WO2015037640A1 - Dispositif et procédé d'identification de substance - Google Patents

Dispositif et procédé d'identification de substance Download PDF

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WO2015037640A1
WO2015037640A1 PCT/JP2014/073997 JP2014073997W WO2015037640A1 WO 2015037640 A1 WO2015037640 A1 WO 2015037640A1 JP 2014073997 W JP2014073997 W JP 2014073997W WO 2015037640 A1 WO2015037640 A1 WO 2015037640A1
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Prior art keywords
substance
spectrum
plasma
ratio
sample
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PCT/JP2014/073997
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English (en)
Japanese (ja)
Inventor
孝男 倉田
淳 伊澤
易 松永
剛 横澤
秀之 堀澤
滋 山口
藤井　隆
修三 江藤
Original Assignee
株式会社Ihi
株式会社アイ・エヌ・シー・エンジニアリング
学校法人東海大学
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Priority to JP2015511752A priority Critical patent/JPWO2015037640A1/ja
Publication of WO2015037640A1 publication Critical patent/WO2015037640A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/718—Laser microanalysis, i.e. with formation of sample plasma

Definitions

  • the present invention relates to a substance specifying device and a substance specifying method for specifying an arbitrary substance.
  • This application claims priority based on Japanese Patent Application No. 2013-186939 for which it applied to Japan on September 10, 2013, and uses the content here.
  • LIBS Laser-induced breakdown spectroscopy
  • a calibration curve between the emission intensity of carbon obtained from the surface of wood through laser-induced breakdown spectroscopy and the air dry density of wood is prepared in advance, and the calibration curve is used regardless of the moisture content of wood.
  • a technique for nondestructively measuring the air dry density of wood from the fluorescence intensity of carbon is disclosed (for example, Patent Document 1).
  • Patent Documents 1 to 3 specify the other in a state where either the plasma temperature or the substance when the pulse laser is irradiated is specified. Therefore, it could not be applied when both the temperature and material of the plasma are unknown or fluctuating.
  • the substance can be specified based on the temperature.
  • the temperature of the plasma is affected by various parameters such as how to apply the laser beam, the distance between the laser device and the sample, and the transmittance in the space between the laser device and the sample. It is difficult to obtain objectively.
  • the surrounding air is entrained, causing an event that air is mixed into the plasma.
  • the measurement result of laser-induced breakdown spectroscopy varies depending on the mixing ratio of air to plasma. Therefore, if not only the above-mentioned temperature but also the mixing ratio can be specified, it should be possible to improve the substance specifying accuracy. However, since the air mixing ratio is also affected by the surrounding atmosphere during the plasma formation, it is difficult to obtain it objectively.
  • the present invention provides a substance specifying apparatus and a substance specifying method capable of appropriately specifying a substance by laser-induced breakdown spectroscopy regardless of the state of the laser apparatus and the atmosphere in which the sample is placed.
  • the purpose is to provide.
  • a first aspect of the present invention is a substance identification device that identifies a substance constituting a sample, and includes an index spectrum obtained by laser-induced breakdown spectroscopy at a plurality of different temperatures of plasma.
  • the peak of emission intensity for a plurality of specific decomposition products of the plasmatized substance in the combination of the peak ratio of H 2 and O 2 at different mixing ratios of air to plasma and the temperature and the mixing ratio A holding unit that holds in advance the ratio, the composition ratio of the plurality of specific decomposition products of the plasmatized substance, and the substance specifying information in which at least one of the spectral shapes of the plasmatized substance is associated with the substance
  • a spectrum deriving unit for deriving a material spectrum by converting the sample into plasma by the laser-induced breakdown spectroscopy.
  • the material spectrum and the index spectral temperature specifying unit for specifying a temperature of the plasma of the sample, based on the peak ratio of the H 2 and O 2 in the derived material spectrum, plasma of the sample
  • a mixture ratio specifying unit for specifying a mixture ratio of air to the gas, a peak ratio of emission intensity for the plurality of specific decomposition products in the sample converted to plasma in the substance spectrum, and the specified plurality of parameters in the sample converted to plasma
  • Deriving at least one of the composition ratio of the decomposition product and the shape of the substance spectrum referring to the substance specifying information, and calculating the derived peak ratio of the emission intensity, the composition ratio, and the shape of the substance spectrum
  • the sample based on the combination of the specified plasma temperature and the mixing ratio.
