JP5769287B2 - Method for producing metal fine particles - Google Patents
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Description
本発明は、金属微粒子の製造方法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に関するものである。
The present invention relates to the production how fine metal particles, more specifically, by heating to uniformly irradiate an electromagnetic wave to the reaction solution, in a short time the metal nanoparticles, that the continuous production those concerning the manufacturing how the fine metal particles to enable.
金属ナノ粒子（金属のナノメーターオーダーの粒子）は、触媒、電極材、抗菌剤などの種々の用途に用いられている。またとりわけ最近はイムノクロマト用標識材料など食品アレルギー検査キット、免疫診断キットなどの分野において高性能、高精度を実現するため要求されている。
そのような材料としては、Ａｇ，Ａｕ，Ｉｒ，Ｐｔ，Ｐｄ，Ｒｈ，Ｒｅ，Ｒｕ，Ｃｕ，Ｎｉ、及びＯｓなどの遷移金属や、Ｃｅ，Ｐｒ，Ｎｄ，Ｐｍ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍなどの希土類元素が挙げられる。
これらの金属ナノ粒子の製造方法としては、粉砕など原料金属を物理的に微細化するトップダウン法と、金属前駆物質から化学反応により微粒子の成長を行う、ボトムアップ法がある。特に１００ｎｍ以下で粒径分布が揃った微粒子を製造するにはボトムアップ法が広く利用されている。特にボトムアップ法の一つである湿式還元法は、様々な種類の金属ナノ粒子を分散性よく製造できることから、研究例が多い。湿式還元法は溶液中の化学反応のため、粒子径の揃ったナノ粒子を製造するには精密な反応温度制御や反応時間の制御が重要となる。このため、均一な温度場、反応場を維持するために、バッチ型の反応器が多く利用されている。しかしバッチ法では、溶液の交換や洗浄など手間が掛かるため工業的な大量生産には向いていないという問題点があった。またマイクロリアクターを用いた連続合成も行われている。しかしマイクロリアクターを利用する方法は、初期コストと運転コスト、反応管の閉塞の問題など解決すべき点がある。
Metal nanoparticles (metal nanometer order particles) are used in various applications such as catalysts, electrode materials, and antibacterial agents. In particular, recently, it has been required to realize high performance and high accuracy in the fields of food allergy test kits and immunodiagnostic kits such as immunochromatographic labeling materials.
Such materials include transition metals such as Ag, Au, Ir, Pt, Pd, Rh, Re, Ru, Cu, Ni, and Os, Ce, Pr, Nd, Pm, Sm, Eu, Gd, and Tb. , Dy, Ho, Er, Tm, and the like.
As a method for producing these metal nanoparticles, there are a top-down method in which the raw material metal is physically refined such as pulverization, and a bottom-up method in which fine particles are grown from a metal precursor by a chemical reaction. In particular, the bottom-up method is widely used for producing fine particles having a uniform particle size distribution at 100 nm or less. In particular, the wet reduction method, which is one of the bottom-up methods, has many examples of research because it can produce various types of metal nanoparticles with good dispersibility. Since the wet reduction method is a chemical reaction in a solution, precise reaction temperature control and reaction time control are important for producing nanoparticles with uniform particle sizes. For this reason, in order to maintain a uniform temperature field and reaction field, batch type reactors are often used. However, the batch method has a problem that it is not suitable for industrial mass production because it takes time and labor to exchange and clean the solution. Continuous synthesis using a microreactor is also performed. However, the method using a microreactor has problems to be solved, such as initial cost and operation cost, and a problem of blocking of a reaction tube.
また金属前駆物質とアルコール溶媒を含有する反応混合物を局在化したマイクロ波またはミリメートル波エネルギーで加熱し、金属粒子を製造する方法が提案されている（特許文献１、特許文献２参照）。しかし、この方法では連続操作ができず、工業的な製造への適用には課題があった。 There has also been proposed a method for producing metal particles by heating a reaction mixture containing a metal precursor and an alcohol solvent with localized microwave or millimeter wave energy (see Patent Document 1 and Patent Document 2). However, this method cannot be operated continuously, and there is a problem in application to industrial production.
しかも、マイクロ波利用の化学反応においては、従来の電磁波照射では、反応管内への電磁波の照射強度にムラが生じるため、再現性に課題があり、また、反応液を攪拌させる必要があり、その多くは、バッチ型反応によって実施されるものであった。一方近年、工業的に金属微粒子、とりわけ高品質な金属ナノ粒子を、効率よく連続生産しうる方法の開発が要望されている。
ナノ粒子をマイクロ波照射によって連続合成を行う試みとしては、非特許文献１がある。これら調理用電子レンジ内に反応管を配置するものであり、反応管への電磁波照射には、空間的な電磁波強度のムラや、時間的な変動を生じることにより均質な温度場の維持が困難で、粒子径分布や粒子性状が不均質となる可能性がある。また特許文献３によるナノ粒子連続合成の試みもある。これは、導波管内に反応管を配置するものであるが、この場合導波管入口部のマイクロ波強度が導波管出口部のマイクロ波強度より高くなることや、反応物にマイクロ波が完全に吸収されないためエネルギー効率が悪いという課題があった。また、特許文献３には、定在波（空胴共振器）によるマイクロ波照射方法も提案されているが、空胴共振器内のマイクロ波分布に依存したマイクロ波照射ムラが発生するおそれがあった。
Moreover, in the chemical reaction using microwaves, the conventional electromagnetic wave irradiation has a problem in reproducibility because of unevenness in the irradiation intensity of the electromagnetic wave into the reaction tube, and it is necessary to stir the reaction liquid. Many were performed by batch-type reactions. On the other hand, in recent years, there has been a demand for industrial development of a method capable of efficiently and continuously producing fine metal particles, particularly high-quality metal nanoparticles.
Non-patent document 1 is an attempt to continuously synthesize nanoparticles by microwave irradiation. A reaction tube is placed in these microwave ovens for cooking, and it is difficult to maintain a uniform temperature field due to uneven electromagnetic wave intensity and temporal fluctuations when irradiating the reaction tube with electromagnetic waves. Therefore, there is a possibility that the particle size distribution and particle properties are not uniform. There is also an attempt for continuous nanoparticle synthesis according to Patent Document 3. In this case, the reaction tube is disposed in the waveguide. In this case, the microwave intensity at the waveguide inlet is higher than the microwave intensity at the waveguide outlet, and the microwave is generated in the reactant. There was a problem that energy efficiency was poor because it was not completely absorbed. Patent Document 3 also proposes a microwave irradiation method using a standing wave (cavity resonator). However, there is a risk that unevenness in microwave irradiation depending on the microwave distribution in the cavity resonator may occur. there were.
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を提供することを目的とするものである。
Accordingly, the present invention provides a narrow metal nanoparticles of particle size distribution, in a short time, in high yields, and with high energy efficiency, a manufacturing how metallic nano-particle material which makes it possible to continuously synthesize It is intended to do.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）金属前駆物質を含有する反応液を、電磁波の定在波ＴＭ ｍｎ０ （ｍは０以上、ｎは１以上の整数）を形成させた共振空胴内に配置された流通管内に流通させるとともに、該共振空胴内の該流通管内に向けて、均一かつ集中的に電磁波を照射し、この電磁波照射により流通管内の電磁波照射空間を流通方向の長さ方向全体にわたって、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であって、
前記電磁波の周波数が２．４〜２．５ＧＨｚであり、且つ、前記流通管の内径が２．９ミリメートル以下である、製造方法。
（２）前記共振空胴がＴＭ ０１０ を形成させた円筒型の共振空胴であり、前記流通管が、該円筒型共振空胴の中心軸に沿って配置されている、（１）記載の金属微粒子の製造方法。
（３）前記流通管が、テフロン（登録商標）製である（１）又は（２）記載の金属微粒子の製造方法。
（４）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（１）〜（３）のいずれか１項に記載の金属微粒子の製造方法。
（５）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（１）〜（４）のいずれか１項に記載の金属微粒子の製造方法。
（６）前記円筒型の共振空胴内にＴＭｍｎ０（ｍは０以上、ｎは１以上の整数）の定在波を安定して形成させるために、円筒型の前記共空胴の内径を変化させる（１）〜（５）のいずれか１項に記載の金属微粒子の製造方法。
（７）前記共振空胴内にＴＭｍｎ０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（１）〜（６）のいずれか１項に記載の金属微粒子の製造方法。
（８）電磁波照射空間を通過した反応液を温度調節器に導入して冷却することを含む、（１）〜（７）のいずれか１項に記載の金属微粒子の製造方法。
The present invention for solving the above-described problems comprises the following technical means.
