WO2022014636A1 - Particle density measurement method and system therefor - Google Patents

Particle density measurement method and system therefor Download PDF

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Publication number
WO2022014636A1
WO2022014636A1 PCT/JP2021/026446 JP2021026446W WO2022014636A1 WO 2022014636 A1 WO2022014636 A1 WO 2022014636A1 JP 2021026446 W JP2021026446 W JP 2021026446W WO 2022014636 A1 WO2022014636 A1 WO 2022014636A1
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dispersion medium
particle size
fine particles
particle
measuring
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PCT/JP2021/026446
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French (fr)
Japanese (ja)
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晴久 加藤
文子 中村
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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 JP2022536417A priority Critical patent/JP7296172B2/en
Publication of WO2022014636A1 publication Critical patent/WO2022014636A1/en

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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
    • G01N9/00—Investigating density or specific gravity of materials; Analysing materials by determining density or specific gravity

Definitions

  • the present invention relates to a particle density measuring method and a system thereof for calculating the density of the fine particles by measuring the particle size distribution and the particle mass distribution of the fine particles in the dispersion medium, respectively.
  • the present invention relates to a particle density measuring method and a system thereof that can calculate the density by separating fine particles of a plurality of kinds of materials having different densities.
  • the measurement of the density of particles in the dispersion medium is incorporated into the production line and used for the control of the raw materials supplied and the verification of the product.
  • the density measurement can provide various information such as the hollowness of hollow particles, the mixing ratio of specific components of alloy particles, and the abundance ratio of different crystals in the particles.
  • the density measurement can provide important information for various controls in the production line.
  • the density of particles can be calculated by measuring the mass and diameter of a single (individual) particle.
  • Non-Patent Document 1 describes a resonance type particle mass measuring method for measuring the mass of fine particles.
  • the mass of the particles in the cantilever can be measured with high accuracy by guiding the dispersion medium containing the fine particles to the thin tube in the cantilever and detecting the change in the resonance frequency of the cantilever. That is, for a thin tube having a constant volume, the resonance frequency of the cantilever changes depending on the difference between the mass when the dispersion medium containing no fine particles (sol only) is filled and the mass when the dispersion medium containing fine particles is filled. However, the mass of the fine particles that is the difference between these masses can be measured.
  • Patent Document 1 for the particle size of a single fine particle, a dispersion medium containing the fine particle is guided in a light-irradiated conduit, and the scattered light intensity from the specific fine particle is measured. There is a method to calculate by. Further, in recent years, even in the case of a flow field, a method of correcting this and measuring the particle size with high accuracy has been proposed.
  • Extracting a single particle from a dispersion medium containing fine particles, measuring the particle size, and measuring by the resonance type particle mass measurement method as described above is troublesome in operation. Therefore, the particle size distribution and the particle mass distribution of a large number of fine particles contained in the dispersion medium can be measured, respectively, and the average particle size and the average particle mass can be obtained, respectively, and the density can be easily calculated. On the other hand, if fine particles of a plurality of types of materials having different densities are contained, these cannot be separated and the density cannot be calculated.
  • the present invention has been made in view of the above-mentioned circumstances, and an object thereof is to separate fine particles of a plurality of kinds of materials having different densities and to separate them in a dispersion medium. It is an object of the present invention to provide a method and a system for measuring the density of fine particles easily and accurately.
  • the present inventors do not obtain the average particle size and the average particle mass from the particle size distribution and the particle mass distribution as described above, but perform mass measurement after making the particle size uniform. I came up with the idea that the mass distribution can be separated into distributions due to density differences.
  • the particle density measuring method is a particle density measuring method for calculating the density of the fine particles by measuring the particle size distribution and the particle mass distribution of the fine particles in the dispersion medium.
  • a particle size distribution measuring step in which the particle size distribution of the fine particles is measured by a particle size measuring device while guiding a dispersion medium, and the dispersion medium sent out from the line are passed through a thin tube provided in the transducer.
  • the particle size distribution measuring step includes a mass distribution measuring step of calculating the particle mass distribution from a change in the resonance frequency of the transducer while sequentially guiding the particles to a narrower conduit thinner than the conduit.
  • a dispersion medium adjusting step of controlling the distribution range of the particle size of the fine particles in the dispersion medium flowing in the inside within a unit time and providing the dispersion medium to the pipeline is included, and the inside of the fine tube is within a unit time. It is characterized in that the distribution range of the particle size of the fine particles in the dispersion medium flowing in the tubule is controlled, and the dispersion medium is provided to the capillary channel.
  • the particle size distribution measuring step may further include a step of adjusting the number concentration of the fine particles in the dispersion medium sent out from the pipeline to provide the dispersion medium to the fine pipeline. According to this feature, the particle mass distribution of fine particles can be obtained with high accuracy, and the density of fine particles in the dispersion medium can be measured easily and accurately even if the fine particles of multiple kinds of materials having different densities are contained. can do.
  • the particle size distribution measuring step may further include a step of providing the dispersion medium sent out from the pipeline to the thin pipeline in an intermittent state. According to this feature, even if fine particles of a plurality of kinds of materials having different densities are contained, the density of the fine particles can be measured easily and accurately.
  • the particle size measuring device may be a device that measures the particle size from the intensity of scattered light from the fine particles while guiding the dispersion medium into the duct irradiated with light, and calculates the particle size distribution. .. According to this feature, the particle size distribution can be measured easily and accurately, and the density of the fine particles in the dispersion medium can be easily and accurately measured even if the fine particles of a plurality of kinds of materials having different densities are contained. Can be measured.
  • a force field acting on the fine particles diffusing in the dispersion medium may be formed, and the fine particles may be arranged in the dispersion medium according to the particle size and guided to the conduit. good.
  • the force field is a flow field in a direction substantially orthogonal to the liquid feeding direction along the flow path of the dispersion medium, and the fine particles may be arranged so as to intersect the liquid feeding direction. .. According to this feature, fine particles can be easily arranged according to the particle size by a flow field, and the density of the fine particles in the dispersion medium can be easily adjusted even if the fine particles of a plurality of kinds of materials having different densities are contained. Moreover, it can be measured with high accuracy.
  • the particle density measuring system is a particle density measuring system for calculating the density of the fine particles by measuring the particle size distribution and the particle mass distribution of the fine particles in the dispersion medium, and the particle density measuring system is described in the pipeline.
  • a particle size distribution measuring unit that measures the particle size distribution of the fine particles with a particle size measuring device while guiding a dispersion medium, and the dispersion medium sent out from the line are used in a thin tube provided in the transducer.
  • the particle size distribution measuring unit includes a mass distribution measuring unit that measures the particle mass distribution from a change in the resonance frequency of the transducer while sequentially guiding the particles to a narrower pipeline thinner than the pipeline.
  • a dispersion medium adjusting unit that controls the distribution range of the particle size of the fine particles in the dispersion medium flowing in the inside within a unit time and provides the dispersion medium to the tube is included, and the inside of the fine tube is within a unit time. It is characterized in that the distribution range of the particle size of the fine particles in the flowing dispersion medium is controlled, and the dispersion medium is provided to the capillary channel.
  • the fine particles of the fine particles even if the fine particles of multiple kinds of materials having different densities are contained, they can be separated, and the fine particles in the dispersion medium can be separated.
  • the density can be measured easily and accurately.
  • the particle size distribution measuring unit may further include a mechanism for adjusting the number concentration of the fine particles in the dispersion medium sent out from the pipeline to provide the dispersion medium to the fine pipeline. According to this feature, the particle mass distribution of fine particles can be obtained with high accuracy, and the density of fine particles in the dispersion medium can be measured easily and accurately even if the fine particles of multiple kinds of materials having different densities are contained. can do.
  • the particle size distribution measuring unit may further include a mechanism for providing the dispersion medium sent out from the pipeline to the thin pipeline in an intermittent state. According to this feature, even if fine particles of a plurality of kinds of materials having different densities are contained, the density of the fine particles can be measured easily and accurately.
  • the particle size measuring device may be a device that measures the particle size from the intensity of scattered light from the fine particles while guiding the dispersion medium into the duct irradiated with light, and calculates the particle size distribution. .. According to this feature, the particle size distribution can be measured easily and accurately, and the density of the fine particles in the dispersion medium can be easily and accurately measured even if the fine particles of a plurality of kinds of materials having different densities are contained. Can be measured.
  • the dispersion medium adjusting unit forms a force field acting on the fine particles diffusing in the dispersion medium, arranges the fine particles in the dispersion medium according to the particle size, and guides the fine particles to the conduit. May be good.
  • the force field is a flow field in a direction substantially orthogonal to the liquid feeding direction along the flow path of the dispersion medium, and the fine particles may be arranged so as to intersect the liquid feeding direction. .. According to this feature, fine particles can be easily arranged according to the particle size by a flow field, and the density of the fine particles in the dispersion medium can be easily adjusted even if the fine particles of a plurality of kinds of materials having different densities are contained. Moreover, it can be measured with high accuracy.
  • FIGS. 1 and 2 An embodiment of the particle density measuring system and the particle density measuring method of the present invention will be described with reference to FIGS. 1 and 2.
  • the particle density measuring system 10 is a system for measuring the density of fine particles using a dispersion medium in which fine particles are dispersed.
  • the particle density measuring system 10 includes a particle size distribution measuring unit 1 for measuring the particle size distribution of fine particles in the dispersion medium, and a mass distribution measuring unit 2 for measuring the particle mass distribution of the fine particles.
  • an eluent introduction unit 11 for introducing a dispersion medium
  • a sample introduction unit 12 for introducing fine particles as a sample into the solution introduced from the eluent introduction unit 11 and dispersing them to form a dispersion medium.
  • the particle size distribution measuring unit 1 includes a particle size measuring device 14 capable of measuring the particle size in the pipeline.
  • the particle size measuring device 14 calculates the particle size of the fine particles by, for example, irradiating the dispersion medium in the conduit with laser light and measuring the scattered light intensity from the fine particles moving in Brownian motion in the dispersion medium. can do.