  • Comprising a substance identification unit for identifying a substance that constitutes the.
  • the substance identification device was converted into plasma in the substance identification apparatus according to the first aspect based on the combination of the substance structural formula and the assumed plasma temperature and mixing ratio.
  • the apparatus further includes a substance specifying information generating unit that generates the substance specifying information by deriving the composition ratio of the plurality of specific decomposed substances of the substance by simulation.
  • the substance identification device is the substance identification device according to the first or second aspect, wherein the index spectrum is a C 2 swan band spectrum.
  • the substance identification device is the substance identification device according to any one of the first to third aspects, wherein the spectrum deriving unit derives the substance spectrum after the thermal equilibrium of the plasma of the sample is established. .
  • the substance identification device is the substance identification apparatus according to any one of the first to fourth aspects, wherein the substance identification unit includes a plurality of specific decompositions in the sample that has been converted into plasma in the substance spectrum. Deriving a plurality of peak ratios of emission intensity relative to an object or composition ratios of the plurality of specific decomposition products in the sample that has been converted to plasma, and specifying the substance by developing the peak ratio or composition ratio of emission intensity in a plurality of dimensions.
  • a substance identification device is assumed as the substance constituting the sample as the substance identification information in the holding unit in the substance identification device according to the first to fourth aspects.
  • the substance identification device is assumed as the substance constituting the sample as the substance identification information in the holding part in the substance identification device according to the first to fourth aspects.
  • a C / H peak ratio which is a ratio between the C peak value and the H peak value of the emission intensity of the plurality of substances, is held, and the substance specifying unit is configured to store the C / H peak ratio held in the holding unit.
  • the C / H peak ratio that is the ratio of the C peak value and the H peak value of the emission intensity of the sample in the substance spectrum, the substance constituting the sample is specified.
  • a substance identification device is assumed as the substance constituting the sample as the substance identification information in the holding unit in the substance identification device according to the first to fourth aspects.
  • the shape of the spectrum of the plurality of substances is retained, and the substance specifying unit compares the shape of the substance spectrum with the shape of the spectrum of the plurality of substances assumed as the substance constituting the sample, A substance constituting the sample is specified.
  • a substance identification method for identifying a substance constituting a sample, the index spectrum obtained by laser-induced breakdown spectroscopy at a plurality of plasma different temperatures, and a plurality of air different from the plasma.
  • a substance spectrum deriving step for deriving a substance spectrum by converting the sample into plasma, and the derived substance spectrum;
  • a plasma temperature specifying step for comparing the torque and the index spectrum to identify the temperature of the plasma of the sample, based on the peak ratio of the H 2 and O 2 in the derived the substance spectrum, the air to the plasma of the sample
  • FIG. 1 is a configuration diagram showing a schematic configuration of the substance identification system 100.
  • the material identification system 100 includes a target holder 110, a laser device 112, a lens 114, a filter 116, a probe 118, an optical fiber 120, and a material identification device 122, and through laser-induced breakdown spectroscopy.
  • the substance to be specified is, for example, an organic compound such as plastic, grain, biological agent, chemical agent, explosive, etc., and an element containing any of C, H, O, and N as an element is assumed.
  • the shape and state of the substance to be specified are not particularly limited. Specifically, the substance to be specified may be solid, liquid, or gas, and may be in a powder, aerosol state, or the like.
  • the target holder 110 in the substance identification system 100 fixes and holds an arbitrary substance (hereinafter simply referred to as a sample) 102 to be identified.
  • the laser device 112 irradiates the sample 102 with, for example, pulse laser light from a femtosecond laser through the lens 114.
  • a femtosecond laser a picosecond laser or a nanosecond laser may be used, and the wavelength of the laser light is not limited.
  • laser light having a wavelength close to the peak value of the spectrum of the sample 102 is used, the laser light itself becomes noise relative to the peak value, and therefore laser light having a wavelength close to the peak value of the spectrum of the sample 102 is avoided. Is desirable. Therefore, here, laser light having a wavelength of 780 nm, an output of 1 mJ, a pulse width of 120 fsec, and a period of 1 kHz is used.
  • the sample 102 receives a laser beam to be turned into plasma and emits light having a wavelength specific to the substance.
  • it is desirable to provide the target holder 110 with a rotation mechanism or the like so that the relative position between the target holder 110 and the laser device 112 can be changed so that the sample 102 is uniformly irradiated with the laser light.
