JP2016113306A - Producing method of nanoparticle - Google Patents
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Abstract
Description
本発明は、ナノ粒子の製造方法に関する。 The present invention relates to a method for producing nanoparticles.
現在、ナノ粒子を用いた研究が盛んに行われている。ナノ粒子とは、一般的に、三次元方向の全てがナノスケール（１ｎｍ〜１００ｎｍ）である粒子である。粒径が１００ｎｍ以下にまで減少すると、表面物性の顕在化や量子サイズ効果が発現し、バルクとは異なった物理的、化学的性質と機能を示すようになる。 Currently, research using nanoparticles is actively conducted. Nanoparticles are particles that are generally nanoscale (1 nm to 100 nm) in all three-dimensional directions. When the particle size is reduced to 100 nm or less, the manifestation of surface physical properties and the quantum size effect are exhibited, and physical and chemical properties and functions different from those of the bulk are exhibited.
粒径が小さい粒子を製造する方法としては、金属塩や錯体から金属を取り出し成長させる成長法と、バルクを小さく粉砕して粒子を得る細分化法の２種類に大別される。 Methods for producing particles having a small particle size are roughly classified into two types: a growth method in which a metal is extracted from a metal salt or complex and grown, and a fragmentation method in which particles are obtained by pulverizing a bulk into small particles.
気相法、液相法などの成長法は、化学反応生成であるため反応種によって組成が限定されるが、原子やイオンから粒子を成長させることができるため、粒径数ｎｍのナノ粒子を調製することができることから、ナノ粒子の製造方法として広く用いられている。
例えば特許文献１では、気相法による半導体ナノ粒子蛍光体の製造方法において、連続した工程で、且つ脱酸素雰囲気下で製造されることを特徴とする半導体ナノ粒子蛍光体の製造方法が開示されている。
Growth methods such as the vapor phase method and the liquid phase method are chemical reaction products, so the composition is limited depending on the reactive species. However, since particles can be grown from atoms and ions, nanoparticles with a particle size of several nanometers Since it can be prepared, it is widely used as a method for producing nanoparticles.
For example, Patent Document 1 discloses a method for producing a semiconductor nanoparticle phosphor, characterized by being produced in a continuous process and in a deoxygenated atmosphere in a method for producing a semiconductor nanoparticle phosphor by a vapor phase method. ing.
また、加水分解や脱水縮合などを利用するゾルゲル法は、組成は限定されるが、粒径や形状を制御できるため、ナノ粒子の製造方法として広く用いられている。
例えば特許文献２では、基板上に、金属アルコキシドを酸触媒の作用により部分加水分解するゾルゲル法で、微細孔を有する酸化膜を形成する酸化膜形成工程と、前記酸化膜を酸性の塩化スズ水溶液と接触させるＳｎ析出工程と、前記微細孔からＳｎ２＋イオンを除去するＳｎ２＋イオン除去工程と、前記酸化膜を金属キレート水溶液と接触させ、前記微細孔中に金属ナノ粒子を析出させる金属ナノ粒子析出工程と、前記微細孔から金属イオンを除去する金属イオン除去工程を備えることを特徴とする金属ナノ粒子無機複合体の製造方法が開示されている。
In addition, the composition of the sol-gel method using hydrolysis, dehydration condensation, and the like is limited, but since the particle size and shape can be controlled, it is widely used as a method for producing nanoparticles.
For example, in Patent Document 2, an oxide film forming step of forming an oxide film having micropores on a substrate by a sol-gel method in which a metal alkoxide is partially hydrolyzed by the action of an acid catalyst, and the oxide film is an acidic tin chloride aqueous solution. A Sn precipitation step for contacting with the metal, a Sn 2+ ion removal step for removing Sn 2+ ions from the micropores, and a metal nanoparticle for bringing the oxide film into contact with a metal chelate aqueous solution and depositing metal nanoparticles in the micropores A method for producing a metal nanoparticle inorganic composite comprising a precipitation step and a metal ion removal step of removing metal ions from the micropores is disclosed.
一方、細分化法はサブミクロン程度の粒径が限界であるが、組成が限定されないという利点がある。
例えば特許文献３では、固体粒子を液体中に混合した処理材料の供給口と吐出口を有するベッセルと、前記ベッセル内で駆動軸により回転されるローターと、ビーズミル用の媒体分離装置を有し、前記ベッセル内に供給された処理材料をビーズミル用の粉砕媒体とともに攪拌して微粉砕し、前記ビーズミル用の媒体分離装置で前記ビーズミル用の粉砕媒体から前記ビーズミルに供給された固体粒子を分離するビーズミルと、上記ビーズミルの供給口に通じる流出口及びビーズミルの吐出口に通じる流入口を有する槽と、前記槽内で回転する撹拌羽根と、前記槽内で超音波を発生する超音波発生装置と、ミキサー用の媒体分離装置を有し、前記撹拌羽根により、前記槽内に供給された処理材料をミキサー用の粉砕媒体とともに攪拌しながら、超音波を照射して固体粒子を微粉砕し、前記ミキサー用の媒体分離装置で前記ミキサー用の粉砕媒体から前記ミキサーに供給された固体粒子を分離するミキサーとを具備することを特徴とする分散または粉砕装置が開示されている。
On the other hand, the subdivision method is limited to a particle size of about submicron, but has an advantage that the composition is not limited.
