JP4688668B2 - Library analysis method and library analysis apparatus - Google Patents

Description

  The present invention relates to a library analysis method and a library analysis apparatus suitable for analyzing a plurality of samples prepared by mixing a plurality of types of raw materials at different ratios, for example, several tens or more using X-ray diffraction measurement. About. In particular, a library analysis method and library analysis suitable for automatically analyzing a plurality of samples forming composition points of a multi-component composition diagram and qualitatively analyzing unknown substances from the plurality of samples forming the composition diagram Relates to the device.

  Taking inorganic materials as an example, recent advances in fine ceramic technology have made it possible to control the crystal structure, composition, crystal grain size, and the like of ceramic materials from the micron to the nanoscale. For this reason, the development of application of ceramic materials to electronic materials and the like is rapidly expanding. Among these, ceramic oxides have a wide range of physical properties such as dielectric properties, magnetic properties, and electrical conductivity. The diversity of functions of ceramic materials means that the parameters to be controlled as ceramic materials are extremely diverse including their non-stoichiometry and crystal structure anisotropy.

  As a result, the conventional method of mixing a plurality of types of inorganic material raw materials as starting materials at different ratios and further firing them to produce ceramic materials one by one, and examining their properties, Not only does it take a tremendous amount of time to reach the material, it is extremely unlikely to lead to accidental discoveries that are beyond intuition and experience.

  Furthermore, when handling the same type of material, if the handling is performed by a plurality of people, the probability of causing an error due to a human error increases. In searching for new ceramic materials, it is possible to automatically analyze materials in addition to systematically controlling the combination of various raw materials by using an automatic processor. Become important. In other words, it is possible to effectively search for new ceramic materials by automating the analysis of materials so that an enormous variety of materials are not accumulated without being analyzed.

  In the case of organic material raw materials as an example, it is well known that, for example, in the field of pharmaceuticals, the covinatorial technique is widely adopted in the development of effective drugs. Also in this field, in addition to generating a huge number of samples with different mixing ratios by mixing multiple types of raw materials accurately and in a short time, if it can be analyzed according to the timing of sample generation, The search for new materials can be expected to make great progress in the scientific and technological fields.

  The inventors have invented a chemical reaction processing apparatus for generating a large number of samples obtained by mixing a plurality of inorganic material raw materials in combinations of different ratios and analyzing these samples, and filed a patent application for this apparatus. (For example, see Patent Document 1). By using this chemical reaction processing apparatus, a large number of chemical products can be obtained and analyzed and evaluated by easy control.

  As a method for qualitative analysis of chemical products, a method using X-rays is most widely adopted (see, for example, Patent Document 2). In this method, there is a qualitative analysis method in which an actual measurement X-ray diffraction profile is obtained by performing X-ray diffraction measurement of a sample and collated with a standard X-ray diffraction profile of a compound obtained by a possible combination of elements contained in the sample. Proposed. However, the conventional qualitative analysis of a large number of chemical products obtained by combinatorial techniques takes a long time for the analysis and is one of the major obstacles in material search. It can be. In particular, in the case of a chemical product obtained by mixing raw materials composed of three or more types of samples at different ratios, the types of samples are enormous, and therefore it is difficult to search for materials.

JP 2001-219052 (pages 3-7, FIG. 2) Japanese Patent No. 345278 (pages 3-6, FIGS. 1-4)

  The present invention is a measured X-ray diffraction profile obtained using, for example, the above-described chemical reaction apparatus developed by the present inventors, and a library composed of many types of samples located at the composition points in the composition diagram. An object of the present invention is to provide a library analysis method and a library analysis apparatus capable of efficiently qualitatively analyzing a compound constituting a sample based on an actual measurement X-ray diffraction profile obtained in the result of measurement by X-ray diffraction measurement. To do.

  In particular, when an unknown substance exists in a sample in a library, an object is to provide a library analysis method and a library analysis apparatus effective for efficiently evaluating the unknown substance and performing a qualitative analysis. .

  The present invention has been made to solve the above-described problems, and compares an actual measurement X-ray diffraction profile of a sample located at a composition point of a composition diagram with a standard X-ray diffraction profile of a database. Thus, three or more kinds of pure compounds are identified, and three kinds of pure compounds are obtained from the measured X-ray diffraction profiles of the samples of the composition points included in the triangle connecting the composition points where the three kinds of pure compounds are located. If a matching X-ray diffraction profile in a compound is deleted and, as a result, if there is a remaining X-ray diffraction profile, the remaining X-ray diffraction profile is identified as another pure compound or cannot be identified Is analyzed, that is, evaluated as an X-ray diffraction profile of an unknown substance.

(1) That is, the library analysis method according to the present invention is formed by mixing so that the combination ratio of n types (n is 3 or more) of raw materials becomes a ratio of composition points different from each other in an n-component composition diagram. A library analysis method for analyzing a library by performing X-ray diffraction measurement on a library consisting of a plurality of samples that are chemical products,
(I) attaching different symbols to the plurality of samples;
(Ii) creating an actual X-ray diffraction profile for each code of the sample by performing X-ray diffraction measurement on each of the plurality of samples;
(Iii) A pure compound is searched by comparing the measured X-ray diffraction profile for each code with a standard X-ray diffraction profile composed of a combination of elements constituting the raw material stored in a compound database. Determining an existing composition point;
(Iv) selecting three points on the same coordinate plane among the composition points where the pure compound exists, and forming one triangle;
(V) The measured X-ray diffraction profile of the sample at each composition point included in the triangle and the standard X-ray diffraction profile of the pure compound at the three points are sequentially collated to match a predetermined correlation or more. Deleting the standard X-ray diffraction profile from the measured X-ray diffraction profile;
(Vi) repeating the step (v) for all the composition point samples included in the one triangle, and storing the measured X-ray diffraction profile remaining after the repetition for each of the codes;
It is characterized by having.

