Spectroscopic measurement apparatus

The spectroscopic measurement device addresses baseline correction challenges by using a movable probe and detachable baseline unit for reference data measurement, enhancing accuracy and compactness.

JP2026022068APending Publication Date: 2026-02-12HITACHI HIGH TECH CORP
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Patent Information

Application Number
JP2024123424
Authority / Receiving Office
JP · JP
Patent Type
Applications
Current Assignee / Owner
Filing Date
2024-07-30
Publication Date
2026-02-12

AI Technical Summary

Technical Problem

Existing spectroscopic measurement devices face challenges in performing baseline correction due to the need for a light branching means between the light guiding means and the object to be measured, which limits the device's compactness and makes it susceptible to environmental influences.

Method used

A spectroscopic measurement device with a probe that moves between measurement and baseline positions, incorporating a detachable baseline measurement unit and a standard substance storage unit to perform baseline correction, allowing for accurate reference data measurement.

Benefits of technology

Enables easy and accurate baseline measurement with reduced environmental influence, facilitating compact device design and improved measurement accuracy.

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Abstract

To provide a spectrometric apparatus capable of easily performing baseline measurement.SOLUTION: The spectroscopic measurement apparatus 1 includes the probe 141 that receives the diffuse reflection light from the suspension liquid 162 when the first measurement irradiation light is irradiated, the baseline measurement unit 170 that includes the standard substance storage unit that stores the standard substance 175 and is attachable to and detachable from the probe 141, and the moving mechanism 121 that moves the position of the probe 141 between the measurement position where the suspension liquid 162 can be measured and the baseline measurement position where the baseline measurement for measuring the reference data used for the baseline correction can be performed, and moves the position of the probe 141 to the baseline measurement position when the baseline measurement is performed. In a state where the baseline measuring unit 170 is attached to the probe 141, the reference substance 175 is irradiated with the second measurement irradiation light, and diffuse reflection light from the reference substance 175 is received by the probe 141 to measure the reference data.SELECTED DRAWING: Figure 1B
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Description

[Technical Field]

[0001] The present invention relates to a spectroscopic measurement device. [Background technology]

[0002] The spectroscopic measuring device is a device for spectroscopically measuring components in suspensions and emulsions.

[0003] A suspension generally refers to a liquid in which solid particles are dispersed in a liquid. On the other hand, an emulsion generally refers to a liquid in which liquid particles generated by emulsification or the like are dispersed in a liquid. In this specification, the term suspension will be used without any distinction between a suspension and an emulsion.

[0004] The spectroscopic method of measuring components in liquids is non-invasive and can be performed without sampling, so it does not alter the object being measured and allows for continuous measurement, making it suitable for use in the pharmaceutical, food, and chemical industries.

[0005] Furthermore, in these fields, there is an increasing need to measure suspensions obtained by cell culture in the pharmaceutical industry, and to measure suspensions of brewed products, dairy products, and the like in the food industry.

[0006] Documents disclosing techniques relating to spectroscopic measurement devices include, for example, Patent Document 1 and Patent Document 2.

[0007] FIG. 7 of Patent Document 1 describes a technique in which a light-transmitting window (31) is attached to the side wall of a reaction vessel (30) and diffuse reflected light is measured by a measurement sensor (A) through the light-transmitting window (31).

[0008] FIG. 1 and the abstract of Patent Document 2 describe a technology for realizing a spectroscopic analyzer capable of more accurate and stable absorption spectrum measurement, which includes a light source (1) that projects light onto a measured object (5) and an analyzing means (6) that measures the spectrum of measurement light or reference light, which is light reflected from the measured object (5), and analyzes the measured object (5). The spectroscopic analyzer includes a light guiding means (7) that guides the measurement light or reference light to the analyzing means (6), a light branching means (8) that can be moved to a position that can reflect or not reflect the light from the light source (1), a control means (11) that moves and controls the position of the light branching means (8), and a standard reflecting means (9) that reflects the light from the light source (1) and uses it as reference light, and the light branching means (8) can be moved to a position where it reflects the light from the light source (1) and irradiates it onto the standard reflecting means (9), and the reference light reflected by the standard reflecting means (9) is incident on the light guiding means (7). [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 9-89657 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-52996 Summary of the Invention [Problem to be solved by the invention]

[0010] In Patent Document 2, in order to improve the accuracy of measurement and analysis, so-called baseline correction is performed using reference light reflected by a so-called standard material. In baseline measurement, which measures this reference light, a light branching means (8) is provided between the light guiding means (7) and the object to be measured (5), and by moving the light branching means (8), it is possible to switch between normal measurement and baseline measurement.

