JP6112025B2 - Data processing device for particle size distribution measurement, particle size distribution measuring device equipped with the same, data processing method for particle size distribution measurement, and data processing program for particle size distribution measurement - Google Patents

Description

  The present invention relates to a data processing apparatus for particle size distribution measurement for calculating particle size distribution data based on light intensity distribution data obtained by receiving light from a sample with a plurality of light receiving elements, and a particle size distribution including the same. The present invention relates to a measurement apparatus, a particle size distribution measurement data processing method, and a particle size distribution measurement data processing program.

  Conventionally, a particle size distribution measuring apparatus has been used to measure the particle size distribution of a particle group in a sample. In a general particle size distribution measuring device, a sample to be measured is irradiated with laser light, and diffracted and scattered light from the sample is received by a plurality of light receiving elements. The particle size distribution of the particles in the sample can be measured.

  In this type of particle size distribution measuring apparatus, it is possible to measure a more accurate particle size distribution if only the diffracted and scattered light that is diffracted and scattered by the sample while maintaining energy can be received by the light receiving element. However, the sample may include particles that emit background light other than diffracted and scattered light, such as fluorescence (see, for example, Patent Document 1 below).

  In such a case, the particle size distribution may not be accurately measured due to the influence of background light. Therefore, a configuration is generally employed in which the influence of background light can be removed using an optical filter that blocks light other than the measurement wavelength. The background light includes not only fluorescence but also Raman scattered light that scatters on the sample with energy changes.

JP 7-92076 A

  However, the conventional configuration as described above has a problem that the cost is increased by providing the optical filter. In addition, when the measurement wavelength and the background light wavelength are close, the background light may not be removed by the optical filter.

  The present invention has been made in view of the above circumstances, a data processing device for particle size distribution measurement capable of accurately measuring the particle size distribution without providing an optical filter, a particle size distribution measuring device equipped with the same, and An object is to provide a data processing method for particle size distribution measurement and a data processing program for particle size distribution measurement.

The particle size distribution measurement data processing apparatus according to the present invention includes an input reception unit, a storage unit, and a calculation unit. The input receiving unit receives input of light intensity distribution data obtained by receiving light from a sample with a plurality of light receiving elements. The storage unit stores, as intensity information, the relative relationship between the received light intensity of each light receiving element for each of diffracted and scattered light diffracted and scattered by the sample while maintaining energy and background light other than the diffracted and scattered light. To do. The arithmetic unit by performing a matrix operation on the light intensity distribution data using the strong degree information, the influence of the background light together with the particle size distribution data that has been removed, calculates the amount of the background light. The intensity information is obtained by adding a column having an element with a value corresponding to a ratio of the background light toward the plurality of light receiving elements to a matrix having the intensity of the diffracted scattered light toward the plurality of light receiving elements. It is.

  According to such a configuration, not only the relative relationship of the received light intensity in each light receiving element with respect to diffracted scattered light but also the relative relationship of the received light intensity in each light receiving element with respect to background light other than the diffracted scattered light is used. Thus, by performing calculations on the light intensity distribution data, it is possible to calculate the particle size distribution data from which the influence of background light has been removed. Thus, since the influence of background light can be removed by calculation, the particle size distribution can be accurately measured without providing an optical filter.

Moreover , since the light quantity of background light can be calculated by calculation together with the particle size distribution data from which the influence of background light has been removed, the particle size distribution and the background light can be analyzed simultaneously.

In addition , it is possible to easily calculate the particle size distribution data from which the influence of background light has been removed using matrix calculation. The front SL matrix elements representing relative relationship of the light-receiving intensity in each light receiving element for diffracting the scattered light, and represents a relative relationship of the light-receiving intensity in the light-receiving elements of the background light other than the diffracted scattered light elements that have been included.

  The background light may include light isotropically emitted from the sample.

  According to such a configuration, it is possible to calculate particle size distribution data from which the influence of light isotropically emitted from the sample is removed. Since the relative relationship of the light receiving intensity in each light receiving element with respect to light emitted isotropically from the sample can be easily calculated based on the arrangement of each light receiving element, an accurate particle size distribution is easily measured. be able to.