  • a multi-angle light scattering detector MALS: MultiAngleLightScattering
  • a known mass measuring device 31 by a resonance type particle mass measuring method can be used for the mass distribution measuring unit 2. That is, the mass measuring device 31 is a device that guides the dispersion medium to the thin tube provided in the vibrator and measures the mass of the dispersion medium in the thin tube from the resonance frequency of the vibrator. That is, the mass measuring device 31 can measure the mass of the fine particles based on the density of the dispersion medium from the change in the resonance frequency, and can measure the particle mass distribution of the fine particles.
  • the oscillator is composed of, for example, a cantilever, and a thin tube is arranged so as to extend from the fixed end of the cantilever to the free end, fold back, and return to the fixed end.
  • the narrow line is a line thinner than the above line.
  • the inner diameter of the narrow conduit is, for example, 500 nm to 300 ⁇ m.
  • the density of the fine particles in the dispersion medium depends on the particle size distribution obtained by the particle size distribution measuring unit 1 and the particle mass distribution obtained by the mass distribution measuring unit 2. Desired. That is, since the cube of the particle size is proportional to the mass, both distributions have a one-to-one correspondence with each particle size and mass, and the density is calculated by dividing the corresponding mass by the volume obtained from the particle size. ..
  • the particle size distribution measuring unit 1 includes a dispersion medium adjusting unit 13.
  • the dispersion medium adjusting unit 13 controls the distribution range of the particle size of the fine particles in the dispersion medium flowing within a unit time in the dispersion medium guided to the small tube of the mass measuring device 31. That is, the distribution range of the particle size of the dispersion medium guided to the thin tube of the mass measuring device 31 is limited by dividing the time for introduction or the like.
  • the volumes of the particles will be the same.
  • the density which is the eigenvalue of the material
  • the mass which is the product of the density and the volume, becomes the jumping value.
  • the particle diameters are not exactly the same, and the distribution range of the particle diameters is controlled and limited so as to be narrow. If the particle diameters are made uniform in this way, the obtained particle mass distribution (mass-number of particles graph) will have as many peaks as the number corresponding to the type of density, and the distribution will be due to the density difference. Can be separated into.
  • the distribution range of the particle diameter is controlled to such an extent that the obtained particle mass distribution can be separated into a distribution due to the density difference.
  • the mass distribution can be separated into the distribution due to the density difference even when fine particles of multiple types of materials with different densities are included, and the corresponding density can be obtained from the particle size distribution and the particle mass distribution. can.
  • the distribution range of the scattered light intensity is wide for the dispersion medium having a large particle size distribution. It can be very widespread.
  • the scattered light intensity changes in proportion to the cube of the particle size
  • the range of the detector that detects the scattered light intensity is greatly exceeded, and some of the samples in the group can be detected by the particle size and some cannot be detected. That is, there is a range in which detection omission occurs depending on the particle size, and if the particle size distribution of the sample is estimated only by the particle size that can be detected, the error becomes very large.
  • the above-mentioned dispersion medium adjusting unit 13 is arranged in front of the particle size measuring device 14, and the distribution range of the particle size of the fine particles in the dispersion medium flowing within a unit time is controlled. That is, the distribution range of the particle size of the dispersion medium guided to the conduit of the particle size measuring device 14 can be limited by dividing the time for introduction or the like. As a result, the particle size measuring device 14 can control the distribution range of the intensity of the scattered light by adjusting the intensity of the laser light to be irradiated according to the limited distribution range of the particle size, and the detection omission of fine particles. Can be very small.
  • Such a dispersion medium adjusting unit 13 is an apparatus capable of forming a force field acting on the fine particles diffusing in the dispersion medium and arranging the fine particles in the dispersion medium according to the particle size, for example, flow field separation.
  • a device according to the method FFF: Field Flow Fractionation
  • FFF Field Flow Fractionation
  • an AF4 apparatus using an asymmetrical flow field flow field separation method (AF4: Asymmetrical Flow Filed Flow Fractionation) using a crossing force field can be used.
  • the AF4 device has a liquid feeding direction along a flow path from the inflow port 16 to the outflow port 18, and by providing a microfiltration membrane 19 on one side wall of the flow path, the AF4 device is substantially in the liquid feeding direction by the dispersion medium 17.
  • the flow field 50 in the orthogonal direction can be formed as a crossing force field.
  • the fine particles 51 once collected at one place on the surface of the microfiltration membrane 19 are diffused from the microfiltration membrane 19 toward the center of the flow path by the flow field 50 orthogonal to the liquid feeding direction, and the particles are diffused from the microfiltration membrane 19 toward the center of the flow path. They are arranged in the dispersion medium so as to be classified according to the difference in diffusion rate based on the diameter. Specifically, the fine particles 51 are arranged in a direction intersecting the liquid feeding direction so that the particle diameter becomes smaller toward the center of the flow path. Further, in the laminar flow along the liquid feeding direction, there is a velocity gradient that increases from the outer periphery of the flow path toward the center.
  • the fine particles 51 having a small particle diameter near the center of the flow path are sequentially advanced in the flow path, and the fine particles 51 are arranged according to the particle size in the liquid feeding direction. That is, the fine particles 51 are arranged according to their particle diameters by the flow field 50 of the flow in the liquid feeding direction and the flow in the direction orthogonal to the flow. It should be noted that fine particles are provided according to a known particle size, such as a method in which a flow path is curved to apply a centrifugal force by liquid feeding in a direction substantially orthogonal to the liquid feeding direction as a force field, or a method using an electric field or a magnetic field. A device for arranging may be used.
  • the dispersion medium adjusting unit 13 can control the distribution range of the particle size of the fine particles flowing in the flow path within a unit time. If this is guided to the conduit of the particle size measuring device 14, the distribution range of the particle diameter of the fine particles in the dispersion medium guided to the conduit can be controlled within a unit time.
  • the dispersion medium adjusting unit 13 may further include a mechanism for adjusting the number concentration and the flow rate of the dispersion medium leading to the particle size measuring device 14.
  • the particle size is measured by the particle size measuring device 14 by diluting the dispersion medium whose particle size distribution has been adjusted in the dispersion medium adjusting unit 13, or separating and concentrating only a part of the dispersion medium. Adjust to make it easier to do.
  • a mechanism for dividing the dispersion medium into pieces for each derived time and a mechanism for adjusting the time until the dispersion medium is introduced into the particle size measuring device 14 may be provided.
  • the particle size distribution measuring unit 1 is further provided with a connecting unit 20 for sequentially guiding the dispersion medium to the mass measuring device 31.
  • the connection unit 20 functions as a number concentration adjusting unit for adjusting the number concentration of fine particles in the dispersion medium introduced into the mass measuring device 31 so as to facilitate mass measurement in the mass measuring device 31.
  • the split 21 is used to avoid the arranged portion of the fine particles in the dispersion medium and separate only the dispersion medium (for example, only the upstream side of the flow in the direction orthogonal to the liquid feeding direction).
  • the number concentration of the fine particles can be increased (concentrated) and sent to the mass distribution measuring unit 2 in a state where the dispersion medium is intermittent.
  • the number concentration per hour can be adjusted and the dispersion medium can be sent to the mass distribution measuring unit 2.
  • a solution to which fine particles are first added may be added to reduce (dilute) the concentration of the number of fine particles, and the dispersion medium may be sent out. Further, the dispersion medium may be divided and guided to the mass measuring device 31 offline by using the preparative mechanism 24.
  • the particle size measuring device 14 and the mass measuring device 31 are each connected to an arithmetic unit (not shown), and the particle size distribution and the particle mass distribution can be calculated by the arithmetic unit.
  • the arithmetic unit can calculate the density of fine particles from the obtained particle size distribution and particle mass distribution. For example, even if the mass distribution is measured by diluting the dispersion medium for which the particle size distribution has been measured, it can be assumed that the distribution ratio of the particle size of the fine particles is constant. The density can be calculated correspondingly.
  • the AF4 AF2000 system (manufactured by Postnova Analytics) was used for the dispersion medium adjusting unit 13.
  • a cellulose thin film Z-MEM-AQU-427N: molecular weight cutoff value of 1000
  • Z-MEM-AQU-427N molecular weight cutoff value of 1000
  • a 0.1% NovaChem Surfactant 100 C-SUR-100 dispersant (manufactured by Postnova Analytics) aqueous solution was used as the solution, and ultrapure water was used as the diluting water.
  • ultrapure water "milli-Q water” purified by an ion exchange filter and a 0.1 ⁇ m filter and containing no fine particles having an electrical resistivity of 18.2 M ⁇ ⁇ cm or more and an organic carbon concentration of 5 ppb or less is used. board.
  • a resonance type mass measuring device Archimedes manufactured by Malvern Panasonic
  • a Nano sensor manufactured by Malvern Panasonic
  • the flow velocity of the dispersion medium adjusting unit 13 in the liquid feeding direction was set to 1.0 mL / min and the fine particles were arranged according to the particle size, they had peaks at two positions of the outflow time. I found out.
  • the peak at the outflow time of 20 to 25 minutes is a fine particle having a particle size of 200 nm
  • the peak at the outflow time of 27 to 37 minutes is a fine particle having a particle size of 300 nm.
  • Such a mixed sample was directly introduced into the thin tube of the mass measuring device 31 without passing through the dispersion medium adjusting unit 13.
  • mass distributions of three peaks were obtained. Further, as shown in FIG. 6, assuming that the particle size of the fine particles dispersed in the dispersion medium is 300 nm, the densities are calculated and the average densities of each of the three peaks are 1.05 and 1.28. , 2.00 g / cm 3 density was calculated. Originally, the densities of polystyrene latex and silica contained in the above-mentioned mixed sample are 1.05 g / cm 3 and 2.00 g / cm 3 , respectively, but in reality, the original densities are 1.28 g / cm 3. A different value has been calculated.
  • the fine particles are arranged by the dispersion medium adjusting unit 13 to separate the vicinity of the original two peaks (200 nm and 300 nm, respectively), and the particle size is measured by the particle size measuring device 14 at each peak.
