JP2019174443A - Method, quantitative device, and quantitative program of quantifying chloride ion concentration of concrete - Google Patents

Abstract

To enable quantifying a concentration of chloride ions in cured concrete easily, quickly, and at a low cost compared with a conventional method.SOLUTION: A chloride ion concentration of a concrete sample to be evaluated is configured to be calculated (S11) by applying a wavelength (S10) based on an emission intensity according to an emission line of the titanium/iron (S8, S9) emission intensity of chlorine calculated by using only the data of the spectral intensity of the spectral intensity data according to the wavelength (S7) for the concrete sample to be evaluated to a regression equation representing the relationship between the chloride ion concentration and chlorine emission intensity calculated by using only the combined data (S3, S4) selected based on the emission intensity according to the emission line of titanium/iron to the regression equation (S5, S6) representing the relationship between chloride ion concentration and chlorine emission intensity of the combined data (S1, S2) of chloride ion concentration of concrete samples and spectral intensity according to the wavelength.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for quantifying a chloride ion concentration of concrete, a quantification device, and a quantification program. More specifically, the present invention relates to a technique for quantifying chloride ion concentration, which is suitable for evaluating the state of corrosion (that is, salt damage) of reinforcing steel bars due to salt infiltration into concrete in reinforced concrete structures.

  When deformation such as cracks or rust dripping is found on the surface of a reinforced concrete structure, in order to confirm the soundness of the reinforced concrete structure, a hammering test or a columnar concrete sample (also called “core”) ) May be collected for physical property testing. In the case of salt damage, the chloride ion concentration is measured and the presence or absence of rebar corrosion occurrence is evaluated.

  As a conventional method for measuring the chloride ion concentration in hardened concrete, there is a potentiometric titration method (Non-Patent Document 1).

Japanese Industrial Standard JIS A 1154 2011: Test method for chloride ions contained in hardened concrete

  However, in the potentiometric titration method of Non-Patent Document 1, since it is necessary to remove the concrete core from the structure, pulverize and titrate the core, there is a problem that much labor, time and cost are required. . For this reason, it is hard to say that versatility is high.

  Therefore, the present invention provides a method for determining the concentration of chloride ions in concrete, a determination device, and a method for determining the concentration of chloride ions in hardened concrete in a simple, quick and inexpensive manner compared to conventional methods. The purpose is to provide a program.

  When the present inventor measured the concentration of chloride ions in hardened concrete based on observation of an emission spectrum (specifically, measurement by laser induced breakdown spectroscopy (also referred to as “LIBS”)), When the amount of titanium contained in the aggregate is large, the peak wavelength of the titanium emission line (specifically, 837.720 nm) and the peak wavelength of the chlorine emission line (specifically, 837.594 nm) Because they are close to each other and the spectrum intensities overlap each other, they cannot be separated into each spectrum, greatly affecting the calculation of the luminescence intensity of chlorine (specifically, the luminescence intensity of chlorine is excessively calculated) I found out.

  The present inventor also used the aggregate contained in the concrete when measuring the concentration of chloride ions in the hardened concrete based on the observation of the emission spectrum (specifically, measurement by laser induced breakdown spectroscopy). When the amount of iron is large, the peak wavelength of the iron emission line (specifically, 837.661 nm) and the peak wavelength of the chlorine emission line (specifically, 837.594 nm) are close to each other. Since the spectrum intensities overlap each other, they cannot be separated into each spectrum, greatly affecting the calculation of chlorine emission intensity (specifically, the chlorine emission intensity is excessively calculated). I found out.

  Therefore, the method of quantifying the chloride ion concentration of the concrete of the present invention is a combination data of the chloride ion concentration of the concrete sample and the spectral intensity for each wavelength other than titanium contained in the concrete and not superimposed on the chlorine emission line. Evaluation based on regression equation that expresses the relationship between chloride ion concentration and chlorine emission intensity calculated using only combined data selected based on emission intensity of titanium emission lines that do not overlap with element emission lines The wavelength selected based on the emission intensity of the titanium emission line that does not overlap with the chlorine emission line and does not overlap with the emission line of elements other than titanium contained in the concrete among the spectral intensity data by wavelength for the target concrete sample Chlorine emission intensity calculated using only data with different spectral intensities is applied to evaluate Chloride ion concentration of the concrete samples are to be calculated.

  The method for quantifying the chloride ion concentration of concrete according to the present invention, or the combination data of the chloride ion concentration of the concrete sample and the spectral intensity for each wavelength other than the iron contained in the concrete that does not overlap with the chlorine emission line. Evaluation based on regression equation that expresses the relationship between chloride ion concentration and chlorine emission intensity calculated using only combined data selected based on emission intensity of iron emission lines that do not overlap with element emission lines Wavelength selected based on emission intensity of iron emission lines that do not overlap with chlorine emission lines and do not overlap with emission lines of elements other than iron contained in concrete among the spectral intensity data for each target concrete sample. The concrete to be evaluated by applying the emission intensity of chlorine calculated using only data of another spectral intensity Chloride ion concentration of sample is to be calculated.

  Further, the concrete chloride ion concentration quantification apparatus of the present invention does not superimpose the spectral intensity data for each wavelength of the concrete sample to be evaluated with the chlorine emission line and the emission lines of elements other than titanium contained in the concrete. A means for selecting based on the emission intensity of the titanium emission line that is not superimposed, a means for calculating the emission intensity of chlorine using only the selected spectral intensity data for each wavelength, and the chloride ion concentration and wavelength of the concrete sample Of the combination data with different spectral intensities, only the combination data selected based on the emission intensity of the titanium emission line that does not overlap with the emission line of chlorine and does not overlap with the emission line of elements other than titanium contained in concrete is used. The above regression formula is used to express the relationship between the chloride ion concentration calculated and the luminescence intensity of chlorine. So that and means for calculating a chloride ion concentration of the concrete samples evaluated was by fitting the emission intensity of chlorine.

  The apparatus for quantifying the chloride ion concentration of concrete according to the present invention, or the spectral intensity data for each wavelength of the concrete sample to be evaluated does not overlap with the chlorine emission line and the emission line of elements other than iron contained in the concrete. A means for sorting based on the emission intensity of iron emission lines not superimposed, a means for calculating the emission intensity of chlorine using only the selected spectral intensity data by wavelength, and the chloride ion concentration and wavelength of the concrete sample Of the combination data with different spectral intensities, only the combination data selected based on the emission intensity of the iron emission lines that do not overlap with the emission lines of chlorine and do not overlap with the emission lines of elements other than iron contained in concrete is used. The calculated chlorine luminescence is expressed in a regression equation representing the relationship between the chloride ion concentration calculated and the luminescence intensity of chlorine. So that and means for calculating a chloride ion concentration of the concrete samples evaluated by applying a degree.

