KR20080074263A - The nano-powder preparation of the transition metal oxide using the basic carbonate salt by the modified combustion technique - Google Patents
The nano-powder preparation of the transition metal oxide using the basic carbonate salt by the modified combustion technique Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000011858 nanopowder Substances 0.000 title claims abstract description 22
- 229910000314 transition metal oxide Inorganic materials 0.000 title abstract description 4
- 238000002485 combustion reaction Methods 0.000 title description 7
- 238000002360 preparation method Methods 0.000 title description 5
- 150000005323 carbonate salts Chemical class 0.000 title description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 150000001768 cations Chemical class 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 20
- -1 zinc cations Chemical class 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000007580 dry-mixing Methods 0.000 claims 2
- 239000000843 powder Substances 0.000 abstract description 40
- 239000002245 particle Substances 0.000 abstract description 36
- 239000002243 precursor Substances 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 5
- 239000012153 distilled water Substances 0.000 abstract description 5
- 238000000498 ball milling Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 4
- 238000003801 milling Methods 0.000 abstract 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 7
- 239000011164 primary particle Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical group [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/008—Pyrolysis reactions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
금속산화물들의 분말들을 제조하는 기법은 수없이 많다. 이들 기법들 중에서 공업적으로 활용되는 기법은 양질의 분말을 낮은 가격에 대량 생산할 수 있는 공정으로 이루어진 기법이 될 것이다. 양질의 분말이라 함은 높은 순도와 균일한 입자크기를 갖고 그리고 구형의 입자들로 분포된 분말을 말한다. 이와 같은 분말을 저렴한 가격에 대량 생산하기 위해 적용하는 기법이 고체 전구체의 열분해이다. 그러나 이 기법의 단점은 생성물의 1차 입자들의 2차 입자들로의 응집을 피할 수 없다는 것이다. 따라서 이 기법으로 전구체를 열분해 할 때, 1차 입자들의 응집 (aggregation)을 억제할 수 있는 수단이 필요하다. 본 발명은 3d 전이금속 산화물인 산화코발트 (Co3O4), 산화니켈 (NiO), 산화구리 (CuO) 및 산화아연 (ZnO)의 나노크기 분말을 이들의 염기성 탄산염을 사용하여 제조하는 기법을 제시한다. 염기성 탄산염이 선택된 이유들 중에 하나는 이 염에 포함된 금속 양이온에 대한 단위질량당 가격이 다른 화합물과 비교하여 가장 저렴하기 때문이다. 또 다른 이유는 열분 해 특성에 있다.There are numerous techniques for producing powders of metal oxides. Among these techniques, industrially utilized techniques will be made up of processes that can mass-produce high quality powders at low prices. Fine powder is a powder with high purity and uniform particle size and distributed into spherical particles. The technique applied to mass production of such powders at low prices is pyrolysis of solid precursors. However, a disadvantage of this technique is that the agglomeration of the primary particles of the product into secondary particles is inevitable. Therefore, when pyrolyzing the precursor with this technique, a means for suppressing the aggregation of primary particles is needed. The present invention provides a technique for preparing nanosize powders of cobalt oxide (Co 3 O 4 ), nickel oxide (NiO), copper oxide (CuO) and zinc oxide (ZnO), which are 3d transition metal oxides, using their basic carbonates. present. One of the reasons for the selection of basic carbonates is that the price per unit mass for the metal cations contained in these salts is the cheapest compared to other compounds. Another reason is the thermal decomposition characteristics.
+2의 원자가를 갖는 금속 양이온에 대한 염기성 탄산염의 일반적인 화학식은 xMCO3ㆍyM(OH)2ㆍzH2O으로 표현된다. 여기서 계수 x, y, 및 z 값은 금속 양이온의 종류와 반응물의 농도, 반응온도 및 반응경로 등의 실험조건에 따라 다르다. 이들 염기성 탄산염들은 온도상승에 따라 탈수된 후에 수산화음이온으로부터 물과 탄산 음이온으로부터 이산화탄소의 방출을 근거로 하여 세 집단으로 분류된다. 첫 번째 집단에 속하는 염기성 탄산염은 물과 이산화탄소를 동시에 방출하며, 두 번째 집단에 속하는 염기성 탄산염들은 두 화합물들을 연차적으로 방출하고, 그리고 세 번째 집단에 속하는 염기성 탄산염은 두 화합물을 독립적으로 방출한다. 코발트, 니켈, 구리 및 아연의 염기성 탄산염들은 첫 번째 집단에 속한다.The general formula of basic carbonates for metal cations with valences of +2 is represented by x MCO 3 · y M (OH) 2 · z H 2 O. The coefficients x , y , and z values depend on the type of metal cation and the experimental conditions such as the concentration of the reactants, the reaction temperature and the reaction path. These basic carbonates are classified into three groups based on the release of carbon dioxide from water and carbonate anions from hydroxide anions after dehydration with temperature rise. Basic carbonates belonging to the first group release water and carbon dioxide simultaneously, basic carbonates belonging to the second group release both compounds annually, and basic carbonates belonging to the third group release both compounds independently. Basic carbonates of cobalt, nickel, copper and zinc belong to the first group.