  • the filter 116 blocks laser light and background light with high emission intensity.
  • the probe 118 receives light emitted from the sample 102. At this time, the light may be condensed using a lens or the like.
  • the optical fiber 120 transmits the light received by the probe 118 to the substance specifying device 122.
  • the substance specifying device 122 separates the radiated light of the sample 102 received through the optical fiber 120 for each of a plurality of wavelengths by a spectroscope 122a using, for example, an ICCD (Intensified Charge-Coupled Device) as a detection unit, and the peak of each wavelength. A value is obtained to derive a spectrum (a spectrum to be actually measured is referred to as a material spectrum), and it is specified which material the sample 102 is. At this time, it is desirable that the substance specifying device 122 accepts the radiated light after a predetermined time (for example, 1 nsec) or more has elapsed since the laser light was irradiated from the laser device 112.
  • a predetermined time for example, 1 nsec
  • the reason for waiting for the elapse of the predetermined time is that the plasma of the sample 102 stably reaches the thermal equilibrium after the elapse of the predetermined time since the laser beam was irradiated. By doing so, the identification accuracy of the sample 102 can be increased.
  • the configuration of the substance identification device 122 will be described in detail.
  • FIG. 2 is a functional block diagram illustrating a schematic configuration of the substance identification device 122.
  • the substance identification device 122 includes a holding unit 130, an operation unit 132, a display unit 134, and a central control unit 136.
  • the holding unit 130 includes a ROM, a nonvolatile RAM, a flash memory, an HDD, and the like.
  • the holding unit 130 includes an index spectrum obtained by laser-induced breakdown spectroscopy at a plurality of different temperatures of plasma, a peak ratio of H 2 and O 2 at a plurality of different mixing ratios of air to the plasma, and a plurality of temperatures.
  • Substance specific information in which peak ratios of emission intensities of a plurality of specific decomposed products converted into plasma and substances are associated with each other in combination with a plurality of mixing ratios is previously stored.
  • the decomposition product is a fragment released from a substance (compound).
  • FIG. 3 is an explanatory diagram for explaining a spectrum of a substance.
  • polyethylene will be described as an example of a substance containing any of C, H, O, and N as an element.
  • the peaks of C, CN, CN, CN, CH, C 2 , C 2 , and C 2 are mainly observed from the left side in FIG.
  • peaks of H 2 and O 2 are also observed.
  • the band near 520 nm where the C 2 peak is observed is called the C 2 swan band.
  • the peak of C 2 or CN there are multiple uses its maximum value as the peak.
  • the degradation product CN is produced as a result of the surrounding air (N 2 in the atmosphere) being entrained when the polyethylene as the sample 102 is turned into plasma (when the plasma expands) and air is mixed into the plasma. Presumed.
  • the material spectrum of the sample 102 varies depending on the temperature of the plasma and the mixing ratio of air to the plasma. Therefore, provided the index spectrum indicative of material spectra for different temperatures, also, it provided a peak ratio of H 2 and O 2 for different mixing ratios.
  • the index spectrum for each temperature will be exemplified.
  • 4A to 4D are explanatory diagrams for explaining an index spectrum for each temperature in the C 2 swan band.
  • one or more degradation products may be included in the sample 102 to be specific target is assumed, for example, the C 2 to C 2 Swan bands, a plurality of temperature selected from the range of temperature of the plasma envisaged
  • a spectrum is derived through laser-induced breakdown spectroscopy, and is held in the holding unit 130 as an index spectrum.
  • the resolution of the plasma temperature is set to 1000 K and four examples of index spectra are shown, but the number of index spectra is not limited, and the larger the number, the better. However, it is desirable to match the resolution of the plasma temperature in the substance specifying information shown below.
  • H 2 and O 2 in the material spectrum of the sample 102 according to the mixing ratio of air to plasma for example, 0%, 10%, 20%, 30%, 40%, 50%.
  • the peak ratio is different.
  • the resolution of the mixing ratio is set to 10%, and six examples of C 2 / CN peak ratios to be described later are shown.
  • the number of C 2 / CN peak ratios is not limited, and the larger the better.
  • the substance is specified based on the combination of the temperature and the mixing ratio and the substance specifying information held in the holding unit 130.
  • FIG. 5 is an explanatory diagram for explaining the substance specifying information.
