JP3059403B2 - X-ray analysis method and apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorescent X
The present invention relates to an X-ray analysis method and apparatus for determining the content of a main component in a sample to be analyzed using a calibration curve based on an intensity ratio between the intensity of the X-ray and the intensity of the scattered X-ray.

[0002]

2. Description of the Related Art As a method for determining the content of metal as a main component in a mineral sample, for example, iron ore, a correlation between the intensity of fluorescent X-rays of iron and the iron content of a standard sample having a known composition is known. There is an X-ray analysis method in which the relationship is obtained in advance as a calibration curve, and the calibration curve is applied to the intensity of the fluorescent X-rays of iron generated from the sample to be analyzed to determine the iron content in the sample to be analyzed. Here, rather than simply using a calibration curve based on the intensity of the fluorescent X-rays of iron, the intensity of the fluorescent X-rays of iron and the scatter X
It is known that the use of a calibration curve based on the intensity ratio with respect to the intensity of the line can reduce the influence of absorption of fluorescent X-rays of iron by coexisting elements contained in the iron ore as a sample. Note that the calibration curve is not limited to a graph, but also includes a graph represented by an equation.

[0003] In order to further reduce the influence and perform accurate analysis, there is an analysis method in which a calibration curve corrected using a correction coefficient relating to the absorption of fluorescent X-rays is applied. Here, by repeatedly calculating the calibration curve for iron and the calibration curve for coexisting components, the content of iron and the content of coexisting components in the sample to be analyzed are obtained. This is a calibration curve based on the intensity of the fluorescent X-ray generated from the element itself, and a known theoretical value is used as the correction coefficient. On the other hand, the calibration curve for iron is a calibration curve based on the intensity ratio between the fluorescent X-rays and the scattered X-rays of iron as described above, and an appropriate theoretical value is not known as a correction coefficient to be used. It is obtained by a multiple regression calculation method from the intensity ratio between the fluorescent X-rays and the scattered X-rays of iron measured and calculated for the iron ore standard sample and the known composition of each standard sample.

[0004]

However, in mineral samples, the composition tends to be constant among the samples in many cases, and it is difficult to prepare a standard sample whose composition changes randomly. Therefore, the correction coefficient obtained by the multiple regression calculation method from a standard sample having such an approximate composition becomes low in reliability, and accurate analysis cannot be performed.

The present invention has been made in view of the above-mentioned conventional problems, and uses the calibration curve based on the intensity ratio of the intensity of the fluorescent X-ray of the main component to the intensity of the scattered X-ray to obtain the main component in the sample to be analyzed. An object of the present invention is to provide an X-ray analysis method and an apparatus for determining the content ratio of, in which a highly reliable correction coefficient is obtained without using an actual standard sample, and an accurate analysis is possible.

[0006]

In order to achieve the above object, according to the method of the first aspect, a sample to be analyzed is first analyzed by using a main component for obtaining a calibration curve based on an intensity ratio between fluorescent X-rays and scattered X-rays. And a coexisting component, and a correction coefficient for the absorption of the coexisting component with respect to the main component is calculated by theoretical calculation assuming the composition of the sample to be analyzed. And
A calibration curve using a correction coefficient is applied to the intensity ratio measured and calculated from the sample to be analyzed to determine the content of the main component in the sample to be analyzed.

According to the first aspect of the present invention, since the correction coefficient is theoretically obtained by assuming the composition of the standard sample, a highly reliable correction coefficient is obtained without using the actual standard sample, and the analysis target sample is obtained. Can be accurately determined.

According to a second aspect of the present invention, a sample stage on which a sample is fixed, an X-ray source for irradiating the sample with primary X-rays, and the intensity of fluorescent X-rays and scattered X-rays generated from the sample are measured. Detection means for performing the detection. Further, for a plurality of standard samples having different compositions, the intensity of the fluorescent X-ray generated from the main component in the standard sample and the intensity of the scattered X-ray generated from the standard sample when the primary X-ray is irradiated are described. There is provided a calibration curve storage means for storing, as a calibration curve, a correlation between the intensity ratio and the content of the main component in the standard sample, which is obtained in advance from the intensity ratio.

Here, it is assumed that the sample to be analyzed is composed of a main component for obtaining a calibration curve based on an intensity ratio between fluorescent X-rays and scattered X-rays, and a coexisting component. This apparatus is provided with correction means for calculating and storing a correction coefficient relating to absorption of the coexisting component to the main component by theoretical calculation based on the assumed composition of the analysis target sample for the analysis target sample thus assumed. ing.

[0010] In addition, the apparatus includes:
Irradiating primary X-rays from the X-ray source, and causing the detection means to measure the intensity of fluorescent X-rays generated from main components in the sample to be analyzed and the intensity of scattered X-rays generated from the sample to be analyzed. Measuring means for calculating and storing the intensity ratio, and applying the calibration curve stored in the calibration curve storing means to the intensity ratio stored in the measuring means using the correction coefficient stored in the correcting means. Content calculating means for determining the content of the main component in the sample to be analyzed. According to the device of the second aspect, the same operation and effect as those of the method of the first aspect are obtained.

In the method according to the third aspect, it is assumed that the sample to be analyzed is composed of a main component for obtaining a calibration curve based on an intensity ratio of the fluorescent X-ray and the scattered X-ray and a coexisting component. One of which is designated as a base component, the other coexisting component is a correction component, and a first virtual sample having a typical composition as a sample to be analyzed, a main component and a base component are compared with the first virtual sample. Is assumed to be a second virtual sample that differs only by a certain amount, and the ratio of the theoretical intensity of the fluorescent X-ray and the scattered X-ray of the main component generated from the first and second virtual samples to the first and second The correlation with the content of the main component in the virtual sample is determined as a virtual calibration curve.

Next, a third virtual sample which differs from the first virtual sample by a certain amount in only the content of one additive component and the base component by a fixed amount is assumed for each additive component, and is generated from the third virtual sample. From the ratio of the theoretical intensity of the fluorescent X-ray and the scattered X-ray of the main component and the virtual calibration curve, a virtual correction coefficient for correcting based on the representative composition is calculated. Further, from the virtual correction coefficient, a reference correction coefficient for correcting based on a composition consisting of only the main component and the base component is calculated. Then, a calibration curve using a reference correction coefficient is applied to the intensity ratio measured and calculated from the sample to be analyzed, and the content of the main component in the sample to be analyzed is obtained.

According to the third aspect of the present invention, since the correction coefficient is theoretically determined by assuming the composition of the standard sample as a typical composition as the sample to be analyzed, the content of the main component in the sample to be analyzed can be more accurately determined. Can be sought.

According to a fourth aspect of the present invention, in the method of the third aspect, a plurality of main components are set, and for each main component, the other main component is included in an additional correction component to calculate the virtual correction coefficient. The reference correction coefficient is calculated from the coefficient.

