KR0136150B1 - Manufacturing method of magnetic iron oxide powder - Google Patents
Manufacturing method of magnetic iron oxide powderInfo
- Publication number
- KR0136150B1 KR0136150B1 KR1019940029121A KR19940029121A KR0136150B1 KR 0136150 B1 KR0136150 B1 KR 0136150B1 KR 1019940029121 A KR1019940029121 A KR 1019940029121A KR 19940029121 A KR19940029121 A KR 19940029121A KR 0136150 B1 KR0136150 B1 KR 0136150B1
- Authority
- KR
- South Korea
- Prior art keywords
- ferric
- ferric hydroxide
- slurry
- iron oxide
- tartaric acid
- Prior art date
Links
- 239000000843 powder Substances 0.000 title claims abstract description 41
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 34
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 34
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 32
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 26
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 22
- 239000011975 tartaric acid Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000007858 starting material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 9
- 239000012266 salt solution Substances 0.000 abstract description 5
- 238000007796 conventional method Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 239000011553 magnetic fluid Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002885 antiferromagnetic material Substances 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YNVZDODIHZTHOZ-UHFFFAOYSA-K 2-hydroxypropanoate;iron(3+) Chemical compound [Fe+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O YNVZDODIHZTHOZ-UHFFFAOYSA-K 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-N iron;hydrochloride Chemical compound Cl.[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-N 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 229910003153 β-FeOOH Inorganic materials 0.000 description 1
Classifications
-
- 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
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Hard Magnetic Materials (AREA)
- Compounds Of Iron (AREA)
Abstract
본 발명은 종래방법과는 달리 출발원료로 제이철염 용액을 사용하고, 이로부터 얻어지는 수산화제이철 수용액중에 타타르산을 첨가하고 수열반응을 시키므로서 초미립상을 갖는 자성산화철 분말을 제조하는 방법을 제공하고자 하는데, 그 목적이 있다.The present invention uses a ferric salt solution as a starting material, unlike the conventional method, to provide a method for producing a magnetic iron oxide powder having a super fine phase by adding a tartaric acid and a hydrothermal reaction in the ferric hydroxide aqueous solution obtained therefrom There is a purpose.
본 발명은 자성산화철 분말의 제조방법에 있어서, 출발원료로 제이철염을 사용하여 이로부터 수산화제이철을 제조하는 단계; 상기 수산화제이철의 철원자를 기준으로 상기 수산화제이철에 타타르산을 2.5×10-4몰양이상의 범위로 첨가하여 2성분 공존 슬러리를 제조하는 단계; 상기 슬러리의 염기도를 10.2-12.75의 범위로 조절하는 단계; 및 상기 슬러리 반응액을 200℃ 이상의 온도범위에서 수열반응시켜 마그네타이트 입자분말로 석출시키는 단계를 포함함을 특징으로 하는 초미립상 자성산화철 분말의 제조방법에 관한 것을 그 요지로 한다.The present invention provides a method for producing magnetic iron oxide powder, comprising: preparing ferric hydroxide therefrom using ferric salt as a starting material; Preparing a two-component coexistence slurry by adding tartaric acid to the ferric hydroxide in the range of 2.5 × 10 -4 molar amount or more based on the iron atom of the ferric hydroxide; Adjusting the basicity of the slurry in the range of 10.2-12.75; And it relates to a method for producing an ultrafine magnetic iron oxide powder, characterized in that it comprises the step of hydrothermally reacting the slurry reaction solution in a temperature range of 200 ℃ or more to magnetite particles powder.
Description
제1도는 본 발명 방법에 따라 제조된 자성산화철 분말의 전자현미경 사진1 is an electron micrograph of a magnetic iron oxide powder prepared according to the method of the present invention
본 발명은 정전복사용의 1성분계 자성토너를 비롯하여 자성유체, 자성도료, 자성잉크 및 흑색안료 등에 사용되는 자성산화철 분말의 제조방법에 관한 것으로서, 보다 상세하게는 분산성이 우수한 초미립상의 자성산화철 분말을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing magnetic iron oxide powders used in magnetic fluids, magnetic paints, magnetic ink and black pigments, including one-component magnetic toners for electrostatic restoration, and more particularly, ultrafine magnetic iron oxide having excellent dispersibility. It relates to a method for producing a powder.
