JP6572598B2 - Nanoparticle size measurement method - Google Patents
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Description
本発明は、フィールドフローフラクショネーション（field flow fractionation：ＦＦＦ）を利用した金属材料中の析出物等のナノ粒子の粒径測定方法に関する。 The present invention relates to a method for measuring the particle size of nanoparticles such as precipitates in metal materials using field flow fractionation (FFF).
フィールドフローフラクショネーション（field flow fractionation：ＦＦＦ）を原理として用いる分析装置は、様々な粒径の微粒子を粒径毎にふるい分け、粒径毎の微粒子の個数密度を測定する装置である。 An analyzer that uses field flow fractionation (FFF) as a principle is a device that screens fine particles having various particle sizes for each particle size and measures the number density of the fine particles for each particle size.
ふるい分けされた微粒子の粒径は、レーザー光を照射して、レイリー散乱光を多角度で検出し、その光の散乱度合いから測定することができる（非特許文献１）。但し、レーザー光の散乱強度は粒径の６乗に比例して小さくなる。このため、特に粒径が５０ｎｍ以下の微粒子の検出は困難である。その一方で、紫外線（ultra violet：ＵＶ）吸収や誘導結合プラズマ（inductively coupled plasma：ＩＣＰ）発光分析法やＩＣＰ質量分析法を利用することで、粒径が５０ｎｍ以下であっても、微粒子の存在や化学成分を検出することが可能である（特許文献１）。しかし、これらの検出手法では微粒子の存在は検出できても、微粒子の粒径を実測することは困難である。そこで、微粒子の粒径の特定には、標準微粒子の透過型電子顕微鏡（transmission electron microscope：ＴＥＭ）観察で得られた平均粒径（以下、ＴＥＭ観察平均粒径ということがある）とＦＦＦにおける保持時間（以下、ＦＦＦ保持時間ということがある）との相関関係を利用したキャリブレーションが行われる。測定対象の微粒子の粒径がシングルナノサイズである場合、キャリブレーションには、金属ナノコロイド粒子が分散した溶液が標準ナノ粒子分散試料として用いられる。 The particle size of the fine particles thus screened can be measured from the degree of light scattering by irradiating laser light, detecting Rayleigh scattered light at multiple angles (Non-Patent Document 1). However, the laser light scattering intensity decreases in proportion to the sixth power of the particle diameter. For this reason, it is particularly difficult to detect fine particles having a particle size of 50 nm or less. On the other hand, by using ultraviolet (UV) absorption, inductively coupled plasma (ICP) emission spectrometry, or ICP mass spectrometry, the presence of fine particles even when the particle size is 50 nm or less. And chemical components can be detected (Patent Document 1). However, even though the presence of fine particles can be detected by these detection methods, it is difficult to actually measure the particle size of the fine particles. Therefore, in order to specify the particle size of the fine particles, the average particle size obtained by transmission electron microscope (TEM) observation of standard fine particles (hereinafter sometimes referred to as TEM observation average particle size) and the retention in FFF Calibration using a correlation with time (hereinafter also referred to as FFF holding time) is performed. When the particle size of the fine particles to be measured is a single nanosize, a solution in which metal nanocolloid particles are dispersed is used as a standard nanoparticle-dispersed sample for calibration.
しかしながら、シングルナノサイズの金属ナノコロイド粒子が分散した溶液を用いて取得されるＦＦＦ保持時間とＴＥＭ観察平均粒径との相関関係は良好なものとならない。例えば、相関線の直線回帰の決定係数Ｒ2が１から大きくずれてしまう。このため、この相関関係を用いて、微粒子の粒径を取得したとしても、その正確性は十分なものとはいえない。 However, the correlation between the FFF retention time obtained using a solution in which single nano-sized metal nanocolloid particles are dispersed and the TEM observation average particle size is not good. For example, the coefficient of determination R 2 for linear regression of the correlation line is greatly deviated from 1. For this reason, even if the particle size of the fine particles is obtained using this correlation, the accuracy is not sufficient.
