JP2007017258A - Composite analyzer and composite analyzing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To perform X-ray diffraction measuring and thermal analytical measuring at the same time with respect to a plurality of samples. <P>SOLUTION: A first arm 20 and a second arm 22 are cooperatively rotated at the same angular velocity in mutually opposite directions at the time of X-ray diffraction measuring due to a concentration method. After the diffusion in a Z-direction is restricted with respect to the elongated linear X-ray beam 30 in the Z-direction by the solar slit 26 on an incident side, powder samples 14 and 16 are simultaneously irradiated with the X-ray beam 30. The diffracted X rays from the sample 14 and the diffracted X rays from the sample 16 are discriminatively detected at least in the Z-direction by a position responsive type X-ray detector 34 after the diffusion in the Z-direction is restricted by the solar slit 32 on a light detecting side. Further, thermal analytical measuring is performed with respect to two powder samples 14 and 16 simultaneously with the X-ray diffractive measuring. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a composite analyzer and a composite analysis method for simultaneously performing X-ray diffraction measurement and thermal analysis measurement on a plurality of samples.

The following Patent Document 1 discloses that X-ray diffraction measurement is performed on a plurality of samples at the same time.
JP 2000-338061 A

  This Patent Document 1 discloses that one row of a plurality of samples arranged in a matrix is simultaneously measured by an X-ray diffraction method. FIG. 22 of this patent document 1 shows an example using a line-shaped X-ray beam. After the line-shaped X-ray beam is reflected by a curved crystal monochromator, a plurality of samples in one row are irradiated. Diffracted X-rays from a plurality of samples are detected by a two-dimensional X-ray detector after passing through a solar slit for limiting longitudinal divergence. By adopting such an optical system, diffracted X-rays from a plurality of samples can be separately detected at different positions on a two-dimensional X-ray detector. Examples of the two-dimensional X-ray detector include an imaging plate and a CCD camera.

In addition, the present invention relates to performing X-ray diffraction measurement and thermal analysis measurement at the same time. This point is disclosed in the following Patent Documents 2 to 4.
JP-A-10-19815 JP-A-11-132777 JP 11-295244 A

  Patent Documents 2 and 3 disclose that X-ray diffraction measurement and thermal analysis measurement (DTA or DSC) are performed simultaneously, and in particular, the structure of a sample holder for that purpose is disclosed. Patent Document 4 discloses a measurement data display method when performing X-ray diffraction measurement and thermal analysis measurement (DTA or DSC) simultaneously. In the techniques described in Patent Document 2 to Patent Document 4, a measurement sample and a standard sample are used for thermal analysis measurement, but only the measurement sample is an object of X-ray diffraction measurement. It is not disclosed to simultaneously measure the samples by X-ray diffraction.

The present invention further relates to performing X-ray diffraction measurement of a sample using a position-sensitive X-ray detector, but using a position-sensitive X-ray detector, particularly a two-dimensional CCD sensor. Electronic recording of diffracted X-rays is disclosed in the following Patent Document 5.
JP-A-2005-91142

  In Patent Document 5, an FFT (Full Frame Transfer / Full Frame Transfer) type two-dimensional CCD sensor is operated by TDI (Time Delay Integration) to enable high-speed and high-sensitivity X-ray diffraction measurement. This patent document 5 also discloses that X-ray diffraction measurement of a powder sample is performed in a state where the Bragg Brentano concentration condition is satisfied.

  As described above, it is known to simultaneously measure a plurality of samples by the X-ray diffraction method, while it is also known to simultaneously perform X-ray diffraction measurement and thermal analysis measurement on the same sample. However, it is not known to simultaneously perform X-ray diffraction measurement and thermal analysis measurement on a plurality of samples, and it is desired to develop an optimal apparatus configuration for that purpose.

  Accordingly, an object of the present invention is to provide a composite analyzer having an optimum apparatus configuration capable of simultaneously performing X-ray diffraction measurement and thermal analysis measurement on a plurality of samples, and a composite analysis method using such an apparatus. Is to provide.

