Measuring device and measuring method

Abstract

The present invention provides a measuring device and a measuring method. The measuring device (10) includes: a generator (121) that irradiates an electromagnetic wave to a measurement object (M) including a substance in which a structural transfer occurs from a first substance having an unstable structure to a second substance having a stable structure due to the intrusion of a foreign object; a receiver (122) that receives an electromagnetic wave including information on the spectroscopic spectrum of the measurement object (M); and a control unit (116) that obtains a measured spectroscopic spectrum based on the electromagnetic wave received by the receiver (122), calculates ratio information between the first substance and the second substance based on the obtained measured spectroscopic spectrum, and generates determination information related to the intrusion of a foreign object based on the ratio information.

Description

[0001] This application claims priority based on Japanese Patent Application No. 2021-058308 filed in Japan on March 30, 2021, and the entire disclosure of that application is incorporated herein by reference. Technical Field

[0002] The present disclosure relates to assay devices and assay methods. Background Art

[0003] Conventionally, there is known a technique for non-destructively measuring the state of a measurement object near its interface and inside the measurement object.

[0004] For example, Patent Document 1 discloses a system for determining the properties of the interface between a first layer and a second layer. This system includes a transmitter that outputs electromagnetic radiation toward a sample; a receiver that receives electromagnetic radiation reflected from or transmitted through the sample; and a data collection device. The system determines material properties, including the bond strength between the first and second layers, based on waveform data representing the electromagnetic radiation reflected from or transmitted through the sample.

[0005]

Prior Technical Literature

[0006] [Patent Literature]

[0007] Patent Document 1: Japanese Patent No. 5684819

[0008] Such existing technologies are effective only after physical defects or damage have occurred, but they are difficult to detect subtle chemical changes in the measurement object. For example, if foreign matter such as moisture penetrates the measurement object, such as an adhesive, the hydrogen bonds at the adhesive interface are irreversibly severed, and even after drying the adhesive, they will not re-bond. In order to indirectly detect such subtle chemical changes in the measurement object, high-precision detection of foreign matter intrusion into the measurement object is required. Summary of the Invention

[0009] An object of the present disclosure is to provide a measuring device and a measuring method capable of detecting with high accuracy the intrusion of foreign matter into a measurement object.

[0010] Several embodiments involve a measuring device comprising: a generator for irradiating electromagnetic waves onto a measuring object including a substance that undergoes structural transition from a first substance having an unstable structure to a second substance having a stable structure due to the intrusion of foreign matter; a receiver for receiving the electromagnetic waves including information on the spectral spectrum of the measuring object; and a control unit for obtaining the measured spectral spectrum based on the electromagnetic waves received by the receiver, calculating ratio information between the first substance and the second substance based on the obtained measured spectral spectrum, and generating judgment information about the intrusion of the foreign matter based on the ratio information.

[0011] Thus, foreign object intrusion into the measurement object can be detected with high precision. For example, the measurement device calculates ratio information between a first substance and a second substance based on the acquired measured spectroscopic spectrum, and generates judgment information regarding the intrusion of a foreign object based on this ratio information. For example, the measurement device uses, as the measurement object, an adhesive to which vaterite has been added in advance as a marker, and observes, by terahertz spectroscopy, the irreversible crystal structure transition from vaterite to calcite caused by moisture.

[0012] Thus, the measurement device can detect moisture intrusion into the adhesive. That is, the user can confirm whether a foreign object has intruded into the measurement object in the past based on non-destructive and non-contact measurement. Thus, even if water intrudes into the adhesive from the outside and then dries, the deterioration of the adhesive caused by moisture can be detected. The measurement device can infer or indirectly detect minute chemical changes in the measurement object. For example, if a foreign object such as moisture intrudes into a measurement object such as an adhesive, the hydrogen bonds at the interface of the adhesive will be irreversibly severed, and no recombination will occur even if the adhesive is dried. The measurement device can infer or indirectly detect such minute chemical changes in the measurement object.

[0013] In the measurement device according to an embodiment, the control unit may also perform a fitting operation process on the acquired measured spectroscopic spectrum based on the reference data and fitting parameters required for calculating the spectroscopic spectrum, and the initial value of the fitting parameter, so as to calculate the ratio of the second substance to the first substance as the ratio information.

[0014] Thus, for example, when a first adherend and a second adherend are bonded by the adhesive with the adhesive as the measurement object sandwiched therebetween, even if the thickness of the portion of the first adherend adjacent to the measurement area is unknown, the thickness of the first adherend is set as a fitting parameter, so that the above ratio can be calculated with high precision together with the thickness of the first adherend. For example, the first adherend and the second adherend are used for a long time in the state of being bonded to the measurement object, and as a result, there is a possibility that the first adherend is cut. Thus, even when the thickness of the first adherend changes from the beginning of the use of the first adherend, the measurement device can calculate the thickness of the first adherend and the above ratio with high precision.

[0015] In the measurement device according to an embodiment, when it is determined that the parameter included in the ratio information increases, the control unit may also generate history information indicating that the foreign object has intruded into the measurement object as the judgment information. Thus, the user can confirm such history information through, for example, a terminal device. By using a terminal device or the like to confirm such history information, the user can easily grasp that a foreign object has intruded into the measurement object.

[0016] In a measurement device according to an embodiment, when it is determined that a parameter included in the ratio information reaches a threshold value, the control unit may generate notification information indicating that the measurement object has deteriorated due to the intrusion of the foreign matter as the determination information. Thus, the user can confirm such notification information via, for example, a terminal device. By using a terminal device or the like to confirm such notification information as a warning, the user can easily grasp that the measurement object has deteriorated due to the intrusion of a foreign matter and the measurement object exceeding the allowable range.

[0017] In a measurement device according to an embodiment, the control unit may also calculate, based on the ratio information, either the time when the foreign matter intrudes into the measurement object or the temperature of the foreign matter when the foreign matter intrudes into the measurement object as the determination information. Thus, the user can confirm this information via, for example, a terminal device. By using a terminal device or the like to confirm this information, the user can easily grasp the parameters related to the intrusion of the foreign matter into the measurement object.

[0018] In one embodiment, the measurement device includes a movable part that moves the measurement device and can scan the irradiation position of the electromagnetic wave with respect to the measurement object. The control unit generates a spatial distribution of the ratio information in the measurement object as the determination information as the measurement device moves based on the movable part. By using a terminal device or the like to confirm such a spatial distribution as a measurement result, the user can easily grasp the deterioration of the measurement object caused by the intrusion of a foreign matter into a wide part of the measurement object.