本発明の目的は、上記の問題を解決するために創案されたものであって、測定対象の粒径が１０ｎｍ以下であっても優れた精度での測定を可能とするナノ粒子の粒径測定方法を提供することにある。 The object of the present invention was devised to solve the above-mentioned problem, and it is possible to measure the particle size of a nanoparticle that enables measurement with excellent accuracy even when the particle size of the measurement object is 10 nm or less. It is to provide a method.
本発明に係るナノ粒子の粒径測定方法は、標準ナノ粒子分散試料に含まれる標準ナノ粒子を透過型電子顕微鏡にて観察し、前記標準ナノ粒子の第１の平均粒径を取得する工程と、前記標準ナノ粒子分散試料に含まれる第１の分散剤の粒径及び前記第１の平均粒径から前記標準ナノ粒子の第１の水力学的粒径を取得する工程と、前記標準ナノ粒子分散試料のフィールドフローフラクショネーションにおける第１の保持時間を取得する工程と、前記第１の水力学的粒径と前記第１の保持時間との相関線を作成する工程と、ナノ粒子及び第２の分散剤を含むナノ粒子分散試料のフィールドフローフラクショネーションにおける第２の保持時間を取得する工程と、前記第２の保持時間に対応する第２の水力学的粒径を前記相関線から取得する工程と、前記第２の水力学的粒径及び前記第２の分散剤の粒径から前記ナノ粒子の粒径を取得する工程と、を有することを特徴とする。 The method for measuring the particle size of nanoparticles according to the present invention includes a step of observing standard nanoparticles contained in a standard nanoparticle-dispersed sample with a transmission electron microscope and obtaining a first average particle size of the standard nanoparticles. Obtaining a first hydrodynamic particle size of the standard nanoparticles from the particle size of the first dispersant contained in the standard nanoparticle-dispersed sample and the first average particle size; and the standard nanoparticles Obtaining a first retention time in field flow fractionation of a dispersed sample; creating a correlation line between the first hydraulic particle size and the first retention time; A step of obtaining a second retention time in field flow fractionation of a nanoparticle-dispersed sample containing two dispersants, and a second hydraulic particle size corresponding to the second retention time from the correlation line A process of acquiring; A step of acquiring a particle size of serial second hydrodynamic particle size and the nanoparticles from the particle size of the second dispersing agent, and having a.
本発明に係るナノ粒子の粒径測定方法によれば、測定対象の粒径が１０ｎｍ以下であっても高精度でナノ粒子の粒径を測定することができる。 According to the method for measuring the particle size of nanoparticles according to the present invention, the particle size of the nanoparticles can be measured with high accuracy even if the particle size of the measurement target is 10 nm or less.
本願発明者らは、従来の技術において、微小な粒子、特にシングルナノサイズの粒子におけるＴＥＭ観察平均粒径とＦＦＦ保持時間との相関関係が良好なものとならない原因について検討した。この結果、相関関係を取得するためのＦＦＦ分析に供する標準ナノ粒子分散試料に含まれる分散剤の種類が当該標準ナノ粒子分散試料に含まれるナノ粒子の粒径に応じて異なっていることが一因であることが判明した。 The inventors of the present application examined the cause of the poor correlation between the TEM observation average particle size and the FFF retention time in the conventional technology, particularly in the case of fine particles, particularly single nano-sized particles. As a result, the type of dispersant contained in the standard nanoparticle dispersed sample subjected to FFF analysis for obtaining the correlation is different depending on the particle size of the nanoparticle contained in the standard nanoparticle dispersed sample. It turned out to be a cause.
