JP3452278B2 - Qualitative analysis method and qualitative analyzer using X-ray diffraction - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a qualitative analysis method and a qualitative analysis apparatus for determining the type and weight composition ratio of internal substances contained in a sample, and in particular, qualitative analysis using X-ray diffraction. The present invention relates to an analysis method and a qualitative analysis device.

[0002]

2. Description of the Related Art The above-mentioned qualitative analysis has been widely performed by utilizing X-ray diffraction. As a qualitative analysis method of this kind, conventionally, a method of performing measurement according to a procedure as shown in FIG. 7 is known. In this measurement method, first,
An X-ray diffraction measurement is performed on the sample to obtain an X-ray diffraction profile. This X-ray profile is a diagram shown on a graph in which the horizontal axis represents the X-ray diffraction angle (2θ) and the vertical axis represents the diffracted X-ray intensity, which is incident on the sample. It shows the diffraction angle of the X-ray diffracted by the sample and the intensity of the diffracted X-ray when the incident angle of the X-ray is changed.

Next, so-called peak search is performed on the obtained X-ray diffraction profile. The peak search is an operation for examining how many times and at what intensity of the diffraction X-ray the diffraction angle (2θ) is generated in the X-ray diffraction profile. After this peak search is completed, a primary search is then performed with reference to the standard peak card.

The standard peak card is, for example, JC
It is widely known as a PDS file, etc., and is a standard X-ray obtained when X-ray diffraction measurement is performed in advance for all kinds of compounds using a standard X-ray optical system.
The peak search results based on the line diffraction profile are summarized in the form of a card for each compound. Practically, this data is stored in the hard disk of the computer, and is read and used when necessary.

In the primary search, the peak position and the peak intensity of the peak search result obtained for the unknown sample are compared with the standard peak card corresponding to various compounds, and it is considered that the peak position and the peak intensity are included in the unknown sample which is now the target. List all compounds, ie internal substances. Of course, many of these listed internal substances include many that are not actually included in the unknown sample. The process until primary search data in a form in which all internal substances are listed up including substances that are not actually included are normally executed automatically by a computer that operates according to predetermined program software.

After completing the primary search, the operator executes a secondary search. That is, standard peak data corresponding to various substances listed in the primary search data is individually called on the CRT for each substance, and the standard peak data and the X-ray diffraction profile obtained for the unknown sample are visually compared. Then, it is determined whether each substance is contained in the unknown sample. This secondary search determines the combination of internal substances contained in the unknown sample.
In practice, it is common to select multiple sets of internal substance combinations that are considered to be more likely than one proper internal substance combination is always selected. Determining which of these selected combinations is the most likely requires very high skill.

[0007]

However, in the above-mentioned conventional qualitative analysis method, since the work until the primary search is relatively uniform, automatic processing using a computer is possible, but the determination in the secondary search is possible. But it required a great deal of skill, and automation was simply impossible.

The present invention has been made to solve the above-mentioned problems, and makes it possible to perform qualitative analysis using X-ray diffraction as automatically as possible, and it is very reliable. It is an object of the present invention to provide a qualitative analysis method and a qualitative analysis device that can obtain high analysis results.

[0009]

To achieve the above object, in the qualitative analysis method according to the present invention, (1) an X-ray diffraction profile is obtained by performing X-ray diffraction measurement on a sample, and (2) ) The type of element contained in the sample is obtained by performing elemental analysis measurement on the sample, and (3)
Select all possible internal substances from the above X-ray diffraction profile with reference to standard peak card data,
(4) A plurality of internal substance combinations are predicted by taking all combinations for all the selected internal substances, and (5) Of all the predicted internal substance combinations, all the elements determined by elemental analysis measurement are calculated. The feature is that internal substance combinations that are not included are deleted from the data.

When this configuration is viewed in correspondence with the embodiment shown in the drawing, the processing from the elemental analysis step (step 101) to the list registration step (step 107) in FIG. 4 corresponds to the configuration of the present invention. There is.

In the above step (5), the internal substance combinations (usually a plurality of sets) that remain without being deleted are all highly likely to be contained in the unknown sample. The result can be directly used as the result of the qualitative analysis. Next, the qualitative analysis apparatus according to the present invention is an qualitative analysis apparatus that determines an internal substance contained in a sample by using X-ray diffraction, and an X-ray diffraction apparatus that performs X-ray diffraction measurement on the sample and On the other hand, an elemental analysis device for performing elemental analysis measurement, a first storage means for storing a standard peak card, a second storage means for storing a calculation result, and an X-ray diffraction profile calculated from the measurement result of the X-ray diffraction device. Means, a means for calculating an internal substance from the X-ray diffraction profile with reference to the standard peak card, and a plurality of internal substance combinations are obtained by taking all combinations for all the selected internal substances. A means for performing an operation and an internal substance combination that does not include all the elements obtained by the elemental analysis measurement among the obtained plurality of internal substance combinations And having a means for remove the Align stored in the second storage means.