통상 마그네타이트 입자분말은 현재 정전복사용의 1성분계 자성토너를 비롯 자성유체, 자성도료. 자성잉크, 흑색안료용등으로 정보산업사회에 없어서는 안될 중요한 기초소재로 광범위하게 사용되고 있다.Magnetite particles are generally used as one-component magnetic toners for electrostatic use, as well as magnetic fluids and magnetic paints. Magnetic ink, black pigment, etc. are widely used as an important basic material for the information industry.
이러한 마그네타이트 분말을 제조하는 방법에는 일반적으로 수용액중에서 직접 마그네타이트 분말을 제조하는 습식법이 사용되는데, 이 습식법에는 제이철염과 제이철염의 혼합염을 알카리로 중화시켜 직접 마그네타이트 입자분말로 석출시키는 중화법 및 제일철염을 알칼리로 중화시킨 후 산화반응시켜 제조하는 침전-산화법이 있다.In general, a wet method of preparing a magnetite powder in an aqueous solution is used as a method of preparing the magnetite powder. In this wet method, a neutralizing method of neutralizing a mixed salt of ferric salt and ferric salt with alkali to precipitate directly into a magnetite particle powder and the first method are used. There is a precipitation-oxidation method in which iron salts are neutralized with alkali and then oxidized.
그러나, 상기 중화법 및 침전-산화법에 의해 제조되는 마그네타이트 분말중 제일철염과 제이철염의 혼합, 중화에 의해 제조되는 마그네타이트 입자분말의 경우에는 대체로 큰입자로 생성되는 반면, 침전-산화법에 의해 제조되는 생성물은 중화법에 의해 제조된 마그네타이트 입자분말의 크기에 비해 매우 미세한 입자로 생성되는 것으로 알려져 있다(Bulltin of the Chemical Society of Japan 47(7), 1646-1650(1974)).However, in the case of the magnetite particle powder prepared by mixing and neutralizing ferrous salt and ferric salt among the magnetite powders produced by the neutralization method and the precipitation-oxidation method, the particles are generally produced as large particles, but are prepared by the precipitation-oxidation method. The product is known to be produced as very fine particles compared to the size of the magnetite particle powder prepared by the neutralization method (Bulltin of the Chemical Society of Japan 47 (7), 1646-1650 (1974)).
따라서, 상기 중화법에 의한 제조방법보다 침전-산화법에 의한 제조방법이 주로 사용되는데, 예를들면 1성분계 자성토너용으로 사용되는 마그네타이트 입자분말은 자성토너 자신이 자성을 가지고 있으므로 2성분계 자성토너에서 사용하는 캐리어(carrier)를 이용하지 않고 토너자신이 수송과 현상을 행하는 것으로서, 주로 침전-산화법에 의해 제조된 마그네타이트 입자분말이 사용되고 있다. 또한 자성유체로 사용되는 마그네타이트 입자분말은 자성분말과 분산매의 분리가 일어나지 않는 미립상의 분말이 사용되고 있는데, 이도 역시 침전-산화법에 의해 제조되는 입자분말이 사용되고 있다.Therefore, the precipitation-oxidation method is mainly used rather than the neutralization method. For example, the magnetite particle powder used for the one-component magnetic toner is magnetic in the two-component magnetic toner because the magnetic toner itself has magnetic properties. As the toner itself transports and develops without using a carrier to be used, magnetite particle powder mainly produced by the precipitation-oxidation method is used. In addition, the magnetite particle powder used as the magnetic fluid is used as a particulate powder that does not separate the magnetic powder and the dispersion medium, which is also used as a particle powder produced by the precipitation-oxidation method.
