JP5345861B2 - X-ray analysis and thermal analysis simultaneous analyzer - Google Patents

Description

  The present invention relates to a simultaneous X-ray analysis and thermal analysis apparatus that simultaneously performs measurement for X-ray analysis and measurement for thermal analysis.

  The X-ray analyzer analyzes the crystal structure, molecular structure, and the like of a sample based on the state of X-rays emitted from the sample when the sample is irradiated with X-rays, such as diffraction rays, scattered rays, and fluorescent X-rays. Device. As such an X-ray analyzer, for example, an X-ray diffractometer that measures the diffraction angle and diffraction line intensity of a diffraction line generated from a sample, and an X-ray scattering apparatus that measures the angle and intensity of scattered radiation generated from a sample In addition, a fluorescent X-ray apparatus for measuring fluorescent X-rays generated from a sample is known.

  The thermal analysis device is a device that measures a change generated in a sample when the temperature of the sample is changed and analyzes the characteristics of the sample based on the change. As such a thermal analysis device, for example, a thermogravimetry (TG) device that measures a change in the weight of a sample according to a temperature change, or a difference in temperature change between a standard substance and a sample according to a change in ambient temperature Differential thermal analysis (DTA) equipment that measures the difference in heat inflow between the reference material and the sample according to changes in the ambient temperature and differential scanning calorimetry (DSC) Devices and the like are known.

  2. Description of the Related Art In recent years, research has been conducted in which a crystal structure change relating to one substance and a characteristic change corresponding to a change in ambient temperature of the same substance are simultaneously measured, and the substance is analyzed based on the measurement results. For example, in the pharmaceutical field, it is important to know the crystal structure of a target substance and to know the change in properties corresponding to the temperature change.

  An X-ray analyzer such as an X-ray diffractometer is suitable as a means for knowing the structural change of a substance. In addition, a thermal analyzer such as a DSC apparatus is suitable as a means for knowing the thermal characteristics of a substance. Each analysis using one of these devices for one substance gives both information about the crystal structure and information about the thermal properties of the substance, so research on the substance, for example, research on pharmaceuticals. You can make dramatic progress.

  In this way, X-ray analysis and thermal analysis are performed simultaneously, and the results of the analysis are simultaneously displayed on the screen of the display device, so that the characteristics of the substance can be grasped quickly and accurately. A simultaneous analysis apparatus is known (see, for example, Patent Document 1).

Japanese Patent Laid-Open No. 11-295244 (pages 2 to 4, FIG. 1)

  By the way, although it is disclosed in the apparatus disclosed in Patent Document 1 that the X-ray analysis result and the thermal analysis result are displayed simultaneously, the measurement conditions for the X-ray analysis and the measurement conditions for the thermal analysis are disclosed. There is no mention of how to decide.

  The conventional method of determining general measurement conditions is to first determine the temperature change conditions for thermal analysis measurement, draw the conditions in your head, or display them on the display screen to correspond to the temperature change conditions. The X-ray analysis measurement conditions such as the 2θ angle measurement range, 2θ angle scanning speed, sampling time, etc. are calculated by the operator using an electronic desk calculator, and the temperature change condition and the X-ray analysis in the head. The overall measurement conditions were evaluated in association with the measurement conditions.

  However, with such a conventional method for determining measurement conditions, it is difficult to quickly, easily and accurately determine objective measurement conditions that are unified among a plurality of measurers. Moreover, it has been difficult to confirm that X-ray analysis measurement and thermal analysis measurement are performed in accordance with target measurement conditions. Furthermore, since it was difficult to accurately grasp measurement conditions and memorize them, it was difficult to derive ideal measurement conditions, and it had to be relied on by chance.

  The present invention has been made in view of the above problems, and in an apparatus that performs both X-ray analysis and thermal analysis at the same time, the measurer can easily and quickly relate the measurement conditions of these analyzes. It is intended to be able to grasp accurately and accurately. Another object of the present invention is to make it possible to always perform the measurement stably and objectively under measurement conditions aimed at X-ray analysis and thermal analysis.

  An X-ray analysis and thermal analysis simultaneous analysis apparatus according to the present invention includes an X-ray analysis apparatus that detects X-rays emitted from a sample when the sample is irradiated with X-rays, and an ambient temperature of the sample. A thermal analysis device that detects a characteristic change that occurs in the sample when it is changed, a measurement control unit that controls the measurement by the X-ray analysis device and the measurement by the thermal analysis device, and X-ray X-ray condition storage means for storing measurement conditions for analytical measurement, thermal condition storage means for storing measurement conditions for thermal analysis measurement, an image display device for displaying an image on a screen according to an image signal, and X A measurement condition display means for displaying both the X-ray analysis measurement condition stored in the line condition storage means and the thermal analysis measurement condition stored in the thermal condition storage means as a graph on the screen of the image display device, and the measurement Is done At any point in at least one time while the between and the measurements not being performed, and having an image display control means for causing the display of the graph by the measurement condition display means.

  In the conventional simultaneous X-ray analysis and thermal analysis apparatus, the operator can imagine in his head how many X-ray diffraction measurements can be performed under thermal analysis measurement conditions such as a temperature rise curve. There was no confirmation on the screen. On the other hand, in this embodiment, by adding a function for displaying both the X-ray analysis measurement conditions and the thermal analysis conditions in the form of a graph on the screen, the measurement conditions of the X-ray analysis measurement and the measurement of the thermal analysis measurement are measured. It became possible to visually recognize the relationship with conditions, and the usability of the device was greatly improved. Compared to conventional methods that rely solely on calculations using a calculator and imagination in the head, measurement conditions can be set quickly and accurately.

