JP4861802B2 - Method for producing Fe / Pd composite nanoparticles - Google Patents
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- JP4861802B2 JP4861802B2 JP2006323876A JP2006323876A JP4861802B2 JP 4861802 B2 JP4861802 B2 JP 4861802B2 JP 2006323876 A JP2006323876 A JP 2006323876A JP 2006323876 A JP2006323876 A JP 2006323876A JP 4861802 B2 JP4861802 B2 JP 4861802B2
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- 239000002131 composite material Substances 0.000 title claims description 21
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Description
本発明は、高密度磁気記録媒体、永久磁石等として使用することのできるＦｅ／Ｐｄ複合ナノ粒子の製造方法に関する。 The present invention relates to a method for producing Fe / Pd composite nanoparticles that can be used as high-density magnetic recording media, permanent magnets, and the like.
磁気記録媒体用材料には、安定した記録保持のために高い保磁力が要求される。このような高い保磁力を有する金属磁性材料として、Ｆｅ／Ｐｔ複合金属磁性粒子が知られている。 A magnetic recording medium material is required to have a high coercive force for stable recording and holding. As a metal magnetic material having such a high coercive force, Fe / Pt composite metal magnetic particles are known.
このＦｅ／Ｐｔ複合金属磁性粒子は、テトラエチレングリコールに鉄アセチルアセトナートと白金アセチルアセトナートを添加し、窒素ガスを吹き込んで高温下で反応させた後、凝集したＦｅ／Ｐｔ粒子を含む懸濁液に、分散剤としてオレイン酸とオレイルアミンを加え、さらにシクロヘキサン、オレイン酸及びオレイルアミンの混合液を加え、振とうすることによって単分散したＦｅ／Ｐｔ複合ナノ粒子として得られることが開示されている（例えば、特許文献１参照）。 This Fe / Pt composite metal magnetic particle is a suspension containing Fe / Pt particles aggregated after iron acetylacetonate and platinum acetylacetonate are added to tetraethylene glycol and reacted under high temperature by blowing nitrogen gas. It is disclosed that mono-dispersed Fe / Pt composite nanoparticles can be obtained by adding oleic acid and oleylamine as a dispersant to the liquid, and further adding a mixed liquid of cyclohexane, oleic acid and oleylamine and shaking. For example, see Patent Document 1).
一方、近年、新たな材料としてＦｅ／Ｐｄ複合ナノ粒子が提案されているが、その合成技術は確立されていない。上記のＦｅ／Ｐｔ複合ナノ粒子の合成法に準じて、鉄アセチルアセトナートとパラジウムアセチルアセトナートを用い、還元することによって合成することが考えられるが、ＦｅはＰｄと複合する速度に比べ、反応系中に存在している酸素と結合する速度が速いため、γ−Ｆｅ2Ｏ3又はＦｅ3Ｏ4が生成するため、満足な結果が得られないという問題がある。 On the other hand, in recent years, Fe / Pd composite nanoparticles have been proposed as a new material, but the synthesis technique has not been established. According to the method for synthesizing the Fe / Pt composite nanoparticles described above, iron acetylacetonate and palladium acetylacetonate can be used for synthesis by reduction, but Fe is more reactive than the rate of complexing with Pd. Since the bonding speed with oxygen existing in the system is high, γ-Fe 2 O 3 or Fe 3 O 4 is produced, so that there is a problem that satisfactory results cannot be obtained.
本発明は、このような問題を解消し、Ｆｅ／Ｐｄ複合ナノ粒子を得ることが可能な製造方法を提供することを目的とする。 An object of the present invention is to provide a production method capable of solving such problems and obtaining Fe / Pd composite nanoparticles.
上記問題点を解決するために本発明によれば、粒径１〜１００ｎｍのＰｄナノ粒子を、界面活性剤、Ｆｅの塩、及び還元剤と混合し、この混合物を加熱してＦｅの塩を構成するＦｅイオンを還元してＰｄナノ粒子上で析出させることを含む、Ｐｄ相をコアとし、Ｆｅ相をシェルとするＦｅ／Ｐｄ複合ナノ粒子の製造方法が提供される。 In order to solve the above problems, according to the present invention, Pd nanoparticles having a particle size of 1 to 100 nm are mixed with a surfactant, a salt of Fe, and a reducing agent, and the mixture is heated to obtain a salt of Fe. There is provided a method for producing Fe / Pd composite nanoparticles having a Pd phase as a core and an Fe phase as a shell, which comprises reducing constituent Fe ions and precipitating them on Pd nanoparticles.