According to a fourth aspect of the present invention, in the method of the third aspect, a plurality of main components for obtaining a calibration curve based on an intensity ratio between the fluorescent X-rays and the scattered X-rays are provided, and a correction coefficient is theoretically calculated for each main component. Is determined, the content of the main component in the sample to be analyzed can be determined more accurately.

An apparatus according to a fifth aspect of the present invention includes a sample stage, an X-ray source, a detecting means, and a calibration curve storing means, as in the apparatus according to the second aspect. Here, the sample to be analyzed is
Assuming that a main component for obtaining a calibration curve based on the intensity ratio of fluorescent X-rays and scattered X-rays and a coexisting component, one of the coexisting components is designated as a base component, and the other coexisting components are added. A first virtual sample having a typical composition as a sample to be analyzed is assumed as a correction component.

According to this apparatus, the theoretical intensity of the fluorescent X-ray generated from the main component in the first virtual sample and the scattered X-ray generated from the first virtual sample are determined based on the assumed composition. The first virtual intensity ratio is calculated by calculating the theoretical intensity of the line and the ratio of both intensities, and the second virtual sample is different from the first virtual sample only in the content of the main component and the base component by a certain amount. Is calculated, and based on the assumed composition, the theoretical intensity of the fluorescent X-ray generated from the main component in the second virtual sample and the theoretical intensity of the scattered X-ray generated from the second virtual sample are calculated. The intensity ratio is calculated as a second virtual intensity ratio, and the correlation between the first and second virtual intensity ratios and the contents of the main components in the first and second virtual samples is obtained and stored as a virtual calibration curve. A virtual calibration curve creating means is provided.

Further, the apparatus assumes a third virtual sample for each of the additive components, which differs from the first virtual sample only in the content of one additive component and the base component by a fixed amount. Based on the composition, the theoretical intensity of the fluorescent X-ray generated from the main component in the third virtual sample and the theoretical intensity of the scattered X-ray generated from the third virtual sample are calculated, and the ratio between the two intensities is calculated. The third virtual intensity ratio is used. The virtual calibration curve stored in the virtual calibration curve creating means is applied to the third virtual intensity ratio to determine the content of the main component in the third virtual sample. In order to match the content of the main component in the virtual sample with the content of the main component in the first virtual sample, a virtual correction coefficient for correcting based on the representative composition is calculated for each additive component, From the virtual correction factor, Min and only composition comprising a base component by calculating a reference correction coefficient for correcting a reference and a reference correction coefficient calculation means for storing.

Furthermore, the sample to be analyzed may further include the X
A primary X-ray is irradiated from a radiation source, and the detection means measures the intensity of fluorescent X-rays generated from the main component in the sample to be analyzed and the intensity of scattered X-rays generated from the sample to be analyzed. Measuring means for calculating and storing the ratio, and for the intensity ratio stored in the measuring means, the calibration curve stored in the calibration curve storing means using the reference correction coefficient stored in the reference correction coefficient calculating means. And a content calculating means for calculating the content of the main component in the sample to be analyzed. According to the apparatus of the fifth aspect, the same operation and effect as those of the method of the third aspect are obtained.

According to a sixth aspect of the present invention, in the apparatus of the fifth aspect, wherein the main component includes a plurality of main components, and the reference correction coefficient calculating means includes, for each main component, another main component included in an additional correction component. A virtual correction coefficient is calculated, and the reference correction coefficient is calculated from the virtual correction coefficient. Claim 6
According to the device of the fourth aspect, the same operation and effect as those of the method of the fourth aspect are obtained.

In the method according to the seventh aspect, it is assumed that the sample to be analyzed is composed of a main component for obtaining a calibration curve based on an intensity ratio of the fluorescent X-ray and the scattered X-ray and a coexisting component. Is designated as a base component, the other coexisting component is an additional component, a first virtual sample having a composition consisting of a main component and a base component, and a main component and a base component compared with the first virtual sample. Is assumed to be different from the second virtual sample by a certain amount, the ratio of the theoretical intensity of the fluorescent X-ray and the scattered X-ray of the main component generated from the first and second virtual samples to the first and second virtual samples The correlation with the content of the main component in the sample is determined as a virtual calibration curve.

Next, as compared with the first virtual sample, a third virtual sample in which only the contents of one additive component and the base component differ by a fixed amount is assumed for each additive component, and is generated from the third virtual sample. A correction coefficient is calculated from the ratio of the theoretical intensity of the fluorescent X-ray and the scattered X-ray of the main component and the virtual calibration curve. Then, a calibration curve using a correction coefficient is applied to the intensity ratio measured and calculated from the sample to be analyzed to determine the content of the main component in the sample to be analyzed.

According to the method of the present invention, a correction coefficient is theoretically directly obtained based on the assumption of a composition consisting of a main component and a base component instead of a typical composition as a sample to be analyzed. Therefore, the function and effect of the method of claim 1 can be more easily obtained.

According to an eighth aspect of the present invention, in the method of the seventh aspect, a plurality of main components are used, and for each main component, the other main component is included in an additional correction component to calculate the correction coefficient.

According to the method of claim 8, in the method of claim 7, a plurality of main components for obtaining a calibration curve based on the intensity ratio between the fluorescent X-rays and the scattered X-rays are provided, and a correction coefficient is theoretically calculated for each main component. Is determined, the content of the main component in the sample to be analyzed can be determined more accurately.

An apparatus according to a ninth aspect includes a sample stage, an X-ray source, detection means, and a calibration curve storage means, as in the apparatus according to the second aspect. Here, the sample to be analyzed is
Assuming that a main component for obtaining a calibration curve based on the intensity ratio of fluorescent X-rays and scattered X-rays and a coexisting component, one of the coexisting components is designated as a base component, and the other coexisting components are added. The first component consisting of a main component and a base component as a correction component
Assume a virtual sample.

According to this apparatus, the theoretical intensity of the fluorescent X-ray generated from the main component in the first virtual sample and the scattered X-ray generated from the first virtual sample are determined based on the assumed composition. The theoretical intensity of the line is calculated, the ratio of the two intensities is calculated to be the first virtual intensity ratio, and the second virtual sample in which the contents of the main component and the base component differ by a fixed amount from the first virtual sample is calculated. Assuming, based on the assumed composition, the theoretical intensity of the fluorescent X-ray generated from the main component in the second virtual sample and the theoretical intensity of the scattered X-ray generated from the second virtual sample are calculated. Is calculated as a second virtual intensity ratio, and the first and second virtual intensity ratios and the first and second virtual intensity ratios are calculated.
There is provided a virtual calibration curve creating means for obtaining and storing a correlation with the content of the main component in the virtual sample as a virtual calibration curve.