  Next, in the simultaneous X-ray analysis and thermal analysis apparatus according to the present invention, the thermal analysis measurement condition may include a temperature change, and the X-ray analysis measurement condition is an X for detecting X-rays emitted from a sample. It may include an angular scanning movement time from the measurement start angle to the measurement end angle by the line detection means, and the measurement condition display means is on coordinates where time is taken on one of the vertical axis and the horizontal axis and temperature is taken on the other. It is preferable that the temperature change is displayed by a line graph, and a line indicating the start and end of the angular scanning movement time is displayed on the time axis. With this configuration, the relationship between the X-ray analysis measurement conditions and the thermal analysis measurement conditions can be grasped very easily on the screen.

  Next, the X-ray analysis and thermal analysis simultaneous analysis apparatus according to the present invention can further include humidity changing means for changing the humidity around the sample, and in this case, the measurement condition display means can change the humidity. Is preferably displayed as a graph superimposed on the X-ray analysis measurement conditions and the thermal analysis measurement conditions.

  In the technical field of the present invention, it may be necessary to change the humidity environment between the X-ray diffractometer and the thermal analyzer. For example, the crystal system of pharmaceuticals and foods may change depending on temperature and humidity. Especially in the Japanese climate, the temperature and humidity change drastically because it is muggy in the summer and dry in the winter. Therefore, it can be said that the environment for synthesizing pharmaceuticals and the environment for storing pharmaceuticals and foods are under poor conditions. Therefore, it is necessary to perform measurement under various atmospheres in advance to clarify how these materials change in an actual environment.

  Therefore, it is necessary to evaluate a thermal change and a crystal structure change of a substance in a humidity atmosphere by using a humidity generator in the simultaneous X-ray analysis and thermal analysis apparatus. By simultaneously performing measurements for X-ray diffraction analysis and thermal analysis in a humidity atmosphere, the structural change of the substance before and after the thermal change of the substance can be easily known. However, if humidity is added to the measurement conditions, the setting of the conditions becomes complicated, so it is difficult to correlate the X-ray diffraction conditions, the temperature conditions, and the humidity conditions in the head.

  In this regard, according to the aspect of the present invention, the measurement conditions can be easily set and confirmed more easily even when the conditions of the humidity atmosphere are added. Moreover, the progress at the time of a measurement can also be confirmed, and also a measurement result can be confirmed sequentially.

  Next, in the simultaneous X-ray analysis and thermal analysis apparatus according to the present invention, it is desirable that the measurement condition display means displays the humidity change by a line graph.

  Next, the X-ray analysis and thermal analysis simultaneous analysis apparatus according to the present invention can further include preliminary measurement means for performing preliminary measurement of thermal analysis using the thermal analysis apparatus. In this case, the measurement condition display means It is desirable to display the result of the preliminary measurement as a graph.

  Next, in the X-ray analysis and thermal analysis simultaneous analysis apparatus according to the present invention, the measurement condition display means includes the X-ray analysis measurement conditions in addition to the graph display of the X-ray analysis measurement conditions and the thermal analysis measurement conditions. It is desirable to display an input screen for inputting the thermal analysis measurement conditions.

  Next, the X-ray analysis and thermal analysis simultaneous analysis apparatus according to the present invention includes measurement data display means for displaying the measurement data by the X-ray analysis apparatus and the measurement data by the thermal analysis apparatus on the screen of the image display device. You can also have. In this case, the measurement data display means sequentially transmits the obtained measurement data to the image display device, so that the measurement data is obtained each time measurement data is obtained from the X-ray analysis device and the thermal analysis device. Is desirably displayed as an image sequentially.

  According to this aspect of the invention, by observing the measurement results that are sequentially displayed during the measurement, the setting of the measurement conditions can be changed during the measurement according to the measurement results. Further, when it is determined that the reaction of the substance is completed during the observation of the measurement result, the measurement can be stopped halfway.

  In the conventional simultaneous X-ray analysis and thermal analysis apparatus, the operator must imagine in his head how many X-ray diffraction measurements can be performed in the temperature rise curve and humidity setting curve. I could not confirm it on the screen. On the other hand, in this embodiment, by adding a function for drawing vertical lines X on the time axis on the screen, the relationship between the measurement conditions of the X-ray analysis measurement and the measurement conditions of the thermal analysis measurement can be visually confirmed. It became possible to recognize, and the usability of the device was greatly improved. Compared to conventional methods that rely solely on calculations using a calculator and imagination in the head, measurement conditions can be set quickly and accurately.

