Amorphous phase quantitative analysis apparatus, amorphous phase quantitative analysis method, and computer program

Abstract

To provide an amorphous phase quantitative analyzer, an amorphous phase quantitative analysis method, and a computer program that can quantify an amorphous phase in a sample containing both crystalline and amorphous phases.SOLUTION: An amorphous phase quantitative analyzer for quantifying an amorphous phase in a sample containing both crystalline and amorphous phases is characterized that it comprises a sample preparation part for measurement that prepares a sample for measurement by adding a standard substance to the sample, an x-ray diffraction measurement part that measures a quantitative value Xa of the crystal phase and a quantitative value Xs of the standard substance contained in the sample for measurement by an x-ray diffraction method, an arithmetic processing part that quantifies a mass fraction Mb of the amorphous phase by calculating a mass fraction Ma of the crystalline phase based on a mass fraction Ms of the standard substance, the quantitative value Xs of the standard substance, and the quantitative value Xa of the crystalline phase, and an output part that displays and outputs a result of the quantitative analysis of the sample.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an amorphous phase quantitative analyzer, an amorphous phase quantitative analysis method, and a computer program. More specifically, it relates to an amorphous phase quantitative analyzer, an amorphous phase quantitative analysis method, and a computer program capable of quantifying an amorphous phase contained in a sample including a phase that cannot be quantified by X-ray diffraction method, i.e., a non-quantifiable phase.

Background Art

[0002] So-called refractories are used as linings for equipment that performs melting treatment of raw materials and heat treatment of materials in industries such as the ceramic industry, metallurgical industry, chemical industry, machinery industry, and glass industry. Refractories are also mainly used in steelmaking equipment such as blast furnaces (smelting furnaces), hot blast furnaces, coke ovens, converters, and electric furnaces for steel. Although amorphous raw materials may be added to refractories for the purpose of improving thermal shock resistance, when heated during use, a part of them may change to a crystalline state, and in that case, the thermal shock resistance of the refractory decreases. Therefore, there is a need to accurately quantify the amorphous ratio of the refractory after it has received heat.

[0003] As a method for quantitatively analyzing the crystal phase contained in such a refractory as a sample, the powder X-ray diffraction (XRD) Rietveld method has become popular. The powder X-ray diffraction (XRD) Rietveld method is a quantitative analysis method that can only be used when the sample is a crystalline compound. When the sample contains an amorphous phase, it is impossible to directly perform quantitative analysis of the crystal phase and amorphous phase contained in the sample by applying the powder X-ray diffraction (XRD) Rietveld method. It is difficult to analyze the powder diffraction pattern (amorphous halo) of the amorphous phase using the powder X-ray diffraction (XRD) Rietveld method.

[0004] Therefore, a method for quantifying amorphous phases has been proposed that allows for the indirect measurement of amorphous mass by preparing a sample mixed with a known amount of internal standard material and analyzing the sample mixed with the internal standard material using powder X-ray diffraction (XRD) Rietveld method. In other words, this method for quantifying amorphous phases involves adding a standard material (SRM) as an internal standard to a sample containing both crystalline and amorphous phases, and performing a quantitative analysis of the amorphous phase based on the powder diffraction pattern of the standard material. This method for quantifying amorphous phases utilizes the fact that the added standard material (SRM) is known.

[0005] In the above method for quantifying the amorphous phase, when the crystalline phase contained in the sample is calculated as a percentage, the amorphous phase is excluded according to the amount of amorphous phase contained in the sample, and the calculation is performed as if the sample were composed of the crystalline phase and the standard substance. In other words, in the above method for quantifying the amorphous phase, the amorphous phase is excluded from the quantitative calculation and the calculation is performed as if the sample were composed of the crystalline phase and the added standard substance (SRM). Therefore, the content ratio of the crystalline phase and the standard substance (SRM) increases according to the proportion of the excluded amorphous phase. Thus, the above method for quantifying the amorphous phase can quantify the amorphous phase in the sample by using the standard substance (SRM) as an indicator and calculating the rate of increase of the crystalline phase in the sample, which increased according to the amount of amorphous phase.

[0006] However, quantitative methods for amorphous phases using standard materials (SRMs) as internal standards have drawbacks in terms of speed and versatility, as they require obtaining individual crystal phase samples for each of the multiple crystalline phases contained in the sample and creating calibration curves.

[0007] To address these challenges, Patent Document 1 proposes a quantitative analyzer for amorphous phases that can perform quantitative analysis of a sample containing the amorphous phase more easily. The quantitative analyzer for amorphous phases described in Patent Document 1 enables quantitative analysis by performing full pattern fitting to the powder diffraction pattern of the sample. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2019-184254 [Overview of the project] [Problems that the invention aims to solve]

[0009] However, the above-mentioned conventional technology still had the following problems that needed to be solved. Specifically, when quantitatively analyzing a sample containing a phase with strong orientation and a layered structure, such as graphite, using the amorphous phase quantitative analyzer described in Patent Document 1, it is necessary to finely and homogenize the sample by grinding to obtain a powder suitable for quantitative analysis. Herein, samples containing graphite may undergo a phase transition during the grinding process.

[0010] Therefore, when performing quantitative analysis of a sample containing graphite, etc., using the amorphous phase quantitative analyzer described in Patent Document 1, the proportion of amorphous phase in the sample before grinding and the proportion of amorphous phase in the sample after grinding may not match. In other words, when performing quantitative analysis of a sample containing graphite, etc., using the amorphous phase quantitative analyzer described in Patent Document 1, the target of quantitative analysis differs before and after grinding. This means that even when performing quantitative analysis of a sample using the amorphous phase quantitative analyzer described in Patent Document 1, there is a problem in that it is not possible to accurately quantify the amorphous phase contained in the sample.

[0011] The present invention has been made in view of the above circumstances, and its objective is to provide an amorphous phase quantitative analyzer, an amorphous phase quantitative analyzer method, and a computer program that can quantify the amorphous phase in a sample containing a crystalline phase and an amorphous phase. Furthermore, the present invention aims to provide an amorphous phase quantitative analyzer, an amorphous phase quantitative analyzer method, and a computer program that can quantify the amorphous phase and the non-quantifiable phase in a sample containing a crystalline phase, an amorphous phase, and a non-quantifiable phase. [Means for solving the problem]

[0012] To solve the above problems and achieve the above objectives, the present invention provides a first amorphous phase quantitative analyzer for quantifying an amorphous phase contained in a sample containing a crystalline phase and an amorphous phase, comprising: a sample preparation unit for preparing a sample for measurement by adding a standard substance to the sample; an X-ray diffraction measurement unit for measuring the quantitative value Xa of the crystalline phase and the quantitative value Xs of the standard substance contained in the sample for measurement by X-ray diffraction; a calculation processing unit for quantifying the mass ratio Mb of the amorphous phase by calculating the mass ratio Ma of the crystalline phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance, and the quantitative value Xa of the crystalline phase; and an output unit for displaying and outputting the quantitative analysis results of the sample.