  • the particle size distribution was obtained (an example of the particle size distribution measurement step). MALS was used as the particle size measuring device 14. Further, the particle mass distribution was obtained by the mass measuring device 31 (an example of the mass distribution measuring step), and the density of the fine particles was recalculated.
  • the result corresponding to the silica density of 2.00 g / cm 3 was obtained for the 200 nm peak. Further, as shown in FIG. 8, the results obtained that the 300 nm peak matched the density of polystyrene latex and silica of 1.05 g / cm 3 and the density of silica of 2.00 g / cm 3.
  • silica fine particles having a particle size of about 200 nm are mixed in the silica aqueous dispersion, and as a result of assuming that the particle size of this sample is 300 nm without passing through the dispersion medium adjusting unit 13. I have calculated the inaccurate value as the density. It is probable that this is because the masses of silica having a particle size of around 200 nm and polystyrene latex having a particle size of around 300 nm could not be separated, so the numerical value located between the densities of both was calculated as the density. ..
  • the fine particles in the dispersion medium adjusting unit 13 and controlling the distribution range of the particle size an example of the dispersion medium adjusting step
  • even a sample in which fine particles having different densities are mixed can be obtained.
  • the mass could be separated corresponding to each of the two densities, and the particle density could be obtained with high accuracy from the particle size distribution.
  • the particle density measurement system 10 can calculate the density of each particle by separating even if it contains fine particles of a plurality of kinds of materials having different densities. Therefore, the particle density measurement system 10 can be used for monitoring and quality control of particle materials in material synthesis and the like, and the hollowness of hollow particles, the mixing ratio of specific components of alloy particles, and the parts having different crystallinity in the particles. It is also possible to estimate the abundance ratio of particles, and various applications are expected.

Abstract

Provided is a method for separating microparticles and easily and accurately measuring the density of the microparticles in a dispersion medium, even when microparticles of a plurality of types of materials having different densities are included.　This particle density measurement includes calculating the density of microparticles by measuring a particle size distribution and a particle mass distribution of the microparticles in the dispersion medium. The method is characterized by including: a particle size distribution measuring step of measuring, by a particle size measurement device, the particle size distribution of the microparticles while introducing the dispersion medium into a conduit; and a mass distribution measuring step of measuring the particle mass distribution from changes in a resonant frequency of an oscillator while sequentially introducing the dispersion medium sent from the conduit into a narrow conduit provided to the oscillator. The particle size distribution measuring step includes a dispersion medium adjusting step of controlling a distribution range of the particle size of the microparticles in the dispersion medium that flows in the conduit within a unit time and providing the dispersion medium to the conduit, so as to control a distribution range of the particle size of the microparticles in the dispersion medium that flows in the narrow conduit within the unit time and provide the dispersion medium to the narrow conduit.

Description

粒子密度測定方法及びそのシステムParticle density measurement method and its system
　本発明は、分散媒中の微小粒子の粒子径分布及び粒子質量分布をそれぞれ測定して前記微小粒子の密度を算出する粒子密度測定方法及びそのシステムに関する。特に、本発明は、密度を異にする複数種類の材質の微小粒子を含んでいてもこれを分離して、密度を算出可能とする粒子密度測定方法及びそのシステムに関する。 The present invention relates to a particle density measuring method and a system thereof for calculating the density of the fine particles by measuring the particle size distribution and the particle mass distribution of the fine particles in the dispersion medium, respectively. In particular, the present invention relates to a particle density measuring method and a system thereof that can calculate the density by separating fine particles of a plurality of kinds of materials having different densities.
　分散媒中の粒子の密度測定は、製造ラインに組み込まれて、供給される原材料の管理や、製造物の検定などに用いられる。例えば、前記密度測定は、中空状の粒子の中空度や、合金粒子の特定成分の混合率、粒子中の異なる結晶の存在比率の各種情報を与え得る。また、分散媒中の粒子の沈降速度は粒子の密度に依存するため、前記密度測定は、製造ラインでの各種制御にも重要な情報を与え得る。粒子の密度は、単一（個々）の粒子の質量と粒子径とを測定して算出できる。 The measurement of the density of particles in the dispersion medium is incorporated into the production line and used for the control of the raw materials supplied and the verification of the product. For example, the density measurement can provide various information such as the hollowness of hollow particles, the mixing ratio of specific components of alloy particles, and the abundance ratio of different crystals in the particles. Further, since the sedimentation rate of the particles in the dispersion medium depends on the density of the particles, the density measurement can provide important information for various controls in the production line. The density of particles can be calculated by measuring the mass and diameter of a single (individual) particle.
　ここで、非特許文献１は、微小粒子の質量を測定する共振式粒子質量測定法について述べている。この方法は、微小粒子を含む分散媒をカンチレバー内の細管に導いて、前記カンチレバーの共振周波数の変化を検出することで、前記細管内の粒子の質量を高い精度で測定できる。つまり、体積一定の細管について、微小粒子を含まない分散媒（溶媒のみ）が満たした場合の質量と、微小粒子を含む分散媒が満たした場合の質量と、の差によってカンチレバーの共振周波数が変化し、これらの質量差となる微小粒子の質量は測定されることができる。細管の径を非常に小さくしたマイクロ流路のようなものを用いて単一の微小粒子だけを含む分散媒を導くことで、前記単一の微小粒子の質量であっても高精度に測定ができて、粒子径を別途、測定すれば、単一の微小粒子の密度を求め得る。 Here, Non-Patent Document 1 describes a resonance type particle mass measuring method for measuring the mass of fine particles. In this method, the mass of the particles in the cantilever can be measured with high accuracy by guiding the dispersion medium containing the fine particles to the thin tube in the cantilever and detecting the change in the resonance frequency of the cantilever. That is, for a thin tube having a constant volume, the resonance frequency of the cantilever changes depending on the difference between the mass when the dispersion medium containing no fine particles (sol only) is filled and the mass when the dispersion medium containing fine particles is filled. However, the mass of the fine particles that is the difference between these masses can be measured. By deriving a dispersion medium containing only a single fine particle using something like a microchannel with a very small diameter of the thin tube, even the mass of the single fine particle can be measured with high accuracy. If the particle size can be measured separately, the density of a single fine particle can be obtained.
　一方、例えば、特許文献１のように、単一の微小粒子の粒子径については、光照射された管路内に微小粒子を含む分散媒を導き、特定の微小粒子からの散乱光強度を測定して算出する方法などがある。また、近年、流動場であっても、これを補正して、粒子径を精度良く測定し得る方法なども提案されている。 On the other hand, for example, as in Patent Document 1, for the particle size of a single fine particle, a dispersion medium containing the fine particle is guided in a light-irradiated conduit, and the scattered light intensity from the specific fine particle is measured. There is a method to calculate by. Further, in recent years, even in the case of a flow field, a method of correcting this and measuring the particle size with high accuracy has been proposed.
国際公開第２０１６／１５９１３１号International Publication No. 2016/159131
　微小粒子を含む分散媒から単一の粒子を抽出し、粒子径を測定するとともに、上記したような共振式粒子質量測定法で測定を行うことは、操作上の手間が掛かる。そこで、分散媒中に含まれる多数の微小粒子の粒子径分布及び粒子質量分布をそれぞれ測定して、それぞれ平均粒子径及び平均粒子質量を求めて、密度を簡便に算出できる。一方で、密度を異にする複数種類の材質の微小粒子を含んでいると、これらを分離できず、密度を算出することができない。 Extracting a single particle from a dispersion medium containing fine particles, measuring the particle size, and measuring by the resonance type particle mass measurement method as described above is troublesome in operation. Therefore, the particle size distribution and the particle mass distribution of a large number of fine particles contained in the dispersion medium can be measured, respectively, and the average particle size and the average particle mass can be obtained, respectively, and the density can be easily calculated. On the other hand, if fine particles of a plurality of types of materials having different densities are contained, these cannot be separated and the density cannot be calculated.
　本発明は、上記したような実情を鑑みてなされたものであって、その目的は、密度を異にする複数種類の材質の微小粒子を含んでいてもこれを分離して、分散媒中の微小粒子の密度を簡便且つ精度良く測定する方法及びそのシステムを提供することにある。 The present invention has been made in view of the above-mentioned circumstances, and an object thereof is to separate fine particles of a plurality of kinds of materials having different densities and to separate them in a dispersion medium. It is an object of the present invention to provide a method and a system for measuring the density of fine particles easily and accurately.
　本発明者らは、上記したような、粒子径分布及び粒子質量分布から、平均粒子径及び平均粒子質量を求めるのではなく、粒子径を揃えておいた上で質量測定を行うことで、粒子質量分布において密度差による分布に分離できることに想到した。 The present inventors do not obtain the average particle size and the average particle mass from the particle size distribution and the particle mass distribution as described above, but perform mass measurement after making the particle size uniform. I came up with the idea that the mass distribution can be separated into distributions due to density differences.
　そこで、本発明による粒子密度測定方法は、分散媒中の微小粒子の粒子径分布及び粒子質量分布を測定して前記微小粒子の密度を算出する粒子密度測定方法であって、管路内に前記分散媒を導きながら前記微小粒子の前記粒子径分布を粒子径測定装置で測定する粒子径分布測定工程と、前記管路から送出されてくる前記分散媒を、振動子に設けられた細管路であって前記管路よりも細い細管路に順次導きながら前記振動子の共振周波数の変化から前記粒子質量分布を算出する質量分布測定工程と、を含み、前記粒子径分布測定工程は、前記管路内を単位時間内に流れる前記分散媒中の前記微小粒子の粒子径の分布範囲を制御し、前記管路に前記分散媒を提供する分散媒調整工程を含み、前記細管路内を単位時間内に流れる前記分散媒中の前記微小粒子の粒子径の分布範囲を制御し、前記細管路に前記分散媒を提供することを特徴とする。 Therefore, the particle density measuring method according to the present invention is a particle density measuring method for calculating the density of the fine particles by measuring the particle size distribution and the particle mass distribution of the fine particles in the dispersion medium. A particle size distribution measuring step in which the particle size distribution of the fine particles is measured by a particle size measuring device while guiding a dispersion medium, and the dispersion medium sent out from the line are passed through a thin tube provided in the transducer. The particle size distribution measuring step includes a mass distribution measuring step of calculating the particle mass distribution from a change in the resonance frequency of the transducer while sequentially guiding the particles to a narrower conduit thinner than the conduit. A dispersion medium adjusting step of controlling the distribution range of the particle size of the fine particles in the dispersion medium flowing in the inside within a unit time and providing the dispersion medium to the pipeline is included, and the inside of the fine tube is within a unit time. It is characterized in that the distribution range of the particle size of the fine particles in the dispersion medium flowing in the tubule is controlled, and the dispersion medium is provided to the capillary channel.
