JP2011137226A5 - Method for producing metal fine particles, metal fine particles produced by this production method, and apparatus for producing metal fine particles - Google Patents

Method for producing metal fine particles, metal fine particles produced by this production method, and apparatus for producing metal fine particles Download PDF

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JP2011137226A5
JP2011137226A5 JP2010271979A JP2010271979A JP2011137226A5 JP 2011137226 A5 JP2011137226 A5 JP 2011137226A5 JP 2010271979 A JP2010271979 A JP 2010271979A JP 2010271979 A JP2010271979 A JP 2010271979A JP 2011137226 A5 JP2011137226 A5 JP 2011137226A5
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本発明は、金属微粒子の製造方法及びこの製造方法により製造される金属微粒子並びに金属微粒子の製造装置に関するものであり、更に詳しくは、反応液に電磁波を均一に照射して加熱することにより、金属ナノ粒子を短時間で、連続的に製造することを可能にする金属微粒子の製造方法及びこの製造方法により製造される金属微粒子並びに金属微粒子の製造装置に関するものである。 The present invention relates to a method for producing metal fine particles, a metal fine particle produced by this production method , and a device for producing metal fine particles . More specifically, the present invention relates to a metal by heating a reaction solution by uniformly irradiating it with electromagnetic waves. The present invention relates to a method for producing fine metal particles that enables continuous production of nanoparticles in a short period of time, a fine metal particle produced by this production method, and an apparatus for producing fine metal particles .

したがって本発明は、粒子径分布の狭い金属ナノ粒子を、短時間で、高い収率で、かつ高エネルギー効率で、連続的に合成することを可能とする金属ナノ粒子材料の製造方法及びこの製造方法により製造される金属微粒子並びに金属微粒子の製造装置を提供することを目的とするものである。 Accordingly, the present invention is a narrow metal nanoparticles of particle size distribution in a short time, in high yields, and with high energy efficiency, a manufacturing method and the manufacturing of the metal nanoparticle material makes it possible to continuously synthesize An object of the present invention is to provide metal fine particles produced by the method and a metal fine particle production apparatus .

本発明の上記金属微粒子の製造は、電磁波の定在波ＴＭ ｍｎ０ （ｍは０以上、ｎは１以上の整数）を形成させることができる共振空洞内に配置された流通管内に金属前駆物質を含有する反応液を流通させ、一方、その流通管の長さ方向にわたって、均一かつ集中的に電磁波を流通管内に向けて照射し、均一に加熱し、金属微粒子を生成させる金属ナノ粒子の連続的製造方法により実施できる。
本発明の製造方法により、好ましくは、平均粒子径が約１００ｎｍ以下の粒子径を有する金属微粒子を製造することができる。本明細書において、金属微粒子の粒子径の平均粒子径は、後述の実施例に示すように、ナノ粒子懸濁液の動的光散乱により測定された値をいう。
本発明に用いられる流通管は、マイクロ波を透過しやすいものが望ましく、該容器の材質としては、例えば、ガラス、石英、アルミナ、フッ素樹脂テフロン（登録商標）、プラスチック、ポリエチル・エーテル・ケトン樹脂などがあげられる。しかし、本発明は、これらに限定されるものではなく、これらと同等の材質のものであれば、同様に使用することができる。
流通管の管壁の厚さは、好ましくは０．０５〜１０ｍｍ、より好ましくは０．１〜２ｍｍである。管壁の厚さを上記範囲にすることにより安定した金属ナノ粒子の連続合成が可能であり、管壁の厚さが薄すぎては反応管としての流通管の形状を維持することが困難であり、また反応管内の圧力変動による破損の可能性があり、厚すぎてはマイクロ波の伝達ロスによる加熱効率の低下という問題を生ずる。
流通管中の金属前駆物質含有液に対する電磁波（マイクロ波）の照射強度は好ましくは０．１ｍＷ〜２０ｋＷ、より好ましくは１ｍＷ〜１００Ｗである。電磁波の照射強度がこの範囲内で、金属前駆体の還元が起こり、金属微粒子が生成する。電磁波強度が低すぎると、金属微粒子が生成せず、高すぎると、流通溶液が沸騰する。また流通管中の金属前駆物質含有液の送液速度は、好ましくは０．１ｍｌ／ｈ〜５ｌ／ｈ、より好ましくは５〜２００ｍｌ／ｈである。送液速度を上記の範囲に調節することにより、目的のサイズの金属微粒子が生成する。送液速度が大きすぎると、液は沸騰しないが粒子径のｎｍオーダーの金属微粒子が得られにくく、小さすぎると液が沸騰し、目的の粒径の金属微粒子が得られにくくなる。 The metal fine particles of the present invention are produced by placing a metal precursor in a flow tube arranged in a resonance cavity that can form an electromagnetic wave standing wave TM mn0 (m is an integer of 0 or more and n is an integer of 1 or more). A continuous reaction of metal nanoparticles that circulates the contained reaction liquid and irradiates electromagnetic waves uniformly and intensively toward the inside of the flow pipe in the length direction of the flow pipe and uniformly heats it to generate metal fine particles. It can be implemented by a manufacturing method.
By the production method of the present invention, preferably, metal fine particles having an average particle size of about 100 nm or less can be produced. In the present specification, the average particle diameter of the metal fine particles refers to a value measured by dynamic light scattering of a nanoparticle suspension, as shown in Examples described later.
The flow tube used in the present invention is preferably one that easily transmits microwaves. Examples of the material of the container include glass, quartz, alumina, fluororesin Teflon (registered trademark), plastic, polyethyl ether ketone resin Etc. However, the present invention is not limited to these, and can be used in the same manner as long as they are made of the same material as these.
The thickness of the pipe wall of the flow pipe is preferably 0.05 to 10 mm, more preferably 0.1 to 2 mm. By making the tube wall thickness within the above range, stable metal nanoparticles can be continuously synthesized. If the tube wall thickness is too thin, it is difficult to maintain the shape of the flow tube as a reaction tube. In addition, there is a possibility of breakage due to pressure fluctuation in the reaction tube, and if it is too thick, there arises a problem that heating efficiency is lowered due to transmission loss of microwaves.
The irradiation intensity of the electromagnetic wave (microwave) with respect to the metal precursor containing liquid in the flow pipe is preferably 0.1 mW to 20 kW, more preferably 1 mW to 100 W. When the irradiation intensity of the electromagnetic wave is within this range, reduction of the metal precursor occurs and metal fine particles are generated. When the electromagnetic wave intensity is too low, metal fine particles are not generated, and when it is too high, the circulating solution boils. The liquid feed rate of the metal precursor containing liquid in the flow pipe is preferably 0.1 ml / h to 5 l / h, more preferably 5 to 200 ml / h. By adjusting the liquid feeding speed to the above range, metal fine particles having a target size are generated. If the liquid feeding speed is too high, the liquid will not boil, but it will be difficult to obtain metal fine particles of the order of nm, and if it is too small, the liquid will boil and it will be difficult to obtain metal fine particles of the desired particle diameter.