[0019] In a measurement device according to an embodiment, the ratio information may also include at least one of the ratio of the second substance to the first substance of the measurement object and the peak intensity of the spectroscopic spectrum. By calculating the ratio of the second substance to the first substance as the ratio information, the measurement device can generate determination information with high precision. By calculating the peak intensity of the spectroscopic spectrum as the ratio information, the measurement device can reduce the calculation load compared with, for example, calculating the ratio of the second substance to the first substance through fitting operation processing or the like.

[0020] In a measurement device according to an embodiment, the substance includes calcium carbonate, the first substance includes calcium carbonate having an orthorhombic crystal structure, and the second substance includes calcium carbonate having a calcite crystal structure. Thus, the measurement device can use calcium carbonate having two crystal structures that can exhibit a significant difference in the presence or absence of an absorption peak near 3.27 THz, and can generate determination information with high precision.

[0021] In a measurement device according to an embodiment, the spectroscopic spectrum may also include at least one of the reflection spectrum and the transmission spectrum of the measurement object.

[0022] For example, by spectroscopic analysis including the reflection spectrum of the object to be measured, when the measuring device bonds the first adherend and the second adherend with the binder to be measured sandwiched therebetween, it is possible to easily detect the intrusion history of foreign matter near the interface on the first adherend side of the object to be measured. For example, the measuring device can easily infer or indirectly detect minute chemical changes such as irreversible cleavage of hydrogen bonds at the interface of the binder.

[0023] For example, by spectroscopic analysis including the transmission spectrum of the object to be measured, the measuring device can easily detect the intrusion history of foreign matter as average information for the entire measurement region along the thickness of the object to be measured.

[0024] For example, when the measuring device acquires both the reflection spectrum and the transmission spectrum of the object to be measured, and the first adherend and the second adherend bond with the binder to be measured sandwiched therebetween, the user can determine from which interface, the interface on the first adherend side or the interface on the second adherend side, the foreign matter has penetrated into the object to be measured. For example, when no intrusion history of foreign matter is detected based on the reflection spectrum of the object to be measured but an intrusion history of foreign matter is detected based on the transmission spectrum of the object to be measured, the user can judge that the foreign matter has penetrated into the object to be measured from the interface on the second adherend side.

[0025] The measurement methods of several embodiments include: a step of irradiating an electromagnetic wave to an object to be measured including a substance in which a structural transfer occurs from a first substance having an unstable structure to a second substance having a stable structure due to the intrusion of foreign matter; a step of receiving the electromagnetic wave including information on the spectroscopic spectrum of the object to be measured; a step of obtaining the actually measured spectroscopic spectrum based on the electromagnetic wave received in the step of receiving the electromagnetic wave; a step of calculating ratio information between the first substance and the second substance based on the obtained actually measured spectroscopic spectrum; and a step of generating judgment information related to the intrusion of the foreign matter based on the calculated ratio information.

[0026] Thereby, it is possible to detect the intrusion of foreign matter into the object to be measured with high precision. For example, based on the obtained actually measured spectroscopic spectrum, ratio information between the first substance and the second substance is calculated, and based on this ratio information, judgment information related to the intrusion of foreign matter is generated. For example, a binder or the like to which vaterite is pre-added as a marker is used as the object to be measured, and an irreversible crystal structure transfer from vaterite to calcite due to moisture is observed by terahertz spectroscopy.

[0027] Accordingly, it is possible to detect the history of moisture intrusion into the binder. That is, the user can confirm whether foreign matter has intruded into the measurement object in the past based on non-destructive and non-contact measurement. Accordingly, even if water intrudes into the binder from the outside and then dries, it is possible to detect the deterioration of the binder caused by moisture. It is possible to infer or indirectly detect minute chemical changes in the measurement object. For example, if foreign matter such as moisture intrudes into a measurement object such as a binder, the hydrogen bonds at the interface of the binder are irreversibly severed and no recombination occurs even if the binder is dried. In the measurement method, it is possible to infer or indirectly detect such minute chemical changes in the measurement object.

[0028] Advantages of the Invention

[0029] According to the present disclosure, it is possible to provide a measurement device and a measurement method capable of detecting the intrusion of foreign matter into a measurement object with high precision. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is a schematic diagram showing the schematic configuration of a measurement system including the measurement device according to the first embodiment of the present disclosure.

[0031] Figure 2 is a graph showing an example of the experimental results of the transmission characteristics of calcium carbonate.

[0032] Figure 3 For explaining Figure 1 a first example of the operation of the measurement device.

[0033] Figure 4 For explaining Figure 1 a second example of the operation of the measurement device.

[0034] Figure 5 For explaining Figure 1 a third example of the operation of the measurement device.

[0035] Figure 6 For explaining Figure 1 a fourth example of the operation of the measurement device.

[0036] Figure 7 For explaining Figure 1 a fifth example of the operation of the measurement device.

[0037] Figure 8 For explaining Figure 1 a sixth example of the operation of the measurement device.

[0038] Figure 9 is a schematic diagram showing the schematic configuration of a measurement system including the measurement device according to the second embodiment of the present disclosure.

[0039] Figure 10 It is a flowchart showing the first example of the operation of the measuring device for Figure 9 .

[0040] Figure 11 It is a flowchart showing the second example of the operation of the measuring device for Figure 9 .

[0041] Explanation of reference numerals

[0042] 1 Measuring system; 10 Measuring device; 11 Control module; 111 Data processing unit; 112 Arithmetic unit; 113 Instruction analysis unit; 114 Spectrum analysis unit; 115 Generator / receiver control unit; 116 Control unit; 117 Storage unit; 12 Measuring module; 121 Generator; 122 Receiver; 123 Movable part; 20 Terminal device; A First adherend; B Second adherend; M Measurement object; R Measurement area. Detailed implementation mode

[0043] Hereinafter, with reference to the drawings, one embodiment of the present invention will be mainly described.

[0044] (First embodiment)

[0045] Figure 1 It is a schematic diagram showing the schematic structure of the measuring system 1 including the measuring device 10 according to the first embodiment of the present disclosure. The measuring device 10 calculates the ratio information between the first substance and the second substance for the measurement object (M) including a substance in which a structural transfer occurs from a first substance having an unstable structure to a second substance having a stable structure due to the intrusion of foreign substances.

[0046] In this specification, "substance" includes, for example, calcium carbonate. "First substance" includes, for example, calcium carbonate having an unstable crystal structure of vaterite. "Second substance" includes, for example, calcium carbonate having a stable crystal structure of calcite. "Measurement object M" includes, for example, an adhesive that bonds the first adherend A and the second adherend B. "Ratio information between the first substance and the second substance" includes, for example, at least one of the ratio of the second substance to the first substance in the measurement object M and the peak intensity of the spectroscopic spectrum described later. In addition, as described later with reference to Figure 2 etc., the peak intensity of the spectroscopic spectrum roughly depends on the ratio of the second substance to the first substance. Therefore, this peak intensity can also replace the ratio of the second substance to the first substance, or in addition, it is included in the ratio information between the first substance and the second substance. "Foreign substances" include, for example, water and water vapor.