　この特徴によれば、微小粒子の粒子径の分布範囲を制御して質量測定を行うことで、密度を異にする複数種類の材質の微小粒子を含んでいても、粒子質量分布においてこれを分離できて、分散媒中の微小粒子の密度を簡便且つ精度良く測定することができる。 According to this feature, by controlling the distribution range of the particle size of the fine particles and performing mass measurement, even if fine particles of multiple types of materials with different densities are included, they are separated in the particle mass distribution. Therefore, the density of fine particles in the dispersion medium can be measured easily and accurately.
　前記粒子径分布測定工程は、前記管路から送出されてくる前記分散媒中の前記微小粒子の個数濃度を調整して、前記分散媒を前記細管路に提供する工程を更に含んでもよい。この特徴によれば、微小粒子の粒子質量分布を精度良く得られ、密度を異にする複数種類の材質の微小粒子を含んでいても、分散媒中の微小粒子の密度を簡便且つ精度良く測定することができる。 The particle size distribution measuring step may further include a step of adjusting the number concentration of the fine particles in the dispersion medium sent out from the pipeline to provide the dispersion medium to the fine pipeline. According to this feature, the particle mass distribution of fine particles can be obtained with high accuracy, and the density of fine particles in the dispersion medium can be measured easily and accurately even if the fine particles of multiple kinds of materials having different densities are contained. can do.
　前記粒子径分布測定工程は、前記管路から送出されてくる前記分散媒を、間欠させた状態で前記細管路に提供する工程を更に含んでもよい。この特徴によれば、密度を異にする複数種類の材質の微小粒子を含んでいても、微小粒子の密度を簡便且つ精度良く測定することができる。 The particle size distribution measuring step may further include a step of providing the dispersion medium sent out from the pipeline to the thin pipeline in an intermittent state. According to this feature, even if fine particles of a plurality of kinds of materials having different densities are contained, the density of the fine particles can be measured easily and accurately.
　前記粒子径測定装置は、光照射された前記管路内に前記分散媒を導きながら前記微小粒子からの散乱光強度から粒子径を測定し、前記粒子径分布を算出する装置であってもよい。この特徴によれば、粒子径分布を簡便に且つ精度よく測定できて、密度を異にする複数種類の材質の微小粒子を含んでいても、分散媒中の微小粒子の密度を簡便且つ精度良く測定することができる。 The particle size measuring device may be a device that measures the particle size from the intensity of scattered light from the fine particles while guiding the dispersion medium into the duct irradiated with light, and calculates the particle size distribution. .. According to this feature, the particle size distribution can be measured easily and accurately, and the density of the fine particles in the dispersion medium can be easily and accurately measured even if the fine particles of a plurality of kinds of materials having different densities are contained. Can be measured.
　前記分散媒調整工程は、前記分散媒中を拡散する前記微小粒子に対して作用する力場を形成し、前記微小粒子を粒子径に従って前記分散媒中に配列させて前記管路に導いてもよい。また、前記力場は、前記分散媒の流路に沿った液送方向とこれに略直交する方向の流れ場であり、前記微小粒子を前記液送方向に交差するように配列させてもよい。この特徴によれば、流れ場によって簡便に微小粒子を粒子径に従って配列させ得て、密度を異にする複数種類の材質の微小粒子を含んでいても、分散媒中の微小粒子の密度を簡便且つ精度良く測定することができる。 In the dispersion medium adjusting step, a force field acting on the fine particles diffusing in the dispersion medium may be formed, and the fine particles may be arranged in the dispersion medium according to the particle size and guided to the conduit. good. Further, the force field is a flow field in a direction substantially orthogonal to the liquid feeding direction along the flow path of the dispersion medium, and the fine particles may be arranged so as to intersect the liquid feeding direction. .. According to this feature, fine particles can be easily arranged according to the particle size by a flow field, and the density of the fine particles in the dispersion medium can be easily adjusted even if the fine particles of a plurality of kinds of materials having different densities are contained. Moreover, it can be measured with high accuracy.
　また、本発明による粒子密度測定システムは、分散媒中の微小粒子の粒子径分布及び粒子質量分布を測定して前記微小粒子の密度を算出する粒子密度測定システムであって、管路内に前記分散媒を導きながら粒子径測定装置で前記微小粒子の前記粒子径分布を測定する粒子径分布測定部と、前記管路から送出されてくる前記分散媒を、振動子に設けられた細管路であって前記管路よりも細い細管路に順次導きながら前記振動子の共振周波数の変化から前記粒子質量分布を測定する質量分布測定部と、を含み、前記粒子径分布測定部は、前記管路内を単位時間内に流れる前記分散媒中の前記微小粒子の粒子径の分布範囲を制御し、前記管に前記分散媒を提供する分散媒調整部を含み、前記細管路内を単位時間内に流れる前記分散媒中の前記微小粒子の粒子径の分布範囲を制御し、前記細管路に前記分散媒を提供することを特徴とする。 Further, the particle density measuring system according to the present invention is a particle density measuring system for calculating the density of the fine particles by measuring the particle size distribution and the particle mass distribution of the fine particles in the dispersion medium, and the particle density measuring system is described in the pipeline. A particle size distribution measuring unit that measures the particle size distribution of the fine particles with a particle size measuring device while guiding a dispersion medium, and the dispersion medium sent out from the line are used in a thin tube provided in the transducer. The particle size distribution measuring unit includes a mass distribution measuring unit that measures the particle mass distribution from a change in the resonance frequency of the transducer while sequentially guiding the particles to a narrower pipeline thinner than the pipeline. A dispersion medium adjusting unit that controls the distribution range of the particle size of the fine particles in the dispersion medium flowing in the inside within a unit time and provides the dispersion medium to the tube is included, and the inside of the fine tube is within a unit time. It is characterized in that the distribution range of the particle size of the fine particles in the flowing dispersion medium is controlled, and the dispersion medium is provided to the capillary channel.
　この特徴によれば、微小粒子の粒子径の分布範囲を制御することで、密度を異にする複数種類の材質の微小粒子を含んでいてもこれを分離できて、分散媒中の微小粒子の密度を簡便且つ精度良く測定することができる。 According to this feature, by controlling the distribution range of the particle size of the fine particles, even if the fine particles of multiple kinds of materials having different densities are contained, they can be separated, and the fine particles in the dispersion medium can be separated. The density can be measured easily and accurately.
　前記粒子径分布測定部は、前記管路から送出されてくる前記分散媒中の前記微小粒子の個数濃度を調整して、前記分散媒を前記細管路に提供する機構を更に含んでもよい。この特徴によれば、微小粒子の粒子質量分布を精度良く得られ、密度を異にする複数種類の材質の微小粒子を含んでいても、分散媒中の微小粒子の密度を簡便且つ精度良く測定することができる。 The particle size distribution measuring unit may further include a mechanism for adjusting the number concentration of the fine particles in the dispersion medium sent out from the pipeline to provide the dispersion medium to the fine pipeline. According to this feature, the particle mass distribution of fine particles can be obtained with high accuracy, and the density of fine particles in the dispersion medium can be measured easily and accurately even if the fine particles of multiple kinds of materials having different densities are contained. can do.
　前記粒子径分布測定部は、前記管路から送出されてくる前記分散媒を、間欠させた状態で前記細管路に提供する機構を更に含んでもよい。この特徴によれば、密度を異にする複数種類の材質の微小粒子を含んでいても、微小粒子の密度を簡便且つ精度良く測定することができる。 The particle size distribution measuring unit may further include a mechanism for providing the dispersion medium sent out from the pipeline to the thin pipeline in an intermittent state. According to this feature, even if fine particles of a plurality of kinds of materials having different densities are contained, the density of the fine particles can be measured easily and accurately.
　前記粒子径測定装置は、光照射された前記管路内に前記分散媒を導きながら前記微小粒子からの散乱光強度から粒子径を測定し、前記粒子径分布を算出する装置であってもよい。この特徴によれば、粒子径分布を簡便に且つ精度よく測定できて、密度を異にする複数種類の材質の微小粒子を含んでいても、分散媒中の微小粒子の密度を簡便且つ精度良く測定することができる。 The particle size measuring device may be a device that measures the particle size from the intensity of scattered light from the fine particles while guiding the dispersion medium into the duct irradiated with light, and calculates the particle size distribution. .. According to this feature, the particle size distribution can be measured easily and accurately, and the density of the fine particles in the dispersion medium can be easily and accurately measured even if the fine particles of a plurality of kinds of materials having different densities are contained. Can be measured.
　前記分散媒調整部は、前記分散媒中を拡散する前記微小粒子に対して作用する力場を形成して、前記微小粒子を粒子径に従って前記分散媒中に配列させて前記管路に導いてもよい。また、前記力場は、前記分散媒の流路に沿った液送方向とこれに略直交する方向の流れ場であり、前記微小粒子を前記液送方向に交差するように配列させてもよい。この特徴によれば、流れ場によって簡便に微小粒子を粒子径に従って配列させ得て、密度を異にする複数種類の材質の微小粒子を含んでいても、分散媒中の微小粒子の密度を簡便且つ精度良く測定することができる。 The dispersion medium adjusting unit forms a force field acting on the fine particles diffusing in the dispersion medium, arranges the fine particles in the dispersion medium according to the particle size, and guides the fine particles to the conduit. May be good. Further, the force field is a flow field in a direction substantially orthogonal to the liquid feeding direction along the flow path of the dispersion medium, and the fine particles may be arranged so as to intersect the liquid feeding direction. .. According to this feature, fine particles can be easily arranged according to the particle size by a flow field, and the density of the fine particles in the dispersion medium can be easily adjusted even if the fine particles of a plurality of kinds of materials having different densities are contained. Moreover, it can be measured with high accuracy.