(1) A reaction solution containing a metal precursor is circulated in a flow tube arranged in a resonance cavity in which a standing wave TM mn0 (m is an integer of 0 or more and n is an integer of 1 or more) of electromagnetic waves is formed . together, toward the flow passage pipe of the co Fusora the barrel, uniform one and centralized refers to electromagnetic wave irradiation, over the whole length direction of the flow direction of the electromagnetic wave irradiation space distribution tube by the electromagnetic wave irradiation, uniformly heated And a method for producing metal fine particles for producing metal fine particles,
The manufacturing method in which the frequency of the electromagnetic wave is 2.4 to 2.5 GHz, and the inner diameter of the flow pipe is 2.9 millimeters or less .
(2) The resonant cavity is a cylindrical resonant cavity in which TM010 is formed, and the flow pipe is disposed along the central axis of the cylindrical resonant cavity . A method for producing fine metal particles.
(3) The method for producing metal fine particles according to (1) or (2) , wherein the flow pipe is made of Teflon (registered trademark) .
(4) the reaction liquid liquid medium used in the method for producing a fine metal particles according to any one of containing a compound having an effect (1) to (3) for reducing the metal compound in the reaction solution.
(5) the reaction mixture or by controlling the temperature of the reaction product solution to uniformly control the particle size of the generate metal fine particles that by the electromagnetic radiation (1) to the metal fine particles according to any one of (4) Production method.
(6) to said cylindrical resonant cavity in the body TM mn0 (m is 0 or more, n represents an integer of 1 or more) in order to form stable standing waves, the internal diameter of the co-cavity cylindrical The method for producing metal fine particles according to any one of (1) to ( 5 ), wherein the metal fine particles are changed.
(7) In order to stably form the standing wave of TM mn0 in the resonant cavity, a mechanism for adjusting the frequency of the electromagnetic wave to be irradiated or a mechanism for exerting an equivalent effect is provided (1) The manufacturing method of the metal microparticles of any one of-( 6 ).
(8) The method for producing metal fine particles according to any one of (1) to (7), comprising introducing the reaction liquid that has passed through the electromagnetic wave irradiation space into a temperature controller and cooling it.
本発明によれば、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。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to synthesize | combine continuously the metal nanoparticle with narrow particle size distribution with a high yield and high energy efficiency in a short time.
本発明方法で製造しうる金属微粒子としては、遷移金属及び典型金属の錯体にあっては、Ａｇ，Ａｕ，Ｉｒ，Ｐｔ，Ｐｄ，Ｒｈ，Ｒｅ，Ｒｕ，及びＯｓなどの遷移金属が最も望ましいが、Ｓｃ，Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｙ，Ｚｒ，Ｎｂ，Ｍｏ，Ｔｃ，Ｗなどの遷移元素、Ａｌ，Ｉｎ，Ｇａ，Ｚｎ，Ｃｄ，Ｓｂ，Ｓｎ，Ｇｅ，Ｂｅ，Ｍｇなどの典型元素であっても差し支えない。 As the metal fine particles that can be produced by the method of the present invention, transition metals such as Ag, Au, Ir, Pt, Pd, Rh, Re, Ru, and Os are most desirable among transition metal and typical metal complexes. , Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, W, and other transition elements, Al, In, Ga, Zn, Cd, Sb, Sn, Ge It may be a typical element such as, Be or Mg.
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.
本発明において金属前駆体を、金属に対する還元作用を有する溶媒に分散もしくは溶解させて電磁波を照射する。このような溶媒としてはアルコール類（メタノール、エタノール、エチレングリコール、ジエチレングリコール、プロピレングリコール、テトラエチレングリコール、グリセロール、ベンジルアルコール、ジプロピレングリコール等）、無機酸（水酸化ホウ素塩、ジメチルアミノボラン、亜リン酸、次亜リン酸、亜硫酸、チオ硫酸ナトリウム、Ｆｅイオン錯体、ヒドラジン等）、有機酸類（クエン酸、リンゴ酸、シュウ酸、ギ酸等）、糖類などが挙げられる。また、本発明において金属前駆物質の含有液に、分散剤を加え、生成する金属微粒子の凝集を防止し、分散安定性を高めるのが好ましい。このような分散剤としてはポリビニルピロリドン、ポリエチレングリコール、ポリビニルアルコール、高分子分散剤などが挙げられる。高分子分散剤とは、顔料表面に対する親和性の高い官能基が導入された高分子量の重合体であって、溶媒和部分を含む構造を有する両親媒性のものである。高分子分散剤としては、マイクロ波を吸収する溶媒に可溶であり、極めて速い還元反応によって瞬時に生成される微粒子を凝集させることなく捕捉し溶媒に分散させることができ、さらに生成されたコロイドの長期安定性に有効である共重合体であることが好ましく、高分子分散剤の数平均分子量は、１０００〜１００万であることが好ましい。高分子分散剤としては、例えば、特開平１１−８０６４７号公報に例示したものを挙げることができ、好ましい高分子分散剤（市販品）としては、ビックケミー社製のＤＩＳＰＥＲＢＹＫ１０２，１０８，１１６，１４５，１８０，２０９６，２１５５，ＢＹＫ９０７６，９０７７、共栄社化学社製フローレンＧ７００，Ｇ９００などを挙げることができる。数平均分子量は１０，０００〜５０，０００のものが特に好ましい。
溶媒としては、沸点の高い溶媒が好適に使用され、これら溶媒を混合して用いることも差し支えない。
In the present invention, the metal precursor is dispersed or dissolved in a solvent having a reducing action on the metal and irradiated with electromagnetic waves. Such solvents include alcohols (methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, tetraethylene glycol, glycerol, benzyl alcohol, dipropylene glycol, etc.), inorganic acids (boron hydroxide salt, dimethylaminoborane, phosphorous acid) Acid, hypophosphorous acid, sulfurous acid, sodium thiosulfate, Fe ion complex, hydrazine, etc.), organic acids (citric acid, malic acid, oxalic acid, formic acid, etc.), saccharides and the like. Further, in the present invention, it is preferable to add a dispersant to the liquid containing the metal precursor to prevent aggregation of the generated metal fine particles and to improve dispersion stability. Examples of such a dispersant include polyvinyl pyrrolidone, polyethylene glycol, polyvinyl alcohol, and a polymer dispersant. The polymer dispersant is a high molecular weight polymer into which a functional group having a high affinity for the pigment surface is introduced, and is an amphiphilic one having a structure including a solvation part. As a polymer dispersing agent, it is soluble in a solvent that absorbs microwaves, and it can capture and disperse the fine particles generated instantaneously by an extremely fast reduction reaction in the solvent without agglomeration. It is preferable that the copolymer is effective for long-term stability, and the number average molecular weight of the polymer dispersant is preferably 1,000 to 1,000,000. Examples of the polymer dispersant include those exemplified in JP-A-11-80647. Preferred polymer dispersants (commercially available products) include DISPERBYK 102, 108, 116, 145 manufactured by Big Chemie. 180, 2096, 2155, BYK9076, 9077, Kyoeisha Chemical Co., Ltd. florene G700, G900, etc. can be mentioned. The number average molecular weight is particularly preferably 10,000 to 50,000.
As the solvent, a solvent having a high boiling point is preferably used, and these solvents may be mixed and used.
本発明において、反応液中の金属前駆体物質の濃度は、好ましくは０．０１ｍＭ〜１０Ｍ、より好ましくは０．１ｍＭ〜３Ｍである。
上記において、送液により流通する金属前駆体物質を含む反応液を上記によって適正にすることにより、ナノメーターサイズの金属微粒子を製造することができる。
本発明は、連続的に供給される前述の反応液に対し、電磁波を照射することで、短時間で、高い収率で、かつ高エネルギー効率で、連続的に、前述の金属微粒子を合成できる方法を提供するものである。以下に、本発明に望ましい電磁波照射方法を説明する。
In the present invention, the concentration of the metal precursor substance in the reaction solution is preferably 0.01 mM to 10M, more preferably 0.1 mM to 3M.
In the above, nanometer-sized metal fine particles can be produced by making the reaction liquid containing the metal precursor substance distributed by liquid feeding appropriate as described above.
In the present invention, the above-mentioned metal fine particles can be synthesized continuously in a short time, in a high yield and with high energy efficiency by irradiating the above-mentioned reaction solution supplied continuously with electromagnetic waves. A method is provided. The electromagnetic wave irradiation method desirable for the present invention will be described below.
一般に、物質がマイクロ波によって加熱されるときの発熱は、次式で表される。 In general, heat generation when a substance is heated by microwaves is expressed by the following equation.
