JP5494461B2 - Spectroscopic analysis method and spectroscopic analysis apparatus - Google Patents

Description

  The present invention relates to a spectroscopic analysis method and a spectroscopic analysis apparatus.

  There is known a method of analyzing physical properties of a sample by irradiating an object sample with electromagnetic waves such as infrared rays, visible light, and ultraviolet rays, and performing spectroscopic analysis of transmitted light transmitted through the sample.

  For example, an organic gas is adsorbed on the porous glass, and the ultraviolet / visible absorption spectrum of the porous glass adsorbed with the organic gas is measured, and the difference from the ultraviolet / visible absorption spectrum of the porous glass before the organic gas adsorption is calculated. To do. There is a method for obtaining the ultraviolet and visible absorption spectra of only the adsorbed organic gas component and analyzing the kind and concentration of the adsorbed gas.

  In addition, the film, which is a mixture of transparent resin and particles made of opaque pigment, is irradiated with light, and the intensity of the light transmitted through the film is received. There is a method for detecting the content.

  Furthermore, there is a method for measuring the amount of moisture contained in the resin film. In this method, the resin film is irradiated with measurement light having a first wavelength that is absorbed by water molecules and reference light having a second wavelength that is not absorbed by water molecules, and light transmitted through the resin film is received. At that time, the measurement light and the reference light are passed through substantially the same optical path, and the amount of moisture contained in the resin film is measured based on the absorbance of both the measurement light and the reference light.

JP 2000-338040 A JP 2002-167872 A JP 2010-121998 A

  In a spectroscopic analysis method and a spectroscopic analysis apparatus, an object is to easily measure the optical properties and mass of a liquid sample.

  According to one aspect of the disclosure below, when an adsorbent that is not adsorbing a liquid sample is irradiated with a first electromagnetic wave in the first wavelength range, the second electromagnetic wave that is transmitted or reflected by the adsorbent is Detecting, adsorbing the liquid sample on the adsorbent, irradiating the adsorbent adsorbing the liquid sample with a third electromagnetic wave in the first wavelength range and transmitting the adsorbent Detecting a reflected fourth electromagnetic wave, obtaining a light physical property information of the liquid sample based on a change of the fourth electromagnetic wave from the second electromagnetic wave, and adsorbing the liquid sample The adsorbent is irradiated with the fifth electromagnetic wave in the second wavelength range, the sixth electromagnetic wave transmitted through the adsorbent is detected, and the adsorption is performed based on the fifth electromagnetic wave and the sixth electromagnetic wave. Measuring the light transmittance of the material, and the light transmittance Obtaining the mass information of the liquid sample based on the step, irradiating the first electromagnetic wave, irradiating the third electromagnetic wave, and irradiating the fifth electromagnetic wave are the same. A spectroscopic analysis method performed in the spectroscopic analysis apparatus is provided.

  According to another aspect of the disclosure, a first light source that irradiates the adsorbent with electromagnetic waves in a first wavelength range, and a second light source that irradiates the adsorbent with electromagnetic waves in a second wavelength range; The first light source irradiates the adsorbent from the first light source, and detects the electromagnetic wave transmitted or reflected by the adsorbent, and the second light source irradiates the adsorbent to the adsorbent. Based on the detection result of the second detection unit for detecting the transmitted electromagnetic wave and the first detection unit, the optical property information of the liquid sample adsorbed on the adsorbent is obtained, and the second There is provided a spectroscopic analysis device including a processing unit that acquires mass information of the liquid sample based on a detection result of the detection unit.

  According to the following disclosure, the optical properties and mass of the liquid sample can be measured while maintaining the state of the liquid sample, so that the measurement efficiency and accuracy can be improved. In particular, even for a very small amount of liquid sample, the liquid sample is not lost during measurement and the state of the liquid sample does not change, so that the optical properties and mass of the liquid sample can be measured without degrading accuracy. .