  In addition, the concrete chloride ion concentration quantification program of the present invention does not superimpose the spectral intensity data for each wavelength of the concrete sample to be evaluated with the chlorine emission line and the emission lines of elements other than titanium contained in the concrete. Sorting process based on emission intensity related to emission line of titanium not superposed, calculation process of chlorine emission intensity using only selected spectral intensity data by wavelength, chloride ion concentration and wavelength of concrete sample Of the combination data with different spectral intensities, only the combination data selected based on the emission intensity of the titanium emission line that does not overlap with the emission line of chlorine and does not overlap with the emission line of elements other than titanium contained in concrete is used. The regression equation expressing the relationship between the chloride ion concentration calculated by So that to perform a process for calculating the constant by chloride ion concentration of the concrete samples evaluated by applying the luminous intensity of chlorine to the computer.

  The quantification program for the chloride ion concentration of the concrete of the present invention, or the spectral intensity data for each wavelength of the concrete sample to be evaluated does not overlap with the chlorine emission lines and the emission lines of elements other than iron contained in the concrete. Sorting based on the emission intensity of the iron emission lines that do not overlap, processing to calculate the emission intensity of chlorine using only the selected spectral intensity data by wavelength, and the chloride ion concentration and wavelength of the concrete sample Of the combination data with different spectral intensities, only the combination data selected based on the emission intensity of the iron emission lines that do not overlap with the emission lines of chlorine and do not overlap with the emission lines of elements other than iron contained in concrete is used. The calculated chlorine ion is represented by a regression equation representing the relationship between the chloride ion concentration calculated and the luminescence intensity of chlorine. It is the process of calculating the chloride ion concentration in the concrete samples evaluated by applying the luminous intensity to be performed by the computer.

  Therefore, according to the quantification method of chloride ion concentration of concrete, the quantification device of chloride ion concentration of concrete, and the quantification program of chloride ion concentration of concrete, the data in which titanium emission lines and iron emission lines are observed strongly By removing the element, the influence of the element which becomes an obstacle to the determination in the determination of the chloride ion concentration of the concrete based on the observation of the emission spectrum is removed.

  The concrete chloride ion concentration quantification method, concrete chloride ion concentration quantification device, concrete chloride ion concentration quantification program according to the present invention include the selection of the combination data and the evaluation object of the concrete sample. The spectral intensity data for each wavelength of the concrete sample may be selected based on the value of the coefficient of variation regarding the emission intensity. In this case, since the data is selected based on the coefficient of variation related to the emission intensity related to the titanium emission line or the iron emission line, the data selection is performed appropriately.

  The concrete chloride ion concentration quantification method, concrete chloride ion concentration quantification device, and concrete chloride ion concentration quantification program of the present invention measure spectral intensities by wavelength by laser-induced breakdown spectroscopy. You may make it be what was done. In this case, the measurement of the spectral intensity for each wavelength is appropriately performed.

  According to the method for determining the chloride ion concentration of concrete, the apparatus for determining the chloride ion concentration of concrete, and the program for determining the chloride ion concentration of concrete, the determination of the chloride ion concentration of the concrete based on the observation of the emission spectrum. It is possible to eliminate the influence of the elements that hinder the inhibition of chloride, so it is possible to improve the accuracy of quantification of the chloride ion concentration, and further improve the reliability as a method of quantifying the chloride ion concentration. It becomes possible.

  The concrete chloride ion concentration quantification method, concrete chloride ion concentration quantification device, and concrete chloride ion concentration quantification program according to the present invention use a coefficient of variation regarding emission intensity in data selection. In this case, since the data can be properly selected, it is possible to ensure the accuracy of quantitative determination of the chloride ion concentration, and as a result, reliability as a quantitative method for determining the chloride ion concentration. Can be further improved.

  The concrete chloride ion concentration quantification method, concrete chloride ion concentration quantification device, and concrete chloride ion concentration quantification program of the present invention, when laser-induced breakdown spectroscopy is used, Since the spectral intensity can be measured appropriately for each wavelength, it is possible to ensure the accuracy of quantitative determination of the chloride ion concentration, and as a result, the reliability of the quantitative determination method of the chloride ion concentration. Further improvement can be achieved.

It is a flowchart explaining an example of embodiment of the determination method of the chloride ion concentration of the concrete of this invention. FIG. 3 is a functional block diagram of a concrete chloride ion concentration quantification apparatus realized by the concrete chloride ion concentration quantification method of the embodiment using the concrete chloride ion concentration quantification program. . (Example 1) It is a figure which shows an example of the comparison with the integration average spectrum intensity | strength of all the data acquired by measuring a concrete sample, and the integration average spectrum intensity | strength of only the extracted data. (Example 1) It is a figure which shows an example of the comparison of the chloride ion concentration based on all the data acquired by measuring a concrete sample, and the chloride ion concentration based only on the extracted data.

  Hereinafter, the configuration of the present invention will be described in detail based on an example of an embodiment shown in the drawings.

  FIG. 1 and FIG. 2 show an example of embodiments of a method for quantifying a concrete chloride ion concentration, a concrete chloride ion concentration quantifying device, and a concrete chloride ion concentration quantifying program according to the present invention.

  The method of quantifying the chloride ion concentration of the concrete according to the present embodiment is the combination data (S1, S2) of the chloride ion concentration of the concrete sample and the spectral intensity for each wavelength, and does not overlap with the chlorine emission line and is applied to the concrete Based on the emission intensity related to the emission line of titanium that does not overlap with the emission line of elements other than titanium included, and the emission intensity related to the emission line of iron that does not overlap with the emission line of chlorine and does not overlap with the emission line of elements other than iron contained in concrete For the concrete sample to be evaluated, the regression equation (S5, S6) representing the relationship between the chloride ion concentration calculated using only the combination data (S3, S4) selected and the luminescence intensity of chlorine is used. Among the spectral intensity data for each wavelength (S7), the brightness of elements other than titanium that do not overlap with the chlorine emission lines and are contained in concrete Are selected based on the emission intensity related to the emission line of titanium that does not overlap with the emission line of titanium and the emission intensity of iron emission line that does not overlap with the emission line of chlorine and does not overlap with the emission line of elements other than iron contained in concrete (S8, S9). ) Chlorine emission intensity (S10) calculated by using only spectral intensity data for each wavelength is applied to calculate the chloride ion concentration of the concrete sample to be evaluated (S11). 1).

  The concrete chloride ion concentration quantification method can be implemented by the concrete chloride ion concentration quantification apparatus according to the present invention. In the concrete chloride ion concentration quantification apparatus of the present embodiment, the spectral intensity data for each wavelength of the concrete sample to be evaluated is not superimposed on the chlorine emission lines and the emission lines of elements other than titanium contained in the concrete are used. A means for sorting based on the emission intensity related to the emission line of titanium that does not overlap, the emission intensity related to the emission line of iron that does not overlap with the emission line of chlorine and does not overlap with the emission line of elements other than iron contained in concrete, and selected Of the combined data of the means for calculating the luminescence intensity of chlorine using only the spectral intensity data for each wavelength and the chloride ion concentration of the concrete sample and the spectral intensity for each wavelength, it does not overlap with the chlorine emission line and the concrete. The emission intensity of the emission line of titanium that does not overlap with the emission line of elements other than titanium contained in Relationship between chloride ion concentration calculated by using only combination data selected based on emission intensity of emission lines of elements other than iron contained in concrete and emission lines of iron not superimposed and emission intensity of chlorine Means for calculating the chloride ion concentration of the concrete sample to be evaluated by applying the calculated luminescence intensity of chlorine to the regression equation representing the above.