The elemental analysis measurement is a measurement for investigating the kinds of elements contained in an unknown sample, the weight composition ratio of those elements, and the like. Specifically, the fluorescent X-ray analysis method,
Various methods such as atomic absorption method or mass spectrometry can be adopted. Fluorescent X-ray analysis is a method of irradiating a sample with primary X-rays (continuous X-rays) and diffracting the X-rays (fluorescent X-rays).
The internal elements of the sample that contributed to the X-ray diffraction are detected by spectrally separating the (rays) with a monochromator. The term “weight composition ratio” is meant to include the weight value of each element itself.

The atomic absorption method is a method for detecting an element contained in a sample by utilizing the phenomenon that the light transmittance when light is transmitted through each element, that is, the absorbance is different depending on each element. Mass spectrometry is a method in which a sample is gasified and ionized, and then passed through a constant electric field to separate each element.

In order to further increase the reliability of the results of the qualitative analysis, the degree of agreement between the standard peak card data corresponding to the internal substance combinations remaining without being deleted and the X-ray diffraction profile obtained for the unknown sample. It is desirable to select an appropriate internal substance combination by comparing the values by visual inspection.

In order to further improve reliability, the weight composition ratio of each element is also obtained by elemental analysis and measurement, and based on the atomic weight of each element and the obtained weight composition ratio of each element. Therefore, it is desirable to obtain the weight composition ratio of each internal substance contained in each internal substance combination.

In order to further improve the reliability, the weight composition ratio of each internal substance contained in each individual internal substance combination is calculated by using the least square method, and the order of the size of the standard deviation at that time is calculated. Therefore, it is desirable to rank according to the accuracy of the determination of internal substance combinations.
For example, the ranking is performed from the smallest standard deviation in order of high accuracy.

[0017]

By simply comparing the X-ray diffraction profile obtained for the unknown sample with the standard peak card data and determining the internal substances, the number of combinations of internal substances that are considered to be contained in the sample becomes extremely large. Narrowing these down to one or a small number of combinations that are considered to be appropriate requires a great deal of skill, and it is extremely unlikely to do this automatically using a computer.

On the other hand, in the present invention, the type of element contained in the unknown sample is measured separately from the X-ray diffraction profile,
The elemental data is used to narrow down the combinations of internal substances. In other words, among the extremely large number of internal substance combinations selected by comparing the X-ray diffraction profile with the standard peak card data, many combinations that are considered to have extremely low probability of being contained in the unknown sample are subject to the operator's subjectivity. It is automatically deleted without being deleted. Therefore, the internal substance combinations that remain without being deleted are highly likely to be contained in the unknown sample, and the number of combinations is narrowed down to a small number.
In this way, qualitative analysis using X-ray diffraction can be performed automatically as much as possible, and extremely reliable analysis results can be obtained.

[0019]

EXAMPLES Example 1 FIG. 1 is a block diagram showing an analysis system using the qualitative analysis method according to the present invention. This analysis system has a computer 1 that controls overall analysis processing, and the computer 1 is a CPU.
It has a (central processing unit) 2, a semiconductor memory 3 for storing various data in a readable and writable manner, and an interface I / F arranged between various external devices. Each interface I / F is equipped with the following devices, that is, an external memory such as a hard disk 4 storing a program for analysis processing and standard peak card data corresponding to various compounds as table data, and an X-ray diffraction measurement. An X-ray diffraction device 8 for performing the measurement, a fluorescent X-ray analysis device 9 for performing the elemental analysis measurement, a printer 18 for making a hard copy of the measurement result on a sheet, and a CRT 6 for displaying the measurement result as an image, etc. Various input / output devices are connected.

The standard peak card is, for example, JC
It is widely known as a PDS file, etc., and is a standard X-ray obtained when X-ray diffraction measurement is performed in advance for all kinds of compounds using a standard X-ray optical system.
The peak search results based on the line diffraction profile are summarized in the form of a card for each compound. The contents of the card are stored in the hard disk 4 in the form of table data.