For example, Patent Document 3 includes a vessel having a supply port and a discharge port for a processing material in which solid particles are mixed in a liquid, a rotor rotated by a drive shaft in the vessel, and a medium separator for a bead mill. The processing material supplied into the vessel is agitated and finely pulverized together with the grinding media for the bead mill, and the bead mill for separating the solid particles supplied to the bead mill from the grinding media for the bead mill by the media separator for the bead mill. A tank having an outlet that leads to the supply port of the beads mill and an inlet that leads to the discharge port of the beads mill, a stirring blade that rotates in the tank, and an ultrasonic generator that generates ultrasonic waves in the tank, A mixing device for a mixer, and with the stirring blade, while stirring the processing material supplied into the tank together with the grinding medium for the mixer, Dispersion or characterized in that it comprises a mixer for finely pulverizing solid particles by irradiating waves and separating the solid particles supplied to the mixer from the pulverizing medium for the mixer by the medium separator for the mixer A grinding device is disclosed.
気相法、液相法、ゾルゲル法などのナノ粒子の製造方法は、化学反応生成であるため粒径の制御を行い易いが、製造できるナノ粒子の組成が化学反応の組み合わせなどに依存するため、粒子の組成が限定されてしまう。
一方、細分化法は物理的に固体を粉砕する方法であるため、組成が限定されないが、粒径の限界がサブミクロン程度であり、ナノ粒子を安定して製造することが困難である。
Nanoparticle production methods such as the gas phase method, liquid phase method, and sol-gel method are easy to control the particle size because they are chemical reaction products, but the composition of the nanoparticles that can be produced depends on the combination of chemical reactions, etc. The composition of the particles is limited.
On the other hand, since the fragmentation method is a method of physically pulverizing a solid, the composition is not limited, but the limit of particle size is about submicron, and it is difficult to stably produce nanoparticles.
本発明はこのような実情に鑑みて成されたものであり、組成を限定することなく、粒径が１００ｎｍ以下のナノ粒子を簡便に製造することができるナノ粒子の製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and provides a method for producing nanoparticles capable of easily producing nanoparticles having a particle size of 100 nm or less without limiting the composition. Objective.
上記目的を達成するため、本発明者らは細分化法によるナノ粒子の製造技術について鋭意検討を行ったところ、以下の本発明を見出した。 In order to achieve the above-mentioned object, the present inventors have conducted intensive studies on a technique for producing nanoparticles by a fragmentation method, and found the following invention.
＜１＞ 固形材料に対し、固体粒子及び液体を含む懸濁液を投射して前記固形材料を摩耗させることにより前記固形材料のナノ粒子を生成させるナノ粒子生成工程と、
前記固形材料の摩耗により生成したナノ粒子を含む懸濁液を回収する回収工程と、
を有するナノ粒子の製造方法。
＜２＞ 前記固体粒子の平均粒子径が０．３μｍ〜１０μｍである＜１＞に記載のナノ粒子の製造方法。
＜３＞ 前記固体粒子が水溶性であり、前記ナノ粒子生成工程において、前記固形材料に対し、前記懸濁液として前記固体粒子が析出した飽和水溶液を投射する＜１＞又は＜２＞に記載のナノ粒子の製造方法。
＜４＞ 前記ナノ粒子の平均一次粒子径が１００ｎｍ以下である＜１＞〜＜３＞のいずれか１つに記載のナノ粒子の製造方法。
＜５＞ 前記回収工程において、前記回収した懸濁液から前記固形材料の摩耗により生成したナノ粒子を含む粒子群を回収する＜１＞〜＜４＞のいずれか１つに記載のナノ粒子の製造方法。
＜６＞ 前記回収した懸濁液に含まれる粒子群に液中プラズマ処理を施して粒子を分散させる分散工程をさらに有する＜１＞〜＜５＞のいずれか１つに記載のナノ粒子の製造方法。
<1> A nanoparticle generation step of generating nanoparticles of the solid material by projecting a suspension containing solid particles and a liquid to the solid material to wear the solid material;
A recovery step of recovering a suspension containing nanoparticles generated by abrasion of the solid material;
The manufacturing method of the nanoparticle which has this.
<2> The method for producing nanoparticles according to <1>, wherein an average particle size of the solid particles is 0.3 μm to 10 μm.
<3> The solid particles are water-soluble, and in the nanoparticle generation step, a saturated aqueous solution in which the solid particles are precipitated as the suspension is projected onto the solid material according to <1> or <2>. A method for producing nanoparticles.
<4> The method for producing nanoparticles according to any one of <1> to <3>, wherein an average primary particle diameter of the nanoparticles is 100 nm or less.
