있는 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법 및 이에 따라 제조된 단분산 산화철 나노입자를 제공하는 것이다. Another object of the present invention is to provide a method for producing monodispersed iron oxide nanoparticles using an ultra-high pressure homogenizer capable of economically manufacturing iron oxide nanoparticles having excellent crystallinity and uniform size and to provide monodispersed iron oxide nanoparticles prepared thereby .
본 발명의 또 다른 목적은, 별도의 산화제, 계면활성제 및 라디칼 제거제 첨가 없이 초고압 균질기의 라디칼 반응을 이용한 단분산 산화철 나노입자의 제조방법 및 이에 따라 제조된 단분산 산화철 나노입자를 제공하는 것이다. Another object of the present invention is to provide a method for preparing monodispersed iron oxide nanoparticles using a radical reaction of an ultra-high pressure homogenizer without adding any additional oxidizing agent, surfactant and radical scavenger, and to provide monodisperse iron oxide nanoparticles prepared thereby.
본 발명은 단분산 산화철 나노입자의 제조방법 및 이에 따라 제조된 단분산 산화철 나노입자에 관한 것이다.The present invention relates to a process for producing monodisperse iron oxide nanoparticles and monodisperse iron oxide nanoparticles produced thereby.
본 발명에서 초고압 균질기의 일예로 도 1을 참고할 수 있다.In the present invention, FIG. 1 can be referred to as an example of the ultra-high pressure homogenizer.
하기 도 1의 초고압 균질기는, 시료 주입구, 유체에 압력을 가하여 주는 압력펌프, 미세 오리피스 노즐 챔버, 열교환기 및 배출구로 이루어 질 수 있다. The ultra-high pressure homogenizer of FIG. 1 may be composed of a sample inlet, a pressure pump for applying pressure to the fluid, a fine orifice nozzle chamber, a heat exchanger and an outlet.
상기 압력펌프는 유체에 압력을 가함으로써, 유체를 미세 오리피스 노즐 챔버로 이동시켜 줄 수 있다.The pressure pump may apply pressure to the fluid to move the fluid to the fine orifice nozzle chamber.
하기 도 2는 미세 오리피스 노즐 챔버의 내부의 일부를 도시한 것이다. 본 발명의 일예로, 챔버에 물을 통과시키는 경우, 물 분자가 해리 되면서 생성되는 OH라디칼들과 이들의 결합으로 산화제인 H2O2가 생성되며, 별도의 산화제의 첨가 없이 단분산 산화철 나노입자를 제조할 수 있다. 또한, 상기 열교환기는 챔버로 유체가 통과하는 경우 발생하는 일부 열을 식혀주기 위한 역할을 할 수 있다.
Figure 2 illustrates a portion of the interior of the fine orifice nozzle chamber. In the present invention, when water is passed through the chamber, H 2 O 2 , which is an oxidant, is generated by the OH radicals formed by dissociation of water molecules and their combination, and monodisperse iron oxide nanoparticles Can be produced. In addition, the heat exchanger may serve to cool some of the heat generated when the fluid passes through the chamber.
이하는 본 발명의 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법에 대해 구체적으로 설명한다.Hereinafter, a method for producing monodispersed iron oxide nanoparticles using the ultra-high pressure homogenizer of the present invention will be described in detail.
본 발명의 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법은,The method for producing monodisperse iron oxide nanoparticles using the ultra-high pressure homogenizer of the present invention comprises:
(a) 수산화철 용액을 제조하는 단계,(a) preparing a solution of iron hydroxide,
(b) 상기 제조된 수산화철 용액을 시료의 주입구에 투입하고 압력펌프에 의해 초고압을 가하는 단계,(b) injecting the prepared iron hydroxide solution into an injection port of a sample and applying ultrahigh pressure to the sample through a pressure pump,
(c) 상기 초고압 시킨 수산화철 용액을 미세 오리피스 노즐 챔버로 통과하여 침전물을 얻는 단계, 및(c) passing the ultrahigh pressure iron hydroxide solution through a fine orifice nozzle chamber to obtain a precipitate, and
(d) 상기 (c)단계의 침전물을 세척하고 건조시키는 단계,(d) washing and drying the precipitate of step (c)
를 포함한다. .
본 발명의 단분산 산화철 나노입자는 상기의 제조방법으로 제조됨으로써, 단분산 산화철 나노입자의 분리 과정이 필요하지 않아 공정이 단순화되어 공정시간이 단축됨과 동시에 결정성이 우수한 균일한 크기의 산화철 나노입자를 제조하는 것에 특징이 있다.The monodisperse iron oxide nanoparticles of the present invention can be produced by the above-described production method, so that the separation process of the monodisperse iron oxide nanoparticles is not necessary, thereby simplifying the process and shortening the process time. In addition, the uniformly sized iron oxide nanoparticles Is produced.
또한, 본 발명은 별도의 산화제의 첨가 및 수열합성 과정 없이 초고압 균질기에 의한 라디칼 반응을 이용함으로써, 공정이 단순화되고 공정시간이 단축되며, 친환경적으로 단분산 산화철 나노입자를 제조하는 것에 특징이 있다.Further, the present invention is characterized in that monodisperse iron oxide nanoparticles are produced in an eco-friendly manner by simplifying the process, shortening the processing time, and utilizing the radical reaction by the ultra-high pressure homogenizer without adding any oxidizer and hydrothermal synthesis.