일반적으로, 고체 전구체의 열분해 기법으로 나노분말을 제조하기 위해서는 고체 전구체는 낮은 온도에서 분해되어야 한다. 위에서 언급한 3d 전이금속 양이온의 염기성 탄산염들 내에 존재하는 수산화음이온과 탄산 음이온들의 대부분은 350 oC 이하에서 분해되고, 그리고 분해되지 않고 남아있는 음이온들은 500 oC 이하의 온도에서 완전히 분해된다. 이들 염들로부터 두 음이온이 없는 순수한 산화물 분말들이 500 oC 이상에서 제조되기 때문에, 이들 염들로부터 나노분말을 제조할 수 없을 것으로 판단된다. 그러나 이들 염들로부터 350 oC 이하에서 얻어진 분말의 특성을 고려한다면, 이들 염들을 적절히 처리하게 되면 이들 염들로부터 나노크기 분말 을 제조할 가능성이 있음을 알 수 있다. In general, in order to prepare nanopowders by the pyrolysis technique of a solid precursor, the solid precursor must be decomposed at a low temperature. Most of the hydroxide and carbonate anions present in the basic carbonates of the 3d transition metal cations mentioned above are decomposed at 350 ° C. or lower, and the remaining anions are decomposed completely at temperatures of 500 ° C. or lower. Since pure oxide powders without two anions from these salts are prepared above 500 ° C., it is believed that nanopowders cannot be prepared from these salts. However, considering the properties of the powders obtained below 350 ° C. from these salts, it can be seen that the nanoscale powders can be prepared from these salts if properly treated.
각각의 염기성 탄산염에 대하여, 방출된 물과 이산화탄소의 총 질량의 절반이 방출되는 온도에서 얻어진 분말의 비표면적 (specific surface area)이 가장 크다. 예를 들면, 염기성 탄산 아연의 경우에 이 조건에서 얻어진 분말의 비표면적은 약 210 m2/g이다. 이 분해온도보다 높은 온도에서 얻어진 분말의 비표면적은 분해온도의 상승과 더불어 급격히 줄어든다. 이 사실은 높은 온도에서 염기성 탄산염을 분해할 때에 생성물입자의 결정성장을 억제하면, 나노분말을 제조할 수 있음을 제시한다. 본 발명에서 결정성장을 억제하기 위하여 사용한 두 가지 기법은 다음과 같다. 하나의 기법은 이종 계면(heterogenous interface)들을 형성시켜 생성물입자들 사이에 상호작용을 약화시키는 것이고 그리고 다른 기법은 생성물분말을 제조에 연소기법(combustion technique)을 적용한 것이다.For each basic carbonate, the specific surface area of the powder obtained at the temperature at which half of the total mass of water and carbon dioxide released is released. For example, in the case of basic zinc carbonate, the specific surface area of the powder obtained under these conditions is about 210 m 2 / g. The specific surface area of the powder obtained at a temperature higher than this decomposition temperature decreases rapidly with the rise of the decomposition temperature. This fact suggests that nanoparticles can be prepared by inhibiting crystal growth of product particles when decomposing basic carbonates at high temperatures. Two techniques used to suppress crystal growth in the present invention are as follows. One technique is to weaken the interactions between the product particles by forming heterogenous interfaces and the other is to apply the combustion technique to the production of the product powder.