[0047] For example, an additive containing a first substance in a prescribed ratio is intentionally doped into the material of the measurement object M. Such an additive includes, for example, any additive that does not affect the bonding function of the measurement object M as a binder. Such an additive is used to make the measurement object M contain the first substance required for measurement in a prescribed ratio and is composed of a substance different from the foreign matter accidentally mixed in. For example, the additive contains the above-mentioned calcium carbonate.

[0048] The measuring device 10 is utilized when a binder or the like, which has a first substance such as vaterite added thereto as a marker, is used as the measurement object M and foreign matter such as water infiltrates the measurement object M from the outside. For example, the measuring device 10 observes, by terahertz spectroscopy, the irreversible crystal structure transition from vaterite to calcite generated by moisture in such a case.

[0049] In addition to the measuring device 10, the measurement system 1 includes a terminal device 20 connected to the measuring device 10 in a communicable manner. The measuring device 10 has a control module 11 and a measurement module 12.

[0050] The terminal device 20 includes, for example, any general-purpose electronic device such as a PC (Personal Computer) or a smartphone. Without being limited thereto, the terminal device 20 may be one or a plurality of server devices capable of communicating with each other, or may be other electronic devices dedicated to the measurement system 1.

[0051] The measurement module 12 includes a module that measures the state of the measurement object M using electromagnetic waves. The measurement module 12 has a generator 121, a receiver 122, and a movable part 123.

[0052] The generator 121 has, for example, any electromagnetic wave source that can irradiate the measurement object M with electromagnetic waves having a frequency in the terahertz region. The receiver 122 includes any receiver that can receive electromagnetic waves, which are electromagnetic waves in the terahertz frequency band, for example, based on the electromagnetic waves irradiated from the generator 121 to the measurement object M, and which include information on the spectroscopic spectrum of the measurement object M.

[0053] In this specification, the electromagnetic waves irradiated from the generator 121 have a frequency in the terahertz region of, for example, 30 THz or less. For example, the electromagnetic waves have a frequency in the terahertz region of 1 to 5 THz. The electromagnetic waves have a frequency in the terahertz region near the absorption peak of calcite described later, for example, 3.27 ± 1 THz. In the first embodiment, the "spectroscopic spectrum" includes, for example, the reflection spectrum of the measurement object M. For example, the spectroscopic spectrum includes the reflection spectrum in the measurement region R, which includes the interface between the first adherend A and the measurement object M and the portion of the measurement object M close to the first adherend A.

[0054] The movable part 123 includes any movable structure that can improve the mobility of the measuring device 10. For example, the movable part 123 includes tires mounted on the measuring module 12. The measuring module 12 can move on the surface of the first adherend A through the tires that make up the movable part 123. The movable part 123 can move the measuring device 10 to scan the irradiation position of the electromagnetic wave of the generator 121 on the measurement object M.

[0055] The control module 11 has a data processing unit 111, an arithmetic unit 112, an instruction analysis unit 113, a spectrum analysis unit 114, and a generator / receiver control unit 115. At least a part of the data processing unit 111, the arithmetic unit 112, the instruction analysis unit 113, the spectrum analysis unit 114, and the generator / receiver control unit 115 can be aggregated to form a control unit 116. The control module 11 also has a storage unit 117 in addition to the control unit 116.

[0056] The control unit 116 includes one or more processors. In one embodiment, the "processor" is a general-purpose processor or a dedicated processor for specific processing, but is not limited thereto. The control unit 116 is communicably connected to each component of the measuring device 10 and controls the overall operation of the measuring device 10.

[0057] The storage unit 117 includes any storage module including HDD (Hard Disk Drive), SSD (Solid State Drive), EEPROM (Electrically Erasable Programmable Read-Only Memory), ROM (Read-Only Memory), and RAM (Random Access Memory), etc. The storage unit 117 can also function as a main storage device, an auxiliary storage device, or a cache memory, for example. The storage unit 117 stores any information for the operation of the measuring device 10 and any information obtained as the operation result of the measuring device 10, etc.

[0058] For example, the storage unit 117 stores the reference data described later required for calculating the ratio information. For example, the storage unit 117 stores the information of the spectroscopic spectrum of the measurement object M obtained by using the measurement module 12. For example, the storage unit 117 stores the information related to the ratio information calculated by the control unit 116. For example, the storage unit 117 can also store system programs and application programs, etc. The storage unit 117 is not limited to being built into the control module 11 and can also include an external storage module connected through a digital input / output port such as USB (Universal Serial Bus).

[0059] For example, the measuring device 10 is arranged on the first adherend A by the user so as to be directly above the bonding interface portion where the measurement is actually performed in the measurement object M. The terminal device 20 receives an input operation from the user and sends an instruction including a measurement execution command and the like to the measuring device 10.

[0060] The data processing unit 111 of the measuring device 10 receives the instruction sent from the terminal device 20 and outputs it to the instruction analysis unit 113. The instruction analysis unit 113 analyzes the content of the instruction sent from the terminal device 20. In the instruction packet, initial setting data is stored together with the measurement execution command. Such initial setting data is stored, for example, in the storage unit 117. In this specification, "initial setting data" includes, for example, reference data, fitting parameters, and initial values of each fitting parameter. In addition, the initial setting data may also include, for example, at least one of the ratio of the second substance to the first substance in the measurement object M in a state where a first substance such as vaterite is added to the measurement object M in advance as a marker and no foreign matter such as water has penetrated into the measurement object M from the outside, and the peak intensity of the spectroscopic spectrum described later as an initial value.

[0061] In the first embodiment, the "reference data" includes, for example, the frequency dependence of the complex refractive index of the first adherend A and the frequency dependence of the complex refractive index of the measurement object M in a state where no additive is added. In addition, the reference data includes the frequency dependence of the complex refractive index of the first substance and the frequency dependence of the complex refractive index of the second substance. In the first embodiment, the "fitting parameters" include, for example, the thickness of the first adherend A, the ratio of the second substance to the first substance, and the concentration of the additive in the measurement object M.

[0062] In this specification, the "ratio of the second substance to the first substance" may also include, for example, the ratio of the second substance when the ratio of the first substance and the ratio of the second substance in the additive are added up to 100%. Without being limited thereto, the ratio of the second substance to the first substance may include, for example, the value obtained by dividing the amount of the second substance in the additive by the amount of the first substance. Such a ratio may be an absolute value or a relative value indicating how much it has changed from the initial value when the initial value is unknown.