  In the above configuration, the “composition diagram” is a ternary system when there are three types of raw materials, and is called a ternary composition diagram. Moreover, when there are four types of raw materials, a quaternary composition diagram is obtained. “Composition point” means the point at which the lines intersect when the edges connecting the vertices constituting the composition diagram are divided into several parts at equal intervals on the coordinates including the composition diagram. This is the point where the line and each side intersect. The analyst can instruct how many vertices are divided on the coordinates. Each composition point indicates the composition ratio of a plurality of raw materials contained in the sample. In addition, a sample can be produced | generated by a fine space | interval by increasing the division | segmentation number of a coordinate. A plurality of composition points on one composition diagram do not necessarily need to be on a line drawn according to the same number of divisions, and the number of divisions may be partially different.

  A “library” is an assembly of a plurality of different samples, for example, formed on a single library plate. It is preferable that a plurality of samples are regularly arranged on one library plate, since it becomes easy to automatically perform X-ray measurement on these samples.

  “N” is generally “3”. If it is “3”, the composition chart can be expressed on a plane, that is, on one coordinate plane, so that the analyst can intuitively understand the composition chart. In addition, when “n” is “4”, there are four coordinate planes that form a side surface of a pyramid (triangular pyramid) and a coordinate plane that is determined in parallel with the number of coordinate divisions. To do. “N” is not particularly limited, but “3” or “4” that can be intuitively understood is preferable. In the current search for new materials, many types of raw materials such as 5-elements, 6-elements, etc. are often combined, but in this case, a ternary composition diagram using pure compounds composed of multiple elements as raw materials. By forming a quaternary composition diagram, a complex system can be targeted.

  “Actual X-ray diffraction profile” is a diagram represented on a graph in which the horizontal axis represents the X-ray diffraction angle (2θ) and the vertical axis represents the diffraction X-ray intensity. It represents 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 incident X-ray is changed. The “standard X-ray diffraction profile stored in the database” is an X-ray diffraction profile obtained when X-ray diffraction measurement is performed in advance for all types of compounds. For example, what is widely known as a JCPDF file has peak search results based on a standard X-ray diffraction profile collected as standard peak cards in the form of cards for various compounds. The ICDD database is also widely known as an actually measured X-ray diffraction profile.

  The method for collating the measured X-ray diffraction profile with the standard X-ray diffraction profile in the database is not particularly limited, and examples thereof include known methods such as a search method using Jade qualitative analysis software.

  A “pure compound” is a compound obtained when a single chemical product is obtained by mixing a plurality of raw materials. If the conditions under which a pure compound can be obtained are understood, the target material can be obtained efficiently and with high purity. Further, when the same pure compound is found at a plurality of composition points, one of the composition points can be set as a composition point where the pure compound exists. More precisely, a coordinate point obtained from a chemical formula of a pure compound can be a composition point where the pure compound exists. In this case, the composition point of the pure compound does not necessarily need to be a coordinate point corresponding to the initially determined coordinate division number.

  In addition, if the sample of each composition point included in the above-described triangle is in an equilibrium state, the following composition region, that is, a composition region of only one kind of pure compound, two kinds of pure compounds are obtained according to Gibbs's law. It is classified into either a mixed composition region or a composition region in which three kinds of pure compounds are mixed. Therefore, if the standard X-ray diffraction profiles of the three types of pure compounds are deleted from the above-mentioned actual X-ray diffraction profiles, if the actual X-ray diffraction profiles remain, there is a possibility that other pure compounds exist or unknown substances exist there. It can be determined that the possibility exists.

  (2) Next, in the library analysis method of (1) above, one composition point of the pure compound is selected, and then the composition point of the pure compound that is closest to the composition point on the same coordinate plane is selected. And then selecting the composition point of the pure compound at the next closest distance on the same coordinate plane to form the one triangle, and further, on the condition that it does not overlap with the one triangle It is desirable to form another triangle from the two composition points forming one side of the triangle and the composition points of the other pure compounds.

  By covering the entire range of the target composition diagram without overlapping with a triangle formed by three composition points, the samples constituting the library can be analyzed without omission.

  (3) Next, in the library analysis method of the above (1) or (2), when a plurality of triangles formed by three of the composition points of the pure compound are formed, all the triangles are formed. It is desirable to repeat the steps (i) to (vi).

  (4) Next, in the library analysis method described in the above (1) to (3), it cannot be identified in the measured X-ray diffraction profile for each code remaining in the result of executing the step (vi). It is desirable to check the standard X-ray diffraction profile of a substance obtained by substituting at least one of the elements constituting the n kinds of raw materials with another element.

  The discovery of an unidentifiable X-ray diffraction profile means that an unknown substance is synthesized by the elements constituting the raw material, and the unknown substance may have a novel crystal structure. Therefore, the crystal structure of the unknown substance can be estimated by comparing the unknown substance with other known compounds. By selecting an element having the same valence as the element of the raw material or an element having a close ionic radius as the element to be replaced, it becomes easy to estimate the crystal structure of the unknown substance.