1 is a diagram schematically showing an embodiment of a simultaneous X-ray analysis and thermal analysis apparatus according to the present invention. It is a block diagram which shows the electrical constitution of the X-ray analysis and thermal analysis simultaneous analysis apparatus of FIG. It is a flowchart which shows operation | movement of the X-ray analysis and thermal analysis simultaneous analysis apparatus of FIG. It is a figure which shows an example of the screen display performed by the image display apparatus which is a component of the X-ray analysis and thermal analysis simultaneous analysis apparatus of FIG. It is a figure which shows another example of the screen display performed by the image display apparatus which is a component of the X-ray analysis and thermal analysis simultaneous analysis apparatus of FIG. It is a figure which shows another example of the screen display performed by the image display apparatus which is a component of the X-ray analysis and thermal analysis simultaneous analysis apparatus of FIG. It is a flowchart which shows operation | movement of other embodiment of the X-ray analysis and thermal analysis simultaneous analysis apparatus which concerns on this invention. It is a figure which shows the example of the screen display corresponding to the flowchart of FIG. It is a figure which shows another example of the screen display performed by the image display apparatus which is a component of the X-ray analysis and thermal analysis simultaneous analysis apparatus of FIG. It is a figure which shows another example of the screen display performed by the image display apparatus which is a component of the X-ray analysis and thermal analysis simultaneous analysis apparatus of FIG.

(First embodiment of simultaneous X-ray analysis and thermal analysis analyzer)
A simultaneous X-ray analysis and thermal analysis apparatus 1 of the present embodiment shown in FIG. 1 is an apparatus that simultaneously performs both X-ray analysis and thermal analysis. In the present embodiment, analysis using X-ray diffraction is performed as X-ray analysis, and DSC (Differential Scanning Calorimetry) analysis is performed as thermal analysis.

  The X-ray analysis and thermal analysis simultaneous analysis apparatus 1 has a sample chamber 2 that is separated from the outside by a partition wall. The sample chamber 2 is preferably separated from the outside in an air-tight and liquid-tight manner. The sample chamber 2 is formed by a metallic partition such as stainless steel. A θ-2θ goniometer (θ-2θ angle measuring device) 3 is provided around the sample chamber 2. Further, an X-ray source 6 is provided on one side outside the sample chamber 2 supported by the goniometer 3, and an X-ray detector 7 is provided on the opposite side outside by being supported by the goniometer 3. As the X-ray detector 7, for example, a zero-dimensional counter having no position resolution such as SC (Scintillation Counter), a semiconductor sensor in which X-ray light receiving elements are linearly arranged in the 2θ angle scanning direction, and the like are used. .

  The θ-2θ goniometer 3 supports a sample 4 to be analyzed. A straight line connecting the center of the X-ray source 6 and the center of the sample 4 is the optical axis of the incident X-ray. A straight line connecting the center of the sample 4 and the center of the X-ray capturing area of the X-ray detector 7 is the optical axis of the X-ray (so-called secondary X-ray) emitted from the sample 4. The θ-2θ goniometer 3 measures both the incident angle θ of the X-ray incident on the sample 4 and the angle 2θ of the secondary X-ray optical axis with respect to the extended line of the incident X-ray optical axis. The angle 2θ is twice the X-ray incident angle θ.

  In the present embodiment, the secondary X-ray is a diffracted ray, but if the X-ray analysis is an analysis using X-ray scattering, the secondary X-ray is a scattered ray, and the X-ray analysis uses a fluorescent X-ray. The secondary X-rays are fluorescent X-rays.

  The goniometer 3 measures the angle θ and the angle 2θ in accordance with a command from the main control device 12 (that is, positions the angle). The angle 2θ is an angle at which the diffraction line emitted from the sample 4 at the angle 2θ can be received by the X-ray detector 7, and this angle 2θ is usually called a diffraction angle 2θ. The X-ray detector 7 detects a diffraction line emitted from the sample 4 and outputs an X-ray intensity signal S0 which is an electric signal indicating the intensity of the diffraction line.

  Among the partition walls constituting the sample chamber 2, the material that can allow the X-ray to travel and maintain the internal airtight state and the liquid-tight state at the portion that intersects the traveling path of the incident X-ray and the secondary X-ray An X-ray transmission window having a structure is provided in advance.

  A standard substance 8 is placed adjacent to the sample 4. The sample 4 is a substance whose characteristics change according to the ambient temperature change (for example, a characteristic change due to dissolution), whereas the standard substance 8 is a substance whose characteristics do not change with respect to the temperature change.

  Inside the sample chamber 2, a temperature sensor 9 and a humidity sensor 11 are provided. The temperature sensor 9 detects the temperatures of the sample 4 and the standard substance 8 and outputs them as a temperature signal S1 that is an electrical signal. The humidity sensor 11 detects the humidity around the sample 4 and the standard material 8 and outputs it as a humidity signal S2 which is an electrical signal. The temperature signal S1 and the humidity signal S2 are transmitted to the main controller 12.

  In the sample chamber 2, a DSC measurement circuit 14, a temperature control device 16, and a humidity control device 17 are attached. The DSC measurement circuit 14 has a calorific value detection element (for example, a thermocouple temperature measuring point) disposed in the vicinity of each of the sample 4 and the standard material 8. The DSC measurement circuit 14 detects the difference in the amount of heat (that is, the heat flow rate) flowing into each of the sample 4 and the standard material 8 using these detection elements. The DSC measurement circuit 14 transmits this heat flow rate to the main controller 12 as a heat quantity signal S3 which is an electrical signal.

  The temperature control device 16 operates according to a command from the main control device 12 and controls the temperature inside the sample chamber 2 (that is, the temperature around the sample 4 and the standard material 8). The temperature control device 16 is configured using, for example, a heater that generates heat when energized, a cooler, or the like. In some cases, no cooler is used. The humidity control device 17 operates in accordance with a command from the main control device 12 to control the humidity inside the sample chamber 2 (that is, the humidity around the sample 4 and the standard material 8). A display 23 as an image display device is connected to the output port of the main controller 12. The display 23 is configured by a liquid crystal display device, for example.