  • a plurality of temperatures selected from a range of assumed plasma temperatures, for example, 3000K, 4000K, 5000K, and 6000K
  • a plurality of mixing ratios selected from a range of air-to-plasma mixing ratios,
  • the C 2 / CN peak ratio which is the CN peak ratio, is tabulated and held in the holding unit 130.
  • the C 2 / CN peak ratio of the emission intensity varies depending on the plasma temperature and the mixing ratio of air to the plasma. Therefore, if the temperature and the mixing ratio are specified, the substance can be specified from the C 2 / CN peak ratio belonging to the specified temperature and mixing ratio. That is, in this embodiment, the plasma and temperature, and the mixing ratio of air to the plasma, to identify the substance by three parameters C 2 / CN peak ratio.
  • the C 2 / CN peak ratio differs depending on the plasma temperature even for the same substance for the following reason.
  • Decomposition products are not produced when the plasma is not formed (low energy state).
  • a substance receives a laser beam, it becomes plasma and is excited and decomposed to a high energy state.
  • not all substances are decomposed.
  • the temperature of the plasma changes according to the intensity of the laser beam and the time after irradiation, the ratio at which the substance is excited / decomposed / bonded changes, and the ratio (composition ratio) of the existing plasma components (decomposed products) changes. .
  • the composition ratios of the decomposed products are different in this way, the emission intensity at a predetermined wavelength also simply differs depending on the number of decomposed products, and the C 2 / CN peak ratio is also different as described above.
  • the same C 2 / CN peak ratio even substance differs by the mixing ratio of air to the plasma for the following reason.
  • the sample 102 is turned into plasma (when the plasma expands), surrounding air is entrained and air is mixed into the plasma. Therefore, the larger the mixing ratio of air to plasma (the mixing ratio of N 2 in the atmosphere), the higher the peak of CN having N as an element relative to the peak of C 2 .
  • the mixing ratio of air to the plasma is increased, C 2 / CN peak ratio becomes smaller.
  • a CN peak having a high peak value can be used for specifying a substance, so that the specifying accuracy is improved.
  • composition ratio of decomposition products is used, but in this embodiment, the peak ratio of decomposition products that can be easily derived by laser-induced breakdown spectroscopy is used.
  • FIG. 6 is an explanatory diagram showing the relationship between the C 2 / CN composition ratio and the C 2 / CN peak ratio for each substance.
  • a simulation is performed under the conditions of a plasma temperature of 4000 K and a mixing ratio of air to the plasma of 30%, and an average value of five measurements of the C 2 / CN peak ratio relative to the C 2 / CN composition ratio of each substance. Is derived.
  • the average value of the C 2 / CN peak ratio with respect to the C 2 / CN composition ratio appears in the vicinity of the straight line indicated by the broken line in FIG. 6, and it can be understood that both are in a proportional relationship.
  • the substance can be specified by evaluation equivalent to the composition ratio.
  • the C 2 / CN peak ratio instead of the C 2 / CN composition ratio that is difficult to derive, the C 2 / CN peak ratio that can be easily derived is used to simplify the substance specifying process.
  • identify C 2 / CN composition ratio may identify the materials using C 2 / CN composition ratio instead of the C 2 / CN peak ratio.
  • the operation unit 132 includes an operation key, a cross key, a joystick, a touch panel superimposed on the display surface of the display unit 134, a remote controller, and the like, and receives an operation input from the user to the substance identification device 122.
  • the display unit 134 includes a liquid crystal display, an organic EL (Electro Luminescence) display, and the like.
  • the operation result input through the operation unit 132, the intermediate result of the specifying process (for example, the derived substance spectrum), the specified substance, and the like are displayed. indicate.
  • the central control unit 136 is configured by a semiconductor integrated circuit including a central processing unit (CPU), a ROM storing programs, a RAM as a work area, and the like, and manages and controls the entire substance specifying device 122.
  • the central control unit 136 also functions as the index spectrum generation unit 140, the substance identification information generation unit 142, the spectrum derivation unit 144, the temperature identification unit 146, the mixture ratio identification unit 148, and the substance identification unit 150.
  • the index spectrum generation unit 140 generates an index spectrum by laser-induced breakdown spectroscopy of a specific decomposition product that has been turned into plasma at a plurality of plasma temperatures in advance preparation.