[0063] The generator / receiver control unit 115 of the measuring device 10 automatically adjusts the position and angle of the generator 121 so as to satisfy a specified generation condition. In the first embodiment, the "specified generation condition" includes, for example, a condition that the electromagnetic wave irradiated by the generator 121 enters the measurement region R at an arbitrary incident angle. For example, the incident angle may be a small angle close to zero degrees or may be zero degrees. That is, the generator 121 may also be set to a measurement position and angle that can be considered to be incident on the measurement region R substantially vertically or vertically. Not limited to the above, the generator / receiver control unit 115 may also use the terminal device 20 through user input to adjust the position and angle of the generator 121 according to the set value transmitted from the terminal device 20.

[0064] The generator / receiver control unit 115 of the measuring device 10 automatically adjusts the position and angle of the receiver 122 so as to satisfy a specified reception condition. In the first embodiment, the "specified reception condition" includes, for example, a condition that the electromagnetic wave reflected at an arbitrary reflection angle in the measurement region R enters the receiver 122. For example, the reflection angle is the same as the above incident angle, and may be a small angle close to zero degrees or may be zero degrees. That is, the receiver 122 may be set to a measurement position and angle that can be considered to be reflected substantially vertically or vertically with respect to the measurement region R. Not limited to the above, the generator / receiver control unit 115 may also use the terminal device 20 through user input to adjust the position and angle of the receiver 122 according to the set value transmitted from the terminal device 20.

[0065] The generator / receiver control unit 115 controls the generator 121 to irradiate the measurement region R with electromagnetic waves in the terahertz band. For example, the generator / receiver control unit 115 uses time-domain spectroscopy (TDS) to output an electromagnetic wave of a short pulse of about 10 ps to several 10 ps through the generator 121. At this time, the generator 121 can output an electromagnetic wave having an arbitrary polarization. For example, the generator 121 can output an electromagnetic wave of linearly polarized light having a P-polarization component, or can also output an electromagnetic wave of linearly polarized light having an S-polarization component.

[0066] The generator / receiver control unit 115 obtains a pulse signal arranged in time series from the receiver 122. For example, the generator / receiver control unit 115 is an electromagnetic wave in the terahertz band, and receives the above-mentioned short-pulse electromagnetic wave using TDS through the receiver 122. At this time, the receiver 122 can receive an electromagnetic wave having an arbitrary polarization according to the electromagnetic wave output from the generator 121. For example, the receiver 122 can receive an electromagnetic wave of linearly polarized light having a P-polarization component, or can also receive an electromagnetic wave of linearly polarized light having an S-polarization component.

[0067] The generator / receiver control unit 115 outputs the acquired pulse signal to the spectrum analysis unit 114. The spectrum analysis unit 114 calculates a spectral spectrum in the frequency domain by performing, for example, Fourier transform processing on the temporal waveform of the pulse signal. For example, the time-series pulse signals output from the receiver 122 correspond to short pulses of electromagnetic waves reflected as reflected waves from the surface of the first adherend A, the measurement region R, the interface between the measurement object M and the second adherend B, and the back surface of the second adherend B. The spectrum analysis unit 114 can also extract the pulse signal at the time corresponding to the reflection in the measurement region R and calculate the spectral spectrum using the above method.

[0068] The operation unit 112 uses the spectral spectrum calculated in the spectrum analysis unit 114 to calculate the ratio information between the first substance and the second substance, as described later. The operation unit 112 generates judgment information (diagnostic information) related to the intrusion of foreign matter based on the calculated ratio information. In this specification, "judgment information" includes, for example, historical information indicating that foreign matter has infiltrated the measurement object M. This is not limited to this, and the judgment information may also include, for example, notification information indicating that the measurement object M has deteriorated due to the intrusion of foreign matter. The judgment information may also include, for example, any one of the time when the foreign matter infiltrated the measurement object M and the temperature of the foreign matter when the foreign matter infiltrated the measurement object M. The judgment information may also include, for example, the spatial distribution of the ratio information in the measurement object M.

[0069] The data processing unit 111 transmits the calculation result of the calculation unit 112 to the terminal device 20. The terminal device 20 displays the received calculation result, that is, the determination information, to the user.

[0070] When a scanning range is specified, the control module 11 moves the measurement module 12 using the tire constituting the movable unit 123 , thereby executing the same measurement process at each measurement point.

[0071] Figure 2 This is a graph showing an example of experimental results of the transmission characteristics of calcium carbonate. Figure 2 , which mainly explains how the unstable vaterite gradually transfers to the stable calcite crystal structure due to foreign matter such as water.

[0072] There are three known crystal structures of calcium carbonate: stable calcite, metastable bainite, and unstable vaterite. Although pyroxenite rarely exists in nature, it can be artificially synthesized through chemical synthesis.

[0073] exist Figure 2In the experimental results shown, the dashed line represents the transmission spectrum of a sample including, for example, vaterite with a yield of weakly 70% and the remaining proportion of boleite. The dashed line represents the result of measuring this sample at normal temperature before water immersion. From the experimental results represented by the dashed line, it can be seen that there is no significant absorption peak near 3.27 THz for vaterite.

[0074] On the other hand, the solid line represents the result when the transmission spectrum of this sample is measured after immersing the sample in water at normal temperature for 24 hours, drying it thoroughly at normal temperature, and then measuring it. It is known that calcium carbonate having a calcite crystal structure has a significant absorption peak at 3.27 THz. From Figure 2 the intensity of the absorption peak at 3.27 THz in the solid line, it can be seen that through contact with water, almost all vaterite undergoes a crystal structure transformation into calcite.

[0075] Calcite is a stable crystal structure and maintains its crystal structure as long as it is not placed in a special environment. Therefore, Figure 2 the experimental results shown indicate that judgment information can be generated by the arithmetic unit 112 by using the spectroscopic spectrum near 3.27 THz.

[0076] Figure 3 is a flowchart for explaining Figure 1 a first example of the operation of the measuring device 10. Refer to Figure 3 to explain an example of the basic process related to the calculation process of the ratio information executed by the control unit 116 of the measuring device 10.

[0077] As a prerequisite, it is assumed that the measurement object M includes an appropriate amount of substances such as calcium carbonate as additives. At the stage of the operation of bonding the measurement object M to the first adherend A and the second adherend B, all or most of this substance has an unstable structure such as a first substance. When the first substance comes into contact with a foreign object, the second substance undergoes an irreversible structure transformation. For example, by monitoring the absorption peak value of the second substance obtained by terahertz spectroscopy and its vicinity, the user can grasp the history information indicating the intrusion of a foreign object into the measurement object M.