(5) Next, the library analyzer according to the present invention is:
(A) A library analyzer for analyzing a library in which samples are formed at a plurality of predetermined sample forming points on a library plate,
(A) The sample is a chemical product obtained by mixing a plurality of types of raw materials in combinations of different ratios.
(C) The ratio is a ratio of composition points of an n-component composition diagram corresponding to the number of types n of the raw materials (n is 3 or more),
(D) Each sample has a different sign,
(E) The library analyzer includes an input unit, an X-ray measurement unit, a control unit, an analysis unit, and a database.
(F) The X-ray measuring means includes coordinate axes in the X-axis direction and the Y-axis direction, reference points predetermined on the X-axis and the Y-axis, and a support base for supporting the library plate. And
(G) The input means is an input means for inputting data on the library and data relating to positions of a plurality of sample formation points on the library plate,
(H) The support can move in the X-axis direction and / or the Y-axis direction to move the sample formation point to the reference point,
(G) The control means
Based on the data regarding the positions of the plurality of sample formation points on the library plate input from the input unit, the X-axis direction and the Y-axis of each of the sample formation points from the reference point of the X-ray measurement unit Calculate the direction deviation,
Based on the deviation, the sample formation point is sequentially moved to the measurement point so that the support is moved,
(Ko) The X-ray measurement means sequentially performs X-ray diffraction measurement on each of the plurality of samples sequentially transferred to the measurement point,
(S) By the analysis means,
(I) creating the measured X-ray diffraction profile for each code of the sample;
(Ii) A pure compound is searched by collating the measured X-ray diffraction profile for each code with a standard X-ray diffraction profile comprising a combination of elements constituting the raw material stored in a compound database. Determining a composition point at which the compound is present;
(Iii) selecting three points on the same coordinate plane among the composition points where the pure compound is present to form one triangle;
(Iv) The measured X-ray diffraction profiles of the samples at the respective composition points included in the triangle and the standard X-ray diffraction profiles of the pure compounds at the three points are sequentially collated to obtain a predetermined correlation or more. Deleting from the measured X-ray diffraction profile the standard X-ray diffraction profile that matches
(V) The step of (iv) is repeated for all the composition point samples included in the one triangle, and the remaining measured X-ray diffraction profile is stored for each code. It is characterized by.

That is, the library analyzer according to the present invention is:
(A) A library analyzer for analyzing a library in which samples are formed at a plurality of predetermined sample forming points on a library plate,
(A) The sample is a chemical product obtained by mixing a plurality of types of raw materials in combinations of different ratios.
(C) The ratio is a ratio of composition points of an n-component composition diagram corresponding to the number of types n of the raw materials (n is 3 or more),
(D) Each sample has a different sign,
(E) The library analyzer includes an input unit, an X-ray measurement unit, a control unit, an analysis unit, and a database.
(F) The X-ray measuring means includes coordinate axes in the X-axis direction and the Y-axis direction, reference points predetermined on the X-axis and the Y-axis, and a support base for supporting the library plate. And
(G) The input means is an input means for inputting data on the library and data relating to positions of a plurality of sample formation points on the library plate,
(H) The support can move in the X-axis direction and / or the Y-axis direction to move the sample formation point to the reference point,
(G) The control means
Based on the data regarding the positions of the plurality of sample formation points on the library plate input from the input unit, the X-axis direction and the Y-axis of each of the sample formation points from the reference point of the X-ray measurement unit Calculate the direction deviation,
Based on the deviation, the sample formation point is sequentially moved to the measurement point so that the support is moved,
(Ko) The X-ray measurement means sequentially performs X-ray diffraction measurement on each of the plurality of samples sequentially transferred to the measurement point,
(Sa) The analysis means is
(I) means for creating the measured X-ray diffraction profile for each code of the sample;
(Ii) A pure compound is searched by collating the measured X-ray diffraction profile for each code with a standard X-ray diffraction profile comprising a combination of elements constituting the raw material stored in a compound database. Means for determining the composition point at which the compound is present;
(Iii) means for selecting three points on the same coordinate plane among the composition points where the pure compound exists, and forming one triangle;
(Iv) The measured X-ray diffraction profiles of the samples at the respective composition points included in the triangle and the standard X-ray diffraction profiles of the pure compounds at the three points are sequentially collated to obtain a predetermined correlation or more. Means for deleting from the measured X-ray diffraction profile the standard X-ray diffraction profile corresponding to
(V) repetitively using the means of (iv) with respect to samples of all composition points included in the one triangle, and storing means for storing the remaining measured X-ray diffraction profiles for each of the codes. Features.

  Examples of the “library data” include, for example, the type of the raw material of the sample constituting the library, the number of coordinate divisions, the code of the sample, and the like. For example, when a part of a library is analyzed, the sample code can be input for the purpose of selecting a sample. “Data on the position of a plurality of sample formation points on the library plate” can be obtained by (a) setting the relationship with the positions of a plurality of sample formation points in advance or (b) determining the type of the library plate. Can be of library plate type.

  According to the library analyzing method and the library analyzing apparatus of the present invention, by identifying three or more kinds of pure compounds, the qualitative properties of chemical products at the composition points in the triangle formed by the composition points of the three kinds of pure compounds. Analysis can be performed efficiently. In addition, qualitative analysis of unknown compounds can be easily performed.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a block diagram showing the library analyzer of the present invention, FIG. 2 is a plan view showing the main part of the measuring means of the library analyzer of the present invention, and FIG. 3 is the library analyzer of the present invention. FIG. 4 is a composition diagram showing the position of a pure compound in the library analysis method of the present invention, and FIG. 5 is assigned a reference numeral to the composition point of the library analysis method of the present invention. FIG. 6 is a composition diagram, FIG. 6 is an analysis result obtained by the library analysis method of the present invention, and FIG. 7 is another analysis result obtained by the library analysis method of the present invention.

  In the present embodiment, an example will be described in which a liquid inorganic material raw material is used as a raw material, an X-ray diffraction measurement is performed using a chemical product as a sample, and the sample is analyzed. In FIG. 1, the control means 1 is connected to the input means 2, the display means 3, the analysis means 4, the database 5, the measurement means 6, the library manufacturing means 7, and the transport means 8 through electrical communication means.