FIG. 1 is a diagram illustrating an overall configuration example of a spectroscopic analyzer. FIG. 2 is a diagram illustrating a configuration example of the light source unit of the spectroscopic analyzer. FIG. 3 is a diagram illustrating a configuration example of a detection unit of the spectroscopic analyzer. FIG. 4 is a flowchart illustrating a procedure for acquiring optical property information of a liquid sample in the spectroscopic analysis apparatus and the spectroscopic analysis method. FIG. 5 is a flowchart illustrating a procedure for acquiring mass information of a liquid sample in the spectroscopic analysis apparatus and the spectroscopic analysis method. FIG. 6 is an optical image when a liquid sample adhered to polyvinyl chloride is adsorbed on a porous polypropylene film. FIG. 7 is a diagram showing an infrared absorption spectrum of a liquid sample. FIG. 8 is a diagram showing the relationship between the total light transmittance of porous polypropylene and the mass of the liquid sample.

  When performing a qualitative / quantitative analysis of a liquid sample by a spectroscopic analysis method or the like, the physical property measurement of the liquid sample and the measurement of the mass of the liquid sample may be performed using different apparatuses. Therefore, the efficiency of the analysis of the liquid sample is poor. In addition, since it is difficult to maintain the state of the liquid sample, there is a problem that the measurement accuracy deteriorates particularly when the amount of the liquid sample is very small.

  In the spectroscopic analysis apparatus and the spectroscopic analysis method according to the present embodiment, the liquid sample is adsorbed to an adsorbent, and the above-mentioned problems are solved by measuring the optical properties and mass of the liquid sample while maintaining the state of the liquid sample. I try to solve it.

  The configuration of the spectroscopic analyzer according to the present embodiment will be described with reference to FIGS.

  FIG. 1 is a diagram illustrating an overall configuration example of a spectroscopic analyzer.

  As shown in FIG. 1, the spectroscopic analyzer passes through the light source unit 10 that irradiates infrared light and visible light, the incident slit 20 through which the infrared light and visible light irradiated from the light source unit 10 pass, and the incident slit 20. The detection result is input from the detection unit 30 via the detection unit 30 for detecting infrared light and visible light transmitted through the adsorbent 32 and the counting circuit 40 and the counting circuit 50, and the computer 60 processes the detection result. And have.

  The detection unit 30 includes an adsorbent 32, a sample chamber 31 in which the adsorbent 32 is installed, an infrared spectroscopic detector 35 that detects infrared rays that have passed through the adsorbent 32, and visible light that has passed through the adsorbent 32. And an integrating sphere (light beam system) 36 for detecting.

  Infrared light and visible light are irradiated from the light source unit 10, and the irradiated light is irradiated to the adsorbent 32 installed in the sample chamber 31 through the entrance slit 20. Infrared light and visible light transmitted through the adsorbent 32 are detected by an infrared spectroscopic detector 35 and an integrating sphere 36, converted into an electrical signal, and input to a computer 60 via a counting circuit 40 and a counting circuit 50 for processing. The

  FIG. 2 is a diagram illustrating a configuration example of the light source unit 10 of the spectroscopic analyzer. As shown in FIG. 2, the light source unit 10 includes an infrared light source 11 that emits infrared light L1A and a visible light source 12 that emits visible light L2A, and further reflects the infrared light L1 and visible light L2. The movable reflecting mirror 33 for guiding to the entrance slit 20 and the reflecting mirror 34 are provided.

  When the infrared light L1A is irradiated from the infrared light source 11, the movable reflecting mirror 13 faces a direction 13a parallel to the infrared L1A, and the infrared L1A goes straight to become the infrared L1B and passes through the incident slit 20.

  When visible light L2A is irradiated from the visible light source 12, the visible light L2A is reflected by the reflecting mirror 14 and becomes visible light L2B. The movable reflecting mirror 13 faces the direction 13b, and the visible light L2B is reflected by the movable reflecting mirror 13 to become visible light L2C, and the visible light L2C passes through the incident slit 20.

  FIG. 3 is a diagram illustrating a configuration example of the detection unit 30 of the spectroscopic analyzer.

  As shown in FIG. 3, in addition to the components shown in the description of the overall configuration example of the spectroscopic analysis device, the detection unit 30 transmits infrared L1 transmitted through the adsorbent 32 to the infrared spectroscopic detector 35. It has a movable reflecting mirror 33 and a reflecting mirror 34 for guiding the visible light L2 that has been guided and passed through the adsorbent 32 to the integrating sphere 36.

  Infrared light L1B and visible light L2C that have passed through the entrance slit 20 enter the adsorbent 32 installed in the sample chamber 31. The infrared rays L1B and visible light L2C are adsorbed by the adsorbent 32 and enter the liquid sample portion 32a that is held.