상기 (a)단계의 수산화철 용액은 산화철 전구체를 증류수에 용해시켜 전구체 수용액을 제조한 후, 침전제 용액을 첨가하여 제조할 수 있다. The iron hydroxide solution of step (a) may be prepared by dissolving an iron oxide precursor in distilled water to prepare a precursor aqueous solution, followed by adding a precipitant solution.
상기 산화철 전구체는 제일철염으로 구체적으로 예를 들면, 염화제일철(FeCl2), 황산제일철(FeSO4) 및 아세트산철(Fe(CH3COO)2)등으로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상을 사용할 수 있다.The iron oxide precursor is a ferrous salt and specifically includes one or more selected from the group consisting of iron chloride (FeCl 2 ), ferrous sulfate (FeSO 4 ) and iron acetate (Fe (CH 3 COO) 2 ) Can be used.
상기 전구체 수용액의 농도는 입자의 크기와 균일도를 결정할 수 있다. 그러므로 0.01 ~ 5 몰인 것이 좋으며, 더욱 좋게는 0.1 ~ 1 몰인 것이 바람직하다.The concentration of the precursor aqueous solution can determine the size and uniformity of the particles. Therefore, it is preferably 0.01 to 5 moles, more preferably 0.1 to 1 mole.
상기 침전제 용액은 Fe2+ 이온 용액을 Fe(OH)2 침전물 제조를 위하여 사용된다. 구체적으로 예를 들면, 암모니아수, 수산화나트륨, 수산화칼륨, 탄산나트륨, 탄산수소나트륨 및 테트라메틸암모늄 등으로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상을 혼합하여 사용할 수 있으며, 가격이 저렴하고, pH 조절이 가장 용이한 수산화나트륨을 사용하는 것이 좋다.The precipitant solution is used to prepare a Fe (OH) 2 precipitate of a Fe 2+ ion solution. Specifically, for example, any one or two or more selected from the group consisting of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate and tetramethylammonium can be mixed and used. It is best to use the easiest sodium hydroxide.
상기 침전제 용액을 사용하여 수산화철 용액을 염기성으로 조절하는 것이 바람직하며, 바람직하게는 pH 9 ~ 13, 더욱 바람직하게는 10 ~ 12로 조절하여 사용하는 것이 좋다. 상기 수산화철 용액의 pH가 9이하인 경우 Fe2+가 Fe(OH)2로 모두 변화하지 못하고 일부 Fe2+ 상태로 남아 있을 수 있으며, pH가 13을 초과하는 경우 세척횟수가 증가하는 문제가 있으므로 pH가 상기 범위인 것이 바람직하다.The precipitant solution is preferably used to adjust the basicity of the iron hydroxide solution to a basic level, preferably pH 9 to 13, more preferably 10 to 12. When the pH of the iron hydroxide solution is 9 or less, Fe 2+ does not change to Fe (OH) 2 and may remain in some Fe 2+ state. When the pH is above 13, Is in the above range.
상기 (b)단계에서 수산화철 용액을 시료의 주입구에 투입하면 자동적으로 압력펌프로 흘러들어갈 수 있으며, 상기 압력펌프는 수산화철 용액을 미세 오리피스 노즐 챔버로 이동시켜주는 역할을 할 수 있다.
In the step (b), when the solution of iron hydroxide is injected into the injection port of the sample, it can be automatically flowed into the pressure pump, and the pressure pump can move the solution of the iron hydroxide into the nozzle chamber of the fine orifice.
상기 미세 오리피스 노즐 챔버는 직경이 작을수록 높은 압력을 가하여 높은 에너지를 발생시킬 수 있지만, 분당 처리량이 감소될 수 있으므로 제한되지는 않으나, 예를 들면 직경이 60 ~ 250 ㎛인 것을 사용하는 것이 바람직하다. 상기 미세 오리피스 노즐 챔버의 온도는 수산화철 용액의 물성에 영향을 주지 않기 위하여 20 ~ 80℃인 것이 바람직하지만, 반드시 이에 제한되지는 않는다. As the diameter of the fine orifice nozzle chamber is small, it is possible to generate a high energy by applying a high pressure, but the throughput per minute can be reduced, so that it is not limited. For example, it is preferable to use a material having a diameter of 60 to 250 μm . The temperature of the micro-orifice nozzle chamber is preferably 20 to 80 ° C in order not to affect the physical properties of the iron hydroxide solution, but is not limited thereto.
상기 (c)단계는 수산화철 용액이 미세 오리피스 노즐 챔버를 통과함으로써, 전단 및 공동 현상으로 높은 에너지가 발생되어 물 분자의 해리로 인한 OH라디칼, H2O2 생성으로 수산화철 용액을 단분산 산화철 나노입자로 제조할 수 있다. 또한, 높은 에너지를 발생시키는 미세오리피스 노즐 챔버는 마치 오토클레이브와 같은 역할 을 수행함으로서 핵생성과 결정성장에 영향을 미칠 수 있다.In the step (c), a high-energy energy is generated due to shear and cavitation by passing the iron hydroxide solution through the fine orifice nozzle chamber, thereby generating OH radicals and H 2 O 2 due to dissociation of water molecules, . In addition, a micro-orifice nozzle chamber that generates high energy can act as an autoclave and affect nucleation and crystal growth.