  The background light may include fluorescence.

  According to such a configuration, the particle size distribution data from which the influence of fluorescence is removed can be calculated. Since fluorescence is considered to be light emitted isotropically from the sample, the relative relationship between the received light intensity of each light receiving element with respect to the fluorescence can be easily calculated based on the arrangement of each light receiving element.

  A particle size distribution measuring apparatus according to the present invention includes a light source that irradiates a sample with light, a plurality of light receiving elements that receive light from the sample, and the data processing apparatus for particle size distribution measurement.

The particle size distribution measurement data processing method according to the present invention includes an input receiving step, a reading step, and a calculation step. In the input receiving step, input of light intensity distribution data obtained by receiving light from the sample with a plurality of light receiving elements is received. In the reading step, the relative relationship of the received light intensity in each light receiving element is stored as intensity information for each of the diffracted and scattered light diffracted and scattered by the sample while maintaining energy and the background light other than the diffracted and scattered light. The intensity information is read from the storage unit. In the calculation step, by performing matrix calculation on the light intensity distribution data using the read intensity information, the light amount of the background light is calculated together with the particle size distribution data from which the influence of the background light has been removed. . The intensity information is obtained by adding a column having an element with a value corresponding to a ratio of the background light toward the plurality of light receiving elements to a matrix having the intensity of the diffracted scattered light toward the plurality of light receiving elements. It is.

The data processing program for particle size distribution measurement according to the present invention causes a computer to function as an input receiving unit, a reading unit, and a calculation unit. The input receiving unit receives input of light intensity distribution data obtained by receiving light from a sample with a plurality of light receiving elements. The reading unit stores, as intensity information, the relative relationship between the received light intensity of each light receiving element for each of diffracted and scattered light that is diffracted and scattered by the sample while maintaining energy, and background light other than the diffracted and scattered light. The intensity information is read from the storage unit. The calculation unit calculates the amount of the background light together with the particle size distribution data from which the influence of the background light has been removed by performing a matrix calculation on the light intensity distribution data using the read intensity information. . The intensity information is obtained by adding a column having an element with a value corresponding to a ratio of the background light toward the plurality of light receiving elements to a matrix having the intensity of the diffracted scattered light toward the plurality of light receiving elements. It is.

  According to the present invention, since the influence of background light can be removed by calculation, the particle size distribution can be accurately measured without providing an optical filter.

It is the schematic which showed the structural example of the particle size distribution measuring apparatus which concerns on one Embodiment of this invention. It is a block diagram for demonstrating the specific structure of the data processor of FIG. It is the flowchart which showed an example of the process by the control part at the time of calculating particle size distribution data and fluorescence amount.

  FIG. 1 is a schematic diagram illustrating a configuration example of a particle size distribution measuring apparatus according to an embodiment of the present invention. This particle size distribution measuring apparatus is for generating particle size distribution data by measuring the relationship between the particle size and the amount of particles of a particle group contained in a sample, and is a measuring unit 1 for measuring a sample. It has.

  The measurement unit 1 includes a light source 11, a condensing lens 12, a spatial filter 13, a collimator lens 14, a flow cell 15, a condensing lens 16, a detector 17, and the like. A sample to be measured is supplied to the flow cell 15 from a supply source such as a circulation sampler 2 in which an ultrasonic transducer is incorporated.

  The light source 11 is composed of, for example, a laser light source, and the measurement light emitted from the light source 11 passes through the condenser lens 12, the spatial filter 13, and the collimator lens 14 to become parallel light. The measurement light thus converted into parallel light is irradiated onto the flow cell 15 to which the sample is supplied, diffracted and scattered by the particle group included in the sample in the flow cell 15, and then detected through the condenser lens 16. The device 17 receives light.

