JPH03104806A - Method for manufacturing magnetic fluid - Google Patents
Method for manufacturing magnetic fluidInfo
- Publication number
- JPH03104806A JPH03104806A JP23841689A JP23841689A JPH03104806A JP H03104806 A JPH03104806 A JP H03104806A JP 23841689 A JP23841689 A JP 23841689A JP 23841689 A JP23841689 A JP 23841689A JP H03104806 A JPH03104806 A JP H03104806A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- particles
- magnetic fluid
- surfactant
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011553 magnetic fluid Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 38
- 239000002923 metal particle Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910001111 Fine metal Inorganic materials 0.000 claims abstract description 7
- 239000010419 fine particle Substances 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical group [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 70
- 229910052742 iron Inorganic materials 0.000 abstract description 35
- 239000002245 particle Substances 0.000 abstract description 29
- 230000005415 magnetization Effects 0.000 abstract description 17
- -1 sodium olefin Chemical class 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000005294 ferromagnetic effect Effects 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 229940049964 oleate Drugs 0.000 description 8
- 230000005291 magnetic effect Effects 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- 239000006247 magnetic powder Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000005347 demagnetization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000005406 washing 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
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 102000011632 Caseins Human genes 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- HBRNMIYLJIXXEE-UHFFFAOYSA-N dodecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCN HBRNMIYLJIXXEE-UHFFFAOYSA-N 0.000 description 1
- 238000009760 electrical discharge machining Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical group CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
く産業上の利用分野〉
本発明は、極めて磁化の高い金属微粒子を磁性粉末とし
て溶媒に分散する磁性流体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Industrial Application Field The present invention relates to a method for producing a magnetic fluid in which fine metal particles with extremely high magnetization are dispersed as magnetic powder in a solvent.
〈従来の技術〉
磁性流体は、液状で磁性を示す材料であり、液相中にコ
ロイドサイズ（直径１０万分の１＋ａｍ程度）の強磁性
微粒子を安定分散させた溶’ｔ（ｌで、磁性材料特有の
ヒステリシス現象が起こらず、液体自体が磁性を有する
ような性質を示すちのである。<Prior art> Magnetic fluid is a material that exhibits magnetism in a liquid state. The characteristic hysteresis phenomenon does not occur, and the liquid itself exhibits magnetic properties.
上記した磁性流体は、燃料添加剤、回転軸シール、物質
の比重差選別、磁気研磨、プリンター用磁気インク、ス
ピーカー用材料など種々の用途に使用され、その製造は
、通常マグネタイトの粒子表面を界面活性剤で被覆し、
磁性粉末として溶媒に分散させるものである。The above-mentioned magnetic fluids are used for various purposes such as fuel additives, rotary shaft seals, specific gravity separation of materials, magnetic polishing, magnetic ink for printers, and materials for speakers. coated with an activator,
It is dispersed in a solvent as a magnetic powder.
このような磁性流体中の磁性粉末の安定分散は、粒子間
のファンデルワールスカ、磁気的引力及び粒子表面に吸
着された界面活性剤の反発力の均衡に由来する。しかし
、マグネタイト粒子が大きくなると、沈降凝集して安定
分散が得られなくなるため、粒径のコントロールが重要
なポイントとなっている。Stable dispersion of magnetic powder in such a magnetic fluid originates from the balance between Van der Waalska's magnetic attraction between the particles and the repulsion of the surfactant adsorbed on the particle surface. However, if the magnetite particles become large, they will settle and agglomerate, making it impossible to obtain stable dispersion, so controlling the particle size is an important point.
一方、飽和磁化の高い磁性流体の開発が望まれており、
鉄やコバルト或いはそれらの合金粒子を分散させた金属
磁性流体が、金属力ルボニルの熱分解、スパークエロー
ジョン法，真空蒸着法、電解析出法などで検討されてい
る。On the other hand, it is desired to develop magnetic fluids with high saturation magnetization.
Metallic magnetic fluids in which particles of iron, cobalt, or their alloys are dispersed have been studied using methods such as thermal decomposition of metallic carbonyl, spark erosion method, vacuum evaporation method, and electrolytic deposition method.
しかし、安定で高い飽和磁化を有する金属磁性流体はま
だ開発途上にあり、現状で最も高い磁化を有する金属磁
性流体としては、コバルト粒子をアルキルナフタレンに
分散させた真空蒸着法で製造した磁性流体が知られてい
る。However, metal magnetic fluids with stable and high saturation magnetization are still under development, and currently the metal magnetic fluids with the highest magnetization are those manufactured by vacuum evaporation in which cobalt particles are dispersed in alkylnaphthalene. Are known.