한편, 지금까지 알려져 있는 종래의 습식법에 의한 마그네타이트 분말의 제조방법을 구체적으로 예를들면 다음과 같이, 제일철이온과 제이철이온의 혼합비가 1:2인 혼합철염 수용액에 알카리 수용액을 첨가하여 제조하는 방법, 제일철염 수용액에 알카리를 첨가하여 수산화제이철 현탁액을 제조한 후 가열, 산화, 반응시켜 제조하는 방법(Bull. Chem. Soc. Jap., 47(7), 1646(1947)), 제일철염 수용액에 알카리를 당량비 1 이하로 첨가하여 수산화제일철 현탁액을 제조한 후 가열, 산화반응시키고 미반응 철이온에 대해 알카리를 당량 이상으로 첨가, 가열, 산화시키는 방법(일 특개소 63-105901, 60-71529), β-FeOOH 수성현탁액을 100-130℃의 반응온도로 수열 처리하여 헤마타이트 입자분말을 제조한 후 이를 후속 열처리하여 마그네타이트 입자분말로 변환시키는 방법(일 특개소 63-209106, 63-162802, 63-210032, 63-162536)등을 들 수 있다.On the other hand, the manufacturing method of the magnetite powder by the conventional wet method known so far specifically, for example, a method of producing by adding an aqueous alkali solution to a mixed iron salt aqueous solution having a mixing ratio of ferrous ions and ferric ions 1: 1: Method of preparing ferric hydroxide suspension by adding alkali to ferric salt aqueous solution, followed by heating, oxidizing and reacting (Bull. Chem. Soc. Jap., 47 (7), 1646 (1947)), to ferrous salt aqueous solution Alkaline is added in an equivalent ratio of 1 or less to prepare ferrous hydroxide suspension, and then heated and oxidized. An alkali is added in an equivalent or more equivalent to unreacted iron ions, and heated and oxidized. , β-FeOOH aqueous suspension was hydrothermally treated at a reaction temperature of 100-130 ° C. to produce hematite particle powder, which was then heat treated to convert to magnetite particle powder. Bovine 63-209106, and the like 63-162802, 63-210032, 63-162536).
그러나, 상기 종래의 제조법은 대부분이 출발원료로 제일철염 또는 제일철염과 제이철염의 혼합용액을 사용하여 침전-산화법 또는 중화법에 의해 제조하는 방법에 기분을 둔 제조방법들로서, 이러한 방법에 의해 제조되는 마그네타이트 분말들은 대부분 ㎛ 단위의 입자이기 때문에 분산성면에서 특성이 저하되는 단점이 있다.However, the conventional manufacturing methods are prepared by the method, which is mostly made by the precipitation-oxidation method or the neutralization method using ferrous salt or a mixed solution of ferrous salt and ferric salt as starting materials. Since the magnetite powders are mostly particles of a micrometer unit, there is a disadvantage in that the properties are deteriorated in terms of dispersibility.
이에 본 발명자들은 연구와 실험을 거듭한 결과, 종래방법과는 달리 출발원료로 제이철염 용액을 사용하여 수용액 반응에 의해 직접 자성산화철 입자분말, 즉 초미립상을 갖는 마그네타이트 입자분말을 제조하는 방법을 개발하기에 이르렀다.Accordingly, the inventors of the present invention have repeatedly conducted research and experiments, and unlike the conventional method, using ferric salt solution as a starting material, a method for producing a magnetic iron oxide particle powder, that is, a magnetite particle powder having ultra fine phase, by an aqueous solution reaction To develop.
따라서, 본 발명은 종래방법과는 달리 출발원료로 제이철염 용액을 사용하고, 이로부터 얻어지는 수산화제이철 수용액중에 타타르산을 첨가하고 수열반응을 시키므로서 초미립상을 나타내어 분산성이 뛰어난 자성산화철 분말을 제조하는 방법을 제공하고자 하는데, 그 목적이 있다.Therefore, the present invention, unlike the conventional method, using a ferric salt solution as a starting material, by adding a tartaric acid to the aqueous solution of ferric hydroxide obtained from the hydrothermal reaction to show the ultra fine phase magnetic iron oxide powder having excellent dispersibility It is to provide a method for manufacturing, the purpose is.
이하, 본 발명을 설명한다.Hereinafter, the present invention will be described.
본 발명은 자성산화철 분말의 제조방법에 있어서, 출발원료로 제이철염을 사용하여 이로부터 수산화제이철을 제조하는 단계; 상기 수산화제이철의 철원자를 기준으로 상기 수산화제이철에 타타르산을 2.5×10-4몰양 이상의 범위로 첨가하여 2성분 공존슬러리를 제조하는 단계; 상기 슬러리의 pH를 10.0-12.75의 범위로 조절하는 단계; 및 상기 슬러리 반응액을 200℃ 이상의 온도범위에서 수열반응시켜 마그네타이트 입자분말로 석출시키는 단계를 포함하는 초미립상의 자성산화철 분말의 제조방법에 관한 것이다.The present invention provides a method for producing magnetic iron oxide powder, comprising: preparing ferric hydroxide therefrom using ferric salt as a starting material; Preparing a two-component coexistence slurry by adding tartaric acid to the ferric hydroxide in the range of 2.5 × 10 -4 molar amount or more based on the iron atom of the ferric hydroxide; Adjusting the pH of the slurry to a range of 10.0-12.75; And a step of hydrothermally reacting the slurry reaction solution at a temperature in a range of 200 ° C. or higher to precipitate into magnetite particle powder.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서 출발원료로 사용하는 제이철염은 유산철, 염산철, 질산철등의 제이철염이라면 모두 사용 가능하다.Ferric salt used as a starting material in the present invention can be used if the ferric salt, such as iron lactate, iron hydrochloride, iron nitrate.