  • the substance identification information generation unit 142 generates substance identification information in which the peak ratio (or composition ratio) of the emission intensity with respect to a plurality of specific decomposed products converted into plasma is associated with the substance in advance preparation.
  • the spectrum deriving unit 144 derives a substance spectrum by converting the sample 102 into plasma using laser-induced breakdown spectroscopy at the time of substance identification.
  • the temperature identification unit 146 identifies the plasma temperature of the sample 102 by comparing the derived substance spectrum with the index spectrum at the time of substance identification.
  • the mixing ratio specifying unit 148 specifies the mixing ratio of air to plasma based on the peak ratio of H 2 and O 2 in the derived substance spectrum when specifying the substance.
  • the substance specifying unit 150 derives the peak ratio of the emission intensity of the decomposition product of the substance spectrum derived by the spectrum deriving unit 144 or the composition ratio of the decomposition product at the time of specifying the substance, and the substance specifying information held in the holding unit 130 is obtained.
  • the substance is specified based on the temperature of the plasma specified by the temperature specifying unit 146 and the mixing ratio specified by the mixing ratio specifying unit 148 and the peak ratio of the emission intensity of the derived decomposition product or the composition ratio of the decomposition product. .
  • the detailed operation of each functional unit will be specifically described below.
  • FIG. 7 is a flowchart showing a processing flow of the substance specifying method.
  • index spectrum, peak ratio of H 2 and O 2 and substance identification information are prepared, and at the time of substance identification, plasma temperature, air-to-plasma mixing ratio, emission intensity peak ratio, substance, etc. I will identify.
  • the index spectrum generation unit 140 in advance preparation, at a plurality of temperatures selected from a range of assumed plasma temperatures, for example, 3000K, 4000K, 5000K, and 6000K, generating an index spectra of C 2 Swan bands (S1).
  • a spectrum actually measured through laser-induced breakdown spectroscopy may be used, or a spectrum derived by theoretical calculation may be used.
  • the C 2 swan band index spectrum is used, but the index spectrum is not limited to the C 2 swan band, and index spectra of various decomposition products serving as indexes can be used.
  • the index spectrum generation unit 140 has a plurality of mixing ratios selected from a range of the mixing ratio of air to plasma assumed in advance preparation, for example, 0%, 10%, 20%, 30%, 40%. , Generate a peak ratio of H 2 and O 2 at 50% (S2).
  • the substance identification information generation unit 142 in advance preparation, selects a plurality of temperatures selected from a range of assumed plasma temperatures, for example, 3000K, 4000K, 5000K, and 6000K. And a plurality of mixing ratios selected from the range of the air-to-plasma mixing ratio, for example, 0%, 10%, 20%, 30%, 40%, and 50%, respectively.
  • a spectrum actually measured through laser-induced breakdown spectroscopy may be used, or a spectrum derived by theoretical calculation may be used.
  • a spectrum derived by theoretical calculation is used.
  • the substance identification information generation unit 142 accepts the structural formula of the substance and the assumed temperature as input values, and based on the structural formula of the substance and the temperature, the substance is converted into plasma and is in thermal equilibrium.
  • the composition ratio of the decomposition product when reaching the value is derived by simulation. Then, by adding the emission intensity of each decomposed product to the derived composition ratio of the decomposed products, spectra as shown in FIGS. 8A to 8D are derived.
  • FIG. 8A shows the spectrum of nylon when the temperature of the plasma is 4000K.
  • FIG. 8B shows the spectrum of polyurethane when the temperature of the plasma is 4000K.
  • FIG. 8C shows the spectrum of polyethylene when the temperature of the plasma is 4000K.
  • FIG. 8D shows the spectrum of polystyrene when the temperature of the plasma is 4000K. Since these spectra can be derived using various existing techniques, detailed procedures thereof are omitted.
  • the substance specifying information generation unit 142 analyzes the spectrum and derives the C 2 / CN peak ratio.
  • Such C 2 / CN peak ratios are selected from a plurality of temperatures selected from a range of assumed materials, a range of temperatures of the assumed plasma, and a range of mixing ratios of air to the assumed plasma.
  • the material specific information is generated by deriving all of the mixing ratios and tabulating them.
  • the spectrum deriving unit 144 instructs the laser device 112 to irradiate the laser beam at the time of specifying the substance, and irradiates the sample 102 held by the target holder 110 with the laser beam.