[0011] However, the technology described in Patent Document 2 requires the placement of a light branching means (8) between the light guiding means (7) and the object to be measured (5), which poses a problem that the distance between the light guiding means (7) and the object to be measured (5) cannot be shortened.

[0012] Therefore, it is difficult to apply the technology of Patent Document 2 to a device in which the light-transmitting window (31) and the measurement sensor (A) are arranged close to each other, as in Patent Document 1, for example.

[0013] Furthermore, as in Patent Document 2, the longer the distance between the light guiding means (7) and the object to be measured (5), the more susceptible it is to the influence of the external environment.

[0014] An object of the present invention is to provide a spectroscopic measurement device that can easily perform baseline measurement. [Means for solving the problem]

[0015] In order to solve the above-mentioned problems, the spectroscopic measuring device of the present invention has a probe that receives diffusely reflected light from the suspension liquid when irradiated with first measurement irradiation light, a standard substance storage unit that stores a standard substance, a baseline measurement unit that is detachable from the probe, and a movement mechanism that moves the position of the probe between a measurement position where the suspension liquid can be measured and a baseline measurement position where baseline measurement can be performed to measure reference data used for baseline correction, and is characterized in that when the baseline measurement is performed, the position of the probe is moved to the baseline measurement position, and with the baseline measurement unit attached to the probe, the standard substance is irradiated with second measurement irradiation light, and the diffusely reflected light from the standard substance is received by the probe to measure the reference data. [Effects of the Invention]

[0016] According to the present invention, a spectroscopic measurement device that can easily perform baseline measurement can be realized.

[0017] Problems, configurations, and effects other than those described above will become apparent from the following description of the preferred embodiments of the invention. [Brief explanation of the drawings]

[0018] [Figure 1A] FIG. 2 is a cross-sectional view of the spectroscopic measurement device of the first embodiment, illustrating a normal measurement state. [Figure 1B] FIG. 2 is a cross-sectional view of the spectroscopic measurement device of the first embodiment, illustrating the state of baseline measurement. [Figure 2A] FIG. 2 is a cross-sectional view of the baseline measurement section of the first embodiment, illustrating the state before attachment to the probe. [Figure 2B] FIG. 2 is a cross-sectional view of the baseline measurement section of the first embodiment, illustrating the state after it has been attached to the probe. [Figure 3] FIG. 10 is a cross-sectional view of the baseline measurement section of Example 2. [Figure 4] FIG. 10 is a cross-sectional view of the baseline measurement section of Example 3. [Figure 5] FIG. 10 is a cross-sectional view of the baseline measurement section in Example 4. [Figure 6] FIG. 10 is a cross-sectional view of the baseline measurement section in Example 5. [Figure 7] FIG. 10 is a cross-sectional view of the baseline measurement section in Example 6. [Figure 8] FIG. 13 is a cross-sectional view of the baseline measurement section of Example 7. [Figure 9] FIG. 10 is a diagram showing an example of the results of baseline measurement in Example 1. [Figure 10] FIG. 10 is a diagram showing an example of the results of baseline measurement in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0019] Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each drawing and each embodiment, the same or similar components are designated by the same reference numerals, and redundant explanations will be omitted. [Example]

[0020] Fig. 1A is a cross-sectional view of the spectroscopic measurement device of Example 1, illustrating a normal measurement state. Fig. 1B is a cross-sectional view of the spectroscopic measurement device of Example 1, illustrating a baseline measurement state. Figs. 1A and 1B are conceptual diagrams illustrating a state in which the spectroscopic measurement device 1 of this example is attached to a pipe 160 having a window material 161, and are cross-sectional views taken perpendicular to the longitudinal direction of the pipe 160.