<5> The nanoparticle according to any one of <1> to <4>, wherein in the recovery step, a particle group including nanoparticles generated by abrasion of the solid material is recovered from the recovered suspension. Production method.
<6> The nanoparticle production according to any one of <1> to <5>, further including a dispersion step of dispersing the particles by subjecting the particles contained in the recovered suspension to plasma treatment in liquid. Method.
本発明によれば、組成を限定することなく、粒径が１００ｎｍ以下のナノ粒子を簡便に製造することができるナノ粒子の製造方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the nanoparticle which can manufacture a nanoparticle with a particle size of 100 nm or less simply without limiting a composition is provided.
本発明のナノ粒子の製造方法は、固形材料に対し、固体粒子及び液体を含む懸濁液を投射して前記固形材料を摩耗させることにより前記固形材料のナノ粒子を生成させるナノ粒子生成工程と、前記固形材料の摩耗により生成したナノ粒子を含む懸濁液を回収する回収工程と、を有する。
回収した懸濁液から少なくとも固形材料の摩耗により生成したナノ粒子を含む粒子群を選別する工程を有してもよいし、回収した懸濁液に含まれる粒子群に液中プラズマ処理を施して粒子を分散させる工程を有してもよい。
The method for producing nanoparticles according to the present invention includes a nanoparticle generation step of generating nanoparticles of the solid material by projecting a suspension containing solid particles and a liquid onto the solid material to wear the solid material. And a recovery step of recovering a suspension containing nanoparticles generated by abrasion of the solid material.
The method may include a step of selecting a particle group including nanoparticles generated by at least solid material abrasion from the recovered suspension, or subjecting the particle group included in the recovered suspension to plasma treatment in liquid. You may have the process of disperse | distributing particle | grains.
従来、微小粒子を作製する場合、細分化法では組成が限定されないものの、サブミクロン程度の粒径が限界であった。例えば、一般的なウェットブラストやサンドブラストなどの方法では、摩耗粉の大きさがサブミクロン以上の大きさとなってしまうため、当該摩耗粉を回収してもナノ粒子を得ることができない。 Conventionally, when producing fine particles, the composition is not limited by the subdivision method, but the particle size of about submicron has been the limit. For example, in a general method such as wet blasting or sand blasting, the size of the wear powder becomes submicron or larger, and thus nanoparticles cannot be obtained even if the wear powder is collected.
そこで、本発明者らは細分化法によってナノメートルオーダー（１００ｎｍ以下）の粒径を有するナノ粒子を製造する方法について検討を重ね、粒子を製造する方法や装置ではなく、皮膜評価方法に着目した。
皮膜評価方法は、一般的に、窒化チタン（ＴｉＮ）、窒化クロム（ＣｒＮ）、ダイヤモンド様カーボン（ＤＬＣ）などの硬質膜の耐摩耗性を評価する試験法である。具体的には、液体にアルミナ粒子などを投射材として混入した懸濁液（スラリー）を、ノズルより被験体である硬質膜の表面に投射し、被験体の減耗量、すなわち摩耗深さと投射の時間や重量の因果関係を明らかにすることで、耐摩耗性を評価する手法である。このような皮膜評価方法では、被験体の摩耗深さはｎｍオーダーで変化するため、投射後のスラリーにはｎｍオーダーの被験体の摩耗粉、すなわち被験体のナノ粒子が含まれると考えられる。そして、本発明者らが投射後のスラリーを精査したところ、投射後のスラリー中に被験体のナノ粒子の存在を確認した。
Accordingly, the present inventors have repeatedly studied a method for producing nanoparticles having a particle size of nanometer order (100 nm or less) by a subdivision method, and focused on a film evaluation method rather than a method or apparatus for producing particles. .
The film evaluation method is generally a test method for evaluating the wear resistance of hard films such as titanium nitride (TiN), chromium nitride (CrN), and diamond-like carbon (DLC). Specifically, a suspension (slurry) in which alumina particles or the like are mixed in the liquid as a projection material is projected from the nozzle onto the surface of the hard film as the subject, and the amount of wear of the subject, that is, the wear depth and the projection It is a technique for evaluating wear resistance by clarifying the causal relationship between time and weight. In such a film evaluation method, since the wear depth of the subject changes in the nm order, it is considered that the slurry after the projection contains the wear powder of the subject in the nm order, that is, the nanoparticles of the subject. And when the present inventors examined the slurry after a projection, the presence of the nanoparticle of a test subject was confirmed in the slurry after a projection.
そこで、本発明者らは、皮膜評価方法を転用し、被験体に替えて、目的のナノ粒子の材料からなる固形材料に対し、投射後のスラリー中に含まれる固形材料の摩耗粉であるナノ粒子を回収することで、組成が限定されずにナノ粒子を製造することができることを見出した。
なお、皮膜評価方法は、被験体の減量や摩耗深さ、密着性など、被験体の膜の特性を評価する方法であるのに対し、本発明は、固形材料の摩耗粉であるナノ粒子を回収し利用する方法であるため、根本的に対象や目的が大きく異なる。本発明では、固形材料全般にわたり、すなわち組成が限定されず、したがって目的とする固形材料のナノ粒子を直接製造し、回収することができる。
以下、本発明のナノ粒子の製造方法について具体的に説明する。
Therefore, the present inventors diverted the film evaluation method to replace the subject with a nanomaterial that is a solid material wear powder contained in the slurry after projection with respect to the solid material made of the target nanoparticle material. It has been found that by collecting the particles, the nanoparticles can be produced without limiting the composition.