The X-ray diffractometer 8 is, for example, as shown in FIG. 2, an X-ray source 10, and a sample rotation system 12 for rotating the unknown sample 11 stepwise or continuously at an appropriate angular velocity, that is, θ rotation. It has an X-ray counter 13 which rotates about the sample 11 in the same direction at an angular velocity twice the θ rotation, that is, 2θ rotation. Reference numeral 14 denotes a divergence prevention slit that restricts the divergence of the X-ray beam in the horizontal direction.
Further, reference numeral 15 indicates a light-receiving slit provided at the focus position of the diffracted X-ray.

The fluorescent X-ray analyzer 9 has, for example, as shown in FIG. 3, an X-ray source 20, a monochromator 16, and an X-ray counter 23 which rotates 2θ about the center point of the monochromator 16. is doing. The unknown sample 21 is arranged at a position where the primary X-ray (continuous X-ray) emitted from the X-ray source 20 strikes. Reference numerals 24 and 25 denote slits that regulate the spread of X-rays. The unknown sample 11 and the fluorescent X-ray analyzer 9 provided to the X-ray diffractometer 8 (FIG. 2).
Regarding the unknown sample 21 to be delivered to, the one sample may be divided into two and mounted on each device, or one sample placed at one sample support position is commonly used. You may do it. In addition, the X-ray source 10
And the X-ray source 20 can be shared by the same X-ray source.

Hereinafter, using the X-ray analysis system having the above-described structure, qualitative analysis is performed on the unknown samples 11 and 21, that is, an analysis for determining what kind of internal substance is contained in the unknown sample. The operation when performing
This will be described with reference to the flowchart shown in FIG.

First, the kinds of elements contained in the sample 21 and the weight composition ratio of each element are measured using the X-ray fluorescence analyzer 9 (FIG. 3) (step 101). In this embodiment, the weight itself is measured as the weight composition ratio.
More specifically, the contents of the measurement will be described. The sample 21 is irradiated with the X-rays emitted from the X-ray source 20, the fluorescent X-rays diffracted by the sample 21 are applied to the monochromator 16, and are dispersed. The counted X-rays are counted by the X-ray counter 23 which moves by 2θ scanning. Since the X-rays separated by the monochromator 16 have a unique diffraction angle corresponding to the internal substance contained in the sample 21, the type of internal substance can be determined from the X-ray diffraction angle counted by the X-ray counter 23. Furthermore, the composition weight of these internal substances can be determined from the intensity of the diffracted X-rays.

Table 4 shows an example of the measurement results thus obtained. In this measurement example, Zn, K, Cl, Ti, and A are used as internal substances contained in the sample.
Seven kinds of elements of l, Si and O are detected. Of course, if the sample to be delivered changes, the type of element detected also changes.

Next, X-ray diffraction measurement is performed using the X-ray diffractometer 8 (FIG. 2) to obtain an X-ray diffraction profile (step 102). Specifically, in FIG. 2, while rotating the sample 11 by θ, the sample 11 is irradiated with X-rays,
At the same time, the X-ray counter 13 is rotated by 2θ and the sample 1
The diffracted X-ray diffracted at 1 is detected. The output of the X-ray counter 13 is guided to the X-ray intensity calculation circuit 17, and the calculation circuit 1
The X-ray intensity (cps: count / second) is calculated by 7.

The CPU 2 (FIG. 1) displays the relationship between the diffraction angle (2θ) of the diffracted X-ray and the X-ray intensity of the diffracted X-ray as a graph on the CRT 6. FIG. 5 shows an example of the graph thus displayed, and the peak figure drawn on this graph is called an X-ray diffraction profile.

When the X-ray diffraction profile is obtained as described above, the CPU 2 (FIG. 1) then executes peak search processing (step 103). This peak search is to obtain the diffraction angle (2θ), X-ray intensity value, etc. for all peak waveforms included in the X-ray diffraction profile. The result of this peak search is hard-copied as a numerical value by the printer 18 as shown in Table 1, or displayed as an image in a form corresponding to the X-ray diffraction profile as shown by the symbol "○" in FIG. To be done. In Table 1, the full width at half maximum is obtained in addition to the diffraction angle (2θ) and the X-ray intensity. As is well known, the full width at half maximum is the peak width at an intensity value of 1/2 of the peak height (that is, X-ray intensity).

Thereafter, the CPU 2 executes the primary search based on the obtained peak search result (step 10).
4). Specifically, the peak angle position and the peak intensity in the standard peak card data corresponding to various substances stored in the hard disk 4 and the result of the peak search for the unknown sample just performed (that is, the peak search data in Table 1) The internal substance considered to be contained in the sample 11 is selected by comparing the peak angle position and the peak intensity at. Usually, multiple types of substances are selected.