  The control unit 1 and the analysis unit 4 include, for example, a calculation control unit such as a CPU (Central Processing Unit) of a computer and a storage medium such as a ROM (Read Only Memory), a RAM (Random Access Memory), and a hard disk. It is a function realization means realized by the configured system.

  For the input means 2, for example, an input device such as a keyboard or a mouse is employed. The display means 3 is configured by a flat display such as a liquid crystal display device. The input means 2 can be a touch panel type input device that is a combination of the screen of the display means 3 and a touch panel, and using this input device is preferable because the operation is simple.

  The database 5 is configured by a storage medium such as a ROM (Read Only Memory), a RAM (Random Access Memory), and a hard disk. Moreover, the measurement means 6 is comprised including the apparatus for conveying an X-ray measuring apparatus and a library, for example. Moreover, the library manufacturing means 7 is comprised including the mechanism suitable in order to manufacture a library, for example. In addition, the transport unit 8 includes, for example, a mechanism suitable for transporting the library manufactured by the library manufacturing unit 7.

  As shown in FIG. 2, the library manufacturing means 7 manufactures a library 21 in which a plurality of samples 9 are formed, one for each of a plurality of predetermined sample forming points 63 on the library plate 62. . The sample 9 is a plurality of chemical products obtained by mixing a plurality of kinds of raw materials in a combination of different ratios, and in this embodiment, 66 chemical products, and the ratio of each raw material is the number n of raw materials (n is 3 or more). The ratio of the composition points in the n-component composition diagram corresponding to.

  The composition diagram can be represented by a triangle as shown in FIG. 5, for example. Since this composition diagram corresponds to the case of using three kinds of raw materials, it is a triangle, and the three vertices of the triangle correspond to the three raw materials. In addition, each point given with each number from 0 to 65 (for convenience, the tenth digit is omitted) represents the composition point.

  The library 21 of FIG. 2 manufactured by the library manufacturing means 7 of FIG. 1 is transported by the transport means 8 and transferred to the measuring means 6 in FIG. 1, and is transferred to the library support 61 shown in FIG. Installed.

  Since a large number of samples 9 are formed by mixing a plurality of raw materials in different ratio combinations, it is possible to reduce a huge amount of work by automatically manufacturing the library 21, and to prevent human error. It can also be avoided. Further, if the library plate 62 is automatically transferred, it is possible to automate from library manufacture to library analysis, so that the work process can be reduced and the effect of avoiding human error is increased.

  Next, a method for automatically manufacturing the library 21 will be described. In the input means 2, (1) identification names and concentrations of plural types of raw materials to be mixed, (2) the number of divisions of coordinates in the composition diagram, and (3) chemical processing conditions of the raw materials to be mixed are input as data. The method for inputting the identification name is performed by inputting the raw material name, inputting the concentration in the identification name previously shown on the input screen provided in the input means, or selecting the identification name. The raw material name and the identification name are made to correspond separately. The chemical treatment conditions are conditions for operating each element in library manufacture, such as the amount of the sample 9 formed on the library plate 62, and drying and heating conditions when a reaction by heating is performed. In addition, when automatically performing from library manufacture to library analysis, in addition to the chemical processing conditions, (4) library analysis conditions are input from the input means 2. The “division number of coordinates in the composition diagram” is the number of divisions when the side connecting the vertices of the composition diagram is divided into several at equal intervals.

  The above data input from the input means 2 is sent to the control means 1. In the control means 1, an n-element composition diagram corresponding to the number n of raw material types input from the input means 2 (n is 3 or more) is created as shown in FIG. 5, for example. Next, a plurality of composition points, which are determined by the number of divisions input from the input means 2, in the present embodiment, 66 composition points are given different symbols as shown in FIG. 5. In FIG. 5, the number of the tenth place is omitted for convenience of illustration. For example, the sign of the vertex is “0”, the sign of the left end of the base is “55”, and the sign of the right end of the base is “65”. Here, the composition point is determined by equally dividing the ratio of each raw material contained in a mixture obtained by mixing a plurality of types of raw materials by the number of divisions. Mixing ratios of a plurality of raw materials at the composition points corresponding to those codes are automatically calculated, and 66 samples 9 having different mixing ratios are automatically generated by the library manufacturing means 7.

  Furthermore, the control means 1 automatically executes operations to be performed by the respective elements regarding the placement of the sample 9 on the sample formation point 63 on the library plate 62 and the chemical processing such as drying and heating. The arrangement is performed by automatically arranging a plurality of samples 9 on the library plate 62 by a predetermined amount in accordance with the chemical processing conditions input by the input means 2. Further, the plurality of samples 9 on the library plate 62 are automatically dried and heated according to the chemical processing conditions input by the input means 2. In this way, the library 21 is manufactured.

  Predetermined measurement using X-rays is automatically and sequentially performed in the measurement means 6 according to the analysis conditions input from the input means 2 for the library 21 obtained as described above, and the result of the measurement The measured X-ray diffraction profile obtained as is stored for each code.

  In FIG. 2, the measuring means 6 includes a support base 61 for supporting the library plate 62, an in-plane rotation system 22 for rotating the support base 61 in a plane, and an in-plane parallel for moving the support base 61 in a plane. And a moving system 23. The support base 61 is provided with a recess 24 that fits into the library plate 62 in order to define the position of the library plate 62. The library plate 62 is supported by the support base 61 without being displaced by being accommodated in the recess 24.

  The in-plane rotation system 22 rotates the support base 61 around a reference line 64 on the coordinates defined by the X-axis and the Y-axis and extending in the direction perpendicular to the paper surface, so-called in-plane rotation. Can do. The reference point 64 is a measurement point in the X-ray diffraction measurement. This in-plane rotation system 22 is suitably used when measuring the sample 9 having anisotropy. This in-plane rotation system 22 is a mechanism for transmitting the rotation of a motor capable of controlling the rotation angle and rotation speed, such as a stepping motor and servo motor, to the support base 61 via a rotation transmission mechanism composed of a worm and a worm wheel. Can be configured.