Further, in this apparatus, a third virtual sample in which only one additive component and a base component differ from the first virtual sample by a fixed amount is assumed for each additive component. Based on the composition, the theoretical intensity of the fluorescent X-ray generated from the main component in the third virtual sample and the theoretical intensity of the scattered X-ray generated from the third virtual sample are calculated, and the ratio between the two intensities is calculated. The third virtual intensity ratio is used. The virtual calibration curve stored in the virtual calibration curve creating means is applied to the third virtual intensity ratio to determine the content of the main component in the third virtual sample. A correction coefficient calculating means is provided for calculating and storing a correction coefficient to be corrected for each additive component so that the content of the main component in the virtual sample matches the content of the main component in the first virtual sample. .

Further, the sample to be analyzed is provided with the X
A primary X-ray is irradiated from a radiation source, and the detection means measures the intensity of fluorescent X-rays generated from the main component in the sample to be analyzed and the intensity of scattered X-rays generated from the sample to be analyzed. Measuring means for calculating and storing the ratio, and applying the calibration curve stored in the calibration curve storing means to the intensity ratio stored in the measuring means, using the correction coefficient stored in the correction coefficient calculating means. Content calculating means for determining the content of the main component in the sample to be analyzed. According to the device of the ninth aspect, the same operation and effect as those of the method of the seventh aspect are obtained.

According to a tenth aspect of the present invention, in the device of the ninth aspect, there are a plurality of main components, and the correction coefficient calculating means includes, for each main component, another main component included in an additional correction component. A coefficient is calculated. Claim 10
According to this device, the same operation and effect as those of the method according to the eighth aspect are obtained.

[0031]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method according to a first embodiment of the present invention will be described. First, an apparatus used in this method will be described with reference to FIG. This device, first,
A sample table 8 on which the samples 3 and 13 are fixed, an X-ray source 1 for irradiating the samples 3 and 13 with primary X-rays 2, and the intensity of fluorescent X-rays 6 and scattered X-rays 9 generated from the samples 3 and 13 And detection means 10 for measuring the The detection means 10 includes the sample 3,
A spectroscope 5 for dispersing the secondary X-rays 4 generated from the X-ray 13, a fluorescent X-ray 6 and a Compton scatter X
Each line 6 comprises a detector 7 for measuring its intensity. In addition, this apparatus is configured such that when a primary X-ray 2 is irradiated on a plurality of standard samples 13 having different compositions,
3, the intensity ratio of the fluorescent X-rays 6 generated from the main components and the intensity ratio of the scattered X-rays 9 generated from the standard sample 13 are determined in advance. And a calibration curve storage means 11 for storing the correlation with the calibration curve.

This apparatus is provided with a virtual calibration curve creating means 12 including a first virtual intensity ratio calculating means 13, a second virtual intensity ratio calculating means 14, and a correlation creating means 15 described below. Here, the operator converts the sample 3 to be analyzed into fluorescent X-rays 6.
One of the coexisting components is designated as a base component, and the other coexisting components are added and corrected components, assuming that a main component for obtaining a calibration curve based on the intensity ratio of the scattered X-ray 9 and the coexisting components is specified. Assuming a first virtual sample having a typical composition as the sample 3 to be analyzed, the virtual calibration curve creating means 12
To enter.

The first virtual intensity ratio calculating means 13 calculates the first
For the virtual sample, the theoretical intensity of fluorescent X-rays generated from the main components in the first virtual sample and the theoretical intensity of scattered X-rays generated from the first virtual sample are calculated based on the assumed composition. The ratio of the intensities is calculated and used as a first virtual intensity ratio.
The second imaginary intensity ratio calculating means 14 assumes a second imaginary sample in which only the contents of the main component and the base component differ by a fixed amount from the first imaginary sample, and based on the assumed composition, Fluorescence X generated from main components in virtual sample
The theoretical intensity of the X-rays and the theoretical intensity of the scattered X-rays generated from the second virtual sample are calculated, and the ratio between the two intensities is calculated as the second virtual intensity ratio. The correlation creating means 15 obtains and stores a correlation between the first and second virtual intensity ratios and the contents of the main components in the first and second virtual samples as a virtual calibration curve.

Further, this apparatus is provided with a reference correction coefficient calculating means 16 including a third virtual intensity ratio calculating means 17, a virtual correction coefficient calculating means 18 and a correction coefficient converting means 19 described below. The third virtual intensity ratio calculating means 17 assumes, for each of the correction components, a third virtual sample in which only the content rates of the one correction component and the base component differ by a fixed amount from the first virtual sample. The theoretical intensity of the fluorescent X-rays generated from the main components in the third virtual sample based on the obtained composition,
The theoretical intensity of the scattered X-ray generated from the third virtual sample is calculated, and the ratio between the two is calculated as the third virtual intensity ratio. The virtual correction coefficient calculation means 18 applies the virtual calibration curve stored in the virtual calibration curve creation means 12 to the third virtual intensity ratio to determine the content of the main component in the third virtual sample, and determines the content. A virtual correction coefficient for correcting based on the representative composition is calculated for each additive component such that the content of the main component in the third virtual sample matches the content of the main component in the first virtual sample. . The correction coefficient conversion unit 19 calculates and stores, from the virtual correction coefficient, a reference correction coefficient for correcting based on a composition consisting of only the main component and the base component.

This apparatus further comprises the following measuring means 20 and content calculating means 21. Measuring means 2
0 indicates that the X-ray source 1
The sample 2 is irradiated with the X-ray 2 and the intensity of the fluorescent X-ray 6 generated from the main component in the sample 3 to be analyzed and the intensity of the scattered X-ray 9 generated from the sample 3 to be analyzed are measured by the detecting means 10. Calculate and store the ratio. The content rate calculation means 21 applies the calibration curve stored in the calibration curve storage means 11 to the intensity ratio stored in the measurement means 20 using the reference correction coefficient stored in the reference correction coefficient calculation means 16. Then, the content of the main component in the sample 3 to be analyzed is obtained.

In this apparatus, when there are a plurality of main components, the reference correction coefficient calculating means 16 calculates the virtual correction coefficient for each main component by including other main components in the additional correction component. Then, the reference correction coefficient is calculated from the virtual correction coefficient. The virtual calibration curve creating means 12 and the reference correction coefficient calculating means 16
Constitute the correction means 23 of this device. further,
The calibration curve storing means 11, the correcting means 23, the measuring means 20, and the content calculating means 21 constitute a control means 22 of the apparatus.