  For example, as shown in FIG. 2, the main controller 12 includes a computer having a CPU (Central Processing Unit) 18, a ROM (Read Only Memory) 19, a RAM (Random Access Memory) 21, and a memory 22. Has been. 2 and 1 are denoted by the same reference numerals. The memory 22 includes a semiconductor memory, a mechanical memory such as a CD (Compact Disk), and other storage media having an arbitrary configuration. The memory is not limited to one type of storage medium, and the memory may be composed of a plurality of types of storage media.

  In the memory 22, a measurement control program 24 that defines the operation of the simultaneous X-ray analysis and thermal analysis apparatus 1 of FIG. 1 and an image display program that generates an image signal for displaying an image on the screen of the display 23. 26 is stored. In the memory 22, various file areas such as a condition storage file 27, a measurement data storage file 28, and an analysis data storage file 29 are provided.

  The condition storage file 27 is a file for storing measurement conditions of X-ray analysis measurement and thermal analysis measurement and other various measurement conditions. The measurement data storage file 28 is a file for storing data obtained by X-ray analysis measurement and thermal analysis measurement and not subjected to secondary processing (hereinafter also referred to as raw data). is there. The analysis data storage file 29 is a file for storing data after the analysis processing is added to the raw data (hereinafter, sometimes referred to as analysis data). The analysis processing includes, for example, diffraction profile peak processing, diffraction profile background processing, and the like.

  The measurement conditions of the X-ray analysis measurement are (1) the measurement start angle and measurement end angle of the diffraction angle 2θ in FIG. 1, (2) the moving speed of the scanning movement of the X-ray detector 7 from the start angle to the end angle, (3) A sampling time or the like that is a time during which the X-ray detector 7 accumulates X-rays with respect to one 2θ angle.

  The measurement conditions for the thermal analysis measurement include, for example, setting of a target temperature and setting of a temperature increase rate. As other measurement conditions, for example, there are a target humidity setting and a humidity increase rate setting.

  The X-ray analysis measurement is performed by the following procedure, for example. That is, in FIG. 1, the temperature control device 16 is operated to change the temperature around the sample 4 over time in a desired state. On the other hand, the humidity control device 17 is operated to set the humidity around the sample 4 to a desired humidity. Thereby, the sample 4 is placed under a desired temperature and humidity.

  Next, the sample 4 is irradiated with X-rays generated from the X-ray source 6 through an X-ray optical element such as a slit or a monochromator. The X-ray incident angle θ and the diffraction line capture angle 2θ by the X-ray detector 7 are scanned and moved from the start angle to the end angle at a predetermined scanning movement speed. During the scanning movement of the X-ray detector 7, the intensity I (2θ) of the diffraction line is detected at every predetermined sampling time. The diffraction line intensity I (2θ) is an intensity value for each diffraction angle value from the start angle to the end angle of the diffraction angle 2θ. This diffraction line intensity I (2θ) is output from the X-ray detector 7 as an X-ray intensity signal S0.

  The thermal analysis measurement is performed by the following procedure, for example. In FIG. 1, in a state where the sample 4 and the standard material 8 are placed at a desired temperature and humidity, the difference between the amount of heat flowing into the sample 4 and the amount of heat flowing into the standard material 8 is measured over time by the DSC measurement circuit 14. To detect. That is, the difference in heat inflow amount is detected corresponding to the passage of time. The difference in the heat inflow amount is output from the DSC measurement circuit 14 as a heat amount signal S3.

Hereinafter, the measurement realized by the measurement control program 24 and the image display program 26 of FIG. 2 will be described with reference to the flowchart of FIG.
First, in step S1, it is checked whether or not the sample 4 (FIG. 1) is placed at a predetermined position. If it is placed (YES in step S1), an instruction for displaying the measurement condition screen in step S2 Check whether the measurement was performed by the measurer. This measurement condition screen is a screen that is used when the measurer sets, edits, and confirms the measurement condition.

  The measurement condition screen 33 is a single image display composed of a measurement condition input screen 31 and a measurement condition display screen 32. Of course, the measurement condition input screen 31 and the measurement condition display screen 32 may be displayed separately. The measurement condition input screen 31 is a display used when a measurer inputs measurement conditions. The measurement condition display screen 32 displays the measurement conditions input through the measurement condition input screen 31 in a form that can be visually recognized.

  It is also possible to adopt a program for inputting by instructing the measurement condition display screen 32 on the screen by pointer display. In this case, the measurement condition display screen 32 also serves as the measurement condition input screen 31. Become.

  In the case of this embodiment, the measurement condition display screen 32 displays the measurement conditions using coordinates with time (min / min) on the horizontal axis and temperature (° C.) and humidity (20 ° C .-%) on the vertical axis. The graph is displayed. In this display, the temperature measurement condition is displayed by a line graph T, the humidity measurement condition is displayed by a line graph Hu, and the scanning start time and end time of the 2θ angle of the X-ray analysis measurement include a plurality of parallel vertical lines. It is displayed on the time axis (that is, the horizontal axis) by the line X.