  The in-plane translation system 23 is a translation system that translates the support base 61 independently in two axial directions, ie, an X axis and a Y axis, which are axes orthogonal to each other. In this way, by moving the support base 61 independently in the X-axis direction and the Y-axis direction, any point on the support base 61 can be carried to a desired position in the plane. The in-plane translation system 23 can be configured using, for example, a so-called XY table. In general, the XY table can be configured by various structures. For example, one table is individually connected to both a feed screw extending in the X-axis direction and a feed screw extending in the Y-axis direction, so that the feed screw in the X-axis direction is used. And the Y-axis direction feed screw can be independently rotationally driven to translate the table in the X-axis direction and the Y-axis direction in a plane.

  The measuring means 6 can move each sample formation point 63, 63,... To the measurement point 64 by appropriately operating the in-plane translation system 23. Specifically, the control means 1 in FIG. 1 is based on the data relating to the positions of the plurality of sample formation points 63, 63,... On the library plate 62 input from the input means 2, and the measurement means 6 in FIG. .. Of the sample formation points 63, 63,... From the reference point 64 are calculated in the X-axis direction and the Y-axis direction. Then, by operating the in-plane translation system 23 of FIG. 2 based on the deviation thus calculated, the respective sample formation points 63, 63,... Are automatically carried to the measurement point 64 sequentially. The support base 61 can be translated.

  When the sample 9 has anisotropy, the in-plane rotation device 22 is operated to automatically rotate the support base 61 around the measurement point set at the position of the reference point 64. Measurement can be performed. Thus, X-ray diffraction measurement can be performed on the sample 9 having no directionality. When the sample 9 is predicted to have anisotropy, the in-plane rotation is performed by inputting information indicating that the sample 9 has anisotropy from the input unit 2 as an analysis condition. Can be automatically performed by an instruction from the control means 1.

  In the present embodiment, the center of the library plate 62 when the support base 61 is placed at the start position before the measurement is the reference point 64, and the coordinate point on the XY coordinate of the reference point 64 is the control means 1. It is remembered. Based on the information of the library plate 62 input from the input means 2, the control means 1 calculates the deviation on the X axis and the deviation on the T axis from the reference point 64 for the 66 sample forming points 63, 63,. Is done. Further, for each type of library plate 62, data of deviation from the reference point 64 of the sample formation point 63 is stored in the control means 1 in advance and collated with the type of the library plate 62 inputted from the input means 2. Thus, the deviation may be obtained.

  In FIG. 2, the upper left corner 65 of the library plate 62 is cut out, and a corner portion bulges out to fit the corner 65 at a position corresponding to the corner 65 of the support base 61. ing. For this reason, the library plate 62 is not installed in the wrong direction. That is, the order of the samples 9 is not mistaken.

  For example, as shown in FIG. 6, the measurement using the X-ray is performed by causing the X-ray R0 emitted from the X-ray source F to enter the measurement point 64 at the incident angle θ and using the sample 9 placed at the measurement point 64. This is performed by detecting the diffracted X-ray R1 with the X-ray detector 66 placed at the diffraction angle 2θ. Note that the diffraction angle 2θ is twice the X-ray incident angle θ, and the X-ray diffraction measurement is performed while rotating the angle θ and the angle 2θ while maintaining this angular relationship. If a binary X-ray detector is used as the X-ray detector 66, the 2θ scanning movement of the X-ray detector is unnecessary.

  Subsequently, the analysis unit 4 in FIG. 1 automatically analyzes the actual measurement profile that is the measurement result by the measurement unit 6. This analysis process will be described with reference to FIG. When the analysis processing routine is entered, in the “sign assignment step” S41, as described above, the plurality of samples 9 are given different codes.

  Next, in “actual X-ray diffraction profile registration step” S42, actual X-ray diffraction profiles of a plurality of samples 9 are created for each sample, that is, for each code of the sample. These measured X-ray diffraction profiles are stored in the analysis unit 4 as a file for each code.

  Next, in the “pure compound search step” S43, by comparing the measured X-ray diffraction profile for each code with the standard X-ray diffraction profile stored in the compound database consisting of combinations of elements constituting the raw material, Pure compounds are searched. Thereby, the composition points 31, 32, 33, and 34 where the pure compound exists are determined in the composition diagram 30 of FIG.

  Next, in “one triangle forming step” S44 in FIG. 3, among the composition points 31, 32, 33, and 34 where the pure compound exists, three points on the same coordinate plane, that is, the composition points 31, 32 and 33 are selected so as not to include the composition point 33 where other pure compounds exist on the coordinate plane, and one triangle 35 is formed. One specific method is to first select one composition point of the pure compound, then select the composition point of the pure compound that is closest to the composition point in the same coordinate plane, and then in the same coordinate plane. The composition point of the pure compound at the next closest distance can be selected to form one triangle.

  Next, in the “profile deletion step” S45, the measured X-ray diffraction profile of the sample at each of the composition points 31, 32, and 34 included in one triangle 35 is a standard X-ray diffraction profile of three pure compounds. The standard X-ray diffraction profiles that are sequentially collated and matched with a predetermined correlation or more are deleted from the measured X-ray diffraction profile. Here, the same is repeated for all the samples of the composition points 31, 32, and 34 included in one triangle 35, and the measured X-ray diffraction profile remaining for each code is stored in the analysis means 4.

  Next, in “another triangle formation step” S46, the composition point 33 of the pure compound is provided on the condition that the two composition points 32 and 34 forming one side of one triangle 35 do not overlap with one triangle 35. From this, another triangle 36 is formed.