一般に、標準ナノ粒子分散試料として用いられる金属ナノコロイド粒子が分散した溶液の作製には溶液還元法が用いられている。この手法は分散剤を溶媒中に予め拡散させた状態で種となる金属イオンを還元していく手法である。分散剤は、当該溶液中で金属ナノコロイド粒子を高効率で分散させるために用いられており、当該溶液中で金属ナノコロイド粒子の表面に付着している。そして、詳細は後述するが、ＦＦＦ分析に供された場合には、ＦＦＦ装置の分離層内において、金属ナノコロイド粒子とこれに付着した分散剤とが一体化したものが一つの構造物として移動している。また、分散剤としては、金属ナノコロイド粒子の粒径に適したものが用いられている。例えば、粒径が２．１ｎｍの金属ナノコロイド粒子の溶液にはグルタチオンが用いられ、粒径が１０．４ｎｍの金属ナノコロイド粒子の溶液にはタンニン酸が用いられる。種類が相違する分散剤の間では、分散剤の粒径も相違する。そして、ＦＦＦ保持時間は上記構造物の粒径、すなわち水力学的粒径の影響を受ける。従って、このＦＦＦ保持時間は、金属ナノコロイド粒子の粒径だけでなく、分散剤の粒径の影響も受ける。 In general, a solution reduction method is used for preparing a solution in which metal nanocolloid particles used as a standard nanoparticle-dispersed sample are dispersed. This technique is a technique in which metal ions that become seeds are reduced in a state in which a dispersant is previously diffused in a solvent. The dispersant is used to disperse the metal nanocolloid particles in the solution with high efficiency, and is attached to the surface of the metal nanocolloid particles in the solution. As will be described in detail later, in the case of FFF analysis, in the separation layer of the FFF device, the metal nanocolloid particles and the dispersant adhering thereto move together as a single structure. doing. In addition, as the dispersant, those suitable for the particle size of the metal nanocolloid particles are used. For example, glutathione is used for a solution of metal nanocolloid particles having a particle size of 2.1 nm, and tannic acid is used for a solution of metal nanocolloid particles having a particle size of 10.4 nm. Among different types of dispersants, the particle size of the dispersant is also different. The FFF holding time is affected by the particle size of the structure, that is, the hydraulic particle size. Therefore, the FFF retention time is influenced not only by the particle size of the metal nanocolloid particles but also by the particle size of the dispersant.
その一方で、ＴＥＭ観察平均粒径は分散剤の粒径の影響を受けない。これは、ＴＥＭ観察は乾燥状態で行われるからである。 On the other hand, the TEM observation average particle size is not affected by the particle size of the dispersant. This is because TEM observation is performed in a dry state.
そして、相関線（検量線）を作成する際に粒径が相違する複数の標準ナノ粒子分散試料についての測定が行われるところ、上記のように、これら標準ナノ粒子分散試料の間で分散剤の種類は必ずしも共通したものとなっていない。ＴＥＭ観察平均粒径は分散剤の種類の影響を受けず、ＦＦＦ保持時間が分散剤の種類の影響を受けるため、ＴＥＭ観察平均粒径とＦＦＦ保持時間との間に良好な相関関係が得られないのである。 Then, when creating a correlation line (calibration curve), measurement is performed on a plurality of standard nanoparticle dispersion samples having different particle diameters. Types are not necessarily common. The average TEM observation particle size is not affected by the type of dispersant, and the FFF retention time is affected by the type of dispersant, so a good correlation is obtained between the TEM observation average particle size and the FFF retention time. There is no.
ここで、図１を用いて、ＦＦＦ法のサイズ分離原理を説明する。ＦＦＦ装置の溶離流出液としては、界面活性剤を含む分離溶液を用いて、まず、クロスフロー１４と呼ばれる液の流れをセルの上方から下方セルに向かって生じさせながら、分離層１６の左側と右側からも液を流し、その間に微粒子を含むサンプル溶液１５を添加する。すると、下方の分離膜２１には大きなサイズの大粒子２０がクロスフロー１４の流れによって押し付けられて張り付く。その一方で、比較的サイズが大きな中粒子１９及び小さな小粒子１８は、クロスフロー１４の流れに打ち勝つだけのブラウン運動を起こすため、分離層１６の下側に位置する分離膜２１に押し付けられることなく、分離層１６の中にサイズ毎に浮遊する状態になる。これをフォーカシングと呼ぶ。この状態にすることで、分離層１６の中に粒子がサイズ毎に並び替えられることとなる。その後、分離層１６の左右から押し付けていた流れを変えて、チャネルフロー１７により、例えば図１の左から右に向かって分離層１６に存在する粒子を右側に押し出していく。
Here, the size separation principle of the FFF method will be described with reference to FIG. As the elution effluent of the FFF apparatus, a separation solution containing a surfactant is used. First, a liquid flow called a
このとき、上から分離膜２１に向かって押さえつける役割のクロスフロー１４の圧力を徐々にゼロまで減らしていくと、分離膜２１に押さえつけられていた粒子が、徐々に小さな粒子から大きな粒子の順で右側から排出される。チャネルフローの右側には、図示していない出口の下流側に光散乱検出器が設けられており、粒子からの散乱光強度の時間変化が記録される。ＦＦＦ保持時間は、各ピークの時刻までの時間である。ここで、時間の起点（ｔ＝０）は、毎測定で同じ条件となるように適宜決めてよい。例えば、フォーカシングの開始あるいはチャネルフローの流出開始のタイミングとすることができる。
At this time, when the pressure of the
なお、ここでは、分離するためにクロスフロー液による押さえつけ力とブラウン運動とを組み合わせることにより、サイズ分離する例を示したが、ＦＦＦの分離原理としては、この他にも、重力、電場、磁場、温度勾配等をかけることにより、より精密に粒子を分離することができる。 In addition, although the example which carried out size separation by combining the pressing force by a crossflow liquid and Brownian motion for separation was shown here, as a separation principle of FFF, besides this, gravity, electric field, magnetic field By applying a temperature gradient or the like, the particles can be separated more precisely.