  The composite analyzer of the present invention comprises the following (a) to (ku). (A) An X-ray source that generates an X-ray beam having a cross-sectional shape perpendicular to the X-ray traveling direction and having an elongated line shape. (A) a first holding unit for holding the powdery first sample, a second holding unit for holding the powdery second sample, and a reference temperature unit, wherein the first holding unit and the second holding unit are provided. A holding part is divided in a longitudinal direction (hereinafter referred to as a Z direction) of the cross section of the X-ray beam, and the first sample and the second sample are irradiated with the X-ray beam at the same time. A first sample temperature detector for detecting the temperature of the first sample; a second sample temperature detector for detecting the temperature of the second sample; and the reference temperature. A sample holder provided with a reference temperature detector for detecting the temperature of the part. (C) Temperature control means for controlling the first sample, the second sample, and the reference temperature unit to desired temperatures. (D) A position sensitive X-ray detector at least in the Z direction, capable of separately detecting the first diffracted X-ray emitted from the first sample and the second diffracted X-ray emitted from the second sample. (E) A Z-direction divergence limiting device that is disposed between the first sample and the second sample and the X-ray detector and limits the divergence of X-rays in the Z direction. (F) A goniometer control device that moves at least two of the X-ray source, the sample holder, and the X-ray detector so as to satisfy the concentration condition of Bragg Brentano. (G) An X-ray diffraction data processing unit that receives the output of the X-ray detector and creates X-ray diffraction data of the first sample and X-ray diffraction data of the second sample. (H) receiving outputs of the first sample temperature detector, the second sample temperature detector, and the reference temperature detector, and generating thermal analysis data of the first sample and thermal analysis data of the second sample; Thermal analysis data processing section.

  The X-ray detector may be a one-dimensional or two-dimensional X-ray detector that is position sensitive in at least the Z direction, but may preferably be a two-dimensional CCD sensor that performs TDI operation.

  The sample holder may be provided with a third holding part for holding a powdery standard sample for thermal analysis, in which case the reference temperature part becomes the standard sample. When the standard sample is not used, the holder main body portion of the sample holder (particularly, the portion between the first holding portion and the second holding portion) can be used as the reference temperature portion.

  The composite analysis method of the present invention comprises the following steps (a) to (e). (A) A step of preparing an X-ray source for generating an X-ray beam in which a cross-sectional shape perpendicular to the X-ray traveling direction is an elongated line. (A) a first holding unit for holding the powdery first sample, a second holding unit for holding the powdery second sample, and a reference temperature unit, wherein the first holding unit and the second holding unit are provided. The section is divided in the longitudinal direction (hereinafter referred to as Z direction) of the cross section of the X-ray beam, and the first sample and the second sample are irradiated with the X-ray beam at the same time. A holding part and the second holding part are arranged, a first sample temperature detector for detecting the temperature of the first sample, a second sample temperature detector for detecting the temperature of the second sample, and the reference temperature part Preparing a sample holder provided with a reference temperature detector for detecting the temperature of the sample. (C) a position sensitive X-ray detector in at least the Z direction capable of separately detecting the first diffracted X-ray emitted from the first sample and the second diffracted X-ray emitted from the second sample; The stage to prepare. (D) In the state where the first sample and the second sample are set to the first temperature, the X-ray beam is simultaneously irradiated to the first sample and the second sample to satisfy the concentration condition of Bragg Brentano. In this state, the X-ray detector is used to simultaneously detect the first diffracted X-ray and the second diffracted X-ray, and the first sample temperature detector, the second sample temperature detector, and the reference Creating thermal analysis data of the first sample and thermal analysis data of the second sample by using an output of a temperature detector; (E) In the state where the first sample and the second sample are set to a second temperature different from the first temperature, the X-ray beam is simultaneously irradiated to the first sample and the second sample, and Bragg The first diffracted X-ray and the second diffracted X-ray are simultaneously detected using the X-ray detector while satisfying the Brentano concentration condition, and the first sample temperature detector and the second diffracted X-ray are detected. Creating thermal analysis data of the first sample and thermal analysis data of the second sample using outputs of the sample temperature detector and the reference temperature detector;

  The incident-side and light-receiving-side Z-direction divergence limiting devices may be anything as long as they can limit the divergence angle in the Z direction narrowly. For example, both can be solar slits. In these Z direction divergence limiting devices, it is preferable to limit the divergence angle in the Z direction to, for example, 0.5 degrees or less.

  As thermal analysis in the present invention, for example, DTA (differential thermal analysis) or DSC (differential scanning calorimetry) can be used. The DSC may be a heat flux type DSC (quantitative DTA) or a heat compensation type DSC.