〈発明が解決しようとする課題〉
しかし、上記した磁性流体の飽和磁化は、僅かに０．
０６６７であり、またこの方法では金属微粒子を迅速に
且つ多量に得ることができないため、コストも極めて高
いものとなっていた。<Problems to be Solved by the Invention> However, the saturation magnetization of the above-mentioned magnetic fluid is only 0.
0667, and since metal fine particles cannot be obtained quickly and in large quantities with this method, the cost is also extremely high.
〈課題を解決するための手段〉
本発明は、上記に鑑み提案されたもので、金属粒子の表
面と強固な化学吸着或いは物理吸着する界面活性剤及び
還元剤を溶解した水溶液中に、金属イオンを添加するこ
とにより、表面に界面活性剤が吸着した金属微粒子を形
成させ、濾過、脱水した後、上記した金属微粒子を溶媒
または水に分散して磁性流体とする磁性流体の製造方法
に関するものである。<Means for Solving the Problems> The present invention was proposed in view of the above, and includes metal ions in an aqueous solution containing a surfactant and a reducing agent that strongly chemically or physically adsorb onto the surface of metal particles. This article relates to a method for producing a magnetic fluid in which fine metal particles are formed on the surface of which a surfactant is adsorbed, and after filtration and dehydration, the fine metal particles are dispersed in a solvent or water to produce a magnetic fluid. be.
本発明の磁性流体の製造方法は、第ｌ工程として、金属
粒子と化学吸着或いは物理吸着する界面活性剤及び還元
剤を水に溶解して水’ａＪｌ夜を作製する。In the first step of the method for producing a magnetic fluid of the present invention, a surfactant and a reducing agent that chemically or physically adsorb metal particles are dissolved in water to prepare water.
上記した金属粒子と化学吸着或いは物理吸着する界面活
性剤としては、オレイン酸ナトリウム、ドデシル硫酸ナ
トリウム、ドデシルアンモニウムアセテート等、或いア
ルキルスルホコハク酸塩、ｎ−アシルアミノ酸とその塩
、ｎ−アルキルトリメチレンジアミン誘導体、ポリオキ
シエチレンアルキルエーテルリン酸塩、アルキルリン酸
塩、などを使用することができ、特にオレイン酸ナトリ
ウムを使用すると、高い磁化を有する金属微粒子を作製
することができる。Surfactants that chemically or physically adsorb the metal particles mentioned above include sodium oleate, sodium dodecyl sulfate, dodecylammonium acetate, alkyl sulfosuccinates, n-acylamino acids and their salts, n-alkyl trimethylene, etc. Diamine derivatives, polyoxyethylene alkyl ether phosphates, alkyl phosphates, etc. can be used, and particularly when sodium oleate is used, metal fine particles with high magnetization can be produced.
また、上記した界面活性剤とともに水に溶解する還元剤
としては，水素化ホウ素塩、次亜リン酸、ヒドラジン、
亜リン酸等を使用することができ、特に水素化ホウ素ナ
トリウムを使用することが望ましい。In addition, reducing agents that dissolve in water together with the above-mentioned surfactants include borohydride salts, hypophosphorous acid, hydrazine,
Phosphorous acid and the like can be used, and it is particularly desirable to use sodium borohydride.
次に、第２工程として、上記した界面活性剤と還元剤と
の水溶液中に金属イオンを添加する。Next, as a second step, metal ions are added to the aqueous solution of the above-mentioned surfactant and reducing agent.
上記した金属イオンとしては、鉄、コバルト、ニッケル
等の強磁性の金属イオン、或いはそれらの潰合イオンを
挙げることができ、水溶液中でイオン化することにより
上記したような金属イオンを生或する金属化合物を添加
するものである。Examples of the above-mentioned metal ions include ferromagnetic metal ions such as iron, cobalt, and nickel, or their collapsing ions. It adds a compound.
上記した金属イオンは、水溶液中に溶解されている還元
剤と反応し、微細な金属粒子を生成するが、その際、水
溶液中には界面活性剤が溶解されているので、生成した
金属粒子の表面に界面活性剤が吸着し、表面を界面活性
剤で被覆された金属微粒子が生成されることになる。The metal ions mentioned above react with the reducing agent dissolved in the aqueous solution to produce fine metal particles, but at this time, since the surfactant is dissolved in the aqueous solution, the generated metal particles The surfactant is adsorbed to the surface, and metal fine particles whose surfaces are coated with the surfactant are produced.