[0021] The spectroscopic measurement device 1 of this embodiment includes a spectroscopic device 100 , an analysis unit 110 , a probe jig 120 , a probe 141 , an irradiation optical fiber 142 , a light-receiving optical fiber 143 , and a baseline measurement unit 170 .

[0022] The spectroscopic device 100 may be, for example, a double-beam spectrophotometer. The spectroscopic device 100 includes a light source 102, a spectrometer 103, and a photodetector 104. One end of an illumination optical fiber 142 is connected to the spectrometer 103. One end of a light-receiving optical fiber 143 is connected to the photodetector 104. The other end of the illumination optical fiber 142 and the other end of the light-receiving optical fiber 143 are bundled and housed in a probe 141. Therefore, the probe 141 of this embodiment is capable of irradiating first and second measurement illumination lights, which will be described later, and functions as both a measurement probe and an illumination probe. The illumination optical fiber 142 and the light-receiving optical fiber 143 are not limited to being composed of a single optical fiber each, and may be composed of multiple optical fibers.

[0023] Light emitted from light source 102 is monochromatized by spectroscope 103 and introduced into illumination optical fiber 142. In the case of normal measurement, as shown in FIG. 1A , light from illumination optical fiber 142 is emitted from probe 141 as first measurement illumination light and is irradiated onto suspension liquid 162 flowing in pipe 160 through window material 161, and a portion of the diffuse reflected light from suspension liquid 162 is received by probe 141 again through window material 161 and enters light-receiving optical fiber 143. The light that has entered light-receiving optical fiber 143 is detected by photodetector 104 as measurement light.

[0024] The light incident on the light-receiving optical fiber 143 includes not only diffusely reflected light from the suspension liquid 162 but also light from the illumination optical fiber 142 that is reflected or scattered on the surface of the window material 161. The reflection and scattering on the surface of the window material 161 here occurs on both the outer surface (the side to which the probe 141 approaches) and the inner surface (the side in contact with the suspension liquid 162) of the window material 161. Furthermore, when the light from the illumination optical fiber 142 and the light incident on the light-receiving optical fiber 143 pass through the window material 161, they are attenuated by light absorption by the material of the window material 161. These effects can be corrected by baseline correction by using the same conditions in baseline measurement as in normal measurements, as will be described later.

[0025] The light source 102 is preferably a white light source having a continuous spectrum. Incandescent lamps, halogen lamps, xenon lamps, white light-emitting diodes, tunable lasers, etc. can be used, but any other light source that can emit light of multiple wavelengths can also be used.

[0026] The spectroscope 103 is preferably a spectroscope using a diffraction grating, but may also be a spectroscope using a prism or an optical filter.

[0027] The photodetector 104 is preferably a photomultiplier tube or a photoconductive element such as PbS or CdS, but may also be a photodiode, PIN diode, pyrometer, or other photodetector.

[0028] The spectroscopic device 100 can output, as measurement values, the light energy measured by the photodetector 104, the reflectance which is the ratio of the light energies measured for the measurement light and the reference light, and the absorbance which is the common logarithm of the reciprocal of the reflectance. The measurement results by the spectroscopic device 100 are analyzed by the analysis unit 110.

[0029] The probe jig 120 has a moving mechanism 121 and a fixing part 123. The spectroscopic measurement device 1 is attached to a pipe 160 via the fixing part 123. The moving mechanism 121 is fixed to the fixing part 123. The probe 141 is fixed to the moving mechanism 121.

[0030] The moving mechanism 121 may be, for example, a linear moving mechanism such as a linear stage. Note that the moving mechanism 121 is not limited to a linear moving mechanism and may be another moving mechanism. The moving mechanism 121 is preferably installed so that the moving direction is approximately perpendicular to the axial direction 163 of the pipe 160 and is oriented so that the probe 141 can be moved toward or away from the pipe 160. As a guide structure for the moving mechanism 121, for example, a dovetail groove system, a ball guide system, or a cross roller guide system may be used as appropriate. Furthermore, as a moving system for the moving mechanism 121, a manual system or an electric system using a rotary motor or a linear motor may be used as appropriate.