Table 2 shows an example of the measurement results thus obtained. In this measurement example, as the internal substance, a plurality of types such as ZnO, SiO ₂ , TiO ₂ , ...
For example, about 48 kinds of substances are selected. In Table 2,
Twenty-two of them are shown. The "reliability coefficient" listed in Table 2 is an index value that indicates whether the probability of being contained in an unknown sample is high or low.
It indicates that the substances with higher numerical values are more likely to be contained. There are various methods for determining specific numerical values, but in general, the degree of coincidence of peak angle positions and the degree of coincidence of peak intensities are often expressed numerically.

Then, in step 105, considering all combinations of the selected internal substances,
Store in the memory 3. For example, Z as the internal substance
Assuming that three kinds of nO, SiO ₂ , and TiO ₂ are selected, the first combination: ZnO, the second combination: SiO _2, the third combination: TiO _2, the fourth combination: ZnO, SiO _2, the fifth combination: ZnO. , TiO ₂ 6th combination: SiO ₂ , TiO ₂ 7th combination: ZnO, SiO ₂ , TiO ₂ 7 types of combinations are listed. Of course, the greater the number of internal substances selected in the primary search in step 104, the greater the number of internal substance combinations.

Thereafter, the process proceeds to step 106 and step 1
Among the internal substance combinations listed in 05,
It is checked whether all the elements measured in step 101 are contained, and if they are contained, the internal substance combination is registered in the memory 3 as a list. on the other hand,
When all of these elements are not included, that is, when some of these elements are not included, the internal substance combination is not registered in the memory 3 and is deleted from the list registration.

In the elemental analysis examples shown in Table 4, Zn, K,
Since seven kinds of elements of Cl, Ti, Al, Si and O were detected, in the case of this example, if all of these seven kinds of elements are not included in the internal substance combination, the combination is not possible. Delete as appropriate. By the way,
The seven combinations from the first combination to the seventh combination exemplified in the above description do not include all of these seven types of elements, and are therefore deleted from the list.
In this way, a plurality of types of internal substance combinations containing all the plurality of elements detected by the elemental analysis measurement are selected in the memory 3.

The internal substance combination thus selected has a high probability of being contained in the sample,
Moreover, since the number of them is narrowed down considerably, it is very meaningful to obtain data on this internal substance combination. For example, for each of a plurality of selected internal substance combinations, the standard peak card data is called from the hard disk 4 and the CRT 6
Which internal substance combination is most suitable by projecting on the CRT 6 and visually comparing the coincidence between the recalled standard peak card data and the X-ray diffraction profile (FIG. 5) obtained for the unknown sample 11. It is possible to determine whether the combination is a proper combination, that is, which internal substance combination is most likely to be contained inside the sample. This visual judgment is much simpler and more reliable than the conventional visual judgment.

If a process as shown in step 109 and step 110 in FIG. 4 is performed instead of the above visual judgment, a highly reliable judgment result can be obtained completely automatically. In the evaluation step shown in step 109, for each of the selected plural internal substance combinations, the composition weight or composition ratio of each substance contained in the combination is obtained. An example of how to obtain it is as follows.

Now, the list registered in step 107 includes an internal substance combination consisting of five types of substances of ZnO, SiO ₂ , TiO ₂ , KCl and Al ₂ O ₃ , and this combination is evaluated. Consider when to do. In addition, in the elemental analysis measurement, it is assumed that the measurement results shown in Table 4 are obtained.

In this case, a table as shown in Table 3 is assumed for convenience. In this table, in the column (D) in the vertical direction, the above 5
The internal substances of the types are arranged, the seven types of composition elements are arranged in the (B) column in the horizontal direction, and the composition weight of each composition element is entered in the (C) column of the horizontal direction. The numerical value under each composition element is the atomic weight of each element. Further, W1 to W5 shown below each internal substance indicate the composition weight of each internal substance to be obtained.

In this table, the numerical value entered in the intersection column between each internal substance and each composition element is a value obtained by multiplying the atomic weight of each element by the number of elements contained in each internal substance. In this table, formulating the weight of each element pays attention to the formula: Zn: 65.37 × W1 = 19.6 K: 39.102 × W4 = 9.77 Cl: 35.453 × W4 = For 8.86 Ti: 47.90 × W3 = 11.9 For Al: 53.963 × W5 = 2.68 For Si: 28.086 × W2 = 4.21 For O: 15.999 × W1 + 31.9988 ×
W2 + 31.998 x W3 + 47.9998 x W5 = 1
Each equation of 9.9 is obtained.