또한 상기 제이철염으로부터 얻어지는 수산화제이철에 첨가하는 첨가제로서는 타타르산(C4O6H6)을 사용하는데, 이 타타르산은 분말상태 그대로 또는 수용액상태로 제조한 후 첨가하여도 무방하다.In addition, tartaric acid (C 4 O 6 H 6 ) is used as an additive to be added to the ferric hydroxide obtained from the ferric salt. The tartaric acid may be added after being prepared in powder form or in aqueous solution.
이때, 본 발명에서는 첨가제로 사용하는 타타르산의 첨가량은 반드시 수산화제이철의 철원자에 대한 몰양 환산값으로 2.5×10-4몰양 이상으로 첨가하는 것이 바람직한데, 그 이유는 상기 타타르산의 첨가량이 2.5×10-4몰양보다 적으면 비자성상의 α-Fe2O3, 또는 α-Fe2O3, γ-Fe2O3, Fe3O4가 혼합되어 있는 혼합상으로 생성되어지기 때문이다.At this time, in the present invention, the amount of tartaric acid used as an additive is preferably added in an amount of 2.5 × 10 −4 or more in terms of molar amount to the iron atom of ferric hydroxide, because the amount of tartaric acid added is 2.5 × 10 -4 is less than molyang is because the non-aqueous phase of α-Fe 2 O 3, or α-Fe 2 O 3, γ -Fe 2 O 3, Fe 3 O 4 is produced by the mixture that is mixed.
또한, 이와같이 하여 얻어지는 2성분 공존슬러리 반응물의 pH를 10.0-12.75 범위내로 조절하는 것이 바람직하다. 상기 반응물의 pH가 12.75 보다 높거나 10.0 보다도 낮으면 비자성상의 α-Fe2O3결정구조와 자성상의 마그네타이트 입자가 혼재하는 혼합상으로 생성되기 때문이다.Moreover, it is preferable to adjust the pH of the bicomponent coexisting slurry reactant obtained in this way to 10.0-12.75. This is because when the pH of the reactant is higher than 12.75 or lower than 10.0, a non-magnetic α-Fe 2 O 3 crystal structure and magnetic phase magnetite particles are formed in a mixed phase.
또한, 상기와 같이 pH가 조절된 슬러리 반응물은 수열반응기를 이용, 수열반응시킬때 반응온도 200℃ 이상에서 반응시키는 것이 바람직한데, 그 이유는 상기 수열반응 온도가 200℃ 이하로 되면 비자성상의 수산화제이철, 또는 α-Fe2O3, γ-Fe2O3, Fe3O4가 혼합되어 있는 혼합상으로 생성되어지기 때문이다.In addition, as described above, the slurry reactant whose pH is adjusted is preferably reacted at a reaction temperature of 200 ° C. or higher when a hydrothermal reaction is carried out using a hydrothermal reactor. This is because it is produced in a mixed phase in which ferric iron or α-Fe 2 O 3 , γ-Fe 2 O 3 , and Fe 3 O 4 are mixed.
이와같이, 본 발명에 의하면 출발원료로 제이철염을 사용하고, 이로부터 얻어지는 수산화제이철에 타타르산을 적정량 첨가하여 수열반응시키므로서 약 100Å 이하의 초상자성(puramagnetism)적 거동을 나타내는 미립상의 자성산하철이 얻어진다.Thus, according to the present invention, by using ferric salt as a starting material, and by adding an appropriate amount of tartaric acid to ferric hydroxide obtained therefrom, hydrothermal reaction, fine particulate ferric acid showing a superamagnetism behavior of about 100 kPa or less is obtained. Lose.