[0031] For example, metal or resin material can be appropriately used as the material of the moving mechanism 121 and the fixed part 123. However, if the suspension liquid 162 is hot, heat is transmitted through the piping 160 and the resin material may be deformed, so metal is preferred, and stainless steel, iron, or aluminum is most preferred.

[0032] The piping 160 has a cylindrical window material 161, a flange 164, and a fixed rod 165, and a suspension liquid 162 flows inside. The window material 161 is sandwiched between flanges 164 on both sides. The flanges 164 on both sides are fixed with four fixed rods 165, so that the window material 161 is fixed to the piping 160.

[0033] The material of the window material 161 may be any light-transmitting material, such as glass, quartz, sapphire, or a transparent resin material. The material of the piping 160 other than the window material 161 (including the flange 164 and the fixed rod 165) may be, for example, a metal or a resin material. However, if the suspension liquid 162 is at a high temperature or flows under high pressure, the resin material may be deformed, so glass or tempered glass is preferred as the material of the window material 161. For the same reason, the material of the piping 160 other than the window material 161 (including the flange 164 and the fixed rod 165) is preferably a metal such as stainless steel or iron.

[0034] 1A, monochromatic light introduced from the spectrometer 100 into the illumination optical fiber 142 is irradiated onto the window material 161 as first measurement illumination light through the probe 141. Part of the light enters the window material 161 from the outer surface as refracted light, and part of this light enters the suspension liquid 162 from the inner surface of the window material 161 as refracted light.

[0035] A part of the light that has entered the suspension liquid 162 is scattered by particles, molecules, etc. inside the suspension liquid 162 and becomes diffusely reflected light, changing its direction of travel, and a part of the light enters the window material 161 again from the inner surface of the window material 161 as refracted light, and further enters the atmosphere from the outer surface of the window material 161 as refracted light, and a part of the light enters the light-receiving optical fiber 143 bundled by the probe 141. The intensity of the light that has entered the light-receiving optical fiber 143 is detected by the photodetector 104 of the spectrometer 100.

[0036] The light incident on the light-receiving optical fiber 143 is absorbed by the molecules and particles inside the suspension liquid 162 as it travels through the suspension liquid 162. Therefore, by measuring the light incident on the light-receiving optical fiber 143 with the spectrometer 100, the effect of light absorption by the components of the suspension liquid 162 can be investigated.

[0037] The angle of the probe 141 is fixed so that the specular reflected light, which is light emitted from the illumination optical fiber 142 and reflected by the surface of the window material 161, does not enter the light-receiving optical fiber 143. This makes it possible to measure the diffuse reflected light while avoiding the specular reflected light.

[0038] Next, baseline measurement will be described. In this embodiment, to enable baseline measurement, the probe 141 is connected to a moving mechanism 121. Furthermore, the moving mechanism 121 is connected to a pipe 160 via a fixed portion 123. Therefore, the position of the probe 141 relative to the window material 161 can be changed using the moving mechanism 121.

[0039] In the case of baseline measurement, as shown in FIG. 1B, the probe 141 is moved to a position away from the window material 161 using the moving mechanism 121, and a detachable baseline measurement unit 170 is attached to the probe 141.

[0040] 2A and 2B are cross-sectional views of the baseline measurement unit of Example 1, illustrating the state before and after attachment to the probe, respectively.

[0041] The baseline measuring unit 170 of this embodiment has a reference material storage unit 176 that stores a reference material 175, and a probe connection unit 173 that is connected to the probe 141. Furthermore, the baseline measuring unit 170 desirably has a reference material window material 174 that is disposed between the reference material 175 and the probe 141. This protects the reference material 175 and makes the baseline measurement conditions closer to those of normal measurement. The probe connection unit 173 also has a first probe connection unit 173A and a second probe connection unit 173B that hold the probe 141 therebetween. The baseline measuring unit 170 of this embodiment has a main body unit 171 in which the reference material storage unit 176 and the first probe connection unit 173A are formed, and a lid unit 172 in which the second probe connection unit 173B is formed. 2B, by placing probe 141 in probe connection section 173 and attaching lid section 172 to main body section 171, probe 141 is sandwiched between first probe connection section 173A and second probe connection section 173B, and baseline measurement section 170 is attached to probe 141. Capability of separating lid section 172 from main body section 171 allows for easy attachment and detachment. Note that the structure of baseline measurement section 170 shown in this embodiment is an example and is not limited to this.