[0078] In step S100, the control unit 116 obtains initial setting data from the terminal device 20 and stores it in the storage unit 117.

[0079] In step S101, the control unit 116 automatically adjusts the position and angle of the generator 121 to meet the specified generation conditions. The control unit 116 automatically adjusts the position and angle of the receiver 122 to meet the specified reception conditions.

[0080] In step S102, the control unit 116 uses the generator 121 automatically adjusted in step S101 to irradiate electromagnetic waves to the measurement area R.

[0081] In step S103, based on the electromagnetic wave irradiated in step S102, the control unit 116 uses the receiver 122 to receive an electromagnetic wave including information on the spectroscopic spectrum of the measurement object M.

[0082] In step S104, based on the electromagnetic wave received by the receiver 122 in step S103, the control unit 116 obtains the reflection spectrum of the measurement object M as the actually measured spectroscopic spectrum.

[0083] In step S105, based on the actually measured reflection spectrum obtained in step S104, the control unit 116 calculates the ratio information between the first substance and the second substance.

[0084] In step S106, the control unit 116 generates determination information related to the intrusion of a foreign object based on the ratio information calculated in step S105. The control unit 116 sends the generated determination information to the terminal device 20.

[0085] Figure 4 is a second example of a flowchart for explaining Figure 1 the operation of the measurement device 10. As Figure 4 shown in the flowchart represents Figure 3 an example of a more specific process of the calculation process in step S105 of Figure 4 . While referring to Figure 3 in more detail, the calculation process in step S105 of

[0086] In the step of calculating the ratio information in step S105, the control unit 116 may also perform a fitting operation process on the actually measured reflection spectrum obtained in step S104 based on the reference data and fitting parameters required for calculating the spectroscopic spectrum, and the initial value of the fitting parameters. Thereby, the control unit 116 can calculate the ratio of the second substance to the first substance as the ratio information.

[0087] In step S200, the control unit 116 reads in the initial setting data.

[0088] In step S201, based on the initial setting data read in step S200, the control unit 116 calculates the reflection spectrum of the measurement object M based on the electromagnetic wave observed by the receiver 122. More specifically, the control unit 116 calculates the reflection spectrum of the measurement object M based on a prescribed physical model formula.

[0089] In step S202, the control unit 116 calculates the error between the reflection spectrum calculated in step S201 and the actually measured reflection spectrum obtained in Figure 3 step S104 of

[0090] In step S203 , the control unit 116 updates the values of the fitting parameters read in step S200 based on the calculation results of step S202 .

[0091] In step S204, the control unit 116 determines whether the error calculated in step S202 is within the set range. For example, the control unit 116 determines whether the least square error across all frequency points is within the set range. If the control unit 116 determines that the error is within the set range, the process ends. If the control unit 116 determines that the error is not within the set range, the process of step S201 is repeated.

[0092] As described above, the control unit 116 calculates fitting parameters based on the measured reflectance spectrum data and the physical model equation through fitting through iterative calculations. The control unit 116 confirms the consistency between the measured data and the physical model equation during each iterative calculation and terminates the fitting calculation process if sufficient convergence is determined.

[0093] Figure 5 Is used to illustrate Figure 1 This is a flowchart of a third example of the operation of the measuring device 10. Figure 5 The flowchart shown shows Figure 3 An example of a more specific flow of the processing in step S106. Figure 5 , while explaining in more detail Figure 3 For example, if the control unit 116 determines that a parameter included in the ratio information has increased, it may generate historical information indicating that a foreign object has entered the measurement target M as the determination information. Below, the ratio of the second substance to the first substance is used as an example of a parameter included in the ratio information, but the same description also applies to the peak intensity of the spectroscopic spectrum.

[0094] In step S300, the control unit 116 determines whether the ratio of the second substance to the first substance calculated in step S105 has increased. For example, the control unit 116 may perform this determination by comparing the ratio of the second substance to the first substance in the measurement object M, stored as initial setting data in the storage unit 117 in step S100 and in a state where foreign matter such as water has not infiltrated the measurement object M from the outside, with the ratio calculated in step S105. If the control unit 116 determines that the ratio of the second substance to the first substance has increased, the process of step S301 is executed. If the ratio of the second substance to the first substance has not increased, that is, if the ratio of the second substance to the first substance has not changed, the control unit 116 executes the process of step S300 again.

[0095] In step S301 , when it is determined in step S300 that the ratio of the second substance to the first substance has increased, the control unit 116 generates history information indicating that foreign matter has invaded the measuring object M as determination information.

[0096] Figure 6 Is used to illustrate Figure 1 Flowchart of a fourth example of the operation of the measuring device 10. Figure 6 The flowchart shown shows Figure 3 An example of a more specific flow of the processing in step S106. Figure 6 More detailed explanation Figure 3 For example, if the control unit 116 determines that the parameter included in the ratio information has reached the threshold value, it may generate notification information indicating that the measurement object M has deteriorated due to the intrusion of foreign matter as the determination information.

[0097] In step S400, the control unit 116 determines whether the ratio of the second substance to the first substance calculated in step S105 has reached the first threshold. If the control unit 116 determines that the ratio of the second substance to the first substance has reached the first threshold, the process of step S401 is executed. If the control unit 116 determines that the ratio of the second substance to the first substance has not reached the first threshold, the process of step S400 is executed again.

[0098] In step S401 , when it is determined in step S400 that the ratio of the second substance to the first substance reaches the first threshold, the control unit 116 generates notification information indicating that the measuring object M has deteriorated due to the intrusion of foreign matter as determination information.

[0099] The first threshold value described above may be appropriately set by the user based on, for example, actual measurement data that correlates the ratio of the second substance to the first substance in the measurement object M, the amount of foreign matter infiltrating the measurement object M, and the degree of deterioration of the measurement object M. In this case, the user may also set the first threshold value in consideration of the resolution of the measurement device 10, the SN ratio, measurement variation, and measurement reproducibility.

[0100] Figure 7 Is used to illustrate Figure 1 Flowchart of a fifth example of the operation of the measuring device 10. Figure 7 The flowchart shown shows Figure 3 An example of a more specific flow of the processing in step S106. Figure 7 More detailed explanation Figure 3 For example, if the control unit 116 determines that the parameter included in the ratio information has reached the threshold value, it may generate notification information indicating that the measurement object M has deteriorated due to the intrusion of foreign matter as the determination information.

[0101] In step S500, the control unit 116 determines whether the peak intensity of the spectroscopic spectrum calculated in step S105 reaches a second threshold based on the spectroscopic spectrum obtained in step S104. That is, the control unit 116 may not perform the fitting operation process in step S105 and only calculate the peak intensity of the spectroscopic spectrum. For example, the control unit 116 determines whether the intensity of the absorption peak near 3.27 THz in the reflection spectrum obtained in step S104 reaches the second threshold. If the control unit 116 determines that the peak intensity reaches the second threshold, the process of step S501 is executed. If the control unit 116 determines that the peak intensity does not reach the second threshold, the process of step S500 is executed again.

