WO2021199797A1 - Procédé de mesure de l'indice de réfraction de particules - Google Patents

Procédé de mesure de l'indice de réfraction de particules Download PDF

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Publication number
WO2021199797A1
WO2021199797A1 PCT/JP2021/006757 JP2021006757W WO2021199797A1 WO 2021199797 A1 WO2021199797 A1 WO 2021199797A1 JP 2021006757 W JP2021006757 W JP 2021006757W WO 2021199797 A1 WO2021199797 A1 WO 2021199797A1
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WIPO (PCT)
Prior art keywords
particles
refractive index
particle
light intensity
scattered light
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PCT/JP2021/006757
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English (en)
Japanese (ja)
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有祐 松浦
文子 中村
加藤　晴久
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国立研究開発法人産業技術総合研究所
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Priority to JP2022511661A priority Critical patent/JP7446008B2/ja
Publication of WO2021199797A1 publication Critical patent/WO2021199797A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/02—Investigating particle size or size distribution
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length

Definitions

  • the present invention relates to a method for measuring the refractive index of fine particles such as Brownian motion in a dispersion medium.
  • Non-Patent Document 1 discloses a method of analyzing an image of scattered light from a single particle and measuring the refractive index of the particle in the dispersion medium. Specifically, a dispersion medium in which particles are dispersed is housed in a transparent optical cell, which is irradiated with laser light, and a video camera via an optical microscope illuminates the scattered light from the particles due to the irradiation of the laser light. Record as a point.
  • the scattered light intensity I of the particles can be measured from the bright spot on the image, and the refractive index n of the particles can be calculated based on the values of I and d.
  • the particle size d is sufficiently smaller than the wavelength of the laser beam, Rayleigh scattering occurs, and the refractive index n can be calculated from Equation 1.
  • n s the refractive index of the dispersion medium
  • I 0 the incident laser light intensity
  • the value of the refractive index n should be calculated because there is a similar relationship between the particle size d, the refractive index n and the high scattering intensity I. Is possible.
  • Non-Patent Document 2 discloses a method of measuring the refractive index of particles while the particles are flowing together with the dispersion medium in an apparatus or the like by applying the above method to particles flowing together with the dispersion medium. Has been done.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to obtain the refractive index of fine particles such as Brownian motion in a dispersion medium more accurately and more easily.
  • the purpose is to provide a method for measuring the refractive index of particles.
  • the present inventors have noted that the proportionality coefficient and the incident laser light intensity I 0 as described above are both invariant under the same optical system, and these are reference particles having a known refractive index ( Hereinafter, it was conceived to estimate from the scattered light intensity I of (referred to as "reference particle").
  • the dispersion medium of refractive index n s a refractive index measuring method of fine particles such as Brownian motion
  • the particle diameter d c and a refractive index n c a first imaging step of obtaining a first continuous image capturing the movement of the bright spot of the irradiated scattered light of the laser beam reference particles at output Q c are dispersed in the dispersion medium to be known
  • said particles to be measured a second imaging step of obtaining a second consecutive images irradiates a laser beam to image the movement of the bright spot of the scattered light output Q o in the same optical system
  • the first imaging step is dispersed in the dispersion medium , from said movement of the bright spot due to the scattered light in the second consecutive images, imaging time the scattered light intensity for the bright points corresponding with particle diameter d o of the particles tau o by time integrating the integrated light intensity L o as well as measure obtains a first cumulative light intensity L
  • the refractive index of particles can be obtained accurately and easily.
  • the image analysis step from the formula A, may be characterized by calculating the refractive index n o. According to such a feature, the refractive index of the particles can be obtained more accurately and easily.
  • the particle size do is calculated from the relationship between the absolute temperature T and the viscosity ⁇ of the dispersion medium after obtaining the mean square displacement ⁇ MS in the plane, where the imaging interval of the second continuous image is ⁇ t. It may be characterized by being done. Further, in the above-described invention, the particle size do may be calculated from the following formula B, where kB is the Boltzmann constant. According to such a feature, the refractive index of the particles can be obtained more easily.
  • the apparatus used for the particle refractive index measuring method includes an optical cell 1, a laser irradiation unit 2, an imaging apparatus 3, and a processing apparatus 4.