[0013] Furthermore, a second amorphous phase quantitative analyzer according to the present invention, developed to solve the above problems and achieve the above objectives, is an amorphous phase quantitative analyzer for quantifying an amorphous phase contained in a sample containing a crystalline phase, an amorphous phase, and a phase that cannot be quantified, and is characterized by comprising: a sample preparation unit for preparing a sample for measurement by adding a standard substance to the sample; an elemental component measurement unit for measuring the mass ratio Mc of elemental components contained in the sample for measurement; an X-ray diffraction measurement unit for measuring the quantitative value Xa of the crystalline phase, the quantitative value Xs of the standard substance, and the quantitative value Xc of the phase that cannot be quantified contained in the sample for measurement by X-ray diffraction; a calculation processing unit for quantifying the mass ratio Mb of the amorphous phase by calculating the mass ratio Ma of the crystalline phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance, the mass ratio Mc of the elemental components, and the quantitative value Xa of the crystalline phase; and an output unit for displaying and outputting the quantitative analysis results of the sample.

[0014] Furthermore, the second amorphous phase quantitative analyzer according to the present invention is (a) The quantitatively determined phase-unavailable includes at least one selected from graphite, molybdenum sulfide, titanium sulfide, tantalum sulfide, and tungsten selenide. (b) The quantitatively determined unphase is graphite, (c) It is considered that a more preferable solution would be for the sample to be a refractory material.

[0015] Furthermore, the first amorphous phase quantitative analysis method according to the present invention is a quantitative analysis method for quantifying an amorphous phase contained in a sample containing a crystalline phase and an amorphous phase, and is characterized by comprising: a first step of preparing a sample for measurement by adding a standard substance to the sample; a second step of measuring the quantitative value Xa of the crystalline phase and the quantitative value Xs of the standard substance contained in the sample for measurement by X-ray diffraction; and a third step of quantifying the mass ratio Mb of the amorphous phase by calculating the mass ratio Ma of the crystalline phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance, and the quantitative value Xa of the crystalline phase.

[0016] Furthermore, the second amorphous phase quantitative analysis method according to the present invention is an amorphous phase quantitative analysis method for quantifying an amorphous phase contained in a sample containing a crystalline phase, an amorphous phase, and a phase that cannot be quantified, and is characterized by comprising: a first step of preparing a sample for measurement by adding a standard substance to the sample; a second step of measuring the mass ratio Mc of the elemental components contained in the sample for measurement; a third step of measuring the quantitative value Xa of the crystalline phase, the quantitative value Xs of the standard substance, and the quantitative value Xc of the phase that cannot be quantified contained in the sample for measurement by X-ray diffraction; and a fourth step of quantifying the mass ratio Mb of the amorphous phase by calculating the mass ratio Ma of the crystalline phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance, the mass ratio Mc of the elemental components, and the quantitative value Xa of the crystalline phase.

[0017] Furthermore, the first computer program according to the present invention is a computer program used to carry out the above-described first quantitative analysis method for amorphous phase, and is a quantitative analysis method for quantifying amorphous phase contained in a sample containing a crystalline phase and an amorphous phase, characterized in that it causes a computer to execute a process including: a first step of preparing a sample for measurement by adding a standard substance to the sample; a second step of measuring the quantitative value Xa of the crystalline phase and the quantitative value Xs of the standard substance contained in the sample for measurement by X-ray diffraction; and a third step of quantifying the mass ratio Mb of the amorphous phase by calculating the mass ratio Ma of the crystalline phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance and the quantitative value Xa of the crystalline phase.

[0018] Furthermore, a second computer program according to the present invention is a computer program used to carry out the second quantitative analysis method of amorphous phase described above, and is a quantitative analysis method of amorphous phase for quantifying amorphous phase contained in a sample containing a crystalline phase, an amorphous phase, and a phase that cannot be quantified, characterized in that it causes a computer to execute a process including: a first step of preparing a sample for measurement by adding a standard substance to the sample; a second step of measuring the mass ratio Mc of elemental components contained in the sample for measurement; a third step of measuring the quantitative value Xa of the crystalline phase, the quantitative value Xs of the standard substance, and the quantitative value Xc of the phase that cannot be quantified contained in the sample for measurement by X-ray diffraction; and a fourth step of calculating the mass ratio Ma of the crystalline phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance, the mass ratio Mc of the elemental components, and the quantitative value Xa of the crystalline phase, thereby quantifying the mass ratio Mb of the amorphous phase. [Effects of the Invention]

[0019] According to the present invention, the amorphous phase in a sample containing a crystalline phase and an amorphous phase can be quantified. Furthermore, according to the present invention, the amorphous phase in a sample containing a crystalline phase, an amorphous phase, and a phase that cannot be quantified can be quantified. [Brief explanation of the drawing]

[0020] [Figure 1]It is a block diagram showing the configuration of the amorphous phase quantitative analyzer according to the first embodiment. [Figure 2] It is a block diagram showing the configuration of the amorphous phase quantitative analyzer according to the second embodiment. [Figure 3] It is a flowchart showing the amorphous phase quantitative analysis method (processing procedure) employed by the amorphous phase quantitative analyzer according to the first embodiment. [Figure 4] It is a flowchart showing the amorphous phase quantitative analysis method (processing procedure) employed by the amorphous phase quantitative analyzer according to the second embodiment.

Embodiments for Carrying out the Invention

[0021] [First Embodiment] Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a block diagram showing the configuration of an amorphous phase quantitative analyzer 100 according to the first embodiment. As shown in FIG. 1, the amorphous phase quantitative analyzer 100 includes a measurement sample preparation unit 101 that prepares a measurement sample by adding a standard substance to a sample, an X-ray diffraction measurement unit 102 that measures the quantitative value Xa of the crystal phase contained in the measurement sample and the quantitative value Xs of the standard substance by X-ray diffraction method, and an arithmetic processing unit 103 that quantifies the mass ratio Mb of the amorphous phase by calculating the mass ratio Ma of the crystal phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance, and the quantitative value Xa of the crystal phase, and an output unit 104 that displays and outputs the quantitative analysis result of the sample. Hereinafter, each member included in the amorphous phase quantitative analyzer of the present embodiment will be described. Note that the amorphous phase quantitative analyzer 100 of the present embodiment may include a process computer or a distributed control system (DCS) that controls each member described below.

[0022] <Measurement Sample Preparation Unit> The amorphous phase quantitative analyzer 100 of this embodiment includes a sample preparation unit 101. The sample preparation unit 101 prepares a sample for measurement to be subjected to X-ray diffraction measurement by an X-ray diffraction measurement unit 102. The sample for measurement consists of a sample to be subjected to quantitative analysis and a standard substance. Therefore, the sample preparation unit 101 can be obtained by grinding and mixing a predetermined amount of the sample to be subjected to quantitative analysis and a predetermined amount of a standard substance (internal standard). For this reason, the sample preparation unit 101 is equipped with a measurement function for measuring the mass of the sample to be subjected to quantitative analysis and the mass of the standard substance contained in the sample for measurement. Furthermore, it is preferable that the sample preparation unit 101 is a container equipped with a stirring function for grinding and mixing the sample to be subjected to quantitative analysis and the standard substance. For example, the sample preparation unit 101 may be a device capable of primary grinding, secondary grinding, and drying of the sample for measurement after grinding of the sample to be subjected to quantitative analysis and the standard substance. Specifically, when primary grinding is performed by vibratory mill grinding, a stainless steel vessel can be used. When secondary grinding and mixing are performed by ball mill mixing, a wide-mouthed propylene bottle (for example, "i-boy" manufactured by AS ONE Corporation) can be used as the mixing container, and zirconia balls can be used as the grinding balls (ball mill).