The film evaluation method is a method for evaluating the characteristics of the subject's film, such as the subject's weight loss, wear depth, and adhesion, whereas the present invention uses nanoparticles that are solid material wear powders. Since it is a method of collecting and using, the object and purpose are fundamentally different. In the present invention, the entire solid material, that is, the composition is not limited, and therefore the nanoparticles of the target solid material can be directly produced and recovered.
Hereinafter, the manufacturing method of the nanoparticle of this invention is demonstrated concretely.
＜ナノ粒子生成工程＞
まず、ナノ粒子の原料となる固形材料に対し、固体粒子及び液体を含む懸濁液（以下、「スラリー」という場合がある。）を投射して固形材料を摩耗させることにより固形材料のナノ粒子を生成させる。このように固形材料に対してスラリーを投射してナノ粒子を生成させる方法として皮膜評価方法を好適に利用することができる。例えば、特開２０１３−５０３７８号公報、特開２０１０−２３７０７３号公報、特開２０１０−２３７０７１号公報、特開２００６−１８４１８８号公報、特開２００１−１８３２７９号公報等に開示されている皮膜評価方法等及びそれに用いられる装置等を利用することができる。
<Nanoparticle production process>
First, a solid material as a raw material of nanoparticles is projected by suspending the solid material by projecting a suspension containing solid particles and a liquid (hereinafter sometimes referred to as “slurry”). Is generated. As described above, the film evaluation method can be suitably used as a method for generating the nanoparticles by projecting the slurry onto the solid material. For example, film evaluation methods disclosed in JP2013-50378, JP2010-237073, JP2010-237071, JP2006-184188, JP2001-183279, etc. Etc. and devices used therefor can be used.
図１は本発明のナノ粒子の製造方法に用いることができる装置の構成の一例を概略的に示している。図１に示す装置は、ナノ粒子の原料となる固形材料（試料片）を設置する試料テーブル、試料テーブルを投射ブースに出し入れする駆動手段、固形材料に投射するスラリーを収容するスラリータンク、水平及び垂直方向に駆動し、投射ブースにおいて固形材料に対してスラリーを投射する投射ノズル、投射ブースからスラリーをスラリータンクに戻す返送ポンプ、スラリーの投射流量及び投射圧力を調整する手段（スラリー流量計、エアー流量計、エアー圧力調整手段、スラリー圧力調整手段）などを備えている。また、排気口、排水口、電源制御手段、動作入力手段（パーソナルコンピュータ）等も備えている。 FIG. 1 schematically shows an example of the configuration of an apparatus that can be used in the method for producing nanoparticles of the present invention. The apparatus shown in FIG. 1 includes a sample table on which a solid material (sample piece) serving as a raw material for nanoparticles is placed, a driving means for taking the sample table into and out of the projection booth, a slurry tank for storing slurry to be projected onto the solid material, Projection nozzle that drives in the vertical direction and projects slurry onto the solid material in the projection booth, return pump that returns the slurry from the projection booth to the slurry tank, means for adjusting the slurry flow rate and pressure (slurry flow meter, air A flow meter, an air pressure adjusting means, a slurry pressure adjusting means). Further, an exhaust port, a drain port, a power source control unit, an operation input unit (personal computer), and the like are also provided.
図１に示す構成を有する装置では、スラリータンクに投入されたスラリーが投射ノズルより固形材料に投射され、固形材料は摩耗により減量する。固形材料の摩耗粉（ナノ粒子）を含んだスラリーは返送ポンプにてスラリータンクに流入し、再び投射ノズルより固形材料に投射される。したがって、投射時間や投射量の増加に伴いスラリーにおける固形材料のナノ粒子濃度を上げることができる。 In the apparatus having the configuration shown in FIG. 1, the slurry charged into the slurry tank is projected onto the solid material from the projection nozzle, and the solid material is reduced due to wear. The slurry containing the wear powder (nanoparticles) of the solid material flows into the slurry tank by the return pump, and is again projected onto the solid material from the projection nozzle. Therefore, the nanoparticle density | concentration of the solid material in a slurry can be raised with the increase in projection time and the projection amount.
（固形材料）
ナノ粒子の原料となる固形材料は特に限定されず、目的とするナノ粒子の材質に応じて選択すればよい。例えば、皮膜評価方法において被験体として一般的に用いられる窒化チタン（ＴｉＮ）、窒化クロム（ＣｒＮ）、ダイヤモンド様カーボン（ＤＬＣ）、グラファイトでもよいし、他の固形材料でもよい。
また、固形材料の形状は特に限定されないが、スラリーを投射して表面をできるだけ均等に摩耗させる観点から基板状であることが好ましい。
(Solid material)
The solid material used as the raw material of the nanoparticles is not particularly limited, and may be selected according to the target material of the nanoparticles. For example, titanium nitride (TiN), chromium nitride (CrN), diamond-like carbon (DLC), graphite, or other solid materials that are generally used as subjects in the film evaluation method may be used.