本発明では、上述のような、照射するマイクロ波周波数が２．４〜２．５ＧＨｚでは内径が２．９ミリメートル以下のサイズの流通管を用いることが重要である。流通管の外径及び長さについては、特に制限されるものではなく、また、キャビティ内に配置される流通管の形状及び構造についても、適宜設計することができる。
In the present invention, it is important to use a flow pipe having an inner diameter of 2.9 mm or less at a microwave frequency of 2.4 to 2.5 GHz as described above. The outer diameter and length of the flow pipe are not particularly limited, and the shape and structure of the flow pipe disposed in the cavity can be designed as appropriate.

Claims (8)

電磁波の定在波ＴＭ ｍｎ０ （ｍは０以上、ｎは１以上の整数）を形成させることができる共振空洞内に配置された流通管内に金属前駆物質を含有する反応液を流通させ、その流通管の長さ方向にわたって、均一かつ集中的に電磁波を流通管内に向けて照射し、均一に加熱し、金属微粒子を生成させる金属微粒子の製造方法。 Electromagnetic standing wave TM mn0 (m is 0 or more, n represents an integer of 1 or more) is circulated reaction solution containing the metal precursor to the distribution pipe disposed within the resonance cavity can be formed, its over the length of the flow tube, uniformly and intensively irradiated toward the electromagnetic wave distribution tube, uniformly heating method of metal fine particles to produce fine metal particles. 前記流通管が、テフロン（登録商標）製である請求項１に記載の金属微粒子の製造方法。 The flow tube, Teflon method for producing metal fine particles according to (registered trademark) der Ru claim 1. 前記反応液に用いる液媒体が、前記反応液の金属化合物を還元する作用を有する化合物を含有する請求項１又は２に記載の金属微粒子の製造方法。 The method for producing metal fine particles according to claim 1 or 2 , wherein the liquid medium used for the reaction liquid contains a compound having an action of reducing the metal compound of the reaction liquid . 前記反応液もしくは反応生成液の温度を制御し、電磁波照射による生成金属微粒子の粒径を均一に制御する請求項１〜３のいずれか１項に記載の金属微粒子の製造方法。 The method for producing metal fine particles according to any one of claims 1 to 3, wherein the temperature of the reaction liquid or reaction product liquid is controlled to uniformly control the particle diameter of the generated metal fine particles by electromagnetic wave irradiation . 前記共振空胴内にＴＭ ｍｎ０ の前記定在波を安定して形成させるために、円筒型の前記共振空胴の内径を変化させる請求項１〜４のいずれか１項に記載の金属微粒子の製造方法。 The metal fine particle according to any one of claims 1 to 4, wherein an inner diameter of the cylindrical resonance cavity is changed in order to stably form the standing wave of TM mn0 in the resonance cavity . Production method. 前記共振空胴内にＴＭ ｍｎ０ の前記定在波を安定して形成させるために、照射する電磁波の周波数を調整する機構もしくはそれと同等の効果を及ぼす機構を有している請求項１〜５のいずれか１項に記載の金属微粒子の製造方法。 6. A mechanism for adjusting the frequency of an electromagnetic wave to be irradiated or a mechanism for exerting an equivalent effect in order to stably form the standing wave of TM mn0 in the resonance cavity. The manufacturing method of the metal microparticle of any one of Claims 1. ＴＭ  TM ｍｎ０mn0 （ｍは０以上、ｎは１以上の整数）の定在波が形成できるキャビティを内部に有する空胴共振器と、前記キャビティにマイクロ波を照射するマイクロ波発振器と、前記キャビティ内に配置された流通管と、前記流通管の片側に取り付けられ、反応液を前記流通管に送液する送液ポンプとを備えた金属微粒子の製造装置。(M is an integer greater than or equal to 0 and n is an integer greater than or equal to 1) A cavity resonator having a cavity capable of forming a standing wave therein, a microwave oscillator for irradiating the cavity with microwaves, and a cavity disposed in the cavity An apparatus for producing fine metal particles, comprising: a distribution pipe, and a liquid feed pump that is attached to one side of the flow pipe and feeds the reaction liquid to the flow pipe. 請求項１〜６のいずれか１項に記載の金属微粒子の製造方法により製造される金属微粒子。  The metal microparticle manufactured by the manufacturing method of the metal microparticle of any one of Claims 1-6.
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