サンプル溶液１５として金属ナノコロイド粒子分散試料が用いられる場合、上記のように、分離層１６内において、金属ナノコロイド粒子とこれに付着した分散剤とが一体化したものが一つの構造物として移動する。そして、ＦＦＦ保持時間は上記構造物の粒径、すなわち水力学的粒径の影響を受ける。従って、このＦＦＦ保持時間は、金属ナノコロイド粒子の粒径だけでなく、分散剤の粒径の影響も受ける。
When a metal nanocolloid particle-dispersed sample is used as the
次に、本発明の実施形態について添付の図面を参照しながら具体的に説明する。本実施形態では、上記の知見に基づき、予め標準ナノ粒子分散試料を用いて水力学的粒径と各分画のＦＦＦ保持時間ＲＴとの相関線（検量線）を作成しておき、これを用いながら測定対象のナノ粒子分散試料中に分散したナノ粒子の粒径を特定する。 Next, embodiments of the present invention will be specifically described with reference to the accompanying drawings. In this embodiment, based on the above knowledge, a correlation line (calibration curve) between the hydrodynamic particle size and the FFF retention time RT of each fraction is prepared in advance using a standard nanoparticle-dispersed sample. The particle size of the nanoparticles dispersed in the nanoparticle dispersed sample to be measured is specified while being used.
先ず、相関線の作成について説明する。相関線の作成に際しては、粒径が相違する種々の標準ナノ粒子分散試料について、ＴＥＭ観察平均粒径ｄＴＥＭ及び分散剤の粒径ｄＤＰを取得する。 First, creation of a correlation line will be described. In creating the correlation line, the TEM observation average particle diameter dTEM and the particle diameter dDP of the dispersant are obtained for various standard nanoparticle dispersed samples having different particle diameters.
ＴＥＭ観察平均粒径ｄＴＥＭは、ＴＥＭ観察により取得することができる。本実施形態では、ＴＥＭで観察される粒子の各最大径を手動で測定し、その平均値をＴＥＭ観察平均粒径ｄＴＥＭとする。 The TEM observation average particle diameter dTEM can be obtained by TEM observation. In the present embodiment, each maximum diameter of particles observed with a TEM is manually measured, and the average value is defined as a TEM observation average particle diameter dTEM.
分散剤の粒径ｄＤＰは、動的光散乱法、静的光散乱法等によって測定することができる。一般に、市販の金属ナノコロイド粒子が分散した溶液に含まれる分散剤の種類はその販売元により表示されている。そして、分散剤の種類が特定されれば、同種の分散剤を含む溶液を調製し、動的光散乱法、静的光散乱法等によって当該溶液中の分散剤の粒径を特定することができる。また、分散剤の粒径はデータベースとして蓄積することができ、粒径が既知の分散剤を使用する場合には、溶媒の種類や分散剤の濃度等が大きく変わらない限りは、既知の粒径を適用することができるので、新たに粒径を測定しなくてもよい。 The particle diameter dDP of the dispersant can be measured by a dynamic light scattering method, a static light scattering method, or the like. In general, the type of dispersant contained in a solution in which commercially available metal nanocolloid particles are dispersed is indicated by the vendor. If the type of dispersant is specified, a solution containing the same type of dispersant can be prepared, and the particle size of the dispersant in the solution can be specified by a dynamic light scattering method, a static light scattering method, or the like. it can. In addition, the particle size of the dispersant can be accumulated as a database, and when using a dispersant with a known particle size, the known particle size is not limited unless the type of solvent or the concentration of the dispersant is significantly changed. Therefore, it is not necessary to newly measure the particle size.