  Under this measurement condition, it can be seen from the humidity condition line Hu that the humidity reaches the target value of 90% after approximately 10 minutes. In normal measurement, X-ray analysis measurement and thermal analysis measurement are performed after the time when the humidity rises to 90%. Further, by looking at the temperature condition line T, the humidity is maintained at 25 ° C. for about 10 minutes to 15 minutes after the humidity is increased to 90%, and is maintained at 50 ° C. for about 20 to 25 minutes, and after about 30 minutes. Is maintained at 70 ° C.

  Regarding the plurality of vertical lines X, when two adjacent lines are viewed, the left line indicates the start point of scanning rotation at a 2θ angle, and the right line indicates the end point of scan rotation. For example, when considering three vertical lines X1, X2, and X3 10 minutes after the horizontal axis (time axis), X1 and X2 indicate the start and end times of one 2θ scanning movement, and X2 And X3 indicate the starting and ending points of another one-time 2θ scanning movement. All vertical lines X other than X1 to X3 have the same meaning.

  In FIG. 1, X-ray detection is performed after one scanning movement of the X-ray detector 7 from the start angle (for example, 2θ = 5 °) to the end angle (for example, 2θ = 40 °) of the diffraction angle 2θ is completed. Means 7 must return to the starting angle in preparation for the next X-ray diffraction measurement. The X-ray condition line X in FIG. 4 does not particularly indicate the return time of the X-ray detection means 7, but the return time is recognized as being included within the time defined by the two vertical lines X. .

  If it is determined in step S2 that an instruction to display the measurement condition screen 33 is issued by the measurer (YES in step S2), the data stored in the condition storage file 27 (FIG. 2) is read. (Step S3). An image signal is generated based on the read data, and the measurement condition screen 33 (FIG. 4), that is, the measurement condition input screen 31 and the measurement condition display screen 32 are displayed according to the image signal (steps S4 and S5). . If the measurement condition is input by the measurer (YES in step S6), the contents of the condition storage file 27 (FIG. 2) are updated according to the input, and the measurement condition screen 33 is displayed again.

In this embodiment, as the temperature condition,
(1) Three types of set temperature = 25 ° C., 50 ° C., and 75 ° C. (2) Temperature increase rate = 3 ° C./min
Is set. Also, 90% is set as the humidity condition.

Furthermore, as X-ray diffraction measurement conditions,
(1) 2θ start angle = 5 °
(2) 2θ end angle = 40 °
(3) Scanning step angle = 0.0200 °, scanning speed = 40 ° / min
Is set.

  As a result of the above input, on the measurement condition display screen 32, the temperature measurement condition is displayed as a line graph T, the humidity measurement condition is displayed as a line graph Hu, and the X-ray diffraction measurement conditions are displayed as a plurality of vertical lines X. The The measurer who has seen these can easily and accurately grasp the measurement condition of the X-ray analysis measurement, the measurement condition of the thermal analysis measurement, and the humidity condition that will be performed from now on. When it is desired to change the measurement condition, the new measurement condition can be set simply, quickly and accurately by changing the condition using the measurement condition input screen 31. And the change content can be recognized easily.

  When the measurement condition display screen 32 has the function of the measurement condition input screen, the X-ray diffraction condition is newly set by dragging (moving) the pointer display on the screen on the time axis (horizontal axis), for example. Can be entered. In this case, the number of the corresponding item in the measurement condition input screen 31 in the upper area of the screen changes in conjunction.

  After the measurement conditions are set as described above, it is determined in step S7 whether or not there has been an instruction to start measurement by the measurer (YES in step S7), and a measurement start command is generated in step S8.

  Then, in FIG. 1, the temperature of the internal region of the sample chamber 2 is controlled according to the temperature measurement condition T of FIG. 4 by the action of the temperature control device 16, and the humidity of the internal region of the sample chamber 2 is determined by the action of the humidity control device 17. And the X-ray diffraction measurement condition is controlled according to the X-ray measurement condition X by the action of the goniometer 3. As a result of this control, diffraction line intensity data I (2θ) is obtained from the X-ray detector 7, and heat flow data (DSC data) is obtained from the DSC measurement circuit 14.

  These obtained data are stored in the measurement data storage file 28 of FIG. 2 in step S9. These data are stored in relation to the elapsed time from the start of measurement. Since the elapsed time is related to the change in the temperature of the sample and the change in the diffraction angle 2θ, the diffraction line intensity data I (2θ) is related to the change in the diffraction angle 2θ and the change in the sample temperature. Related.

  In step S10, the CPU 18 generates image data for displaying the data every time measurement data is obtained. When the measurer gives an instruction to display data (YES in step S11), the generated image data is transmitted to the image display driver in the display 23 of FIG. The measurement data is displayed on the top (step S12). In this case, instead of the measurement condition screen 33 of FIG. 4, the measurement data is displayed side by side or superimposed.

  FIG. 5 shows an example of the data display of the measurement result displayed as described above. In the measurement result screen 34 shown in FIG. 5, the left part 36 shows the result of X-ray analysis measurement, and the right part 37 shows the result of DSC measurement. The X-ray measurement result display 36 draws a plurality of diffraction line profiles 35 parallel to each other along the vertical direction on coordinates with the diffraction angle 2θ on the horizontal axis and the diffraction line intensity I on the vertical axis. Has been created by that. Each diffraction line profile 35 extends in the horizontal direction over a 2θ angle scanning region of 2θ = 5 ° (start angle) on the horizontal axis scale to 2θ = 40 ° (end angle).