  At this time, normal diffracted scattered light such as Rayleigh scattered light and Mie scattered light is diffracted and scattered by the sample while retaining energy, and is received by the detector 17. However, some samples may contain particles that emit background light other than normal diffraction scattered light. The background light is incident light other than the light to be measured (normal diffracted scattered light), and can be exemplified by fluorescence, Raman scattered light scattered by the sample with energy change, and the like.

  The detector 17 is for detecting light from the sample, and is composed of, for example, a photodiode array. The detector 17 includes, for example, a plurality of (for example, 64) light receiving elements 171 formed with ring-shaped or semi-ring-shaped detection surfaces having different radii, concentrically around the optical axis of the condenser lens 16. The light from the sample is incident on each light receiving element 171 at an angle corresponding to each position. Therefore, the detection signal of each light receiving element 171 of the detector 17 represents the intensity of light corresponding to the incident angle.

  The detection signal of each light receiving element 171 of the detector 17 is converted from an analog signal to a digital signal by the A / D converter 3 and then input to the data processing device 5 via the communication unit 4. . Thereby, light intensity distribution data in which the element number of each light receiving element 171 of the detector 17 is associated with the light receiving intensity in each light receiving element 171 is input to the data processing device 5.

  The data processing device 5 constitutes a data processing device for particle size distribution measurement for processing data when measuring the particle size distribution of the sample. The data processing device 5 is configured by a computer, for example, and includes a control unit 51, an operation unit 52, a display unit 53, a storage unit 54, and the like.

  The control unit 51 includes, for example, a CPU (Central Processing Unit), and each unit such as an operation unit 52, a display unit 53, and a storage unit 54 is electrically connected. The operation unit 52 includes, for example, a keyboard and a mouse, and the user can perform input work and the like by operating the operation unit 52.

  The display unit 53 can be configured by a liquid crystal display, for example, and the user can perform work while confirming the display content of the display unit 53. The storage unit 54 can be configured by, for example, a ROM (Read Only Memory), a RAM (Random Access Memory), a hard disk, and the like.

  FIG. 2 is a block diagram for explaining a specific configuration of the data processing device 5 of FIG. The control unit 51 in the present embodiment functions as an input reception unit 511, a calculation unit 512, a reading unit 513, and the like when the CPU executes a program. A light intensity distribution data storage unit 541, a particle size distribution data storage unit 542, an intensity information storage unit 543, and the like are allocated to the storage unit 54.

  The input reception unit 511 receives data input from the measurement unit 1 via the communication unit 4. Light intensity distribution data obtained by receiving light from the sample by the plurality of light receiving elements 171 of the detector 17 is input by the input receiving unit 511 and stored in the light intensity distribution data storage unit 541.

  The calculation unit 512 calculates particle size distribution data by performing calculation on the light intensity distribution data stored in the light intensity distribution data storage unit 541. In this embodiment, the relative relationship between the received light intensities of the light receiving elements 171 of the detector 17 is stored in the intensity information storage unit 543 as intensity information, and the calculation by the calculation unit 512 is performed using the intensity information. It has come to be. At this time, the intensity information stored in the intensity information storage unit 543 is read by the reading unit 513, and calculation is performed by the calculation unit 512 using the read intensity information.

When calculating the particle size distribution data, the relationship of the following formula (1) can be used.

Here, s, q, and A are represented by the following formulas (2) to (4).

The s is light intensity distribution data (vector). Each element s _i (i = 1, 2,..., M) in s is connected to the side sensor provided on the side of the flow cell 15 or the flow cell 15 in addition to the light receiving elements 171 of the detector 17. On the other hand, the intensity of light received by a rear sensor (none of which is shown) provided on the side opposite to the detector 17 side.

Of each element q _j (j = 1, 2,..., N, n + 1) in q, elements q _{1 to} q _n are granularity distribution data (vectors) expressed as frequency distribution%. When the particle size range to be measured (maximum particle size is x ₁ , minimum particle size is x _{n + 1} ) is divided into n and each particle size interval is [x _j , x _{j + 1} ], elements q _{1 to} q _n are , The particle amount corresponding to each particle diameter section [x _j , x _{j + 1} ].