  The concrete chloride ion concentration quantification method and the concrete chloride ion concentration quantification apparatus can be implemented or realized by executing a concrete chloride ion concentration quantification program on a computer. In the description according to the present embodiment, a concrete chloride ion concentration quantification method is implemented by executing a concrete chloride ion concentration quantification program on a computer, and a concrete chloride ion concentration quantification device is provided. The case where it is realized will be described.

  FIG. 2 shows the overall configuration of a computer 10 (which is also a concrete chloride ion concentration quantification apparatus 10 in the present embodiment) for executing the concrete chloride ion concentration quantification program 17 of the present embodiment.

  This computer 10 (concrete chloride ion concentration determination device 10) includes a control unit 11, a storage unit 12, an input unit 13, a display unit 14, and a memory 15, which are connected to each other by a signal line such as a bus. ing.

  The control unit 11 performs calculations related to the control of the entire computer 10 and the quantification of the chloride ion concentration of concrete according to the concrete chloride ion concentration quantification program 17 stored in the storage unit 12, for example, CPU ( Central processing unit).

  The storage unit 12 is a device that can store at least data and programs, and is, for example, a hard disk.

  The input unit 13 is an interface (that is, an information input mechanism) for giving at least an operator's command and various information to the control unit 11, and is, for example, a keyboard or a mouse. For example, a plurality of types of interfaces such as a keyboard and a mouse may be provided as the input unit 13.

  The display unit 14 performs drawing / display of characters, figures, images, and the like under the control of the control unit 11 and is, for example, a display.

  The memory 15 is a memory space that is a work area when the control unit 11 executes various controls and calculations, and is, for example, a RAM (abbreviation of Random Access Memory).

  Further, a signal line such as a bus or a wide area network line can be transmitted to the computer 10 as necessary, so that signals such as data and control commands can be transmitted to and received from the computer 10 (that is, input / output). The data server 20 may be connected. Further, the computer 10 may be accessible to a cloud server (not shown) via a network such as the Internet as necessary.

  Then, the control unit 11 of the computer 10 (hereinafter referred to as “concrete chloride ion concentration quantification apparatus 10”) executes the concrete chloride ion concentration quantification program 17 to execute the evaluation. Spectral intensity data by wavelength for concrete samples does not overlap with the emission line of chlorine and does not overlap with the emission line of the titanium emission line that does not overlap with the emission line of elements other than titanium contained in concrete or the emission line of chlorine In addition, the first variation coefficient calculating unit 11a and the first data selecting unit 11b that perform the process of selecting based on the emission intensity related to the bright line of the iron that does not overlap with the bright line of the element other than iron contained in the concrete are selected. A first emission intensity calculator 11c that performs processing for calculating the emission intensity of chlorine using only the spectral intensity data for each wavelength; Of the combined data of the chloride ion concentration of the concrete sample and the spectral intensity for each wavelength, the emission intensity of the titanium emission line that does not overlap with the chlorine emission line and does not overlap with the emission line of elements other than titanium contained in the concrete, Chloride ion concentration and chlorine calculated using only combination data selected based on emission intensity of iron emission lines that do not overlap with chlorine emission lines and do not overlap with elements other than iron contained in concrete A second variation coefficient calculation unit 11e, which performs a process of calculating the chloride ion concentration of the concrete sample to be evaluated by applying the calculated chlorine emission intensity to a regression equation representing the relationship between A second data selection unit 11f, a second emission intensity calculation unit 11g, and a concentration calculation unit 11h are configured.

  The procedure according to the present invention mainly includes a calibration curve creation-related process (from S1 to S6) and a chloride ion concentration determination-related process (from S7 to S11).

  And as a procedure at the time of carrying out the quantification method of the chloride ion concentration of concrete, in order to create a calibration curve, first, the chloride ion concentration of a concrete sample is measured (S1).

  When preparing a calibration curve, a plurality of concrete samples having different chloride ion concentrations are used.

  As a sample for preparing a calibration curve, for example, a concrete sample prepared by kneading sodium chloride is used.

  A concrete sample in which sodium chloride is mixed is, for example, a concrete specimen prepared by placing a predetermined amount of sodium chloride during mortar mixing, and laying and curing a plurality of fresh concretes with different concentrations of sodium chloride. Created from. By being transferred to a plurality of layers, diffusion due to the sodium chloride concentration gradient occurs until the concrete hardens, and an integrated concrete specimen is produced in which the sodium chloride concentration gradient is developed after placement.

  The concrete specimen prepared as described above is cut along a plane parallel to the sodium chloride concentration boundary surface during placement (in other words, a plane orthogonal to the sodium chloride concentration gradient after placement) A plurality of concrete samples having different sodium chloride concentrations according to the concentration gradient (referred to as “concentration measurement samples”) are created.

  A sample number is assigned to each concentration measurement sample. The sample number is uniquely and uniquely assigned to each of the concentration measurement samples so that the concentration measurement samples can be distinguished from each other and individually identified.

  A potentiometric titration method is used for each of the concentration measurement samples prepared by cutting a concrete specimen having a sodium chloride concentration gradient. For example, “Japanese Industrial Standards JIS A 1154 2011: in hardened concrete” The chloride ion concentration is measured by performing an analysis in accordance with the “test method for chloride ions contained in”.

  By measuring the chloride ion concentration using the potentiometric titration method, data on the chloride ion concentration of each sample for concentration measurement is acquired.

  As a result of the processing of S1, combination data of the sample number and the chloride ion concentration value is acquired.

  Further, the spectral intensity of the concrete sample is measured (S2).

  When the chloride ion concentration is measured using the potentiometric titration method in the processing of S1, the powder obtained by crushing the sample for concentration measurement is compression-molded, and the concentration of sodium chloride prepared in the processing of S1 is different. A plurality of samples (referred to as “LIBS samples”) corresponding to the respective concentration measurement samples are prepared.

  Each of the LIBS samples is given the same sample number as the original concentration measurement sample of the powder used when the LIBS sample is compression molded.

  By preparing the concentration measurement sample and the LIBS sample from the concrete specimen as described above, it is possible to collect many types of samples having different chloride ion concentrations from a small amount of concrete.

  For each of the LIBS samples prepared by compressing and molding the concentration measurement sample powder, the spectral intensity for each wavelength is measured using LIBS. That is, a pulsed laser beam is irradiated on the LIBS sample, the concrete is ablated, and the emission spectrum from the plasma substance is measured, and the spectrum intensity for each wavelength is specified based on this emission spectrum. . Since LIBS itself is a well-known technique, details thereof are omitted here (see, for example, Japanese Patent Application Laid-Open No. 2013-190411 and Japanese Patent No. 3500159).