次いで、粒径が相違する種々の標準ナノ粒子分散試料について、ＴＥＭ観察平均粒径ｄＴＥＭ及び分散剤の粒径ｄＤＰから水力学的粒径ｄＨＤを取得する。水力学的粒径ｄＨＤは次の式（１）により求められる。
ｄＨＤ＝ｄＴＥＭ＋２×ｄＤＰ ・・・（１）
Next, for various standard nanoparticle dispersed samples having different particle diameters, the hydrodynamic particle diameter dHD is obtained from the TEM observation average particle diameter dTEM and the particle diameter dDP of the dispersant. The hydrodynamic particle diameter dHD is obtained by the following equation (1).
dHD = dTEM + 2 × dDP (1)
また、標準ナノ粒子分散試料ごとにＦＦＦ保持時間ＲＴを取得する。そして、標準ナノ粒子分散試料の各々の水力学的粒径ｄＨＤ及びＦＦＦ保持時間ＲＴを用いて、水力学的粒径ｄＨＤとＦＦＦ保持時間ＲＴとの相関線を作成する。 Further, the FFF retention time RT is acquired for each standard nanoparticle dispersed sample. Then, a correlation line between the hydrodynamic particle size dHD and the FFF retention time RT is created using the hydrodynamic particle size dHD and the FFF retention time RT of each standard nanoparticle dispersed sample.
また、測定対象とするナノ粒子分散試料のＦＦＦ保持時間ＲＴｘを取得する。次いで、このＦＦＦ保持時間ＲＴｘを相関線に照らし合わせて、ＦＦＦ保持時間ＲＴｘに対応する水力学的粒径ｄＨＤｘを取得する。その後、このナノ粒子分散試料について、水力学的粒径ｄＨＤｘ及び分散剤の粒径ｄＤＰｘからナノ粒子分散試料に含まれるナノ粒子の粒径ｄｘを取得する。粒径ｄｘは次の式（２）により求められる。ここで、粒径ｄＤＰｘはナノ粒子分散試料に含まれる分散剤の粒径である。
ｄｘ＝ｄＨＤｘ−２×ｄＤＰｘ ・・・（２）
Further, the FFF retention time RTx of the nanoparticle dispersed sample to be measured is acquired. Next, the FFF retention time RTx is collated with the correlation line to obtain the hydraulic particle size dHDx corresponding to the FFF retention time RTx. Thereafter, for this nanoparticle-dispersed sample, the particle size dx of the nanoparticles contained in the nanoparticle-dispersed sample is obtained from the hydrodynamic particle size dHDx and the particle size dDPx of the dispersant. The particle size dx is obtained by the following equation (2). Here, the particle size dDPx is the particle size of the dispersant contained in the nanoparticle-dispersed sample.
dx = dHDx−2 × dDPx (2)
このようにして、測定対象とするナノ粒子分散試料に含まれるナノ粒子の粒径を測定することができる。 In this way, the particle size of the nanoparticles contained in the nanoparticle dispersed sample to be measured can be measured.