[0023] The sample to be quantitatively analyzed by the amorphous phase quantitative analyzer 100 of this embodiment is not particularly limited, as long as it is a sample containing an amorphous phase or a sample that forms an amorphous phase upon heating. Furthermore, the sample to be quantitatively analyzed may be a sample whose form changes from a crystalline phase to an amorphous phase upon exposure to heat. In addition, the sample to be quantitatively analyzed may be a sample containing crystalline, amorphous, and non-quantifiable phases. The non-quantifiable phases include at least one selected from graphite, molybdenum sulfide, titanium sulfide, tantalum sulfide, and tungsten selenide. In particular, the amorphous phase quantitative analyzer 100 of this embodiment is suitably used for quantitative analysis of samples containing graphite as a non-quantifiable phase among the compounds constituting the non-quantifiable phases.

[0024] The samples for quantitative analysis are taken from refractories. Refractories are materials used for lining equipment in industries that handle high temperatures (metallurgical, chemical, ceramics, machinery, glass, etc.) for melting raw materials or heating materials. Here, refractories refer to shaped refractories with a maximum operating temperature of 1500°C or higher, unshaped refractories with a maximum operating temperature of 800°C or higher, refractory mortar, and refractory insulating bricks. From the perspective of manufacturing method, refractories are classified into (i) molded bricks and blocks (electroformed refractories, fired refractories, unfired refractories) and (ii) unshaped substrates (stamping materials, spray and coating materials, cast substrates, mortars, etc.). Examples of refractories from which samples for quantitative analysis are taken include quartz, clayey, mullite, alumina, zirconite, zirconia, dolomite, magnesia, spinel, magnesia-chromium, and carbon-containing refractories.

[0025] The standard substance contained in the measurement sample prepared by the measurement sample preparation unit 101 forms an internal standard phase contained in the measurement sample. This standard substance serves as an internal standard used in the quantitative analysis of the amorphous phase by the so-called internal standard method. As the standard substance, it is possible to select one that is not included in the measurement sample in order to accurately perform the quantitative analysis of the sample to be measured. Examples of standard substances that can be included in the measurement sample include high-purity silicon powder, lanthanum hexaboride (LaB6), zinc oxide (ZnO), titanium oxide (TiO2), chromium oxide (Cr2O3), cerium oxide (CeO2), and aluminum oxide (α-Al2O3). Among these standard substances, high-purity silicon powder is preferred because high-purity raw materials are readily available. High-purity silicon powder has conventionally been used as a standard for the diffraction peak and the shape of the diffraction peak in powder diffraction. The particle size of the high-purity silicon powder is preferably 1 to 10 μm. If the particle size of the high-purity silicon powder is 1 μm or larger, it is preferable because the X-ray diffraction peak of the pulverized silicon will not be sharp, and there is no risk of it being unsuitable as a standard substance. Furthermore, if the particle size of the high-purity silicon powder is 10 μm or smaller, it is preferable because the reproducibility of the X-ray diffraction peak intensity and the uniformity of mixing will not be negatively affected.

[0026] The measurement sample preparation unit 101 controls the rotation speed and rotation time of the container so that the particle size of the prepared measurement sample falls within a predetermined range. Finally, the measurement sample preparation unit 101 stops the stirring and mixing of the sample to be quantitatively analyzed and the reference substance to obtain a measurement sample. The measurement sample preparation unit 101 measures the mass of the prepared measurement sample, the mass of the sample contained in the measurement sample, and the mass of the reference substance. The measurement sample prepared by the measurement sample preparation unit 101 is supplied to the X-ray diffraction measurement unit 102. Further, the measurement sample preparation unit 101 acquires the measured mass of the measurement sample, the mass of the sample contained in the measurement sample, and the mass of the reference substance as measurement data. These measurement data are transmitted to the arithmetic processing unit 103.

[0027] <X-ray diffraction measurement unit> The amorphous phase quantitative analysis apparatus 100 of the present embodiment includes an X-ray diffraction measurement unit 102. The X-ray diffraction measurement unit 102 performs X-ray diffraction measurement (XRD measurement) on the measurement sample supplied from the measurement sample preparation unit 101. The X-ray diffraction measurement unit 102 measures the quantitative value Xa of the crystal phase in the sample to be quantitatively analyzed contained in the measurement sample and the quantitative value Xs of the reference substance. Note that the X-ray diffraction measurement unit 102 can only measure the quantitative value of the crystal phase in the sample to be quantitatively analyzed, and cannot measure the quantitative value of the amorphous phase in the sample.

[0028] The X-ray diffraction measurement unit 102 is a device that can measure the diffraction intensity on the wide-angle side (2θ>1~2°) with respect to the X-ray incident direction. The X-ray diffraction measurement unit 102 is appropriately selected according to the distance between the measurement sample prepared by the measurement sample preparation unit 101 and the X-ray diffraction measurement unit 102. Note that the X-ray diffraction measurement unit 102 may be 0-dimensional, 1-dimensional, or 2-dimensional.

[0029] The X-ray diffraction measurement unit 102 acquires the measured quantitative value Xa of the crystal phase in the sample to be quantitatively analyzed and the quantitative value Xs of the reference substance as XRD quantitative values, and transmits these quantitative values to the measurement arithmetic processing unit 103.

[0030] <Arithmetic processing unit> The amorphous phase quantitative analyzer 100 of this embodiment includes a calculation processing unit 103. The calculation processing unit 103 calculates the mass percentage Mb of the amorphous phase contained in the sample based on the mass of the sample to be measured acquired as measurement data by the sample preparation unit 101, the mass of the sample and the mass of the standard substance contained in the sample, and the quantitative value Xa of the crystalline phase in the sample and the quantitative value Xs of the standard substance acquired as XRD quantitative values ​​by the X-ray diffraction measurement unit 102. The method for calculating the mass percentage Mb of the amorphous phase contained in the sample is not particularly limited.

[0031] For example, the arithmetic processing unit 103 calculates the mass ratio Ms of the standard substance based on measurement data consisting of the mass of the sample to be measured transmitted from the measurement sample preparation unit 101, and the mass of the sample and the standard substance contained in the measurement sample. Here, the mass ratio Ms of the standard substance is obtained by dividing the mass of the standard substance by the mass of the measurement sample consisting of the sample to be quantitatively analyzed and the standard substance. Furthermore, the arithmetic processing unit 103 uses the quantitative value Xs of the standard substance transmitted from the X-ray diffraction measurement unit 102 to calculate the ratio (Ms / Xs) of the mass ratio Ms of the standard substance to the quantitative value Xs of the standard substance.