A method for calculating the particle size distribution data by using only those elements q ₁ to q _n are known, in the present embodiment, added to the elements q ₁ to q _n, yet another element q _{n + 1} The feature is that the vector q is used. The element q _{n + 1} represents the amount of background light other than normal diffraction scattered light.

For q _{n + 1} elements _q 1 to q _n except, usually, a volume basis is used, so as to satisfy the following formula (5), i.e. normalized such that the total is 100% of each element _q 1 to q _n Is done.

A is a coefficient matrix for converting q to light intensity distribution data s. Of the elements a _{i, j} (i = 1, 2,..., M, j = 1, 2,..., N, n + 1) in A, the elements a _{i, j} (i = 1, 2, ,..., M, j = 1, 2,..., N) are obtained when unit intensity particle beams belonging to each particle diameter section [x _j , x _{j + 1} ] are irradiated with unit intensity measurement light. This is the received light intensity of normal diffracted scattered light in the i-th light receiving element 171. That is, with respect to diffracted and scattered light that is diffracted and scattered by the sample while maintaining energy, the relative relationship of the received light intensity in each light receiving element 171 is expressed by each element a _{i, j} (i = 1, 2,..., M). , J = 1, 2,..., N).

The value of each element a _{i, j} (i = 1, 2,..., M, j = 1, 2,..., N) in A is obtained using the refractive index of the particle as one of the parameters. It can be theoretically calculated in advance. For example, when the particle diameter is sufficiently larger than the wavelength of the measurement light from the light source 11 (for example, 10 times or more), it can be calculated using Fraunhofer diffraction theory. On the other hand, when the particle diameter is about the same as or smaller than the wavelength of the measurement light from the light source 11, it can be calculated using Mie scattering theory.

On the other hand, each element _a i of the A, j (i = 1,2, ···, m, j = 1,2, ···, n, n + 1) of the element _{a i,} j (i = 1 , 2,..., M, j = n + 1) is the received light intensity of the background light in the i-th light receiving element 171 when the unit volume of the particle group is irradiated with the measurement light of unit intensity. That is, with respect to background light other than normal diffracted scattered light, the relative relationship of the received light intensity in each light receiving element 171 is expressed by each element a _{i, j} (i = 1, 2,..., M, j = n + 1). It is represented by

In the present embodiment, a case where the background light is fluorescent will be described. When the sample emits fluorescence by the measurement light irradiated to the sample, it is considered that the fluorescence is emitted isotropically from the sample. Here, isotropic means that light is emitted uniformly in all directions centered on the sample, for example. Thus, when fluorescence is emitted from the sample isotropically, the values of the elements a _{i, j} (i = 1, 2,..., M, j = n + 1) in A are as follows. For example, the value is proportional to the solid angle at which each light receiving element 171 faces particles in a sample that emits fluorescence.

  As described above, A in the present embodiment is a matrix representing the relative relationship of the received light intensity at each light receiving element 171 for each of normal diffraction scattered light and fluorescence, and the matrix A is intensity information as intensity information. It is stored in the storage unit 543. As shown in FIG. 2, the matrix A stored as intensity information in the intensity information storage unit 543 is read by the reading unit 513, and the calculation unit 512 performs matrix calculation on the light intensity distribution data using the matrix A. By doing so, it is possible to easily calculate the particle size distribution data and the amount of fluorescence from which the influence of fluorescence has been removed. The calculated particle size distribution data and fluorescence amount are stored in the particle size distribution data storage unit 542.

In the matrix calculation by the calculation unit 512, the vector q is obtained by the following equation (6) based on the above equation (1). Where ^AT is a transposed matrix of A. In this case, the elements q _{1 to} q _n in the obtained vector q are the particle size distribution data, and the element q _{n + 1} is the fluorescence amount.

In the present embodiment, not only the relative relationship of the received light intensity at each light receiving element 171 for normal diffraction scattered light but also the relative relationship of the received light intensity at each light receiving element 171 for fluorescence is collectively used. By performing the calculation for calculating the particle size distribution, it is possible to simultaneously calculate the assumed fluorescence amount based on the particle size distribution data (elements q _{1 to} q _n ) from which the influence of fluorescence has been removed and the amount of fluorescence light. Thus, since the influence of fluorescence can be removed by calculation, the particle size distribution can be accurately measured without providing an optical filter.