本実施形態によれば、ＴＥＭ観察平均粒径とＦＦＦ保持時間との相関線ではなく、水力学的粒径とＦＦＦ保持時間との相関線を用いているため、優れた精度でナノ粒子の粒径を測定することができる。また、本実施形態を、例えば、鋼材から抽出した微細な析出物のサイズ個数密度分布の測定に適用した場合には、析出強化量の見積もりの正確性が向上し、鋼材の設計指針としての利用価値が向上するといった利点が得られる。ＦＦＦ装置を用いる分析方法は、バイオテクノロジー、ナノテクノロジー、有機材料等の分野において広く使用されている。本実施形態はこれらの分析方法に適用することもできる。 According to this embodiment, since the correlation line between the hydrodynamic particle size and the FFF retention time is used instead of the correlation line between the TEM observation average particle size and the FFF retention time, the nanoparticle particles can be obtained with excellent accuracy. The diameter can be measured. Moreover, when this embodiment is applied to, for example, the measurement of the size number density distribution of fine precipitates extracted from steel, the accuracy of estimation of the precipitation strengthening amount is improved and used as a design guide for steel. Benefits include increased value. Analysis methods using FFF devices are widely used in fields such as biotechnology, nanotechnology, and organic materials. The present embodiment can also be applied to these analysis methods.
次に、本願発明者らが行った実験に基づいて本発明の効果について更に詳細かつ具体的に説明する。 Next, the effects of the present invention will be described in more detail and specifically based on experiments conducted by the present inventors.
この実験では、標準ナノ粒子分散試料として、４種類のＡｕ標準ナノ粒子分散試料を用いた。これら４種類のＡｕ標準ナノ粒子分散試料に含まれるＡｕ標準ナノ粒子のＴＥＭ観察を行ったところ、ＴＥＭ観察平均粒径ｄＴＥＭは２．１ｎｍ〜１０．４ｎｍであった。また、平均粒径が２．１ｎｍのＡｕ標準ナノ粒子分散試料には分散剤としてグルタチオン（ＧＳＨ）が含まれ、その他の３種類のＡｕ標準ナノ粒子分散溶試料は分散剤としてタンニン酸が含まれていた。図２（ａ）にグルタチオンの構造式を示し、図２（ｂ）にタンニン酸の構造式を示す。これら分散剤の粒径ｄＤＰを測定した結果及び分子量等を表１に示す。なお、粒径ｄＤＰは、分散剤を超純水中に分散させた液体試料を調製し、２５℃にて、Ｍａｌｖｅｒｎ社製の動的光散乱装置ゼータサイザーナノＳを用いて測定された９０°散乱光から算出した値である。 In this experiment, four kinds of Au standard nanoparticle dispersion samples were used as standard nanoparticle dispersion samples. When TEM observation of Au standard nanoparticles contained in these four types of Au standard nanoparticle dispersion samples was performed, the TEM observation average particle diameter dTEM was 2.1 nm to 10.4 nm. In addition, an Au standard nanoparticle dispersion sample having an average particle diameter of 2.1 nm contains glutathione (GSH) as a dispersant, and the other three kinds of Au standard nanoparticle dispersion samples contain tannic acid as a dispersant. It was. FIG. 2A shows the structural formula of glutathione, and FIG. 2B shows the structural formula of tannic acid. The results of measuring the particle diameter dDP of these dispersants and the molecular weight are shown in Table 1. The particle size dDP was 90 ° measured by preparing a liquid sample in which a dispersant was dispersed in ultrapure water and using a dynamic light scattering device Zeta Sizer Nano S manufactured by Malvern at 25 ° C. It is a value calculated from scattered light.
その後、各Ａｕ標準ナノ粒子分散試料について、展開溶媒として０．０５ｗｔ％のドデシル硫酸ナトリウム（ＳＤＳ）溶液を１ｍＬ／ｍｉｎの流速で流しながら、ＦＦＦ保持時間ＲＴを取得した。このときの条件を表２に示す。図２（ｃ）にタンニン酸の構造式を示す。 Thereafter, for each Au standard nanoparticle-dispersed sample, an FFF retention time RT was obtained while flowing 0.05 wt% sodium dodecyl sulfate (SDS) solution as a developing solvent at a flow rate of 1 mL / min. Table 2 shows the conditions at this time. FIG. 2C shows the structural formula of tannic acid.
次いで、ＴＥＭ観察平均粒径ｄＴＥＭとＦＦＦ保持時間ＲＴとの相関線を作製した。この結果を図３（ａ）に示す。この相関線の直線回帰の決定係数Ｒ2は０．９８０１であった。 Next, a correlation line between the TEM observation average particle diameter dTEM and the FFF retention time RT was prepared. The result is shown in FIG. The coefficient of determination R 2 for linear regression of this correlation line was 0.9801.