この中で、｜Ｅ｜［Ｖ／ｍ］，｜Ｈ｜［Ａ／ｍ］は、それぞれマイクロ波の電界強度、磁界強度であり、σ［Ｓ／ｍ］は電気伝導度、ｆ［１／ｓｅｃ］はマイクロ波の周波数、ε０［Ｆ／ｍ］は真空中の誘電率、ε’’は誘電損率、μ０［Ｈ／ｍ］は真空の透磁率、μ’’は磁気損率である。 Among these, | E | [V / m] and | H | [A / m] are the electric field strength and magnetic field strength of the microwave, respectively, σ [S / m] is the electric conductivity, and f [1 / sec] is the microwave frequency, ε 0 [F / m] is the dielectric constant in vacuum, ε ″ is the dielectric loss factor, μ 0 [H / m] is the magnetic permeability in vacuum, and μ ″ is the magnetic loss factor. It is.
このうち、上記式１の右辺の第２項で表される電界による発熱及び第３項で表される磁界による発熱が、マイクロ波加熱に大きな影響を与えることが多い。ここでは、第２項の電界による発熱を例にとり、説明するが、上記式１の第１項や第３項についても、同様に当てはまるものである。 Of these, the heat generated by the electric field represented by the second term on the right side of Equation 1 and the heat generated by the magnetic field represented by the third term often have a great influence on the microwave heating. Here, the heat generation by the electric field of the second term will be described as an example, but the same applies to the first term and the third term of the above formula 1.
マイクロ波加熱による発熱量を大きくするには、誘電損率ε’’が大きい物質を選ぶか、電界強度を大きくすることが有効であることが、上記式１から分かる。このため、誘電損率の小さい物質（非極性物質）のマイクロ波加熱は難しい。このような物質を加熱するには、電界強度Ｅを大きくするか、物質の誘電損率を見かけ上大きくすることが有効であることが分かる。 From the above formula 1, it can be seen that it is effective to select a substance having a large dielectric loss factor ε ″ or increase the electric field strength in order to increase the amount of heat generated by microwave heating. For this reason, microwave heating of a substance having a low dielectric loss factor (non-polar substance) is difficult. In order to heat such a substance, it can be seen that it is effective to increase the electric field strength E or to increase the dielectric loss factor of the substance apparently.
電界強度Ｅを大きくするためには、マイクロ波を特定の部位に集中させるように照射すること、見かけ上の誘電損率を大きくするためには、被加熱対象物質と流通管壁（すなわち、反応管壁）との間の相互作用を有効に用いること、を実現することが必要とされる。 In order to increase the electric field strength E, the microwave is irradiated so as to concentrate on a specific part, and in order to increase the apparent dielectric loss rate, the substance to be heated and the flow pipe wall (that is, reaction) It is necessary to realize the effective use of the interaction with the (wall).
一般に、電界強度を高めるためには、大型のマイクロ波発生器を利用する必要があるが、そのために、装置の大型化や価格が上がるなど課題があり、また、マイクロ波の漏えいや部分的な異常加熱が起こるなど、装置設計も困難になってしまうなどの課題がある。マイクロ波を集中させ、特定の部位に電界強度が極大になるマイクロ波照射方法を構築することで、上記問題を解決しつつ、電界強度を大きくすることが可能となる。 In general, in order to increase the electric field strength, it is necessary to use a large microwave generator. However, there are problems such as an increase in the size and price of the device, and leakage of microwaves and partial There is a problem that the device design becomes difficult, such as abnormal heating. By concentrating microwaves and constructing a microwave irradiation method in which the electric field strength is maximized at a specific site, it is possible to increase the electric field strength while solving the above problems.
本発明では、マイクロ波を特定の部位に集中して照射できる機構として、定在波を形成するシングルモードキャビティを用いる方法を使用する。シングルモードキャビティ中では、電磁界強度の強い場所と弱い場所の時間変化がないため、強い場所にマイクロ波の被加熱対象物質を配置することで、効果的なマイクロ波加熱が可能になる。
ここでシングルモードキャビティとは、特定の定在波を安定に形成することができるマイクロ波照射空間内のことをいう。定在波とは、波形が進行せずに止まって振動しているように見える波動のことで、電界強度が０の場所と、電界強度の強い場所の位置が変化しない状態が作られる。特に円筒型の共振空胴（キャビティ）により、ＴＭｎｍ０モード（ｎは０以上、ｍは１以上の整数）の定在波を形成した場合、円筒中心軸に配置した反応管流路部分に、マイクロ波を集中して照射することができるうえ、中心軸の軸方向には電界強度の分布が一様になり、反応液は常に制御された電界強度のマイクロ波を照射させることができる。このとき、反応管流路をマイクロ波を透過しやすい材料で構成することで、マイクロ波は内部の溶液に直接到達し、反応液を直接誘電加熱することができる。誘電加熱は、従来の伝熱による加熱よりきわめて短時間に発熱させることができるため、所定の反応温度になるよう溶液を迅速に加熱できる。また、反応液中の金属前駆体物質の化学反応が、マイクロ波照射により促進される場合もある。この場合は、加熱に必要な時間だけでなく、反応時間の短縮も期待できる。
本発明に用いられる電磁波照射手段は、電磁波を反応液に集中して照射できるものが好ましい。
例えば、電界を集中できる構造の電磁波照射空間の一つとして、空胴共振器とよばれる空間を利用した、特定の定在波を安定に形成できる容器を用いる方法がある。図２は円筒型の空胴共振器内に形成されたＴＭ０１０とよばれる定在波の電界強度分布を示したものである。図中（Ａ）は空胴共振器１１の全体図、（Ｂ）は上記（Ａ）に対応する、空胴共振器の円筒内径方向と電界強度との関係を示すグラフ、（Ｃ）は上記（Ａ）に対応する空胴共振器の円筒の軸方向と電界強度との関係を示すグラフである。図２（Ａ）において、１１は空胴共振器、１２はマイクロ波照射口であり、図２（Ｂ）のグラフは空胴共振器１１の半径方向に対する電界強度を示す（横軸が空胴共振器１１の半径と対応している）。ＴＭ０１０の定在波を用いれば、円筒の中心部に電界を集中できることがわかる。図２（Ｃ）のグラフは空胴共振器１１の中心軸上の軸方向に対する電界強度を示す（縦軸が円筒空胴の中心軸上の位置に対応している）。ＴＭ０１０の定在波を用いれば、円筒中心軸上の電界強度は、位置によらず均一であることがわかる。つまり、円筒内に形成したＴＭ０１０の定在波を有する空胴共振器を用い、その円筒の中心軸に沿って配置したチューブ状の反応器は、つねに強力でかつ均一な電界をもつマイクロ波を照射することが可能となる。図２では、ＴＭ０１０について説明したが、ＴＭｍｎ０（ｍは０以上、ｎは１以上の整数）の定在波も、円筒の半径方向に電界の集中する場所があり、中心軸に平行な部位では均一な電界強度を有するため、同様に利用することができる。また、図２では電界で説明したが、電磁波は磁界による加熱作用もあるため、磁界が強くなる部分を利用しても同様な効果を得ることができる。
In the present invention, a method using a single mode cavity that forms a standing wave is used as a mechanism capable of irradiating a microwave concentratedly on a specific part. In a single mode cavity, there is no time change between a strong electromagnetic field intensity and a weak electromagnetic field intensity. Therefore, an effective microwave heating can be performed by arranging a microwave heating target material in a strong area.
Here, the single mode cavity refers to a microwave irradiation space in which a specific standing wave can be stably formed. A standing wave is a wave that appears to oscillate without a waveform progressing, and a state in which the position of a place where the electric field intensity is 0 and a place where the electric field intensity is strong does not change is created. In particular, when a standing wave of TMnm0 mode (n is an integer of 0 or more and m is an integer of 1 or more) is formed by a cylindrical resonance cavity (cavity), a microchannel is formed in the reaction tube channel portion arranged on the central axis of the cylinder. In addition to being able to irradiate the waves in a concentrated manner, the electric field intensity distribution is uniform in the axial direction of the central axis, and the reaction liquid can always be irradiated with microwaves having a controlled electric field intensity. At this time, by configuring the reaction tube channel with a material that easily transmits microwaves, the microwaves directly reach the internal solution, and the reaction liquid can be directly dielectrically heated. Since the dielectric heating can generate heat in a much shorter time than the conventional heating by heat transfer, the solution can be heated quickly to a predetermined reaction temperature. In addition, the chemical reaction of the metal precursor substance in the reaction solution may be promoted by microwave irradiation. In this case, not only the time required for heating but also the reduction of the reaction time can be expected.
The electromagnetic wave irradiation means used in the present invention is preferably one that can irradiate the electromagnetic wave in a concentrated manner on the reaction solution.