이하, 본 발명을 실시예를 통하여 구체적으로 설명한다.Hereinafter, the present invention will be described in detail through examples.
실시예 1Example 1
발명예 (1-5)Inventive Example (1-5)
제이철염(FeC136H2O) 32.4g을 물에 용해하여 용량 300㎖로 조제한 제이철염 수용액(0.4M)에 수산화나트륨 14.4g을 물에 용해하여 100㎖로 조제한 알카리 수용액(3.6M, R=3)을 첨가, 교반하여 수산화제이철 침전물을 생성시켰다. 생성된 수산화제이철 침전물에 잔존하고 있는 전해질 염을 수세에 의해 충분히 제거한 후 여과하여 수산화제이철 케익을 얻고, 이를 340㎖의 물에 투입, 교반하여 재분산으로 슬러리화하였다. 수산화제이철 슬러리에 타타르산을 수산화제이철의 철원자에 대한 몰양 환산값(타타르산 몰양/Fe(g))으로 2.5×10-4몰양(0.838g), 3.5×10-4몰양(1.006g), 3.5×10-4몰양(1.235g), 4×10-4몰양(1.341g), 5×10-4 몰양(1.677g)을 각각 물 50㎖에 용해한 타타르산 수용액을 첨가한 후 알카리 수용액으로 반응물의 pH를 11.0으로 조절하고, 이를 수열반응기에 투입, 승온속도 약 2℃/min으로 200℃ 까지 승온시켜 1시간 유지하여 수열반응시켰다. 수열반응 후 생성물은 pH가 중성이 되도록 충분히 수세하고 여과한 후 건조하여 시료분말을 제조하였다. 제조된 생성물의 결정구조는 X-ray 분석하여 조사하였으며, 입자형상은 전자현미경으로 관찰하였고, 시료분말의 자기적 특성은 VSM(Vibrating Sample Magnetometer)으로 인가자장 5KOe 조건하에서 측정하여 하기표 1에 그 결과를 나타내었다.Alkaline aqueous solution (3.6M, R = 32.4 g of ferric salt (FeC1 3 6H 2 O) dissolved in water and prepared in 300 ml of ferric salt solution (0.4 M) was dissolved in water to make 100 ml by dissolving 14.4 g of sodium hydroxide in water). 3) was added and stirred to form a ferric hydroxide precipitate. The electrolyte salt remaining in the resulting ferric hydroxide precipitate was sufficiently removed by washing with water, followed by filtration to obtain a ferric hydroxide cake, which was poured into 340 ml of water, stirred and slurried by redispersion. 2.5 x 10 -4 molar amount (0.838 g), 3.5 x 10 -4 molar amount (1.006 g), in terms of the molar amount of tartaric acid in the ferric hydroxide slurry to the iron atom of ferric hydroxide (molar amount of tartaric acid / Fe (g)), 3.5 x 10 -4 molar amount (1.235 g), 4 x 10 -4 molar amount (1.341 g) and 5 x 10-4 molar amount (1.677 g) were added to the aqueous solution of tartaric acid dissolved in 50 ml of water, respectively. PH was adjusted to 11.0, and this was added to a hydrothermal reactor, and the temperature was raised to 200 ° C. at a rate of about 2 ° C./min. After hydrothermal reaction, the product was washed with water sufficiently to neutralize the pH, filtered and dried to prepare a sample powder. The crystal structure of the prepared product was investigated by X-ray analysis, the particle shape was observed by electron microscopy, and the magnetic properties of the sample powder were measured under VKO (Vibrating Sample Magnetometer) under an applied magnetic field of 5KOe. The results are shown.
비교예 (1-3)Comparative Example (1-3)
수산화제이철 슬러리에 타타르산을 수산화제이철 슬러리의 철원자 1g에 대해 타타르산 몰양 환산값으로 1×10-4몰양(0.3353g), 1.5×10-4몰양(0.5029g), 2×10-4몰양(0.6706g)으로 각각 첨가한 것을 제외하고는 상기 발명예와 동일한 방법으로 실시하고, 그 결과를 하기표 1에 나타내었다.Tartaric acid was added to the ferric hydroxide slurry in 1 x 10 -4 molar amount (0.3353 g), 1.5 x 10 -4 molar amount (0.5029 g), and 2 x 10 -4 molar amount relative to 1 g of the iron atom of the ferric hydroxide slurry. Except for each addition (0.6706g), and the same method as in the invention example, the results are shown in Table 1 below.