第３工程としては、上記のように生成した金属微粒子を
濾過し、脱水するが、濾過法及び脱水法は常法に準じて
行うものでよい。In the third step, the metal fine particles generated as described above are filtered and dehydrated, and the filtration method and dehydration method may be carried out according to conventional methods.
そして、第４工程として、上記のように得られる金属微
粒子の扮体を溶媒に分散して磁性流体とする。従って、
本発明は、前記した第１〜３工程で得られた金属微粒子
を磁性粉末として使用するものである。Then, as a fourth step, the disguised metal particles obtained as described above are dispersed in a solvent to form a magnetic fluid. Therefore,
The present invention uses the metal fine particles obtained in the first to third steps described above as magnetic powder.
本発明の磁性流体の製造方法は、上記したような４つの
工程より構成されるものであり、飽和磁化の高い磁性流
体を製造することができるりのである。The method for manufacturing a magnetic fluid of the present invention is comprised of the four steps described above, and is capable of manufacturing a magnetic fluid with high saturation magnetization.
上記した本発明において、界面活性剤としてオレイン酸
ナトリウム、還元剤として水素化ホウ素ナトリウム、金
属イオンとして第一鉄イオンを用いた組合せは、極めて
好適であり、例えば、オレイン酸ナトリウムの濃度が０
． ２ｍｏｌ／βであり、水素化ホウ素ナトリウムの濃
度が３ Ｘ １０−”ｍｏｌ／ｊ２の水２’８ ？ｌｌ
中に硫酸第〜鉄の水溶７夜を一度に添加し、撹拌して表
面にオレイン酸イオンが吸着している鉄微粒子を生成さ
せたが、この鉄微粒子は粒径が０．５〜２ｎｍの範囲に
あり、その飽和磁化は約１．２Ｔであった。この反応は
、
４ＦｅＳＯ， ＋ ＮａＢＨ４＋ ８ＮａＯｌ｛ 一４
Ｆｅ ＋ＮａＢＯｉ ＋４ＮａｚＳＯ＜ ＋６｝
ＩＪ − （ａ）４ＦｅＳＯ＜ ＋ ２ＮａＢＨ４
＋６ＮａＯＨ 一２ＦｅＪ ＋Ｈｘ ＋４Ｎａ２Ｓ
Ｏ４＋６ＨＪ ・・・（ｂ）の式が考えられる６生成
した鉄微粒子中のホウ素含有量は、メチレン抽出吸光光
度法で測定したところ、全鉄１ｇあたりホウ素は０，０
３〜０．０４ｇであり，上記した （ｂ）式の反応が主
反応と推定される。生成した鉄微粒子は、Ｘ線回折より
、α鉄の （１１０１． （２００）のブロードな回折
線が認められた。In the present invention described above, the combination of using sodium oleate as a surfactant, sodium borohydride as a reducing agent, and ferrous ion as a metal ion is extremely suitable. For example, the concentration of sodium oleate is 0.
．． 2 mol/β and the concentration of sodium borohydride is 3 × 10-” mol/j2 of water 2'8?ll
An aqueous solution of ferrous sulfate to ferric sulfate was added at once to the solution and stirred to produce iron particles with oleate ions adsorbed on the surface. The saturation magnetization was approximately 1.2T. This reaction is as follows: 4FeSO, + NaBH4+ 8NaOl{ -4
Fe +NaBOi +4NazSO< +6}
IJ − (a) 4FeSO< + 2NaBH4
+6NaOH -2FeJ +Hx +4Na2S
O4 + 6HJ ... Equation (b) can be considered 6 The boron content in the generated iron particles was measured by methylene extraction spectrophotometry, and the boron content per gram of total iron was 0.0.
3 to 0.04 g, and the reaction of formula (b) above is estimated to be the main reaction. X-ray diffraction of the produced iron particles revealed a broad diffraction line of α iron (1101. (200)).
この７夜を濾過し、脱水して得られる濾過物をケロシン
中に分散させたところ、鉄微粒子８％を含み、飽和磁化
が約０． １丁である安定な金属磁性流体を得ることが
できた。When the filtrate obtained by filtering and dehydrating these 7 nights was dispersed in kerosene, it contained 8% of iron fine particles and had a saturation magnetization of about 0. A stable metal magnetic fluid was obtained.