本発明による粒子密度測定システムのブロック図である。It is a block diagram of the particle density measurement system by this invention. 図１の要部のブロック図である。It is a block diagram of the main part of FIG. 分散媒調整部の例を示す原理図である。It is a principle diagram which shows the example of the dispersion medium adjustment part. 分散媒調整部による粒子の流出時間と粒子数の関係を示す度数分布のグラフである。It is a graph of the frequency distribution which shows the relationship between the outflow time of a particle by a dispersion medium adjustment part, and the number of particles. 混合試料を質量測定装置に導いた場合の質量分布のグラフである。It is a graph of the mass distribution when the mixed sample is guided to the mass measuring device. 図５の質量分布に基づき粒子径を３００ｎｍと仮定した場合の密度分布のグラフである。It is a graph of the density distribution when the particle diameter is assumed to be 300 nm based on the mass distribution of FIG. 粒子密度測定システムでの混合試料の密度の算出結果（２００ｎｍピーク）のグラフである。It is a graph of the calculation result (200 nm peak) of the density of the mixed sample by the particle density measurement system. 粒子密度測定システムでの混合試料の密度の算出結果（３００ｎｍピーク）のグラフである。It is a graph of the calculation result (300 nm peak) of the density of the mixed sample by the particle density measurement system.
　本発明の粒子密度測定システム及び粒子密度測定方法の１つの実施形態について図１及び図２を用いて説明する。 An embodiment of the particle density measuring system and the particle density measuring method of the present invention will be described with reference to FIGS. 1 and 2.
　図１に示すように、粒子密度測定システム１０は、微小粒子を分散させた分散媒を用いて微小粒子の密度を測定するためのシステムである。粒子密度測定システム１０は、分散媒中の微小粒子の粒子径分布を測定する粒子径分布測定部１と、微小粒子の粒子質量分布を測定する質量分布測定部２とを備える。また、最上流には、分散媒を導入する溶離液導入部１１と、溶離液導入部１１から導入された溶液に試料である微小粒子を導入して分散させて分散媒とする試料導入部１２とを備える。 As shown in FIG. 1, the particle density measuring system 10 is a system for measuring the density of fine particles using a dispersion medium in which fine particles are dispersed. The particle density measuring system 10 includes a particle size distribution measuring unit 1 for measuring the particle size distribution of fine particles in the dispersion medium, and a mass distribution measuring unit 2 for measuring the particle mass distribution of the fine particles. Further, in the uppermost stream, an eluent introduction unit 11 for introducing a dispersion medium and a sample introduction unit 12 for introducing fine particles as a sample into the solution introduced from the eluent introduction unit 11 and dispersing them to form a dispersion medium. And prepare.
　図２を併せて参照すると、粒子径分布測定部１は、管路内の粒子径を測定できる粒子径測定装置１４を含む。粒子径測定装置１４は、例えば、この管路内の分散媒にレーザー光を照射し、分散媒中をブラウン運動する微小粒子からの散乱光強度を測定することで、微小粒子の粒子径を算出することができる。典型的には、多角度光散乱検出器（ＭＡＬＳ：Multi Angle Light Scattering）を用い得る。 With reference to FIG. 2, the particle size distribution measuring unit 1 includes a particle size measuring device 14 capable of measuring the particle size in the pipeline. The particle size measuring device 14 calculates the particle size of the fine particles by, for example, irradiating the dispersion medium in the conduit with laser light and measuring the scattered light intensity from the fine particles moving in Brownian motion in the dispersion medium. can do. Typically, a multi-angle light scattering detector (MALS: MultiAngleLightScattering) can be used.
　質量分布測定部２には、共振式粒子質量計測法による公知の質量測定装置３１を用い得る。すなわち、質量測定装置３１は、振動子に設けられた細管路に分散媒を導き、振動子の共振周波数から細管路内の分散媒の質量を測定する装置である。つまり、質量測定装置３１は、共振周波数の変化から分散媒の密度に基づき微小粒子の質量を測定でき、微小粒子の粒子質量分布を測定できる。振動子は、例えばカンチレバーからなり、このカンチレバーの固定端から自由端に延びて折り返して固定端に戻るように、細管路を配置させている。細管路は、前記管路よりも細い管路である。細管路の内径は、例えば５００ｎｍ～３００μｍである。 A known mass measuring device 31 by a resonance type particle mass measuring method can be used for the mass distribution measuring unit 2. That is, the mass measuring device 31 is a device that guides the dispersion medium to the thin tube provided in the vibrator and measures the mass of the dispersion medium in the thin tube from the resonance frequency of the vibrator. That is, the mass measuring device 31 can measure the mass of the fine particles based on the density of the dispersion medium from the change in the resonance frequency, and can measure the particle mass distribution of the fine particles. The oscillator is composed of, for example, a cantilever, and a thin tube is arranged so as to extend from the fixed end of the cantilever to the free end, fold back, and return to the fixed end. The narrow line is a line thinner than the above line. The inner diameter of the narrow conduit is, for example, 500 nm to 300 μm.
　ここで、微小粒子の密度が１種類であれば、粒子径分布測定部１によって得た粒子径分布と質量分布測定部２によって得た粒子質量分布とによって、分散媒中の微小粒子の密度が求められる。すなわち、粒子径の３乗が質量に比例するため、両分布は各粒子径、質量で１対１に対応し、対応する質量を粒子径から得られる体積で除することで密度が算出される。 Here, if the density of the fine particles is one type, the density of the fine particles in the dispersion medium depends on the particle size distribution obtained by the particle size distribution measuring unit 1 and the particle mass distribution obtained by the mass distribution measuring unit 2. Desired. That is, since the cube of the particle size is proportional to the mass, both distributions have a one-to-one correspondence with each particle size and mass, and the density is calculated by dividing the corresponding mass by the volume obtained from the particle size. ..
　ところが、密度を異にする複数種類の材質の微小粒子を含んでいる場合には、上記したような分布の対応が得られない。つまり、粒子径と質量とを対応させることが難しくなる。 However, when fine particles of multiple types of materials with different densities are contained, the above-mentioned distribution cannot be obtained. That is, it becomes difficult to make the particle size correspond to the mass.
　そこで、粒子密度測定システム１０では、粒子径分布測定部１は分散媒調整部１３を備える。分散媒調整部１３は、質量測定装置３１の細管路に導かれる分散媒において単位時間内に流れる分散媒中の微小粒子の粒子径の分布範囲を、制御する。つまり、質量測定装置３１の細管路に導かれる分散媒について、導入される時間を区切ること等をして、粒子径の分布範囲を限定する。 Therefore, in the particle density measuring system 10, the particle size distribution measuring unit 1 includes a dispersion medium adjusting unit 13. The dispersion medium adjusting unit 13 controls the distribution range of the particle size of the fine particles in the dispersion medium flowing within a unit time in the dispersion medium guided to the small tube of the mass measuring device 31. That is, the distribution range of the particle size of the dispersion medium guided to the thin tube of the mass measuring device 31 is limited by dividing the time for introduction or the like.
　ここで、仮に粒子径の同じ微小粒子のみであった場合、粒子の体積は同一となる。一方、材料の固有値である密度は材料毎に異なる飛び飛びの値となるため、密度と体積の積である質量は飛び飛びの値となる。 Here, if only fine particles having the same particle diameter are used, the volumes of the particles will be the same. On the other hand, since the density, which is the eigenvalue of the material, has a different jumping value for each material, the mass, which is the product of the density and the volume, becomes the jumping value.
　実際には、粒子径が全く同じとなることはなく、粒子径の分布範囲を狭くなるように制御し、限定する。このように粒子径を揃えておけば、得られる粒子質量分布（質量－粒子数のグラフ）は、密度の種類に対応する数だけ分布の峰（ピーク）を持つことになり、密度差による分布に分離できる。換言すれば、密度を異にする複数種類の材質の微小粒子を含む場合に、得られる粒子質量分布を密度差による分布に分離できる程度に粒子径の分布範囲を制御する。これによって、密度を異にする複数種類の材質の微小粒子を含む場合であっても質量の分布を密度差による分布に分離できて、粒子径分布と粒子質量分布から対応する密度を求めることができる。 Actually, the particle diameters are not exactly the same, and the distribution range of the particle diameters is controlled and limited so as to be narrow. If the particle diameters are made uniform in this way, the obtained particle mass distribution (mass-number of particles graph) will have as many peaks as the number corresponding to the type of density, and the distribution will be due to the density difference. Can be separated into. In other words, when fine particles of a plurality of types of materials having different densities are included, the distribution range of the particle diameter is controlled to such an extent that the obtained particle mass distribution can be separated into a distribution due to the density difference. As a result, the mass distribution can be separated into the distribution due to the density difference even when fine particles of multiple types of materials with different densities are included, and the corresponding density can be obtained from the particle size distribution and the particle mass distribution. can.
　また、粒子径測定装置１４においても管路に導入される分散媒に含まれる粒子径の分布範囲を制御することが好ましい。 Further, it is also preferable to control the distribution range of the particle size contained in the dispersion medium introduced into the pipeline in the particle size measuring device 14.