나노입자를 제조하는 대부분의 방법은 고온에서 복잡한 공정 조건으로 반응시키므로 설비에 대한 제반 조건들의 제약이 많지만, 본 발명에 따른 단분산 산화철 나노입자의 제조방법은 상온에서 초고압 균질기에 통과시킴으로써 단분산 산화철 나노입자를 합성할 수 있으며, 공정 시간이 단축됨에 따라 생산성 향상이 기대되며, 제조설비가 단순해지는 이점이 있다.Since most of the methods for producing nanoparticles react with complex process conditions at high temperatures, there are many restrictions on the conditions of the apparatus. However, the monodisperse iron oxide nanoparticles according to the present invention are produced by passing monodisperse iron oxide nanoparticles at room temperature through an ultra- Nanoparticles can be synthesized. As the process time is shortened, the productivity is expected to be improved and the manufacturing facility is simplified.
본 발명의 초고압 균질기에 따른 물 분자의 라디칼 반응은 하기 반응식 1로 나타낼 수 있으나, 반드시 이에 제한되지는 않는다.The radical reaction of water molecule according to the ultra-high pressure homogenizer of the present invention can be represented by the following
[반응식 1][Reaction Scheme 1]
H2O → H + OH·H 2 O → H + OH
H + H· → H2 H + H - > H 2
OH·+ OH· → H2O2 OH + OH - > H 2 O 2
상기 반응식 1은, 초고압 균질기에 의하여 물 분자가 해리되면서 생성되는 OH 라디칼들과 이들의 결합으로 산화제인 H2O2가 생성된다. 따라서 별도의 산화제의 첨가 및 수열합성 과정 없이 수산화철 수용액으로부터 단분산 산화철을 얻을 수 있다. In the
본 발명의 초고압 균질기에 의한 산화철 나노입자의 제조는 하기 반응식 2로 나타낼 수 있으며, 반드시 이에 제한되지는 않는다.The preparation of the iron oxide nanoparticles by the ultra-high pressure homogenizer of the present invention can be represented by the following
[반응식 2][Reaction Scheme 2]
3Fe(OH)2 + H2O2 → Fe3O4 + 4H2O3Fe (OH) 2 + H 2 O 2 ? Fe 3 O 4 + 4H 2 O
상기 단분산 산화철은 FeO + Fe2O3의 혼합 산화물로 Fe2+와 Fe3+가 함께 존재하게 된다. 따라서 Fe2+가 모두 Fe3+로 산화되는 것을 막고 Fe2+와 Fe3+가 함께 존재하도록 산화-환원 분위기를 조절하기 위해서 초고압 균질기의 압력을 500 ~ 2,000 bar, 통과횟수는 1 ~ 20회 인 것이 바람직하다. The monodisperse iron oxide is a mixed oxide of FeO + Fe 2 O 3 , and Fe 2+ and Fe 3+ coexist. Therefore, Fe 2+ is oxidized to both prevents the oxidation to Fe 3+ exist with the Fe 2+ and Fe 3+ - the pressure of the ultra-high pressure homogenizer to adjust the reducing
또한, 상기 통과횟수는 (b) ~ (c) 단계 중 열교환기로부터 고압펌프로 이송되는 과정을 여러 번 반복 하여 산화철 나노입자를 제조할 수 있으며, 바람직하게는 재순환이송관에 의해 이송되는 과정을 1 ~ 20 회 반복함으로써, 산화철을 단분산 산화철 나노입자로 제조할 수 있으나, 반드시 이에 제한되는 것은 아니다.In addition, the number of times of passage may be varied by repeating the process of transferring from the heat exchanger to the high-pressure pump during the steps (b) to (c) several times to produce iron oxide nanoparticles, By repeating 1 to 20 times, the iron oxide can be produced as monodispersed iron oxide nanoparticles, but the present invention is not limited thereto.
상기 (d)단계는 상기 (c)단계의 침전물을 세척하고 건조시키는 단계이다. 상기 세척은 증류수, 메탄올 및 에탄올 등을 사용하는 것이 바람직하나, 세척 후 용이하게 제거될 수 있는 용액이면 이에 제한되지는 않는다.The step (d) is a step of washing and drying the precipitate of step (c). The washing is preferably performed using distilled water, methanol, ethanol, or the like, but it is not limited thereto as long as it is a solution that can be easily removed after washing.
상기 건조는 시료의 수분을 제거하기 위하여 50 ~ 100 ℃에서 3 ~ 10 시간 동안 건조하는 것이 바람직하다.The drying is preferably performed at 50 to 100 ° C for 3 to 10 hours in order to remove moisture from the sample.
본 발명의 상기 단분산 산화철 나노입자는 구형의 형상을 가지며, 입자크기가 10 ~ 30 ㎚ 인 초상자성 산화철 나노입자를 제조 할 수 있다. The monodisperse iron oxide nanoparticles of the present invention have a spherical shape and can produce super magnetic iron oxide nanoparticles having a particle size of 10 to 30 nm.
본 발명에 따른 단분산 산화철 나노입자는 초고압 균질기를 이용하여 입도 분포가 균일하고, 결정성이 높으며, 또한, 초고압 균질기의 압력 및 통과횟수를 조절함으로써 생성되는 나노입자의 크기와 물성 등을 손쉽게 조절할 수 있는 것에 특징이 있다.The monodisperse iron oxide nanoparticles according to the present invention can be easily and uniformly dispersed by using an ultra-high pressure homogenizer, uniform in particle size distribution, high in crystallinity, and capable of controlling the size and physical properties of nanoparticles produced by controlling the pressure and frequency of passage of the ultra- It is characterized by controllability.