Using this apparatus, in the method of the first embodiment, the content of the main component in the sample 3 to be analyzed is obtained as follows. The case where the analysis target sample 3 is iron ore will be described as an example. First, the sample 3 to be analyzed is attached to the sample table 8, the primary X-rays 2 generated from the X-ray source 1 are irradiated by the measuring means 20, and the generated secondary X-rays 4 are applied to the spectroscope 5. The intensity of each of the incident fluorescent X-rays 6 and the Compton scattered X-rays 6 is measured by the detector 7. Here, in general, when a metal element or a coexisting element as a main component is contained only as an oxide in one form in the analysis target sample 3, it is treated as an oxide and its content is analyzed. If it is included, treat it as a single element and analyze its content. In the present embodiment, Fe O, to handle easily iron ore containing iron as the analysis sample 3 with Fe ₂ O _3, etc. different forms, the major component assuming iron alone analyze the iron content . Specifically, the sample 3 to be analyzed is divided into a main component that is a simple substance of iron, an additive component among coexisting components, such as silicon dioxide and calcium oxide, and a residue specified as a base component among coexisting components, that is, oxygen. Suppose that

In the present invention, the main component means a component for which a calibration curve is obtained based on the intensity ratio between fluorescent X-rays and scattered X-rays.
The additive component refers to a component for obtaining a calibration curve based on X-ray fluorescence, and the analysis value of the content is used to correct the analysis value of the main component. The main component is not always limited to one in the sample 3 to be analyzed. For example, in the method of the present embodiment, manganese oxide is treated as an additional component, but the intensity ratio between fluorescent X-rays and scattered X-rays is determined. If a calibration curve is obtained and treated as a main component, manganese oxide other than iron may be used as a main component as long as accurate analysis can be performed as a whole.

Now, a calibration curve for iron (formula (1))
And by repeated calculation of the calibration curve for pressure correction component containing coexisting elements i viewed from iron (equation (2)), the content W _i of content W _Fe and pressure correction component of iron in the analysis sample 3 is determined Can be Note that the coexisting element j in the formula (2)
Is a coexisting element j as viewed from the element i, and includes iron.

[0040]

(Equation 1)

[0041]

(Equation 2)

Here, equation (1) is an equation representing a calibration curve based on a composition consisting only of iron and oxygen (hereinafter referred to as a reference calibration curve to distinguish it from a virtual calibration curve described later).
In the method of the present embodiment, the expression in the first parenthesis on the right side is stored in the calibration curve storage means 11, and indicates the uncorrected iron content by the reference calibration curve, and the reference calibration curve constants a, b, and
c. The expression in the second bracket is the fluorescent X-ray of iron 6
Is a correction term relating to absorption of iron, and includes a reference correction coefficient α _j for iron of coexisting element j, which is corrected based on a composition consisting only of iron and oxygen. In the conventional method, the standard sample 13 was measured, and both the standard calibration curve constants a, b, and c and the standard correction constant α _j were experimentally obtained. The present invention is characterized in that the reference correction coefficient α _j is theoretically obtained on the assumption of a standard sample without using the actual standard sample 13. In Equation (1), for the sake of simplicity, what should be expressed as α _Fej is α _j , and a _Fe , b _Fe , and c _Fe are a, b, and
c and the subscript _Fe are abbreviated.

In the method of the present embodiment, the iron ore as the sample 3 to be analyzed has a typical composition and the iron content is W
Assuming a first virtual sample which is a _Fem , the virtual calibration curve creating means 12 calculates the theoretical intensity of the fluorescent X-rays generated from iron in the first virtual sample and the first virtual sample based on the assumed composition. The theoretical intensity of the generated Compton scattered X-rays is calculated, and the ratio between the two is calculated as a first virtual intensity ratio ^T1 _IFe . The calculation of the theoretical strength has been conventionally performed by a so-called fundamental parameter method. Also, as compared with the first virtual sample, a second virtual sample is assumed in which the iron content is higher by a certain amount ΔW _Fe , the oxygen content is lower by ΔW _Fe by that amount, and the other contents are unchanged. Similarly, the second virtual intensity ratio ^T2 _IFe is calculated based on the assumed composition. The correlation between the first and second virtual intensity ratios ^T1 _IFe and ^T2 _IFe and the iron contents W _Fem and W _Fem + ΔW _Fe in the first and second virtual samples is represented by a straight line virtual calibration curve. In the form of the following equation (3).
This virtual calibration curve is based on a representative composition, and is obtained and stored by the virtual calibration curve creating means 12. Note that the subscript ^T means a numerical value based on a hypothesis.

[0044]

(Equation 3)

Further, the reference correction coefficient calculating means 16 compares the first correction sample with the first virtual sample, so that the content of one additional correction component, for example, silicon dioxide, is larger by a certain amount ΔW _Si and the content of oxygen is smaller by ΔW _Si , Assuming a third virtual sample in which the other contents do not change, based on the assumed composition,
The third virtual intensity ratio ^T3 I _Fe is calculated in the same manner as described above, and the third
The above-mentioned virtual calibration curve, that is, equation (3) is applied to the virtual intensity ratio ^T3 I _Fe to determine the iron content ^T X _Fe in the third virtual sample. The iron content of the third virtual sample is assumed to be the same as the iron content of the first virtual sample. Since the third virtual sample is larger in the additive component by only ΔW _{Si than} silicon dioxide, the virtual content of silicon with respect to iron is The correction coefficient ^T α _Si is obtained from the following equation (4). At this time, W _Fe = W _Fem .

[0046]

(Equation 4)

[0047] Similarly, for each pressure correction component, assuming the third virtual samples, corrected on the basis of the typical composition, the virtual correction coefficient ^T alpha _j to iron is obtained from the following equation (5).

[0048]

(Equation 5)

It should be noted that the content W _j of the additive component containing the coexisting element j in the third virtual sample is the same as the content W _jm of the same component in the first virtual sample, that is, the representative composition, expressed by the following equation (6). In a relationship.

[0050]

(Equation 6)

By substituting equation (6) into equation (5), the following equation (7) can be obtained.

[0052]

(Equation 7)

Here, paying attention to the product of ^T x _Fe of the formula (7) and the first parenthesis, and comparing it with the formula (5), the ^T x _Fe is a typical composition of a certain sample. The uncorrected iron content based on the reference virtual calibration curve. The expression in the first parenthesis indicates that the sample has a content of the added component containing the coexisting element j which is smaller than the representative composition by W _jm. It is small, that is, does not include an additional correction component, and means that a correction corresponding thereto is added. That is, the product of ^T x _Fe and the first parenthesis represents the corrected iron content of the sample consisting of only iron and oxygen. In other words, as shown in the following equation (8), the additive component is also Regarding the sample 3 to be analyzed,
A composition consisting only of iron and oxygen, which is content X _Fe iron uncorrected by the reference calibration curve as a reference.

[0054]

(Equation 8)

Therefore, as shown in the following equation (9), X _Fe is the same as the equation in the first parenthesis on the right side of equation (1).

[0056]

(Equation 9)

Since both equations (7) and (1) represent the corrected iron content W _Fe , equation (7) can be expressed by the following equation (10). It can be transformed as in equation (11).