  Next, the “profile deletion step” S47 is executed in the same manner as in step S45. The third triangle 37 is formed from the composition point 31 of the pure compound on the condition that the two composition points 33 and 34 forming one side of the other triangle and the other triangle 36 do not overlap. Step S47 is also executed for these. If the fourth, fifth,... Triangles can be formed, “YES” is determined in the step S48, the process returns to the step S46 to similarly form a triangle, and the step S47 is sequentially executed.

  Next, in the “peak search step” S49, the remaining actual measured X-ray diffraction profile is compared with the standard X-ray diffraction profile stored in the database to search for compounds and identify other pure compounds. . If another pure compound is identified (YES in step S50), the process returns to step S44 and the subsequent steps are repeated.

  Next, in the “unknown substance search step” S51, at least one of the measured X-ray diffraction profiles for each code remaining in the result of step S47 and each of n kinds of raw material elements is set as another element. The replaced standard X-ray diffraction profile is collated. If there is a profile with a high degree of coincidence, the substance corresponding to the profile is likely to have a new crystal structure, and thus a more detailed analysis is performed.

  The reason for substituting at least one of the n kinds of raw material elements with other elements in the “step of searching for unknown substances” in S51 is that a compound that is out of phase theory has a lattice constant or the like from a known crystal structure. This is because the crystal structure may be estimated by searching for a standard X-ray diffraction profile that may be misaligned and replaced with another element having an atomization or a close ionic radius.

  The library analyzer according to the present invention will be described more specifically. Each unit in FIG. 1 is unitized, and a library analyzer can be configured by combining various units. In this specification, “unit” means that it can be handled as one structure, for example, it can be carried as one structure, and can be transferred to another structure as one structure. Technical contents such as being able to be connected electrically, being able to be electrically connected to another structure as one structure, and the like.

  That is, as a combination of the library analyzers, the combination of the control unit 1, the input unit 2 and the measurement unit 6 is the minimum necessary combination, and the control unit, the input unit and the measurement unit can be combined with each other. Is possible. Here, the measuring means 6 is an X-ray measuring unit. If necessary, the display means 3, the analysis means 4, and the database 5 can be provided as a display unit, an analysis unit, and a database unit, respectively. It is also effective to add the library manufacturing means 7 and the transport means 8 as a library manufacturing unit and a transport unit, respectively, in order to automatically perform from library manufacture to library analysis. The database 5 can also use an external database by connecting to the control means 1 via a communication line.

  In the library analyzer of FIG. 1, various processes such as weighing, mixing, serving, drying, heat treatment, X-ray diffraction, analysis and the like are performed. These processes are executed by appropriately operating various components included in each means of FIG. 1 constituting the library analyzer. The control means 1 automatically and continuously executes the operation of each component described above according to the identification names of a plurality of types of raw materials input from the input means 2 and corresponding to the ratio for each composition point. It has a function to make it.

  Further, the control unit 1 is connected to an analysis unit 4 that performs analysis for collation. The analysis unit 4 has a function of performing phase identification by collating with the database 5 and displaying the analysis result shown on the composition diagram on the screen of the display unit 3.

  The library manufacturing means 7 performs the following series of processes. That is, first, a liquid inorganic material raw material is weighed by a dispensing pipette and then dispensed into a mixing container. Next, a sample is produced | generated by mixing the sample in the dispensed mixing container using a stirring rod. Next, the obtained sample is separated with a preparative pipette and then arranged on the library plate 62 of FIG. The library plate 62 is made of, for example, platinum, and the same number of sample forming portions 63 are formed in the library plate 62 by 66 concave portions (that is, wells). The preparative pipette arranges a plurality of samples 9 on the library plate 62 by placing one sample on each of the 66 sample forming portions 63. Next, the library 21 is manufactured by drying and heating the arranged samples 9. Heating is performed by firing the prepared sample 9 in an electric furnace.

  In this embodiment, the measuring means 6 is configured as an X-ray measurement unit. This X-ray measurement unit measures individual X-ray diffraction profiles of a plurality of samples 9 constituting the library 21 and further records the standard X-ray diffraction profiles stored in the database 5 of FIG. (E.g., JCPDS file or ICDD database). Further, the measuring means 6 has a function of outputting the format-converted data for each sample code corresponding to each sample 9 on the library plate 62 on a one-to-one basis.

  The analyzing unit 4 stores each measured X-ray diffraction profile output from the measuring unit 6 and sent via the control unit 1 as a file for each code in a predetermined storage area, and further stores the stored file in the database 5. The known phase in the product is extracted by comparing with the standard X-ray diffraction profile stored in, and further the X-ray diffraction profile of the unknown phase is extracted. Further, the analysis means 4 extracts diffraction patterns for all the samples 9 on the library plate 62, and if the number of starting materials is “n”, the analysis collation result is plotted in the n-element system space. For example, FIG. Or on the composition diagram 30 as shown in FIG. The composition diagram in which the product is plotted can be registered (that is, stored in a predetermined storage area). Here, it is preferable that the combination of a plurality of types of raw materials, chemical treatment conditions, analysis conditions, and the like can be stored as data, because the number of operations can be reduced.

  Next, an embodiment of a library analysis method using the library analyzer of the present invention will be described. As a specific compound synthesis example, a system composed of the element Ni—Zn—Fe will be described.

  As liquid inorganic material raw materials which are starting materials, (1) NiO slurry concentration 1.0 mol / l with water as dispersion medium, (2) ZnO slurry concentration 1.0 mol / l aqueous solution with water as dispersion medium, and (3) Three types of Fe2O3 slurry concentrations of 0.5 mol / l using water as a dispersion medium were used.