[표 1]TABLE 1
상기 표1에 나타낸 바와같이 타타르산 첨가량이 2.5×10-4몰양 이상으로 첨가된 발명예(1-5)의 경우에는 자성을 띄는 마그네타이트 입자분말로 생성되고 있음을 확인할 수 있었다. 그러나, 첨가량이 2.5×10-4몰양 이하로 첨가된 비교예(1-3)의 경우에는 반강자성체인 α-Fe2O3또는 α-Fe2O3, γ-Fe2O3, Fe3O4등이 혼합되어 있는 혼합상으로 석출되고 있음을 알 수 있었다.As shown in Table 1, in the case of Inventive Example (1-5) in which the amount of tartaric acid was added in an amount of 2.5 × 10 −4 or more, it was confirmed that magnetic particles were produced as magnetite particles. However, in the case of Comparative Example (1-3) in which the added amount was added in an amount of 2.5 × 10 -4 or less, α-Fe 2 O 3 or α-Fe 2 O 3 , γ-Fe 2 O 3 , Fe 3 , which are antiferromagnetic materials O 4, etc. was found that is precipitated onto the mixture which is mixed.
실시예 2Example 2
발명예 (6-9)Inventive Example (6-9)
제이철염(FeC136H2O) 32.4g을 물에 용해하여 용량 300㎖로 조제한 제이철염 수용액(0.4M)에 수산화나트륨 14.4g을 물에 용해하여 100㎖로 조제한 알카리 수용액 (3.6M, R=3)을 첨가, 교반하여 수산화제이철 침전물을 생성시켰다. 생성된 수산화제이철 침전물에 잔존하고 있는 전해질 염을 수세에 의해 충분히 제거한 후 여과하여 수산화제이철 케익을 얻고, 이를 340㎖의 물에 투입, 교반하여 재분산으로 슬러리화하였다. 수산화제이철 슬러리에 타타르산을 수산화제이철의 철원자에 대한 몰양 환산값(타타르산 몰양/Fe(g))으로2.5×10-4몰양(0.838g)을 물 50㎖에 용해한 타타르산 수용액을 첨가한 후 알카리 수용액으로 반응물의 pH 를 10.0, 12.0, 12.50, 12.75으로 각각 조절하고, 이를 수열반응기에 투입, 승온속도 약 2℃/min으로 200℃까지 승온시켜 1시간 유지하여 수열반응시켰다. 수열반응 후 생성물은 pH가 중성이 되도록 충분히 수세하고 여과한 후 건조하여 시료분말을 제조하였다. 제조된 생성물의 결정구조는 X-ray 분석하여 조사하였으며, 입자형상은 전자현미경으로 관찰하였고, 시료분말의 자기적 특성은 VSM(Vibrating Sample Magnetometer)으로 인가자장 5KOe 조건하에서 측정하여 하기표 2에 그 결과를 나타내었다.Alkaline aqueous solution (3.6M, R = 32.4 g of ferric salt (FeC1 3 6H 2 O) dissolved in water and prepared in 300 ml of ferric salt solution (0.4 M) dissolved in water in 100 ml) 3) was added and stirred to form a ferric hydroxide precipitate. The electrolyte salt remaining in the resulting ferric hydroxide precipitate was sufficiently removed by washing with water, followed by filtration to obtain a ferric hydroxide cake, which was poured into 340 ml of water, stirred and slurried by redispersion. To the ferric hydroxide slurry, tartaric acid solution in which 2.5 x 10 -4 molar amount (0.838 g) was dissolved in 50 ml of water in terms of the molar amount (tartaric acid molar / Fe (g)) in terms of the molar amount of the iron atom of ferric hydroxide was added. Then, the pH of the reactants was adjusted to 10.0, 12.0, 12.50, and 12.75, respectively, with an aqueous alkali solution, which was added to a hydrothermal reactor and heated to 200 ° C. at a heating rate of about 2 ° C./min for 1 hour to maintain hydrothermal reaction. After hydrothermal reaction, the product was washed with water sufficiently to neutralize the pH, filtered and dried to prepare a sample powder. The crystal structure of the prepared product was investigated by X-ray analysis, the particle shape was observed by electron microscopy, and the magnetic properties of the sample powder were measured under VKO (Vibrating Sample Magnetometer) under an applied magnetic field of 5KOe. The results are shown.