  The method of laser beam irradiation is not limited to a specific mode as long as at least one laser beam is irradiated to the LIBS sample to generate plasma. For example, a single laser beam is used. It may be irradiated, or two laser beams may be irradiated coaxially, or one may be irradiated obliquely or perpendicularly to the normal direction of the concrete. good.

  In this embodiment, laser irradiation and emission spectrum measurement are performed a plurality of times for one LIBS sample. However, laser irradiation and emission spectrum measurement may be performed only once for one LIBS sample.

  By measuring the emission spectrum using LIBS, spectral intensity data for each wavelength for each laser irradiation of the LIBS sample (in other words, the number of times of laser irradiation) is acquired.

  As a result of the processing of S1 and S2, the combination data of the chloride ion concentration value and the spectral intensity by wavelength of each concrete sample (that is, the sample for concentration measurement, the sample for LIBS prepared from the sample for concentration measurement) It is obtained as data for each laser irradiation (in other words, data for the number of times of laser irradiation).

  In this embodiment, a plurality of combination data of the sample number assigned to the concentration measurement sample / LIBS sample, the value of the chloride ion concentration, and the spectrum intensity for each wavelength are accumulated and recorded as data for each laser irradiation. The file is stored (in other words, saved) in the data server 20 as the concentration intensity combination database 21.

  Next, the coefficient of variation regarding the emission intensity related to the specific element is calculated based on the spectral intensity for each wavelength acquired by the process of S2 (S3).

  In the present invention, a chlorine (Cl) emission line (specifically, the peak wavelength is 837.594 nm when the chloride ion concentration is measured based on observation of an emission spectrum (for example, measurement by laser-induced breakdown spectroscopy). ) And titanium (Ti) emission line (specifically, peak wavelength is 837.720 nm) and iron (Fe) emission line (specifically, peak wavelength is 837.661 nm). Based on the inventor's knowledge that the accuracy decreases, attention is paid to the titanium emission line and the iron emission line. In the description of the present invention, titanium and iron are referred to as “specific elements”.

  Specifically, paying attention to the titanium emission line that does not overlap with the chlorine emission line and does not overlap with the emission line of elements other than titanium contained in concrete (in other words, the titanium emission line that can be observed as titanium alone), The spectral intensity data in which the titanium emission line is observed strongly (in other words, the data of the laser irradiation times in which the titanium emission line is observed strongly) is excluded from the analysis target. This operation is equivalent to extracting only data obtained by measuring a portion where the emission intensity of titanium is weak, that is, a portion where the titanium content is relatively small, from the spectral intensity data obtained by the processing of S2. To do.

  As a result, when the emission intensity of titanium calculated by focusing on the emission line of titanium alone is strong, the influence of the emission line of titanium, which may overlap with the emission line of chlorine, on the emission intensity of chlorine (specifically, The emission intensity of chlorine is considered to be excessively calculated). By removing the data from the analysis, the influence of titanium is removed and the emission intensity of chlorine is accurately calculated accordingly. It becomes like this.

  Table 1 below shows specific titanium emission lines that do not overlap with chlorine emission lines and do not overlap with elements other than titanium contained in concrete (in other words, titanium emission lines that can be observed as titanium alone). (Strictly speaking, there are two types of emission lines, atomic beams and ion beams, for each element, but these are collectively treated as emission lines for each element). The bright lines listed in Table 1 below are called “titanium-focused bright lines”.

  Also, pay attention to the iron emission line that does not overlap with the chlorine emission line and does not overlap with the emission line of elements other than iron contained in concrete (in other words, the iron emission line that can be observed as iron alone), and the iron emission line. The spectral intensity data (in other words, the data of the laser irradiation times in which the iron emission line is strongly observed) is excluded from the analysis target. This operation is equivalent to extracting only data obtained by measuring a portion where the emission intensity of iron is weak, that is, a portion where the iron content is relatively small, from the spectral intensity data obtained by the processing of S2. To do.

  As a result, when the emission intensity of iron calculated by paying attention to the emission line of iron alone is strong, the influence of the emission line of iron, which may overlap with the emission line of chlorine, on the emission intensity of chlorine (specifically, Is considered to be over-calculated), the data is excluded from the analysis and the effect of iron is removed, and the emission intensity of chlorine is accurately calculated accordingly. It becomes like this.

  Table 2 below shows the iron emission lines that do not overlap with the emission lines of chlorine and do not overlap with the emission lines of elements other than iron contained in concrete (in other words, the iron emission lines that can be observed as iron alone). (Strictly speaking, there are two types of emission lines, atomic beams and ion beams, for each element, but these are collectively treated as emission lines for each element). The bright lines listed in Table 2 below are called “iron-focused bright lines”.

  In order to select the combination data acquired by the processes of S1 and S2, the coefficient of variation CV regarding the emission intensity defined by the following Equation 1 is obtained for each spectral intensity for each wavelength obtained for each laser irradiation.

In Equation 1, CV: coefficient of variation regarding emission intensity, N: number of data points used in obtaining CV (in other words, number of wavelengths), λ: wavelength, I (λ): spectral intensity at wavelength λ, I _B (λ): Represents a spectral value corresponding to a wavelength λ on a straight line passing through spectral intensity positions at wavelengths λ ₁ and λ ₂ or at wavelengths λ ₃ and λ ₄ , respectively.

The denominator on the right side of Equation 1 is the maximum difference between the spectral intensity I (λ) for each wavelength λ and the spectral value I _B (λ) on the baseline in the wavelength λ range from λ ₁ to λ _2. Value (symbol: max).

The wavelengths λ ₁ and λ ₂ are at both ends of the emission line of the specific element related to the calculation of the coefficient of variation CV (in other words, both ends of the broadening of the emission line related to the specific element and both ends of the emission line wavelength range of the specific element). Corresponding wavelength.

The straight line passing through the spectral intensity positions at the wavelengths λ ₁ and λ ₂ related to Equation 1 corresponds to the baseline of the spectrum.

In addition, the numerator on the right side of Equation 1 represents the difference between the spectral intensity I (λ) for each wavelength λ in the wavelength λ range from λ ₃ to λ ₄ and the spectral value I _B (λ) on the baseline. This is the square root of the value obtained by dividing the sum of the squares by the number N of wavelengths λ included in the wavelength λ ₃ to λ ₄ range.

The wavelengths λ ₃ and λ ₄ are wavelengths corresponding to both ends of the wavelength region where no bright line is observed in the wavelength region close to the bright line of the specific element.

The straight line passing through the spectral intensity positions at the wavelengths λ ₃ and λ ₄ related to Equation 1 corresponds to the baseline of the spectrum.