  When the infrared light L1A is irradiated from the infrared light source 11, the movable reflecting mirror 33 faces the direction 33a parallel to the infrared L1C transmitted through the adsorbent 32, and the infrared L1C goes straight to become the infrared L1D. The infrared L1D is received by the infrared spectroscopic detector 35. The detection result of the infrared spectroscopic detector 35 is input to the computer 60, and the second infrared absorption spectrum of the adsorbent 32 not adsorbing the liquid sample and the first of the adsorbent 32 adsorbing the liquid sample. An infrared absorption spectrum is measured.

  When visible light L2A is irradiated from the visible light source 12, the movable reflecting mirror 33 faces the direction 33b, and the visible light L2D transmitted through the adsorbent 32 is reflected by the movable reflecting mirror 33 to become visible light L2E. The visible light L2E is further reflected by the reflecting mirror 34 to become visible light L2F, and the visible light L2F is received by the integrating sphere 36. The detection result of the integrating sphere 36 is input to the computer 60, and the light transmittance of the adsorbent 32 adsorbing the liquid sample is measured.

  Next, the operation procedure of the spectroscopic analyzer according to the present embodiment and the procedure of the spectroscopic analysis method will be described with reference to FIGS.

  FIG. 4 is a flowchart illustrating a procedure for acquiring optical property information of a liquid sample in the spectroscopic analysis apparatus and the spectroscopic analysis method.

  As shown in FIG. 4, an adsorbent 32 that does not adsorb a liquid sample is placed in the sample chamber 31, and the adsorbent 32 is irradiated with infrared rays L1 from the infrared light source 11 (step S1).

  The infrared ray L1 that has passed through the adsorbent 32 is detected by the infrared spectroscopic detector 35, and the detection result is input to the computer 60. And the 2nd infrared absorption spectrum of the adsorbent 32 which has not adsorb | sucked the liquid sample is measured (step S2).

  Then, the adsorbent 32 is made to adsorb and hold the liquid sample to be measured for optical properties and mass (step S3).

  Next, the adsorbent 32 that has adsorbed the liquid sample is placed in the sample chamber 31, and the infrared light L11 is irradiated to the adsorbent 32 from the infrared light source 11 (step S4).

  The infrared ray L1 that has passed through the adsorbent 32 is detected by the infrared spectroscopic detector 35, and the detection result is input to the computer 60. And the 1st infrared absorption spectrum of the adsorbent 32 which adsorb | sucked the liquid sample is measured (step S5).

  The computer 60 calculates the difference spectrum between the first infrared absorption spectrum and the second infrared absorption spectrum, and acquires the infrared absorption spectrum of the liquid sample (step S6).

  The acquired infrared absorption spectrum of the liquid sample is displayed on, for example, a display of the computer 60 (step S7). By analyzing the infrared absorption spectrum of the displayed liquid sample, it is possible to obtain optical property information about the components of the liquid sample.

  FIG. 5 is a flowchart illustrating a procedure for acquiring mass information of a liquid sample in the spectroscopic analysis apparatus and the spectroscopic analysis method.

  First, the visible light L2 is irradiated from the visible light source 12 to the adsorbent 32 that has adsorbed the liquid sample (step S8).

  The visible light L2 that has passed through the adsorbent 32 is detected by the integrating sphere 36, and the detection result is input to the computer 60. Then, the light transmittance of the adsorbent 32 that has adsorbed the liquid sample is measured (step S9).

  The computer 60 calculates the mass of the liquid sample from the measured light transmittance and the characteristic curve of the mass of the liquid sample adsorbed on the adsorbent 32 and the light transmittance of the adsorbent 32 (step S10).

  This characteristic curve is, for example, like the curve shown in FIG. The curve shown in FIG. 8 is given by the following equation (1).

  Then, the mass of the liquid sample is displayed on, for example, a display of the computer 60 (step S11).

  In the spectroscopic analysis apparatus and spectroscopic analysis method according to the present embodiment, when the second infrared absorption spectrum of the adsorbent 32 that has not adsorbed the liquid sample is known in advance, step S1 in FIG. Step S2 can be omitted.

  The light transmittance measured in this embodiment may be the total light transmittance measured by the integrating sphere 36, but the light transmittance may be a spectral transmittance measured by a spectrophotometer.