For example, as one of electromagnetic wave irradiation spaces having a structure capable of concentrating an electric field, there is a method of using a container that can stably form a specific standing wave using a space called a cavity resonator. FIG. 2 shows the electric field strength distribution of a standing wave called TM010 formed in a cylindrical cavity resonator. In the figure, (A) is an overall view of the cavity resonator 11, (B) is a graph corresponding to (A) above, showing the relationship between the cylindrical inner diameter direction of the cavity resonator and the electric field strength, and (C) is the above-mentioned graph. It is a graph which shows the relationship between the axial direction of the cylinder of the cavity resonator corresponding to (A), and electric field strength. 2A, 11 is a cavity resonator, 12 is a microwave irradiation port, and the graph of FIG. 2B shows the electric field strength in the radial direction of the cavity resonator 11 (the horizontal axis is the cavity). This corresponds to the radius of the resonator 11). With the standing wave of TM 010, it can be seen that concentrate the electric field in the center of the cylinder. The graph of FIG. 2C shows the electric field strength with respect to the axial direction on the central axis of the cavity resonator 11 (the vertical axis corresponds to the position on the central axis of the cylindrical cavity). With the standing wave of TM 010, the electric field intensity on the cylinder center axis is found to be uniform regardless of position. In other words, using a cavity resonator having a standing wave of TM010 formed in a cylinder, a tubular reactor arranged along the central axis of the cylinder always has a microwave with a strong and uniform electric field. Can be irradiated. In FIG. 2, TM 010 has been described. However, a standing wave of TM mn0 (m is an integer of 0 or more and n is an integer of 1 or more) has a place where an electric field concentrates in the radial direction of the cylinder and is parallel to the central axis. Since the region has a uniform electric field strength, it can be used similarly. Further, although an electric field has been described in FIG. 2, since electromagnetic waves also have a heating action by a magnetic field, the same effect can be obtained even when a portion where the magnetic field is strong is used.
もうひとつの電界集中方法として、電磁波を反射させるミラーを用いる方法もある。特開２００６−１７３０６９号及び同２００６−２８６５８８号の各公報に記載されているような、楕円型の電磁波反射空間を用いた方法を用いることができる。楕円の一つの焦点から電磁波を供給させれば、もうひとつの焦点に電磁波を集中させることができる。この焦点の部分に反応液が通過するように反応管を配置することで同様の効果を得ることができる。 As another electric field concentration method, there is a method using a mirror that reflects electromagnetic waves. A method using an elliptical electromagnetic wave reflection space as described in JP-A Nos. 2006-173069 and 2006-286588 can be used. If electromagnetic waves are supplied from one focal point of the ellipse, the electromagnetic waves can be concentrated on the other focal point. A similar effect can be obtained by arranging the reaction tube so that the reaction solution passes through the focal portion.
本発明では、シングルモードキャビティの空胴共振器として、例えば、ＴＭ０１０シングルモードキャビティの他に、ＴＭ１１０モードキャビティ、ＴＭ２１０モードキャビティ、ＴＭ０２０モードキャビティ、ＴＥ０１モードキャビティなどが用いられる。また、流通管としては、照射するマイクロ波周波数が２．４〜２．５ＧＨｚでは内径２．９ｍｍ以下のミリメートルサイズの流通管、例えば、１．５ｍｍ以上２ｍｍ以下、１ｍｍ以上１．５ｍｍ以下、０．５ｍｍ以上１ｍｍ以下の流通管が用いられる。照射するマイクロ波周波数が２．４ＧＨより小さい場合は、流通管の太さはより太くても良いが、マイクロ波周波数が２．５ＧＨｚより大きな場合は、より細い流通管が望ましい。 In the present invention, as a cavity resonator of a single mode cavity, for example, a TM 110 mode cavity, a TM 210 mode cavity, a TM 020 mode cavity, a TE 01 mode cavity and the like are used in addition to a TM 010 single mode cavity. In addition, as a flow tube, when a microwave frequency to be irradiated is 2.4 to 2.5 GHz, a millimeter-size flow tube having an inner diameter of 2.9 mm or less, for example, 1.5 mm to 2 mm, 1 mm to 1.5 mm, 0 A flow pipe of 5 mm or more and 1 mm or less is used. If the microwave frequency to be irradiated is smaller than 2.4 GH, the thickness of the flow tube may be larger, but if the microwave frequency is larger than 2.5 GHz, a thinner flow tube is desirable.
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.
本発明では、キャビティ内に配置する流通管の本数は、単数に限らず、複数配置することも適宜可能であり、また、複数の流通管を適宜の接続方法で接続して配置することで、流通する溶液に対するマイクロ波加熱効率を向上させることが可能である。単数の流通管を配置する方式に限らず、例えば２〜８本の流通管を配置する方式や、単数であっても、螺旋型の流通管を配置する方式など、適宜の方式を採用することができる。 In the present invention, the number of flow pipes arranged in the cavity is not limited to a single one, and a plurality of flow pipes can be appropriately arranged, and a plurality of flow pipes are connected and arranged by an appropriate connection method. It is possible to improve the microwave heating efficiency for the flowing solution. Not only the method of arranging a single flow pipe, but also adopting an appropriate method such as a method of arranging 2 to 8 flow pipes or a method of arranging a spiral flow pipe even if a single flow pipe is used. Can do.
本発明では、流通管の内径を２．９ｍｍ以下のミリメートルサイズに細くすることにより、所期の効果が得られるが、流通管の内側に対して、上述のような、流通管の内側と流通する溶液との接触面積を拡大できる適宜の加工を施すことで、更にその効果を向上させることができる。 In the present invention, the desired effect can be obtained by reducing the inner diameter of the flow pipe to a millimeter size of 2.9 mm or less. The effect can be further improved by performing appropriate processing that can expand the contact area with the solution to be performed.
本発明では、見かけの誘電損率を大きくする方法として、被加熱対象物質とそれを保持する容器（流通管）壁面とに生じる相互作用を用いることを一つの特徴としている。例えば、帯電した壁面近傍の被加熱対象物質の分子は、壁面の電荷により、誘電分極が生じる。誘電分極は、電荷の偏りが生じる現象であり、この電荷の偏りにより、マイクロ波の吸収が高くなる。 In the present invention, as a method for increasing the apparent dielectric loss factor, one feature is to use an interaction that occurs between a substance to be heated and a wall surface of a container (circulation pipe) that holds the substance to be heated. For example, dielectric polarization occurs in the molecules of the material to be heated near the charged wall surface due to the wall surface charge. Dielectric polarization is a phenomenon in which a charge bias occurs, and microwave absorption increases due to this charge bias.
本発明では、流通管表面による誘電分極を高めるために、流通管の接触面積を広くする手段が採用される。例えば、容器を小さくすることにより、反応液の体積当たりの表面積を高める方法、また、流通管を、図に示すように、細長くする方法、扁平にする方法、などが採用される。 In the present invention, in order to increase the dielectric polarization due to the surface of the flow pipe, means for widening the contact area of the flow pipe is employed. For example, a method of increasing the surface area per volume of the reaction liquid by reducing the container, a method of elongating the flow pipe as shown in the drawing, a method of flattening, etc. are employed.
本発明では、前述のように、電界を集中させた部位に、流通管に保持した反応液を配置することで、非極性溶媒をもマイクロ波加熱することが可能である。本発明では、反応液の流体を流通させる流通管が用いられる。 In the present invention, as described above, the nonpolar solvent can also be microwave-heated by disposing the reaction liquid held in the flow tube at the site where the electric field is concentrated. In the present invention, a flow pipe for circulating the fluid of the reaction solution is used.
前記の流通管の長さ方向に均一かつ集中的に電磁波を照射する（マイクロ波加熱する）。これにより流通管内の電磁波照射空間の反応液を流通方向にわたって均一に集中的に加熱できる。本明細書において、電磁波を均一に照射するとは、マイクロ波照射空間のうち、反応管部分に高いエネルギー密度の空間を形成させることをいい、均一に照射するとはこの反応管部分のどの位置でも、一様なエネルギー密度を有することをいう。この手段として、前記のように、例えば、流通管の照射空間内に定在波を形成する共振空胴を設けることが好ましい。このために用いる金属微粒子合成装置を図面を参照して説明する。 Irradiate electromagnetic waves uniformly and intensively in the length direction of the flow pipe (microwave heating). Thereby, the reaction liquid in the electromagnetic wave irradiation space in the flow pipe can be heated uniformly and concentrated in the flow direction. In this specification, to uniformly irradiate electromagnetic waves means to form a high energy density space in the reaction tube portion of the microwave irradiation space, and to uniformly irradiate at any position of this reaction tube portion, It means having a uniform energy density. As this means, as described above, for example, it is preferable to provide a resonant cavity that forms a standing wave in the irradiation space of the flow tube. A metal fine particle synthesizer used for this purpose will be described with reference to the drawings.