Note that the numerator on the right side of Equation 1 is defined as the standard deviation of the spectral intensity in the emission line wavelength region of a specific element when a sample having a specific element (ie, titanium, iron) content of zero is measured. Corresponds to the original definition. However, for example, the aggregate contains a slight amount of titanium, and it is not easy to prepare a sample having a composition equivalent to that of concrete and having zero titanium content. For this reason, in Formula 1, the standard deviation of the emission intensity using the spectrum in the wavelength region where the bright line is not observed in the wavelength region close to the bright line of titanium (that is, the range of λ ₃ to λ ₄ specifically in Formula 1). Is to be evaluated.

Here, Formula 1 may be changed as long as it is a definition of a coefficient of variation defined by statistics, that is, a value obtained by dividing a standard deviation of a certain signal intensity by its arithmetic average. Specifically, the denominator of Equation 1 corresponds to the intensity of the peak of the bright line, but may be an average value of the bright line, that is, mean {I (λ) −I _B (λ), λ = λ _{1 to} λ ₂ }. If a concrete sample containing no titanium is prepared, λ ₃ and λ ₄ may be λ ₁ and λ ₂ .

Furthermore, the variation coefficient as an index for selecting the combination data is not limited to the variation coefficient CV defined by Equation 1, but in a specific wavelength range (from the above-described wavelengths λ ₁ to λ ₂₎ . If it is an index that can determine whether or not the emission intensity in the corresponding wavelength range varies with respect to the emission intensity in a predetermined wavelength range (wavelength range corresponding to the above-mentioned wavelengths λ ₃ to λ ₄ ), It may be defined in any way (in other words, calculated).

  The coefficient of variation CV is calculated for the selected bright line after at least one of the bright lines of titanium attention is selected, and for the selected bright line after selection of at least one of the bright lines of iron focus. Calculated.

  At this time, only the titanium noticed bright line (at least one of them) may be selected, or only the iron noticed bright line (at least one of them) may be selected. That is, only one of the titanium-focused bright line and the iron-focused bright line may be selected to calculate the variation coefficient CV.

  In the present embodiment, the first variation coefficient calculation unit 11a of the control unit 11 reads the spectral intensity data for each wavelength of the combination data recorded in the concentration intensity combination database 21 stored in the data server 20, For each combination data (in other words, for each laser irradiation), the value of the coefficient of variation CV is calculated by Equation 1.

  Then, the value of the variation coefficient CV calculated for each combination data recorded in the concentration intensity combination database 21 by the first variation coefficient calculation unit 11a is associated with each of the combination data, in other words. It is added to each of the combination data and included in the concentration intensity combination database 21.

  The concentration intensity combination database 21 is the data server 20 as a data file in which a plurality of combination data of the sample number, chloride ion concentration value, spectral intensity for each wavelength, and variation coefficient CV value are accumulated and recorded by the processing of S3. Saved in.

  Next, combination data is selected based on the variation coefficient regarding the light emission intensity calculated by the process of S3 (S4).

  In the present embodiment, the first data selection unit 11b of the control unit 11 reads combination data from the density intensity combination database 21 to which information on the variation coefficient is added in the process of S3, and the value of the variation coefficient CV is confirmed. The

  Then, when the value of the coefficient of variation CV is equal to or greater than a certain value, the first data selection unit 11b records and stores the combination data (that is, data for one laser irradiation) in the data file and extracts the combination. It is stored (in other words, saved) as the database 22 in the data server 20. The value of the coefficient of variation CV used as a data selection standard (that is, the “constant value” in the above) is called a “selection threshold”.

  That is, among the combination data recorded in the density intensity combination database 21 by the processing up to S3, the combination data whose variation coefficient CV is equal to or greater than the selection threshold is recorded in the extraction combination database 22, while the variation coefficient CV. Combination data whose value is smaller than the selection threshold is not recorded in the extracted combination database 22.

  The selection threshold value Ts is not limited to a specific value. Since the emission intensity at the emission line of titanium is strong, the emission line of titanium with a peak wavelength of 837.720 nm is the emission line of chlorine (specifically, the peak The influence of the superposition of the wavelength of 837.594 nm on the emission intensity of chlorine is suppressed, and since the emission intensity of the iron-focused emission line is strong, the iron emission line having a peak wavelength of 837.661 nm is the chlorine emission line. (Specifically, it is appropriately set to an appropriate value in consideration of suppressing the influence on the luminescence intensity of chlorine due to superposition with a peak wavelength of 837.594 nm).

  Specifically, for example, the selection threshold value Ts may be set to any value within a range of about 0 to 2 (that is, approximately 0 ≦ Ts ≦ 2). Is preferably set to any value in the range (that is, 0 <Ts ≦ 1), and most preferably set to about 1 (that is, Ts≈1, particularly Ts = 1).

  The selection threshold is set in consideration of the threshold corresponding to titanium set to suppress the influence of titanium on the emission intensity of chlorine and the suppression of the influence of iron on the emission intensity of chlorine. A threshold value corresponding to the iron may be prepared.

  Next, the luminescence intensity of chlorine is calculated based on the spectral intensity for each wavelength acquired by the process of S2 for each combination data selected by the process of S4 (S5).

  The emission intensity of chlorine is determined from the peak of the emission line to the base line after a straight line connecting both ends of the emission line of the chlorine (specifically, the peak wavelength is 837.594 nm) is defined as the baseline of the emission line. Is calculated by calculating the signal strength of.

  In the present embodiment, the first emission intensity calculation unit 11c of the control unit 11 reads the combination data recorded in the extraction combination database 22 stored in the data server 20 in the process of S4, and the sample number is the same. The spectrum emission intensity for each wavelength of the combination data (that is, the chloride ion concentration is the same) is integrated for each wavelength and averaged, and the luminescence intensity of chlorine is calculated.

  Then, the first emission intensity calculation unit 11c stores in the memory 15 the combination data of the chloride ion concentration value and the chlorine emission intensity value.

  Next, the combination data of the chloride ion concentration and the luminescence intensity of chlorine acquired by the processing up to S5 is used to calculate an expression representing the relationship between the two (S6).

  In the present embodiment, the regression equation calculation unit 11d of the control unit 11 reads the combination data of the chloride ion concentration value and the chlorine emission intensity value stored in the memory 15 in the process of S5, and the combination data Is used to calculate a regression equation that expresses the relationship between chloride ion concentration and the emission intensity of chlorine, in other words, an approximate expression that expresses the chloride ion concentration dependence of the emission intensity of chlorine. .

  The method of regression (in other words, the type of regression equation) is not limited to a specific one, and may be linear regression or curved regression. Further, the regression analysis method (in other words, the regression equation / regression coefficient calculation method) is not limited to a specific method, and specifically, for example, a least square method may be used.

  Then, the regression equation calculation unit 11d records the parameters related to the calculated regression equation in a data file and stores them in the storage unit 12 as the regression equation parameter file 18.

  The regression equation calculated in the process of S6 functions as a calibration curve for obtaining the chloride ion concentration from the emission intensity of the chlorine emission line obtained by measuring the emission spectrum for the sample whose chloride ion concentration is unknown.