본 발명은 독성이 있는 계면활성제나 기타 분산제를 사용하지 않기 때문에 산화철 나노입자 분리 공정이 필요하지 않고, 산화제를 첨가하여 고온에서 수열합성 반응을 하는 대신 초고압 균질기에 의한 라디칼 반응을 이용함으로써, 공정이 단순화되고 공정시간이 단축되며, 친환경적으로 산화철 나노입자를 제조할 수 있다.Since the present invention does not use a toxic surfactant or other dispersant, it does not require a separation process of iron oxide nanoparticles. Instead of using a hydrothermal synthesis reaction at a high temperature by adding an oxidizing agent, a radical reaction by an ultra- It is possible to simplify the manufacturing process, shorten the processing time, and produce iron oxide nanoparticles in an environmentally friendly manner.
본 발명의 단분산 산화철 나노입자는 균일한 입도 분포와 높은 결정성을 나타내므로, 자기센서, 자기광학소자, 자성잉크, 중금속 폐수처리, MRI 조영제, 약물 전달시스템 및 온열치료 등의 산화철 나노입자 응용분야에 유용하게 이용할 수 있다.The monodispersed iron oxide nanoparticles of the present invention exhibit uniform particle size distribution and high crystallinity, and thus can be applied to magnetic iron oxide nanoparticles such as magnetic sensors, magneto-optical elements, magnetic ink, heavy metal waste water treatment, MRI contrast agent, drug delivery system, And can be usefully used in fields.
도 1은 본 발명에서 이용된 초고압 균질기의 모식도를 도시한 것이다.
도 2는 본 발명의 초고압 균질기의 미세 오리피스 노즐 챔버의 내부를 도시한 것이다.
도 3은 본 발명에 따른 산화철 나노입자의 제조과정을 나타낸 흐름도이다.
도 4는 본 발명에 따른 실시예 1 내지 9 및 비교예 1에 따라 제조된 산화철 나노입자를 분말 X-선 회절 분석기로 분석한 결과를 나타낸 그래프이다.
도 5는 본 발명에 따른 실시예 1 내지 9 및 비교예 1에 따라 제조된 산화철 나노입자의 분말 X-선 회절 분석으로부터 Scherrer 식으로 계산된 산화철입자의 크기를 나타낸 그래프이다.
도 6은 본 발명에 따른 실시예 1, 4, 7 및 비교예 1에서 제조된 산화철 나노입자의 투과전자현미경 사진이다.
도 7은 본 발명에 따른 실시예 7, 8, 9 및 비교예 1에서 제조된 산화철 나노입자의 투과전자현미경 사진이다.
도 8은 본 발명에 따른 실시예 9 및 비교예 2에서 제조된 산화철 나노입자의 투과전자현미경 사진이다.
도 9는 본 발명에 따른 실시예 1, 4, 7, 8, 9 및 비교예 1, 2에서 제조된 산화철 나노입자의 자기특성을 나타낸 그래프이다.1 is a schematic diagram of an ultra-high pressure homogenizer used in the present invention.
Figure 2 shows the interior of the micro-orifice nozzle chamber of the inventive ultra-high pressure homogenizer.
3 is a flowchart illustrating a process for preparing iron oxide nanoparticles according to the present invention.
4 is a graph showing the results of analysis of iron oxide nanoparticles prepared according to Examples 1 to 9 and Comparative Example 1 by the powder X-ray diffractometer.
FIG. 5 is a graph showing the sizes of iron oxide particles calculated by Scherrer's formula from powder X-ray diffraction analysis of iron oxide nanoparticles prepared according to Examples 1 to 9 and Comparative Example 1 according to the present invention.
6 is a transmission electron micrograph of the iron oxide nanoparticles prepared in Examples 1, 4 and 7 and Comparative Example 1 according to the present invention.
7 is a transmission electron micrograph of the iron oxide nanoparticles prepared in Examples 7, 8 and 9 and Comparative Example 1 according to the present invention.
8 is a transmission electron micrograph of the iron oxide nanoparticles prepared in Example 9 and Comparative Example 2 according to the present invention.
9 is a graph showing the magnetic properties of the iron oxide nanoparticles prepared in Examples 1, 4, 7, 8 and 9 and Comparative Examples 1 and 2 according to the present invention.
이하는 본 발명을 보다 구체적으로 설명하기 위하여, 일예를 들어 설명하는바, 본 발명이 하기 실시예에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
[실시예 1][Example 1]
염화제일철(준세이) 2.01 g을 수용액 100 ㎖에 가하여 0.1 M 염화제일철 용액을 제조하였다. 상기 제조한 0.1 M 염화제일철 수용액 100 ㎖에 수산화나트륨(삼전순약) 1.02 g을 30㎖ 증류수에 용해시켜 제조한 0.85 M 수산화나트륨 용액을 첨가하여 상온에서 5분간 혼합하고 녹색의 수산화제일철 현탁액을 제조하였다. 상기 수산화제일철 현탁액을 500 bar의 압력으로 초고압 균질기(일신오토클레이브, NH-300)에 1회 통과시켜 검정색 침전물을 얻었다. 상기 침전물은 증류수와 에탄올을 사용하여 잔류 이온을 세척한 뒤, 80℃에서 6시간 동안 건조시켜 산화철 나노입자를 얻었다. 상기방법으로 물성을 측정한 결과를 표 1, 도 4 내지 6 및 9에 나타내었다.