비교예 (4-8)Comparative Example (4-8)
수산화제이철 슬러리에 타타르산을 첨가한 후 알카리 수용액으로 반응물의 pH를 3.0, 5.0, 7.0, 9.0, 13.0으로 각각 조절한 것을 제외하고는 상기 발명예와 동일한 방법으로 실시하고, 그 결과를 하기표 2에 나타내었다.After adding tartaric acid to the ferric hydroxide slurry, the reaction was carried out in the same manner as in the invention, except that the pH of the reactants was adjusted to 3.0, 5.0, 7.0, 9.0, and 13.0 with an aqueous alkali solution. Shown in
[표 2]TABLE 2
상기 표 2에 나타낸 바와같이, 반응물의 pH 가 10.0-12.75 범위로 조절된 발명예(6-9)의 경우에는 마그네타이트 입자분말로 생성되나, pH가 상기 발명예보다 낮거나 높은 비교예(4-8)의 경우에는 반강자성체인 α-Fe2O3와 마그네타이트가 혼합되어 있는 혼합상으로 석출되고 있음을 확인할 수 있었다.As shown in Table 2, in the case of Inventive Example (6-9) in which the pH of the reactant is adjusted to the range of 10.0-12.75, it is produced as magnetite particle powder, but the pH is lower or higher than the Inventive Example (4- In the case of 8), it was confirmed that the precipitate was formed in the mixed phase in which the anti-ferromagnetic material α-Fe 2 O 3 and the magnetite were mixed.
실시예 3Example 3
발명예 (10-12)Inventive Example (10-12)
제이철염(FeC136H2O) 32.4g을 물에 용해하여 용량300㎖로 조제한 제이철염 수용액(0.4M)에 수산화나트륨 14.4g을 물에 용해하여 100㎖로 조제한 알카리 수용액(3.6M, R=3)을 첨가, 교반하여 수산화제이철 침전물을 생성시켰다. 생성된 수산화제이철 침전물에 잔존하고 있는 전해질 염을 수세에 의해 충분히 제거한 후 여과하여 수산화제이철 케익을 얻고, 이를 340㎖ 의 물에 투입, 교반하여 재분산으로 슬러리화하였다. 수산화제이철 슬러리에 타타르산을 수산화제이철의 철원자에 대한몰양 환산값(타타르산 몰양/Fe(g))으로 2.5x10-4몰양(0.838g)을 물 50㎖에 용해한 타타르산 수용액을 첨가한 후 알카리 수용액으로 반응물의 pH를 11.0으로 조절하고, 이를 수열반응기에 투입, 승온속도 2℃/min로 반응온도 220, 250, 300℃까지 승온시켜 1시간 유지하여 수열반응시켰다. 수열반응 후 생성물은 pH가 중성이 되도록 충분히 수세하고 여과한 후 건조하여 시료분말을 제조하였다. 제조된 생성물의 결정구조는 X-ray 분석하여 조사하였으며, 입자형상은 전자현미경으로 관찰하였고, 시료분말의 자기적 특성은 VSM(Vibrating Sample Magnetometer)으로 인가자장 5KOe 조건하에서 측정하여 하기표 3에 그 결과를 나타내었으며, 반응온도 300℃에서 제조된 생성물의 입자사진을 제1도에 나타내었다.Alkaline aqueous solution (3.6M, R = 32.4 g of ferric salt (FeC1 3 6H 2 O) dissolved in water and prepared in 100 ml of sodium hydroxide in an aqueous solution of ferric salt (0.4 M) prepared in 300 ml capacity (3.6 M, R = 3) was added and stirred to form a ferric hydroxide precipitate. The electrolyte salt remaining in the produced ferric hydroxide precipitate was sufficiently removed by washing with water, followed by filtration to obtain a ferric hydroxide cake, which was poured into 340 ml of water, stirred and slurried by redispersion. To the ferric hydroxide slurry was added tartaric acid solution in which 2.5x10 -4 molar amount (0.838 g) was dissolved in 50 ml of water in terms of the molar amount (tartaric acid molarity / Fe (g)) of tartaric acid to the iron atom of ferric hydroxide. The pH of the reactant was adjusted to 11.0 with an aqueous alkali solution, and this was added to a hydrothermal reactor, and the reaction temperature was maintained for 1 hour by raising the reaction temperature to 220, 250, 300 ° C. at a heating rate of 2 ° C./min. After hydrothermal reaction, the product was washed with water sufficiently to neutralize the pH, filtered and dried to prepare a sample powder. The crystal structure of the prepared product was investigated by X-ray analysis, the particle shape was observed by electron microscope, and the magnetic properties of the sample powder were measured under VKO (Vibrating Sample Magnetometer) under an applied magnetic field of 5KOe. The results are shown, and a particle photograph of the product prepared at the reaction temperature of 300 ° C. is shown in FIG. 1.