  The DSC measurement result display 37 is drawn on the coordinates in which the horizontal axis represents heat quantity (Heat Flow / mW), temperature (Temperature / ° C.), and humidity (%), and the vertical axis represents elapsed time (min). It is. Reference numeral 38 is a DSC curve obtained by measurement, and reference numeral 39 is a temperature change curve.

  In steps S10 to S12, image data is generated every time measurement data is obtained, and the image data is sequentially transmitted to the image driver. Therefore, every time measurement data is obtained, that is, in real time, the diffraction line profile 35, the DSC curve 38, and the temperature change curve 39 are gradually drawn on the measurement result screen 34 of FIG. Then, when the measurement end condition is reached (YES in step S15), for example, when the final X-ray diffraction measurement 41 on the measurement condition display screen 32 in FIG. The diffraction measurement and the thermal analysis measurement are finished (step S16). Thus, when all measurements are completed, all measurement data obtained by the measurement are displayed on the measurement result screen 34 as shown in FIG.

  If the measurer wishes to analyze the data, for example, background reduction processing or peak search processing (YES in step S17), the desired analysis is performed on the obtained data, and further obtained by the analysis. The obtained data, that is, analysis data is stored in the analysis data storage file 29 of FIG. 2 (step S18). Although not shown in the flowchart of FIG. 3, the obtained analysis data is displayed in a display form similar to that of FIG. 6 in accordance with an instruction from the measurer.

Next, the properties of the measurement result screen 34 shown in FIGS. 5 and 6 will be briefly described.
In the time defined by two vertical lines X adjacent to each other among a plurality of vertical lines (X-ray condition lines) X drawn on the measurement condition display screen 32 in FIG. A single X-ray diffraction measurement at 0 ° is performed. Then, the X-ray diffraction measurement for each time is continuously repeated. As a result, the diffraction line profiles 35 are drawn parallel to each other at intervals in the vertical direction in the X-ray measurement result display 36 of FIG. 5 or 6.

  While each X-ray diffraction measurement is repeatedly performed, that is, while each diffraction line profile 35 is sequentially drawn in FIG. 6, the ambient temperature of the sample 4 is the temperature change curve 39 of the DSC measurement result display 37. Has changed. Therefore, when the temperature change curve 39 is not vertical (a state in which the same temperature is maintained), each X-ray diffraction measurement is performed under different temperature conditions.

  In this embodiment, each diffraction line profile 35, each temperature range when the profile is obtained, and each DSC measurement result corresponding to the temperature range are displayed in association with each other. Specifically, each diffraction line profile 35 is displayed at a horizontal position in a direction along the horizontal axis of the graph with respect to the sample temperature range on the temperature change curve 39 when the diffraction line profile 35 is measured. Yes.

  More specifically, the time on the vertical axis (time axis) of the DSC measurement result display 37 indicates time data of the DSC curve 38 and the temperature change curve 39. The measurement start time of each diffraction line profile 35, that is, the position on the vertical axis of 2θ = 5 ° of each diffraction line profile 35 coincides with the time on the vertical axis (time axis) of the DSC measurement result display 37. .

  If each angle position between 2θ = 5 ° and 40 ° of each diffraction line profile 35 is made to exactly match the time axis, each diffraction line profile 35 becomes an upward-sloping profile (that is, according to an increase in 2θ). It should be a profile that goes up by the elapsed time). However, in the display method of the present embodiment, only the left end point (that is, the measurement start point) of each diffraction line profile 35 is matched with the time on the time axis, and the base line of each diffraction line profile 35 is the horizontal axis (time axis). Are displayed in parallel. Thereby, the X-ray measurement result display 36 is easy to see.

  Note that the point to be coincident with the time on the vertical axis of the DSC measurement result display 37 in each diffraction line profile 35 is not limited to the measurement start point (left end point), and may be a center point or an arbitrary intermediate point, or may be measured. It may be the end point (right end point).

  As is apparent from the above description, the DSC curve 38 and the temperature change curve 39 in the DSC measurement result display 37 follow the vertical axis (time axis), and the X-ray measurement result display 36 shows the diffraction line profile 35 in the vertical axis direction. The position also follows the vertical axis (time axis) of the DSC measurement result display 37. Accordingly, each diffraction line profile 35 has a corresponding relationship with an intersection or an intersection region of the temperature change curve 39 and the DSC curve 38 when each profile is horizontally extended in the right lateral direction.

  Therefore, for example, the lowest diffraction line profile 35a is created within a temperature range of 22.0 ° C. to 23.0 ° C., and the second diffraction line profile 35b from the bottom is 23.0 ° C. to 24.0 ° C. If created within the temperature range of ° C., the bottom diffraction line profile 35a is drawn in the horizontal direction of the 22.0 ° C. to 23.0 ° C. portion of the temperature change curve 39, The second diffraction line profile 35b is drawn in the horizontal direction of the portion of the temperature change curve 39 at 23.0 ° C to 24.0 ° C.

  As understood from the above, in the X-ray measurement result display 36, the numerical value of the X-ray intensity (Intensity) graduated on the vertical axis represents each diffraction line profile 35 drawn next to those numerical values. It does not directly indicate the peak intensity value, but indirectly indicates the magnitude of the X-ray intensity corresponding to the peak height of each diffraction line profile 35. In the present embodiment, it is not important to know the exact magnitude of each peak intensity in each diffraction profile 35, but the difference in peak generation position between each diffraction profile and the difference in approximate peak intensity are divided. Therefore, the display method such as the X-ray measurement result display 36 of the present embodiment is very convenient for the measurer.