[0058]

(Equation 10)

[0059]

[Equation 11]

That is, the virtual correction coefficient ^T for correcting the absorption of the fluorescent X-rays 6 of iron with reference to the representative composition by the reference correction coefficient calculating means 16 using equation (10).
α _j and content W of additive component in typical composition
_{From jm} , a reference correction coefficient α _j for correcting based on a composition consisting of only iron and oxygen is obtained and stored. Note that the calibration curve for the additive component, that is, the correction coefficient α _ij in the equation (2),
A known theoretical value is used. Further, as described above, the reference calibration curve constants a, b, and c in the equation (1) are experimentally obtained as in the conventional method, and are stored in the calibration curve storage unit 11. The calibration curve constants a _i ,
b _i and c _i are similarly obtained experimentally.

Accordingly, a reference calibration curve (Equation (1)) for iron and a calibration curve (Equation (2)) for the correction component are expressed, and the fluorescent X-rays of iron measured by the content calculating means 21. Ratio I between intensity and Compton scattered X-ray intensity
Equations (1) and (2) are applied to _Fe (calculated and stored by the measuring means 20) and the measured fluorescent X-ray intensity I _{i of} the element i, respectively, and the two equations are repeatedly calculated. the content W _i of content W _Fe and pressure correction component of iron in the analysis sample 3 is obtained.

For example, when manganese oxide is also treated as a main component, the reference correction coefficient calculating means 16 calculates a reference correction coefficient α _j for each of the main components of iron and manganese oxide. At this time, the virtual correction coefficient ^T _αj is calculated by including other main components in the additional correction component. That is, when calculating the reference correction coefficient α _Mnj for manganese oxide, iron is _treated in the same manner as the additional correction component, and ^T α
_When calculating the virtual correction coefficient ^T α _Mnj including _MnFe and calculating the reference correction coefficient α _Fej for iron, the manganese oxide is _treated in the same manner as the additional correction component, and the virtual correction coefficient ^T α including ^T _FeMn is also included. _{Calculate Fej} .

The reference correction coefficient α _j for the absorption of the fluorescent X-ray 6 of iron in the iron ore obtained by the method of the first embodiment is shown in the following Table 1 for each additional correction component including the coexisting element j. .

[0064]

[Table 1]

Further, the iron ore sample No. 1
And No. The iron content W _Fe in Example 2 was determined based on the standard value obtained by chemical analysis and the first correction factor α _{j shown in} Table 1.
Table 2 below shows the analysis values of the method of the embodiment and the analysis values of the conventional method based on the correction coefficients obtained by the multiple regression calculation method. From Table 2,
According to the method of the first embodiment, it is clear that the iron content W _Fe can be determined more accurately than in the conventional method.

[0066]

[Table 2]

As described above, according to the method of the first embodiment, the standard correction coefficient α _j is theoretically obtained by assuming the composition of the standard sample as a typical composition as a sample to be analyzed. A highly reliable reference correction coefficient α _j without using
Is obtained, and the iron content W _Fe can be accurately obtained even in an iron ore in which the composition tends to be constant among the samples 3. When a plurality of main components are used, the correction coefficient is theoretically obtained for each main component, so that the content of the main component in the analysis target sample 3 can be obtained more accurately.

Next, a method according to the second embodiment of the present invention will be described. First, an apparatus used in this method will be described with reference to FIG. In this apparatus, as compared with the apparatus used in the method of the first embodiment, the first virtual sample assumed and input does not have a typical composition as a sample to be analyzed, but includes a main component and a base component. Points and
The only difference is that the following correction coefficient calculating means 24 is provided in place of the reference correction coefficient calculating means 16 (FIG. 1), and the other points are the same. Description is omitted. The correction coefficient calculating means 24
It includes the following third virtual intensity ratio calculating means 17 and correction coefficient calculating means 25.

The third virtual intensity ratio calculating means 17 calculates the first virtual intensity ratio
Assuming a third virtual sample for each additive component in which only the content of one additive component and the base component differ from the virtual sample by a fixed amount, and based on the assumed composition, the third virtual sample in the third virtual sample The theoretical intensity of the fluorescent X-ray generated from the component and the theoretical intensity of the scattered X-ray generated from the third virtual sample are calculated, and the ratio between the two intensities is calculated as the third virtual intensity ratio.
The correction coefficient calculation means 25 applies the virtual calibration curve stored in the virtual calibration curve creation means 12 to the third virtual intensity ratio, determines the content of the main component in the third virtual sample, and A correction coefficient to be corrected is calculated and stored for each additive component so that the content of the main component in the three virtual samples matches the content of the main component in the first virtual sample.

Also in this apparatus, when there are a plurality of main components, the correction coefficient calculating means 24 calculates the correction coefficients for each main component by including other main components in the additional correction components. It is. The virtual calibration curve creating means 12 and the correction coefficient calculating means 24 constitute a correcting means 26 of the apparatus. Further, the calibration curve storing means 11, the correcting means 26, the measuring means 20, and the content calculating means 21 are provided in the control means 2 of this apparatus.
7.

Using this apparatus, in the method of the second embodiment, the content of the main component in the sample 3 to be analyzed is obtained as follows. Again, the case where the analysis target sample 3 is iron ore will be described as an example. The intensity measurement of the fluorescent X-ray 6 and the Compton scattered X-ray 6 for the analysis target sample 3 and the handling of the main component, the coexisting component, the correction component, and the base component (residue) are the same as those in the first embodiment. It is. Although the above-described equation (1) is used in the method of the second embodiment, there is no distinction between the virtual correction coefficient and the reference correction coefficient, as described later.

In the method of the second embodiment, the analysis target sample 3
Iron ore is a binary system of iron and oxygen, and the iron content is W
Assuming a first virtual sample which is a _Fem , the virtual calibration curve creating means 12 calculates the theoretical intensity of the fluorescent X-rays generated from iron in the first virtual sample and the first virtual sample based on the assumed composition. The theoretical intensity of the generated Compton scattered X-rays is calculated, and the ratio between the two is calculated as a first virtual intensity ratio ^T1 _IFe . The calculation of the theoretical strength has been conventionally performed by a so-called fundamental parameter method. Further, as compared with the first virtual sample, a second virtual sample in which the iron content is higher by a certain amount ΔW _Fe and the oxygen content is lower by ΔW _Fe by that amount is assumed, and based on the assumed composition, ^Next , the second virtual intensity ratio ^T2 _IFe is calculated. And
First and second virtual intensity ratio and ^T1 I _Fe, ^T2 I _Fe, the iron content in the first and second virtual sample W _Fem, W _Fem + Δ
The correlation with W _Fe is determined in the form of equation (3) as a virtual calibration curve that is a straight line. In the method of the second embodiment, ^T x _{Fe in the} formula (3) is an uncorrected iron content based on a virtual calibration curve based on a binary system composed of iron as a main component and oxygen as a base component. Rate. This virtual calibration curve is obtained and stored by the virtual calibration curve creating means 12.