[0102] In step S501, if it is determined in step S500 that the peak intensity reaches the second threshold, the control unit 116 generates notification information indicating deterioration of the measurement object M due to the intrusion of foreign matter as determination information.

[0103] The above second threshold can also be appropriately set by the user based on, for example, measured data associating the peak intensity of the spectroscopic spectrum of the measurement object M with the amount of foreign matter infiltrating the measurement object M and the degree of deterioration of the measurement object M. At this time, the user can also consider the resolution, SN ratio, measurement deviation, and measurement reproducibility of the measuring device 10, etc. when setting the second threshold.

[0104] Figure 8 is for explaining Figure 1 the operation of the measuring device 10 Figure 8 in the sixth example. As shown Figure 3 in the flowchart, it represents Figure 8 an example of a more specific process of the process in step S106 Figure 3 of. Referring to

[0105]

[0106] In step S600, the control unit 116 acquires either the time when the foreign matter penetrates into the measurement object M or the temperature of the foreign matter when it penetrates into the measurement object M. The control unit 116 can acquire this information from the terminal device 20 by using the input of the user of the terminal device 20.

[0107] In step S601, the control unit 116 calculates the other based on the ratio of the second substance to the first substance calculated in step S105 and the information acquired in step S600.

[0108] In addition to or instead of the various determination information as described above, the control unit 116 can also generate a spatial distribution of the ratio information between the first substance and the second substance in the measurement object M as determination information in association with the movement of the measurement device 10 based on the movable unit 123.

[0109] According to the measurement device 10 of the first embodiment as described above, it is possible to detect the intrusion of foreign matter into the measurement object M with high accuracy. For example, the measurement device 10 calculates the ratio information between the first substance and the second substance based on the acquired measured spectroscopic spectrum, and generates determination information regarding the intrusion of foreign matter based on this ratio information. For example, the measurement device 10 uses, as the measurement object M, a binder to which vaterite is added in advance as a marker, and observes the irreversible crystal structure transition from vaterite to calcite generated by moisture through terahertz spectroscopy.

[0110] Thereby, the measurement device 10 can detect the moisture intrusion history into the binder. That is, the user can confirm whether a foreign matter has penetrated into the measurement object M in the past based on non-destructive and non-contact measurement. Thereby, even if water penetrates into the binder from the outside and then dries, it is possible to detect the deterioration of the binder caused by moisture. The measurement device 10 can estimate or indirectly detect minute chemical changes in the measurement object M. For example, if a foreign matter such as moisture penetrates into the measurement object M such as a binder, the hydrogen bonds at the interface of the binder are irreversibly cut off, and no recombination occurs even if the binder is dried. The measurement device 10 can estimate or indirectly detect such minute chemical changes in the measurement object M.

[0111] The measuring device 10 calculates the ratio of the second substance to the first substance by performing fitting operation processing on the obtained measured spectroscopic spectrum. Thus, for example, even if the thickness of the portion adjacent to the measurement region R in the first adherend A is unknown, the thickness of the first adherend A can also be set as a fitting parameter, so that the above ratio can be calculated with high precision together with the thickness of the first adherend A. For example, when the first adherend A and the second adherend B are used for a long time in a state bonded by the measurement object M, there is a possibility that the first adherend A is shaved off as a result. In this way, even when the thickness of the first adherend A changes from the start of use of the first adherend A, the measuring device 10 can calculate the above ratio with high precision together with the thickness of the first adherend A.

[0112] If the measuring device 10 determines that the parameter included in the ratio information increases, it generates history information, so that the user can confirm such history information through, for example, the terminal device 20. By using the terminal device 20 or the like to confirm such history information, the user can easily grasp the intrusion of foreign matter into the measurement object M.

[0113] If the measuring device 10 determines that the parameter included in the ratio information reaches a threshold value, it generates notification information, so that the user can confirm such notification information through, for example, the terminal device 20. By using the terminal device 20 or the like to confirm such notification information as a warning, the user can easily grasp that the measurement object M deteriorates beyond the allowable range due to the intrusion of foreign matter.

[0114] The measuring device 10 calculates either the time when foreign matter intrudes into the measurement object M or the temperature of the foreign matter when it intrudes into the measurement object M based on the ratio information. Thus, the user can confirm this information through, for example, the terminal device 20. By using the terminal device 20 or the like to confirm this information, the user can easily grasp the parameters related to the intrusion of foreign matter into the measurement object M.

[0115] The measuring device 10 generates a spatial distribution of the ratio information in the measurement object M, so that the user can confirm such a spatial distribution through, for example, the terminal device 20. By using the terminal device 20 or the like to confirm such a spatial distribution as a measurement result, the user can easily grasp the deterioration of the measurement object M caused by the intrusion of foreign matter into a wide part of the measurement object M.

[0116] The measuring device 10 can generate judgment information with high precision by calculating the ratio of the second substance to the first substance as the ratio information. The measuring device 10 calculates the peak intensity of the spectroscopic spectrum as the ratio information, so that the calculation load can be reduced compared with, for example, calculating the ratio of the second substance to the first substance by fitting operation processing or the like.

[0117] The first substance includes calcium carbonate having an orthorhombic vaterite structure, and the second substance includes calcium carbonate having a trigonal calcite crystal structure. Thus, the measuring device 10 uses calcium carbonate having two crystal structures that can exhibit a significant difference in the presence or absence of an absorption peak near 3.27 THz, and can generate determination information with high accuracy.

[0118] By including the reflection spectrum of the measurement object M in the spectroscopic spectrum, the measuring device 10 can easily detect the intrusion history of foreign substances near the interface on the side of the first adherend A in the measurement object M. For example, the measuring device 10 can easily estimate or indirectly detect minute chemical changes such as the irreversible cleavage of hydrogen bonds at the interface of the adhesive.

[0119] In the measurement system 1 of the first embodiment described above, it has been described that the measuring device 10 and the terminal device 20 are configured as different devices, but this is not limiting. The measuring device 10 and the terminal device 20 may be integrally formed in one device.

[0120] In the first embodiment described above, fitting parameters such as the thickness of the first adherend A, the ratio of the second substance to the first substance, and the concentration of additives in the measurement object M have been described, but this is not limiting. The fitting parameters may include, for example, at least the ratio of the second substance to the first substance.