  Next, in the present embodiment, when the measurer instructs the measurement result screen 34 to perform predetermined screen processing so that the measurer can accurately grasp the measurement result (in step S13). YES), the process proceeds to step S14, and a predetermined screen processing program is executed. Specifically, the measurer indicates an arbitrary diffraction line profile 35, for example, the eighth diffraction line profile 35 from the bottom indicated by arrow A in FIG. 6, and clicks a mouse button as an input device ( When selected, the diffraction line profile 35 is displayed with a thicker line (or a different color) than the other diffraction line profiles 35.

  On the right side of the selected diffraction line profile 35, the temperature range when the diffraction line profile 35 is obtained is displayed numerically (arrow B), for example, “108.0-110.2”. At the same time, the corresponding temperature range portion C of the temperature change curve 39 and the corresponding DSC portion D of the DSC curve 38 are also displayed in bold lines (or different colors). If you click again, the selection is canceled, the thick line is removed, and the normal thickness is restored.

  On the other hand, when a portion C of the temperature change curve 39 or a portion D of the DSC curve 38 is clicked, these portions are regarded as selected and are displayed with bold lines (or different colors), and at the same time, corresponding diffraction The line profile 35 is displayed as a thick line (or a different color). Further, the temperature range is displayed numerically on the right side of the selected diffraction line profile.

  As described above, the diffraction line profile 35, the temperature change curve 39, and the DSC curve 38 are visually displayed in association with each other, and a thick line is indicated by clicking on a portion for which a correspondence relationship is desired. Since the correspondence between the curves can be easily, quickly and clearly recognized by display and numerical display, the crystal structure and characteristics of the sample 4 can be easily and accurately determined.

  In the conventional simultaneous X-ray analysis and thermal analysis apparatus, the operator must imagine in his head how many X-ray diffraction measurements can be performed in the temperature rise curve and humidity setting curve. I could not confirm it on the screen. On the other hand, in the present embodiment, by adding a function of drawing a delimiter vertical line X on the time axis on the measurement condition screen 33 in FIG. 4, the measurement conditions for the X-ray diffraction measurement and the measurement conditions for the DSC analysis measurement are added. It is possible to visually recognize the relationship between the device and the usability of the device has been greatly improved. Compared to conventional methods that rely solely on calculations using a calculator and imagination in the head, measurement conditions can be set quickly and accurately.

  Furthermore, in the present embodiment, the measurement condition screen 33 of FIG. 4 is displayed on the screen according to the instructions of the measurer whenever necessary before, during, or after the measurement. The measurement conditions can be checked whenever necessary.

(Modification)
In the above embodiment, in FIG. 4, the intervals between the plurality of X-ray condition vertical lines X are all set equal. That is, the time taken for one X-ray diffraction measurement that ends at a start angle of 5 ° to an end angle of 40 ° was the same for all X-ray diffraction measurements. Instead of this, the X-ray detector scan speed is lowered at the part that the measurer needs on the time axis, and the X-ray diffraction measurement is performed slowly over time, or vice versa. It is possible to increase the scanning speed and quickly. When the measurement time is long, the interval between adjacent vertical lines X in FIG. 4 is widened, and when the measurement time is short, the interval between vertical lines X is narrowed. As described above, the measurement conditions for the X-ray analysis measurement and the measurement conditions for the thermal analysis measurement can be set visually, easily, quickly and accurately.

(Second embodiment of simultaneous X-ray analysis and thermal analysis analyzer)
Next, another embodiment of the simultaneous X-ray analysis and thermal analysis apparatus according to the present invention will be described with reference to FIGS. FIG. 8 shows a measurement condition screen 53 corresponding to the embodiment. FIG. 7 is a flowchart showing the control for displaying the measurement condition screen 53.

  The measurement condition screen 53 shown in FIG. 8 has a measurement condition input screen 31 and a measurement condition display screen 32, which is the same as the measurement condition screen 33 shown in FIG. This embodiment is different from the embodiment shown in FIG. 4 in that (1) DSC measurement is performed as a preliminary measurement before performing actual X-ray diffraction measurement and DSC measurement, and (2) obtained by the preliminary DSC measurement. The obtained DSC curve 54 is displayed so as to be superimposed on each of the humidity condition line Hu, the temperature condition line T, and the X-ray condition line X in the measurement condition display screen 32, and (3) the sample 4 (see FIG. This is because the actual measurement was performed after replacing 1) with a new one.

  Note that the new sample and the pre-measured sample are samples having the same components. For example, when a certain amount of substance is given as a sample, a part of the substance is set as a sample for preliminary measurement, and the rest is set as a sample for actual measurement. The reason for exchanging the sample is that when the thermal analysis of the preliminary measurement is performed, the sample subjected to the preliminary measurement is altered.

  In this embodiment, the preliminary measurement means for performing the preliminary DSC measurement is configured by the main controller 12, the DSC measurement circuit 14, the temperature controller 16, and the humidity controller 17 in FIG.