図１は、マイクロ波利用化学反応装置の構成例を示す。図１の装置は、マイクロ波発振器・制御器６、ＴＭ０１０キャビティ２、送液ポンプ３、からなる。キャビティは、内部に円筒型の空間を有する金属製の空胴共振器として構成したものである。この空間は、ＴＭ０１０と呼ばれる定在波が形成できるように、その内寸を適宜設定することができる。 FIG. 1 shows a configuration example of a microwave-based chemical reaction apparatus. The apparatus shown in FIG. 1 includes a microwave oscillator / controller 6, a TM 010 cavity 2, and a liquid feed pump 3. The cavity is configured as a metal cavity resonator having a cylindrical space inside. The internal dimensions of this space can be set as appropriate so that a standing wave called TM010 can be formed.
ＴＭ０１０の定在波は図２中の下のグラフに示すよう中心部に電界が集中しており、軸に沿っては均一な電界強度分布を有している。この中心軸に沿って、貫通するように、石英ガラス管等から構成される反応管７を設置する。反応液８が、この石英ガラス管を流通できるように、片側に、送液ポンプ３を取り付けた。石英ガラス管の反対側には、流体の温度を計測できるように、温度計５として熱電対を取り付けた。また、内部の電界強度を計測するために、電界モニター４を取り付けた。 The standing wave of TM 010 has an electric field concentrated at the center as shown in the lower graph in FIG. 2, and has a uniform electric field intensity distribution along the axis. A reaction tube 7 composed of a quartz glass tube or the like is installed so as to penetrate along the central axis. A liquid feed pump 3 was attached to one side so that the reaction liquid 8 could flow through this quartz glass tube. A thermocouple was attached as a thermometer 5 on the opposite side of the quartz glass tube so that the temperature of the fluid could be measured. An electric field monitor 4 was attached in order to measure the internal electric field strength.
マイクロ波発振器・制御器６から発生したマイクロ波は、マイクロ波照射口１を介して円筒型のＴＭ０１０キャビティ２に照射される。このときのマイクロ波の発振周波数もしくは円筒型キャビティ２の内径を、キャビティ２内部にＴＭ０１０の定在波が形成できるよう調整することができる。このとき、電界モニター４からの信号をもとに、ＴＭ０１０の定在波が形成されているか知ることができる。もし、定在波が形成されていない場合は、マイクロ波発振器・制御器６から発振されるマイクロ波発振周波数を変化させるか、キャビティ内径を調整するなどにより、定在波が形成されるよう、フィードバック制御を行ってもよい。
マイクロ波発振器・制御器６には、キャビティからの反射波を低減させるため、整合器を組み込んでも良い。また、反射波により、マイクロ波発振器や制御器の破損を防ぐために、反射波を吸収するアイソレータを組み込んでも良い。
The microwave generated from the microwave oscillator / controller 6 is irradiated to the cylindrical TM 010 cavity 2 through the microwave irradiation port 1. The oscillation frequency or the inner diameter of the cylindrical cavity 2 of the microwave in this case, can be adjusted to a standing wave of TM 010 in the cavity 2 can be formed. At this time, based on a signal from the field monitor 4, it is possible to know the standing wave of TM 010 is formed. If the standing wave is not formed, the standing wave is formed by changing the microwave oscillation frequency oscillated from the microwave oscillator / controller 6 or adjusting the cavity inner diameter. Feedback control may be performed.
The microwave oscillator / controller 6 may incorporate a matching unit in order to reduce the reflected wave from the cavity. Further, an isolator that absorbs the reflected wave may be incorporated in order to prevent the microwave oscillator and the controller from being damaged by the reflected wave.
反応管としては、内径１ｍｍ、外径３ｍｍ、長さ２００ｍｍのテフロン管を用いた。このうち、長さ方向の１００ｍｍの部分をキャビティ内に入れ、この部分にマイクロ波が照射されるようにした。ただし、反応管の長さやマイクロ波照射部の長さは、これ以上でも以下でもよい。マイクロ波出力は、反応管出口に設置した温度計５の値を一定に保てるよう、マイクロ波発振器・制御器６を介して自動調製してもよい。反応管温度を測る方法としては、放射温度計により反応管外壁の温度を非接触で測る方法もある。 As the reaction tube, a Teflon tube having an inner diameter of 1 mm, an outer diameter of 3 mm, and a length of 200 mm was used. Among these, a 100 mm portion in the length direction was placed in the cavity, and microwaves were irradiated to this portion. However, the length of the reaction tube and the length of the microwave irradiation unit may be longer or shorter. The microwave output may be automatically adjusted via the microwave oscillator / controller 6 so that the value of the thermometer 5 installed at the outlet of the reaction tube can be kept constant. As a method for measuring the temperature of the reaction tube, there is also a method of measuring the temperature of the outer wall of the reaction tube in a non-contact manner using a radiation thermometer.
本発明を実現するための、第２の構成例を図２３に示す。これは反応液の供給方法としては、別々の調製した２種類以上の原料溶液を個別のポンプを用いて供給し、マイクロ波キャビティ２に流入する直前により、混合器１３により混合し、反応液とするものである。たとえば、金属前駆物質と添加物の反応性が高い場合などは、マイクロ波照射前に目的外の反応の進行が進み、目的外の粒子径分布を持つ金属ナノ粒子が合成される可能性があるが、本構成ではそのような場合でも、粒子径の揃った金属ナノ粒子の製造が可能である。 FIG. 23 shows a second configuration example for realizing the present invention. As a method for supplying the reaction solution, two or more kinds of raw material solutions prepared separately are supplied using individual pumps, and mixed by the mixer 13 immediately before flowing into the microwave cavity 2, and the reaction solution and To do. For example, when the reactivity between the metal precursor and the additive is high, the progress of unintended reaction may proceed before microwave irradiation, and metal nanoparticles having an unintended particle size distribution may be synthesized. However, in this configuration, even in such a case, metal nanoparticles having a uniform particle diameter can be produced.
本発明を実現するための、第３の構成例を図２４に示す。これは、マイクロ波照射後の反応液を別の温度調節器１４に導入するものである。反応時間が遅い場合は温度調節器で適切な温度に加温することで、金属ナノ粒子の成長を促進させることができる。また、反応時間が早い反応液の場合は、冷却することで、金属ナノ粒子の成長を停止させ、均一な粒径をもつ金属ナノ粒子の製造を行うことが可能である。 FIG. 24 shows a third configuration example for realizing the present invention. This is to introduce the reaction solution after microwave irradiation into another temperature controller 14. When the reaction time is slow, the growth of the metal nanoparticles can be promoted by heating to an appropriate temperature with a temperature controller. In the case of a reaction solution having a fast reaction time, it is possible to produce metal nanoparticles having a uniform particle size by cooling to stop the growth of metal nanoparticles.
本発明を実現するための、第４の構成例を図２５に示す。これは、マイクロ波照射後の反応液を再循環させ、再びマイクロ波を照射するものである。長時間マイクロ波を照射する必要がある場合に適した構成である。 A fourth configuration example for realizing the present invention is shown in FIG. In this method, the reaction liquid after microwave irradiation is recirculated and the microwave is irradiated again. This configuration is suitable when it is necessary to irradiate microwaves for a long time.
次に本発明を実施例に基づきさらに詳細に説明するが、本発明はこれに限定されるものではない。
図１に示すマイクロ波利用化学反応装置を用い、ＴＭ０１０キャビティ中心軸に沿って反応管として内径１ｍｍ、外径３ｍｍ長さ２００ｍｍのテフロン反応管を取り付けた。テフロン反応管の片側からエチレングリコールに溶解させた反応原料をシリンジポンプにより供給した。反応原料には、１００ｍｍの区間で均一なエネルギー分布をもつマイクロ波が照射される。これにより溶液温度が上昇する。溶液の温度は、ＴＭ０１０キャビティのマイクロ波照射空間の出口から１０ｍｍ離れた部分に挿入された熱電対により温度の計測を行い、この部分の温度が一定になるようマイクロ波電力の調整をフィードバック制御により行っている。
マイクロ波の周波数としては、後述の実施例２５では、２．４５ＧＨｚと５．８ＧＨｚのものを用い、それ以外では、２．４５ＧＨｚのものを用いた。
EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited to this.