연소기법은 연료와 산화제를 사용하여 금속산화물 분말을 제조하는 기법이다. 이 기법은, 연료와 산화제의 반응과 함께 발생하는 연소열이 생성물이 합성되는데 관여하기 때문에, 고체상태반응(solid state reaction)으로 생성물이 제조되는 온도보다 낮은 온도에서 물질을 제조할 수 있다는 장점이 있다. 따라서 이 기법은, 생성물입자들은 제조온도가 상승할수록 입자들의 크기가 커지기 때문에, 나노분말의 제조에 부적합한 것으로 보인다. 연소에 의한 온도 상승은 소량의 연료와 그 연료의 양에 대응되는 양의 산화제를 사용함으로써 해결할 수 있다. Combustion is a technique for producing metal oxide powder using fuel and oxidant. This technique has the advantage of being able to produce materials at temperatures lower than the temperature at which the product is produced in a solid state reaction, because the heat of combustion that occurs with the reaction of the fuel and the oxidant is involved in the synthesis of the product. . This technique therefore appears to be unsuitable for the production of nanopowders, since the product particles increase in size as the production temperature increases. The temperature rise by combustion can be solved by using a small amount of fuel and an amount of oxidant corresponding to the amount of the fuel.
지금까지 보고된 바로, 연료로서 구연산, 장뇌, 또는 요소와 같은 유기물이나 히드라진 등이 사용되고, 그리고 산화제로는 주로 질산 음이온이 사용되고 있 다. 본 발명에서는 염기성 탄산염, 진한 질산(HNO3), 그리고 마론 산(HOOCCH2COOH)을 사용하기 때문에, 연료는 마로네이트(-OOCCH2COO-) 염이, 산화제는 질산(NO3 -) 염이 된다. 염기성 탄산염 내에 존재하는 탄산 음이온과 수산화 음이온의 분해는 흡열 반응이고, 그리고 마로네이트 음이온의 연소는 발열 반응이다. 따라서 질산과 마론 산의 사용량을 조절하여, 연소시에 발생하는 열량을 조절하게 되면, 이 기법으로 나노분말이 제조될 것으로 기대된다.As reported so far, organic materials such as citric acid, camphor, or urea and hydrazine are used as fuels, and nitrate anions are mainly used as oxidants. According to the present invention because it uses a basic carbonate, concentrated nitric acid (HNO 3), and maroon acid (HOOCCH 2 COOH), fuel is mellow carbonate salt (- OOCCH 2 COO - -) salt, the oxidizing agent is nitrate (NO 3) do. The decomposition of the carbonate anion and the hydroxide anion present in the basic carbonate is an endothermic reaction, and the combustion of the maronate anion is an exothermic reaction. Therefore, by controlling the amount of nitric acid and maronic acid used to control the amount of heat generated during combustion, this technique is expected to produce nanopowders.
또한, 본 발명에서 생성물입자들의 결정성장을 억제하기 위해 도입된 기법이 생성물인 산화물의 나노분말과 전구체인 염기성 탄산염을 혼합하여 분쇄하는 과정이다. 이 과정에서 산화물 입자들은 전구체 입자들의 표면에 흡착하여 이종 계면을 형성하여 전구체 입자들의 응집을 억제할 뿐만 아니라, 전구체 분말로부터 생성물분말이 만들어지는 과정에서 생성물입자들의 응집을 방해할 것으로 기대한다. 물론, 마론 산과 질산을 염기성 탄산염에 가하여 생성된 마로네이트 염, 질산염 그리고, 남아 있는 염기성 탄산염들 사이에 이종 계면이 형성된다. 그렇지만, 이 기법을 적용하여 얻은 분말입자들이 균일한 크기를 갖는다. In addition, the technique introduced in order to suppress the crystal growth of the product particles in the present invention is a process of mixing and grinding the nanopowder of the oxide as a product and the basic carbonate as a precursor. In this process, the oxide particles are adsorbed on the surface of the precursor particles to form a heterogeneous interface to suppress the aggregation of the precursor particles, and is expected to interfere with the aggregation of the product particles during the production of the product powder from the precursor powder. Of course, a heterogeneous interface is formed between the maronate salt, the nitrate, and the remaining basic carbonates formed by adding maronic acid and nitric acid to the basic carbonate. However, the powder particles obtained by applying this technique have a uniform size.