2.01 g of ferrous chloride (Junsei) was added to 100 ml of aqueous solution to prepare a 0.1 M ferrous chloride solution. A 0.85 M sodium hydroxide solution prepared by dissolving 1.02 g of sodium hydroxide (Phenoxygen) in 30 ml of distilled water was added to 100 ml of the 0.1 M ferrous chloride aqueous solution prepared above, and the mixture was mixed at room temperature for 5 minutes to prepare a green ferric hydroxide suspension . The ferrous hydroxide suspension was passed once through an ultra-high pressure homogenizer (Il Shin autoclave, NH-300) at a pressure of 500 bar to obtain a black precipitate. The precipitate was washed with distilled water and ethanol to remove residual ions, and then dried at 80 DEG C for 6 hours to obtain iron oxide nanoparticles. The results of measuring the physical properties by the above method are shown in Tables 1, 4 to 6 and 9.
[실시예 2][Example 2]
상기 실시예 1에서 수산화제일철 현탁액을 초고압 균질기에 3회 통과시킨 것을 제외하고 실시예 1과 동일한 방법으로 산화철 나노입자를 제조하였으며, 상기 방법으로 물성을 측정한 결과를 표 1, 도 4, 5 및 도 9에 나타내었다.
The iron oxide nanoparticles were prepared in the same manner as in Example 1 except that the ferrous hydroxide suspension was passed through the ultra-high pressure homogenizer three times in Example 1. The results of measuring the physical properties by the above method are shown in Tables 1, Is shown in Fig.
[실시예 3][Example 3]
상기 실시예 1에서 수산화제일철 현탁액을 초고압 균질기에 5회 통과시킨 것을 제외하고 실시예 1과 동일한 방법으로 산화철 나노입자를 제조하였으며, 상기 방법으로 물성을 측정한 결과를 표 1, 도 4, 5 및 도 9에 나타내었다.
Iron oxide nanoparticles were prepared in the same manner as in Example 1 except that the ferrous hydroxide suspension was passed through an ultra-high pressure homogenizer five times in Example 1, and the physical properties of the iron oxide nanoparticles were measured. The results are shown in Tables 1, 4, 5, Is shown in Fig.
[실시예 4][Example 4]
상기 실시예 1에서 1,000 bar의 압력을 가한 것을 제외하고 실시예 1과 동일한 방법으로 산화철 나노입자를 제조하였으며, 상기 방법으로 물성을 측정한 결과를 표 1, 도 4 내지 6 및 도 9에 나타내었다.
Iron oxide nanoparticles were prepared in the same manner as in Example 1 except that the pressure was applied at 1,000 bar in Example 1, and physical properties of the iron oxide nanoparticles were measured. The results are shown in Tables 1, 4 to 6 and 9 .
[실시예 5][Example 5]
상기 실시예 1에서 1,000 bar의 압력을 가하고, 수산화제일철 현탁액을 초고압 균질기에 3회 통과시킨 것을 제외하고 실시예 1과 동일한 방법으로 산화철 나노입자를 제조하였으며, 상기 방법으로 물성을 측정한 결과를 표 1, 도 4, 5 및 도 9에 나타내었다.
Iron oxide nanoparticles were prepared in the same manner as in Example 1 except that the pressure of 1,000 bar was applied to the suspension of Example 1 and the ferrous hydroxide suspension was passed through the ultra-high pressure homogenizer three times. 1, Figs. 4 and 5, and Fig.
[실시예 6][Example 6]
상기 실시예 1에서 1,000 bar의 압력을 가하고, 수산화제일철 현탁액을 초고압 균질기에 5회 통과시킨 것을 제외하고 실시예 1과 동일한 방법으로 산화철 나노입자를 제조하였으며, 상기 방법으로 물성을 측정한 결과를 표 1, 도 4, 5 및 도 9에 나타내었다.
Iron oxide nanoparticles were prepared in the same manner as in Example 1 except that the pressure of 1,000 bar was applied to the suspension of Example 1 and the suspension of ferrous hydroxide was passed through the ultra-high pressure homogenizer five times. 1, Figs. 4 and 5, and Fig.
[실시예 7][Example 7]
상기 실시예 1에서 1,500 bar의 압력을 가한 것을 제외하고 실시예 1과 동일한 방법으로 산화철 나노입자를 제조하였으며, 상기 방법으로 물성을 측정한 결과를 표 1, 4 내지 7 및 도 9에 나타내었다.
Iron oxide nanoparticles were prepared in the same manner as in Example 1 except that the pressure was applied at 1,500 bar in Example 1, and physical properties of the iron oxide nanoparticles were measured. The results are shown in Tables 1, 4 to 7, and FIG.
[실시예 8][Example 8]
상기 실시예 1에서 1,500 bar의 압력을 가하고, 수산화제일철 현탁액을 초고압 균질기에 3회 통과시킨 것을 제외하고 실시예 1과 동일한 방법으로 산화철 나노입자를 제조하였으며, 상기 방법으로 물성을 측정한 결과를 표 1, 도 4, 5, 7 및 도 9에 나타내었다.
Iron oxide nanoparticles were prepared in the same manner as in Example 1, except that the pressure of 1,500 bar was applied to the suspension of Example 1, and the ferrous hydroxide suspension was passed through the ultra-high pressure homogenizer three times. 1, Figs. 4, 5, 7 and Fig. 9.
[실시예 9][Example 9]
상기 실시예 1에서 1,500 bar의 압력을 가하고, 수산화제일철 현탁액을 초고압 균질기에 5회 통과시킨 것을 제외하고 실시예 1과 동일한 방법으로 산화철 나노입자를 제조하였으며, 상기 방법으로 물성을 측정한 결과를 표 1, 도 4, 5 및 도 7 내지 9에 나타내었다.