Further, the shape of the solid material is not particularly limited, but is preferably a substrate from the viewpoint of projecting the slurry and wearing the surface as evenly as possible.
（懸濁液）
ナノ粒子の原料となる固形材料に投射する懸濁液（スラリー）は、固体粒子及び液体を含むスラリーである。スラリーの投射圧力、投射量、投射時間などが、固形材料の摩耗によって生成するナノ粒子の粒径、粒度分布などの制御パラメータとなる。
(Suspension)
The suspension (slurry) projected onto the solid material that is the raw material of the nanoparticles is a slurry containing solid particles and a liquid. The projection pressure, the projection amount, the projection time, etc. of the slurry are control parameters such as the particle size and particle size distribution of the nanoparticles generated by the wear of the solid material.
固体粒子は、固形材料をｎｍオーダーで摩耗することできるように固形材料の材質に応じて選択すればよい。例えば、水中で安定な、金、白金、インジウム、等の単体、アルミナ、シリカ、ジルコニア、窒化ケイ素等の酸化物、窒化物等の粒子、あるいは、それらの複合粒子などが挙げられる。 The solid particles may be selected according to the material of the solid material so that the solid material can be worn on the order of nm. For example, a simple substance such as gold, platinum, or indium that is stable in water, an oxide such as alumina, silica, zirconia, or silicon nitride, or a particle such as nitride, or a composite particle thereof may be used.
また、固形材料に投射するスラリーとしては、投射材となる固体粒子が水溶性であり、固体粒子が析出した飽和水溶液も好適に用いることができる。
例えば、水などの液体（溶媒）中にＫＢｒ、ＮａＣｌなどの水溶性の溶質（固体粒子）が析出した飽和水溶液をスラリーとして用いて固形材料に投射すれば、投射後のスラリーには固形材料の摩耗によって生成したナノ粒子のほかに水溶性の固体粒子が含まれる。回収したスラリーに液体を加えるか、液体を除いた粒子群を液体で洗い流して固体粒子を溶かせば、ナノ粒子のみを容易に回収することができる。
In addition, as a slurry to be projected onto a solid material, a saturated aqueous solution in which solid particles serving as a projection material are water-soluble and solid particles are precipitated can be suitably used.
For example, if a saturated aqueous solution in which water-soluble solutes (solid particles) such as KBr and NaCl are precipitated in a liquid (solvent) such as water is used as a slurry and projected onto a solid material, In addition to nanoparticles generated by abrasion, water-soluble solid particles are included. If a liquid is added to the recovered slurry, or the particle group excluding the liquid is washed away with the liquid to dissolve the solid particles, only the nanoparticles can be easily recovered.
投射材としての固体粒子のサイズは固形材料をｎｍオーダーで摩耗することができるように固形材料の材質に応じて選択すればよい。通常、固体粒子の粒径が小さいほど固形材料の摩耗により小径の粒子が得られるが、摩耗速度は遅く、生産性は低くなる。一方、固体粒子の粒径が大きいほど固形材料の摩耗速度が速くなるが、生成される粒子の粒径は大きくなる。生産性及び得られる粒子の粒径の観点から、投射材となる固体粒子の平均粒子径は０．３μｍ〜１０μｍの範囲内であることが好ましく、２μｍ〜３μｍの範囲内であることがより好ましい。 The size of the solid particles as the projection material may be selected according to the material of the solid material so that the solid material can be worn on the order of nm. Usually, the smaller the particle size of the solid particles, the smaller the particles are obtained by the wear of the solid material, but the wear rate is slower and the productivity is lower. On the other hand, the larger the particle size of the solid particles, the faster the wear rate of the solid material, but the larger the particle size of the generated particles. From the viewpoint of productivity and the particle size of the obtained particles, the average particle size of the solid particles to be the projection material is preferably in the range of 0.3 μm to 10 μm, and more preferably in the range of 2 μm to 3 μm. .
なお、投射材である固体粒子の「平均粒子径」は、１００個を電子顕微鏡で観察して各粒子の最大径を測定し、算術平均した値である。この固体粒子の平均粒子径は凝集粒子の平均粒子径であってもよい。 The “average particle diameter” of the solid particles as the projection material is a value obtained by observing 100 particles with an electron microscope, measuring the maximum diameter of each particle, and calculating an arithmetic average. The average particle size of the solid particles may be the average particle size of the aggregated particles.
スラリーに含まれる液体は、固形材料及び固体粒子に対して不活性であれば特に限定されない。コスト、環境負荷の軽減の観点から水が好ましいが、他の液体であってもよい。 The liquid contained in the slurry is not particularly limited as long as it is inert to the solid material and solid particles. Although water is preferable from the viewpoint of cost and environmental load reduction, other liquids may be used.