In addition, since the fluorescence amount (element q _{n + 1} ) can be calculated together with the particle size distribution data (elements q _{1 to} q _n ) from which the influence of fluorescence has been removed, the particle size distribution and fluorescence can be analyzed simultaneously. . This is the i- _{th when} each element a _{i, j} (i = 1, 2,..., M, j = n + 1) in the matrix A irradiates a unit volume of particle light with unit intensity measurement light. This is because the light receiving intensity of fluorescence in the light receiving element 171 is set accurately.

However, in calculating the particle size distribution data (elements q _{1 to} q _n ) from which the influence of fluorescence has been removed, elements a _{i, j} (i = 1, 2,..., M, j = The absolute value of n + 1) need not be exact. That is, if the relative proportions of the elements a _{i, j} (i = 1, 2,..., M, j = n + 1) in the matrix A are accurate, the calculated particle size distribution data (elements q ₁ to q q _n ) is an almost accurate value, and the particle size distribution data from which the influence of fluorescence is removed can be favorably calculated. However, the value of each element a _{i, j} (i = 1, 2,..., M, j = n + 1) is equal to the other element a _{i, j} (i = 1, 2,...) In the matrix A. , M, j = 1, 2,..., N) is less likely to cause an error in calculation during calculation, and the calculation accuracy is higher.

  In particular, in this embodiment, as an example of light isotropically emitted from a sample, particle size distribution data from which the influence of fluorescence is removed can be calculated. Since the relative relationship of the light receiving intensity in each light receiving element 171 with respect to light emitted isotropically from the sample can be easily calculated based on the arrangement of each light receiving element 171, an accurate particle size distribution can be easily obtained. Can be measured.

  FIG. 3 is a flowchart showing an example of processing by the control unit 51 when calculating the particle size distribution data and the fluorescence amount. First, measurement is performed in the measurement unit 1 so that each light receiving element 171 of the detector 17 receives light from the sample, and the light intensity distribution data s obtained thereby is received by the input reception unit 511 (step S101: Input reception step).

  Thereafter, the matrix A as intensity information is read from the intensity information storage unit 543 by the reading unit 513 (step S102: reading step). Then, as shown in the above equation (6), the calculation unit 512 performs calculation on the light intensity distribution data s using the matrix A, thereby calculating the particle size distribution data and the fluorescence amount from which the influence of fluorescence is removed ( Step S103: calculation step).

  As long as the background light isotropically emitted from the sample, not only the fluorescence but also other background light such as Raman scattered light is emitted from the sample, the calculation of the background light is performed by the above matrix A. The particle size distribution data from which the influence has been removed can be calculated. Therefore, the background light is not limited to fluorescence but may include background light other than fluorescence, such as Raman scattered light, or may be background light that does not include fluorescence.

  However, when the background light emitted from the sample is not isotropic, it is necessary to add a column corresponding to the ratio of the light toward each light receiving element 171 to the matrix A. As described above, if each element of the matrix A is appropriately set, the background light may include not only isotropic light emitted from the sample but also light that is not isotropic. The light emitted may not be included.

  In the above embodiment, the configuration in which the data processing device 5 for generating the particle size distribution data is provided in the particle size distribution measuring device has been described. However, the configuration is not limited to such a configuration, and a configuration in which the data processing device 5 is provided separately from the particle size distribution measuring device may be used. In this case, the light intensity distribution data output from the measurement unit 1 of the particle size distribution measuring device may be configured to be input to the data processing device 5 via wired communication or wireless communication, or a storage medium ( It may be configured such that the data is once stored in (not shown) and then input to the data processing device 5 from the storage medium.