양질의 금속산화물 나노분말을 제조하는 것이 본 발명이 추구하는 방향이다. 분말의 특성을 지배하는 인자들은 순도, 생성물의 결정성, 입자의 평균크기와 입자크기의 분포, 그리고 입자의 형태(morphology) 등이다. 본 발명에서 제조하고자 하는 산화물들은 무정형 상이 존재하지 않고 그리고 생성물 내에 존재하는 불순물이 분해되지 않는 염이므로, 분말순도와 생성물의결정성보다는 입자의 평균크기, 입자들의 분포 및 입자의 형태에 본 발명은 초점이 맞추어져 있다.Producing a high quality metal oxide nanopowder is a direction pursued by the present invention. Factors governing the properties of the powder are purity, crystallinity of the product, distribution of the average and particle sizes of the particles, and particle morphology. Since the oxides to be prepared in the present invention are salts in which there is no amorphous phase and impurities present in the product are not decomposed, the present invention focuses on the average size of particles, the distribution of particles, and the shape of particles, rather than powder purity and product crystallinity. Is aligned.
분말을 구성하고 있는 입자는 1차 입자와 2차 입자로 분류된다. 분말 내에 입자들이 서로 응집되어 있다면, van der Waals 인력에 의해 1차 입자들이 응집체를 형성하고 있는 경우를 제외하고, 1차 입자의 크기는 의미가 없다. 따라서 본 발명이 이루고자 하는 과제는 주로 1차 입자들로 구성된 100 nm 이하의 구형 나노분말을 제조하는 것이다. Particles constituting the powder are classified into primary particles and secondary particles. If the particles are agglomerated with each other in the powder, the size of the primary particles is meaningless unless the primary particles are formed by the van der Waals attraction. Therefore, an object of the present invention is to produce a spherical nanopowder of 100 nm or less mainly composed of primary particles.
염기성 탄산염, 마론 산, 진한 질산 그리고 나노크기의 생성물분말을 사용하여 나노분말을 제조하는 과정은 다음과 같다.The process for preparing nanopowders using basic carbonate, maronic acid, concentrated nitric acid and nano-sized product powder is as follows.
① 사용한 염기성 탄산염의 양에 대하여 미리 결정한 양의 나노크기의 생성물분말을 염기성 탄산염과 함께 실온, 공기 중에서 혼합한다. 예를 들면,염기성 탄산 니켈을 사용한다면, 생성물분말은 산화니켈이 된다. 산화물 내에 금속 양이온의 몰수와 염기성 탄산염 내에 금속 양이온의 몰수비는 0.01에서 0.1까지이다. 이 비는 산화물 입자크기가 커질수록 커진다.(1) About the amount of basic carbonate used, the nano-size product powder of predetermined amount is mixed with basic carbonate in room temperature and air. For example, if basic nickel carbonate is used, the product powder is nickel oxide. The molar ratio of the metal cations in the oxide to the metal cations in the basic carbonate is from 0.01 to 0.1. This ratio increases as the oxide particle size increases.
② 위의 분말에 질산, 마론 산 및 증류수를 넣는다. 볼 밀링(ball milling)과 함께 가열하면서 가한 증류수를 제거한다. 질산과 금속 양이온의 몰수비는 0.10에서 0.5까지이고, 그리고 마론 산과 질산의 몰수비는 0.10에서 0.30까지이다.② Put nitric acid, maronic acid and distilled water in the above powder. Distilled water is removed while heating with ball milling. The molar ratio of nitric acid to metal cations is from 0.10 to 0.5, and the molar ratio of maronic acid to nitric acid is from 0.10 to 0.30.
③ 앞 과정에서 얻어진 분말을 분쇄한 다음, 분말시료를 주어진 온도에서 열분해를 한다.③ Pulverize the powder obtained in the previous step, and then pyrolyze the powder sample at the given temperature.
이들 과정을 아래의 실시 예에서 구체적으로 설명한다.These processes will be described in detail in the following examples.
<실시 예 - 1> 산화코발트 나노분말의 제조Example 1 Preparation of Cobalt Oxide Nanopowders
0.2 몰의 코발트 양이온을 포함하고 있는 염기성 탄산 코발트, 2CoCO3ㆍ3Co(OH)2의 분말과 평균입자의 크기가 15 nm인 산화코발트(Co3O4) 0.803 g를 넣고, 볼 밀링하였다. 여기서 산화코발트 내에 코발트 양이온과 염기성 탄산염 내에 코발트 양이온의 몰수비는 0.05이다. 볼 밀링은 6시간 동안 실온, 공기 중에서 수행하였다. 여기에 진한 질산 0.02 몰과 고체 마론 산 0.005 몰, 그리고 증류수 100 mL를 가하고 2시간 동안 볼 밀링하였다. 계속해서 80 oC에서 진공과 함께 내용물을 건조하였다. 건조된 내용물을 분쇄하고 난 다음, 350 oC로 가열된 전기로에서 열분해를 하였다. 질산과 탄산염과의 몰수비는 0.10이고, 그리고 마론 산과 질산의 몰수비는 0.25이다.Basic cobalt carbonate, powder of 2CoCO 3 .3Co (OH) 2 containing 0.2 mol of cobalt cation and 0.803 g of cobalt oxide (Co 3 O 4 ) having an average particle size of 15 nm were added and ball milled. Here, the molar ratio of the cobalt cation in cobalt oxide and the cobalt cation in basic carbonate is 0.05. Ball milling was carried out for 6 hours at room temperature and in air. To this was added 0.02 mol of concentrated nitric acid, 0.005 mol of solid maronic acid, and 100 mL of distilled water, followed by ball milling for 2 hours. The contents were then dried with vacuum at 80 ° C. The dried contents were ground and then pyrolyzed in an electric furnace heated to 350 ° C. The molar ratio between nitric acid and carbonate is 0.10, and the molar ratio between maronic acid and nitric acid is 0.25.