Iron oxide nanoparticles were prepared in the same manner as in Example 1 except that the pressure of 1,500 bar was applied to the suspension of Example 1 and the ferrous hydroxide suspension was passed through the ultra-high pressure homogenizer five times. 1, 4, 5 and 7 to 9.
[비교예 1][Comparative Example 1]
염화제일철(준세이) 2.01 g을 수용액 100 ㎖에 가하여 0.1 M 염화제일철 용액을 제조하였다. 상기 제조한 0.1 M 염화제일철 수용액 100 ㎖에 수산화나트륨(삼전순약) 1.02 g을 30㎖ 증류수에 용해시켜 제조한 0.85 M 수산화나트륨 용액을 첨가하여 상온에서 1시간 동안 균일하게 교반하여 침전물을 얻었다. 상기 침전물은 증류수와 에탄올을 사용하여 잔류 이온을 세척한 뒤, 80℃에서 6시간 동안 건조시켜 산화철 나노입자를 얻었다. 상기방법으로 물성을 측정한 결과를 표 1, 도 4 내지 7 및 도 9에 나타내었다.
2.01 g of ferrous chloride (Junsei) was added to 100 ml of aqueous solution to prepare a 0.1 M ferrous chloride solution. 0.85 M sodium hydroxide solution prepared by dissolving 1.02 g of sodium hydroxide (Phenoxygen) in 30 ml distilled water was added to 100 ml of the 0.1 M ferrous chloride aqueous solution prepared above, and the mixture was uniformly stirred at room temperature for 1 hour to obtain a precipitate. The precipitate was washed with distilled water and ethanol to remove residual ions, and then dried at 80 DEG C for 6 hours to obtain iron oxide nanoparticles. The results of measuring the physical properties by the above method are shown in Table 1, Figs. 4 to 7, and Fig.
[비교예 2][Comparative Example 2]
염화제일철(준세이) 2.01 g을 수용액 100 ㎖에 가하여 0.1 M 염화제일철 용액을 제조하였다. 상기 제조한 0.1 M 염화제일철 수용액 100 ㎖에 수산화나트륨(삼전순약) 1.02 g을 30㎖ 증류수에 용해시켜 제조한 0.85 M 수산화나트륨 용액을 첨가하여 상온에서 250 W의 파워로 1시간 동안 초음파 조사를 실시하여 침전물을 얻었다. 상기 침전물은 증류수와 에탄올을 사용하여 잔류 이온을 세척한 뒤, 80℃에서 6시간 동안 건조시켜 산화철 나노입자를 얻었다. 상기방법으로 물성을 측정한 결과를 표 1, 도 8 및 도 9에 나타내었다.
2.01 g of ferrous chloride (Junsei) was added to 100 ml of aqueous solution to prepare a 0.1 M ferrous chloride solution. A 0.85 M sodium hydroxide solution prepared by dissolving 1.02 g of sodium hydroxide (tertiary octane) in 30 ml of distilled water was added to 100 ml of the 0.1 M ferrous chloride aqueous solution prepared above, and ultrasonic irradiation was performed at a power of 250 W for 1 hour at room temperature To obtain a precipitate. The precipitate was washed with distilled water and ethanol to remove residual ions, and then dried at 80 DEG C for 6 hours to obtain iron oxide nanoparticles. The results of measuring the physical properties by the above method are shown in Tables 1, 8 and 9.
[비교예 3][Comparative Example 3]
염화제일철(준세이) 2.01 g을 수용액 100 ㎖에 가하여 0.1 M 염화제일철 용액을 제조하였다. 상기 제조한 0.1 M 염화제일철 수용액 100 ㎖에 수산화나트륨(삼전순약) 1.02 g을 30㎖ 증류수에 용해시켜 제조한 0.85 M 수산화나트륨 용액을 첨가하여 상온에서 30분 동안 교반한 후 수산화제일철 현탁액을 제조하였다. 상기 수산화제일철 수용액에 1.0 MeV의 전자빔 에너지 3.0 mA의 전류로 300 kGy의 조사선량이 되도록 조사하여 침전물을 얻었다. 상기 침전물은 증류수와 에탄올을 첨가하여 잔류 이온을 세척한 뒤, 60℃에서 6시간 동안 건조시켜 산화철 나노입자를 얻었다. 상기방법으로 물성을 측정한 결과를 표 1에 나타내었다.
2.01 g of ferrous chloride (Junsei) was added to 100 ml of aqueous solution to prepare a 0.1 M ferrous chloride solution. A 0.85 M sodium hydroxide solution prepared by dissolving 1.02 g of sodium hydroxide (Phenoxygen) in 30 ml of distilled water was added to 100 ml of the 0.1 M ferrous chloride aqueous solution prepared above, stirred at room temperature for 30 minutes, and a ferrous hydroxide suspension was prepared . A precipitate was obtained by irradiating the ferric hydroxide aqueous solution at an irradiation dose of 300 kGy at a current of 3.0 mA with an electron beam energy of 1.0 MeV. The precipitate was washed with distilled water and ethanol to remove residual ions, and then dried at 60 ° C. for 6 hours to obtain iron oxide nanoparticles. Table 1 shows the results of measuring the physical properties by the above method.