スラリー中の固体粒子の濃度は固形材料をｎｍオーダーで摩耗することができるように固形材料、固体粒子の材質及び粒径に応じて適宜選択すればよいが、固形材料をｎｍオーダーで効率的に摩耗させてナノ粒子を得る観点から、０．１〜１０．０質量％であることが好ましく、３．０〜５．０質量％であることがより好ましい。 The concentration of the solid particles in the slurry may be appropriately selected according to the solid material and the material and particle size of the solid particles so that the solid material can be worn in the nm order. From the viewpoint of obtaining nanoparticles by abrasion, the content is preferably 0.1 to 10.0% by mass, and more preferably 3.0 to 5.0% by mass.
固形材料に対し、スラリーを投射させる流量は、固形材料の材質、固体粒子の粒径等にもよるが、固形材料をｎｍオーダーで効率的に摩耗させてナノ粒子を得る観点から、１００Ｌ／ｍｉｎ〜１５０Ｌ／ｍｉｎの流量で照射することが好ましい。 The flow rate at which the slurry is projected onto the solid material depends on the material of the solid material, the particle size of the solid particles, etc., but from the viewpoint of obtaining nanoparticles by efficiently wearing the solid material on the order of nm, 100 L / min Irradiation is preferably performed at a flow rate of ˜150 L / min.
また、固形材料にスラリーを投射する際、固形材料に超音波を印加してもよい。例えば、固形材料を超音波印加可能なテーブルに固定して超音波を印加しながらスラリーを投射することでナノ粒子化が促進され、また、親水化や表面修飾を図ることもできる。 Further, when the slurry is projected onto the solid material, ultrasonic waves may be applied to the solid material. For example, the solid material is fixed on a table to which ultrasonic waves can be applied and the slurry is projected while applying ultrasonic waves, whereby nanoparticulation is promoted, and hydrophilization and surface modification can also be achieved.
上記のように皮膜評価方法を利用したナノ粒子生成工程によれば、固形材料の摩耗により平均一次粒子径が１００ｎｍ以下のナノ粒子を得ることができる。なお、固形材料の摩耗によって生じるナノ粒子の「平均一次粒子径」は、１００個の一次粒子を電子顕微鏡で観察して各粒子の最大径を測定し、算術平均した値である。 According to the nanoparticle production | generation process using the film | membrane evaluation method as mentioned above, a nanoparticle with an average primary particle diameter of 100 nm or less can be obtained by abrasion of a solid material. The “average primary particle diameter” of the nanoparticles generated by wear of the solid material is an arithmetic average value obtained by observing 100 primary particles with an electron microscope and measuring the maximum diameter of each particle.
固形材料に対し、スラリーを投射して固形材料を摩耗させることでナノ粒子を含むスラリーが得られる。スラリーを固形材料に１回当てて得たスラリーを回収してもよいが、固形材料の摩耗により生成するナノ粒子の濃度を高めるため、スラリーを循環させて固形材料に投射することでスラリー中のナノ粒子の濃度を高めることが好ましい。 A slurry containing nanoparticles is obtained by projecting the slurry on the solid material to wear the solid material. The slurry obtained by applying the slurry to the solid material once may be collected, but in order to increase the concentration of nanoparticles generated by wear of the solid material, the slurry is circulated and projected onto the solid material to increase the concentration of nanoparticles. It is preferable to increase the concentration of the nanoparticles.
＜回収工程＞
ナノ粒子生成工程後、固形材料の摩耗により生成したナノ粒子を含む懸濁液（スラリー）を回収する。
回収されたスラリーには投射材としての固体粒子と固形材料の摩耗により生成したナノ粒子が含まれる。例えば、ナノ粒子の原料となるカーボンチップに対し、投射材としてアルミナを含むスラリーを投射した後のスラリーの概念図を図２に示す。投射後のスラリー３０中には、液体４０と、投射材であるアルミナ粒子１０の他にカーボンチップの摩耗粉（ナノ粒子）２０が含まれている。
<Recovery process>
After the nanoparticle generation step, a suspension (slurry) containing nanoparticles generated by abrasion of the solid material is collected.
The recovered slurry contains solid particles as a projection material and nanoparticles generated by wear of the solid material. For example, FIG. 2 shows a conceptual diagram of a slurry after projecting a slurry containing alumina as a projection material onto a carbon chip that is a raw material for nanoparticles. In the slurry 30 after the projection, carbon chip wear powder (nanoparticles) 20 is contained in addition to the liquid 40 and the alumina particles 10 as the projection material.