A Teflon reaction tube having an inner diameter of 1 mm, an outer diameter of 3 mm, and a length of 200 mm was attached as a reaction tube along the center axis of the TM010 cavity using the microwave chemical reaction apparatus shown in FIG. A reaction raw material dissolved in ethylene glycol was supplied from one side of a Teflon reaction tube by a syringe pump. The reaction raw material is irradiated with microwaves having a uniform energy distribution in a section of 100 mm. This raises the solution temperature. The temperature of the solution is measured by a thermocouple inserted in a portion 10 mm away from the exit of the microwave irradiation space of the TM 010 cavity, and the microwave power adjustment is feedback controlled so that the temperature of this portion becomes constant. It is done by.
As the frequency of the microwave, those of 2.45 GHz and 5.8 GHz were used in Example 25 described later, and those of 2.45 GHz were used otherwise.
反応原料を含んだ溶液はマイクロ波照射により粒子形成が促進され、反応管出口では、ナノ粒子懸濁液として回収される。ナノ粒子懸濁液は、紫外可視吸収スペクトルメータ（日立Ｕ−３３１０）により吸収スペクトルを測定した。また動的光散乱（ＭＡＬＶＥＲＮ ＩＮＳＴＲＵＭＥＮＴＳ製Ｚｅｔａｓｉｚｅｒ Ｎａｎｏ−Ｓ）により粒子径の測定を行った。回収されたナノ粒子を乾燥したものをＴＥＭ（ＦＥＩ製ＴＥＣＮＡＩ Ｇ２）により観測した。反応後の溶液は孔径０．０２μｍのフィルターにより濾過し、合成した金属粒子と未反応液を分離した。このうち未反応液中に含まれる原料物質の濃度を誘導結合型原子吸光装置（セイコーインスツルメンツ製、ＳＰＳ１５００）により分析し、以下の式より反応率を求めた。
反応率＝（１−未反応液に含まれる原料物質の濃度）÷（反応前溶液に含まれる原料物質の濃度）×１００％
Particle formation of the solution containing the reaction raw material is promoted by microwave irradiation, and is recovered as a nanoparticle suspension at the reaction tube outlet. The nanoparticle suspension was measured for the absorption spectrum with an ultraviolet-visible absorption spectrum meter (Hitachi U-3310). The particle size was measured by dynamic light scattering (Zetasizer Nano-S manufactured by MALVERN INSTRUMENTS). The recovered nanoparticles obtained by drying was observed by TEM (FEI manufactured TECNAI G 2). The solution after the reaction was filtered through a filter having a pore size of 0.02 μm to separate the synthesized metal particles and the unreacted liquid. Among these, the concentration of the raw material contained in the unreacted solution was analyzed by an inductively coupled atomic absorption device (manufactured by Seiko Instruments Inc., SPS1500), and the reaction rate was determined from the following equation.
Reaction rate = (1-concentration of raw material contained in unreacted liquid) ÷ (concentration of raw material contained in pre-reaction solution) × 100%
表１、２に実施例として用いた反応原料の組成を示す。マイクロ波の周波数としては、後述の実施例２５では、２．４５ＧＨｚと５．８ＧＨｚのものを用い、それ以外では、２．４５ＧＨｚのものを用いた。
実施例１〜１６については、金属前駆物質として硝酸銀を用い、液媒体としてエチレングリコールを用いて、銀ナノ粒子の合成を行ったものである。添加剤としてポリビニルピロリドンを加えることで、粒子サイズの調整や合成した銀ナノ粒子の安定化を行っている。反応原料は特に記述がない限り、送液速度１０ｍｌ／ｈで行った。照射マイクロ波パワーは１５Ｗであり、そのときの溶液温度は１６０℃であった。
Tables 1 and 2 show the compositions of the reaction raw materials used as examples. As the frequency of the microwave, those of 2.45 GHz and 5.8 GHz were used in Example 25 described later, and those of 2.45 GHz were used otherwise.
In Examples 1 to 16, silver nanoparticles were synthesized using silver nitrate as the metal precursor and ethylene glycol as the liquid medium. By adding polyvinylpyrrolidone as an additive, the particle size is adjusted and the synthesized silver nanoparticles are stabilized. The reaction raw materials were carried out at a liquid feed rate of 10 ml / h unless otherwise specified. The irradiation microwave power was 15 W, and the solution temperature at that time was 160 ° C.
実施例１〜３には、添加剤のポリビニルピロリドンの数平均分子量を変えた場合、合成された銀ナノ粒子に及ぼす影響を調べたものである。このときの反応原料の供給速度は１０ｍｌ／ｈであり、１５Ｗのマイクロ波を連続的に照射している。反応液の温度は、１６０℃であった。図３に、合成された銀ナノ粒子の粒子径分布を示す。添加剤の組成を変えることで、目的とする銀ナノ粒子の粒子サイズを調整可能なことがわかる。 In Examples 1 to 3, the effect on the synthesized silver nanoparticles when the number average molecular weight of the polyvinylpyrrolidone additive was changed was investigated. The supply rate of the reaction raw material at this time is 10 ml / h, and 15 W of microwaves is continuously irradiated. The temperature of the reaction solution was 160 ° C. FIG. 3 shows the particle size distribution of the synthesized silver nanoparticles. It can be seen that the particle size of the target silver nanoparticles can be adjusted by changing the composition of the additive.
実施例４〜８には、添加剤のポリビニルピロリドンの添加量を変えた場合、合成された銀ナノ粒子に及ぼす影響を調べたものである。このときの反応原料の供給速度は１０ｍｌ／ｈであり、１５Ｗのマイクロ波を連続的に照射している。反応液の温度は、１６０℃であった。図４に、合成された銀ナノ粒子の粒子径分布を示す。添加剤の添加量を変えることで、目的とする銀ナノ粒子の粒子サイズを調整可能なことがわかる。 In Examples 4 to 8, the influence on the synthesized silver nanoparticles when the addition amount of the additive polyvinylpyrrolidone was changed was examined. The supply rate of the reaction raw material at this time is 10 ml / h, and 15 W of microwaves is continuously irradiated. The temperature of the reaction solution was 160 ° C. FIG. 4 shows the particle size distribution of the synthesized silver nanoparticles. It turns out that the particle size of the target silver nanoparticle can be adjusted by changing the addition amount of the additive.
実施例９〜１４には、金属前駆物質である硝酸銀の濃度を変えた場合、合成された銀ナノ粒子に及ぼす影響を調べたものである。このときの反応原料の供給速度は１０ｍｌ／ｈであり、１５Ｗのマイクロ波を連続的に照射している。反応液の温度は、１６０℃であった。図５に、合成された銀ナノ粒子の粒子径分布を示す。硝酸銀の添加量を変えることで、目的とする銀ナノ粒子の粒子サイズを調整可能なことがわかる。図６は、実施例１４において溶液の供給速度１００ｍｌ／ｈ、反応温度１６０℃の条件で合成した銀ナノ粒子の透過電子顕微鏡画像である。平均粒子径９．８ｎｍで、標準偏差が０．９とＣＶ値が９．２％（５０個分析の結果））の分布をもつ粒子径の均一な銀ナノ粒子が合成されている。 In Examples 9 to 14, the effect on the synthesized silver nanoparticles when the concentration of silver nitrate as the metal precursor was changed was examined. The supply rate of the reaction raw material at this time is 10 ml / h, and 15 W of microwaves is continuously irradiated. The temperature of the reaction solution was 160 ° C. FIG. 5 shows the particle size distribution of the synthesized silver nanoparticles. It can be seen that the target silver nanoparticle size can be adjusted by changing the amount of silver nitrate added. 6 is a transmission electron microscope image of silver nanoparticles synthesized in Example 14 under the conditions of a solution supply rate of 100 ml / h and a reaction temperature of 160 ° C. FIG. Silver nanoparticles having a uniform particle diameter having an average particle diameter of 9.8 nm, a standard deviation of 0.9, and a CV value of 9.2% (result of analysis of 50 particles) are synthesized.