  • the optical cell 1 is an optically transparent cell in which a dispersion medium 102 in which particles 101 are dispersed is retained or circulated.
  • the laser irradiation unit 2 includes a condenser such as a lens, and is arranged so that the laser beam 2L can be irradiated to the dispersion medium 102 in the optical cell 1 in the y-axis direction.
  • the image pickup device 3 is arranged so that the scattered light generated from the particles 101 can be imaged as an image in the xy plane so that the optical axis is along the z-axis direction toward the optical cell 1.
  • the image pickup device 3 can preferably use an image pickup element such as a CCD (Charge Coupled Device) sensor or a CMOS (Complementary Metal Oxide Semiconductor) sensor via an optical microscope or the like, and images of the above-mentioned scattered light at regular time intervals. It is possible to continuously image at the imaging interval ⁇ t of the above and output it as continuous image data.
  • an image pickup element such as a CCD (Charge Coupled Device) sensor or a CMOS (Complementary Metal Oxide Semiconductor) sensor via an optical microscope or the like, and images of the above-mentioned scattered light at regular time intervals. It is possible to continuously image at the imaging interval ⁇ t of the above and output it as continuous image data.
  • the processing device 4 includes an image analysis unit 41 that analyzes data of continuous images continuously output from the image pickup device 3, and particle information analysis that calculates the particle size and the refractive index of the particles based on the result of this image analysis.
  • a unit 42 and a data storage unit 43 for storing these analysis results together with measurement conditions and the like are provided.
  • the procedure of the particle refractive index measurement method will be described with reference to FIG. 3 with reference to FIG.
  • the reference particle is a particle whose refractive index is known at least
  • the measurement target particle is a particle whose refractive index is to be measured. ..
  • the processing common to the reference particle and the particle to be measured may be simply described as “particle”.
  • the dispersion medium in which the particles are dispersed is retained or circulated in the optical cell 1, and while the laser irradiation unit 2 irradiates the laser beam 2L, the image pickup device 3 continuously captures an image of the scattered light from the particles ( S1: First imaging step).
  • the image pickup device 3 captures the scattered light generated from the particles irradiated with the laser beam L2 at regular time intervals ⁇ t, and transmits the obtained group of images as continuous images to the processing device 4.
  • a continuous image is obtained by scattered light of particles (S2: second imaging step).
  • the reference particles were used in the first imaging step, and the measurement target particles were used in the second imaging step.
  • the order of the first imaging step S1 and the second imaging step S2 may be interchanged.
  • the obtained continuous image is image-analyzed by the image analysis unit 41 and the particle information analysis unit 42 (S3: image analysis step).
  • S3 image analysis step
  • both the continuous image of the reference particle and the continuous image of the measurement target particle are analyzed.
  • the particle information analysis unit 42 obtains the particle size of the corresponding particle based on the mean square displacement of the bright spot calculated by the image analysis unit 41. Specifically, since the particles corresponding to luminescent spot P (i) has Brownian motion in the dispersion medium, the particle diameter d (i) is (in the xy plane) 2D mean square displacement delta MS
  • the following equation 2 that connects the self-diffusivity coefficient D of the particle with And Stokes-Einstein's formula can be calculated by the following formula 3.
  • k B Boltzmann constant
  • T absolute temperature
  • ⁇ viscosity of the dispersion medium.
  • k B Boltzmann constant
  • T absolute temperature
  • ⁇ viscosity of the dispersion medium
  • the representative value is, for example, an average value or a median value. When a reference particle having a known particle size is used, it is not necessary to obtain the particle size of the reference particle.
  • the particle information analysis unit 42 calculates the refractive index of the particles.
  • a relationship of L ⁇ I ⁇ is established between the integrated light intensity L of the observed bright spot and the scattered light intensity I of the particles corresponding to the bright spot ( ⁇ : imaging time of the imaging device 3). Since the relationship of I 0 ⁇ Q is established between the incident laser light intensity I 0 and the output Q of the laser irradiation unit 2, the above equation 1 holds between the scattered light intensity I and the refractive index n of the particles. , It is rewritten as the following equation 4 using only one constant C (hereinafter referred to as constant C) related to the entire optical system of the device that imaged the particles.
  • L the integrated light intensity of the bright spot corresponding to the particle
  • Q the output of the laser light irradiating the particle
  • ⁇ the imaging time
  • n the refractive index of the particle
  • n s the refractive index of the dispersion medium