  First, identification names of the above three kinds of liquid inorganic material raw materials, their molar concentrations, the number of divisions of coordinates in the composition diagram, chemical treatment conditions, and analysis conditions were input from the input means 2 to the control means 1. The number of coordinate divisions in the composition diagram was “10”. At this time, for the liquid inorganic substance raw materials, the identification names were selected by inputting the concentrations to the raw material 1, raw material 2, and raw material 3 displayed on the screen as the identification names. When the input is completed, the composition diagram 30 shown in FIG. At this time, there are 66 combinations of the composition ratios of the raw materials.

  Subsequently, 66 kinds of mixing ratios of the three inorganic material raw materials were automatically calculated according to the division number 10 of the coordinates in the composition diagram 30. Subsequently, 66 samples with different mixing ratios were automatically generated according to chemical processing conditions. Here, the chemical treatment conditions refer to the stirring time, stirring conditions, and the like of the liquid inorganic material raw material and, if necessary, the conditions such as the atmospheric temperature and the atmospheric gas.

  Subsequently, 66 liquid samples are automatically placed on one platinum library plate 62 having the sample forming portion 63 which is the 66 concave portions (that is, wells) shown in FIG. 2 according to the chemical processing conditions. Arranged. Here, the chemical treatment condition refers to a serving amount, a tray temperature, an atmospheric temperature, an atmospheric gas, a drying condition for a liquid sample, and the like.

  Next, the plurality of samples 9 on the library plate 62 were automatically heat-treated according to chemical treatment conditions. Here, the chemical treatment conditions include a temperature rising rate, a heating temperature, a heating time, a cooling rate, an atmospheric gas, and the like. The heating temperature was 1373 degrees as an absolute temperature, and the library 21 was heated at this temperature for a predetermined time. The atmosphere gas was air.

  The library plate 62 constituting the library 21 was fixed on the support base 61 of the measuring means 6 by manual operation. Subsequently, the support 61 was automatically transferred so that the sample formation point 63 automatically moved to the measurement point 64.

  Further, for each of the 66 samples 9 on the library plate 62 subjected to the heat treatment, an actual measurement X-ray diffraction profile is obtained by measurement while the support base 61 is automatically rotated in-plane, and the data of the profile is determined in advance. Stored in the storage area. Then, the stored data was converted into a format that can be collated with a standard X-ray diffraction data file (for example, ICDD database) stored in the database 5 of FIG. Further, the measured X-ray diffraction profile obtained by data conversion was stored in the analysis means 4 for each sample code in a one-to-one correspondence with each sample 9 on the library plate 62. Here, the analysis conditions include an X-ray irradiation angle, an X-ray intensity, a rotation of a support base, and the like.

  Furthermore, a pure compound was searched by comparing the measured X-ray diffraction profile for each code with the profile of a compound that is a standard X-ray diffraction profile stored in the database 5 and composed of a combination of elements constituting the raw material. . Specifically, first, each measured X-ray diffraction profile output from the measuring means 6 sent via the control means 1 is converted into the standard X-ray diffraction of NiO, ZnO, Fe2O3 in the ICDD database stored in the database 5. The result of FIG. 6 was obtained by collating with the profile. From the chemical formula, pure compound NiO having a composition point of 0, pure compound ZnO having a composition point of 55, and pure compound Fe2O3 having a composition point of 65 were determined.

  From the above results, one triangle was formed with reference numerals 0, 55, and 65. At this point, since only the pure compound composed of one kind of metal element is collated, the composition point of the pure compound could be determined very quickly. However, the search for the presence of pure compounds composed of two or more metal elements was omitted.

  Next, the measured X-ray diffraction profile of one triangle, that is, the sample of the entire composition point in the composition diagram 30 is sequentially compared with the standard X-ray diffraction profiles of NiO, ZnO, and Fe2O3, and a predetermined correlation is established. The standard X-ray diffraction profile that coincided with the above was used as the actual X-ray diffraction profile, and the actual X-ray diffraction profile remaining for each code was stored in the analysis means 4.

  The remaining measured X-ray diffraction profile stored in the analysis means 4 is compared with the standard X-ray diffraction profile of a compound that is stored in the database 5 and that is composed of a combination of elements Ni, Zn, and Fe constituting the raw material. As a result, the result of FIG. 7 was obtained. That is, NiFe2O4, ZnFe2O4, (Ni, Zn) Fe2O4 was identified as a pure compound.

  Here, since pure compounds other than NiO, ZnO, and Fe2O3 have been identified, five triangles to which the phase rule is applied are formed based on the composition points based on the chemical formula of NiO, ZnO, Fe2O3, NiFe2O4, ZnFe2O4, (Ni, Zn) Fe2O4. For each of these triangles, when the standard X-ray diffraction profile of the pure compound at the apex of the triangle was deleted from the measured X-ray diffraction profile of the composition point contained in the triangle, the significant measured X-ray diffraction profile was In addition, it was confirmed that only a known crystal structure exists in this system.

(Effect of this embodiment)
According to the library analysis method of this embodiment, it is possible to efficiently perform qualitative analysis by X-ray diffraction of a large number of samples forming the composition points of the composition diagram. Further, it is possible to perform a qualitative analysis of an unknown substance from an X-ray diffraction profile that cannot be identified, thereby making it possible to discover a new substance.

(Other embodiments)
As mentioned above, although embodiment and the Example of this invention were described with reference to drawings, the concrete structure of this invention is not restricted to these embodiment etc., The design of the range which does not deviate from the summary of this invention is carried out. Even if there is a change, the change is included in the present invention.
For example, the composition diagram is not limited to a three-component system and may be a four-component system or more. For example, in a 4-component system, it is possible to visually display a composition diagram with a triangular pyramid. The number of coordinate divisions may be less than “10” or greater than “20”. Of course, the number may be between “10” and “20”.