一方、鉄微粒子の表面に吸看する界面活性剤の吸着層が
、１０人以下のような極めて薄い場合には、溶媒によっ
ては磁気的吸引力及びファンデルワールス力が、混合効
果や容積制限効果よりも大きくなり、鉄微粒子同志が溶
媒中で凝集を起こすことがある。従って、粒子間のポテ
ンシャル曲線の考察より、上記した鉄微粒子の表面をさ
らに厚い吸着層を形成するような界面活性剤を用いて被
覆する必要がある。On the other hand, when the adsorption layer of surfactant adsorbing on the surface of iron particles is extremely thin (less than 10 particles), depending on the solvent, magnetic attraction force and van der Waals force may cause a mixing effect or a volume-limiting effect. The iron particles may become larger than each other, causing aggregation of iron particles in the solvent. Therefore, from consideration of the potential curve between particles, it is necessary to coat the surface of the above-mentioned iron fine particles with a surfactant that forms a thicker adsorption layer.
本発明は、上記に鑑み、第２発明として、前記した第１
〜３工程で得られた金属微粒子の表面に吸着している界
面活性剤を除去し、上記界面活性剤とは別種の界面活性
剤を表面に吸着させることにより得られる金属微粒子を
磁性粉末とする磁性流体の製造方法を提案するものであ
る。In view of the above, the present invention provides the above-mentioned first invention as a second invention.
- Remove the surfactant adsorbed on the surface of the metal fine particles obtained in step 3, and make the metal fine particles obtained by adsorbing a different type of surfactant from the above surfactant to the surface as magnetic powder. This paper proposes a method for manufacturing magnetic fluid.
上記した第２発明の製造方法によると、まず、界面活性
剤及び還元剤を溶解した水溶液（＝前記した第１工程）
中に、金属イオンを添加（＝前記した第２工程）し、そ
の後、濾過、脱水（＝前記した第３工程）し、得られた
金属微粒子を適宜な溶媒中で洗浄し、金属微粒子の表面
に吸着している界面活性剤を除去する。例えば界面活性
剤がオレイン酸塩である場合にはｎ−プロビルアルコー
ル中で加熱することにより洗浄し、金属微粒子の表面に
形成されたオレイン酸イオンの被覆層を剥離する。According to the production method of the second invention described above, first, an aqueous solution in which a surfactant and a reducing agent are dissolved (=the first step described above)
Metal ions are added therein (=the second step described above), followed by filtration and dehydration (=the third step described above), and the obtained metal fine particles are washed in an appropriate solvent to remove the surface of the metal fine particles. Remove the surfactant adsorbed on the For example, when the surfactant is an oleate salt, it is washed by heating in n-propyl alcohol to peel off the coating layer of oleate ions formed on the surface of the metal fine particles.
次に、除去した界面活性剤とは別種の界面活性剤を金属
微粒子の表面に吸着させるが、上記した別種の界面活性
剤としてはタンパク質、カゼイン、アルブミン、ヘモグ
ロビンを使用することができる。Next, a different type of surfactant than the removed surfactant is adsorbed onto the surface of the metal fine particles, and protein, casein, albumin, or hemoglobin can be used as the above-mentioned different type of surfactant.
そして、上記のように得られる金属微粒子の扮体を溶媒
に分散することにより、安定で、飽和磁化の高い磁性流
体を製造することができるものである。By dispersing the disguised metal particles obtained as described above in a solvent, a stable magnetic fluid with high saturation magnetization can be produced.
従って、前記した本発明の製造方法により得られる磁性
流体が、溶媒中において凝集しても、上記したように金
属微粒子の表面に吸着した界面活性剤を除去して別種の
界面活性剤を吸着することにより，安定に分散すること
ができる金属微粒子を作製することができ、安定な磁性
流体を形成することができる。Therefore, even if the magnetic fluid obtained by the above-described production method of the present invention aggregates in the solvent, the surfactant adsorbed to the surface of the metal fine particles is removed and a different type of surfactant is adsorbed as described above. By doing so, metal fine particles that can be stably dispersed can be produced, and a stable magnetic fluid can be formed.
く実施例〉 以下に本発明の実施例を示す。Example Examples of the present invention are shown below.