비교예 (9-10)Comparative Example (9-10)
수산화제이철 슬러리에 타타르산을 첨가한 반응물 용액을 수열반응온도 140,180℃에서 각각 1시간 유지하여 수열반응시킨 것을 제외하고는 상기 발명예와 동일한 방법으로 실시하고, 그 결과를 하기표 3에 나타내었다.Except that the reactant solution to which the tartaric acid was added to the ferric hydroxide slurry was hydrothermally reacted by maintaining the hydrothermal reaction temperature at 140 and 180 ° C. for 1 hour, and the results are shown in Table 3 below.
[표 3]TABLE 3
상기 표 3에 나타낸 바와같이, 수열반응온도가 200℃ 이상의 범위에서 실시된 발명예(10-12)의 경우에는 입자크기가 약 100Å 정도인 마그네타이트 입자로 석출되고 있으나, 그 이하의 온도에서 실시된 비교예(9-10)의 경우에는 비자성성의 Fe(OH)3또는 α-Fe2O3, Fe3O4, γ-Fe2O3등이 혼재하는 혼합상으로 생성되고 있음을 알 수 있었다.As shown in Table 3, in the case of Inventive Example (10-12) in which the hydrothermal reaction temperature was performed in the range of 200 ° C. or higher, it was precipitated as magnetite particles having a particle size of about 100 kPa, but was carried out at a temperature below that. In Comparative Example (9-10), it can be seen that nonmagnetic Fe (OH) 3 or α-Fe 2 O 3 , Fe 3 O 4 , γ-Fe 2 O 3, etc., are formed in a mixed phase. there was.
일반적으로 습식법에 의해 제조되는 마그네타이트 입자분말의 자기적 특성은 포화자화값이 80-90emu/g 정도, 보자력이 100-1800e 정도의 자기적 특성값을 나타내는 것으로 알려져 있는 것과 비교하면 본 발명에 의해 제조된 마그네타이트 입자분말의 보자력 특성이 낮은 값을 나타내고 있는데, 이는 상기 표3과 제1도에 나타낸 생성물의 사진에서 관찰할 수 있는 바와같이, 본 발명에 의해 제조된 입자크기가 약 100Å 정도인 미립상 상태로 석출되는데 기인하는 것으로 사료된다. 이것은 마그네타이트 입자분말의 단자구(single domain) 크기가 일반적으로 약 400Å정도로 알려져 있는데, 이보다 더 작아지면 초상자성(paramagnetism)적 거동을 나타내게 된다는 사실로 부터 짐작해볼 수 있다.In general, the magnetic properties of magnetite particles prepared by the wet method are prepared by the present invention as compared with those known to exhibit magnetic property values of about 80-90 emu / g in saturation magnetization and about 100-1800e in coercive force. The coercive properties of the magnetite particles powders exhibited low values, which can be observed in the photographs of the products shown in Table 3 and FIG. 1 above. It is believed to be due to precipitation in the state. This is presumably due to the fact that the size of the single domain of magnetite particles powder is generally about 400Å, and the smaller size shows paramagnetism behavior.
상술한 바와같이, 본 발명에서 제조되는 생성물은 입도가 매우 균일한 초미립상의 마그네타이트 입자분말로 제조되기 때문에 정보산업 필수적으로 사용되고 있는 자성토너, 자성잉크, 자성유체등으로의 응용에 매우 적합할 것으로 기대된다.As described above, the product produced in the present invention is made of ultra-fine magnetite particle powder having a very uniform particle size, and thus, it is suitable for application to magnetic toner, magnetic ink, magnetic fluid, and the like, which are used in the information industry. It is expected.
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