  According to the present invention, X-ray diffraction measurement and thermal analysis measurement can be performed simultaneously on a plurality of samples, so that X-ray diffraction data and thermal analysis data can be obtained simultaneously under the same measurement conditions for different samples. Comparison of measurement results between samples becomes easy and accurate. In addition, subtle differences between different samples can be clearly represented. For example, how subtle differences in the sample itself (difference in the degree of hydration of the sample, differences in crystallinity and orientation) respond to changes in external conditions (temperature, humidity, etc.) You can investigate. Or even if it is the same sample, it can be investigated what kind of response is carried out according to external conditions about the case where a solvent is dripped at the sample, and the case where it is not dripped.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a perspective view of the main configuration of an embodiment of the composite analyzer of the present invention, and FIG. 2 is a front view thereof. However, in FIG. 2, the vicinity of the sample holder 12 is a cross-sectional view passing through the sample 14 (16).

  In FIG. 1 and FIG. 2, this combined analyzer is capable of separately filling two kinds of powder samples 14 and 16 in the sample holder 12, and simultaneously measuring these two kinds of powder samples by X-ray diffraction measurement. Thermal analysis measurement is possible. The composite analyzer includes a stationary central portion 18, and a rotatable first arm 20 and second arm 22. The first arm 20 can rotate around a horizontal rotation center line 24, and the second arm 22 can also rotate around the same rotation center line 24. During X-ray diffraction measurement by the concentration method, the first arm 20 and the second arm 22 rotate in the opposite directions at the same angular velocity. A mechanism that rotates the first arm 20 and the second arm 22 is a goniometer.

  An X-ray tube (only the X-ray focal point 10 is shown), an incident side solar slit 26 and a diverging slit 28 are mounted on the first arm 20. In this embodiment, the X-ray tube is a rotating anti-cathode X-ray tube, and a line focus X-ray focal point 10 is used so that a line-shaped X-ray beam can be extracted. The X-ray beam 30 from the X-ray focal point 10 has a long and narrow cross-sectional shape perpendicular to the X-ray traveling direction. The cross-sectional dimension of the X-ray beam 30 in the vicinity of the X-ray focal point 10 is, for example, 1 mm × 10 mm.

  The incident side solar slit 26 is disposed between the X-ray focal point 10 and the samples 14 and 16. The incident-side solar slit 26 reduces the divergence angle in the longitudinal direction (hereinafter referred to as the Z direction) of the cross section of the X-ray beam 30 (the divergence angle in the direction perpendicular to the diffraction plane, that is, the divergence angle of the longitudinal divergence). In this embodiment, the divergence angle in the Z direction is limited to within 0.5 degrees so that the X-ray beam 30 is parallelized in the Z direction.

  The divergent slit 28 is disposed between the incident side solar slit 26 and the samples 14 and 16. The divergence slit 28 limits the divergence angle in the plane perpendicular to the Z direction of the X-ray beam 30 (the divergence angle in the diffraction plane, that is, the divergence angle of lateral divergence) to a predetermined angle. For example, the divergence angle of lateral divergence is set to about 2 degrees.

  A light receiving side solar slit 32 and an X-ray detector 34 are mounted on the second arm 22. The light-receiving side solar slit 32 limits the divergence angle in the Z direction of the diffracted X-rays 36 emitted from the samples 14 and 16 to a small divergence angle. In this embodiment, the divergence angle in the Z direction is 0.5. The diffracted X-ray 36 is made parallel in the Z direction by limiting it to within the range.

  A sample stage 38 is fixed to the stationary part 18, and the sample holder 12 can be attached on the sample stage 38. The upper surface of the sample stage 38 is horizontal, and the sample holder 12 is also arranged horizontally. As shown in an enlarged view in FIG. 3, the sample holder 12 can be filled with a powdery first sample 14, a powdery second sample 16, and a powdery standard sample 40. The first sample 14 and the second sample 16 are objects of X-ray diffraction measurement, and are also objects of thermal analysis measurement. The standard sample 40 is irrelevant to the X-ray diffraction measurement, and functions as a reference temperature unit for determining a reference temperature for the thermal analysis measurement of the first sample 14 and the second sample 16.

  The first sample 14 and the second sample 16 are divided in the Z direction, and have a positional relationship such that the first sample 14 and the second sample 16 are simultaneously irradiated with the linear X-ray beam 30.

  Next, the structure of the sample holder 12 will be described in detail. 4 is a plan view of the sample holder 12, and FIG. 5 is a sectional view taken along line 5-5 of FIG. In FIG. 4, the sample holder 12 can hold a powdery first sample 14, a powdery second sample 16, and a powdery standard sample 40. The planar dimension of each sample, that is, the planar dimension of a recess described later, has a width W in the Z direction of about 5 mm and a length L in a direction perpendicular to the width W of about 20 mm.