実施例１ （鉄微粒子の生成）
水素化ホウ素ナトリウムの濃度が０． ０２ｍｏｌ／
１２である水溶液に、オレイン酸ナトリウムの濃度が７
．２Ｘ １０−３１ＩＩｏｌ／βである水溶液を混合し
、純水を添加して全量を２．３４とする．
次に、上記の混合水溶演に硫酸第一鉄の濃度が０． ２
１Ｉｌｏｌ／の水溶液１００ｃｃを一度に添加し、十分
撹拌したところ、水溶液中に微細な黒色粒子が生成した
。上記した微細な黒色粒子は、表面にオレイン酸イオン
が吸着した鉄微粒子である。また、この時の反応溶ｌ夜
中のオレイン酸イオンの濃度は３．ＯＸ １０−”ｍｏ
ｌ／βであり、飽和磁化は鉄１ｇあたり１．７丁を示し
た。Example 1 (Generation of iron fine particles) The concentration of sodium borohydride was 0. 02mol/
12, the concentration of sodium oleate is 7
．． Mix an aqueous solution of 2X 10-31 IIol/β and add pure water to make the total volume 2.34. Next, the concentration of ferrous sulfate was added to the above mixed water solution at a concentration of 0. 2
When 100 cc of a 1 Ilol/aqueous solution was added at once and thoroughly stirred, fine black particles were generated in the aqueous solution. The above-mentioned fine black particles are iron fine particles having oleate ions adsorbed on their surfaces. Also, the concentration of oleate ions in the reaction solution at this time was 3. OX 10-”mo
l/β, and the saturation magnetization was 1.7 magnets per gram of iron.
上記のように生成した鉄微粒子は、Ｘ線回折より、α鉄
の（１１０）、（２００）の回折線が認められた。In the iron fine particles produced as described above, α-iron (110) and (200) diffraction lines were observed by X-ray diffraction.
また、メチレン抽出吸光光度法の測定より、ホウ素を３
〜４重量％を含有し、吸着したオレイン酸イオンの量よ
り約１０ｎｍの粒径を有する鉄微粒子が生成したことが
推定された。In addition, from the measurement of methylene extraction spectrophotometry, it was found that 3
It was estimated that iron fine particles containing ~4% by weight and having a particle size of about 10 nm were produced based on the amount of adsorbed oleate ions.
第１図にオレイン酸ナトリウムの添加量を変化させて生
成したα鉄の （１１０）面におけるＸ線の回折線の半
値幅、粒子へのオレイン酸ナトリウムの吸着量及びＢＥ
Ｔ法から求めた比表面積を示した。この図よりオレイン
酸ナトリウムの添加量が２． ＯＸ １０−”ｍｏｌ／
βまで増加するとともに生成する鉄微粒子の比表面積は
増加し、鉄微粒子が微細化されることを示している。Figure 1 shows the half-width of the X-ray diffraction line on the (110) plane of α-iron produced by varying the amount of sodium oleate added, the amount of sodium oleate adsorbed onto the particles, and the BE.
The specific surface area determined by the T method is shown. From this figure, the amount of sodium oleate added is 2. OX 10-”mol/
As β increases, the specific surface area of the generated iron fine particles increases, indicating that the iron fine particles become finer.
さらに、生成した鉄微粒子の減磁曲線を第２図に示した
。同図より明らかなように、オレイン酸ナトリウムの濃
度が増加するにつれて保持力と残留磁化は低下した。ま
た、高い還元温度（７５℃）で生成させた鉄微粒子は、
常温（２０℃）で生成させた鉄微粒子よりも高い保持力
と残留磁化を示した。さらに、常温において３．ＯＸ
１０−”ｍｏｌ／４２のオレイン酸ナトリウムの濃度で
反応させた鉄微粒子の残留磁化及び保持力は、共に低下
し、粒径は１０ｎｍ以下となり、超常磁性に近づいたと
考えられる。Furthermore, the demagnetization curve of the produced iron fine particles is shown in FIG. As is clear from the figure, as the concentration of sodium oleate increased, the coercive force and residual magnetization decreased. In addition, iron fine particles produced at a high reduction temperature (75°C) are
It showed higher coercive force and residual magnetization than iron fine particles produced at room temperature (20°C). Furthermore, 3. OX
Both the residual magnetization and the coercive force of the iron particles reacted at a concentration of 10-''mol/42 sodium oleate decreased, and the particle size became 10 nm or less, which is considered to approach superparamagnetism.