２番目の発明によれば、粒径１〜１００ｎｍのＰｄナノ粒子を、界面活性剤、Ｆｅの塩、及び還元剤と混合し、この混合物を加熱してＦｅの塩を構成するＦｅイオンを還元してＰｄナノ粒子上で析出させてＦｅ／Ｐｄ複合ナノ粒子を形成し、次いでこのナノ粒子を水素雰囲気下で熱処理することを含む、磁性ナノ粒子の製造方法が提供される。 According to the second invention, Pd nanoparticles having a particle size of 1 to 100 nm are mixed with a surfactant, Fe salt, and a reducing agent, and this mixture is heated to reduce Fe ions constituting the Fe salt. There is provided a method for producing magnetic nanoparticles comprising depositing on Pd nanoparticles to form Fe / Pd composite nanoparticles and then heat treating the nanoparticles under a hydrogen atmosphere.
本発明によれば、Ｐｄナノ粒子を核とし、このＰｄナノ粒子の表面上にＦｅを析出させ、Ｆｅのシェルを形成することにより、ナノスケールオーダーで複合したＦｅ／Ｐｄ複合ナノ粒子を得ることができる。またこのＦｅ／Ｐｄ複合ナノ粒子を水素雰囲気下で熱処理することにより、Ｌ１0ＦｅＰｄコアＦｅシェル型複合ナノ粒子を得ることができる。 According to the present invention, Fe / Pd composite nanoparticles composited on the nanoscale order are obtained by using Pd nanoparticles as a nucleus and depositing Fe on the surface of the Pd nanoparticles to form a shell of Fe. Can do. Further, by heat-treating the Fe / Pd composite nanoparticles in a hydrogen atmosphere, L1 0 FePd core Fe shell composite nanoparticles can be obtained.
以下、本発明のＦｅ／Ｐｄ複合ナノ粒子の製造方法を詳細に説明する。本発明のＦｅ／Ｐｄ複合ナノ粒子の製造方法においては、まずＰｄナノ粒子を、界面活性剤、Ｆｅの塩、及び還元剤と混合する。混合順序は問題ではないが、Ｐｄナノ粒子の分散性を高めるため、界面活性剤を含む溶媒中にＰｄナノ粒子を加え、次いでＦｅの塩、及び還元剤を加えることが好ましい。 Hereinafter, the method for producing Fe / Pd composite nanoparticles of the present invention will be described in detail. In the method for producing Fe / Pd composite nanoparticles of the present invention, first, Pd nanoparticles are mixed with a surfactant, a salt of Fe, and a reducing agent. The order of mixing is not a problem, but in order to increase the dispersibility of Pd nanoparticles, it is preferable to add Pd nanoparticles in a solvent containing a surfactant, and then add a salt of Fe and a reducing agent.
Ｐｄナノ粒子は、粒径が１〜１００ｎｍ、好ましくは１〜１０ｎｍである粒子である。このＰｄナノ粒子は常法によって形成することができ、例えばＰｄの塩を溶媒中で還元することによってＰｄ粒子を析出させることによって形成する。 Pd nanoparticles are particles having a particle size of 1 to 100 nm, preferably 1 to 10 nm. The Pd nanoparticles can be formed by a conventional method. For example, the Pd nanoparticles are formed by precipitating Pd particles by reducing a salt of Pd in a solvent.
界面活性剤としては、オレイルアミン、オレイン酸、テトラエチレングリコール、ドデシルベンゼンスルホン酸ナトリウム、フェニルホスホン酸、ミリスチル酸、ドデカンチオール、ドデシルアミン等を用いることができる。この界面活性剤の添加量はＦｅの塩の３０倍モルとすることが好ましい。 As the surfactant, oleylamine, oleic acid, tetraethylene glycol, sodium dodecylbenzenesulfonate, phenylphosphonic acid, myristic acid, dodecanethiol, dodecylamine and the like can be used. The addition amount of this surfactant is preferably 30 moles of the Fe salt.