回収したスラリーに含まれる粒子１０，２０の比重、大きさ、形状等の差異を利用し、ろ過、遠心分離、液中プラズマ等によって、回収したスラリーから固形材料の摩耗により生成したナノ粒子を含む粒子群を分離回収することもできる。
図３に、固形材料にスラリーを投射してスラリーを回収した後、遠心分離処理した後の概念図を示す。投射材としての固体粒子１０と固形材料から生成したナノ粒子２０を含むスラリーに対して遠心分離処理を行うと、図３に示すように重量の重いアルミナ粒子成分１０Ｂは沈殿する。
また、例えば固体粒子よりもナノ粒子の比重が小さい場合は、遠心分離によってスラリーの上層においてナノ粒子の濃度を高めることができる。
Utilizing differences in specific gravity, size, shape, etc. of particles 10 and 20 contained in the recovered slurry, including nanoparticles generated by abrasion of solid material from recovered slurry by filtration, centrifugation, plasma in liquid, etc. The particle group can also be separated and recovered.
FIG. 3 shows a conceptual diagram after projecting the slurry onto the solid material and collecting the slurry, followed by centrifugal separation. When the centrifugal separation process is performed on the slurry containing the solid particles 10 as the projection material and the nanoparticles 20 generated from the solid material, the heavy alumina particle component 10B precipitates as shown in FIG.
For example, when the specific gravity of nanoparticles is smaller than that of solid particles, the concentration of nanoparticles can be increased in the upper layer of the slurry by centrifugation.
また、回収したスラリーをフィルター等でろ過し、目的とするナノ粒子の濃度を高めるたり、粒度分布を狭めてもよい。図４−１は、回収したスラリーを濾過して粒子を選別する概念図である。例えば、図３に示すように遠心分離処理によってナノ粒子の濃度を高めた上澄み液３０Ａを抽出し、ナノ粒子２０が透過するフィルター３２でろ過することでナノ粒子２０の濃度をさらに高めたろ液３０Ｂを得ることができる。 The recovered slurry may be filtered with a filter or the like to increase the concentration of the target nanoparticles or narrow the particle size distribution. FIG. 4A is a conceptual diagram of selecting particles by filtering the recovered slurry. For example, as shown in FIG. 3, a supernatant 30A having a higher concentration of nanoparticles by centrifugation is extracted and filtrated by a filter 32 through which the nanoparticles 20 permeate to thereby further increase the concentration of the nanoparticles 20 by filtration 30B. Can be obtained.
また、前記したように、水溶性の固体粒子が析出した飽和水溶液のスラリーを用いてナノ粒子生成工程を行うことができる。図４−２は、回収したスラリーを濾過しながら純水などで洗い流して、粒子を選別する概念図である。水溶性の固体粒子１０Ａは溶け、ナノ粒子２０のみを確実に分離回収することができる。 Further, as described above, the nanoparticle generation step can be performed using a slurry of a saturated aqueous solution in which water-soluble solid particles are precipitated. FIG. 4-2 is a conceptual diagram of selecting particles by washing the recovered slurry with pure water while filtering. The water-soluble solid particles 10A are dissolved, and only the nanoparticles 20 can be reliably separated and recovered.
＜分散工程＞
回収したスラリーに含まれる粒子は凝集して２次粒子を形成している場合がある。そこで、回収したスラリーに含まれる粒子群に液中プラズマ処理を施して粒子を分散させてもよい。図５はナノ粒子生成工程後のスラリーに対して液中プラズマ処理を行う概念図である。ナノ粒子生成工程後、回収したスラリーに含まれる粒子群に対して液中プラズマ処理を施すことで粒子の表面が親水化し、凝集した粒子２２を分散させることができる。
<Dispersing process>
The particles contained in the recovered slurry may aggregate to form secondary particles. Therefore, the particles may be dispersed by subjecting the particles contained in the recovered slurry to plasma treatment in liquid. FIG. 5 is a conceptual diagram in which in-liquid plasma treatment is performed on the slurry after the nanoparticle generation step. After the nanoparticle generation step, the particle surface contained in the recovered slurry is subjected to in-liquid plasma treatment so that the surface of the particles becomes hydrophilic and the aggregated particles 22 can be dispersed.
また、液中プラズマ処理を施す際、凝集粒子２２の分散を促進させるため、ナノ粒子の表面極性基に応じて界面活性化剤等の分散剤を添加してもよい。 Moreover, when performing the plasma treatment in a liquid, in order to promote dispersion | distribution of the aggregated particle 22, you may add dispersing agents, such as surfactant, according to the surface polar group of a nanoparticle.
なお、液中プラズマ処理は、ナノ粒子生成工程後に回収したスラリーに対して行ってもよいし、回収したスラリーに対し、遠心分離、ろ過等によって粒子を選別した後、液中プラズマ処理を行って分散させてもよい。 The in-liquid plasma treatment may be performed on the slurry recovered after the nanoparticle generation step, or the recovered slurry is subjected to in-liquid plasma treatment after selecting particles by centrifugation, filtration, or the like. It may be dispersed.
本発明の方法によれば、化学反応生成を利用することなく、物理的にナノ粒子の製造・回収が可能となることから、組成が限定されることなく、あらゆる固形材料のナノ粒子を製造することが可能となる。 According to the method of the present invention, it is possible to physically produce and collect nanoparticles without using chemical reaction generation, so that nanoparticles of any solid material can be produced without limiting the composition. It becomes possible.
以下、実施例について説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, examples will be described, but the present invention is not limited to the following examples.