[표 1][Table 1]
산화철 나노입자의 결정구조 분석Crystal Structure Analysis of Iron Oxide Nanoparticles
본 발명의 제조방법으로 제조된 산화철 나노입자의 결정성을 알아보기 위하여 분말 X-선 회절 분석기(Rigaku, SmartLab)를 이용하여 결정성을 분석하고 그 결과를 도 4에 나타내었다. Crystallinity of the iron oxide nanoparticles prepared by the manufacturing method of the present invention was analyzed using a powder X-ray diffractometer (Rigaku, SmartLab) and the results are shown in FIG.
도 4에 나타난 바와 같이, 상기 실시예에서 제조된 입자는 산화철(Fe3O4)로 나타났지만, 초고압 균질기를 통과 시키지 않은 비교예 1의 경우 산화철과 FeOOH가 혼합된 것으로 나타났다. 이로부터 초고압 균질기를 이용하여 제조된 산화철은 결정성이 높고, 불순물이 없는 순수한 산화철로 합성됨을 확인하였다.As shown in FIG. 4, the particles produced in the above example were shown as iron oxide (Fe 3 O 4 ), but in the case of Comparative Example 1 in which the ultra-high pressure homogenizer was not passed, iron oxide and FeOOH were mixed. From these results, it was confirmed that the iron oxide prepared using the ultra - high pressure homogenizer had high crystallinity and was synthesized as pure iron oxide free of impurities.
또한, 분말 X-선 회절분석 결과로부터 Scherrer 공식을 이용하여 제조된 산화철 나노입자의 평균입자 크기를 구하였다. 평균입자의 크기는 도 5에 나타내었으며, 초고압 균질기의 압력과 통과 횟수에 따라 입자의 크기 조절이 가능한 것을 확인하였다.From the powder X-ray diffraction analysis results, the average particle size of the iron oxide nanoparticles prepared using the Scherrer formula was determined. The average particle size is shown in FIG. 5, and it is confirmed that the particle size can be controlled according to the pressure and the number of passes of the ultra-high pressure homogenizer.
도 5에서 실시예 9의 경우 초고압균질기 1,500 bar에서 5회 통과시켰음에도 불구하고 1,500 bar에서 3회 통과시킨 경우보다 입자크기가 큰 것을 확인하였다. 이는 5회 통과부터 결정성장 속도가 가속화 되어 나타나는 현상으로 보인다. 입자크기는 핵생성 시간과 결정성장 시간에 따라 달라진다. 핵생성 시간은 짧을수록, 결정성장 시간은 길수록 입자크기는 감소하게 되며, 따라서 1500 bar 3회 통과 이상부터는 결정 성장이 가속화되기 때문에 다시 입자크기가 증가하는 것으로 나타난다.In FIG. 5, it was confirmed that the particle size of Example 9 was larger than that in Example 3 when the ultra-high pressure homogenizer was passed five times at 1,500 bar and then passed three times at 1,500 bar. This seems to be a phenomenon that the crystal growth rate accelerates from the fifth pass. Particle size depends on nucleation time and crystal growth time. The shorter the nucleation time and the longer the crystal growth time, the smaller the particle size. Therefore, the particle size is increased again because the crystal growth is accelerated more than 1500
산화철 나노입자의 크기 및 형태 분석Size and morphology analysis of iron oxide nanoparticles
본 발명의 제조방법으로 제조된 산화철 나노입자의 크기 및 형태를 알아보기 위해 투과전자현미경(TEM, FEI, TecnaiG2 F30 S-Twin)으로 분석하고, 그 결과를 도 6, 7 및 8에 나타내었다. The size and shape of the iron oxide nanoparticles prepared by the manufacturing method of the present invention were analyzed with a transmission electron microscope (TEM, FEI, TecnaiG 2 F30 S-Twin), and the results are shown in FIGS. 6, 7 and 8 .
그리드(Grid)는 탄소가 코팅된 지름 3 ㎜ 구리 그리드를 사용하였다.The grid was a 3 mm diameter copper grid coated with carbon.
도 6 및 도 7에 나타난 바와 같이, 본 발명에 따른 실시예 1, 4, 7, 8 및 9에서 제조된 산화철 나노입자의 모양은 구형으로 나타났으며, 산화철 나노입자의 평균 크기는 각각 24, 22, 20, 17, 22 ㎚인 것으로 확인하였다. 하지만, 비교예 1에서 제조된 입자들은 구형의 산화철과 막대 모양의 FeOOH등 단일상이 아닌 것으로 나타났고, 크기 분포 또한 불균일한 것으로 관찰되었다.As shown in FIGS. 6 and 7, the iron oxide nanoparticles prepared in Examples 1, 4, 7, 8, and 9 according to the present invention showed spherical shapes, and the average sizes of the iron oxide nanoparticles were 24, 22, 20, 17, and 22 nm, respectively. However, the particles produced in Comparative Example 1 were not single phase such as spherical iron oxide and rod-shaped FeOOH, and the size distribution was also observed to be non-uniform.
도 8에 나타난 바와 같이, 비교예 2의 초음파 조사를 통해 제조된 산화철 입자 역시 막대 모양의 FeOOH가 함께 나타나는 것으로 확인하였다.As shown in FIG. 8, it was confirmed that the iron oxide particles produced by the ultrasonic irradiation of Comparative Example 2 also showed sticky FeOOH.