その一方で、（１）式を用いてＴＥＭ観察平均粒径ｄＴＥＭ及び分散剤の粒径ｄＤＰから水力学的粒径ｄＨＤを求め、水力学的粒径ｄＨＤとＦＦＦ保持時間ＲＴとの相関線を作成した。この結果を図３（ｂ）に示す。この相関線の直線回帰の決定係数Ｒ2は０．９９７８であり、非常に良好な値が得られた。 On the other hand, the hydrodynamic particle diameter dHD is obtained from the TEM observation average particle diameter dTEM and the dispersant particle diameter dDP using the equation (1), and the correlation line between the hydraulic particle diameter dHD and the FFF retention time RT is obtained. Created. The result is shown in FIG. The coefficient of determination R 2 for linear regression of this correlation line was 0.9978, and a very good value was obtained.
その後、１ｇのモデル鋼材中から電解抽出した析出物が分散したナノ粒子分散試料を作製した。電解抽出操作は、アセチルアセトン系電解液に予め界面活性剤等の分散剤を適宜添加しておき、定電流電解抽出（５００ｍＡ、２ｈｒ）で行った。そして、分散剤として分子量が２８８．３８ｇ／ｍｏｌのドデシル硫酸ナトリウムを用いてナノ粒子分散試料のＦＦＦ保持時間ＲＴｘを取得し、このＦＦＦ保持時間ＲＴｘを相関線に照らし合わせて、水力学的粒径ｄＨＤｘを取得した。続いて、（２）式を用いて水力学的粒径ｄＨＤｘ及び分散剤の粒径ｄＤＰｘからナノ粒子分散試料に含まれるナノ粒子の粒径ｄｘを取得した。ドデシル硫酸ナトリウムの動的光散乱法によって吸着サイズを測定したところ、この値は０．７３ｎｍであり、これを分散剤の粒径ｄＤＰｘとして用いた。 Then, the nanoparticle dispersion | distribution sample in which the precipitate extracted electrolytically from 1g model steel materials was produced. The electrolytic extraction operation was performed by constant current electrolytic extraction (500 mA, 2 hr) by adding a dispersant such as a surfactant as appropriate to the acetylacetone-based electrolytic solution in advance. Then, using a sodium dodecyl sulfate having a molecular weight of 288.38 g / mol as a dispersant, the FFF retention time RTx of the nanoparticle dispersion sample is obtained, and the FFF retention time RTx is compared with the correlation line to obtain a hydraulic particle size. dHDx was obtained. Subsequently, the particle size dx of the nanoparticles contained in the nanoparticle-dispersed sample was obtained from the hydrodynamic particle size dHDx and the particle size dDPx of the dispersant using the equation (2). When the adsorption size was measured by the dynamic light scattering method of sodium dodecyl sulfate, this value was 0.73 nm, and this was used as the particle size dDPx of the dispersant.
また、ＦＦＦ装置からの流出液を逐次ＩＣＰプラズマ質量分析装置（ＩＣＰ−ＭＳ）に導入してＴｉの信号強度を測定した。この結果を図４に示す。図４の横軸は、上記の方法で取得した粒径ｄｘを示し、縦軸はＴｉの信号強度を示す。図４において信号強度のピークを示す粒径ｄｘは３．８ｎｍであった。一方、ＴＥＭ観察平均粒径とＦＦＦ保持時間との相関線を用いて取得した粒径は３．５ｎｍであった。 Further, the effluent from the FFF apparatus was sequentially introduced into an ICP plasma mass spectrometer (ICP-MS), and the signal intensity of Ti was measured. The result is shown in FIG. The horizontal axis in FIG. 4 indicates the particle size dx obtained by the above method, and the vertical axis indicates the signal intensity of Ti. In FIG. 4, the particle size dx showing the peak of the signal intensity was 3.8 nm. On the other hand, the particle size acquired using the correlation line between the TEM observation average particle size and the FFF retention time was 3.5 nm.