  In FIG. 5, the sample holder 12 includes a plate-shaped holder body 42 made of metal and having a substantially rectangular shape. A first recess 44, a second recess 46 and a third recess 48 are formed in the holder body 42. These recesses are sized to accommodate the sample container. The first container 50 filled with the powdery first sample 14 is housed in the first recess 44, and the second container 52 filled with the powdery second sample 16 is housed in the second recess 46, and the powdery standard The third container 54 filled with the sample 40 is stored in the third recess 48. The first concave portion 44 corresponds to the first holding portion in the present invention, and the second concave portion 46 corresponds to the second holding portion in the present invention. The standard sample 40 corresponds to the reference temperature part. As the material of the holder body 42, for example, copper, silver, or aluminum can be used if it is used at a relatively low temperature (maximum temperature is about 600 to 800 ° C.). If the maximum temperature is about 1100 ° C., for example, nickel can be used. If the maximum temperature reaches about 1200 to 1500 ° C., for example, platinum or platinum-rhodium (90% Pt-10% Rh) can be used. For samples that easily react with metals, quartz glass can be used.

  A first heat sensitive plate 56 is fixed to the bottom of the first recess 44, and the bottom surface of the first container 50 is in contact with the upper surface of the first heat sensitive plate 56. Similarly, a second heat sensitive plate 58 is fixed to the bottom of the second recess 46, the bottom surface of the second container 52 is in contact with the upper surface of the second heat sensitive plate 58, and the third heat sink 58 is in contact with the bottom of the third recess 48. The heat sensitive plate 60 is fixed, and the bottom surface of the third container 54 contacts the upper surface of the third heat sensitive plate 60. A contact point of the first thermocouple 62 is bonded to the back side of the first heat sensitive plate 56, and the temperature of the first sample 14 is transmitted to the first thermocouple 62 through the first container 50 and the first heat sensitive plate 56. Similarly, the contact point of the second thermocouple 64 is adhered to the back side of the second heat sensitive plate 58, and the temperature of the second sample 16 is changed to the second thermocouple 64 via the second container 52 and the second heat sensitive plate 58. It is transmitted to. The contact point of the third thermocouple 66 is adhered to the back side of the third heat sensitive plate 60, and the temperature of the standard sample 40 is transmitted to the third thermocouple 66 through the third container 54 and the third heat sensitive plate 60.

  The first terminals of the first thermocouple 62, the second thermocouple 64, and the third thermocouple 66 are connected to each other. The thermoelectromotive force between the second terminal of the first thermocouple 62 and the second terminal of the third thermocouple 66 is measured by a thermal analysis data processing unit to be described later, and this electromotive force is measured by the first sample 14 and the standard sample 40. This corresponds to a temperature difference ΔT1. Similarly, the thermoelectromotive force between the second terminal of the second thermocouple 64 and the second terminal of the third thermocouple 66 corresponds to the temperature difference ΔT2 between the second sample 16 and the standard sample 40.

  As an example of changing the sample holder, the standard sample 40 can be omitted. 6 is a plan view of the sample holder 12a from which the standard sample 40 is omitted, and FIG. 7 is a sectional view taken along line 7-7 of FIG. In FIG. 6, the sample holder 12a can hold the first sample 14 and the second sample 16, but there is no portion for holding the standard sample. As shown in FIG. 7, the sample holder 12a includes a first recess 44, a second recess 46, a first container 50, a second container 52, a first heat sensitive plate 56, a second heat sensitive plate 58, a first thermocouple 62, The second thermocouple 64 is the same as the sample holder 12 shown in FIG. A characteristic of the sample holder 12a in FIG. 7 is that the contact of the third thermocouple 66 is bonded to the portion 68 of the holder body 42a between the first recess 44 and the second recess 46. The portion 68 of the holder main body 42a functions as a reference temperature portion, and the temperature is detected by the third thermocouple 66 as the reference temperature. When thermal analysis measurement is performed using a standard sample omission sample holder, the accuracy of the thermal analysis data is expected to be slightly inferior to that of using a standard sample. The advantage is that the sample holder can be made smaller and the space to be heated can be reduced.