  • the spectrum deriving unit 144 derives a substance spectrum by receiving the radiated light under a condition in which the thermal equilibrium of the plasma is established, that is, a predetermined time after the laser beam is irradiated from the laser device 112, in order to improve the specific accuracy of the sample 102 (S4). ).
  • a material spectrum as shown in FIG. 9 is derived. At this point, none of the temperature of the plasma, the mixing ratio of air to the plasma, and the material are known.
  • the temperature specifying unit 146 compares the derived substance spectrum with the index spectrum when specifying the substance, and specifies the plasma temperature of an arbitrary substance (S5). As described above, in the same decomposed product (here, C 2 swan band), it is possible to confirm radiated light having different emission intensities depending on temperature at a plurality of specific wavelengths. Therefore, the temperature of the plasma in the sample 102 can be estimated depending on how the emission intensity is distributed in the substance spectrum.
  • FIGS. 10A to 10C are explanatory diagrams for explaining the operation of the temperature specifying unit 146.
  • the temperature specifying unit 146 derives the substance spectrum shown in FIG. 9 (shown by a solid line in FIGS. 10A to 10C) derived from the spectrum deriving unit 144 and each index spectrum of the C 2 swan band at plasma temperatures of 3000K, 4000K, and 5000K. (Indicated by a broken line in FIGS. 10A to 10C) and the degree of correlation is determined. For this determination, for example, the difference between the substance spectrum and the index spectrum is derived through the least square method or the like, and the plasma temperature of the index spectrum that minimizes the difference is set as the plasma temperature of the substance spectrum.
  • the temperature specifying unit 146 specifies the plasma temperature of the substance spectrum as 4000K. .
  • the temperature of plasma is affected by various parameters such as how to apply laser light, the distance between the laser device 112 and the sample 102, and the transmittance in the space between the laser device 112 and the sample 102. It is difficult to obtain objectively from the atmosphere. However, in this embodiment, since the temperature of the plasma can be specified through the spectrum, it is not affected by various parameters regardless of the test atmosphere. Therefore, the distance between the laser beam and the sample 102 can also be set freely. For example, remote measurement in which the laser beam is irradiated from a remote location can be performed.
  • the temperature of the plasma can be specified with high accuracy regardless of the magnitude of the energy of the laser beam, the energy of the laser beam can be reduced, the power consumption of the laser beam can be reduced, It is also possible to irradiate the sample 102 with light from a longer distance.
  • the mixing ratio specifying unit 148 specifies the mixing ratio of air to the plasma of an arbitrary substance based on the peak ratio of H 2 and O 2 in the derived substance spectrum when specifying the substance. (S6).
  • the substance spectrum changes depending on the mixing ratio of the air mixed when it is turned into plasma. Therefore, the air mixing ratio in the sample 102 can be estimated depending on how the emission intensity is distributed in the substance spectrum.
  • the mixing ratio specifying unit 148 has a peak ratio of H 2 and O 2 in the substance spectrum shown in FIG.
  • the mixing ratio of air to plasma is affected by the atmosphere around the sample 102 at the time of plasma formation, and it is difficult to obtain the value objectively.
  • the mixing ratio of air to plasma can be specified through the spectrum, it is not affected by various parameters regardless of the test atmosphere. Therefore, the space (atmosphere) for placing the sample 102 can be freely determined.
  • the substance specifying unit 150 derives the peak ratio or composition ratio of emission intensity for a plurality of specific decomposition products in the substance spectrum at the time of specifying the substance, and the temperature and mixing ratio specifying unit 148 specified by the temperature specifying unit 146 A substance is specified based on the substance specifying information in the mixing ratio of air to the specified plasma (S7).
  • the substance identifying unit 150 determines a C 2 / CN peak ratio, which is a ratio between the C 2 peak value and the CN peak value in FIG.
  • a C 2 / CN peak ratio which is a ratio between the C 2 peak value and the CN peak value in FIG.
  • the substance specifying unit 150 refers to the substance specifying information in FIG. 5, and the C 2 / CN peak ratio in the column of the temperature 4000 K specified by the temperature specifying unit 146 and the mixing ratio 10% specified by the mixing ratio specifying unit 148. It is determined whether or not there is a substance that approximates 0.2326.
  • the substance specifying unit 150 specifies the substance showing the substance spectrum as shown in FIG. 9 as “polystyrene”. In this way, the substance specifying device 122 can specify which substance the sample 102 is composed of.