実施例２（鉄微粒子からの才レイン酸ナトリウムの除去
）
上記した実施例１で生成した鉄微粒子は、膜厚約１ｒ＋
ｍのオレイン酸イオンで被覆されているが、ケロシン中
においては、磁気的吸引力、ファンデルワールス力が、
混合効果や容積制限効果よりち大となるため、凝集を起
こした。これを透過型電子顕微鏡で確認したところ、粒
径２０ｎｍ程度の巨大な凝集体を形成していた。Example 2 (Removal of sodium oleate from iron fine particles) The iron fine particles produced in Example 1 described above had a film thickness of about 1r+
Although it is coated with m oleate ions, in kerosene, the magnetic attraction force and van der Waals force are
This was greater than the mixing effect and volume restriction effect, causing aggregation. When this was confirmed using a transmission electron microscope, it was found that huge aggregates with a particle size of about 20 nm were formed.
そこで、鉄微粒子の表面に吸着している第１層目のオレ
イン酸イオンを除去するために、ｎ−プロビルアルコー
ル中に鉄微粒子を入れ、８０℃に加熱してｌＯ分間撹拌
した。この分散液を透過型電子顕微鏡で観察したところ
、凝集していた鉄微粒子がばらばらになり、１０ｎｍ程
度に分かれたことが確認された。Therefore, in order to remove the first layer of oleic acid ions adsorbed on the surface of the iron particles, the iron particles were placed in n-propyl alcohol, heated to 80° C., and stirred for 10 minutes. When this dispersion was observed with a transmission electron microscope, it was confirmed that the iron fine particles that had been aggregated were separated into particles of about 10 nm.
また、ＢＥＴ法による比表面積測定結果より、ｎ−プロ
ビルアルコールによる洗浄後の鉄微粒子の比表面積は１
．５倍に増加し、鉄微粒子からオレイン酸イオンが除去
されたことが推定された。Furthermore, from the specific surface area measurement results using the BET method, the specific surface area of iron fine particles after washing with n-propyl alcohol is 1
．． It was estimated that oleate ions were removed from the iron particles.
実施例３（オイルベースの磁性流体の作製）実施例２で
洗浄して得られた鉄微粒子を、ケロシン中に入れ、Ｄｕ
ｏｍｅｅｎ ＴＤＯ及びＤＩＮＰＰ−４等の界面活性剤
を添加して１時間超音波で分散させたところ、ケロシン
中に鉄微粒子が安定に分散した磁性流体が得られた。上
記した鉄微粒子は、表面にＤｕｏｍｅｅｎ ＴＤＯ及び
ＤＩＮＰＰ−４が吸看して被覆層を形成したものであっ
た。また、上記した溶７夜中のケロシンを蒸発させると
、さらに濃厚な磁性流体が得られた。Example 3 (Preparation of oil-based magnetic fluid) The iron particles obtained by washing in Example 2 were placed in kerosene, and Du
When surfactants such as omeen TDO and DINPP-4 were added and dispersed using ultrasonic waves for 1 hour, a magnetic fluid in which fine iron particles were stably dispersed in kerosene was obtained. The above-mentioned iron fine particles had Duomeen TDO and DINPP-4 adsorbed on the surface to form a coating layer. Furthermore, when the kerosene in the solution described above was evaporated, an even more concentrated magnetic fluid was obtained.
〈発明の効果〉
以上説明したように、本発明の磁性流体の製造方法によ
ると、極めて飽和磁化の高い磁性流体を作製することが
できる。<Effects of the Invention> As explained above, according to the method for producing a magnetic fluid of the present invention, a magnetic fluid with extremely high saturation magnetization can be produced.
また、本発明は、溶解、准合、濾過、脱水という極めて
容易な方法で行うものであり、特殊な装置及び特殊な処
理技術を必要としないので、安価な磁性流体を、迅速に
且つ大量に製造することができるものである。In addition, the present invention can be carried out using an extremely easy method of dissolving, associating, filtering, and dehydrating, and does not require special equipment or special processing techniques. Therefore, inexpensive magnetic fluid can be produced quickly and in large quantities. It is something that can be manufactured.
従って、本発明の磁性流体の製造方法は、磁気シール、
ダンパー、センサー、医療等の各種の応用分野の発展に
大きく貢献することが期待できるものである。Therefore, the method for producing a magnetic fluid of the present invention includes a magnetic seal,
It is expected that this product will greatly contribute to the development of various applied fields such as dampers, sensors, and medical care.