  In FIG. 1 and FIG. 2, the illustration of the heating device existing around the sample holder is omitted. The structure of a sample heating apparatus of the type that can perform X-ray diffraction measurement and thermal analysis measurement at the same time is disclosed in, for example, Patent Document 2 or Patent Document 3 described above. A structure can be adopted.

  Next, the X-ray detector 34 will be described with reference to FIGS. The X-ray detector 34 is a two-dimensional CCD sensor capable of TDI operation. FIG. 8 is a perspective view showing the positional relationship between the first sample 14 and the second sample 16 and the X-ray detector 34. During X-ray diffraction measurement, as shown in FIG. 2, the X-ray focal point 10 rotates θ clockwise in FIG. 2, while the X-ray detector 34 rotates θ counterclockwise in FIG. Then, as shown in FIG. 2, an X-ray beam 30 having a predetermined divergence angle in a plane perpendicular to the Z direction is irradiated at an incident angle θ over a relatively wide area of the samples 14 and 16. X-rays 36 are detected by an X-ray detector 34 existing in the 2θ direction with respect to the X-ray beam 30. Therefore, the composite analyzer shown in FIG. 2 is an optical system of the Bragg-Brentano concentration method for the X-ray diffraction method. With such an optical system, the powder diffraction patterns of the samples 14 and 16 can be recorded by the CCD sensor 34.

  In FIG. 8, considering a region 70 elongated in the Z direction on the sample 14 and the sample 16, the diffracted X-ray 36 generated from this region 70 has the highest intensity near the center in the vertical direction of the CCD sensor 34 that rotates θ. However, a predetermined intensity distribution is shown in the vertical direction around this point. When the two-dimensional CCD sensor 34 of TDI operation is used, such an intensity distribution is recorded simultaneously (that is, a portion that is blocked by the light receiving slit and is not detected in the normal concentration method is also recorded), so high speed. Makes it possible to measure with high sensitivity.

  The diffracted X-rays emitted from the first sample 14 are detected by pixels included in the left half region 72 of the CCD sensor 34. Further, the diffracted X-rays emitted from the second sample 16 are detected by pixels included in the right half region 74 of the CCD sensor 34.

  FIG. 9 is a configuration diagram of the CCD sensor 34. This CCD sensor is a full frame transfer (FFT) type CCD sensor capable of TDI operation. This CCD sensor includes N rows × M columns of pixels, and is arranged so that the column transverse direction coincides with the Z direction. In this embodiment, pixels of 512 rows × 512 columns are included. In each column, the light receiving portions 76 are arranged in order from the first row to the Nth row. Each light receiving section 76 constitutes one pixel and is a potential well (electron well) for accumulating charges. The N light receiving sections from the first row to the Nth row constitute an analog vertical shift register. When an X-ray hits the light receiving unit 76, signal charges are generated in the light receiving unit and accumulated therein. The accumulated charge is transferred to the next row every time a vertical transfer clock signal is received. The pulse interval of the vertical transfer clock signal corresponds to the transfer period of the TDI operation. The final Nth row charge is transferred to the analog horizontal shift register 78. The horizontal shift register 78 includes potential wells from the first column to the Mth column. The charge in each column on the horizontal shift register 78 is transferred to the next column every time a horizontal transfer clock signal is received. The charge in the last potential well in the Mth column is converted into an analog voltage signal at the output unit 80 and output.

  In the combined analyzer shown in FIG. 2, in order to record the diffraction pattern by operating the CCD sensor 34 in the TDI operation while rotating the CCD sensor 34 by the θ rotation, the speed of the θ rotation and the transfer frequency of the TDI operation of the CCD sensor 34 are recorded. Must be set in the prescribed relationship. For this purpose, it is convenient to provide the CCD sensor with a transfer timing signal in accordance with the control of the θ rotation speed from the goniometer control device side. More specifically, the transfer frequency of the TDI operation multiplied by the size of the CCD sensor pixel in the charge transfer direction (row crossing direction in FIG. 8) is set equal to the moving speed of the rotating CCD sensor. . In order to record the diffraction pattern on the θ-rotating CCD sensor by operating the CCD sensor in the TDI operation, the CCD sensor is always in an exposure state during the TDI operation.