  In order to realize such a display, the main control apparatus of the present embodiment executes the control shown in the flowchart in FIG. This flowchart is different from the flowchart in the previous embodiment shown in FIG. 3 in steps S6 to S8 and S11 in FIG. In step S6, it is checked whether or not preliminary measurement of DSC is performed. If it is determined that preliminary measurement is to be performed (YES in step S6), preliminary measurement of DSC is performed (step S7). Further, the DSC data obtained by the preliminary measurement is displayed in the measurement condition display screen 32 as a DSC curve as indicated by reference numeral 54 in FIG. In step S11, it is checked whether or not the sample 4 (FIG. 1) has been replaced. If it has been replaced (YES in step S11), a measurement start command is generated in step S12.

The following steps are the same between the flowchart of FIG. 7 and the flowchart of FIG.

  Also in the present embodiment, as shown in FIG. 8, by adding a function of drawing a delimitation vertical line X on the time axis (horizontal axis) in the measurement condition display screen 32 of the measurement condition screen 53, X-ray diffraction It became possible to visually recognize the relationship between measurement conditions (for example, 2θ scanning speed) and DSC measurement conditions (for example, temperature change), and the usability of the apparatus was greatly improved.

  Furthermore, according to the present embodiment, the measurer can determine the measurement condition X of the X-ray diffraction measurement in consideration of the DSC curve characteristic 54 in addition to the measurement condition T of the temperature change. For example, the number of X-ray diffraction measurements can be set to a desired number corresponding to the position where the calorific value greatly changes in the DSC curve 54 after the preliminary measurement. Thereby, the measurement conditions for the X-ray diffraction measurement and the thermal analysis measurement can be set to the best conditions in a short time without repeating trial and error.

(Other embodiments)
The present invention has been described with reference to the preferred embodiments. However, the present invention is not limited to the embodiments, and various modifications can be made within the scope of the invention described in the claims.
For example, in the above-described embodiment, an X-ray diffractometer is exemplified as the X-ray analyzer and a DSC apparatus is exemplified as the thermal analyzer. An X-ray apparatus or the like may be used. The thermal analysis device is not limited to a DSC device, and may be a DTA device or the like.

In the display example of the measurement conditions shown in FIG. 4, in addition to the line graph display of the humidity change Hu and the temperature change T, a plurality of vertical lines X defining the X-ray measurement conditions are drawn. As shown in FIG. 9, the display of the humidity change Hu may be stopped, and only the line graph display of the temperature change T and the plurality of vertical lines X defining the X-ray measurement conditions may be drawn.
In FIG. 4, the humidity Hu is kept constant and the temperature T is changed stepwise. Instead, as shown in FIG. 10, the temperature T is kept constant and the humidity Hu is changed stepwise. It may be changed.

Claims (7)

An X-ray analyzer for detecting X-rays emitted from the sample when the sample is irradiated with X-rays by an X-ray detection means;
A thermal analysis device that detects a change in characteristics generated in the sample when the ambient temperature of the sample is changed; and
Measurement control means for controlling the measurement by the X-ray analyzer and the measurement by the thermal analyzer to be performed simultaneously;
X-ray condition storage means for storing measurement conditions for X-ray analysis measurement;
Thermal condition storage means for storing measurement conditions for thermal analysis measurement;
An image display device that displays an image on a screen according to an image signal;
Measurement condition display means for displaying both the X-ray analysis measurement conditions stored in the X-ray condition storage means and the thermal analysis measurement conditions stored in the thermal condition storage means as a graph on the screen of the image display device. And
The measurement condition display means displays the graph at any time within at least one of the time during which the measurement is not performed and the time during which the measurement is performed. Line analysis and thermal analysis simultaneous analyzer. The thermal analysis measurement condition includes a temperature change,
The X-ray analysis measurement conditions include an angular scanning movement time from the measurement start angle to the measurement end angle by the X-ray detection means for detecting X-rays emitted from the sample,
The measurement condition display means displays the temperature change in a line graph on the coordinate with time taken on one of the vertical axis and the horizontal axis and the temperature on the other, and the start and end of the angular scanning movement time. 2. The X-ray analysis and thermal analysis simultaneous analysis apparatus according to claim 1, wherein a line indicating each is displayed on a time axis. A humidity changing means for changing the humidity around the sample;
3. The X-ray analysis and heat according to claim 1, wherein the measurement condition display unit displays the change in humidity as a graph superimposed on the X-ray analysis measurement condition and the thermal analysis measurement condition. Simultaneous analysis equipment for analysis. 4. The X-ray analysis and thermal analysis simultaneous analysis apparatus according to claim 3, wherein the measurement condition display means displays the humidity change by a line graph. It further includes preliminary measurement means for performing preliminary measurement of thermal analysis using the thermal analyzer,
5. The X-ray analysis and thermal analysis simultaneous analysis apparatus according to claim 1, wherein the measurement condition display unit displays the preliminary measurement result as a graph. The measurement condition display means displays an input screen for inputting the X-ray analysis measurement condition and the thermal analysis measurement condition in addition to the graph display of the X-ray analysis measurement condition and the thermal analysis measurement condition. The X-ray analysis and thermal analysis simultaneous analysis apparatus according to any one of claims 1 to 5, wherein the X-ray analysis and thermal analysis simultaneous analysis apparatus is characterized. Measurement data display means for displaying the measurement data by the X-ray analyzer and the measurement data by the thermal analyzer on the screen of the image display device;
The measurement data display means sequentially transmits both obtained measurement data to the image display device,
The X-ray according to any one of claims 1 to 6, wherein the measurement data is sequentially displayed as an image every time measurement data is obtained from the X-ray analysis device and the thermal analysis device. Analytical and thermal analysis simultaneous analyzer.

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