  Then, the light transmittance in the characteristic curve between the mass of the liquid sample adsorbed on the adsorbent 32 and the light transmittance of the adsorbent 32 is the same as that of the integrating sphere 36 or spectroscopic in the spectroscopic analysis apparatus and spectroscopic analysis method of the present embodiment. It is the light transmittance of the adsorbent 32 for visible light in the same wavelength range as the visible light detected by the photometer.

  The adsorbent 32 is preferably a porous organic polymer film.

  The adsorbent 32 is irradiated with infrared rays L1 in order to acquire optical property information of the liquid sample, and with visible light L2 in order to acquire mass information of the liquid sample. However, the electromagnetic wave with which the adsorbent 32 is irradiated in order to acquire the optical property information of the liquid sample may be an electromagnetic wave in the first wavelength range that interacts with the liquid sample. In addition, the electromagnetic wave applied to the adsorbent 32 in order to acquire the mass information of the liquid sample has a specific relationship between the mass of the liquid sample adsorbed on the adsorbent 32 and the light transmittance of the adsorbent 32. An electromagnetic wave having a wavelength range of may be sufficient.

  In addition, about the electromagnetic wave of the 1st wavelength range irradiated to the adsorbent 32, you may make it acquire the optical property information of a liquid sample by detecting the electromagnetic wave of the 1st wavelength range which permeate | transmits the adsorbent 32. However, the electromagnetic property in the wavelength range 1 that reflects the adsorbent 32 may be detected to acquire the optical property information of the liquid sample.

  Moreover, the optical path of the infrared rays L1 and the optical path of the visible light L2 are not limited to the optical paths shown in FIGS. The optical path of the infrared light L1 and the optical path of the visible light L2 are such that the infrared light L1 irradiated from the infrared light source 11 passes through or reflects through the adsorbent 32 and is received by the infrared spectroscopic detector 35. If the visible light L2 emitted from the light source 12 passes through the adsorbent 32 and is received by the integrating sphere 36, an arbitrary optical path can be taken.

  In the spectroscopic analysis method and spectroscopic analysis apparatus according to the present embodiment described above, the optical properties and mass of the liquid sample are maintained in the same apparatus while adsorbing the liquid sample to the adsorbent 32 and maintaining the state of the liquid sample. Since measurement can be performed, the efficiency and accuracy of measurement can be improved.

  Further, since it is not necessary to put out the adsorbent 32 outside the apparatus, even in a very small amount of liquid sample, the liquid sample is not lost during measurement and the state of the liquid sample does not change, so that the accuracy is not deteriorated. Measurement of optical properties and mass of a liquid sample is possible.

  Next, using a porous polypropylene film as the adsorbent 32 and using a liquid adhered in polyvinyl chloride as the liquid sample, the optical properties and mass of the liquid sample are measured by the spectroscopic analysis method according to this embodiment. I do. Since polypropylene has water repellency, only a desired oily component can be adsorbed and retained as a liquid sample.

  FIG. 6A is a drawing based on an optical image of a porous polypropylene film before adsorption of the liquid sample, and FIGS. 6B and 6C are optical images of the porous polypropylene film after adsorption of the liquid sample. It is the figure drawn based on.

  The image of sample B shown in FIG. 6C is an image when a larger amount of liquid sample is adsorbed to the porous polypropylene film than the image of sample A shown in FIG. It can be seen that when a liquid sample is adsorbed on a porous polypropylene film, a circular adsorption site is formed.

  FIG. 7 is a diagram showing an infrared absorption spectrum of Sample B. This infrared absorption spectrum is obtained by the spectroscopic analysis method according to this embodiment. That is, the infrared absorption spectrum shown in FIG. 7 includes the second infrared absorption spectrum of the porous polypropylene film that has not adsorbed the liquid sample and the first infrared absorption spectrum of the porous polypropylene film that has adsorbed the liquid sample. The spectrum is measured and obtained from the difference spectrum between the first infrared absorption spectrum and the second infrared absorption spectrum.

In the infrared absorption spectrum shown in Figure 7, 1723cm ^-1, 1273cm ^-1, around 1122cm ^-1, esters of C = O, a very strong peak assigned to stretching vibration of C-O is observed. Further, 1600 cm ^-1, in the vicinity of 1580 cm ^-1, with approximately equal intensity, the phthalic acid ester 1,2-substitution characteristic sharp peaks observed. Furthermore, characteristic peaks are also observed in the vicinity of 1073 cm ⁻¹ and 743 cm ⁻¹ . From the above, it can be seen that the main component of Sample B is a phthalate ester.