＜実施例＞
イオン交換水２９０ｇに、投射材として平均粒子径２〜３μｍのアルミナ粒子１０ｇを添加した懸濁液（スラリー）を調製した。
また、製造するナノ粒子の原料（固形材料）として、１０ｍｍ角及び厚さ１ｍｍで、灰分２０ｐｐｍ以下のカーボンチップを用いた。カーボンチップの密度は２．２６ｇ／ｃｍ３である。
<Example>
A suspension (slurry) was prepared by adding 10 g of alumina particles having an average particle diameter of 2 to 3 μm as a projection material to 290 g of ion-exchanged water.
Further, as a raw material (solid material) of the nanoparticles to be produced, a carbon chip having a 10 mm square and a thickness of 1 mm and having an ash content of 20 ppm or less was used. The density of the carbon chip is 2.26 g / cm 3 .
カーボンチップを図１に示す構成の装置の試験片設置部（テーブル）に設置し、スラリータンクにスラリーを入れた後、スラリーを循環させつつカーボンチップに対してスラリーを８時間投射した。
投射後のスラリー中には、投射材であるアルミナ粒子の他にカーボンチップの摩耗粉が含まれている。回収した投射後のスラリーに対して遠心分離処理を行い、重量の重いアルミナ粒子成分を沈殿させた（図３）。上澄み液を抽出し、濾過後（図４−１）、液中プラズマ処理（図５）を行った。
The carbon chip was set on a test piece setting portion (table) of the apparatus having the configuration shown in FIG. 1, and the slurry was put into a slurry tank.
In the slurry after projection, carbon chip wear powder is contained in addition to the alumina particles as the projection material. Centrifugation treatment was performed on the recovered slurry after projection to precipitate heavy alumina particle components (FIG. 3). The supernatant liquid was extracted, filtered (FIG. 4-1), and then subjected to plasma treatment in liquid (FIG. 5).
＜評価＞
Ｓｉ基板上に抽出液を滴下して乾燥させ、表面に約２０ｎｍの厚みで金蒸着を施した後、走査電子顕微鏡での観察及びＥＤＸ（エネルギー分散型Ｘ線）分析を行った。
図６及び図７に走査電子顕微鏡による観察結果の一例を示す。図６及び図７より、カーボンチップから得られた粒子が１００ｎｍ以下のナノ粒子となっていることがわかる。
また、図７（Ｂ）に見られるようにカーボンチップのナノ粒子が凝集して二次粒子を形成している部分も存在するが、これは上記の液中プラズマ処理などの処理条件を変更することで、分散、凝集を制御できる。
<Evaluation>
The extract was dropped on the Si substrate and dried, and gold deposition was performed on the surface with a thickness of about 20 nm, followed by observation with a scanning electron microscope and EDX (energy dispersive X-ray) analysis.
FIG. 6 and FIG. 7 show an example of the observation result by the scanning electron microscope. 6 and 7 that the particles obtained from the carbon chip are nanoparticles of 100 nm or less.
Further, as shown in FIG. 7B, there is a portion where the carbon chip nanoparticles aggregate to form secondary particles, but this changes the processing conditions such as the above-described plasma treatment in liquid. Thus, dispersion and aggregation can be controlled.
図８にＥＤＸ分析結果を示す。図８より、粒子の大きさが１００ｎｍ以下であり、かつＥＤＸ点分析結果より粒子の組成がカーボンであることがわかる。 FIG. 8 shows the EDX analysis results. FIG. 8 shows that the particle size is 100 nm or less, and the particle composition is carbon from the EDX point analysis result.
本発明のナノ粒子の製造方法は、組成が限定されることなく、種々の固形材料のナノ粒子の製造に適用することができる。本発明は、例えば、ｎｍサイズの導電性粉末材料を用いた導電性インキの製造に利用することができる。 The method for producing nanoparticles of the present invention can be applied to the production of nanoparticles of various solid materials without limiting the composition. The present invention can be used, for example, for the production of conductive ink using a conductive powder material of nm size.
１０ 固体粒子（投射材）
１０Ａ 水溶性の固体粒子
１０Ｂ 粗大な固体粒子
２０ ナノ粒子
２２ 凝集粒子
３０ 懸濁液（スラリー）
３０Ａ 上澄み液
３２ フィルター
３０Ｂ ろ液
４０ 液体
10 Solid particles (projection material)
10A Water-soluble solid particles 10B Coarse solid particles 20 Nano particles 22 Aggregated particles 30 Suspension (slurry)
30A Supernatant liquid 32 Filter 30B Filtrate 40 Liquid
Claims (6)
前記固形材料の摩耗により生成したナノ粒子を含む懸濁液を回収する回収工程と、
を有するナノ粒子の製造方法。 A nanoparticle generation step of generating nanoparticles of the solid material by projecting a suspension containing solid particles and a liquid to the solid material to wear the solid material;
A recovery step of recovering a suspension containing nanoparticles generated by abrasion of the solid material;
The manufacturing method of the nanoparticle which has this.
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