[0032] The calculation processing unit 103 then uses the quantitative value Xa of the crystalline phase in the sample transmitted from the X-ray diffraction measurement unit 102 to calculate the mass ratio Ma of the crystalline phase in the sample by multiplying the quantitative value Xa of the crystalline phase in the sample by the ratio (Ms / Xs) of the mass ratio Ms of the standard substance to the quantitative value Xs of the standard substance. Here, the sample for measurement consists of the sample to be quantitatively analyzed and the standard substance, and the sample to be quantitatively analyzed is composed of a crystalline phase and an amorphous phase. The sum of the mass ratios of each component constituting the sample for measurement is 100, which is the sum of the mass ratio Ma of the crystalline phase, the mass ratio Ms of the standard substance, and the mass ratio Mb of the amorphous phase. The calculation processing unit 103 can calculate the mass ratio Mb of the amorphous phase by subtracting the mass ratio Ma of the crystalline phase and the mass ratio Ms of the standard substance from the sum of the mass ratios of each component constituting the sample for measurement, which is 100. Finally, the calculation processing unit 103 excludes the mass percentage Ms of the standard substance and calculates the ratio of the mass percentage Ma of the crystalline phase and the mass percentage Mb of the amorphous phase before the addition of the standard substance.

[0033] In this way, the calculation processing unit 103 calculates the mass percentage Ma of the crystalline phase contained in the sample to be measured by measuring the mass percentage Ms of the added standard substance and the quantitative value Xs of the standard substance, and quantifies the amorphous phase contained in the sample by calculating the ratio of the mass percentage Ma of the crystalline phase to the mass percentage Mb of the amorphous phase.

[0034] <Output section> The amorphous phase quantitative analyzer 100 of this embodiment includes an output unit 104 that displays and outputs the quantitative analysis results of a sample. The output unit 104 includes any display, such as a liquid crystal display and an organic EL display. The output unit 104 is capable of displaying a screen based on output data and signals. The output unit 104 may also be a print output, printer, or plotter.

[0035] Table 1 shows an example of quantitative analysis results of a sample displayed and output by the output unit 104 of the amorphous phase quantitative analyzer 100 of this embodiment. As shown in Table 1, the output unit 104 can display the raw material of the sample to be quantitatively analyzed, the sampling location, and the proportion of crystalline and amorphous phases contained in the sample after heating as quantitative results.

[0036] [Table 1]

[0037] As described above, the amorphous phase quantitative analyzer of this embodiment includes a sample preparation unit for measurement, an X-ray diffraction measurement unit that measures the quantitative value Xa of the crystalline phase contained in the sample for measurement and the quantitative value Xs of the standard substance by X-ray diffraction, and a calculation processing unit that quantifies the mass ratio Mb of the amorphous phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance, and the quantitative value Xa of the crystalline phase. Therefore, it is possible to quantify the amorphous phase contained in a sample that contains both a crystalline phase and an amorphous phase.

[0038] [Second Embodiment] Figure 2 is a block diagram showing the configuration of an amorphous phase quantitative analyzer according to the second embodiment. As shown in Figure 2, the amorphous phase quantitative analyzer 200 according to this embodiment is characterized by comprising: a sample preparation unit 201 that prepares a sample for measurement by adding a standard substance to the sample; an X-ray diffraction measurement unit 202 that measures the quantitative value Xa of the crystalline phase contained in the sample for measurement, the quantitative value Xs of the standard substance, and the quantitative value Xc of the non-quantifiable phase by X-ray diffraction; an elemental component measurement unit 203 for measuring the mass ratio Mc of the elemental components contained in the sample for measurement; a calculation processing unit 204 that quantifies the mass ratio Mb of the amorphous phase by calculating the mass ratio Ma of the crystalline phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance, the mass ratio Mc of the elemental components, and the quantitative value Xa of the crystalline phase; and an output unit 205 that displays and outputs the quantitative analysis results of the sample.

[0039] The amorphous phase quantitative analyzer 200 of this embodiment is used for the quantitative analysis of a sample having a crystalline phase, an amorphous phase, and a phase that cannot be quantitatively analyzed. In particular, the amorphous phase quantitative analyzer 200 is suitably used for the quantitative analysis of the amorphous phase contained in a sample that contains graphite as a phase that cannot be quantitatively analyzed among the compounds that constitute the phase that cannot be quantitatively analyzed.

[0040] Here, the compounds constituting the quantitatively unquantifiable phase in the sample targeted for quantitative analysis by the amorphous phase quantitative analyzer 200 may include at least one selected from graphite, molybdenum sulfide, titanium sulfide, tantalum sulfide, and tungsten selenide. These compounds constituting the quantitatively unquantifiable phase are intercalation compounds. Intercalation compounds are formed by strong covalent bonds within their layers, and by van der Waals forces between their layers. Furthermore, intercalation compounds are easily exfoliated, highly oriented, and exhibit a large bias in the number of layers. For these reasons, it is difficult to quantify intercalation compounds such as graphite by applying X-ray diffraction to measure the quantitative value of the intercalation compounds. Moreover, in order to apply X-ray diffraction to measure the quantitative value of intercalation compounds such as graphite, it is necessary to finely grind the intercalation compounds contained in the sample. By finely grinding the intercalation compounds contained in the sample, the intercalation compounds undergo a phase transition. Even if one attempts to quantify a sample containing intercalation compounds that have undergone such a phase transition by grinding using X-ray diffraction, it is not possible to accurately quantify the intercalation compounds such as graphite contained in the sample.

[0041] From this perspective, the amorphous phase quantitative analyzer 200 of this embodiment is capable of quantifying the amorphous phase in a sample containing a phase that cannot be quantified, such as graphite. Its technical features include further comprising an elemental component measuring unit 203 for measuring the mass ratio Mc of elemental components contained in the sample for quantification, and a calculation processing unit 204 for quantifying the mass ratio Mb of the amorphous phase. The characteristic components of the amorphous phase quantitative analyzer 200 of this embodiment will be described below.

[0042] <Elemental component measurement section> The amorphous phase quantitative analyzer 200 of this embodiment includes an elemental component measuring unit 203 for measuring the mass ratio Mc of elemental components contained in the sample to be measured. The elemental component measuring unit 203 measures the total mass (TE) of elemental components constituting the quantitatively undetectable phase contained in the sample to be quantitatively analyzed as the total elemental value (TE value). The elemental component measuring unit 203 is not particularly limited as long as it is capable of measuring the total mass (TE) of elemental components constituting the quantitatively undetectable phase contained in the sample. For example, the elemental component measuring unit 203 may be an elemental analysis measuring device by combustion analysis, an inductively coupled plasma (ICP) device, or a combination thereof.

[0043] For example, if the quantitatively undetectable phase in the sample contains graphite, the elemental component measurement unit 203 must be a device capable of measuring the total carbon value (TC value). Specifically, the elemental component measurement unit 203 may be a carbon analyzer that applies the combustion-infrared absorption method in accordance with JIS R2011:2007. Here, the above carbon analyzers are broadly classified into high-frequency induction heating furnaces and tubular electric resistance furnaces depending on the heating combustion method. The elemental component measurement unit 203 equipped in the amorphous phase quantitative analyzer 200 of this embodiment may employ either method of carbon analyzer. The elemental component measurement unit 203 measures carbon dioxide (CO2) and carbon monoxide (CO) generated when a sample containing a quantitatively undetectable phase such as graphite undergoes complete combustion using the infrared absorption method. The elemental component measurement unit 203 uses the measured carbon dioxide (CO2) and carbon monoxide (CO) results to measure the amount of elements such as carbon contained in the sample before complete combustion. Furthermore, carbon dioxide (CO2) and carbon monoxide (CO) may be measured using a Fourier transform infrared spectrophotometer (FT-IR).