実施例１５は、長時間の連続合成をおこなったものである。その際の溶液温度の時間変化を図７に、マイクロ波照射パワー（ＴＭ０１０キャビティーへの入射波―反射波）を図８に示す。このときの反応原料の供給速度は１０ｍｌ／ｈであり、５時間以上にわたって連続的に銀ナノ粒子の合成を行っている。図９には、１時間後ごとにサンプリングした反応後溶液の粒子分布を示す。１５ｎｍ程度の非常に小さく、揃った粒子が合成されていることがわかる。また、図１０には吸収スペクトルを示す。吸収スペクトルでは３９５ｎｍの銀ナノ粒子特有の吸収スペクトルが確認されている。図７、図８、図９、図１０からあきらかなように、長時間にわたって安定した銀ナノ粒子が連続的に合成できていることがわかる。このときの、金属前駆物質が金属ナノ粒子に変換された、反応添加率を分析したところ、いずれの時間帯においても９５％以上であり、高効率に金属ナノ粒子が製造できている。 In Example 15, continuous synthesis for a long time was performed. The time change of the solution temperature at that time is shown in FIG. 7, and the microwave irradiation power (incident wave-reflected wave to TM010 cavity) is shown in FIG. The supply rate of the reaction raw material at this time is 10 ml / h, and the silver nanoparticles are continuously synthesized over 5 hours or more. FIG. 9 shows the particle distribution of the post-reaction solution sampled every hour. It can be seen that very small and uniform particles of about 15 nm are synthesized. FIG. 10 shows an absorption spectrum. In the absorption spectrum, an absorption spectrum peculiar to 395 nm silver nanoparticles is confirmed. As is apparent from FIGS. 7, 8, 9, and 10, it can be seen that stable silver nanoparticles can be synthesized continuously over a long period of time. When the reaction addition rate at which the metal precursor was converted into metal nanoparticles at this time was analyzed, it was 95% or more in any time zone, and metal nanoparticles could be produced with high efficiency.
実施例７の条件において、反応液の送液速度を変えた結果を図１１に示す。送液速度１０ｍｌ／ｈから２００ｍｌ／ｈで実施した。１０ｍｌ／ｈから１００ｍｌ／ｈでは、合成される銀ナノ粒子の粒子径分布に大きな違いはないが、２００ｍｌ／ｈでは粒子の均一性が著しく損なわれていることがわかる。粒子が均一性であるとは粒子サイズ分布が所定値を中心に狭い分布範囲にあることを言う。これは、マイクロ波照射空間が１００ｍｍであり、送液速度が速い場合、銀ナノ粒子合成に必要なマイクロ波が十分照射されていないためと考えられる。このような場合、マイクロ波照射空間であるＴＭ０１０キャビティを長いものに交換すればよいと考えられる。ＴＭ０１０キャビティの特徴として、円筒長を長くしても、均一なマイクロ波照射空間を作り出すことができる。 FIG. 11 shows the result of changing the liquid feeding speed of the reaction liquid under the conditions of Example 7. The feeding speed was 10 ml / h to 200 ml / h. From 10 ml / h to 100 ml / h, there is no significant difference in the particle size distribution of the synthesized silver nanoparticles, but at 200 ml / h, the uniformity of the particles is significantly impaired. The term “particle is uniform” means that the particle size distribution is in a narrow distribution range centering on a predetermined value. This is presumably because the microwave irradiation space is 100 mm and the microwave necessary for silver nanoparticle synthesis is not sufficiently irradiated when the liquid feeding speed is high. In such a case, it is considered that the TM 010 cavity that is the microwave irradiation space may be replaced with a long one. As a feature of the TM010 cavity, a uniform microwave irradiation space can be created even if the cylinder length is increased.
実施例１５および実施例１６は、溶媒を変化させて合成される銀ナノ粒子の粒子径分布の違いを調べたものである。図１２にグリセロール溶媒（反応温度 ２００℃）、図１３にベンジルアルコール溶媒（反応温度１８０度）で行ったときの合成された銀ナノ粒子の粒径分布を示す。エチレングリコール以外の液溶媒においても、金属ナノ粒子の合成が可能であることがわかる。 In Example 15 and Example 16, the difference in the particle size distribution of silver nanoparticles synthesized by changing the solvent was examined. FIG. 12 shows the particle size distribution of the synthesized silver nanoparticles when glycerol solvent (reaction temperature 200 ° C.) is used, and FIG. 13 shows benzyl alcohol solvent (reaction temperature 180 ° C.). It can be seen that the metal nanoparticles can be synthesized even in a liquid solvent other than ethylene glycol.
実施例１７として金ナノ粒子の合成を行った。金属前駆物質として塩化金酸を、液溶媒として水を用い、還元剤としてクエン酸を反応液に加えた。反応温度９０℃送液速度５ｍｌ／ｈで金ナノ粒子の合成をおこなったときの、反応後溶液の粒径分布を図１４に示す。銀ナノ粒子同様、粒子径分布のそろった金ナノ粒子の連続合成が可能であることがわかる。 As Example 17, gold nanoparticles were synthesized. Chloroauric acid was used as a metal precursor, water was used as a liquid solvent, and citric acid was added as a reducing agent to the reaction solution. FIG. 14 shows the particle size distribution of the post-reaction solution when gold nanoparticles were synthesized at a reaction temperature of 90 ° C. and a liquid feed rate of 5 ml / h. It can be seen that gold nanoparticles having a uniform particle size distribution can be continuously synthesized as well as silver nanoparticles.
実施例１８および実施例１９は白金ナノ粒子およびパラジウムナノ粒子の合成例である。図１５は反応温度１６０℃ 送液速度１０ｍｌ／ｈで合成した場合の白金粒子およびパラジウム粒子の粒子径分布を示す。銀ナノ粒子同様に、粒子径の揃った粒子の合成が可能であることがわかる。
実施例２０および実施例２１は、生産性を考慮し、金属前駆物質を高濃度とした場合の、合成された粒子に及ぼす影響を調べたものである。図１６は、反応温度１６０℃、送液速度１０ｍｌ／ｈで合成した場合の銀ナノ粒子および白金ナノ粒子の粒径分布を示している。金属前駆物質を高濃度として合成した場合においても、粒子径分布の揃った粒子が合成されることがわかる。
実施例２２〜２４は、添加剤として高分子分散剤を用いた場合の、合成された粒子に及ぼす影響を調べたものである。実施例２２〜２４で使用した高分子分散剤は数平均分子量が１０，０００〜５０，０００の分散剤である。図１７は実施例２２の条件で合成した銀ナノ粒子、図１８は実施例２３の条件で合成した白金ナノ粒子、図１９は実施例２４の条件で合成した白金ナノ粒子の透過電子顕微鏡画像である。粒子径の揃った球形のナノ粒子が合成されていることがわかる。
実施例２５は、照射したマイクロ波の周波数を変えた場合の、合成された粒子に及ぼす影響を調べたものである。図２０は、マイクロ波周波数が２．４５ＧＨｚおよび５．８ＧＨｚで合成した銀ナノ粒子の粒子径分布を示している。マイクロ波周波数が５．８ＧＨｚにおいても、粒子径分布の揃った銀ナノ粒子が合成されていることがわかる。
実施例２６は、図１で示される構成例と図２３で示される第２の構成例にて、銀ナノ粒子を合成した場合の、合成された粒子に及ぼす影響を比較したものである。図２１は反応温度１６０℃ 総送液速度１０ｍｌ／ｈで合成した場合の銀ナノ粒子の粒子径分布を示している。硝酸銀を含むエチレングリコール溶液と、添加剤を含むエチレングリコール溶液を個別に供給した場合においても、粒子径分布の揃った銀ナノ粒子が合成されることがわかる。
実施例２７は、図２４で示される第３の構成例にて銀ナノ粒子を合成した場合の、合成された粒子に及ぼす影響を調べたものである。図２２は、温度調節器を用いて冷却した場合における銀ナノ粒子の透過電子顕微鏡画像である。粒子径の揃った球形の銀ナノ粒子が合成されていることがわかる。
Examples 18 and 19 are synthesis examples of platinum nanoparticles and palladium nanoparticles. FIG. 15 shows the particle size distribution of platinum particles and palladium particles when synthesized at a reaction temperature of 160 ° C. and a liquid feed rate of 10 ml / h. It turns out that the synthesis | combination of the particle | grains with a uniform particle diameter is possible like silver nanoparticle.
In Example 20 and Example 21, in consideration of productivity, the influence on the synthesized particles when the concentration of the metal precursor is high is examined. FIG. 16 shows the particle size distribution of silver nanoparticles and platinum nanoparticles when synthesized at a reaction temperature of 160 ° C. and a liquid feed rate of 10 ml / h. It can be seen that even when the metal precursor is synthesized at a high concentration, particles having a uniform particle size distribution are synthesized.
In Examples 22 to 24, the effect of using a polymer dispersant as an additive on the synthesized particles was examined. The polymer dispersant used in Examples 22 to 24 is a dispersant having a number average molecular weight of 10,000 to 50,000. 17 is a silver nanoparticle synthesized under the conditions of Example 22, FIG. 18 is a platinum nanoparticle synthesized under the conditions of Example 23, and FIG. 19 is a transmission electron microscope image of the platinum nanoparticles synthesized under the conditions of Example 24. is there. It can be seen that spherical nanoparticles having a uniform particle size are synthesized.