Solving these equations using the method of least squares,
The composition weights W1 to W5 are obtained, and the standard deviation at this time is also obtained. Table 5 shows an example of the evaluation results thus obtained. The numerical value shown in parentheses after each internal substance is the composition weight of each internal substance obtained as described above. In Table 5, No. 1-No. Although only the results for four types of internal substance combinations of 4 are shown, the evaluation results for more internal substance combinations can be shown if necessary.

At step 110 (FIG. 4), focusing on the standard deviation of each combination when the composition weight is obtained by the method of least squares, the ordering is performed in the order of the combination with the highest probability contained in the sample. Specifically, it is assumed that the probability is higher from the combination with the smallest standard deviation.

The measurement results obtained when elemental analysis is carried out using a fluorescent X-ray analyzer (FIG. 3) (Table 4)
Regarding the composition weight ratio of, there are many cases in which errors that differ from element to element are included. This error can be calculated empirically for each element. Therefore, when the calculation is performed using the method of least squares in the process from Table 3 to Table 5, it is desirable to weight the determination result of the internal substance according to the error of the measurement result of the elemental analysis measurement. This makes it possible to obtain a more reliable determination result.

Example 2 In order to further improve the analysis accuracy, it is possible to include a processing step of comprehensive judgment as shown in step 111 in FIG. This comprehensive judgment is performed by comparing the following three analysis processing steps, that is, (1) the plurality of internal substance combinations registered in step 107 with the degree of coincidence with the X-ray diffraction profile obtained for the unknown sample. , A processing step of determining the order of the internal substance combination (matching degree comparison processing step), and (2) the ranking processing step of step 110, that is, step 1
Process steps for determining the order of internal substance combinations based on the standard deviation when the weight composition ratio of internal substances is calculated using the least squares method for each of the plurality of internal substance combinations registered in 07 No standard deviation ranking process), and (3) Step 10
A processing step (standard deviation ranking processing step in which errors are taken into consideration), in which weighting is added to the ranking process in step 110 in accordance with the error included in the measurement result of the elemental analysis measurement in 1 to determine the ranking regarding the internal substance combination The final judgment result is given by taking all the results of each processing step into consideration.

Various concrete methods for such comprehensive judgment can be considered. For example, the individual results of the above (1) to (3) are arranged on a CRT or hardcopy on a sheet and arranged by an operator to visually compare them,
It can be judged empirically and subjectively. Above (1)
Since the results of each of the processes (3) to (3) are highly reliable data, it is possible to obtain a highly reliable determination result even by the above visual determination.

Further, instead of such a visual method,
It is also possible to obtain an objective determination result that does not depend on the subjectivity of the operator by numerically expressing the results of the above processes (1) to (3) and expressing each numerical value mathematically. According to such mathematical expression processing, all processing up to the final determination result can be automatically processed by the computer.

The following method can be considered as a specific example of such a numerical determination process. Now, referring to Table 2, what can be considered as an internal substance is ZnO, SiO.
It is assumed that there are four kinds of ₂ , ₂ , TiO ₂ , and KCl. Of course, in reality, many internal substances listed in Table 2 must be taken into consideration, but here, for the sake of simplicity, only the above three types will be considered. In step 107, a combination that satisfies the condition of step 106 is registered in a list from among all combinations of these four types of internal substances. In order to simplify the description, for example, a combination of the first set: ZnO, SiO ₂ , TiO ₂ second set: SiO ₂ , TiO ₂ , KCl third set: ZnO, TiO ₂ , KCl It is assumed that it is registered in the list.

In the matching degree comparison processing step (1), matching data α1, α2, α3 are obtained for each of the combinations of the first to third sets. The matching data means that the number of peaks of the standard peak card data corresponding to each combination of the first to third sets and the number of peaks obtained from the X-ray diffraction profile of the unknown sample match. It is a value indicating whether or not. Expressing this as a numerical value, let P be the total number of peaks obtained from the X-ray diffraction profile for the unknown sample, and regard the unknown sample among the peaks of the standard peak card data corresponding to each combination of the first to third sets. Let N be the number of peaks that match the peak, and divide the reliability coefficient (see Table 2) of each internal substance such as ZnO and SiO ₂ by 1000 to obtain S 1, S 2 ,.
, Sn (n is the number of internal substances selected by the primary search data), the matching data α is expressed as α = (N / P) x (S1 x S2 x ... x Sn) To be done.

Now, assuming that the matching data of each combination of the first to third sets are α1, α2 and α3, respectively, and their values are α1>α2> α3, (1)
The order of accuracy regarding the combination of internal substances in the process of comparing the degree of coincidence is as follows: 1st group (ZnO, SiO ₂ , TiO ₂ ) = α 1 2nd group: 2nd group (SiO ₂ , TiO ₂ , KCl) = [alpha] 2 3-position: a third set _{(ZnO, TiO 2, KCl)} = α3 ‥‥‥ (a).