  The data processing device 5 is not limited to a configuration in which the light intensity distribution data input from the measurement unit 1 is temporarily stored in the light intensity distribution data storage unit 541 and then used for calculation, but the light input from the outside The intensity distribution data may be used as it is for the calculation of the calculation unit 512. Note that the calculation unit 512 is not limited to a configuration that uses a matrix for light intensity distribution data, and may be configured to perform a calculation without using a matrix.

  In addition to providing the data processing device for particle size distribution measurement for generating the particle size distribution data, like the data processing device 5 according to the above embodiment, the computer functions as the data processing device for particle size distribution measurement. It is also possible to provide a program (data processing program for particle size distribution measurement) for the purpose. In this case, the program may be configured to be provided in a state stored in a storage medium, or may be configured to provide the program itself via wired communication or wireless communication. .

DESCRIPTION OF SYMBOLS 1 Measurement part 2 Circulation sampler 3 A / D converter 4 Communication part 5 Data processing apparatus 11 Light source 12 Condensing lens 13 Spatial filter 14 Collimator lens 15 Flow cell 16 Condensing lens 17 Detector 51 Control part 52 Operation part 53 Display part 54 storage unit 171 light receiving element 511 input reception unit 512 calculation unit 513 reading unit 541 light intensity distribution data storage unit 542 particle size distribution data storage unit 543 intensity information storage unit

Claims (6)

An input receiving unit that receives input of light intensity distribution data obtained by receiving light from a sample with a plurality of light receiving elements;
A storage unit that stores, as intensity information, a relative relationship of received light intensity in each light receiving element for each of diffracted scattered light that is diffracted and scattered by a sample while retaining energy, and background light other than the diffraction scattered light,
By performing the matrix operation with respect to the light intensity distribution data using the strong degree information, wherein with the background light particle size distribution data is removed the effect of, and an arithmetic unit for calculating the amount of the background light,
The intensity information is obtained by adding a column having an element with a value corresponding to a ratio of the background light toward the plurality of light receiving elements to a matrix having the intensity of the diffracted scattered light toward the plurality of light receiving elements. A data processing apparatus for particle size distribution measurement, characterized in that The data processing apparatus for particle size distribution measurement according to claim 1 , wherein the background light includes light isotropically emitted from a sample. 3. The data processing apparatus for particle size distribution measurement according to claim 2 , wherein the background light includes fluorescence. A light source for irradiating the sample with light;
A plurality of light receiving elements for receiving light from the sample;
A particle size distribution measuring device comprising the data processing device for particle size distribution measurement according to any one of claims 1 to 3 . An input receiving step for receiving input of light intensity distribution data obtained by receiving light from the sample by a plurality of light receiving elements;
From each of the diffracted scattered light that is diffracted and scattered by the sample while retaining energy, and the background light other than the diffracted scattered light, from the storage unit that stores the relative relationship of the received light intensity in each light receiving element as intensity information, A reading step of reading the intensity information;
A calculation step of calculating the amount of the background light together with the particle size distribution data from which the influence of the background light has been removed by performing a matrix operation on the light intensity distribution data using the read intensity information. ,
The intensity information is obtained by adding a column having an element with a value corresponding to a ratio of the background light toward the plurality of light receiving elements to a matrix having the intensity of the diffracted scattered light toward the plurality of light receiving elements. A data processing method for particle size distribution measurement, characterized by An input receiving unit that receives input of light intensity distribution data obtained by receiving light from a sample with a plurality of light receiving elements;
From each of the diffracted scattered light that is diffracted and scattered by the sample while retaining energy, and the background light other than the diffracted scattered light, from the storage unit that stores the relative relationship of the received light intensity in each light receiving element as intensity information, A reading unit for reading the intensity information;
By performing a matrix operation on the light intensity distribution data using the read intensity information, a computer as a calculation unit that calculates the amount of the background light together with the particle size distribution data from which the influence of the background light has been removed. to function,
The intensity information is obtained by adding a column having an element with a value corresponding to a ratio of the background light toward the plurality of light receiving elements to a matrix having the intensity of the diffracted scattered light toward the plurality of light receiving elements. A data processing program for particle size distribution measurement characterized by

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