　つまり、光照射された管路内に分散媒を導きながら微小粒子からの散乱光強度から粒子径を測定する粒子径測定装置１４において、粒子径分布の大きい分散媒では散乱光強度の分布範囲が非常に広範囲となる場合がある。例えば、ミー散乱の場合には粒子径の３乗、レイリー散乱の場合には粒子径の６乗に比例して、散乱光強度が変化するためである。その結果、散乱光強度を検出する検出器のレンジを大きく超えてしまい、１群の試料の中に粒子径によって検出できるものと検出できないものとが存在してしまう。つまり、粒子径によって検出漏れとなってしまう範囲が存在し、検出できる粒子径によってのみ試料の粒子径分布を推定すると誤差が非常に大きくなってしまう。 That is, in the particle size measuring device 14 that measures the particle size from the scattered light intensity from the fine particles while guiding the dispersion medium into the light-irradiated conduit, the distribution range of the scattered light intensity is wide for the dispersion medium having a large particle size distribution. It can be very widespread. For example, in the case of Mie scattering, the scattered light intensity changes in proportion to the cube of the particle size, and in the case of Rayleigh scattering, it changes in proportion to the sixth power of the particle size. As a result, the range of the detector that detects the scattered light intensity is greatly exceeded, and some of the samples in the group can be detected by the particle size and some cannot be detected. That is, there is a range in which detection omission occurs depending on the particle size, and if the particle size distribution of the sample is estimated only by the particle size that can be detected, the error becomes very large.
　そこで、上記した分散媒調整部１３を粒子径測定装置１４の前段に配置し、単位時間内に流れる分散媒中の微小粒子の粒子径の分布範囲を制御する。つまり、粒子径測定装置１４の管路に導かれる分散媒について、導入される時間を区切ること等をすることで粒子径の分布範囲を限定できるようにする。これによって、粒子径測定装置１４は、限定された粒子径の分布範囲に合わせて照射するレーザー光の強度を調整することなどによって、散乱光の強度の分布範囲を制御でき、微小粒子の検出漏れを非常に少なくできる。 Therefore, the above-mentioned dispersion medium adjusting unit 13 is arranged in front of the particle size measuring device 14, and the distribution range of the particle size of the fine particles in the dispersion medium flowing within a unit time is controlled. That is, the distribution range of the particle size of the dispersion medium guided to the conduit of the particle size measuring device 14 can be limited by dividing the time for introduction or the like. As a result, the particle size measuring device 14 can control the distribution range of the intensity of the scattered light by adjusting the intensity of the laser light to be irradiated according to the limited distribution range of the particle size, and the detection omission of fine particles. Can be very small.
　このような分散媒調整部１３としては、分散媒中を拡散する微小粒子に対して作用する力場を形成し、微小粒子を粒子径に従って分散媒中に配列させ得る装置、例えば、流動場分離法（ＦＦＦ：Field Flow Fractionation）による装置を用い得る。 Such a dispersion medium adjusting unit 13 is an apparatus capable of forming a force field acting on the fine particles diffusing in the dispersion medium and arranging the fine particles in the dispersion medium according to the particle size, for example, flow field separation. A device according to the method (FFF: Field Flow Fractionation) can be used.
　図３に示すように、分散媒調整部１３に用いるＦＦＦとしては、例えば、交差力場を用いる非対称流れ場流動場分離法（ＡＦ４：Asymmetrical Flow Filed Flow Fractionation）を利用したＡＦ４装置を用い得る。ＡＦ４装置は、流入口１６から流出口１８に向かう流路に沿った液送方向を有し、流路の一方の側壁に精密ろ過膜１９を設けることで、分散媒１７による液送方向に略直交する方向の流れ場５０を、交差力場として形成できる。この液送方向に直交する流れ場５０により、一旦、精密ろ過膜１９の表面の１か所に集められた微小粒子５１は、精密ろ過膜１９から流路中心に向けて拡散して、その粒子径に基づく拡散速度の違いによって分級するように分散媒中に配列される。具体的には、流路の中心に近づくにつれて粒子径を小さくするように、液送方向に交差する方向に微小粒子５１が配列される。さらに、液送方向に沿った層流においては流路外周から中心に向けて速くなる速度勾配がある。そのため、流路の中心近くの粒子径の小さな微小粒子５１から順に流路を進み、液送方向にも粒子径によって微小粒子５１が配列される。つまり、液送方向の流れとこれに直交する方向の流れとの流れ場５０によって、微小粒子５１をその粒子径によって配列させる。なお、流路を湾曲させて液送方向に対して略直交する方向に液送による遠心力を力場として付与する方法や、電場や磁場を利用する方法など、公知の粒子径によって微小粒子を配列させる装置を用いてもよい。 As shown in FIG. 3, as the FFF used for the dispersion medium adjusting unit 13, for example, an AF4 apparatus using an asymmetrical flow field flow field separation method (AF4: Asymmetrical Flow Filed Flow Fractionation) using a crossing force field can be used. The AF4 device has a liquid feeding direction along a flow path from the inflow port 16 to the outflow port 18, and by providing a microfiltration membrane 19 on one side wall of the flow path, the AF4 device is substantially in the liquid feeding direction by the dispersion medium 17. The flow field 50 in the orthogonal direction can be formed as a crossing force field. The fine particles 51 once collected at one place on the surface of the microfiltration membrane 19 are diffused from the microfiltration membrane 19 toward the center of the flow path by the flow field 50 orthogonal to the liquid feeding direction, and the particles are diffused from the microfiltration membrane 19 toward the center of the flow path. They are arranged in the dispersion medium so as to be classified according to the difference in diffusion rate based on the diameter. Specifically, the fine particles 51 are arranged in a direction intersecting the liquid feeding direction so that the particle diameter becomes smaller toward the center of the flow path. Further, in the laminar flow along the liquid feeding direction, there is a velocity gradient that increases from the outer periphery of the flow path toward the center. Therefore, the fine particles 51 having a small particle diameter near the center of the flow path are sequentially advanced in the flow path, and the fine particles 51 are arranged according to the particle size in the liquid feeding direction. That is, the fine particles 51 are arranged according to their particle diameters by the flow field 50 of the flow in the liquid feeding direction and the flow in the direction orthogonal to the flow. It should be noted that fine particles are provided according to a known particle size, such as a method in which a flow path is curved to apply a centrifugal force by liquid feeding in a direction substantially orthogonal to the liquid feeding direction as a force field, or a method using an electric field or a magnetic field. A device for arranging may be used.
　再び図１及び図２を参照すると、分散媒調整部１３は、単位時間内に流路を流れる微小粒子の粒子径の分布範囲を制御できる。これを粒子径測定装置１４の管路に導けば、単位時間内に管路に導かれる分散媒中の微小粒子の粒子径の分布範囲を制御することができる。なお、図示を省略したが、分散媒調整部１３は、さらに粒子径測定装置１４へ導く分散媒の個数濃度や流量を調整する機構を備えていてもよい。例えば、分散媒調整部１３において粒子径分布を調整された分散媒を希釈したり、分散媒の一部分のみを取り分けて濃縮したりすること等をして、粒子径測定装置１４で粒子径を測定し易いように調整する。また、分散媒を導出される時間毎に区切って分取する機構や、粒子径測定装置１４に導入されるまでの時間を調整する機構を設けてもよい。 With reference to FIGS. 1 and 2 again, the dispersion medium adjusting unit 13 can control the distribution range of the particle size of the fine particles flowing in the flow path within a unit time. If this is guided to the conduit of the particle size measuring device 14, the distribution range of the particle diameter of the fine particles in the dispersion medium guided to the conduit can be controlled within a unit time. Although not shown, the dispersion medium adjusting unit 13 may further include a mechanism for adjusting the number concentration and the flow rate of the dispersion medium leading to the particle size measuring device 14. For example, the particle size is measured by the particle size measuring device 14 by diluting the dispersion medium whose particle size distribution has been adjusted in the dispersion medium adjusting unit 13, or separating and concentrating only a part of the dispersion medium. Adjust to make it easier to do. Further, a mechanism for dividing the dispersion medium into pieces for each derived time and a mechanism for adjusting the time until the dispersion medium is introduced into the particle size measuring device 14 may be provided.
　一方、粒子径分布測定部１には、質量測定装置３１に分散媒を順次導くための接続部２０を更に備えることが好ましい。接続部２０は、質量測定装置３１において質量測定を容易とするように、質量測定装置３１に導入される分散媒中の微小粒子の個数濃度を調整する個数濃度調整部として機能する。例えば、スプリット２１を用いて分散媒中の微小粒子の配列された部分を避けて、分散媒のみを（例えば、液送方向と直交する方向の流れの上流側のみを）仕切るようにして取り分けて、微小粒子の個数濃度を上昇（濃縮）させ、分散媒を間欠させた状態で質量分布測定部２へ送出することができる。また、流量制御機構２２としてシリンジポンプまたはダイヤフラムポンプ等を用いることによって流量を調整することで、時間当たりの個数濃度を調整し、分散媒を質量分布測定部２へ送出することができる。また、希釈機構２３として最初に微小粒子を加えた溶液を追加して、微小粒子の個数濃度を低下（希釈）させて、分散媒を送出させてもよい。また、分取機構２４を用いて、分散媒を分割してオフラインにて質量測定装置３１に導いてもよい。 On the other hand, it is preferable that the particle size distribution measuring unit 1 is further provided with a connecting unit 20 for sequentially guiding the dispersion medium to the mass measuring device 31. The connection unit 20 functions as a number concentration adjusting unit for adjusting the number concentration of fine particles in the dispersion medium introduced into the mass measuring device 31 so as to facilitate mass measurement in the mass measuring device 31. For example, the split 21 is used to avoid the arranged portion of the fine particles in the dispersion medium and separate only the dispersion medium (for example, only the upstream side of the flow in the direction orthogonal to the liquid feeding direction). , The number concentration of the fine particles can be increased (concentrated) and sent to the mass distribution measuring unit 2 in a state where the dispersion medium is intermittent. Further, by adjusting the flow rate by using a syringe pump, a diaphragm pump or the like as the flow rate control mechanism 22, the number concentration per hour can be adjusted and the dispersion medium can be sent to the mass distribution measuring unit 2. Further, as the dilution mechanism 23, a solution to which fine particles are first added may be added to reduce (dilute) the concentration of the number of fine particles, and the dispersion medium may be sent out. Further, the dispersion medium may be divided and guided to the mass measuring device 31 offline by using the preparative mechanism 24.