Next, rank measurement is performed without considering the error (2). Results of the measurement, the first set to third set of standard deviations for each combination a first set _{(ZnO, SiO 2, TiO 2} ) = α6 second set _{(SiO 2, TiO 2, KCl} ) = α5 third Assuming that the group (ZnO, TiO ₂ , KCl) = α4 and their values are α4 <α5 <α6, the smaller the standard deviation, the higher the probability of being included as an internal substance combination. : the third set _{(ZnO, TiO 2, KCl)} = α4 2 -position: the second set _{(SiO 2, TiO 2, KCl} ) = α5 3 -position: the first set _{(ZnO, SiO 2, TiO 2} ) = α6 ‥‥ (B)

Next, rank measurement is performed in consideration of the error (3). Results of the measurement, the first set to third set of standard deviations for each combination a first set _{(ZnO, SiO 2, TiO 2} ) = α7 second set _{(SiO 2, TiO 2, KCl} ) = α9 third Assuming that the group (ZnO, TiO ₂ , KCl) = α8 and α7 <α8 <α9, the order is: 1st group: 1st group (ZnO, SiO ₂ , TiO ₂ ) = α7 2nd group: ZnO (ZnO) , TiO ₂ , KCl) = α8 3rd position: Second set (SiO ₂ , TiO ₂ , KCl) = α9 ... (C).

Rank result (A) by the coincidence degree comparison measurement (1), rank result (B) by the standard deviation rank measurement (2) considering error, and rank by the standard deviation rank measurement (3) considering error When compared with the result (C), the rankings are all different. When actually looking at an unknown sample, the combination of internal substances contained in the sample is always one, so theoretically different rank results such as (A), (B), and (C) are obtained. You can't be. However, under the present circumstances, when the measurement is actually performed, the above-described different ranking results are obtained due to various causes.

If the judgment is ended by performing only one kind of the above-mentioned rank judgment measurements (1) to (3), the rank result obtained is not reliable. It may become. On the other hand, the results (A) to (1) to (3) in the ranking determination measurement
If (B) is comprehensively judged, it is possible to obtain a judgment result having high reproducibility and therefore high reliability.

For example, with respect to the results of (A) to (C) above, rank coefficients α1, α2, α3 for the same combination are used.
, ........, α1 × (1−α6) × (1−α7) for the first set (ZnO, SiO ₂ , TiO ₂ ) and α2 × for the second set (SiO ₂ , TiO ₂ , KCl) (1-α5) × (1-α9) With respect to the third set (ZnO, TiO ₂ , KCl), values such as α3 × (1-α4) × (1-α8) (D) are obtained.

In the above equation (D), the values obtained by subtracting them from 1 for α4 to α9 are taken as follows. For α1 to α3, the first, second, third, ...
, While the rankings for α4 to α9 are ranked as 1st, 2nd, 3rd, and so on in descending order of their values. This is to unify.

Since the above equation (D) is a value obtained by mathematically integrating the results of the respective rank determination measurements of (1) to (3), the magnitudes of these values are compared and the first to third groups are compared. By determining the rank of the accuracy of the content combination of the set, it is possible to make a judgment with very good reproducibility. In addition,
In the formula (D), the first, second, third, ...

The present invention has been described above with reference to the preferred embodiments, but the present invention is not limited to the embodiments and can be variously modified within the technical scope described in the claims.
For example, the X-ray diffractometer shown in FIG. 2 is merely an example, and an X-ray diffractometer having any other structure can be used. Further, the fluorescent X-ray analyzer shown in FIG. 3 is also merely an example, and a fluorescent X-ray analyzer having any other structure can be used. Further, as an apparatus for performing elemental analysis measurement, any apparatus other than the fluorescence X-ray analysis apparatus such as an atomic absorption measurement apparatus, a mass spectrometry apparatus, etc. can be used.

[0056]

According to the qualitative analysis method using X-ray diffraction according to the first aspect, the qualitative analysis using X-ray diffraction can be automatically performed as much as possible, and the reliability is very high. The analysis result can be obtained.

According to the qualitative analysis method using X-ray diffraction according to the second aspect, highly reliable determination can be performed by a simple method.

According to the qualitative analysis method using X-ray diffraction as set forth in claim 3, the weight composition ratio of each internal substance can be known.
It is possible to obtain a determination result with high utility value.

According to the qualitative analysis method using X-ray diffraction described in claim 4, the final judgment result can be obtained completely automatically.