[0044] <Processing Unit> Furthermore, the amorphous phase quantitative analyzer 200 of this embodiment includes a calculation processing unit 204 that quantifies the mass ratio Mb of the amorphous phase by calculating the mass ratio Ma of the crystalline phase. The calculation processing unit 204 calculates the mass ratio Mb of the amorphous phase contained in the sample based on the mass of the sample to be measured acquired as measurement data by the sample preparation unit 201, the mass of the sample and the mass of the standard substance contained in the sample, the quantitative value Xa of the crystalline phase in the sample, the quantitative value Xs of the standard substance acquired as XRD quantitative values ​​by the X-ray diffraction measurement unit 202, and the mass ratio Mc of the elemental components based on the total elemental values ​​(TE values) of the elemental components contained in the sample. The method for calculating the mass ratio Mb of the amorphous phase contained in the sample is not particularly limited.

[0045] For example, the calculation processing unit 204 calculates the mass ratio Ms of the standard substance based on measurement data consisting of the mass of the sample to be measured transmitted from the measurement sample preparation unit 201, and the mass of the sample and the standard substance contained in the measurement sample. Here, the mass ratio Ms of the standard substance is obtained by dividing the mass of the standard substance by the mass of the measurement sample consisting of the sample to be quantitatively analyzed and the standard substance. Furthermore, the calculation processing unit 204 uses the quantitative value Xs of the standard substance transmitted from the X-ray diffraction measurement unit 202 to calculate the ratio (Ms / Xs) of the mass ratio Ms of the standard substance to the quantitative value Xs of the standard substance.

[0046] The calculation processing unit 204 then uses the quantitative value Xa of the crystalline phase in the sample transmitted from the X-ray diffraction measurement unit 202 to calculate the mass ratio Ma of the crystalline phase in the sample by multiplying the quantitative value Xa of the crystalline phase in the sample by the ratio (Ms / Xs) of the mass ratio Ms of the standard substance to the quantitative value Xs of the standard substance. Here, the sample for measurement consists of the sample to be quantitatively analyzed and the standard substance, and the sample to be quantitatively analyzed consists of a crystalline phase, a non-quantifiable phase and an amorphous phase. The sum of the mass ratios of each component constituting the sample for measurement is 100, which is the sum of the mass ratio Ma of the crystalline phase, the mass ratio Ms of the standard substance, the mass ratio Mb of the amorphous phase, and the mass ratio Mc of the elemental component that forms the non-quantifiable phase. The calculation processing unit 204 can calculate the mass ratio Mb of the amorphous phase by subtracting the mass ratio Ma of the crystalline phase, the mass ratio Ms of the standard substance, and the mass ratio Mc of the non-quantifiable phase from the sum of the mass ratios of each component constituting the sample for measurement, which is 100. Finally, the calculation processing unit 204 excludes the mass percentage Ms of the standard substance and calculates the ratio of the mass percentage Ma of the crystalline phase to the mass percentage Mc of the elemental components that form the quantitatively unquantifiable phase and the mass percentage Mb of the amorphous phase.

[0047] In this way, the calculation processing unit 204 measures the mass percentage Ms of the added standard substance and the quantitative value Xs of the standard substance, and further uses the mass percentage Mc of the elemental components constituting the quantitatively unquantifiable phase contained in the sample to be measured to calculate the mass percentage Ma of the crystalline phase contained in the sample to be measured. By calculating the ratio of the mass percentage Ma of the crystalline phase, the mass percentage Mc of the elemental components forming the quantitatively unquantifiable phase, and the mass percentage Mb of the amorphous phase, the amorphous phase contained in the sample can be quantified.

[0048] Table 2 shows an example of quantitative analysis results of a sample displayed and output by the output unit 205 of the amorphous phase quantitative analyzer 200 of this embodiment. As shown in Table 2, the output unit 205 can display the raw material of the sample to be quantitatively analyzed, the sampling location, and the proportion of crystalline phase, non-quantifiable phase (such as graphite), and amorphous phase contained in the sample after heating as quantitative results.

[0049] [Table 2]

[0050] As described above, the amorphous phase quantitative analyzer 200 of this embodiment further comprises an elemental component measuring unit 203 for measuring the mass ratio Mc of elemental components contained in the sample to be measured, and a calculation processing unit 204 for quantifying the mass ratio Mb of the amorphous phase by calculating the mass ratio Ma of the crystalline phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance, the mass ratio Mc of the elemental components, and the quantitative value Xa of the crystalline phase. Therefore, it is possible to quantify the amorphous phase contained in a sample that includes a crystalline phase, an amorphous phase, and a phase that cannot be quantified.

[0051] [Third Embodiment] The third embodiment is a quantitative analysis method for quantifying the amorphous phase contained in a sample containing a crystalline phase and an amorphous phase. Figure 3 is a flowchart showing the amorphous phase quantitative analysis method (processing procedure) using the amorphous phase quantitative analyzer according to the above embodiment. As shown in Figure 3, the amorphous phase quantitative analysis method of this embodiment is characterized by including: a first step S301 of preparing a sample for measurement by adding a standard substance to the sample; a second step S302 of measuring the quantitative value Xa of the crystalline phase and the quantitative value Xs of the standard substance contained in the sample for measurement by X-ray diffraction; and a third step S303 of quantifying the mass ratio Mb of the amorphous phase by calculating the mass ratio Ma of the crystalline phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance, and the quantitative value Xa of the crystalline phase. The following describes each step included in the amorphous phase quantitative analysis method of this embodiment. Furthermore, each step included in the amorphous phase quantitative analysis method of this embodiment may be managed by a process computer or distributed control system (DCS) included in the amorphous phase quantitative analysis apparatus of the above embodiment.

[0052] <Step 1: Adding a standard substance to the sample to prepare a sample for measurement> The amorphous phase quantitative analysis method of this embodiment includes a first step S301 of preparing a measurement sample. The first step is a measurement sample preparation step, and a measurement sample to be subjected to X-ray diffraction measurement used in the second step is prepared. The measurement sample consists of a sample to be subjected to quantitative analysis and a standard substance. The first step is performed by pulverizing and mixing a predetermined amount of the sample to be subjected to quantitative analysis and a predetermined amount of the standard substance (internal standard) (S301).

[0053] <Second step of measuring the quantitative values of each component by X-ray diffraction method> The amorphous phase quantitative analysis method of this embodiment includes a second step S302 of measuring the quantitative values of each component by X-ray diffraction method. The second step performs X-ray diffraction measurement (XRD measurement) on the measurement sample prepared in the first step. In the second step, the quantitative value Xa of the crystal phase in the sample to be subjected to quantitative analysis contained in the measurement sample and the quantitative value Xs of the standard substance are measured (S302).

[0054] <Third step of quantifying the mass fraction Mb of the amorphous phase> The amorphous phase quantitative analysis method of this embodiment includes a third step S303 of quantifying the mass fraction Mb of the amorphous phase by calculating the mass fraction Ma of the crystal phase. The third step is an amorphous phase calculation step. In the third step, the mass fraction Ma of the crystal phase is calculated based on the mass fraction Ms of the standard substance, the quantitative value Xs of the standard substance, and the quantitative value Xa of the crystal phase, thereby calculating the mass fraction Mb of the amorphous phase and quantifying the amorphous phase.