  FIG. 10 is a storage area array diagram of a storage device that temporarily stores the raw measurement data output from the output unit 80 of FIG. The measurement raw data is represented by a symbol S, and the measurement raw data in the first column of the first channel is represented as S (1,1). The measured raw data S (1,1), S (1,2), S (1,3),..., S (1, M) from the first column to the Mth column of the first channel are Stored in M storage areas for channels. Similarly, the data after the second channel is also stored in the respective storage areas. The direction in which the channel number increases is the direction in which θ increases (that is, the direction in which the diffraction angle 2θ increases). If the measurement raw data of the two-dimensional array stored in this way is displayed on a display device or the like as it is, a two-dimensional image is obtained. Also, if the data from the first column to the Mth column is summed and one data (total data) is assigned to one channel, such as T (1), T (2),... , One-dimensional measurement result. When displaying a diffraction pattern, the horizontal axis represents the diffraction angle 2θ, and the vertical axis represents the total data of the channel numbers at θ corresponding to 2θ. Details of such X-ray diffraction measurement using a two-dimensional CCD sensor of TDI operation are described in detail in the above-mentioned Patent Document 5.

  In this embodiment, as shown in FIG. 8, a large number of pixels of the CCD sensor 34 are divided into two regions 72 and 74 on the left and right sides, and the recorded values in the column crossing direction are summed separately. In FIG. 11, 512 rows × 512 columns of pixels are divided into two left and right areas 72 and 74 in FIG. 8 (corresponding to dividing into two areas in the upper and lower directions in FIG. 11), and recording in the column transverse direction is performed separately. It is a storage area arrangement | sequence diagram which shows a mode that a value is totaled. The first channel will be described. T (1, 1) is the sum of the measured raw data from the first column to the 256th column existing in the region 72, and the 257th column to the 512th column existing in the region 74. The total of the measured raw data up to is T (1,2). The total value T (1,1) for the plurality of pixels included in the region 72 is the intensity of the diffracted X-rays emitted from the first sample 14. On the other hand, the total value T (1,2) for the plurality of pixels included in the region 74 is the intensity of the diffracted X-rays emitted from the second sample 16. The same applies to the second and subsequent channels. Therefore, if the diffraction pattern is displayed based on the recording data of the area 72 of the CCD sensor 34, the powder diffraction pattern of the first sample 14 is obtained, and if the diffraction pattern is displayed based on the recording data of the area 74 of the CCD sensor 34, the second pattern is obtained. The powder diffraction pattern of the sample 16 is obtained.

  Actually, in FIG. 8, the diffracted X-rays from the first sample 14 and the diffracted X-rays from the second sample 16 are slightly mixed in the pixels near the boundary between the region 72 and the region 74 of the CCD sensor 34. (Because the divergence in the Z direction cannot be completely reduced to zero), when taking the total value in the column transverse direction as shown in FIG. It may be excluded from the total value in the transverse direction.

  Next, with reference to FIG. 12, the relationship between the control unit and the structure unit of the composite analyzer shown in FIG. 1 will be described. The X-ray tube 82 is supplied with power from a high voltage power supply 84. The goniometer 86 is a mechanism for rotationally driving the first arm 20 and the second arm 22 of FIG. 1, and is controlled by the goniometer control device 88. The output of the X-ray detector 34 is sent to an X-ray diffraction data processing unit 90, which generates X-ray diffraction data for the first sample and X-ray diffraction data for the second sample. . The first sample, the second sample, and the reference temperature section are heated by the heating device 92 so as to have a desired temperature. The heating device 92 is controlled by a temperature control device 94. In order to obtain thermal analysis data of the first sample and the second sample, usually, measurement data is obtained for many temperatures in a predetermined measurement temperature range. In the present invention, it is necessary to set the first sample, the second sample, and the reference temperature section to a plurality of temperatures (at least the first temperature and the second temperature) and acquire thermal analysis data. The temperature control device 94 has a function of setting such a plurality of temperatures. In order to change the reference temperature in accordance with a predetermined program temperature, the output of the reference temperature detector 66 (corresponding to the third thermocouple 66 in FIG. 5) is fed back to the temperature controller 94, and the temperature of the reference temperature section is May be feedback-controlled. A reference temperature detector 66, a first sample temperature detector 62 (corresponding to the first thermocouple 62 in FIG. 5), and a second sample temperature detector 64 (corresponding to the second thermocouple 64 in FIG. 5). The output is sent to the thermal analysis data processing unit 96, and the thermal analysis data processing unit 96 calculates the first temperature difference ΔT1 and the second temperature difference ΔT2 as shown in FIG. Thermal analysis data of the first sample and thermal analysis data of the second sample are created.