　なお、粒子径測定装置１４及び質量測定装置３１はそれぞれ図示しない演算装置に接続され、演算装置によって粒子径分布及び粒子質量分布を算出できる。また、演算装置は、得られた粒子径分布及び粒子質量分布から微小粒子の密度を算出できる。例えば、粒子径分布を測定した分散媒を希釈して質量分布を測定しても、微小粒子の粒子径の分布割合は一定であると仮定できるので、これに基づき粒子径分布と粒子質量分布を対応させて密度を算出できる。 The particle size measuring device 14 and the mass measuring device 31 are each connected to an arithmetic unit (not shown), and the particle size distribution and the particle mass distribution can be calculated by the arithmetic unit. In addition, the arithmetic unit can calculate the density of fine particles from the obtained particle size distribution and particle mass distribution. For example, even if the mass distribution is measured by diluting the dispersion medium for which the particle size distribution has been measured, it can be assumed that the distribution ratio of the particle size of the fine particles is constant. The density can be calculated correspondingly.
　なお、これらの処理は、分散媒調整部１３の分散媒の個数濃度や流量を調整する機構や、接続部２０の機構を適宜選択することで、オンライン又はオフラインのいずれかで行うことができる。 Note that these processes can be performed either online or offline by appropriately selecting a mechanism for adjusting the number concentration and flow rate of the dispersion medium in the dispersion medium adjusting unit 13 and a mechanism for the connection unit 20.
［測定例］
　次に、上記した粒子密度測定システム１０による粒子密度の測定結果について、図４～図８を用いて説明する。 [Measurement example]
Next, the measurement results of the particle density by the above-mentioned particle density measurement system 10 will be described with reference to FIGS. 4 to 8.
　市販のポリスチレンラテックス水分散液（藤倉化成社製W15E181：粒子径３００ｎｍ）、市販のシリカ水分散液（ＭＳＰ社製NS-0200A、Micromod社製43-00-302：粒子径３００ｎｍ）を混合した混合試料を用いて、以下の検討を行った。 A mixture of a commercially available polystyrene latex aqueous dispersion (W15E181 manufactured by Fujikura Kasei Co., Ltd .: particle diameter 300 nm) and a commercially available silica aqueous dispersion liquid (MSP manufactured NS-0200A, Micromod manufactured by 43-00-302: particle diameter 300 nm). The following studies were conducted using the sample.
　分散媒調整部１３にはＡＦ４：ＡＦ２０００システム（Postnova Analytics社製）を用いた。メンブランとしてセルロース薄膜（Z-MEM-AQU-427N：分子量のカットオフ値は１０００）を用い、そのチャネルを３５０μｍ厚さとした。溶液としては、０．１％NovaChem Surfactant 100：C-SUR-100分散剤（Postnova Analytics社製）水溶液を用い、希釈水としては超純水を用いた。なお、超純水には、イオン交換フィルター及び０．１μｍフィルターで精製した、電気抵抗率１８．２ＭΩ・ｃｍ以上で有機炭素濃度を５ｐｐｂ以下とする微小粒子を含まない「ミリＱ水」を用いた。 The AF4: AF2000 system (manufactured by Postnova Analytics) was used for the dispersion medium adjusting unit 13. A cellulose thin film (Z-MEM-AQU-427N: molecular weight cutoff value of 1000) was used as a membrane, and the channel was 350 μm thick. A 0.1% NovaChem Surfactant 100: C-SUR-100 dispersant (manufactured by Postnova Analytics) aqueous solution was used as the solution, and ultrapure water was used as the diluting water. For the ultrapure water, "milli-Q water" purified by an ion exchange filter and a 0.1 μm filter and containing no fine particles having an electrical resistivity of 18.2 MΩ · cm or more and an organic carbon concentration of 5 ppb or less is used. board.
　また、質量測定装置３１には共振式質量測定装置Archimedes（Malvern Panalytical社製）を用い、質量測定にはNano sensor（Malvern Panalytical社製）を用いた。 In addition, a resonance type mass measuring device Archimedes (manufactured by Malvern Panasonic) was used for the mass measuring device 31, and a Nano sensor (manufactured by Malvern Panasonic) was used for mass measurement.
　図４に示すように、分散媒調整部１３の液送方向の流速を１．０ｍＬ／ｍｉｎとして粒子径による微小粒子の配列をさせたところ、流出時間の２か所の位置にピークを有することが判った。２０～２５分の流出時間におけるピークは２００ｎｍの粒子径をもつ微小粒子であり、２７～３７分の流出時間におけるピークは３００ｎｍの粒子径を有する微小粒子である。 As shown in FIG. 4, when the flow velocity of the dispersion medium adjusting unit 13 in the liquid feeding direction was set to 1.0 mL / min and the fine particles were arranged according to the particle size, they had peaks at two positions of the outflow time. I found out. The peak at the outflow time of 20 to 25 minutes is a fine particle having a particle size of 200 nm, and the peak at the outflow time of 27 to 37 minutes is a fine particle having a particle size of 300 nm.
　このような混合試料を、分散媒調整部１３を経由させずに、直接、質量測定装置３１の細管路に導入した。 Such a mixed sample was directly introduced into the thin tube of the mass measuring device 31 without passing through the dispersion medium adjusting unit 13.
　図５に示すように３つの峰の質量分布が得られた。さらに、図６に示すように、分散媒中に分散している微小粒子の粒子径を３００ｎｍと仮定し、密度を算出すると３つの峰のそれぞれについて、平均密度として、１．０５、１．２８、２．００ｇ／ｃｍ３の密度が算出された。本来、上記した混合試料に含まれるポリスチレンラテックス及びシリカの密度はそれぞれ１．０５ｇ／ｃｍ３、及び、２．００ｇ／ｃｍ３であるが、実際には、１．２８ｇ／ｃｍ３という本来の密度とは異なる数値が算出されてしまった。 As shown in FIG. 5, mass distributions of three peaks were obtained. Further, as shown in FIG. 6, assuming that the particle size of the fine particles dispersed in the dispersion medium is 300 nm, the densities are calculated and the average densities of each of the three peaks are 1.05 and 1.28. , 2.00 g / cm 3 density was calculated. Originally, the densities of polystyrene latex and silica contained in the above-mentioned mixed sample are 1.05 g / cm 3 and 2.00 g / cm 3 , respectively, but in reality, the original densities are 1.28 g / cm 3. A different value has been calculated.
　そこで、分散媒調整部１３で微小粒子を配列させて本来の２つのピーク（それぞれ２００ｎｍ及び３００ｎｍ）の近辺をそれぞれ分取し、さらに各ピークにおいて粒子径測定装置１４にて粒子径を測定し、粒子径分布を得た（粒子径分布測定工程の一例）。なお、粒子径測定装置１４には、ＭＡＬＳを用いた。さらに、質量測定装置３１によって粒子質量分布を得て（質量分布測定工程の一例）、微小粒子の密度を算出し直した。 Therefore, the fine particles are arranged by the dispersion medium adjusting unit 13 to separate the vicinity of the original two peaks (200 nm and 300 nm, respectively), and the particle size is measured by the particle size measuring device 14 at each peak. The particle size distribution was obtained (an example of the particle size distribution measurement step). MALS was used as the particle size measuring device 14. Further, the particle mass distribution was obtained by the mass measuring device 31 (an example of the mass distribution measuring step), and the density of the fine particles was recalculated.
　図７に示すように、２００ｎｍピークについてはシリカの密度である２．００ｇ／ｃｍ３に合致する結果が得られた。また、図８に示すように、３００ｎｍピークについてはポリスチレンラテックス及びシリカの密度である１．０５ｇ／ｃｍ３及びシリカの密度である２．００ｇ／ｃｍ３に合致する結果が得られた。 As shown in FIG. 7, the result corresponding to the silica density of 2.00 g / cm 3 was obtained for the 200 nm peak. Further, as shown in FIG. 8, the results obtained that the 300 nm peak matched the density of polystyrene latex and silica of 1.05 g / cm 3 and the density of silica of 2.00 g / cm 3.
　つまり、今回の試料ではシリカ水分散液に粒子径を２００ｎｍ付近とするシリカの微小粒子が混在しており、この試料について分散媒調整部１３を経由させずに粒子径を３００ｎｍと仮定した結果、不正確な値を密度として算出してしまった。これは、２００ｎｍ付近の粒子径を有するシリカと３００ｎｍ付近の粒子径を有するポリスチレンラテックスとの質量を分離できなかったために、両者の密度の間に位置する数値を密度として算出してしまったと考えられる。これに対し、分散媒調整部１３で微小粒子を配列させて、粒子径の分布範囲を制御した（分散媒調整工程の一例）ことで、密度の異なる微小粒子の混在する試料でも、得られた粒子質量分布の中で質量を２つの密度のそれぞれに対応させて分離でき、粒子径分布から粒子密度を高い精度で求めることができた。 That is, in this sample, silica fine particles having a particle size of about 200 nm are mixed in the silica aqueous dispersion, and as a result of assuming that the particle size of this sample is 300 nm without passing through the dispersion medium adjusting unit 13. I have calculated the inaccurate value as the density. It is probable that this is because the masses of silica having a particle size of around 200 nm and polystyrene latex having a particle size of around 300 nm could not be separated, so the numerical value located between the densities of both was calculated as the density. .. On the other hand, by arranging the fine particles in the dispersion medium adjusting unit 13 and controlling the distribution range of the particle size (an example of the dispersion medium adjusting step), even a sample in which fine particles having different densities are mixed can be obtained. In the particle mass distribution, the mass could be separated corresponding to each of the two densities, and the particle density could be obtained with high accuracy from the particle size distribution.