[0042] In the case of baseline measurement, light irradiated from the irradiation optical fiber 142 is emitted from the probe 141 as second measurement irradiation light and is irradiated onto the standard material 175 through the window material 174 for the standard material, and a portion of the diffuse reflected light from the standard material 175 is received by the probe 141 again through the window material 174 for the standard material and enters the receiving optical fiber 143.

[0043] The angle of the probe 141 is fixed so that the specularly reflected light, which is the light irradiated from the irradiation optical fiber 142 and reflected by the surface of the reference material window material 174, does not enter the light-receiving optical fiber 143. In other words, the baseline measurement unit 170 is attached to the probe 141 at an angle such that the specularly reflected light of the second measurement irradiation light irradiated onto the reference material 175 does not enter the probe 141. This makes it possible to measure the diffusely reflected light while avoiding the specularly reflected light.

[0044] Furthermore, when the baseline measurement unit 170 is attached to the probe 141, it is possible to irradiate the reference material 175 with the second measurement irradiation light while blocking external light irradiating the reference material 175. This makes it possible to suppress the influence of external light.

[0045] The main body 171 and the lid 172 can be made of, for example, metal or resin material as appropriate. However, if a resin material is used, the material must be opaque to block external light. Even if the material is opaque, if it is thin, some light will still pass through, so it is desirable that the intensity of external light incident on the light-receiving optical fiber 143 be below the lower detection limit of the photodetector 104. For these reasons, the main body 171 and the lid 172 are preferably made of a metal such as aluminum.

[0046] The material of the window material 174 for the reference material is preferably the same as the material of the window material 161. Therefore, glass or tempered glass is preferred as the material of the window material 174 for the reference material. Furthermore, the thickness of the window material 174 for the reference material is preferably the same as the thickness of the window material 161. The reason why the window material 174 for the reference material and the window material 161 are preferably made of the same material and have the same thickness is that if the amount of detected light during baseline measurement and the amount of detected light during measurement of the suspension liquid 162 do not match, the intensity of the detected light relative to the dynamic range of the amount of detected light of the spectrometer 100 will mismatch, making correction difficult. Therefore, as long as there is no mismatch in the intensity of the detected light relative to the dynamic range of the amount of detected light of the spectrometer 100, the material and thickness of the window material 174 for the reference material and the window material 161 do not necessarily need to be the same.

[0047] The material of the reference material 175 is preferably a material having an isotropic diffuse reflectance, and for example, barium sulfate, alumina, or fluororesin can be appropriately used. From the viewpoint of durability of the material, fluororesin is more preferable.

[0048] Below, the results of baseline measurements when 5 mm thick tempered glass was used as the window material for the reference material 174 and fluororesin was used as the reference material 175 will be described.

[0049] FIG. 9 shows an example of the results of the baseline measurement in Example 1. FIG. 9 shows absorbance spectra obtained in the baseline measurement in the wavelength range of 1000 to 1800 nm. In FIG. 9, the horizontal axis represents wavelength (nm) and the vertical axis represents the difference in absorbance. Note that absorbance can be calculated using log(1 / R), where R is the reflectance. However, to evaluate repeatability, the absorbance on the vertical axis is shown as the difference from the average absorbance spectrum of the initial measurement (not shown). FIG. 9 shows a total of five absorbance spectra measured each time the baseline measurement unit 170 was attached to and detached from the probe 141. It can be seen from FIG. 9 that the absorbance spectra obtained in the baseline measurement in this example do not exhibit wavelength dependency.

[0050] Fig. 10 shows an example of the results of baseline measurement in Example 1. Fig. 10 shows the average absorbance and error (standard deviation) in the wavelength range of 1000 to 1800 nm for each of the five absorbance spectra shown in Fig. 9. In Fig. 10, the vertical axis represents the average absorbance difference, and the horizontal axis represents the first to fifth measurements. Fig. 10 shows that the variation in the average absorbance due to repeated measurements is within the error range, indicating that measurements are performed with good reproducibility.