[0121] In the first embodiment described above, it has been described that the measurement object M contains an adhesive that bonds the first adherend A and the second adherend B, but this is not limiting. The measurement object M may also include any object that can calculate its state based on the information of the spectroscopic spectrum. For example, the measurement object M may not be sandwiched between the first adherend A and the second adherend B. For example, the measurement object M may include any object of solid, liquid, and gas. For example, the measurement object M may include a liquid flowing in a pipe corresponding to the first adherend A. If there is also a substance in such a liquid that undergoes a structural transfer from the first substance having an unstable structure to the second substance having a stable structure due to the intrusion of foreign substances, the measuring device 10 can generate determination information from outside the pipe.

[0122] In the first embodiment described above, it has been described that the measuring device 10 uses an adhesive or the like in which vaterite is pre-added as a marker as the measurement object M, but this is not limiting. In addition to adding or substituting the first substance, the measurement object M may be included, for example, in a state where the first substance is directly disposed by scattering or embedding at the interface on the side of the first adherend A of the measurement object M. Thus, even when foreign substances do not penetrate deep into the measurement object M but only penetrate the interface on the side of the first adherend A of the measurement object M, for example, the measuring device 10 can generate determination information related to the intrusion of foreign substances.

[0123] In the above first embodiment, it has been described that the electromagnetic wave irradiated by the generator 121 has a frequency in the terahertz region, but it is not limited thereto. For example, not limited to terahertz waves, electromagnetic waves having frequencies in any region may be used. For example, if the first adherend A is extremely thin, electromagnetic waves in the mid-infrared region may be used.

[0124] (Second Embodiment)

[0125] Figure 9 FIG. is a schematic diagram showing a schematic configuration of a measurement system 1 including a measurement device 10 according to a second embodiment of the present disclosure. Refer to Figure 9 and mainly explain the structure of the measurement device 10 according to the second embodiment.

[0126] The difference between the measurement device 10 of the second embodiment and the measurement device 10 of the first embodiment is that it is not Figure 1 of the reflection type as described above, but Figure 9 of the transmission type as described above. Regarding other structures, functions, effects, and modification examples of the measurement device 10, they are the same as those of the first embodiment, and the corresponding explanations also apply to the measurement device 10 of the second embodiment. Hereinafter, the same reference numerals are given to the same constituent parts as those of the first embodiment, and their explanations are omitted. Mainly explain the differences from the first embodiment.

[0127] In the second embodiment, the "spectroscopic spectrum" includes, for example, the transmission spectrum of the measurement object M. For example, the spectroscopic spectrum includes the average absorption spectrum in the measurement region R along the thickness direction of the measurement object M.

[0128] In the second embodiment, the "reference data" includes, for example, the frequency dependence of the complex refractive index of the first adherend A, the frequency dependence of the complex refractive index of the second adherend B, and the frequency dependence of the complex refractive index of the measurement object M in a state where no additive is added. In addition, the reference data includes the frequency dependence of the complex refractive index of the first substance and the frequency dependence of the complex refractive index of the second substance. Further, the reference data includes the thickness of the first adherend A and the thickness of the second adherend B. In the second embodiment, the "fitting parameter" includes, for example, the thickness of the measurement object M, the ratio of the second substance to the first substance, and the concentration of the additive in the measurement object M.

[0129] The generator / receiver control unit 115 of the measuring device 10 automatically adjusts the position and angle of the generator 121 so as to satisfy the specified generation conditions. In the second embodiment, the "specified generation conditions" include, for example, the condition that the electromagnetic wave irradiated by the generator 121 enters and transmits through the measurement area R at an arbitrary incident angle. For example, the incident angle can be a small angle close to zero degrees or zero degrees. That is, the generator 121 can also be set to a position and angle where it can be incident on the measurement area R approximately vertically or regarded as vertically incident for measurement. Without being limited to the above, the generator / receiver control unit 115 can also use the terminal device 20 to be input by the user, and adjust the position and angle of the generator 121 according to the set value sent from the terminal device 20.

[0130] The generator / receiver control unit 115 of the measuring device 10 automatically adjusts the position and angle of the receiver 122 so as to satisfy the specified reception conditions. In the second embodiment, the "specified reception conditions" include, for example, the condition that the electromagnetic wave transmitted at an arbitrary exit angle in the measurement area R enters the receiver 122. For example, the exit angle can be a small angle close to zero degrees or zero degrees. That is, the receiver 122 can be set to a position and angle where it can be transmitted approximately vertically or regarded as vertically transmitted with respect to the measurement area R for measurement. Without being limited to the above, the generator / receiver control unit 115 can also use the terminal device 20 to be input by the user, and adjust the position and angle of the receiver 122 according to the set value sent from the terminal device 20.

[0131] Figure 10 is for explaining Figure 9 a first example of the operation of the measuring device 10. Refer to Figure 10 to explain an example of the basic process related to the calculation process of the ratio information executed by the control unit 116 of the measuring device 10.

[0132] In step S700, the control unit 116 obtains the initial setting data from the terminal device 20 and stores it in the storage unit 117.

[0133] In step S701, the control unit 116 automatically adjusts the position and angle of the generator 121 so as to satisfy the specified generation conditions. The control unit 116 automatically adjusts the position and angle of the receiver 122 so as to satisfy the specified reception conditions.

[0134] In step S702, the control unit 116 uses the generator 121 that has been automatically adjusted in step S701 to irradiate the measurement area R with electromagnetic waves.

[0135] In step S703, the control unit 116 receives, based on the electromagnetic wave irradiated in step S702, the electromagnetic wave including the information of the spectroscopic spectrum of the measurement object M using the receiver 122.

[0136] In step S704, the control unit 116 obtains the transmission spectrum of the measurement object M as the actually measured spectroscopic spectrum based on the electromagnetic wave received by the receiver 122 in step S703.

[0137] In step S705, the control unit 116 calculates the ratio information between the first substance and the second substance based on the actually measured transmission spectrum obtained in step S704.

[0138] In step S706, the control unit 116 generates determination information related to the intrusion of a foreign object based on the ratio information calculated in step S705. The control unit 116 sends the generated determination information to the terminal device 20.

[0139] Figure 11 is for explaining Figure 9 a second example of the operation of the measurement device 10. As Figure 11 shown in the flowchart represents Figure 10 an example of a more specific process of the calculation process in step S705 of Figure 11 . Refer to Figure 10 for a more detailed explanation of the calculation process in step S705 of

[0140] In the step of calculating the ratio information in step S705, the control unit 116 performs a fitting operation process on the actually measured transmission spectrum obtained in step S704 based on the reference data and fitting parameters and initial values of the fitting parameters required for calculating the spectroscopic spectrum. Thereby, the control unit 116 calculates the ratio of the second substance to the first substance.