図面は本発明の実施例を示すもので、第１図はオレイン
酸ナトリウムの添加量を変化させて生成したａ鉄の （
１１０）面におけるＸ線の回折線の半値幅、粒子へのオ
レイン酸ナトリウムの吸着量及びＢＥＴ法から求めた比
表面積を示す図、第２図はオレイン酸イオンで被覆され
た鉄微粒子の減磁曲線である。The drawings show examples of the present invention, and Figure 1 shows the results of a-iron (
Figure 2 shows the half width of the X-ray diffraction line on the 110) surface, the adsorption amount of sodium oleate on the particles, and the specific surface area determined from the BET method. Figure 2 shows the demagnetization of iron fine particles coated with oleate ions. It is a curve.
Claims (4)
する界面活性剤及び還元剤を溶解した水溶液中に、金属
イオンを添加することにより、表面に界面活性剤が吸着
した金属微粒子を形成させ、濾過、脱水した後、上記し
た金属微粒子を溶媒または水に分散して磁性流体とする
磁性流体の製造方法。(1) By adding metal ions to an aqueous solution containing a surfactant and a reducing agent that strongly chemically or physically adsorb to the surface of metal particles, fine metal particles with the surfactant adsorbed on the surface are formed. , filtration, dehydration, and then dispersing the above metal fine particles in a solvent or water to produce a magnetic fluid.
する界面活性剤及び還元剤を溶解した水溶液中に、金属
イオンを添加することにより、表面に界面活性剤が吸着
した金属微粒子を形成させ、濾過、脱水して得られる金
属微粒子を溶媒で洗浄して表面に吸着している界面活性
剤を除去し、上記界面活性剤とは別種の界面活性剤を吸
着させることにより得られる金属微粒子を溶媒または水
に分散して磁性流体とする磁性流体の製造方法。(2) By adding metal ions to an aqueous solution containing a surfactant and a reducing agent that strongly chemically or physically adsorb to the surface of metal particles, fine metal particles with the surfactant adsorbed on the surface are formed. The metal fine particles obtained by filtration and dehydration are washed with a solvent to remove the surfactant adsorbed on the surface, and the metal fine particles obtained by adsorbing a different type of surfactant from the above surfactant. A method for producing a magnetic fluid by dispersing it in a solvent or water.
（１）または（２）に記載の磁性流体の製造方法。(3) The method for producing a magnetic fluid according to claim (1) or (2), wherein the surfactant is sodium oleate.
１）、（２）、（３）のいずれかに記載の磁性流体の製
造方法。(4) Claim in which the reducing agent is sodium borohydride (
The method for producing a magnetic fluid according to any one of 1), (2), and (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1238416A JP3005799B2 (en) | 1989-09-16 | 1989-09-16 | Manufacturing method of magnetic fluid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1238416A JP3005799B2 (en) | 1989-09-16 | 1989-09-16 | Manufacturing method of magnetic fluid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03104806A true JPH03104806A (en) | 1991-05-01 |
| JP3005799B2 JP3005799B2 (en) | 2000-02-07 |
Family
ID=17029885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1238416A Expired - Lifetime JP3005799B2 (en) | 1989-09-16 | 1989-09-16 | Manufacturing method of magnetic fluid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3005799B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000076699A1 (en) * | 1999-06-15 | 2000-12-21 | Kimoto, Masaaki | Ultrafine composite metal powder and method for producing the same |
| JP2005220435A (en) * | 2003-10-22 | 2005-08-18 | Mitsuboshi Belting Ltd | Method of producing metal nanoparticle and dispersion of metal nanoparticle |
| JP2009252873A (en) * | 2008-04-03 | 2009-10-29 | Seiko Epson Corp | Magnetic fluid and damper |
| JP2011518254A (en) * | 2008-04-28 | 2011-06-23 | タタ ケミカルズ リミテッド | Method for preparing silver nanoparticles |
| JP2013033980A (en) * | 2012-09-20 | 2013-02-14 | Seiko Epson Corp | Metal powder for magnetic fluid |
| CN108701521A (en) * | 2016-02-29 | 2018-10-23 | 洛德公司 | Additive for magneto-rheological fluid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6116793A (en) * | 1985-06-12 | 1986-01-24 | 株式会社東芝 | Steam iron |
| JPS6139369A (en) * | 1984-07-31 | 1986-02-25 | Toshiba Corp | Fuel cell power generation plant |
-
1989
- 1989-09-16 JP JP1238416A patent/JP3005799B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6139369A (en) * | 1984-07-31 | 1986-02-25 | Toshiba Corp | Fuel cell power generation plant |
| JPS6116793A (en) * | 1985-06-12 | 1986-01-24 | 株式会社東芝 | Steam iron |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000076699A1 (en) * | 1999-06-15 | 2000-12-21 | Kimoto, Masaaki | Ultrafine composite metal powder and method for producing the same |