[0051] From the above, it can be seen that measurement of the diffuse reflectance of the standard material 175, i.e., baseline measurement, can be carried out easily and with good reproducibility.

[0052] Furthermore, baseline measuring unit 170 can be detached from probe 141. Furthermore, if baseline measuring unit 170 is configured to be portable without being fixed to, for example, probe jig 120, baseline measuring unit 170 does not need to be constantly installed near the measurement target and can be stored in a cleaner environment, making it possible to prevent contamination and deterioration.

[0053] The analysis unit 110 performs baseline correction on the measurement data obtained by measuring the suspension liquid 162 with the probe 141, using reference data obtained in baseline measurement. This allows accurate measurements even if there are fluctuations in the amount of detected light that occur when measurements are performed continuously over a long period of time. Factors that cause fluctuations in the amount of detected light include fluctuations in the amount of light due to deterioration of the light source 102, fluctuations in transmittance due to dirt or deterioration of optical components, and fluctuations in the detected value due to dirt or deterioration of the light-receiving element. Such fluctuations can be corrected by baseline correction, in which reference light is measured using a standard material 175 whose diffuse reflectance is known and is considered to remain unchanged over time.

[0054] Furthermore, in the baseline measurement, it is desirable that the positional relationship between the standard substance 175, the second measurement irradiation light, and the probe 141 at the baseline measurement position is approximately the same as the positional relationship between the suspension 162, the first measurement irradiation light, and the probe 141 at the measurement position for normal measurement. This allows for more accurate baseline correction.

[0055] In this embodiment, a double-beam wavelength-dispersive spectrophotometer is used as the spectroscopic device 100. However, the spectroscopic device 100 may be a single-beam wavelength-dispersive spectrophotometer or a Fourier transform spectrophotometer. The measured values ​​obtained by these spectrophotometers may include the number of photons, the output voltage or output current of the photodetector 104, as well as the optical energy, reflectance, and absorbance. The spectroscopic device 100 may also be a fluorescence spectrophotometer. In this case, the measured value may be, for example, fluorescence intensity. The spectroscopic device 100 may also be a Raman spectrophotometer. In this case, the measured value may be Raman scattering intensity.

[0056] In this example, a configuration is described in which suspension liquid 162 flows through piping 160 having a window material 161, and probe 141 receives diffusely reflected light from suspension liquid 162 through window material 161. With this configuration, probe 141 is not immersed in suspension liquid 162, and therefore adhesion of suspension liquid 162 to probe 141 does not affect measurement.

[0057] As described above, the spectroscopic measurement device 1 of this embodiment includes a probe 141 that receives diffusely reflected light from the suspension liquid 162 when irradiated with the first measurement irradiation light, a reference material storage unit that stores the reference material 175, a baseline measurement unit 170 that is detachable from the probe 141, and a movement mechanism 121 that moves the position of the probe 141 between a measurement position where the suspension liquid 162 can be measured and a baseline measurement position where baseline measurement can be performed to measure reference data used for baseline correction. When performing baseline measurement, the position of the probe 141 is moved to the baseline measurement position, and with the baseline measurement unit 170 attached to the probe 141, the reference material 175 is irradiated with the second measurement irradiation light, and the diffusely reflected light from the reference material 175 is received by the probe 141 to measure the reference data. This allows baseline measurement to be performed easily.

[0058] Furthermore, the baseline measurement position can be set at a position farther from the suspension liquid 162 than the measurement position for normal measurements, so the baseline measurement unit 170 can be easily attached and detached at the baseline measurement position, and in normal measurements, the probe 141 can be brought closer to the suspension liquid 162 for measurement, allowing for accurate measurements. [Example]

[0059] FIG. 3 is a cross-sectional view of the baseline measurement section of the second embodiment.

[0060] Example 2 is a modification of Example 1, and the baseline measurement unit 170 of this example is not separated from the main body 171 and the cover 172 as in Example 1, but is attached to the probe 141 by a probe connection part 173 provided on the main body 171. As a fixing method, a structure in which the probe 141 and the probe connection part 173 are fixed with a screw, or a quick coupling structure provided on the probe 141 and the probe connection part 173 can be used as appropriate.