  Next, in order to quantify the chloride ion concentration of the evaluation object, the spectrum intensity of the concrete sample is measured (S7).

  In the processing of S7, for example, concrete samples (referred to as “evaluation target samples”) collected from various concrete frames or the like which are targets for evaluation of the corrosion status of reinforcing bars are used.

  The shape or size of the sample to be evaluated is not limited to a specific shape or size, for example, a shape or size having a dimension in the depth direction corresponding to the depth to be analyzed from the concrete body surface or The shape and size that can be collected from the concrete frame to be evaluated are taken into consideration, and the like can be appropriately adjusted.

  Specifically, for example, the core collected in accordance with the concept such as the dimensions of the specimen in “Japanese Industrial Standards JIS A 1107: Core sampling method and compressive strength test method” is evaluated in the processing of S7. It can be used as a target sample.

  Here, the depth direction from the concrete surface in the evaluation target concrete frame from which the evaluation target sample is collected is referred to as “sample axial direction”.

  Then, for each sample to be evaluated, LIBS is used to measure the spectral intensity for each wavelength. The measurement of the spectrum intensity is performed in the same manner as the process of S2 described above.

  In this embodiment, the spectrum intensity is measured by acquiring the distribution of the spectrum intensity on the surface of the sample to be evaluated in the direction of the sample axis, in other words, the change in the spectrum intensity due to the difference in depth from the concrete body surface. In order to achieve this, a plurality of positions (that is, a plurality of depths with respect to the depth from the surface of the concrete body) in a plurality of positions with respect to the sample axial direction and a plurality of positions with the same position with respect to the sample axial direction ( In other words, it is performed at a plurality of positions where the depth from the surface of the concrete frame is the same. However, laser irradiation and emission spectrum measurement may be performed without paying attention to the position in the sample axis direction, and laser irradiation and emission spectrum measurement may be performed at a certain position in the sample axis direction. The measurement may be performed only once.

  At this time, a plurality of positions in a band-shaped range having a predetermined width in a direction orthogonal to the sample axial direction are bundled as a plurality of positions in, for example, a central position (in other words, depth) of the band-shaped range. You may do it.

  The measurement of the spectral intensity relating to the sample to be evaluated may be performed on the cut surface by cutting the sample to be evaluated in the axial direction of the sample, or may be performed on the outer peripheral surface of the sample to be evaluated. Anyway.

  By measuring the emission spectrum using LIBS, the position of the sample to be evaluated in the direction of the sample axis for each laser irradiation (in other words, the number of times of laser irradiation) (that is, the depth from the surface of the concrete frame) and Combination data with spectral intensity for each wavelength is acquired.

  In the present embodiment, a data file in which a plurality of combination data of the position in the sample axis direction and the spectrum intensity for each wavelength for the sample to be evaluated is stored as data for each laser irradiation is recorded as the position intensity combination database 23. It is stored (in other words, saved) in the data server 20.

  Next, the coefficient of variation relating to the emission intensity related to the specific element is calculated based on the spectral intensity for each wavelength acquired by the process of S7 (S8).

  As for the spectral intensity data related to the sample to be evaluated, in order to select these spectral intensity data, each spectral intensity for each wavelength obtained for each laser irradiation is specified in the same manner as the above-described processing of S3 for the LIBS sample. A variation coefficient CV related to the emission intensity related to the element is calculated by Equation 1.

  The emission lines of the specific elements involved in the calculation of the coefficient of variation CV for the sample to be evaluated are the same as the “titanium emission line” and the “iron emission line” in the description relating to the processing of S3 described above. In addition, the coefficient of variation CV related to the sample to be evaluated is basically calculated for the same bright line (one or more) as the bright line selected in the process of S3 among the bright lines of titanium and bright lines of iron. , It may be calculated for a bright line (one or more) different from the bright line selected in the process of S3.

  In this embodiment, the second variation coefficient calculation unit 11e of the control unit 11 reads the spectral intensity data for each wavelength of the combination data recorded in the position intensity combination database 23 stored in the data server 20, For each combination data (in other words, for each laser irradiation), the value of the coefficient of variation CV is calculated by Equation 1.

  Then, after the second coefficient of variation calculation unit 11e associates the value of the coefficient of variation CV calculated for each combination data recorded in the position intensity combination database 23 with each of the combination data, In other words, after being added to each of the combination data, it is stored in the memory 15.

  By the process of S8, combination data of the position in the sample axis direction, the spectral intensity for each wavelength, and the value of the variation coefficient CV is stored in the memory 15.

  Next, combination data is selected based on the variation coefficient regarding the light emission intensity calculated by the process of S8 (S9).

  As for the spectral intensity data regarding the sample to be evaluated, the coefficient of variation CV regarding the emission intensity related to the specific element for each of the spectral intensities by wavelength obtained for each laser irradiation, as in the above-described processing of S4 for the LIBS sample. Sorting is performed based on the value of.

  In the present embodiment, the second data selection unit 11f of the control unit 11 adds the information related to the coefficient of variation in the process of S8 and then reads the combination data stored in the memory 15, and the value of the coefficient of variation CV is changed. It is confirmed.

  When the value of the coefficient of variation CV is equal to or greater than the selection threshold, the combination data (that is, data for one laser irradiation) is recorded and accumulated in the data file by the second data selection unit 11f, and the selection combination. It is stored in the memory 15 as a data (collection).

  That is, among the combination data stored in the memory 15 by the processing of S7 and S8, the combination data whose variation coefficient CV is equal to or greater than the selection threshold value is stored in the memory 15 as (a set of) selection combination data. The combination data whose variation coefficient CV is smaller than the selection threshold is not stored in the memory 15 as the selection combination data (set).

  The concept regarding the setting of the selection threshold value used in the process of S9 is the same as the concept of setting the selection threshold value Ts in the description related to the process of S4 described above. The selection threshold value is basically the same value as the value set in the process of S4, but a value different from the value set in the S4 process may be used.

  Next, the luminescence intensity of chlorine is calculated based on the spectrum intensity acquired by the process of S7 for each of the combination data selected by the process of S9 (S10).

  The luminescence intensity of chlorine is calculated and calculated by the same method as the process of S5.

  In the present embodiment, the selected combination data stored in the memory 15 in the process of S9 is read by the second emission intensity calculation unit 11g of the control unit 11 and the position in the sample axial direction is the same. The spectral intensity for each wavelength of the combination data is integrated for each wavelength and averaged, and then the luminescence intensity of chlorine is calculated.

  Then, the combination data of the position in the sample axial direction and the value of the luminescence intensity of chlorine is stored in the memory 15 by the second luminescence intensity calculation unit 11g.

  Next, the chloride ion concentration is calculated using the regression equation calculated by the process of S6 and the luminescence intensity of chlorine calculated by the process of S10 (S11).

  In the present embodiment, the concentration calculation unit 11h of the control unit 11 reads parameters relating to the regression equation from the regression equation parameter file 18 stored in the storage unit 12 in the process of S6, and stores them in the memory 15 in the process of S10. The combined data is read.