　以上のように、粒子密度測定システム１０は、密度を異にする複数種類の材質の微小粒子を含んでいてもこれを分離して、それぞれの粒子の密度の算出を可能である。よって、粒子密度測定システム１０は、材料合成などにおける粒子材料のモニタリングや品質管理に用いることができ、中空状粒子の中空度、合金粒子の特定成分の混合率、粒子中の結晶性の異なる部分の存在比率などを推定することも可能となり、多様な応用が期待される。 As described above, the particle density measurement system 10 can calculate the density of each particle by separating even if it contains fine particles of a plurality of kinds of materials having different densities. Therefore, the particle density measurement system 10 can be used for monitoring and quality control of particle materials in material synthesis and the like, and the hollowness of hollow particles, the mixing ratio of specific components of alloy particles, and the parts having different crystallinity in the particles. It is also possible to estimate the abundance ratio of particles, and various applications are expected.
　ここまで本発明による代表的な実施例及びこれに基づく改変例について説明したが、本発明は必ずしもこれらに限定されるものではない。当業者であれば、添付した特許請求の範囲を逸脱することなく、種々の代替的な実施例を見出すことができるだろう。 Although typical examples according to the present invention and modifications based on the same have been described so far, the present invention is not necessarily limited to these. Those skilled in the art will be able to find various alternative examples without departing from the attached claims.

Claims (12)

  1. 　分散媒中の微小粒子の粒子径分布及び粒子質量分布を測定して前記微小粒子の密度を算出する粒子密度測定方法であって、
    　管路内に前記分散媒を導きながら前記微小粒子の前記粒子径分布を粒子径測定装置で測定する粒子径分布測定工程と、
    　前記管路から送出されてくる前記分散媒を、振動子に設けられた細管路であって前記管路よりも細い細管路に順次導きながら前記振動子の共振周波数の変化から前記粒子質量分布を測定する質量分布測定工程と、を含み、
    　前記粒子径分布測定工程は、前記管路内を単位時間内に流れる前記分散媒中の前記微小粒子の粒子径の分布範囲を制御し、前記管路に前記分散媒を提供する分散媒調整工程を含み、前記細管路内を単位時間内に流れる前記分散媒中の前記微小粒子の粒子径の分布範囲を制御し、前記細管路に前記分散媒を提供することを特徴とする粒子密度測定方法。     It is a particle density measuring method for calculating the density of the fine particles by measuring the particle size distribution and the particle mass distribution of the fine particles in the dispersion medium.
    A particle size distribution measuring step in which the particle size distribution of the fine particles is measured by a particle size measuring device while guiding the dispersion medium into the pipeline.
    The particle mass distribution is obtained from the change in the resonance frequency of the vibrator while sequentially guiding the dispersion medium sent out from the pipe to the fine pipes provided in the vibrator, which are thinner than the pipes. Including the mass distribution measurement step to be measured,
    The particle size distribution measuring step is a dispersion medium adjusting step of controlling the distribution range of the particle size of the fine particles in the dispersion medium flowing in the pipeline within a unit time and providing the dispersion medium to the pipeline. A method for measuring particle density, which comprises controlling the distribution range of the particle size of the fine particles in the dispersion medium flowing in the fine tube within a unit time, and providing the dispersion medium to the fine tube. ..
  2. 　前記粒子径分布測定工程は、前記管路から送出されてくる前記分散媒中の前記微小粒子の個数濃度を調整して、前記分散媒を前記細管路に提供する工程を更に含むことを特徴とする請求項１記載の粒子密度測定方法。 The particle size distribution measuring step is characterized by further including a step of adjusting the number concentration of the fine particles in the dispersion medium sent out from the conduit and providing the dispersion medium to the fine conduit. The particle density measuring method according to claim 1.
  3. 　前記粒子径分布測定工程は、前記管路から送出されてくる前記分散媒を、間欠させた状態で前記細管路に提供する工程を更に含むことを特徴とする請求項１記載の粒子密度測定方法。 The particle density measuring method according to claim 1, wherein the particle size distribution measuring step further includes a step of providing the dispersion medium sent out from the conduit to the thin conduit in an intermittent state. ..
  4. 　前記粒子径測定装置は、光照射された前記管路内に前記分散媒を導きながら前記微小粒子からの散乱光強度から粒子径を測定し、前記粒子径分布を算出する装置であることを特徴とする請求項１記載の粒子密度測定方法。 The particle size measuring device is characterized in that it measures the particle size from the intensity of scattered light from the fine particles while guiding the dispersion medium into the duct irradiated with light, and calculates the particle size distribution. The particle density measuring method according to claim 1.
  5. 　前記分散媒調整工程は、前記分散媒中を拡散する前記微小粒子に対して作用する力場を形成し、前記微小粒子を粒子径に従って前記分散媒中に配列させて前記管路に導くことを特徴とする請求項１記載の粒子密度測定方法。 In the dispersion medium adjusting step, a force field acting on the fine particles diffusing in the dispersion medium is formed, and the fine particles are arranged in the dispersion medium according to the particle size and guided to the conduit. The particle density measuring method according to claim 1, wherein the particle density is measured.
  6. 　前記力場は、前記分散媒の流路に沿った液送方向とこれに略直交する方向の流れ場であり、前記微小粒子を前記液送方向に交差するように配列させることを特徴とする請求項５記載の粒子密度測定方法。 The force field is a flow field in a direction substantially orthogonal to the liquid feeding direction along the flow path of the dispersion medium, and is characterized in that the fine particles are arranged so as to intersect the liquid feeding direction. The particle density measuring method according to claim 5.
  7. 　分散媒中の微小粒子の粒子径分布及び粒子質量分布を測定して前記微小粒子の密度を算出する粒子密度測定システムであって、
    　管路内に前記分散媒を導きながら前記微小粒子の前記粒子径分布を粒子径測定装置で測定する粒子径分布測定部と、
    　前記管路から送出されてくる前記分散媒を、振動子に設けられた細管路であって前記管路よりも細い細管路に順次導きながら前記振動子の共振周波数の変化から前記粒子質量分布を測定する質量分布測定部と、を含み、
    　前記粒子径分布測定部は、前記管路内を単位時間内に流れる前記分散媒中の前記微小粒子の粒子径の分布範囲を制御し、前記管路に前記分散媒を提供する分散媒調整部を含み、前記細管路内を単位時間内に流れる前記分散媒中の前記微小粒子の粒子径の分布範囲を制御し、前記細管路に前記分散媒を提供することを特徴とする粒子密度測定システム。     It is a particle density measurement system that calculates the density of the fine particles by measuring the particle size distribution and the particle mass distribution of the fine particles in the dispersion medium.
    A particle size distribution measuring unit that measures the particle size distribution of the fine particles with a particle size measuring device while guiding the dispersion medium into the pipeline.
    The particle mass distribution is obtained from the change in the resonance frequency of the vibrator while sequentially guiding the dispersion medium sent out from the pipe to the fine pipes provided in the vibrator, which are thinner than the pipes. Including the mass distribution measuring unit to be measured,
    The particle size distribution measuring unit controls the distribution range of the particle size of the fine particles in the dispersion medium flowing in the pipeline within a unit time, and provides the dispersion medium to the pipeline. A particle density measuring system comprising, controlling the distribution range of the particle size of the fine particles in the dispersion medium flowing in the fine tube within a unit time, and providing the dispersion medium to the fine tube. ..
  8. 　前記粒子径分布測定部は、前記管路から送出されてくる前記分散媒中の前記微小粒子の個数濃度を調整して、前記分散媒を前記細管路に提供する機構を更に含むことを特徴とする請求項７記載の粒子密度測定システム。 The particle size distribution measuring unit is further characterized by including a mechanism for adjusting the number concentration of the fine particles in the dispersion medium sent out from the pipeline to provide the dispersion medium to the fine pipeline. 7. The particle density measuring system according to claim 7.
  9. 　前記粒子径分布測定部は、前記管路から送出されてくる前記分散媒を、間欠させた状態で前記細管路に提供する機構を更に含むことを特徴とする請求項７記載の粒子密度測定システム。 The particle density measuring system according to claim 7, wherein the particle size distribution measuring unit further includes a mechanism for providing the dispersion medium sent out from the pipeline to the thin pipeline in an intermittent state. ..
  10. 　前記粒子径測定装置は、光照射された前記管路内に前記分散媒を導きながら前記微小粒子からの散乱光強度から粒子径を測定し、前記粒子径分布を算出する機構であることを特徴とする請求項７記載の粒子密度測定システム。 The particle size measuring device is characterized by being a mechanism for calculating the particle size distribution by measuring the particle size from the scattered light intensity from the fine particles while guiding the dispersion medium into the light-irradiated conduit. 7. The particle density measuring system according to claim 7.
  11. 　前記分散媒調整部は、前記分散媒中を拡散する前記微小粒子に対して作用する力場を形成して、前記微小粒子を粒子径に従って前記分散媒中に配列させて前記管路に導くことを特徴とする請求項７記載の粒子密度測定システム。 The dispersion medium adjusting unit forms a force field acting on the fine particles diffusing in the dispersion medium, arranges the fine particles in the dispersion medium according to the particle size, and guides the fine particles to the conduit. 7. The particle density measuring system according to claim 7.
  12. 　前記力場は、前記分散媒の流路に沿った液送方向とこれに略直交する方向の流れ場であり、前記微小粒子を前記液送方向に交差するように配列させることを特徴とする請求項１１記載の粒子密度測定システム。 The force field is a flow field in a direction substantially orthogonal to the liquid feeding direction along the flow path of the dispersion medium, and is characterized in that the fine particles are arranged so as to intersect the liquid feeding direction. The particle density measuring system according to claim 11.
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Publication number Priority date Publication date Assignee Title
JPH032543A (en) * 1989-05-29 1991-01-08 Oval Eng Co Ltd Density and viscosity meter
JP2004340897A (en) * 2003-05-19 2004-12-02 Shimadzu Corp Mass density measuring method of airborne particle in atmospheric air
JP2007051916A (en) * 2005-08-17 2007-03-01 Osaka Univ Mass measuring instrument and mass measuring method
WO2009131175A1 (en) * 2008-04-25 2009-10-29 新日本製鐵株式会社 Method of determining particle size distribution of fine particles contained in metallic material
JP2015132614A (en) * 2008-05-01 2015-07-23 マイクロ モーション インコーポレイテッド Vibratory flow meter for determining one or more flow fluid characteristics of multi-phase flow fluid
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