얻어진 분말의 입자 크기는 Scherrer 식에 의한 X-선 회절 피크의 선폭 기법(line-broadening technique)과 BET 방법으로 산출한 비표면적으로부터 산출하였다. Scherrer 식은 다음과 같다.The particle size of the obtained powder was calculated from the line-broadening technique of the X-ray diffraction peak by the Scherrer equation and the specific surface area calculated by the BET method. The Scherrer expression is
여기서 D는 분말입자의 크기, k는 0.89로 상수, λ는 사용한 X-선의 파장, β는 라디안의 FWHM (full width at half-maximum) 값, θ는 회절각의 절반값이다. 위의 과정을 거쳐 제조한 산화 코발트에 대하여, 구리 타깃(λ= 1.5418 Å)을 사용하여 얻은 X-선회절도에서 2θ= 36.78o에서 최대 회절 피크가 관찰되었고, 이 피크에 대한 FWHM 값은 0.83o였다. 이들 값들로부터 계산된 평균입자의 크기는 10 nm이다. 또한 얻어진 산화코발트의 비표면적은 42.6 m2/g이였다. 이값과 밀도로부터 계산된 입자의 크기는 23.3 nm이다.Where D is the size of the powder particles, k is a constant of 0.89, λ is the wavelength of X-rays used, β is the full width at half-maximum (FWHM) value in radians, and θ is the half value of the diffraction angle. For the cobalt oxide prepared through the above procedure, the maximum diffraction peak was observed at 2θ = 36.78 o in the X-ray diffractogram obtained using the copper target (λ = 1.5418 kPa), and the FWHM value for this peak was 0.83 o. It was. The average particle size calculated from these values is 10 nm. In addition, the specific surface area of the obtained cobalt oxide was 42.6 m 2 / g. The particle size calculated from this value and density is 23.3 nm.
<실시 예 - 2> 산화니켈의 나노분말의 제조Example 2 Preparation of Nanopowders of Nickel Oxide
산화니켈 분말제조에 NiCO3ㆍ2Ni(OH)2ㆍ2H2O와 18 nm의 입자크기를 갖는 산화니켈을 사용하였다. 산화니켈과 염기성 탄산 니켈 내에 니켈 양이온의 몰수비는 0.01이고, 질산과 염기성 탄산 니켈 내에 니켈 양이온의 몰수비는 0.5이고, 마론 산과 질산의 몰수비는 0.20이다. 얻어진 산화니켈 분말에 대하여, 2θ= 43.25o 에 최대 피크의 FWHM 값은 0.52이다. 이들 값들로부터 계산된 평균입자의 크기는 16 nm이다. 52.1 m2/g의 비표면적으로부터 계산된 입자크기는 19 nm이다.Nickel oxide having a particle size of 18 nm with NiCO 3 .2Ni (OH) 2 .2H 2 O was used for preparing nickel oxide powder. The molar ratio of nickel cations in nickel oxide and basic nickel carbonate is 0.01, the molar ratio of nickel cations in nitric acid and basic nickel carbonate is 0.5, and the molar ratio of maronic acid and nitric acid is 0.20. With respect to the obtained nickel oxide powder, the FWHM value of the largest peak at 2θ = 43.25 ° is 0.52. The average particle size calculated from these values is 16 nm. The particle size calculated from a specific surface area of 52.1 m 2 / g is 19 nm.