[0073] Further, the correction coefficient calculating unit 24, as compared with the first virtual samples, one pressure correction component for example silicon dioxide contains predetermined amount [Delta] W _Si in content, the content of oxygen is only [Delta] W _Si less , assuming a third virtual samples unchanged other content, based on the assumed composition, third calculating a virtual intensity ratio ^T3 I _Fe in the same manner as described above, in the third virtual intensity ratio ^T3 I _Fe Applying the virtual calibration curve, ie, equation (3), the iron content ^T in the third virtual sample
_Find X _Fe . In the method of the second embodiment,
Since the first virtual sample does not contain any additive component, the constant amount ΔW _Si is the content itself of the third virtual sample with respect to silicon dioxide, and at the same time, the difference from the content of the first virtual sample. is there. The iron content of the third virtual sample is assumed to be the same as that of the first virtual sample.
Since only silicon dioxide is included in the additive component only in ΔW _Si, a virtual correction coefficient ^T α _Si
Is obtained from the above equation (4). At this time, W _Fe = W _Fem .

Similarly, assuming a third virtual sample for each additive component, the correction coefficient α _j for iron is calculated by the equation (5)
As ^T α _j . In the method according to the second embodiment, ΔW _{j in} the equation (5) is the content itself of the third virtual sample with respect to the additive component including the coexisting element j, and at the same time, the content ratio of the first virtual sample. It is also the difference. That is, the correction coefficient α _j is obtained and stored by the correction coefficient calculation means 24. Thereafter, by the content rate calculating means 21,
Procedure to content W _i of content W _Fe and pressure correction component of iron in the analysis sample 3 is required is the same as the method of the first embodiment. As described above, in the method of the second embodiment, as the iron ore that is the analysis target sample 3, the first and second virtual samples that are binary systems of iron and oxygen are assumed, and the correction coefficient α that is easily obtained is used. _j is directly used in the calibration curve applied to the actual sample 3 to be analyzed, that is, the equation (1). According to the method of the second embodiment, the correction coefficient α _j is theoretically directly directly based on the composition of the main component and the base component on the assumption of the composition consisting of the main component and the base component instead of the typical composition as the sample 3 to be analyzed. Since it is obtained, an operation effect similar to the method of the first embodiment can be obtained more easily.

For example, when manganese oxide is also handled as a main component, the correction coefficient calculating means 24 calculates a correction coefficient α _j for each of the main components of iron and manganese oxide. At this time, the correction coefficient α _j is calculated by including the other main components in the additive component. That is, when calculating the correction coefficient alpha _Mnj for manganese oxide, iron also including handling alpha _MnFe like the pressure correction component correction coefficient alpha
_When calculating _Mnj and calculating the correction coefficient α _Fej for iron, manganese oxide is _treated in the same manner as the correction component and α
_The correction coefficient α _Fej is calculated including _FeMn . in this way,
When there are a plurality of main components, the correction coefficient α _j is theoretically obtained for each main component, so that the content of the main component in the analysis target sample 3 can be obtained more accurately.

Note that, in the methods of the first and second embodiments,
Fe O, due to the analysis sample 3 iron ore containing iron Fe ₂ O _3, etc. different forms, the elementary iron as a main component, oxygen which is a residue of the coexisting components based components, other coexisting components ( Although silicon dioxide, calcium oxide, etc.) were used as correction components, for example, when the copper ore containing copper in the form of CuO alone is the sample 3 to be analyzed, there is no residual component, but Copper (CuO) may be used as the main component, silicon dioxide among the coexisting components may be used as the base component, and the other coexisting components may be used as the correction component. In this case, the base component, silicon dioxide, is also analyzed by the calibration curve (Equation (2)), similarly to the correction component. The present invention is not limited to mineral samples such as iron ore and copper concentrate, and can be applied to a wide range of objects.

[0077]

As described above in detail, according to the first or second aspect of the present invention, since the correction coefficient is theoretically obtained by assuming the composition of the standard sample, the reliability can be obtained without using the actual standard sample. Thus, a highly-correctable correction coefficient is determined, and the content of the main component in the sample to be analyzed can be accurately determined.

According to the third or fifth aspect of the present invention,
Since the correction coefficient is theoretically determined by assuming the composition of the standard sample as a typical composition as the sample to be analyzed, the content of the main component in the sample to be analyzed can be determined more accurately.

Further, according to the invention of claim 4 or 6, in the invention of claim 3 or 5, a plurality of main components for obtaining a calibration curve based on an intensity ratio between fluorescent X-rays and scattered X-rays are set, and Since the correction coefficient is theoretically determined for, the content of the main component in the sample to be analyzed can be determined more accurately.

Furthermore, according to the invention of claim 7 or 9, instead of a typical composition as a sample to be analyzed, a composition consisting of a main component and a base component is assumed, and theoretically directly based on the composition. Claim 1
Alternatively, the function and effect according to the second aspect of the invention can be more easily obtained.

Further, according to the invention of claim 8 or 10, in the invention of claim 7 or 9, each of the main components for obtaining a calibration curve based on the intensity ratio between the fluorescent X-ray and the scattered X-ray is plural, and Since the correction coefficient is theoretically determined for the component, the content of the main component in the sample to be analyzed can be determined more accurately.

[Brief description of the drawings]

FIG. 1 is a front view showing an X-ray analyzer used for a method according to a first embodiment of the present invention.

FIG. 2 is a front view showing an X-ray analyzer used for a method according to a second embodiment of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... X-ray source, 2 ... primary X-ray, 3 ... sample to be analyzed, 6 ... fluorescent X-ray, 8 ... sample stage, 9 ... scattered X-ray, 10 ... detection means,
11: calibration curve storage means, 12: virtual calibration curve creation means, 1
3 ... standard sample, 16 ... reference correction coefficient calculation means, 20 ... measurement means, 21 ... content rate calculation means, 23, 26 ... correction means, 24 ... correction coefficient calculation means.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-7-306168 (JP, A) JP-A-9-269305 (JP, A) Hirotomo Ochi et al., "Glass by X-ray fluorescence analysis" Of Shimadzu -Correction of coexisting elements in lead glass- ", Shimadzu review, 1981, Vol. 38, No. 1, p13-19 (58) Field surveyed (Int. Cl. ⁷ , DB name) G01N 23/22-23/227 JICST file (JOIS)

Claims (10)