  • d The particle size of the particles.
  • the constant C is a value unique to the device that depends on a large number of variables based on the specifications of the members used as the optical system, such as the numerical aperture of the device, the magnification of the objective lens, and the sensitivity of the camera. It is difficult to ask. Therefore, in this embodiment, we try to measure the refractive index of the particles without depending on this constant C.
  • the subscript of the variable for the reference particle is "c", and the subscript for the particle to be measured is "o". That is, for the reference particles, Q c: output of the laser beam at the time of imaging, tau c: imaging time, L c: integrated intensity of a corresponding bright spot, n c: refractive index of the particles, d c: particle size There, the measurement target particles, Q o: output of the laser beam at the time of imaging, tau o: imaging time, L o: the integrated light intensity of the corresponding bright spot, n o: a refractive index of the particles, d o: particle size Is.
  • the output of the laser beam and the imaging time may be different for both the reference particle and the measurement target particle. It is also possible to obtain the constant C in advance using the formulas 4 and 5 for the reference particle and calculate the refractive index using the formulas 4 and 5 in which the constant C is substituted for the particle to be measured.
  • the above-mentioned method for measuring the refractive index of particles can also be performed as follows.
  • the relationship of the exposure time ⁇ imaging device 3 is taken into account that it is a finite length, linking the self-diffusion coefficient D of the mean square displacement delta MS and particles
  • the particle size may be derived by setting the time interval ⁇ t in the equation (Equation 2) as ( ⁇ t ⁇ / 3). That is, the following equation 2'may be used instead of equation 2.
  • the particle size of each particle and the integrated light intensity of the corresponding bright spot may be used. good. In this case, the refractive index of each particle to be measured can be obtained.
  • correction may be added in consideration of the fact that the laser beam 2L has an intensity distribution within the irradiation range.
  • the constant C is a function of the position (that is, the x, y coordinate values) in the captured image
  • the constant C (x, y) is obtained from the integrated light intensity of the reference particle.
  • the refractive index of the particle to be measured may be obtained from the value of the constant C corresponding to the xy coordinate value of the bright spot of the particle to be measured.
  • the particle size, the refractive index of the particles, and the scattered light intensity are related by the equation 1 based on the Rayleigh scattering theory, but a theory other than the Rayleigh scattering theory may be used.
  • the relationship between the particle size, the refractive index of the particles, and the scattered light intensity can be determined based on the Mie scattering theory. In this case, only the right side of the equation 5 is changed, and the others are the same. That is, the reference particle and the measurement target particles light intensity ratio L o / L c, it is possible to calculate the refractive index n o of the measurement target particles.
  • Polystyrene latex (PSL) particles having a particle diameter of 100 nm were used as reference particles, and PSL particles having a particle diameter of 60 nm and silica particles having a particle diameter of 80 nm were used as measurement target particles (hereinafter, referred to as PSL100, PSL60, and Silicona80, respectively). .. Water was used as the dispersion medium.
  • the laser irradiation unit 2 includes a solid-state laser capable of irradiating 2L of laser light having a wavelength of 532 nm, and an optical system that collects light so that the beam diameter becomes 200 ⁇ m at the position of imaging in the optical cell 1 by the imaging device 3.
  • the image pickup apparatus 4 includes an optical microscope equipped with a 10x objective lens and a CMOS (sCMOS) camera for scientific measurement equivalent to 6.5 ⁇ m square per pixel.
  • the time (imaging) interval ⁇ t of the sCMOS camera is 33.3 ms.
  • the output Q c of the laser irradiation unit 2 was set to 100 mW, and the imaging time ⁇ c of the imaging device 3 was set to 33.2 ms.
  • the output Q o of the laser irradiation unit 2 was set to 1500 mW, and the imaging time ⁇ o of the imaging device 3 was set to 33.2 ms.
  • Table 1 shows the average particle size as the measurement results of the particle size of the reference particle and the particle to be measured.
  • FIG. 4 shows the actual measurement results of the integrated light intensity of each bright spot for the above-mentioned reference particles and the particles to be measured as a cumulative distribution.
  • the horizontal axis of the figure represents a value obtained by correcting the integrated light intensity L with the output (Q c or Q o ) of the laser irradiation unit 2 and the imaging time ( ⁇ c or ⁇ o) of the imaging device 3.
  • the refractive index of the particle to be measured can be easily obtained from the measurement results of the particle diameter and the integrated light intensity of the reference particle and the particle to be measured by the above-mentioned particle refractive index measurement method.