  Subsequently, for each combination data read by the concentration calculation unit 11h, the value of the luminescence intensity of chlorine in the combination data is applied to the regression equation (in other words, substituted), and the chloride ion concentration Is calculated. By this calculation, combined data of the position in the sample axial direction and the chloride ion concentration is obtained.

  By the above treatment, the chloride ion concentration by depth from the surface of the concrete frame can be quantitatively obtained.

  And the control part 11 displays the chloride ion density according to the depth from the concrete frame surface calculated by the above-mentioned processing, for example on the display part 14, or saves it in the storage part 12 as a data file. The processing related to the position-intensity combination database 23 regarding the concrete sample (that is, the evaluation target sample) that has been handled so far is terminated (END).

  According to the method of quantifying the chloride ion concentration of concrete, the quantification device of the chloride ion concentration of concrete, and the quantification program of the chloride ion concentration of concrete, the titanium emission line and the iron emission line are strongly observed. As a result, the influence of the elements that hinder the determination can be removed in the determination of the chloride ion concentration of the concrete based on the observation of the emission spectrum. For this reason, it becomes possible to improve the quantification accuracy of the chloride ion concentration, and it is possible to improve the reliability as a quantification method of the chloride ion concentration.

  Although the above-described embodiment is an example of a preferred embodiment for carrying out the present invention, the embodiment of the present invention is not limited to the above-described embodiment, and the present invention is not limited to the scope of the present invention. The invention can be variously modified.

  For example, in the above-described embodiment, a concrete sample mixed with sodium chloride is used in the process of creating a calibration curve, but the sample that can be used in the process of creating a calibration curve is that in the above-described embodiment. It is not limited to this, and any concrete sample containing sodium chloride may be used. Specifically, for example, a concrete sample sprayed with a sodium chloride solution may be used. A concrete sample sprayed with a sodium chloride solution can be prepared, for example, by exposing a concrete specimen after placement and curing to a salt spray environment. Specifically, for example, a specimen is placed inside a test tank where the ambient temperature is kept at 40 ° C. and the relative humidity is kept at 90%, and 45 liters of NaCl 3% aqueous solution is sprayed once every 24 hours for 3 minutes. A concrete sample with a known concentration can be prepared by exposing it to the environment for about 140 to 150 days. You may make it use the concrete sample extract | collected from the actual concrete structure as a sample used in the process of preparation of a calibration curve.

  In the above-described embodiment, a concrete sample (that is, a sample for concentration measurement, a sample for LIBS) is created from an integral concrete specimen in which a sodium chloride concentration gradient is developed after placement in the calibration curve creation process. However, the sample preparation method that can be used in the process of preparing the calibration curve is not limited to that in the above-described embodiment, and may be a method in which concrete samples having different sodium chloride concentrations can be prepared. Anything is acceptable. Specifically, for example, the amount of sodium chloride to be mixed may be adjusted to be different, or the concentration of the sodium chloride solution to be sprayed may be adjusted to be different.

  In the above-described embodiment, the chloride ion concentration of the concrete sample is measured by the potentiometric titration method in the process of creating the calibration curve. However, the chloride ion concentration measuring method is limited to the potentiometric titration method. Any method may be used as long as the chloride ion concentration of the concrete sample can be measured.

  In the above embodiment, the emission spectrum of the concrete sample is measured by laser induced breakdown spectroscopy (LIBS). However, the method of measuring the emission spectrum is not limited to LIBS, and the concrete sample is measured. Any method may be used as long as the emission spectrum can be measured. Specifically, for example, spark-induced breakdown spectroscopy (also referred to as “SIBS” (abbreviation of Spark-Induced Breakdown Spectroscopy)) may be used.

  In the above-described embodiment, the data selection in the processes of S3 and S4 and the data selection in the processes of S8 and S9 are performed based on the variation coefficient CV related to the emission intensity. The index used and used is not limited to the coefficient of variation CV in the above-described embodiment, and any index can be used as long as it can select data in which titanium emission lines and iron emission lines are strongly observed. It may be something like this. Specifically, for example, the emission intensity of titanium or the emission intensity of iron itself may be used as an index.

  In the above-described embodiment, attention is paid to both the titanium emission line and the iron emission line. However, attention to both the titanium emission line and the iron emission line is not essential in the present invention. For example, if the aggregate contained in concrete has a particularly large amount of titanium, it may be possible to focus only on the titanium emission line, or if the aggregate contained in concrete has a particularly large amount of iron. You may make it pay attention only to the bright line of iron.

  In the above-described embodiment, the calibration curve is created by the processing from S1 to S6. However, every time the determination of the chloride ion concentration of the concrete sample / evaluation target sample is performed, the calibration curve is generated. The creation is not an essential configuration in the present invention, and a calibration curve that has already been created may be used.

  The example which verified the validity of the quantitative determination method of the chloride ion concentration of the concrete concerning this invention is described using FIG.3 and FIG.4.

  The value of the coefficient of variation CV related to the spectral intensity obtained by integrating and averaging all the spectral data obtained by measuring the concrete sample and the emission intensity of the titanium emission line (specifically, 841236 nm) The result was as shown in FIG. 3 by comparing the spectral intensities obtained by integrating and averaging only the extracted spectral data.

  From the results shown in FIG. 3, it is confirmed that the emission intensity of titanium is almost zero in the spectrum obtained by integrating the extracted data and averaging, that is, the spectrum intensity data in which the emission line of titanium is observed strongly. It was confirmed that it was properly removed.

Note that the wavelength lambda ₁ and lambda ₂ in Fig. 3, which corresponds respectively to the _two wavelengths lambda ₁ and lambda in Equation 1, the bright lines (specifically titanium according to the calculation of the coefficient of variation CV, 841 .236 nm).

Also, the wavelength lambda ₃ and lambda ₄ in FIG. 3, which corresponds respectively to the ₄ wavelength lambda ₃ in Equation 1 lambda, bright lines observed at the wavelength region close to the emission line of titanium as a specific element It is a wavelength corresponding to both ends of the wavelength range that is not performed.

  The value of the coefficient of variation CV related to the emission intensity of the chloride ion concentration and the titanium emission line (specifically, 841.2236 nm) calculated using all the spectral data obtained by measuring the concrete sample. The result shown in FIG. 4 was obtained by comparing the value of the chloride ion concentration calculated using only the spectral data extracted when 1.

  When all the spectrum data is integrated without extracting data, and the chloride ion concentration is obtained by a calibration curve method, a potentiometric titration method (specifically, Japanese Industrial Standards JIS A 1154 2011: Hardened concrete is used. It is confirmed that it is higher than the measurement result of the chloride ion concentration by the chloride ion test method), that is, the emission intensity of chlorine is excessive due to the influence of the emission line of the specific element superimposed on the emission line of chlorine. It was confirmed that it would be calculated.

  On the other hand, when the chloride ion concentration was obtained using only the extracted data, the result obtained by the potentiometric titration method was in good agreement with CV = 1.