  FIG. 8 is a diagram showing the relationship between the total light transmittance (%) of the porous polypropylene film on which the liquid sample is adsorbed and the mass (μg) of the liquid sample corresponding to the adsorbed sample B. The results indicated by the circles are the results obtained by measurement, and the curve is represented by the above formula (1). The total light transmittance of the sample B obtained by the spectroscopic analysis method according to this embodiment is 13 (%). Therefore, the mass of the sample B is calculated as 20 (μg) from the equation (1).

  Using the spectroscopic analysis method and spectroscopic analysis apparatus according to the present embodiment, a calibration curve that represents the relationship between the light transmittance and mass of a specific liquid sample whose infrared absorption spectrum has a desired peak intensity can be created. it can. The calibration curve is created by examining the light transmittance of a liquid sample having a desired peak intensity and a known mass. A calibration curve can be generated by examining this light transmittance for several known mass liquid samples.

  Moreover, the spectroscopic analysis method and spectroscopic analysis apparatus according to the present embodiment can be applied to a small amount of attached oil such as insulating oil attached to an electronic component or the like. That is, by adsorbing and holding a small amount of adhering oil to the adsorbent 32 as a liquid sample, the state of the minute amount of adhering oil is maintained during measurement, and the optical properties of the adhering oil are lost without losing the minute amount of adhering oil. Information and mass information can be acquired.

DESCRIPTION OF SYMBOLS 10 ... Light source part, 11 ... Infrared light source, 12 ... Visible light source, 13, 33 ... Movable reflector, 14, 34 ... Reflector, 20 ... Incident slit, 30 ... Detection part, 31 ... Sample chamber, 32 ... Adsorption Material 35 ... Infrared spectroscopic detector 36 ... Integrating sphere

Claims (6)

A step of detecting a second electromagnetic wave transmitted or reflected by the adsorbent when the adsorbent not adsorbing the liquid sample is irradiated with the first electromagnetic wave in the first wavelength range;
Adsorbing the liquid sample on the adsorbent;
Irradiating the adsorbent adsorbing the liquid sample with a third electromagnetic wave in the first wavelength range and detecting a fourth electromagnetic wave transmitted or reflected by the adsorbent;
Obtaining optical property information of the liquid sample based on a change of the fourth electromagnetic wave from the second electromagnetic wave;
The adsorbent that has adsorbed the liquid sample is irradiated with a fifth electromagnetic wave in a second wavelength range, and a sixth electromagnetic wave that has passed through the adsorbent is detected, and the fifth electromagnetic wave and the sixth electromagnetic wave are detected. Measuring the light transmittance of the adsorbent based on electromagnetic waves;
Obtaining mass information of the liquid sample based on the light transmittance,
The step of irradiating the first electromagnetic wave, the step of irradiating the third electromagnetic wave, and the step of irradiating the fifth electromagnetic wave are performed in the same spectral analyzer.   In the step of obtaining the mass information, the mass information of the liquid sample is obtained based on a characteristic curve of the light transmittance and the mass of the liquid sample adsorbed on the adsorbent. The spectroscopic analysis method according to claim 1.   The spectroscopic analysis method according to claim 1, wherein the adsorbent is a porous organic polymer film.   The spectroscopic analysis method according to claim 1, wherein the first wavelength range is an infrared region.   The spectroscopic analysis method according to any one of claims 1 to 4, wherein the second wavelength range is a visible light region. A first light source that irradiates the adsorbent with electromagnetic waves in a first wavelength range;
A second light source that irradiates the adsorbent with electromagnetic waves in a second wavelength range;
A first detection unit that detects an electromagnetic wave that is applied to the adsorbent from the first light source and is transmitted or reflected by the adsorbent;
A second detection unit that detects electromagnetic waves that are applied to the adsorbent from the second light source and transmitted through the adsorbent;
Based on the detection result of the first detection unit, the optical property information of the liquid sample adsorbed on the adsorbent is obtained, and on the basis of the detection result of the second detection unit, And a processing unit that acquires mass information.

Images