  • the temperature of the plasma and the mixing ratio of air to the plasma regardless of changes in parameters such as the distance between the laser device 112 and the sample 102 and the atmosphere in which the sample 102 is placed. Even when all of the substances are unknown, the substances can be appropriately identified by laser-induced breakdown spectroscopy.
  • the substance was identified using the C 2 / CN peak ratio.
  • the C 2 / CN peak ratio between substances is approximate and difficult to distinguish, or the C 2 / CN peak ratio actually measured due to spectral measurement variations is the original C 2 / CN peak ratio may deviate. Therefore, the substance specifying unit 150 derives a plurality of emission intensity peak ratios for a plurality of specific decomposition products in the substance spectrum, and specifies the substance by expanding the emission intensity peak ratio in two dimensions (multiple dimensions). Also good.
  • FIG. 11 is an explanatory diagram for explaining identification of a substance using two types of peak ratios.
  • the CH / CN peak ratio which is the ratio of the CH peak to the CN peak
  • the peak ratio is two-dimensionally represented such that the horizontal axis indicates the C 2 / CN peak ratio and the vertical axis indicates the CH / CN peak ratio.
  • regions nylon region 210, polyurethane region 212, polyethylene region 214, polystyrene region 216) are provided for each substance, and the emission intensity of a plurality of specific decomposition products in the substance spectrum is shown.
  • a substance corresponding to that region is specified.
  • the simulated substances ⁇ ... nylon, ⁇ ... polyurethane, ⁇ ... polyethylene, ⁇
  • polystyrene is included in the corresponding region.
  • one point may be provided in each substance, and which substance may be specified according to the Mahalanobis distance from that point. As described above, by developing in a plurality of dimensions using a plurality of peak ratios, the substance identification accuracy can be improved.
  • PCA Principal Component Analysis
  • PLS-DA Partial Least Squares Discriminant Analysis
  • the substance is specified based on the peak ratio of the emission intensity, but when the composition ratio of the plasma decomposition product can be directly grasped, the composition ratio of the plasma decomposition product is tabulated.
  • the substance can be specified based on the composition ratio of the decomposition product.
  • the substance is specified based on the temperature of the plasma on the assumption that the atmospheric pressure is 1 atm. However, if the atmospheric pressure is not 1 atm, the substance is specified by adding a parameter of atmospheric pressure to the temperature. It is also possible to generate information and identify substances based on temperature and pressure.
  • step S7 and identify materials using C 2 / CN peak ratio.
  • C / H peak ratio which is the ratio between the C peak value and the H peak value.
  • the substance is specified based on the peak ratio of the emission intensity.
  • the substance specifying information the spectrum shapes of a plurality of substances assumed as substances constituting the sample are stored in a database in advance, and the shape of the substance spectrum of the sample 102 is compared with the spectrum shapes stored in the database. Then, the substance with the smallest difference is identified as the substance constituting the sample 102.
  • the present invention can be used for a substance specifying device and a substance specifying method for specifying an arbitrary substance.

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  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

　La présente invention concerne un dispositif d'identification de substance (122) doté de : une unité de mémoire (130) qui mémorise préalablement le spectre d'index de plasma à une pluralité de températures, le rapport de pic de H2 et O2 dans une pluralité de rapports de mélange de l'air au plasma, et des informations d'identification de substance dans lesquelles une substance est associée au rapport de pic d'intensité d'émission lumineuse ou au rapport de composition par rapport à une pluralité de produits de décomposition, ou la forme du spectre ; une unité de dérivation de spectre (144) qui utilise la spectroscopie d'émission atomique sur plasma produit par laser pour transformer un échantillon (102) en plasma et dérive le spectre de substance associé ; une unité d'identification de température (146) qui compare le spectre de substance et le spectre d'index et identifie la température du plasma de la substance ; une unité d'identification de rapport de mélange (148) qui identifie le rapport de mélange sur la base du rapport de pic de H2 et O2 dans le spectre de substance ; et une unité d'identification de substance (150) qui dérive le rapport de pic d'intensité d'émission lumineuse ou le rapport de composition par rapport à une pluralité définie de produits de décomposition dans le spectre de substance, ou la forme de spectre du spectre de substance, se rapporte aux informations d'identification de substance et identifie la substance.
PCT/JP2014/073997 2013-09-10 2014-09-10 Dispositif et procédé d'identification de substance WO2015037640A1 (fr)

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