  FIG. 13 is a graph showing the measurement results when X-ray diffraction measurement and thermal analysis measurement of two samples are simultaneously performed using the composite analyzer shown in FIG. The first sample is crystalline Terfenadine and the second sample is amorphous terfenadine. As the sample holder, the standard material omitted type sample holder 12a shown in FIGS. 6 and 7 was used. In FIG. 13, the left side is a DSC curve graph and an X-ray diffraction pattern graph of crystalline terfenadine. As for the X-ray diffraction pattern, the X-ray diffraction pattern obtained at that time is displayed at a position corresponding to each temperature of the DSC curve. Note that the X-ray diffraction pattern shows only typical diffraction peaks. In addition, the diffraction pattern at each temperature is shown by thinning out appropriately, and in particular, the low-angle part (the part where the diffraction peak appears) is the high-angle part in order to avoid the complexity of the drawing. Only a few (1/4) diffraction patterns are shown. The display of the X-ray diffraction measurement result and the thermal analysis measurement result side by side in the form shown in FIG. 13 is described in detail in the above-mentioned Patent Document 4.

  On the right side of FIG. 13, a DSC curve graph and an X-ray diffraction pattern graph of amorphous terfenadine are shown. In this way, X-ray diffraction measurement and thermal analysis measurement are simultaneously performed on two samples, crystalline and amorphous, so that different measurements under the same conditions can be made compared to the case of measuring a single sample separately. As a result, the X-ray diffraction information and the thermal analysis information based on the difference in the sample can be accurately compared.

The present invention is not limited to the above-described embodiments, and the following modifications are possible.
(1) The sample to be measured is not limited to two types, and three or more types may be measured simultaneously.

(2) In order to limit the vertical divergence, other divergence angle limiting means may be used instead of the solar slit. For example, by disposing a spectroscope instead of a solar slit, the X-rays can be monochromatized and parallelized, and the vertical divergence can be made extremely small.

(3) Instead of the two-dimensional CCD sensor for TDI operation, a position-sensitive one-dimensional or two-dimensional arbitrary X-ray detector in at least the Z direction can be used. In order to implement the present invention, in principle, it is not necessary to be position sensitive in the θ direction (2θ direction), so a position sensitive type in the Z direction is sufficient. In that case, it may be provided with a large number of pixels in the Z direction, or may be a position sensitive type divided into only two regions according to two types of measurement samples.

(4) The incident side solar slit may be omitted.

It is a perspective view of the main composition of one example of the compound analyzer of the present invention. It is a front view of the compound analyzer of FIG. It is the perspective view which expanded and showed the sample holder. It is a top view of a sample holder. FIG. 5 is a sectional view taken along line 5-5 of FIG. It is a top view of the example of a change of a sample holder. FIG. 7 is a cross-sectional view taken along line 7-7 in FIG. 6. It is a perspective view which shows the positional relationship of a sample and an X-ray detector. It is a block diagram of a CCD sensor. FIG. 10 is a storage area array diagram of a storage device that temporarily stores measurement raw data output from the output unit of FIG. 9. FIG. 9 is a storage area array diagram showing a state in which 512 rows × 512 columns of pixels are divided into two left and right areas in FIG. 8 and recording values in the column transverse direction are summed separately. It is explanatory drawing explaining the relationship between the control part and structure part of the composite analyzer of FIG. It is a graph of a measurement result.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 X-ray focus 12 Sample holder 14 1st sample 16 2nd sample 24 Rotation center line 26 Incident side solar slit 28 Diverging slit 30 X-ray beam 32 Receiving side solar slit 34 X-ray detector 36 Diffraction X-ray 38 Sample stand 40 Standard Sample 42 Holder main body 44 First concave portion 46 Second concave portion 48 Third concave portion 56 First thermal plate 58 Second thermal plate 60 Third thermal plate 62 First thermocouple 64 Second thermocouple 66 Third thermocouple 68 Portion 82 X-ray tube 84 High voltage power supply 86 Goniometer 88 Goniometer control device 90 X-ray diffraction data processing unit 92 Heating device 94 Temperature control device 96 Thermal analysis data processing unit

Claims (6)