(57) [Claims] 1. A method of irradiating primary X-rays to a plurality of standard samples having different compositions and having different compositions, the intensity of fluorescent X-rays generated from main components in the standard sample and the intensity of scattered X-rays generated from the standard sample. Measure the intensity and calculate the ratio of the two intensities, determine the correlation between the intensity ratio and the content of the main component in the standard sample in advance as a calibration curve, and irradiate the sample to be analyzed with primary X-rays. Then, the intensity of the fluorescent X-rays generated from the main components in the sample to be analyzed and the intensity of the scattered X-rays generated from the sample to be analyzed are measured, and the ratio between the two intensities is calculated. An X-ray analysis method for determining the content of a main component in a sample to be analyzed by applying the method, wherein the sample to be analyzed is a main component for obtaining a calibration curve based on an intensity ratio between the fluorescent X-ray and the scattered X-ray; Assuming that The correction factor for the absorption of minute,
Calculate by theoretical calculation assuming the composition of the sample to be analyzed, apply a calibration curve using the correction coefficient to the intensity ratio measured and calculated from the sample to be analyzed, and determine the content of the main component in the sample to be analyzed. An X-ray analysis method comprising: 2. A sample stage on which a sample is fixed, an X-ray source for irradiating the sample with primary X-rays, detection means for measuring the intensity of fluorescent X-rays and scattered X-rays generated from the sample, For a plurality of known and different standard samples, the primary X
The ratio of the intensity of the fluorescent X-rays generated from the main components in the standard sample to the intensity of the scattered X-rays generated from the standard sample when irradiated with the X-rays is calculated in advance. Curve storage means for storing the correlation with the content of the sample as a calibration curve, a main component for obtaining a calibration curve based on the intensity ratio of fluorescent X-rays and scattered X-rays, and an analysis target sample assumed to comprise coexisting components Correction means for calculating and storing a correction coefficient relating to absorption of a main component of a coexisting component to a main component by theoretical calculation based on an assumed composition of a sample to be analyzed; X-rays are irradiated, and the detection means measures the intensity of fluorescent X-rays generated from the main components in the sample to be analyzed and the intensity of scattered X-rays generated from the sample to be analyzed, and calculates the ratio between the two intensities. Applying the calibration curve stored in the calibration curve storage means using the correction coefficient stored in the correction means to the intensity ratio stored in the measurement means, An X-ray analysis apparatus comprising: a content calculation unit for determining a content of a component. 3. A method of irradiating primary X-rays to a plurality of standard samples having different compositions and different in intensity, the intensity of fluorescent X-rays generated from main components in the standard sample and the intensity of scattered X-rays generated from the standard sample. Measure the intensity and calculate the ratio of the two intensities, determine the correlation between the intensity ratio and the content of the main component in the standard sample in advance as a calibration curve, and irradiate the sample to be analyzed with primary X-rays. Then, the intensity of the fluorescent X-rays generated from the main components in the sample to be analyzed and the intensity of the scattered X-rays generated from the sample to be analyzed are measured, and the ratio between the two intensities is calculated. An X-ray analysis method for determining the content of a main component in a sample to be analyzed by applying the method, wherein the sample to be analyzed is a main component for obtaining a calibration curve based on an intensity ratio between the fluorescent X-ray and the scattered X-ray; Assuming that One as a base component, the other coexisting component as an additive component, and assuming a first virtual sample having a typical composition as a sample to be analyzed, based on the assumed composition, Theoretical intensity of fluorescent X-rays generated from the main components of
The theoretical intensity of the scattered X-rays generated from the first virtual sample is calculated, and the ratio of the two intensities is calculated as the first virtual intensity ratio. Compared with the first virtual sample, only the content of the main component and the base component is reduced. Assuming a second virtual sample that differs by a certain amount, based on the assumed composition, the theoretical intensity of the fluorescent X-ray generated from the main component in the second virtual sample and the scattered X-ray generated from the second virtual sample are calculated. The theoretical intensity is calculated, and the ratio of the two intensities is calculated as a second virtual intensity ratio. The correlation between the first and second virtual intensity ratios and the contents of the main components in the first and second virtual samples is virtually calculated. Determined as a calibration curve, a third virtual sample in which only one additive component and a base component differ from the first virtual sample by a fixed amount for each additive component is assumed, and based on the assumed composition, Fireflies generated from main components in the third virtual sample The theoretical intensity of X-rays and the theoretical intensity of scattered X-rays generated from the third virtual sample are calculated, and the ratio between the two intensities is calculated as a third virtual intensity ratio. Apply a line to the third
The content of the main component in the virtual sample is obtained, and the content of the main component in the obtained third virtual sample is calculated as
A virtual correction coefficient to be corrected based on the representative composition is calculated for each additive component so as to match the content of the main component in the first virtual sample, and a main component and a base component are calculated from the virtual correction coefficient. A reference correction coefficient for correcting based on the composition consisting of only the components is calculated, and a calibration curve using the reference correction coefficient is applied to the intensity ratio measured and calculated from the sample to be analyzed, and the content of the main component in the sample to be analyzed. X-ray analysis method, characterized in that: 4. The virtual correction coefficient according to claim 3, wherein a plurality of main components are included, and for each main component, the virtual correction coefficient is calculated by including another main component in an additional correction component. X-ray analysis method for calculating coefficients. 5. A sample stage on which a sample is fixed, an X-ray source for irradiating the sample with primary X-rays, a detecting means for measuring the intensity of fluorescent X-rays and scattered X-rays generated from the sample, For a plurality of known and different standard samples, the primary X
The ratio of the intensity of the fluorescent X-rays generated from the main components in the standard sample to the intensity of the scattered X-rays generated from the standard sample when irradiated with the X-rays is calculated in advance. Curve storage means for storing the correlation with the content of the sample as a calibration curve, a main component for obtaining a calibration curve based on the intensity ratio of fluorescent X-rays and scattered X-rays, and an analysis target sample assumed to comprise coexisting components Where one of the coexisting components is designated as a base component, the other coexisting component is an additional component, and the first virtual sample is assumed to have a typical composition as a sample to be analyzed. Based on the composition obtained, the first