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
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Abstract

[Problème] Fournir un procédé de mesure de l'indice de réfraction de particules, avec lequel l'indice de réfraction de particules microscopiques qui, par exemple, présentent un mouvement brownien dans un milieu de dispersion est obtenu avec précision et aisément. [Solution] Selon la présente invention, des particules de référence pour lesquelles le diamètre de particule dc et l'indice de réfraction nc sont déjà connus sont dispersées dans un milieu de dispersion ayant un indice de réfraction ns, la dispersion résultante est irradiée avec une lumière laser à une sortie Qc pendant un temps d'imagerie τc, et le mouvement de points lumineux de lumière diffusée est capturé pour obtenir des premières images consécutives. De plus, les particules à mesurer sont dispersées dans le milieu de dispersion, la dispersion résultante est irradiée avec une lumière laser à Une sortie Qo pendant un temps d'imagerie τo au moyen du même système optique que dans la première étape d'imagerie, et le mouvement de points lumineux de lumière diffusée est capturé pour obtenir des deuxièmes images consécutives. Le diamètre de particule do des particules et l'intensité de lumière intégrée Lo obtenus par intégration temporelle des intensités de lumière diffusée pour des points brillants correspondants au cours du temps d'imagerie τo sont mesurés à partir du mouvement des points brillants causé par la lumière diffusée dans les deuxièmes images consécutives, l'intensité de lumière intégrée Lc obtenue par intégration temporelle des intensités de lumière diffusée pour les points lumineux des particules de référence à partir des premières images consécutives au cours du temps d'imagerie τc est déduite, et l'indice de réfraction no des particules est calculé à partir du rapport d'intensité de lumière Lo/Lc.
PCT/JP2021/006757 2020-03-31 2021-02-24 Procédé de mesure de l'indice de réfraction de particules WO2021199797A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022270204A1 (fr) * 2021-06-21 2022-12-29 富士フイルム株式会社 Dispositif de mesure de particules et procédé de mesure de particules
WO2023139741A1 (fr) * 2022-01-21 2023-07-27 株式会社日立ハイテク Appareil de mesure de particule

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05172732A (ja) * 1991-12-25 1993-07-09 Hitachi Electron Eng Co Ltd 液体中微粒子検出装置およびその検出方法
JPH1183724A (ja) * 1997-06-23 1999-03-26 Bayer Corp フローサイトメトリーの標準およびキャリブレーターとして使用するための合成ポリマー粒子
JP2012515351A (ja) * 2009-01-16 2012-07-05 ニューヨーク ユニバーシティー ホログラフィビデオ顕微鏡観察を伴う自動的リアルタイム粒子特徴付け及び三次元速度測定
WO2017069260A1 (fr) * 2015-10-23 2017-04-27 株式会社カワノラボ Dispositif d'analyse de particules
JP2018179971A (ja) * 2017-04-14 2018-11-15 リオン株式会社 粒子測定装置および粒子測定方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05172732A (ja) * 1991-12-25 1993-07-09 Hitachi Electron Eng Co Ltd 液体中微粒子検出装置およびその検出方法
JPH1183724A (ja) * 1997-06-23 1999-03-26 Bayer Corp フローサイトメトリーの標準およびキャリブレーターとして使用するための合成ポリマー粒子
JP2012515351A (ja) * 2009-01-16 2012-07-05 ニューヨーク ユニバーシティー ホログラフィビデオ顕微鏡観察を伴う自動的リアルタイム粒子特徴付け及び三次元速度測定
WO2017069260A1 (fr) * 2015-10-23 2017-04-27 株式会社カワノラボ Dispositif d'analyse de particules
JP2018179971A (ja) * 2017-04-14 2018-11-15 リオン株式会社 粒子測定装置および粒子測定方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022270204A1 (fr) * 2021-06-21 2022-12-29 富士フイルム株式会社 Dispositif de mesure de particules et procédé de mesure de particules
WO2023139741A1 (fr) * 2022-01-21 2023-07-27 株式会社日立ハイテク Appareil de mesure de particule

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JPWO2021199797A1 (fr) 2021-10-07

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