[0141] In step S800, the control unit 116 reads in the initial setting data.

[0142] In step S801, the control unit 116 calculates the transmission spectrum of the measurement object M based on the electromagnetic wave observed by the receiver 122 based on the initial setting data read in step S800. More specifically, the control unit 116 calculates the transmission spectrum of the measurement object M based on a prescribed physical model formula.

[0143] In step S802, the control unit 116 calculates the error between the transmission spectrum calculated in step S801 and the actually measured transmission spectrum obtained in Figure 10 step S704 of

[0144] In step S803, the control unit 116 updates the values of the respective fitting parameters read in step S800 based on the calculation result of step S802.

[0145] In step S804, the control unit 116 determines whether the error calculated in step S802 is within a set range. For example, the control unit 116 determines whether the least square error at all frequency points is within the set range. If the control unit 116 determines that the error is within the set range, the process ends. If the control unit 116 determines that the error is not within the set range, the process of step S801 is executed again.

[0146] As described above, the control unit 116 calculates fitting parameters based on the measured data of the transmission spectrum and the physical model formula through fitting based on iterative calculations. In each iterative calculation, the control unit 116 confirms the degree of agreement between the measured data and the physical model formula, and if it determines that sufficient convergence has occurred, the fitting calculation process ends.

[0147] According to the measuring device 10 of the second embodiment described above, by including the transmission spectrum of the measurement object M in the spectroscopic spectrum, the measuring device 10 can easily detect the intrusion history of foreign matter as average information of the entire measurement region R along the thickness of the measurement object M. For example, since the electromagnetic wave irradiated by the generator 121 has a frequency in the terahertz region, the transmissivity of any measurement object M can be obtained more reliably. Thereby, the measuring device 10 can more reliably detect the state of the deep part of the measurement object M.

[0148] In the above second embodiment, the fitting parameters are described as including, for example, the thickness of the measurement object M, the ratio of the second substance to the first substance, and the concentration of the additive in the measurement object M, but are not limited thereto. The fitting parameters may further include at least one of the thickness of the first adherend A and the thickness of the second adherend B.

[0149] Although the present disclosure has been described based on the respective drawings and embodiments, those skilled in the art should note that various modifications and changes can be made based on the present disclosure. Therefore, it should be noted that these modifications and changes are included within the scope of the present disclosure. For example, the functions included in each component or each step can be reconfigured in a logically consistent manner, multiple components or steps can be combined into one, or divided.

[0150] For example, the present disclosure can also be implemented as a program or a storage medium of a program that records the processing content for describing the functions of the above-described measuring device 10. It is desired to understand that the scope of the present disclosure also includes these.

[0151] For example, the shapes, arrangements, directions, and numbers of the above-described respective components are not limited to the contents illustrated in the above description and drawings. The shapes, arrangements, directions, and numbers of the respective components can be arbitrarily configured as long as the functions can be realized.

[0152] For example, the measuring device 10 may execute only either of the processes described in the above first and second embodiments, or may execute both in parallel. For example, by obtaining both the reflection spectrum and the transmission spectrum of the measurement object M with the measuring device 10, the user can grasp from which interface of the first adherend A side and the second adherend B side the foreign matter has penetrated into the measurement object M. For example, when the penetration history of the foreign matter is not detected based on the reflection spectrum of the measurement object M, and on the other hand, the penetration history of the foreign matter is detected based on the transmission spectrum of the measurement object M, the user can determine that the foreign matter has penetrated into the measurement object M from the interface on the second adherend B side.

Claims

1. A measuring device, comprising: a generator that irradiates an electromagnetic wave to a measurement object; a receiver that receives the electromagnetic wave including information on the spectral spectrum of the measurement object, wherein a substance contained in the measurement object changes due to the intrusion of a foreign substance into the measurement object and undergoes a structural transition from a first substance having an unstable structure to a second substance having a stable structure; and a control unit that obtains the actually measured spectral spectrum based on the electromagnetic wave received by the receiver, calculates ratio information between the first substance and the second substance based on the obtained actually measured spectral spectrum, and generates determination information regarding the intrusion of the foreign substance based on the ratio information, the substance includes calcium carbonate, the first substance includes calcium carbonate having an orthorhombic vaterite crystal structure, the second substance includes calcium carbonate having a trigonal calcite crystal structure.

2. The measuring device according to claim 1, wherein the control unit performs a fitting operation process on the obtained actually measured spectral spectrum according to reference data and fitting parameters required for calculating the spectral spectrum, and an initial value of the fitting parameters, so as to calculate a ratio of the second substance to the first substance as ratio information.

3. The measuring device according to claim 1, wherein when it is determined that a parameter included in the ratio information increases, the control unit generates history information indicating that the foreign substance has intruded into the measurement object as the determination information.

4. The measuring device according to any one of claims 1 to 3, wherein when it is determined that a parameter included in the ratio information reaches a threshold value, the control unit generates notification information indicating that the measurement object has deteriorated due to the intrusion of the foreign substance as the determination information.

5. The measuring device according to any one of claims 1 to 3, wherein the control unit calculates, based on the ratio information, either the time when the foreign substance intrudes into the measurement object or the temperature of the foreign substance when the foreign substance intrudes into the measurement object as the determination information.

6. The measuring device according to any one of claims 1 to 3, wherein the measuring device includes a movable part that moves the measuring device and can scan an irradiation position of the electromagnetic wave with respect to the measurement object, the control unit generates a spatial distribution of the ratio information in the measurement object as the determination information along with the movement of the measuring device based on the movable part.

7. The measuring device according to any one of claims 1 to 3, wherein the ratio information includes at least one of a ratio of the second substance to the first substance of the measurement object and a peak intensity of the spectral spectrum.

8. The measuring device according to any one of claims 1 to 3, wherein the spectral spectrum includes at least one of a reflection spectrum and a transmission spectrum of the measurement object.

9. A measuring method, comprising: a step of irradiating an electromagnetic wave to a measurement object; The step of receiving the electromagnetic wave including the information of the spectroscopic spectrum of the measurement object, wherein the substance contained in the measurement object changes due to the intrusion of a foreign substance into the measurement object, and the structure of the first substance with an unstable structure is transferred to the second substance with a stable structure; The step of obtaining the actually measured spectroscopic spectrum according to the electromagnetic wave received in the step of receiving the electromagnetic wave; The step of calculating the ratio information between the first substance and the second substance according to the obtained actually measured spectroscopic spectrum; and The step of generating judgment information related to the intrusion of the foreign substance based on the calculated ratio information, The substance includes calcium carbonate, The first substance includes calcium carbonate having an orthorhombic crystal structure of vaterite, The second substance includes calcium carbonate having a rhombohedral crystal structure of calcite.

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