도 6, 7 및 8을 참조하면, 본 발명에 따른 실시예에 의해 제조된 산화철은 구형의 형태를 갖으며, 산화철 단일상을 갖는 반면 단순 교반 및 초음파 조사를 통해 제조된 비교예의 산화철들은 막대 모양의 FeOOH가 함께 존재하며, 불균일한 입자 크기 분포를 갖는 것으로 나타났다. 또한, 실시예를 통해 합성된 산화철들은 25 ㎚이하의 입자로 제조된 것을 확인 할 수 있었다.6, 7 and 8, iron oxides prepared by the examples according to the present invention have spherical shapes and iron oxide single phases, while the comparative iron oxides produced by simple agitation and ultrasonic irradiation have rod shapes ≪ / RTI > of FeOOH were present together and had an uneven particle size distribution. In addition, it was confirmed that the iron oxides synthesized through the examples were made with particles of 25 nm or less.
단분산 산화철 나노입자의 자기적 특성분석Analysis of magnetic properties of monodisperse iron oxide nanoparticles
본 발명의 제조방법으로 제조된 산화철 나노입자의 자기적 특성을 알아보기 위하여 상온에서 진동시료자기측정기(Vibrating Sample Magnetometer)로 자기특성을 분석하고, 도 9 및 표 1에 나타내었다.In order to examine the magnetic properties of the iron oxide nanoparticles produced by the production method of the present invention, magnetic characteristics were analyzed with a vibrating sample magnetometer at room temperature and shown in FIG. 9 and Table 1.
실시예 7과 8은 보자력과 잔류자화값이 0으로 초상자성 특성을 갖는 것을 확인하였다. 또한, 10 KOe에서 측정된 자화값은 덩어리 상태의 시료에 대한 포화자화값인 92 emu/g에 비하면 훨씬 작은 값이다. ㎚크기에서의 이러한 자화값의 감소는 입자의 크기가 작아지면서 발생하는 불완전한 결정학적 구조 및 표면효과로 인한 스핀 기울어짐에 의한 것으로 확인되었다.
In Examples 7 and 8, it was confirmed that the coercive force and the residual magnetization value were zero and that the super magnetism characteristics were obtained. Also, the magnetization value measured at 10 KOe is much smaller than the saturation magnetization value of 92 emu / g for the bulk sample. The reduction of the magnetization value at the ㎚ size was confirmed to be due to the incomplete crystallographic structure and the spin tilt due to the surface effect caused by the reduction of the particle size.
10 : 시료주입구
11 : 압력펌프
12 : 압력게이지
13 : 열교환기
14 : 배출구
15 : 재순환이송관
20 : 미세 오리피스 노즐 챔버
21 : 오리피스10: Sample inlet
11: Pressure pump
12: Pressure gauge
13: Heat exchanger
14: Outlet
15: recirculation transfer pipe
20: fine orifice nozzle chamber
21: Orifice
Claims (10)
b) 상기 a)단계의 침전물을 세척하고 건조시키는 단계,
를 포함하는 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법. a) preparing a hydroxide iron solution by mixing iron oxide precursor, distilled water and precipitant solution, passing the solution through an ultra-high pressure homogenizer at a pressure of 500 to 2,000 bar at room temperature to obtain a precipitate, and
b) washing and drying the precipitate of step a)
Wherein the monodisperse iron oxide nanoparticles are prepared by using an ultra-high pressure homogenizer.
상기 수산화철 용액은 산화철 전구체를 증류수에 용해시켜 전구체 수용액을 제조한 후 침전제 용액을 첨가하여 수산화철 용액을 제조하는 것인 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법.The method according to claim 1,
Wherein the iron hydroxide solution is prepared by dissolving an iron oxide precursor in distilled water to prepare a precursor aqueous solution and then adding a precipitation agent solution to prepare a solution of iron hydroxide, wherein the ultra-high pressure homogenizer is used.
상기 산화철 전구체는 염화제일철(FeCl2), 황산제일철(FeSO4) 또는 아세트산철(Fe(CH3COO)2)에서 선택되는 어느 하나인 것인 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법.3. The method of claim 2,
Wherein the iron oxide precursor is any one selected from ferrous chloride (FeCl 2 ), ferrous sulfate (FeSO 4 ), and iron acetate (Fe (CH 3 COO) 2 ).
상기 침전제 용액은 암모니아수, 수산화나트륨, 수산화칼륨, 탄산나트륨, 탄산수소나트륨 및 테트라메틸암모늄의 군에서 선택되는 어느 하나 또는 둘 이상인 것인 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법.3. The method of claim 2,
Wherein the precipitant solution is one or more selected from the group consisting of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate and tetramethylammonium.
상기 전구체 수용액은 농도가 0.01 ~ 5 몰인 것인 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법. 3. The method of claim 2,
Wherein the precursor aqueous solution has a concentration of 0.01 to 5 moles.
상기 초고압 균질기에 포함된 미세 오리피스 노즐 챔버는 직경이 60 ~ 250 ㎛인 것인 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법.The method according to claim 1,
Wherein the micro-orifice nozzle chamber included in the ultra-high pressure homogenizer has a diameter of 60 to 250 占 퐉.
상기 미세 오리피스 노즐 챔버 온도는 20 ~ 80℃인 것인 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법.The method according to claim 6,
Wherein the micro-orifice nozzle chamber temperature is 20 to 80 ° C.
상기 a)단계에서 얻은 침전물을 상기 초고압 균질기에 1 ~ 20 회 반복 통과 시키는 것인 초고압 균질기를 이용한 단분산 산화철 나노입자의 제조방법. The method according to claim 1,
Wherein the precipitate obtained in the step a) is repeatedly passed through the ultra-high pressure homogenizer for 1 to 20 times, thereby producing a monodisperse iron oxide nanoparticle using an ultra-high pressure homogenizer.
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