| US6730400B1 (en) | 1999-06-15 | 2004-05-04 | Teruo Komatsu | Ultrafine composite metal particles and method for manufacturing same |
| JP2011052326A (en) * | 1999-06-15 | 2011-03-17 | Akio Komatsu | Ultrafine composite metal particles and method for manufacturing the same |
| JP4732645B2 (en) * | 1999-06-15 | 2011-07-27 | 丸山 稔 | Method for producing metal composite ultrafine particles |
| JP2005220435A (en) * | 2003-10-22 | 2005-08-18 | Mitsuboshi Belting Ltd | Method of producing metal nanoparticle and dispersion of metal nanoparticle |
| JP2009252873A (en) * | 2008-04-03 | 2009-10-29 | Seiko Epson Corp | Magnetic fluid and damper |
| JP2011518254A (en) * | 2008-04-28 | 2011-06-23 | タタ ケミカルズ リミテッド | Method for preparing silver nanoparticles |
| JP2013033980A (en) * | 2012-09-20 | 2013-02-14 | Seiko Epson Corp | Metal powder for magnetic fluid |
| CN108701521A (en) * | 2016-02-29 | 2018-10-23 | 洛德公司 | Additive for magneto-rheological fluid |
| US11518957B2 (en) | 2016-02-29 | 2022-12-06 | Lord Corporation | Additive for magnetorheological fluids |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3005799B2 (en) | 2000-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Roca et al. | Structural and magnetic properties of uniform magnetite nanoparticles prepared by high temperature decomposition of organic precursors | |
| Primc et al. | Hydrothermal synthesis of ultrafine barium hexaferrite nanoparticles and the preparation of their stable suspensions | |
| Charles | The preparation of magnetic fluids | |
| Abbas et al. | Facile sonochemical synthesis of high-moment magnetite (Fe 3 O 4) nanocube | |
| Xia et al. | Novel complex-coprecipitation route to form high quality triethanolamine-coated Fe 3 O 4 nanocrystals: their high saturation magnetizations and excellent water treatment properties | |
| Li et al. | Direct hydrothermal synthesis of single-crystalline triangular Fe 3 O 4 nanoprisms | |
| WO2018062478A1 (en) | Epsilon-type iron oxide magnetic particle, method for manufacturing same, magnetic powder formed from magnetic particles, magnetic paint, and magnetic recording medium | |
| JP5924657B2 (en) | Method for producing ferromagnetic iron nitride particle powder, anisotropic magnet, bonded magnet and dust magnet | |
| JP2016169148A (en) | Surface-modified ferrous oxide magnetic particle powder and method for producing the same | |
| Davoodi et al. | Investigation of the effective parameters on the synthesis of strontium hexaferrite nanoparticles by chemical coprecipitation method | |
| Chen et al. | Controllable synthesis of magnetic Fe3O4 particles with different morphology by one-step hydrothermal route | |
| JP4860386B2 (en) | Method for producing nickel-iron alloy nanoparticles | |
| Rahdar et al. | Preparation of super paramagnetic iron oxide nanoparticles and investigation their magnetic properties | |
| JP2008081818A (en) | Method for producing precursor powder of nickel-ferroalloy nanoparticle, precursor powder of nickel-ferroalloy nanoparticle, method for producing nickel-ferroalloy nanoparticle, and nickel-ferroalloy nanoparticle | |
| JPS6139369B2 (en) | ||
| US3726664A (en) | Magnetic alloy particle compositions and method of manufacture | |
| JP3005799B2 (en) | Manufacturing method of magnetic fluid | |
| Saeed et al. | Mild hydrothermal synthesis of Ni-Cu nanoparticles | |
| Lv et al. | Controllable synthesis and magnetism of iron oxides nanorings | |
| US3859130A (en) | Magnetic alloy particle compositions and method of manufacture | |
| Hou et al. | Biphasic liquid interface derived magnetite nanocrystals: synthesis, properties and growth mechanism | |
| JP3023795B2 (en) | Water-based magnetic fluid and method for producing the same | |
| JP2008179841A (en) | Method for producing nickel-iron-molybdenum alloy nanoparticle, and nickel-iron-molybdenum alloy nanoparticle | |
| O'connor et al. | Nanophase magnetic materials: synthesis and properties | |
| Senapati et al. | Synthesis, magnetic properties and catalytic activity of hierarchical cobalt microflowers |