  From the above, it was confirmed that according to the method for quantifying the chloride ion concentration of concrete according to the present invention, the chloride ion concentration is appropriately calculated.

10 Computer / Concrete Chloride Ion Determination Device 11 Control Unit 11a First Variation Coefficient Calculation Unit 11b First Data Selection Unit 11c First Luminescence Intensity Calculation Unit 11d Regression Equation Calculation Unit 11e Second Variation Coefficient Calculation Unit 11f Second data selection unit 11g Second emission intensity calculation unit 11h Concentration calculation unit 12 Storage unit 13 Input unit 14 Display unit 15 Memory 17 Quantitative program for chloride ion concentration of concrete 18 Regression parameter file 20 Data server 21 Concentration intensity combination database 22 Extraction combination database 23 Position intensity combination database

Claims (12)

  Based on the emission intensity of the titanium emission line that does not overlap with the chlorine emission line and does not overlap with the emission line of elements other than titanium contained in the concrete among the combined data of the chloride ion concentration of the concrete sample and the spectral intensity by wavelength. The regression equation that expresses the relationship between the chloride ion concentration calculated using only the selected combination data and the luminescence intensity of chlorine, and in the spectral intensity data by wavelength for the concrete sample to be evaluated, Of chlorine that is calculated by using only the spectral intensity data for each wavelength selected based on the emission intensity of the titanium emission line that does not overlap with the emission line of elements other than titanium contained in the concrete. The chloride ion concentration of the concrete sample to be evaluated is calculated by applying the luminescence intensity. Quantitative methods of chloride ion concentration of concrete characterized by.   Based on the emission intensity of the iron emission line that does not overlap with the chlorine emission line and does not overlap with the emission line of elements other than iron contained in the concrete among the combined data of chloride ion concentration and spectral intensity by wavelength of the concrete sample The regression equation that expresses the relationship between the chloride ion concentration calculated using only the selected combination data and the luminescence intensity of chlorine, and in the spectral intensity data by wavelength for the concrete sample to be evaluated, Of chlorine that is calculated by using only spectral intensity data for each wavelength selected based on the emission intensity of iron emission lines that do not overlap with the emission lines of elements other than iron contained in concrete. The chloride ion concentration of the concrete sample to be evaluated is calculated by applying the luminescence intensity. Quantitative methods of chloride ion concentration of the cleat.   2. The selection of the combination data for the concrete sample and the selection of the spectral intensity data for each wavelength for the concrete sample to be evaluated are performed based on the value of the coefficient of variation relating to the emission intensity. Or the quantification method of the chloride ion concentration of concrete of 2 description.   3. The method for quantifying the chloride ion concentration of concrete according to claim 1 or 2, wherein the spectral intensity for each wavelength is measured by laser-induced breakdown spectroscopy.   Means for selecting spectral intensity data for each wavelength of the concrete sample to be evaluated based on the emission intensity of the titanium emission line that does not overlap with the chlorine emission line and does not overlap with the emission line of elements other than titanium contained in the concrete; The method of calculating the luminescence intensity of chlorine using only the selected spectral intensity data for each wavelength and the combined data of the chloride ion concentration of the concrete sample and the spectral intensity for each wavelength are superimposed on the chlorine emission line. Between the chloride ion concentration calculated using only the combination data selected based on the emission intensity of the titanium emission line that does not overlap with the emission line of elements other than titanium contained in the concrete and the emission intensity of chlorine. By applying the luminescence intensity of the chlorine calculated in the regression equation representing the relationship of Pull quantification device of chloride ion concentration of the concrete, characterized in that it comprises a means for calculating a chloride ion concentration.   Means for selecting spectral intensity data for each wavelength of the concrete sample to be evaluated based on the emission intensity of the iron emission line that does not overlap with the emission line of chlorine and does not overlap with the emission line of elements other than iron contained in the concrete; The method of calculating the luminescence intensity of chlorine using only the selected spectral intensity data for each wavelength and the combined data of the chloride ion concentration of the concrete sample and the spectral intensity for each wavelength are superimposed on the chlorine emission line. Between the chloride ion concentration calculated by using only the combination data selected based on the emission intensity of the iron emission lines not overlapped with the emission lines of elements other than iron contained in the concrete and the emission intensity of chlorine. By applying the calculated luminescence intensity of chlorine to the regression equation representing the relationship of Quantification device of chloride ion concentration of the concrete, characterized in that it comprises a means for calculating the emissions concentration.   The selection of the combination data for the concrete sample and the selection of the spectral intensity data for each wavelength for the concrete sample to be evaluated are performed based on the value of the coefficient of variation regarding the emission intensity. 6. The quantitative determination apparatus for chloride ion concentration of concrete according to 6.   The apparatus for quantifying the chloride ion concentration of concrete according to claim 5 or 6, wherein the spectral intensity for each wavelength is measured by laser-induced breakdown spectroscopy.   A process of selecting spectral intensity data for each wavelength of the concrete sample to be evaluated based on the emission intensity of the titanium emission line that does not overlap with the chlorine emission line and does not overlap with the emission line of elements other than titanium contained in the concrete; The process of calculating the emission intensity of chlorine using only the selected spectral intensity data for each wavelength and the combined data of the chloride ion concentration of the concrete sample and the spectral intensity for each wavelength are superimposed on the chlorine emission line. Between the chloride ion concentration calculated using only the combination data selected based on the emission intensity of the titanium emission line that does not overlap with the emission line of elements other than titanium contained in the concrete and the emission intensity of chlorine. By applying the luminescence intensity of the chlorine calculated in the regression equation representing the relationship of Concrete chloride ion concentration quantification program of which it is characterized by causing the processing for calculating the chloride ion concentration of the pull to the computer.   A process of selecting spectral intensity data for each wavelength of the concrete sample to be evaluated based on the emission intensity of the iron emission line that does not overlap with the emission line of chlorine and does not overlap with the emission line of elements other than iron contained in the concrete; The process of calculating the emission intensity of chlorine using only the selected spectral intensity data for each wavelength and the combined data of the chloride ion concentration of the concrete sample and the spectral intensity for each wavelength are superimposed on the chlorine emission line. Between the chloride ion concentration calculated by using only the combination data selected based on the emission intensity of the iron emission lines not overlapped with the emission lines of elements other than iron contained in the concrete and the emission intensity of chlorine. By applying the calculated luminescence intensity of chlorine to the regression equation representing the relationship of Concrete chloride ion concentration quantification program of which it is characterized by causing the processing for calculating the emission concentration in the computer.   The selection of the combination data for the concrete sample and the selection of the spectral intensity data for each wavelength of the concrete sample to be evaluated are performed based on the value of the coefficient of variation relating to the emission intensity. 10. A quantitative determination program for chloride ion concentration of concrete according to 10.   11. The program for quantifying the chloride ion concentration of concrete according to claim 9 or 10, wherein the spectral intensity for each wavelength is measured by laser-induced breakdown spectroscopy.