The theoretical intensity of the fluorescent X-rays generated from the main components in the virtual sample and the theoretical intensity of the scattered X-rays generated from the first virtual sample are calculated, and the ratio between the two intensities is calculated as the first virtual intensity ratio. Assuming a second virtual sample in which only the contents of the main component and the base component differ by a certain amount compared to the first virtual sample, the fluorescence generated from the main component in the second virtual sample is based on the assumed composition. The theoretical intensity of X-rays and the theoretical intensity of scattered X-rays generated from the second virtual sample are calculated, and the ratio between the two intensities is calculated as a second virtual intensity ratio. Virtual calibration curve creating means for obtaining and storing a correlation with the content of the main component in the first and second virtual samples as a virtual calibration curve, and comparing the first virtual sample with one of the additive component and the base component. The third virtual trial in which only the content differs by a certain amount The theoretical intensity of fluorescent X-rays generated from the main components in the third virtual sample and the theoretical intensity of scattered X-rays generated from the third virtual sample are determined based on the assumed composition. Is calculated, and the ratio between the two intensities is calculated as a third virtual intensity ratio. The virtual calibration curve stored in the virtual calibration curve creating means is applied to the third virtual intensity ratio to calculate the third virtual intensity ratio. The content of the main component is determined, and the content of the main component in the third virtual sample is corrected based on the representative composition so as to match the content of the main component in the first virtual sample. A reference correction coefficient calculating means for calculating a virtual correction coefficient for each additive component, calculating and storing a reference correction coefficient for correcting the composition based on only the main component and the base component from the virtual correction coefficient, For target samples Irradiating primary X-rays from the X-ray source, and causing the detection means to measure the intensity of fluorescent X-rays generated from main components in the sample to be analyzed and the intensity of scattered X-rays generated from the sample to be analyzed. Measuring means for calculating and storing the ratio of the two intensities; and the intensity ratio stored in the measuring means, stored in the calibration curve storing means using the reference correction coefficient stored in the reference correction coefficient calculating means. An X-ray analysis apparatus including: a content rate calculating unit that applies a calibration curve to determine a content rate of a main component in a sample to be analyzed. 6. The virtual correction coefficient according to claim 5, wherein a plurality of main components are provided, and the reference correction coefficient calculating means calculates the virtual correction coefficient for each main component by including another main component in an additional correction component. An X-ray analyzer for calculating the reference correction coefficient from the virtual correction coefficient. 7. A method of irradiating primary X-rays to a plurality of standard samples having different compositions and having different intensities, the intensity of fluorescent X-rays generated from main components in the standard sample and the intensity of scattered X-rays generated from the standard sample. Measure the intensity and calculate the ratio of the two intensities, determine the correlation between the intensity ratio and the content of the main component in the standard sample in advance as a calibration curve, and irradiate the sample to be analyzed with primary X-rays. Then, the intensity of the fluorescent X-rays generated from the main components in the sample to be analyzed and the intensity of the scattered X-rays generated from the sample to be analyzed are measured, and the ratio between the two intensities is calculated. An X-ray analysis method for determining the content of a main component in a sample to be analyzed by applying the method, wherein the sample to be analyzed is a main component for obtaining a calibration curve based on an intensity ratio between the fluorescent X-ray and the scattered X-ray; Assuming that One as a base component, the other coexisting component as an additive component, assuming a first virtual sample having a composition consisting of a main component and a base component, and calculating the first virtual sample based on the assumed composition. Theoretical intensity of fluorescent X-rays generated from the main components of
The theoretical intensity of the scattered X-rays generated from the first virtual sample is calculated, and the ratio of the two intensities is calculated to be the first virtual intensity ratio. Compared with the first virtual sample, the content of the main component and the base component is constant. Assuming a second virtual sample that differs by an amount, based on the assumed composition, the theoretical intensity of the fluorescent X-ray generated from the main component in the second virtual sample and the theoretical intensity of the scattered X-ray generated from the second virtual sample And a ratio between the two intensities is calculated as a second virtual intensity ratio. The correlation between the first and second virtual intensity ratios and the contents of the main components in the first and second virtual samples is virtually calibrated. A third virtual sample, which is different from the first virtual sample by only a certain amount in the content of one additive component and a base component by a fixed amount, is assumed for each additive component, and based on the assumed composition, Fluorescence X generated from main components in 3 virtual samples Is calculated, and the theoretical intensity of the scattered X-ray generated from the third virtual sample is calculated, and the ratio between the two intensities is calculated as the third virtual intensity ratio. The virtual calibration curve is added to the third virtual intensity ratio. Apply, third
The content of the main component in the virtual sample is obtained, and the content of the main component in the obtained third virtual sample is calculated as
A correction coefficient to be corrected is calculated for each additive component so as to match the content of the main component in the first virtual sample, and a calibration curve using the correction coefficient is calculated for the intensity ratio measured and calculated from the sample to be analyzed. An X-ray analysis method comprising: calculating a content of a main component in a sample to be analyzed by applying the method. 8. The X-ray analysis method according to claim 7, wherein there are a plurality of main components, and for each of the main components, the other main components are included in an additional correction component to calculate the correction coefficient. 9. A sample stage on which a sample is fixed, an X-ray source for irradiating the sample with primary X-rays, detection means for measuring the intensity of fluorescent X-rays and scattered X-rays generated from the sample, For a plurality of known and different standard samples, the primary X
The ratio of the intensity of the fluorescent X-rays generated from the main components in the standard sample to the intensity of the scattered X-rays generated from the standard sample when irradiated with the X-rays is calculated in advance. Curve storage means for storing the correlation with the content of the sample as a calibration curve, a main component for obtaining a calibration curve based on the intensity ratio of fluorescent X-rays and scattered X-rays, and an analysis target sample assumed to comprise coexisting components Where one of the coexisting components is designated as a base component, the other coexisting component is an additive component, and the first virtual sample is assumed to have a composition consisting of a main component and a base component. Based on the composition obtained, the first
The theoretical intensity of the fluorescent X-rays generated from the main components in the virtual sample and the theoretical intensity of the scattered X-rays generated from the first virtual sample are calculated, and the ratio between the two intensities is calculated as the first virtual intensity ratio. Assuming a second virtual sample in which the contents of the main component and the base component differ from the first virtual sample by a fixed amount, based on the assumed composition, the fluorescence X generated from the main component in the second virtual sample is determined. The theoretical intensity of the X-rays and the theoretical intensity of the scattered X-ray generated from the second virtual sample are calculated, and the ratio between the two intensities is calculated as the second virtual intensity ratio. Virtual calibration curve creating means for obtaining and storing a correlation with the content of the main component in the first and second virtual samples as a virtual calibration curve, and comparing the first virtual sample with one additional correction component and base component A third virtual sample whose ratio differs only by a certain amount Assumed for each additive component, the theoretical intensity of fluorescent X-rays generated from the main component in the third virtual sample and the theoretical intensity of scattered X-rays generated from the third virtual sample are determined based on the assumed composition. Calculating the ratio of the two intensities to obtain a third virtual intensity ratio, and applying the virtual calibration curve stored in the virtual calibration curve creating means to the third virtual intensity ratio to obtain a main component in the third virtual sample. Is calculated, and a correction coefficient to be corrected is calculated for each additive component so that the obtained main component content in the third virtual sample matches the obtained main component content in the first virtual sample. Correction factor calculating means for storing and storing the sample to be analyzed; irradiating the sample to be analyzed with primary X-rays from the X-ray source; And the intensity of the scattered X-rays Measuring means for calculating and storing the ratio of the two intensities, and the intensity ratio stored in the measuring means, stored in the calibration curve storing means using the correction coefficient stored in the correction coefficient calculating means. An X-ray analysis apparatus comprising: a content calculating means for applying a calibration curve to obtain a content of a main component in a sample to be analyzed. 10. The method according to claim 9, wherein the main component is plural, and the correction coefficient calculating means calculates the correction coefficient for each main component by including another main component in an additional correction component. X-ray analyzer.