[0061] According to this embodiment, in addition to the effects of the first embodiment, the operation of combining the main body part 171 and the lid part 172 during baseline measurement is no longer necessary, and the operation can be carried out more easily. [Example]

[0062] FIG. 4 is a cross-sectional view of the baseline measurement section of the third embodiment.

[0063] The third embodiment is a modification of the first embodiment, and the baseline measurement unit 170 of this embodiment has a standard substance window member 174 shaped to surround the standard substance 175 .

[0064] According to this embodiment, in addition to the effect of the first embodiment, it becomes possible to use a material having fluidity such as a liquid, powder, or gas as the material of the reference material 175. [Example]

[0065] FIG. 5 is a cross-sectional view of the baseline measurement section of the fourth embodiment.

[0066] Example 4 is a modification of Example 1, and the baseline measurement unit 170 of this example does not have a reference material window material 174, and the probe 141 and the reference material 175 are arranged opposite each other. If there is no problem with deterioration of the reference material 175 or baseline correction even without the reference material window material 174, the reference material window material 174 can be omitted as in this example. [Example]

[0067] FIG. 6 is a cross-sectional view of the baseline measurement section of the fifth embodiment.

[0068] Example 5 is a modification of Example 1, and the baseline measurement unit 170 of this example does not irradiate the second measurement irradiation light from the probe 141 as in Example 1, but irradiates the second measurement irradiation light from a position different from the probe 141. Specifically, the irradiation optical fiber 142 is not bundled with the probe 141, but is bundled with a separate irradiation probe 144. The irradiation probe 144 is attached to the baseline measurement unit 170. The angles of the probe 141 and the irradiation probe 144 are set so that the light irradiated from the irradiation optical fiber 142 is oriented in a direction such that specular reflection light reflected by the surface of the reference material window material 174 does not enter the light-receiving optical fiber 143.

[0069] According to this embodiment, a configuration in which the probe 141 and the irradiation probe 144 are separated can be realized. [Example]

[0070] FIG. 7 is a cross-sectional view of the baseline measurement section of Example 6.

[0071] The sixth embodiment is a modification of the fifth embodiment, in which a light source (not shown) is installed inside the irradiation probe 144, and the irradiation optical fiber 142 is omitted.

[0072] According to this embodiment, the irradiation optical fiber 142 can be omitted. [Example]

[0073] FIG. 8 is a cross-sectional view of the baseline measurement section of Example 7.

[0074] Example 7 is a modified example of Example 1, and in this example, the structure of the probe 141 is different from that of Example 1, and the probe 141 is attached to the main body 171 of the baseline measurement unit 170 by the probe connection part 173 in a direction normal to the surface of the reference material 175.

[0075] Light emitted from an illumination optical fiber 142 provided at the end of the probe 141 is irradiated within the range of an illumination cone 181 whose apex angle is a spread angle according to the numerical aperture. On the other hand, the light-receiving optical fiber 143 can receive light directed toward the fiber end face within the range of a light-receiving cone 182 whose apex angle is a spread angle according to the numerical aperture.

[0076] By positioning the illumination optical fiber 142 and the light-receiving optical fiber 143 so that the circles formed by projecting the illumination cone 181 and the light-receiving cone 182 onto the reference material 175 overlap, a portion of the diffusely reflected light from the reference material 175 can be received by the light-receiving optical fiber 143.

[0077] Considering the case where light emitted from the illumination optical fiber 142 is reflected on the surface of the reference material 175 and returns to the end of the probe 141, this region is a circle formed when light emitted in the direction of the generatrix of the illumination cone 181 is specularly reflected on the surface of the reference material 175 and projected as specularly reflected light 183 onto the end of the probe 141. Therefore, by locating the light-receiving optical fiber 143 outside this circle, it is possible to prevent the specularly reflected light 183 from being received.

[0078] By using a light-receiving optical fiber 143 having a numerical aperture larger than that of the illumination optical fiber 142, the light-receiving optical fiber 143 can be positioned so that it receives a portion of the diffusely reflected light from the reference material 175 and does not receive the specularly reflected light 183.