According to the qualitative analysis method using X-ray diffraction according to the fifth aspect, since elemental analysis measurement is performed using X-rays, it becomes possible to share parts with the X-ray diffraction device. Therefore, it is structurally advantageous.

[0061]

[Table 1] Peak search data ───────────────────────────────────   Peak NO. 2θ intensity half-value width Peak NO. 2θ intensity half-value width ───────────────────────────────────      1 20.600 531 0.094 24 50.100 3489 0.118      2 20.780 2246 0.141 25 52.480 763 0.141      3 25.240 19992 0.141 26 53.820 3499 0.165      4 25.480 1805 0.094 27 54.820 928 0.071      5 26.580 11044 0.118 28 55.000 3583 0.141      6 28.280 16687 0.118 29 55.220 520 0.047      7 31.700 12306 0.118 30 55.260 440 0.047      8 34.360 9127 0.118 31 56.540 8004 0.118      9 35.080 1875 0.141 32 56.700 493 0.047     10 36.180 20703 0.141 33 57.200 356 0.047     11 36.460 1381 0.118 34 57.440 1605 0.141     12 36.860 1277 0.141 35 58.560 2161 0.141     13 37.720 4793 0.141 36 59.900 2517 0.094     14 38.280 442 0.141 37 62.040 684 0.141     15 38.500 1410 0.141 38 62.620 3090 0.094     16 39.400 877 0.118 39 62.800 7053 0.118     17 40.240 802 0.071 40 65.700 622 0.118     18 40.440 7349 0.141 41 66.320 3901 0.118     19 42.380 944 0.118 42 67.680 1461 0.118     20 43.280 1898 0.141 43 67.900 6034 0.141     21 45.740 437 0.141 44 68.100 2383 0.118     22 47.480 4932 0.118 45 68.260 914 0.071     23 47.980 6034 0.141 46 68.660 11261 0.047 ───────────────────────────────────

[0062]

[Table 2] Primary search data     ───────────────────────────────       NO. Card NO. Chemical formula Standard peak agreement Reliability                                           Number number coefficient     ───────────────────────────────        1 36-1451 Zn O 13 13 1000        2 33-1161 Si O2 28 23 958        3 21-1272 Ti O2 18 15 954        4 41-1476 K Cl 9 8 940        5 29-1155 Ag Zn 7 4 800        6 28-0439 Au Ag Zn2 11 8 749        7 43-0596 Si O2 6 4 741        8 25-0982 Ti Hl.924 5 3 740        9 14-0255 Ag (Cl .Br) 9 6 730       10 35-1152 Cu Zn5 8 6 704       11 42-1468 Al2 O3 25 9 695       12 03-0798 Ca2 Si 6 5 691       13 43-1484 Al2 O3 25 9 683       14 40-0547 Cs2 K Cu F6 10 6 671       15 35-1332 K3 U F6 6 4 663       16 17-0385 Zr O0.35 12 7 648       17 30-0970 Rb2 K Mo F6 9 6 644       18 24-0186 Ca Ni Si4 O10 35 20 626       19 10-0302 K Se H 14 7 625       20 26-1141 Fe2 Si 6 4 623       21 17-0584 Cu3 V O4 7 4 623       22 22-1326 Ag Cl 11 6 613     ───────────────────────────────

[0063]

[Table 3] Data for evaluation   ───────────────────────────────────   (B) → Zn K Cl Ti Al Si O   (D) 65.37 39.102 35.453 47.902 26.9815 28.086 15.9994    ↓   ───────────────────────────────────   Zn O 65.37 − − − − − 15.9994   (W1)   ───────────────────────────────────   Si O2 − − − − − 28.086 31.9988   (W2)   ───────────────────────────────────   Ti O2 − − − 47.90 − − 31.9988   (W3)   ───────────────────────────────────   K Cl − 39.102 35.453 − − − −   (W4)   ───────────────────────────────────   Al2 O3 − − − − 53.963 − 47.9982   (W5)   ───────────────────────────────────   (C) → 19.6 9.77 8.86 11.9 2.68 4.21 19.9   ───────────────────────────────────

[0064]

[Table 4] Elemental analysis measurement results           ────────────────────────────               Ingredient Content (composition weight) Composition ratio           ────────────────────────────               Zn 19.6 0.2548           ────────────────────────────               K 9.77 0.1270           ────────────────────────────               Cl 8.86 0.1150           ────────────────────────────               Ti 11.9 0.1547           ────────────────────────────               Al 2.68 0.0348           ────────────────────────────               Si 4.21 0.0547           ────────────────────────────               O 19.9 0.2587           ────────────────────────────             Total 76.921           ────────────────────────────