界面活性剤としてオレイルアミン又はオレイン酸を用いる場合、これらは溶媒としても機能するが、必要に応じて溶媒を添加してもよい。この溶媒としては、Ｆｅ粒子の析出反応において加熱するため、沸点の高い、かつ安定であるものが好ましく、例えば１−オクタノール、オクチルエーテル、オクタデセン、スクアレン、テトラエチレングリコール、トリフェニルメタン等を用いることができる。 When oleylamine or oleic acid is used as the surfactant, these also function as a solvent, but a solvent may be added as necessary. As this solvent, since it heats in the precipitation reaction of Fe particle | grains, what has a high boiling point and is stable is preferable, for example, 1-octanol, octyl ether, octadecene, squalene, tetraethylene glycol, triphenylmethane etc. are used. Can do.
Ｆｅの塩としては、有機配位子を有する金属錯体であることが好ましく、例えばアセチルアセトナート塩、酢酸塩、塩化物等が挙げられる。具体的には、鉄(II)アセチルアセトナート、鉄(III)アセチルアセトナート等を用いることができる。このＦｅの塩の添加量はＰｄの３倍モル程度とすることが好ましい。 The Fe salt is preferably a metal complex having an organic ligand, and examples thereof include acetylacetonate salts, acetate salts, and chlorides. Specifically, iron (II) acetylacetonate, iron (III) acetylacetonate, or the like can be used. The amount of Fe salt added is preferably about 3 times the molar amount of Pd.
還元剤としては、一価アルコール、ポリオール（多価アルコール）、又はジフェニルシランを用いることが好ましい。一価アルコールとしては、特に限定されないが、例えば１−オクタノール、１−デカノール、１−ドデカノール等を用いることができ、還元を行う反応温度より高い沸点を有するものが好ましい。ポリオールとしては、特に限定されないが、例えば１，２−オクタンジオール、１，２−ドデカンジオール、１，２−テトラデカンジオール、１，２−ヘキサデカンジオール等を用いることができ、還元を行う反応温度より高い沸点を有するものが好ましい。この還元剤の添加量は、Ｆｅの塩の１０倍モル以上とすることが好ましい。 As the reducing agent, it is preferable to use monohydric alcohol, polyol (polyhydric alcohol), or diphenylsilane. Although it does not specifically limit as monohydric alcohol, For example, 1-octanol, 1-decanol, 1-dodecanol etc. can be used, and what has a boiling point higher than the reaction temperature which performs a reduction | restoration is preferable. The polyol is not particularly limited, and for example, 1,2-octanediol, 1,2-dodecanediol, 1,2-tetradecanediol, 1,2-hexadecanediol, and the like can be used. Those having a high boiling point are preferred. The amount of the reducing agent added is preferably 10 moles or more of the Fe salt.
還元を行う反応温度は、通常１５０℃以上、好ましくは１８０℃以上である。また反応時間は、反応温度や用いる材料等によって異なるが、通常は数分〜数時間である。 The reaction temperature for carrying out the reduction is usually 150 ° C. or higher, preferably 180 ° C. or higher. Moreover, although reaction time changes with reaction temperature, the material to be used, etc., it is usually several minutes-several hours.
以上のようにしてＰｄナノ粒子が分散して存在する溶媒中でＦｅ粒子を析出させることにより、Ｐｄ粒子をコアとし、ＦｅをシェルとしたＦｅ／Ｐｄ複合ナノ粒子を得ることができる。この粒子の大きさは通常１〜２０ｎｍである。 By precipitating Fe particles in a solvent in which Pd nanoparticles are dispersed as described above, Fe / Pd composite nanoparticles having Pd particles as a core and Fe as a shell can be obtained. The size of the particles is usually 1 to 20 nm.
こうして得られたＦｅ／Ｐｄ複合ナノ粒子表面には、一部Ｆｅ3Ｏ4が存在することがあり、この場合、熱処理することにより、Ｆｅ3Ｏ4が還元されながらＰｄと混ざり、ＦｅＰｄ（部分的に規則化が進行したＬ１0ＦｅＰｄ）を形成するため、磁気特性を高めることができる。熱処理条件としては４％Ｈ2／Ａｒ下５００℃で３時間とすることが好ましい。 Fe 3 O 4 may be partially present on the surface of the Fe / Pd composite nanoparticles thus obtained. In this case, Fe 3 O 4 is mixed with Pd while being reduced by heat treatment, and FePd (partial Therefore, the magnetic properties can be improved because the ordered L1 0 FePd) is formed. The heat treatment condition is preferably 3 hours at 500 ° C. under 4% H 2 / Ar.