[0079] Although the present embodiment has been described with reference to an example in which the window material 174 for the reference material is omitted, the window material 174 for the reference material may be provided.

[0080] According to this embodiment, the angle at which the probe 141 is attached can be set to the normal direction of the surface of the reference material 175, making the work easier to carry out.

[0081] Although the embodiments of the present invention have been described above, the present invention is not limited to the configurations described in the embodiments, and various modifications are possible within the scope of the technical concept of the present invention. In addition, some or all of the configurations described in each embodiment may be combined and applied. [Explanation of symbols]

[0082] 1: Spectrometer 100: Spectroscopic device 102: Light source 103: Spectrometer 104: Photodetector 110: Analysis Department 120: Probe jig 121: Movement mechanism 123: Fixed part 141: Probe 142: Optical fiber for illumination 143: Optical fiber for receiving light 144: Irradiation probe 160: Piping 161: Window material 162: Suspension liquid 163: Axial direction 164: Flange 165: Fixed rod 170: Baseline measurement section 171: Main body 172: Lid 173: Probe connection part 173A: First probe connection 173B: Second probe connection 174: Window material for standard materials 175: Standard material 176: Standard Material Storage 181: Irradiation cone 182: Reception cone 183: Specular reflection light

Claims

1. a probe that receives diffuse reflected light from the suspension liquid when the first measurement irradiation light is irradiated; a baseline measurement unit that has a standard substance storage unit that stores a standard substance and is detachable from the probe; a movement mechanism that moves the position of the probe between a measurement position where the suspension liquid can be measured and a baseline measurement position where baseline measurement can be performed to measure reference data used for baseline correction, When performing the baseline measurement, the position of the probe is moved to the baseline measurement position, and with the baseline measurement unit attached to the probe, second measurement irradiation light is irradiated onto the standard substance, and diffuse reflected light from the standard substance is received by the probe, thereby measuring the reference data.

2. In claim 1, A spectroscopic measurement device characterized in that the baseline measurement position is farther from the suspension liquid than the measurement position.

3. In claim 1, The suspension flows through a pipe having a window material, The probe receives the diffusely reflected light from the suspension through the window material.

4. In claim 1, The spectroscopic measurement device is characterized in that the baseline measurement unit is portable.

5. In claim 1, The spectroscopic measurement device is characterized in that the probe is capable of irradiating the first measurement irradiation light and the second measurement irradiation light.

6. In claim 1, The spectroscopic measurement device according to claim 1, wherein the baseline measurement unit has a probe connection unit that is connected to the probe.

7. In claim 6, The spectroscopic measurement device is characterized in that, when attached to the probe, the baseline measurement unit is capable of irradiating the standard substance with the second measurement irradiation light while blocking external light irradiated onto the standard substance.

8. In claim 6, The spectroscopic measurement device is characterized in that the baseline measurement unit is attached to the probe at an angle such that specular reflection light of the second measurement irradiation light irradiated onto the standard substance does not enter the probe.

9. In claim 6, A spectroscopic measurement device characterized in that the positional relationship between the standard substance, the second measurement irradiation light, and the probe at the baseline measurement position is approximately the same as the positional relationship between the suspension liquid, the first measurement irradiation light, and the probe at the measurement position.

10. In claim 6, The spectroscopic measurement device according to claim 1, wherein the baseline measurement unit has a window material for a standard substance that is disposed between the standard substance and the probe.

11. In claim 6, The spectroscopic measurement device is characterized in that, when the baseline measurement is performed, the second measurement irradiation light is irradiated from the probe.

12. In claim 6, The spectroscopic measurement device is characterized in that, when the baseline measurement is performed, the second measurement irradiation light is irradiated from a position different from that of the probe.

13. In claim 6, the probe connection section has a first probe connection section and a second probe connection section that sandwich the probe; The baseline measurement unit has a main body portion in which the standard substance storage unit and the first probe connection unit are formed, and a lid portion in which the second probe connection unit is formed.

14. In claim 1, A spectroscopic measurement device comprising an analysis unit that performs baseline correction using the reference data on measurement data obtained by measuring the suspension liquid with the probe.

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