[0055] In the third step, based on the mass of the measurement sample measured in the first step and the measurement data consisting of the mass of the sample and the mass of the standard substance contained in the measurement sample, the mass fraction Ms of the standard substance is calculated. Here, the mass fraction Ms of the standard substance is obtained by dividing the mass of the standard substance by the mass of the measurement sample consisting of the sample for quantitatively analyzing the mass of the standard substance and the standard substance. Further, in the third step, using the quantitative value Xs of the standard substance measured in the second step, the ratio (Ms / Xs) of the mass fraction Ms of the standard substance to the quantitative value Xs of the standard substance is calculated.

[0056] Then, in the third step, using the quantitative value Xa of the crystalline phase in the sample measured in the second step, the mass percentage Ma of the crystalline phase in the sample is calculated by multiplying the quantitative value Xa of the crystalline phase in the sample by the ratio of the mass percentage Ms of the standard substance to the quantitative value Xs of the standard substance (Ms / Xs). Here, the sample to which the amorphous phase quantitative analysis method of this embodiment is applied consists of the sample to be quantitatively analyzed and the standard substance, and the sample to be quantitatively analyzed is composed of a crystalline phase and an amorphous phase. The sum of the mass percentages of each component constituting the sample to be measured is 100, which is the sum of the mass percentage Ma of the crystalline phase, the mass percentage Ms of the standard substance, and the mass percentage Mb of the amorphous phase. In the third step, the mass percentage Mb of the amorphous phase is calculated by subtracting the mass percentage Ma of the crystalline phase and the mass percentage Ms of the standard substance from the sum of the mass percentages of each component constituting the sample to be measured (100). Finally, in the third step, the ratio of the mass percentage Ma of the crystalline phase to the mass percentage Mb of the amorphous phase is calculated.

[0057] For example, let's consider a case where the sample to be quantitatively analyzed contains one crystalline phase and one amorphous phase. A crystalline standard substance is added to the sample at a concentration of 10% by mass. The quantitative value Xs of the standard substance contained in the sample prepared after the addition of the standard substance to the sample to be quantitatively analyzed was 15.6, and the quantitative value Xa of the crystalline phase was 84.4. As a result, the ratio of the mass percentage Ms of the standard substance to the quantitative value Xs of the standard substance (Ms / Xs) is 10 / 15.6. By multiplying the quantitative value Xa of the crystalline phase, which is 84.4, by the ratio of the mass percentage Ms of the standard substance to the quantitative value Xs of the standard substance (Ms / Xs), which is 10 / 15.6, the mass percentage Ma of the crystalline phase contained in the sample is calculated to be 84.4 × 10 / 15.6, which is 54% by mass. By subtracting the mass percentages of the standard substance and the crystalline phase (10% by mass + 54% by mass) from the total sample mass of 100, the mass percentage Mb of the amorphous phase is calculated to be 36% by mass. By calculating the ratio of the mass percentage Ma of the crystalline phase (54% by mass) to the mass percentage Mb of the amorphous phase (36% by mass), the amorphous phase in the sample before the addition of the standard substance can be quantified.

[0058] Thus, in the third step, the mass percentage Ma of the crystalline phase contained in the sample to be measured is calculated by using the mass percentage Ms of the standard substance added in the first step and the quantitative value Xs of the standard substance measured in the second step. The ratio of the mass percentage Ma of the crystalline phase to the mass percentage Mb of the amorphous phase is then calculated, and the amorphous phase contained in the sample is quantified.

[0059] As described above, the amorphous phase quantitative analysis method of this embodiment can quantify the amorphous phase contained in a sample containing both a crystalline phase and an amorphous phase by calculating the mass ratio Ma of the crystalline phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance, and the quantitative value Xa of the crystalline phase.

[0060] [Fourth Embodiment] The fourth embodiment is a quantitative analysis method for quantifying the amorphous phase contained in a sample that includes a crystalline phase, an amorphous phase, and a non-quantifiable phase. Figure 4 is a flowchart showing the amorphous phase quantitative analysis method (processing procedure) employed by the amorphous phase quantitative analyzer described above. As shown in Figure 4, the amorphous phase quantitative analysis method of this embodiment is characterized by further comprising: a first step S401 of preparing a sample for measurement by adding a standard substance to the sample; a second step S402 of measuring the quantitative value Xa of the crystalline phase, the quantitative value Xs of the standard substance, and the quantitative value Xc of the non-quantifiable phase contained in the sample for measurement by X-ray diffraction; a third step S403 of measuring the mass ratio Mc of the elemental components contained in the sample for measurement; and a fourth step S404 of quantifying the mass ratio Mb of the amorphous phase by calculating the mass ratio Ma of the crystalline phase based on the mass ratio Ms of the standard substance, the quantitative value Xs of the standard substance, the mass ratio Mc of the elemental components, and the quantitative value Xa of the crystalline phase.

[0061] Herein, the amorphous phase quantitative analysis method of this embodiment is technically characterized by a third step S403, which measures the mass ratio Mc of elemental components contained in the sample for measurement, and a fourth step S404, which quantifies the mass ratio Mb of the amorphous phase by calculating the mass ratio Ma of the crystalline phase. The following describes each step included in the amorphous phase quantitative analysis method of this embodiment.

[0062] <First step of preparing a measurement sample by adding a standard substance to the sample> The amorphous phase quantitative analysis method of this embodiment includes a first step S401 of preparing a measurement sample. The first step is a measurement sample preparation step, and a measurement sample that is the object of X-ray diffraction measurement used in the second step and a measurement sample that is the object for measuring the total elemental value (T.E value) of the elemental components used in the third step are prepared. The measurement sample consists of a sample to be quantitatively analyzed and a standard substance. The first step is performed by pulverizing and mixing a predetermined amount of the sample to be quantitatively analyzed and a predetermined amount of the standard substance (internal standard) (S401). In the first step included in the amorphous phase quantitative analysis method of this embodiment, the sample to be quantitatively analyzed contains a non-quantifiable phase such as crystalline, amorphous, and graphite.

[0063] <Second step of measuring the quantitative values of each component by X-ray diffraction method> The amorphous phase quantitative analysis method of this embodiment includes a second step S402 of measuring the quantitative values of each component by X-ray diffraction method. The second step performs X-ray diffraction measurement (XRD measurement) on the measurement sample prepared in the first step. In the second step, the quantitative value Xa of the crystal phase in the sample to be quantitatively analyzed contained in the measurement sample and the quantitative value Xs of the standard substance are measured (S402). Although the quantitative value Xc of the non-quantifiable phase is also calculated, a phase transition occurs during pulverization for measurement, and the value of the quantitative value Xc is not accurate.

[0064] <Third step of measuring the mass ratio Mc of elemental components> The amorphous phase quantitative analysis method of this embodiment includes a third step S403 of measuring the mass ratio Mc of the elemental components contained in the measurement sample. The third step performs mass analysis on the elemental components such as graphite that constitute the non-quantifiable phase contained in the measurement sample prepared in the first step. In the third step, the total mass (T.E) of the elemental components that constitute the non-quantifiable phase contained in the sample to be quantitatively analyzed is measured as the total elemental value (T.E value). In the third step, for example, when the non-quantifiable phase contained in the sample is formed from graphite, the total carbon value (T.C value) is measured.