パラジウムアセチルアセトナート（Ｐｄ(acac)2）0.17mmol、ＴＯＰ1.1mmol及びオレイルアミン1.1mmolを混合し、250℃までゆっくり昇温させ、250℃にて３０分間保持し、精製することによって粒径５ｎｍのＰｄナノ粒子を得た。 Mixing 0.17 mmol of palladium acetylacetonate (Pd (acac) 2 ), 1.1 mmol of TOP and 1.1 mmol of oleylamine, slowly raising the temperature to 250 ° C., holding at 250 ° C. for 30 minutes, and purifying to a particle size of 5 nm Pd nanoparticles were obtained.
このＰｄナノ粒子0.085mmolを三口フラスコに入れ、オクタノール10mL、鉄アセチルアセトナート（Ｆｅ(acac)3）0.22mmol、オレイルアミン3.4mmol及びオレイン酸3.4mmolを加えた。反応容器内に攪拌子を入れ、マグネチックスターラーを用いて攪拌を行い、マントルヒーターで加熱した。溶液中の不純物や溶存酸素を取り除くため、反応容器内を減圧状態に、溶液を攪拌しながら１１０℃まで加熱し、１時間保持した。その後、反応容器内を窒素置換し、昇温速度２℃／分で１８０℃まで上温させ、１８０℃で１時間保持し反応させた。次いで、貧溶媒であるエタノールを10mL加え、遠心分離することによって反応物を沈殿させ、余分な有機物を取り除く精製処理を行った。 0.085 mmol of this Pd nanoparticle was placed in a three-necked flask, and 10 mL of octanol, 0.22 mmol of iron acetylacetonate (Fe (acac) 3 ), 3.4 mmol of oleylamine and 3.4 mmol of oleic acid were added. A stirrer was placed in the reaction vessel, stirred using a magnetic stirrer, and heated with a mantle heater. In order to remove impurities and dissolved oxygen in the solution, the reaction vessel was heated to 110 ° C. with stirring under a reduced pressure, and held for 1 hour. Thereafter, the inside of the reaction vessel was replaced with nitrogen, the temperature was raised to 180 ° C. at a rate of temperature rise of 2 ° C./min, and the reaction was carried out by maintaining at 180 ° C. for 1 hour. Subsequently, 10 mL of ethanol, which is a poor solvent, was added, and the reaction product was precipitated by centrifuging to perform a purification treatment to remove excess organic matter.
この溶液中に分散しているＦｅ／Ｐｄ複合ナノ粒子を合成石英基板上及びＴＥＭグリッド上に滴下し、イメージ炉内にて４％Ｈ2／Ａｒフロー下（流量４００ｍＬ／分）、５００℃（昇温速度１０℃／分）で１時間及び３時間処理した。 The Fe / Pd composite nanoparticles dispersed in this solution are dropped on a synthetic quartz substrate and a TEM grid, and are placed in an image furnace under a 4% H 2 / Ar flow (flow rate 400 mL / min) at 500 ° C. ( The temperature was increased at a heating rate of 10 ° C./min for 1 hour and 3 hours.
この粒子の熱処理前後のＴＥＭ像を図１に示す。酸化鉄相及び鉄相は融合しているが、コア部のＰｄ（もしくはＦｅＰｄ）ナノ粒子部分の融合は確認されていない。また、この粒子の熱処理前後のＸＲＤパターンを図２に示す。図２より、熱処理によりＦｅ3Ｏ4が還元されながらＰｄと混ざり、ＦｅＰｄ（部分的に規則化が進行したＬ１0ＦｅＰｄ）を形成していることが確認された。これらのことから、Ｐｄナノ粒子の粒径が顕著に変わることなく、ＦｅＰｄ（部分的Ｌ１0ＦｅＰｄ）が形成され、その周囲をα−Ｆｅが覆った構造をとっていることが予想される。加えて、反応時間を長くすることにより、規則化の促進を行うことが可能であると予想される。 A TEM image of the particles before and after heat treatment is shown in FIG. Although the iron oxide phase and the iron phase are fused, the fusion of the Pd (or FePd) nanoparticle part in the core part has not been confirmed. Moreover, the XRD pattern before and behind heat processing of this particle | grain is shown in FIG. From FIG. 2, it was confirmed that Fe 3 O 4 was mixed with Pd while being reduced by heat treatment to form FePd (L1 0 FePd partially ordered). From these facts, it is expected that FePd (partial L1 0 FePd) is formed without significantly changing the particle diameter of the Pd nanoparticles, and that the periphery thereof is covered with α-Fe. In addition, it is expected that regularization can be promoted by increasing the reaction time.
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