[0065]

[Table 5] Evaluation results   ───────────────────────────────────     Internal substance (composition weight W) standard deviation      NO.   ───────────────────────────────────       1 ZnO (0.30), SiO2 (0.15), TiO2 (0.25), KCl (0.25) 0.05              Al2O3 (0.05)   ───────────────────────────────────       2 SiO2 (0.16), TiO2 (0.25), KCl (0.25), AgZn (0.3) 9.53              Al2O3 (0.056)   ───────────────────────────────────       3 KCl (0.25), AuAgZn2 (0.15), SiO2 (0.19) 25.86              TiH1.924 (0.25), Al2O3 (0.07)   ───────────────────────────────────       4 KCl (0.25), AuAgZn2 (0.15), SiO2 (0.2) 36.58              TiH1.924 (0.25), AgCl (0.00), Al2O3 (0.07)   ───────────────────────────────────

[0066]

[Brief description of drawings]

FIG. 1 is a block diagram showing a configuration of a measurement system for carrying out a qualitative analysis method using X-ray diffraction according to the present invention.

FIG. 2 is a diagram schematically showing an example of an X-ray diffractometer.

FIG. 3 is a diagram schematically showing an example of a fluorescent X-ray analyzer.

FIG. 4 is a flowchart showing a flow of measurement executed by the control system shown in FIG.

FIG. 5 is a graph showing an example of an X-ray diffraction profile.

FIG. 6 is a diagram showing a state in which peak search data is displayed as an image on a CRT.

FIG. 7 is a flowchart showing a flow of measurement in a conventional qualitative analysis method using X-ray diffraction.

[Explanation of symbols]

1 computer 6 CRT 10 X-ray source 11 unknown sample 12 Sample rotation system 13 X-ray counter 14 Divergence prevention slit 15 Light receiving slit 16 Monochromator 20 X-ray source 21 unknown sample 23 X-ray counter 24,25 slits

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-296950 (JP, A) JP-A-3-245047 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G01N 23/00-23/227

Claims (6)

(57) [Claims] 1. A qualitative analysis method for determining an internal substance contained in a sample by using X-ray diffraction, wherein an X-ray diffraction profile is obtained by performing X-ray diffraction measurement on the sample, and an element for the sample is obtained. Determine the types of elements contained in the sample by performing analytical measurements, select all possible internal substances from the above X-ray diffraction profile by referring to the standard peak card data, and select all combinations for all the selected internal substances. X is characterized by predicting a plurality of combinations of internal substances by taking the combination of internal substances that does not contain all the elements obtained by elemental analysis measurement from all the predicted combinations of internal substances. Qualitative analysis method using line diffraction. 2. The qualitative analysis method according to claim 1, wherein
X-ray diffraction characterized by selecting an appropriate internal substance combination by comparing the degree of agreement between the standard peak card data corresponding to the internal substance combination that remains without being deleted and the above X-ray diffraction profile. Qualitative analysis method used. 3. The qualitative analysis method according to claim 2,
In addition to the type of element by elemental analysis measurement, the weight composition ratio of each element is also obtained, and based on the atomic weight of each element and the weight composition ratio of each element obtained, each internal substance contained in each internal substance combination A qualitative analysis method using X-ray diffraction, which comprises determining a weight composition ratio of. 4. A qualitative analysis method using X-ray diffraction according to any one of claims 1 to 3 ,
A qualitative analysis method using X-ray diffraction, characterized in that the elemental analysis measurement is performed by fluorescent X-ray analysis. 5. The qualitative analysis method using X-ray diffraction according to any one of claims 2 to 4 ,
A qualitative analysis method using X-ray diffraction, wherein the determination result of the internal substance is weighted according to the error included in the measurement result of the elemental analysis measurement. 6. A qualitative analyzer for determining an internal substance contained in a sample by using X-ray diffraction, and an X-ray diffractometer for performing X-ray diffraction measurement on the sample, and elemental analysis measurement for the sample An elemental analysis device, a first storage means for storing a standard peak card, a second storage means for storing a calculation result, a means for calculating an X-ray diffraction profile from a measurement result of the X-ray diffraction device, the standard peak A means for performing an operation for selecting an internal substance from the X-ray diffraction profile by referring to the card, and a means for performing an operation for obtaining a plurality of combinations of internal substances by taking all combinations for all the selected internal substances, Delete the internal substance combination that does not contain all the elements determined by the elemental analysis measurement from the plurality of internal substance combinations obtained above. Qualitative analysis apparatus characterized by comprising a means for storing the serial second storage means.