[0065] <Fourth step: Quantifying the mass percentage Mb of the amorphous phase> The amorphous phase quantitative analysis method of this embodiment includes a fourth step S404 in which the mass percentage Mb of the amorphous phase is quantified by calculating the mass percentage Ma of the crystalline phase. The fourth step is an amorphous phase calculation step. In the fourth step, the mass percentage Mb of the amorphous phase is calculated by calculating the mass percentage Ma of the crystalline phase based on the mass percentage Ms of the standard substance, the quantitative value Xs of the standard substance, the quantitative value Xa of the crystalline phase, and the mass percentage Mc of the elemental components that form the non-quantifiable phase, thereby quantifying the amorphous phase.

[0066] In the fourth step, the mass ratio Ms of the standard substance is calculated based on the measurement data consisting of the mass of the sample measured in the first step, the mass of the sample contained in the sample, and the mass of the standard substance. Here, the mass ratio Ms of the standard substance is obtained by dividing the mass of the standard substance by the mass of the sample measured, which consists of the sample to be quantitatively analyzed and the standard substance. Furthermore, in the fourth step, the ratio (Ms / Xs) of the mass ratio Ms of the standard substance to the quantitative value Xs of the standard substance is calculated using the quantitative value Xs of the standard substance measured in the second step.

[0067] Then, in the fourth step, the quantitative value Xa of the crystalline phase in the sample measured in the second step and the mass ratio Mc of the elemental component that forms a quantitatively unquantifiable phase, such as graphite, in the sample measured in the third step are used to calculate the mass ratio Ma of the crystalline phase in the sample by multiplying the quantitative value Xa of the crystalline phase in the sample by the ratio (Ms / Xs) of the mass ratio Ms of the standard substance and the quantitative value Xs of the standard substance. Here, the sample to which the amorphous phase quantitative analysis method of this embodiment is applied consists of the sample to be quantitatively analyzed and the standard substance, and the sample to be quantitatively analyzed consists of a crystalline phase, an amorphous phase and a quantitatively unquantifiable phase such as graphite. The sum of the mass ratios of each component constituting the sample to be measured is 100, which is the sum of the mass ratio Ma of the crystalline phase, the mass ratio Ms of the standard substance, the mass ratio Mb of the amorphous phase, and the mass ratio Mc of the elemental component that forms a quantitatively unquantifiable phase such as graphite. In the fourth step, the mass percentage Mb of the amorphous phase is calculated by subtracting the mass percentage Ma of the crystalline phase, the mass percentage Ms of the standard substance, and the mass percentage Mc of the elemental component that forms the quantitatively undetectable phase, such as graphite, from the sum of the mass percentages of each component constituting the sample for measurement, which is 100. Finally, in the fourth step, the ratio of the mass percentage Ma of the crystalline phase, the mass percentage Mc of the elemental component that forms the quantitatively undetectable phase, such as graphite, and the mass percentage Mb of the amorphous phase is calculated by excluding the mass percentage Ms of the standard substance.

[0068] As described above, the amorphous phase quantitative analysis method of this embodiment includes the steps of measuring the mass ratio Mc of elemental components contained in the sample for measurement and calculating the mass ratio Ma of the crystalline phase to quantify the mass ratio Mb of the amorphous phase. Therefore, it is possible to quantify the amorphous phase contained in a sample that includes a crystalline phase, an amorphous phase, and a phase that cannot be quantified.

[0069] [Fifth Embodiment] The fifth embodiment is a computer program used to carry out a quantitative analysis method for amorphous phases in a sample containing a crystalline phase and an amorphous phase, or a computer program used to carry out a quantitative analysis method for amorphous phases in a sample containing a crystalline phase, an amorphous phase and a phase that cannot be quantified. That is, the computer program of this embodiment is a computer program used to carry out the quantitative analysis method for amorphous phases of the above embodiment.

[0070] In other words, the computer program of this embodiment can also be realized as a program describing the processing content that realizes each function of the amorphous phase quantitative analyzer of the above embodiment, or as a storage medium that records the program. It should be understood that these are also included in the technical scope of the present invention. The computer program of this embodiment may be supplied directly or remotely to the system or device. Therefore, a program installed on a computer to realize the above embodiment of the present invention on a computer, a medium storing the program, and a WWW (World Wide Web) server that allows the program to be downloaded are also included in the technical scope of the present invention. Furthermore, a non-temporary computer-readable medium storing a program that causes a computer to execute the processing steps for carrying out the amorphous phase quantitative analysis method of the above embodiment is also included in the technical scope of the present invention.

[0071] As described above, the computer program of this embodiment is configured to implement each step of the amorphous phase quantitative analysis method of the above embodiment, so that the amorphous phase in a sample containing a crystalline phase and an amorphous phase, or a sample containing a crystalline phase, an amorphous phase and a phase that cannot be quantified, can be quantified.

[0072] [Other embodiments] Although the present invention has been described above with reference to embodiments, the present invention is not limited to the above embodiments. Various modifications to the structure and details of the present invention can be made, as can be understood by those skilled in the art within the technical scope of the present invention. [Examples]

[0073] The effects of the present invention will be described in detail below based on examples, but the present invention is not limited to these examples. (Example 1) First, an Al2O3-SiO2-C refractory material, which is a sample for measurement using the amorphous phase quantitative analyzer of the present invention, was prepared. Aluminum oxide (Al2O3), graphite (C), and glass (SiO2) were used as the compositional components of the Al2O3-SiO2-C refractory material. Silicon (Si) was used as the standard substance for the Al2O3-SiO2-C refractory material. The compositional ratios of the measurement sample, consisting of the Al2O3-SiO2-C refractory material and the standard substance silicon (Si), were set to 63% by mass for aluminum oxide (Al2O3), 9% by mass for graphite (C), 18% by mass for glass (SiO2), and 10% by mass for silicon (Si). Table 3 shows the compositional values ​​of Production Example 1, the measurement sample prepared in Example 1.

[0074] [Table 3]

[0075] The quantitative value Xa of the crystalline phase (Al2O3) and the quantitative value Xs of the standard substance (Si) in the sample were quantified by X-ray diffraction. The XRD quantitative values ​​of each sample were quantified using the above X-ray diffraction method using an X-ray diffraction analyzer (manufactured by Rigaku Corporation: product name "RINT-UltimaIII"). The quantitative value Xa of the crystalline phase, the quantitative value Xs of the standard substance, and the quantitative value Xc of the non-quantifiable phase (graphite) in the sample were measured using the X-ray diffraction analyzer.

[0076] For the above-mentioned sample used for measurement, the mass percentage Ms of the standard substance was calculated, and the ratio (Ms / Xs) between the mass percentage Ms of the standard substance and the quantitative value Xs of the standard substance was calculated using the measured quantitative value Xs of the standard substance. Using the quantitative value Xa of the crystalline phase in the sample, the mass percentage Ma of the crystalline phase in the sample was calculated by multiplying the quantitative value Xa of the crystalline phase in the sample by the ratio (Ms / Xs) between the mass percentage Ms of the standard substance and the quantitative value Xs of the standard substance. The mass percentage Mb of the amorphous phase was calculated by subtracting the mass percentage Ma of the crystalline phase, the mass percentage Mc of the elemental component forming the non-quantifiable phase, and the mass percentage Ms of the standard substance from the sum of the mass percentages of each component constituting the sample, which is 100. Finally, excluding the mass percentage Ms of the standard substance, the ratio of the mass percentage Ma of the crystalline phase, the mass percentage Mb of the amorphous phase, and the mass percentage Mc of the elemental component forming the quantitatively unquantifiable phase was calculated and used as the quantitative value of the amorphous phase (glass: amorphous) contained in each sample. Table 4 shows the results of quantitative analysis of the compositional components of the measurement samples using the amorphous phase quantitative analyzer of the present invention.