In Example 25, the influence on the synthesized particles when the frequency of the irradiated microwave was changed was examined. FIG. 20 shows the particle size distribution of silver nanoparticles synthesized at microwave frequencies of 2.45 GHz and 5.8 GHz. It can be seen that silver nanoparticles having a uniform particle size distribution were synthesized even at a microwave frequency of 5.8 GHz.
Example 26 is a comparison of the effects on the synthesized particles when silver nanoparticles are synthesized in the configuration example shown in FIG. 1 and the second configuration example shown in FIG. FIG. 21 shows the particle size distribution of silver nanoparticles when synthesized at a reaction temperature of 160 ° C. and a total liquid feeding rate of 10 ml / h. It can be seen that silver nanoparticles having a uniform particle size distribution are synthesized even when an ethylene glycol solution containing silver nitrate and an ethylene glycol solution containing an additive are separately supplied.
In Example 27, the influence on the synthesized particles when silver nanoparticles were synthesized in the third configuration example shown in FIG. 24 was examined. FIG. 22 is a transmission electron microscope image of silver nanoparticles when cooled using a temperature controller. It can be seen that spherical silver nanoparticles with uniform particle diameters are synthesized.
１ マイクロ波照射口
２ ＴＭ０１０キャビティ
３ 送液ポンプ
４ 電界モニター
５ 温度計
６ マイクロ波発振器・制御器
７ 反応管
８ 反応液
１１ 空胴共振器
１２ マイクロ波照射口
１３ 混合器
１４ 温度調節器
1 Microwave Irradiation Port 2 TM 010 Cavity 3 Liquid Pump 4 Electric Field Monitor 5 Thermometer 6 Microwave Oscillator / Controller 7 Reaction Tube 8 Reaction Liquid 11 Cavity Resonator 12 Microwave Irradiation Port 13 Mixer 14 Temperature Controller
Claims (8)
前記電磁波の周波数が２．４〜２．５ＧＨｚであり、且つ、前記流通管の内径が２．９ミリメートル以下である、製造方法。 The reaction liquid containing the metal precursor is circulated in a flow tube disposed in a resonance cavity in which an electromagnetic wave standing wave TM mn0 (m is an integer of 0 or more and n is an integer of 1 or more) is formed, Irradiate a uniform and concentrated electromagnetic wave toward the flow pipe in the resonance cavity, and uniformly heat the electromagnetic wave irradiation space in the flow pipe over the entire length in the flow direction by this electromagnetic wave irradiation. A method for producing metal fine particles to be produced ,
The manufacturing method in which the frequency of the electromagnetic wave is 2.4 to 2.5 GHz, and the inner diameter of the flow pipe is 2.9 millimeters or less .
And cooling by introducing the reaction solution which has passed through the electromagnetic wave irradiation space temperature controller, method for producing metal fine particles according to any one of claims 1-7.
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| US20200374994A1 (en) * | 2019-01-22 | 2020-11-26 | Jiangnan University | Microwave Processing Equipment for Continuous Flow Liquids |
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| JP5769287B2 (en) * | 2009-12-05 | 2015-08-26 | 国立研究開発法人産業技術総合研究所 | Method for producing metal fine particles |
| JP5888804B2 (en) * | 2011-07-11 | 2016-03-22 | 国立研究開発法人産業技術総合研究所 | Method for producing metal fine particles |
| WO2013039117A1 (en) * | 2011-09-12 | 2013-03-21 | 独立行政法人産業技術総合研究所 | Continuous synthesis method for metal core and oxide shell core-shell structure nanoparticles, continuous synthesis apparatus for same, and core-shell structure nanoparticles |
| JP6362206B2 (en) * | 2013-09-19 | 2018-07-25 | 株式会社新光化学工業所 | Copper nanoparticle colloid, copper nanoparticle, copper nanoparticle paste using the same, copper nanoparticle core-shell metal, copper nanoparticle colloid production apparatus, copper nanoparticle colloid production method |
| JP6393344B2 (en) * | 2014-12-22 | 2018-09-19 | 株式会社新光化学工業所 | Nanoparticle production method and production apparatus, and nanoparticle produced thereby |
| JP6145601B2 (en) * | 2016-02-10 | 2017-06-14 | 国立研究開発法人産業技術総合研究所 | Method for producing metal fine particles and solvent containing metal fine particles for microwave irradiation |
| JP2017226916A (en) * | 2016-06-20 | 2017-12-28 | 株式会社新光化学工業所 | Production method of fine particles and production apparatus and fine particles |
| JP7233041B2 (en) * | 2016-08-10 | 2023-03-06 | 矢崎総業株式会社 | Hydrogen production equipment |
| JP6795424B2 (en) * | 2017-02-22 | 2020-12-02 | トヨタ自動車株式会社 | Manufacturing method of silver nanoparticles |
| JP7018644B2 (en) * | 2017-10-18 | 2022-02-14 | 国立研究開発法人産業技術総合研究所 | Reaction product manufacturing equipment and its method |
| JP7239297B2 (en) * | 2018-10-22 | 2023-03-14 | トヨタ自動車株式会社 | Method for producing silver nanowires |
| WO2023162235A1 (en) * | 2022-02-28 | 2023-08-31 | 株式会社安川電機 | Metal wire joining method and metal wire joining system |
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| WO1988005035A1 (en) * | 1986-12-30 | 1988-07-14 | Hallsworth & Associates Pty. Limited | Improvements in or relating to the formation of metal alkoxides and metal powders by the use of microwave radiation |
| US5471037A (en) * | 1992-08-18 | 1995-11-28 | E. I. Du Pont De Nemours And Company | Process for preparing polymeric material with microwave |
| EP0946414B1 (en) * | 1996-11-04 | 2005-06-29 | Materials Modification, Inc. | Microwave plasma chemical synthesis of ultrafine powders |
| JP3005683B1 (en) * | 1999-03-05 | 2000-01-31 | 大阪大学長 | Method for producing ultrafine particles and ultrafine particles |
| JP2001044175A (en) * | 1999-07-26 | 2001-02-16 | Shibaura Mechatronics Corp | Plasma processing apparatus |
| JP3740528B2 (en) * | 2002-02-05 | 2006-02-01 | 独立行政法人産業技術総合研究所 | Fine particle manufacturing method |
| US6833019B1 (en) * | 2003-01-31 | 2004-12-21 | The United States Of America As Represented By The Secretary Of The Navy | Microwave assisted continuous synthesis of nanocrystalline powders and coatings using the polyol process |
| JP2005133128A (en) * | 2003-10-29 | 2005-05-26 | Canon Inc | Apparatus and method for plasma treatment |
| JP4759668B2 (en) * | 2004-05-11 | 2011-08-31 | 株式会社Ｉｄｘ | Microwave heating device |
| JP4022590B2 (en) * | 2005-03-25 | 2007-12-19 | 株式会社エーイーティー | Microwave plasma generator |
| KR100809982B1 (en) * | 2006-09-21 | 2008-03-06 | 삼성전기주식회사 | Method for manufacturing copper nanoparticles using microwave |
| JP2008202125A (en) * | 2007-02-22 | 2008-09-04 | Tokai Rubber Ind Ltd | Method for manufacturing nanoparticle-containing solution, and conductive paste |
| JP2008246394A (en) * | 2007-03-30 | 2008-10-16 | 3R Corp | Method and apparatus for producing nanoparticle |
| JP2009064603A (en) * | 2007-09-05 | 2009-03-26 | Iwatani Internatl Corp | Conductive paste for mlcc |
| JP5268047B2 (en) * | 2007-09-25 | 2013-08-21 | 株式会社Ｉｄｘ | Microwave chemical reactor |
| KR100956684B1 (en) * | 2007-10-26 | 2010-05-10 | 삼성전기주식회사 | Manufacturing apparatus of nano-metal |
| JP5300014B2 (en) * | 2009-03-10 | 2013-09-25 | 独立行政法人産業技術総合研究所 | Method and apparatus for continuous microwave irradiation to fluid |
| JP5769287B2 (en) * | 2009-12-05 | 2015-08-26 | 国立研究開発法人産業技術総合研究所 | Method for producing metal fine particles |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200374994A1 (en) * | 2019-01-22 | 2020-11-26 | Jiangnan University | Microwave Processing Equipment for Continuous Flow Liquids |
| US11805578B2 (en) * | 2019-01-22 | 2023-10-31 | Jiangnan University | Microwave processing equipment for continuous flow liquids |
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| JP2020111831A (en) | 2020-07-27 |
| JP2017218667A (en) | 2017-12-14 |
| JP2015180776A (en) | 2015-10-15 |
| JP6436305B2 (en) | 2018-12-12 |
| JP2011137226A (en) | 2011-07-14 |
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