また、ナノ粒子分散試料中の析出物の粒径をＴＥＭ観察により測定したところ、図５に示す結果が得られた。この結果から、ピークの粒径は４．１ｎｍであった。なお、析出物の形状は板状であり、このＴＥＭ観察では各析出物の最大径を手動で測定した。 Moreover, when the particle size of the precipitate in the nanoparticle-dispersed sample was measured by TEM observation, the results shown in FIG. 5 were obtained. From this result, the particle size of the peak was 4.1 nm. In addition, the shape of the precipitate was plate-shaped, and in this TEM observation, the maximum diameter of each precipitate was measured manually.
以上のことから、水力学的粒径を用いる方法によれば、より正確性が高い粒径の測定が可能であるといえる。 From the above, it can be said that according to the method using the hydraulic particle size, it is possible to measure the particle size with higher accuracy.
１４：クロスフロー
１５：サンプル溶液
１６：分離層
１７：チャネルフロー
１８：小粒子
１９：中粒子
２０：大粒子
２１：分離膜
14: Cross flow 15: Sample solution 16: Separation layer 17: Channel flow 18: Small particles 19: Medium particles 20: Large particles 21: Separation membrane
Claims (3)
前記標準ナノ粒子分散試料に含まれる第１の分散剤の粒径及び前記第１の平均粒径から前記標準ナノ粒子の第１の水力学的粒径を取得する工程と、
前記標準ナノ粒子分散試料のフィールドフローフラクショネーションにおける第１の保持時間を取得する工程と、
前記第１の水力学的粒径と前記第１の保持時間との相関線を作成する工程と、
ナノ粒子及び第２の分散剤を含むナノ粒子分散試料のフィールドフローフラクショネーションにおける第２の保持時間を取得する工程と、
前記第２の保持時間に対応する第２の水力学的粒径を前記相関線から取得する工程と、
前記第２の水力学的粒径及び前記第２の分散剤の粒径から前記ナノ粒子の粒径を取得する工程と、
を有することを特徴とするナノ粒子の粒径測定方法。 Observing standard nanoparticles contained in the standard nanoparticle-dispersed sample with a transmission electron microscope, and obtaining a first average particle size of the standard nanoparticles;
Obtaining a first hydrodynamic particle size of the standard nanoparticles from the particle size of the first dispersant contained in the standard nanoparticle dispersion sample and the first average particle size;
Obtaining a first retention time in field flow fractionation of the standard nanoparticle dispersed sample;
Creating a correlation line between the first hydraulic particle size and the first retention time;
Obtaining a second retention time in field flow fractionation of a nanoparticle dispersed sample comprising nanoparticles and a second dispersant;
Obtaining a second hydraulic particle size corresponding to the second retention time from the correlation line;
Obtaining the particle size of the nanoparticles from the second hydraulic particle size and the particle size of the second dispersant;
A method for measuring the particle size of nanoparticles, comprising:
前記第２の水力学的粒径をｄＨＤｘ、前記第２の分散剤の粒径をｄＤＰｘ、前記ナノ粒子の粒径をｄｘとしたとき、下記（２）式が成り立つことを特徴とする請求項１に記載のナノ粒子の粒径測定方法。
ｄＨＤ＝ｄＴＥＭ＋２×ｄＤＰ ・・・（１）
ｄｘ ＝ｄＨＤｘ−２×ｄＤＰｘ ・・・（２） When the first average particle size is dTEM, the first hydraulic particle size is dHD, and the particle size of the first dispersant is dDP, the following equation (1) holds:
The following equation (2) is satisfied, where dHDx is the second hydraulic particle size, dDPx is the particle size of the second dispersant, and dx is the particle size of the nanoparticles. 2. The method for measuring the particle size of nanoparticles according to 1.
dHD = dTEM + 2 × dDP (1)
dx = dHDx−2 × dDP x (2)
前記第２の分散剤を含む第２の溶液を用いて動的光散乱法により前記第２の分散剤の粒径を測定することを特徴とする請求項１又は２に記載のナノ粒子の粒径測定方法。 The particle size of the first dispersant is measured by a dynamic light scattering method using the first solution containing the first dispersant,
3. The nanoparticle particle according to claim 1, wherein the particle size of the second dispersant is measured by a dynamic light scattering method using the second solution containing the second dispersant. Diameter measurement method.
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