[0077] [Table 4]

[0078] (Examples 2-8) The measurement samples for Production Examples 2 to 8 were prepared in the same manner as in Example 1, except that the proportions of the constituent components of the measurement sample, which consisted of an Al2O3-SiO2-C refractory material and silicon (Si) as a standard substance, were changed. Table 3 shows the composition values ​​of the measurement samples prepared in Production Examples 2 to 8. Furthermore, quantitative analysis was performed on the measurement samples obtained in Production Examples 2 to 8 to determine the compositional components of the measurement samples. Table 4 shows the results of the quantitative analysis of the compositional components of the measurement samples.

[0079] Comparing Manufacturing Examples 1-8 in Table 3 with the corresponding Examples 1-8 in Table 4, it became clear that the compositional components of the measurement samples in both cases were almost identical. For example, focusing on Example 1, the compositional components of Manufacturing Example 1, the measurement sample in Table 1, are 63% by mass of aluminum oxide (Al2O3), 9% by mass of graphite (C), 18% by mass of glass (SiO2), and 10% by mass of silicon (Si). In contrast, the compositional components of Example 1 in Table 2 are calculated as follows: mass percentage of aluminum oxide (Al2O3): Ma 62.5% by mass, mass percentage of graphite (C): Mc 9.1% by mass, mass percentage of glass (amorphous): Mb 18.4% by mass, and mass percentage of metallic silicon (Si): Ms 10% by mass. In other words, the amorphous phase quantitative analyzer of the present invention can accurately quantify the proportion of amorphous phase contained in refractories.

[0080] The present invention has been described above based on the drawings and embodiments, but it should be noted that those skilled in the art will find it easy to make various modifications and alterations based on this disclosure. Therefore, it should be noted that these modifications and alterations are within the scope of the present invention. For example, the functions included in each component, each process, etc., can be rearranged in a logically consistent manner, and multiple means and steps, etc., can be combined into one or separated. [Industrial applicability]

[0081] The present invention relates to a technique for quantifying the amorphous phase contained in a sample that includes a crystalline phase, an amorphous phase, and a phase that cannot be quantified. It can be suitably used to quantify the amorphous phase in a sample after a portion of the amorphous phase has been transformed into a crystalline phase due to heat. For this reason, the present invention is suitably used for quantifying the amorphous phase contained in samples such as refractories, and is extremely useful in industries such as ceramics, metallurgy, chemical, machinery, and glass. [Explanation of Symbols]

[0082] 100 Amorphous Phase Quantitative Analyzer 101 Sample preparation unit for measurement 102 X-ray diffraction measurement section 103 Arithmetic Processing Unit 104 Output section 200 Amorphous Phase Quantitative Analyzer (for samples containing phases that cannot be quantitatively analyzed) 201 Sample preparation section for measurement 202 X-ray diffraction measurement section 204 Arithmetic Processing Unit 203 Elemental component measurement section 205 Output section

Claims

1. An amorphous phase quantitative analyzer for quantifying the amorphous phase contained in a sample that includes a crystalline phase, an amorphous phase, and a phase that cannot be quantified, A sample preparation unit for preparing a sample for measurement by adding a standard substance to the aforementioned sample, An elemental component measuring unit for measuring the mass percentage Mc of the elemental component that forms the quantitatively unphased element contained in the sample for measurement, An X-ray diffraction measuring unit that measures the quantitative value Xa of the crystalline phase contained in the measurement sample, the quantitative value Xs of the standard substance, and the quantitative value Xc of the phase that cannot be quantified by X-ray diffraction, A calculation processing unit that quantifies the mass percentage Mb of the amorphous phase by subtracting the mass percentage Ma of the crystalline phase, calculated based on the mass percentage Ms of the standard substance, the quantitative value Xs of the standard substance, and the quantitative value Xa of the crystalline phase, the mass percentage Ms of the standard substance, and the mass percentage Mc of the elemental component forming the quantitatively unquantifiable phase, from the sum of the mass percentages of each component constituting the measurement sample, which is 100. A quantitative analyzer for amorphous phases, characterized by comprising an output unit for displaying and outputting the quantitative analysis results of the sample.

2. The amorphous phase quantitative analyzer according to claim 1, characterized in that the quantitatively determined phase includes at least one selected from graphite, molybdenum sulfide, titanium sulfide, tantalum sulfide, and tungsten selenide.

3. The amorphous phase quantitative analyzer according to claim 1 or 2, characterized in that the quantitatively unquantifiable phase is graphite.

4. The amorphous phase quantitative analyzer according to any one of claims 1 to 3, characterized in that the sample is a refractory material.

5. A quantitative analysis method for amorphous phases in a sample containing a crystalline phase, an amorphous phase, and a phase that cannot be quantified, A first step involves adding a standard substance to the aforementioned sample to prepare a sample for measurement, A second step involves measuring the mass percentage Mc of the elemental component that forms the quantitatively unphased component contained in the sample for measurement, A third step involves measuring the quantitative value Xa of the crystalline phase contained in the sample for measurement, the quantitative value Xs of the standard substance, and the quantitative value Xc of the phase that cannot be quantified by X-ray diffraction. A method for quantitative analysis of an amorphous phase, comprising a fourth step of quantifying the mass percentage Mb of the amorphous phase by subtracting the mass percentage Ma of the crystalline phase calculated based on the mass percentage Ms of the standard substance, the quantitative value Xs of the standard substance, and the quantitative value Xa of the crystalline phase, the mass percentage Ms of the standard substance, and the mass percentage Mc of the elemental component forming the quantitatively unquantifiable phase from the sum of the mass percentages of each component constituting the measurement sample, which is 100.

6. A computer program used to carry out the amorphous phase quantitative analysis method described in claim 5, A first step involves adding a standard substance to the aforementioned sample to prepare a sample for measurement, A second step involves measuring the mass percentage Mc of the elemental component that forms the quantitatively unphased component contained in the sample for measurement, A third step involves measuring the quantitative value Xa of the crystalline phase contained in the sample for measurement, the quantitative value Xs of the standard substance, and the quantitative value Xc of the phase that cannot be quantified by X-ray diffraction. A computer program characterized by causing a computer to perform a process that includes a fourth step of quantifying the mass percentage Mb of the amorphous phase by subtracting the mass percentage Ma of the crystalline phase, calculated based on the mass percentage Ms of the standard substance, the quantitative value Xs of the standard substance, and the quantitative value Xa of the crystalline phase, the mass percentage Ms of the standard substance, and the mass percentage Mc of the elemental component forming the quantitatively unquantifiable phase, from the sum of the mass percentages of each component constituting the measurement sample, which is 100.

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