<실시 예 - 3> 산화구리의 나노분말의 제조Example 3 Preparation of Nanopowders of Copper Oxide
산화구리 분말제조에 CuCO3ㆍCu(OH)2와 20 nm의 입자크기를 갖는 산화구리를 사용하였다. 산화물과 탄산염 내에 구리 양이온들 간에 몰수비는 0.1, 질산과 탄산염 내에 구리 양이온의 몰수비는 0.20, 마론 산과 질산의 몰수비는 0.10이다. 얻어진 산화구리 분말에 대하여, 2θ= 35.60o 에 최대 피크의 FWHM 값은 0.40이다. 이들 값들로부터 계산된 평균입자의 크기는 20 nm이다. 41.9 m2/g의 비표면적으로부 터 계산된 입자크기는 22 nm이다.Copper oxide powder with CuCO 3 .Cu (OH) 2 and a particle size of 20 nm was used for the production of copper oxide powder. The molar ratio between copper cations in oxides and carbonates is 0.1, the molar ratio of copper cations in nitric acid and carbonates is 0.20, and the molar ratio of maronic acid and nitric acid is 0.10. With respect to the obtained copper oxide powder, the FWHM value of the largest peak at 2θ = 35.60 ° is 0.40. The average particle size calculated from these values is 20 nm. The particle size calculated from the specific surface area of 41.9 m 2 / g is 22 nm.
<실시 예 - 4> 산화아연의 나노분말의 제조Example 4 Preparation of Nanopowders of Zinc Oxide
산화아연 분말제조에 2ZnCO3ㆍ3Zn(OH)2ㆍH2O와 21 nm 크기의 산화아연을 사용하였다. 산화물과 탄산염 내에 아연 양이온들 간에 몰수비는 0.05, 질산과 탄산염 내에 아연 양이온의 몰수비는 0.50, 마론 산과 질산의 몰수비는 0.10이다. 얻어진 산화아연 분말에 대하여, 2θ= 36.35o 에 최대 피크의 FWHM 값은 0.40이다. 이들 값들로부터 계산된 평균입자의 크기는 22 nm이다. 38.5 m2/g의 비표면적으로부터 계산된 입자크기는 24 nm이다.2ZnCO 3 .3Zn (OH) 2 .H 2 O and 21 nm zinc oxide were used to prepare zinc oxide powder. The molar ratio between zinc cations in oxides and carbonates is 0.05, the molar ratio of zinc cations in nitric acid and carbonates is 0.50, and the molar ratio of maronic acid and nitric acid is 0.10. With respect to the obtained zinc oxide powder, the FWHM value of the largest peak at 2θ = 36.35 ° is 0.40. The average particle size calculated from these values is 22 nm. The particle size calculated from the specific surface area of 38.5 m 2 / g is 24 nm.
X-선 회절 기법으로 산출한 평균입자 크기와 비표면적으로부터 계산된 입자크기는 서로 비교가 된다. 따라서 만들진 분말들은 주로 1차 입자들로 구성되어 있음을 알 수 있다.The average particle size calculated by the X-ray diffraction technique and the particle size calculated from the specific surface area are compared with each other. Therefore, it can be seen that the powders are mainly composed of primary particles.
본 발명에서 이들 산화물의 나노분말을 제조하게 된 계기는 이들 분말들을 전구체로 하여 스피넬 페라이트(Cu0 .4Zn0 .6Fe2O4)와 같은 혼합된 산화물들을 제조하는데 사용하기 위함이다. 혼합된 산화물을 제조하는데 나노분말을 사용하게 되면, 서브마이크로미터 크기의 분말을 사용하는 것보다 200~300 OC의 낮은 온도에서 생성물이 제조된다. 그러므로 본 발명에서 제조된 분말들은 전구체 분말로 사용될 가능성이 클 것으로 기대된다. 이외에도 나노분말들이 다양하게 사용될 것으로 기대하고 있다. 염기성 탄산염의 분해할 때, 나노분말을 사용한 본 발명이 하나의 예가 될 것이다.The fabricated nano-powders of these oxides in the present invention, the meter is intended for use in preparing a mixed oxide such as spinel ferrite (Cu 0 .4 Zn 0 .6 Fe 2 O 4) to these powders in the precursor. The use of nanopowders to produce mixed oxides produces products at temperatures lower than 200-300 O C than using submicrometer-sized powders. Therefore, it is expected that the powders prepared in the present invention are likely to be used as precursor powders. In addition, it is expected that nano powders will be used in various ways. In the decomposition of basic carbonates, the present invention using nanopowders will be one example.
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