A complex analyzer with:
(A) An X-ray source that generates an X-ray beam having a cross-sectional shape perpendicular to the X-ray traveling direction and having an elongated line shape.
(A) a first holding unit for holding the powdery first sample, a second holding unit for holding the powdery second sample, and a reference temperature unit, wherein the first holding unit and the second holding unit are provided. The section is divided in the longitudinal direction (hereinafter referred to as Z direction) of the cross section of the X-ray beam, and the first sample and the second sample are irradiated with the X-ray beam at the same time. A holding part and the second holding part are arranged, a first sample temperature detector for detecting the temperature of the first sample, a second sample temperature detector for detecting the temperature of the second sample, and the reference temperature part A sample holder provided with a reference temperature detector for detecting the temperature of the sample.
(C) Temperature control means for controlling the first sample, the second sample, and the reference temperature unit to desired temperatures.
(D) A position sensitive X-ray detector at least in the Z direction, capable of separately detecting the first diffracted X-ray emitted from the first sample and the second diffracted X-ray emitted from the second sample.
(E) A Z-direction divergence limiting device that is disposed between the first sample and the second sample and the X-ray detector and limits the divergence of X-rays in the Z direction.
(F) A goniometer control device that moves at least two of the X-ray source, the sample holder, and the X-ray detector so as to satisfy the concentration condition of Bragg Brentano.
(G) An X-ray diffraction data processing unit that receives the output of the X-ray detector and creates X-ray diffraction data of the first sample and X-ray diffraction data of the second sample.
(H) receiving outputs of the first sample temperature detector, the second sample temperature detector, and the reference temperature detector, and generating thermal analysis data of the first sample and thermal analysis data of the second sample; Thermal analysis data processing section.   2. The composite analyzer according to claim 1, wherein the X-ray detector is a two-dimensional CCD sensor that performs a TDI operation.   3. The composite analyzer according to claim 1, wherein the sample holder includes a third holding unit that holds a powdery standard sample for thermal analysis, and the reference temperature unit is the standard sample. A combined analyzer characterized by   3. The composite analyzer according to claim 1, wherein the sample holder includes a plate-like holder body, and the holder body is formed with a first recess and a second recess, and the first recess is the A first holding part is configured, the second recess constitutes the second holding part, and a portion of the holder body between the first recess and the second recess is the reference temperature part. Combined analyzer.   5. The composite analyzer according to claim 1, wherein the thermal analysis data processing unit outputs outputs of the first sample temperature detector, the second sample temperature detector, and the reference temperature detector. And a first temperature difference that is a difference between the temperature of the first sample and the temperature of the reference temperature portion, and a second difference that is a difference between the temperature of the second sample and the temperature of the reference temperature portion. Obtaining a temperature difference, creating thermal analysis data of the first sample based on the first temperature difference, and creating thermal analysis data of the second sample based on the second temperature difference. Characteristic composite analyzer. A combined analysis method comprising the following steps:
(A) A step of preparing an X-ray source for generating an X-ray beam in which a cross-sectional shape perpendicular to the X-ray traveling direction is an elongated line.
(A) a first holding unit for holding the powdery first sample, a second holding unit for holding the powdery second sample, and a reference temperature unit, wherein the first holding unit and the second holding unit are provided. The section is divided in the longitudinal direction (hereinafter referred to as Z direction) of the cross section of the X-ray beam, and the first sample and the second sample are irradiated with the X-ray beam at the same time. A holding part and the second holding part are arranged, a first sample temperature detector for detecting the temperature of the first sample, a second sample temperature detector for detecting the temperature of the second sample, and the reference temperature part Preparing a sample holder provided with a reference temperature detector for detecting the temperature of the sample.
(C) a position sensitive X-ray detector in at least the Z direction capable of separately detecting the first diffracted X-ray emitted from the first sample and the second diffracted X-ray emitted from the second sample; The stage to prepare.
(D) In the state where the first sample and the second sample are set to the first temperature, the X-ray beam is simultaneously irradiated to the first sample and the second sample to satisfy the concentration condition of Bragg Brentano. In this state, the X-ray detector is used to simultaneously detect the first diffracted X-ray and the second diffracted X-ray, and the first sample temperature detector, the second sample temperature detector, and the reference Creating thermal analysis data of the first sample and thermal analysis data of the second sample by using an output of a temperature detector;
(E) In the state where the first sample and the second sample are set to a second temperature different from the first temperature, the X-ray beam is simultaneously irradiated to the first sample and the second sample, and Bragg The first diffracted X-ray and the second diffracted X-ray are simultaneously detected using the X-ray detector while satisfying the Brentano concentration condition, and the first sample temperature detector and the second diffracted X-ray are detected. Creating thermal analysis data of the first sample and thermal analysis data of the second sample using outputs of the sample temperature detector and the reference temperature detector;

Images