  Further, the raw material is not limited to liquid, and may be a solid obtained by solidifying powder or the like. Furthermore, the raw material may be an organic material as long as it forms a crystal structure.

  According to the library analyzer of the present invention, even a composition in which a plurality of inorganic material raw materials are mixed at tens to hundreds of mixing ratios can be efficiently and accurately analyzed. Can handle numbers and facilitates discovery of new substances.

It is a block diagram which shows the library analyzer of this invention. It is a top view which shows the principal part of the measurement means of the library analyzer of this invention. It is a flowchart which shows the analysis method performed by the library analyzer of this invention. It is a composition figure showing the position of a pure compound considered by the library analysis method of the present invention. It is a figure which shows the state which attached | subjected the code | symbol to the several composition point which comprises the composition diagram used with the library analysis method of this invention. It is the analysis result obtained by implementing the library analysis method of this invention. It is another analysis result obtained by implementing the library analysis method of this invention.

Explanation of symbols

1. 1. control means 2. input means; Display means, 4. Analytical means,
5. Database, 6. 6. Measuring means Library manufacturing means, 8. Conveying means,
9. Sample, 21. Library, 22. In-plane rotation system, 23. In-plane translation system,
24. Recess, 30. Composition diagram, 31, 32, 33, 34. Composition point of pure compound,
35. One triangle, 36, 37. Other triangles, 61. Library support,
62. Library plate, 63. Sample formation point, 64. Reference point (measurement point),
65. Corner

Claims (5)

X-ray library consisting of a plurality of samples that are chemical products mixed so that the combination ratio of n kinds (n is 3 or more) of raw materials is a ratio of composition points different from each other in an n-component composition diagram A library analysis method for analyzing using diffraction,
(1) attaching different symbols to the plurality of samples;
(2) creating an actual X-ray diffraction profile for each code of the sample by performing X-ray diffraction measurement on each of the plurality of samples;
(3) A pure compound is searched by comparing the measured X-ray diffraction profile for each code with a standard X-ray diffraction profile comprising a combination of elements constituting the raw material stored in a compound database. Determining a composition point at which the compound is present;
(4) selecting three points on the same coordinate plane among the composition points where the pure compound exists to form one triangle;
(5) The X-ray diffraction profile of the sample corresponding to each composition point included in the triangle and the standard X-ray diffraction profile of the pure compound at the three points are sequentially collated to determine in advance Deleting the standard X-ray diffraction profile that matches more than the correlation from the measured X-ray diffraction profile;
(6) The step of (5) is repeated for all the composition point samples included in the one triangle, and the measured X-ray diffraction profile remaining after the repetition is stored for each code.
A library analysis method characterized by comprising: Select the composition point of the pure compound, then select the composition point of the pure compound that is the closest to the composition point on the same coordinate plane, and then the composition point of the pure compound that is the next closest distance on the same coordinate plane To form the one triangle,
The other triangle is formed from two composition points forming one side of the one triangle and another composition point of the pure compound under a condition that the triangle does not overlap with the one triangle. Item 2. The library analysis method according to Item 1.   The step (1) to (6) is repeated for all triangles when a plurality of triangles formed by three of the composition points of the pure compound are formed. The library analysis method according to claim 2. The library analysis method according to at least one of claims 1 to 3,
Among the measured X-ray diffraction profiles for each symbol remaining in the result of executing the step (6), at least one of the elements constituting the n types of raw materials is set as another element. A library analysis method comprising collating the standard X-ray diffraction profile of a substance obtained by replacement. A library analyzer for analyzing a library in which one sample is formed at each of a plurality of predetermined sample forming points on a library plate,
The sample is a chemical product obtained by mixing a plurality of types of raw materials in different ratio combinations,
The ratio is a ratio of composition points of an n-component composition diagram corresponding to the number of types n (n is 3 or more) of the raw materials,
Each of the samples has a different sign,
The library analyzer includes an input unit, an X-ray measurement unit, a control unit, an analysis unit, and a database.
The X-ray measuring means includes coordinate axes in the X-axis direction and the Y-axis direction, reference points predetermined on the X-axis and the Y-axis, and a support base for supporting the library plate, The support base can move in the X-axis direction and / or the Y-axis direction to move the sample formation point to the reference point,
The input means is an input means for inputting data on the library and data on the positions of a plurality of sample formation points on the library plate,
The control means includes
Based on the data regarding the positions of the plurality of sample formation points on the library plate input from the input unit, the X-axis direction and the Y-axis of each of the sample formation points from the reference point of the X-ray measurement unit Calculate the direction deviation,
Based on the deviation, the sample formation point is sequentially moved to the measurement point so that the support is moved,
The X-ray measurement means sequentially performs X-ray diffraction measurement on each of the plurality of samples sequentially transferred to the measurement point,
By the analysis means,
(1) creating the measured X-ray diffraction profile for each code of the sample;
(2) A pure compound is searched by comparing the measured X-ray diffraction profile for each code with a standard X-ray diffraction profile composed of a combination of elements constituting the raw material stored in the compound database. Determining a composition point at which the compound is present;
(3) a step of selecting three points on the same coordinate plane among the composition points where the pure compound exists to form one triangle;
(4) The measured X-ray diffraction profiles of the samples at the respective composition points included in the triangle and the standard X-ray diffraction profiles of the pure compounds at the three points are sequentially collated to obtain a predetermined correlation or more. Deleting from the measured X-ray diffraction profile the standard X-ray diffraction profile that matches
(5) The step of (4) is repeated for all the composition point samples included in the one triangle, and the remaining measured X-ray diffraction profile is stored for each code. A library analyzer characterized by

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