JP5024968B2 - X-ray and thermal analyzer - Google Patents

Description

  The present invention relates to an X-ray and thermal analysis apparatus that simultaneously performs measurement for X-ray analysis and measurement for thermal analysis. In particular, the present invention relates to an X-ray and thermal analyzer that automatically and continuously measures a plurality of samples.

  Conventionally, Patent Document 1 discloses an X-ray and thermal analysis apparatus that simultaneously performs measurement for X-ray analysis and measurement for thermal analysis. In this type of apparatus, generally, a sample is accommodated in a furnace body, and the furnace body is further accommodated in a partition wall. When measuring a plurality of samples sequentially, the partition is removed manually by the measurer and the sample is exchanged each time measurement for one sample is completed.

  Conventionally, Patent Document 2 discloses a sample transport device suitably used for a thermal analysis device. In this thermal analyzer, the heat sink 13 as a furnace body is accommodated in a heat insulating container, that is, the partition wall 9, and the upper opening of the heat sink 13 and the upper opening of the partition wall 9 are covered with the cover 7. According to this sample transport device, a plurality of sample containers 52 are sequentially transported one by one between the sample placement unit 18 a in the partition wall 9 and the turntable 36 by the sample transport unit 4. When the sample is transported, the cover 7 is removed from the upper openings of the partition wall 9 and the heat sink 13.

Japanese Patent Laid-Open No. 11-295244 (pages 2 to 4, FIG. 1) JP 2004-264096 A (pages 4-8, FIGS. 4, 5, 6)

  When performing X-ray measurement and thermal analysis measurement simultaneously, the partition and the furnace body must be provided with portions for allowing X-rays to pass. In some cases, a cover for covering the upper opening of the furnace body also requires a portion for allowing X-rays to pass therethrough. In addition, in order to realize the automation of measurement, it is necessary to consider automatically taking in and out the sample and the cover to and from the partition wall and the furnace body.

  When such a sample or cover is taken in or out, when the sample container or cover is placed at a predetermined position for receiving measurement, they should not block the X-ray path. Because of these problems, conventionally, the X-ray measurement and the thermal analysis measurement are simultaneously and sequentially repeated for a plurality of samples (hereinafter sometimes referred to as the simultaneous measurement of the X-ray and the thermal analysis). It was considered very difficult to do. In fact, although proposals have been made to perform automatic measurement in the case of X-ray measurement alone or thermal analysis measurement alone, with regard to an apparatus that performs X-ray measurement and thermal analysis measurement at the same time, automatic measurement for a plurality of samples is possible. No measurements were made.

  The present invention has been made in order to solve the above-described problems, and a plurality of samples to be subjected to simultaneous measurement of X-rays and thermal analysis in a state surrounded by a furnace body, a cover, and a partition wall. In some cases, an object of the present invention is to provide an X-ray and thermal analyzer capable of automatically exchanging and measuring those samples sequentially.

  The first X-ray and thermal analysis apparatus according to the present invention includes (1) an inner side container placing part on which a sample container containing a sample is placed, and (2) an opening that accommodates the inner side container placing part. A furnace body provided; (3) a partition wall containing the furnace body and provided with an opening; (4) an opening / closing lid for opening and closing the opening of the partition wall; and (5) placed on the inner side container placing portion. A thermal analysis measuring device for performing measurement for thermal analysis on the sample contained in the sample container; and (6) X-rays are applied to the sample contained in the sample container placed on the inner side container placement unit. An X-ray measurement device for detecting secondary X-rays emitted from the sample when irradiated by an X-ray detector; and (7) can be placed on an inner element mounting portion in the partition wall; An internal element that can be removed from the side element mounting portion, and (8) the sample container provided on the outside of the partition wall (9) an external element mounting portion provided outside the partition wall for placing the internal element; and (10) the internal container mounting portion and the external side. (11) the opening and closing; and a transport means for transporting the sample container to and from the container mounting section, and further transporting the internal element between the inner element mounting section and the outer element mounting section. A lid, the thermal analysis measurement device, the X-ray measurement device, and a control means for controlling the operation of the transfer means, (12) the sample container has a portion through which X-rays can pass. (13) The control means (a) in the state where the internal element is placed on the internal element mounting portion and the opening / closing lid closes the opening of the partition wall, and / or Alternatively, the measurement is performed using the X-ray measurement apparatus, and (a) the opening / closing lid is The sample container is placed between the outer container placing portion and the inner container placing portion in a state where the opening is opened and the inner element is placed on the outer element placing portion. (C) sequentially transferring the plurality of sample containers arranged on the outer-side container mounting portion by the transfer means through the opening of the partition wall and the opening of the furnace body; When the sample container is disposed on the inner side container placement section, the transport means aligns a portion of the sample container that can pass X-rays with an X-ray passage in the X-ray measurement apparatus. And

According to the X-ray and thermal analysis apparatus according to the present invention, the sample container can be transported between the inside of the furnace body and the outside of the furnace body by the transporting means through the opening of the furnace body and the opening of the partition wall. Measurements can be automatically and repeatedly performed while being exchanged by the conveying means.
Moreover, since the sample container has a part that can pass X-rays, X-ray measurement can be performed without any trouble by matching the part with the X-ray path of the X-ray measuring apparatus. Of course, thermal analysis measurement can be performed without any problem.
In addition, when the sample container is placed in the furnace, the transfer means automatically aligns the portion of the sample container that can pass X-rays with the X-ray passage of the X-ray measurement apparatus, so that a plurality of samples are automatically detected. Repeated X-ray measurements can be performed stably under certain conditions.

  In the above configuration, the “internal element” is an element provided inside the partition wall, and for example, a lid or the like disposed above the furnace body can be considered. In the present invention, since thermal analysis measurement and X-ray measurement are performed simultaneously, an “internal element” such as a lid is arranged at a position that does not block the X-ray path in X-ray measurement, or a structure that does not block the X-ray path. It is desirable to have (that is, a portion that can pass X-ray).

If the internal elements are inevitably arranged at positions that block the X-ray path, the X-rays can pass through the internal elements regardless of the angle at which the internal elements are arranged at predetermined positions. It is desirable that the internal element is configured.
In addition, when the internal element must be disposed at a position that blocks the X-ray path, and only a part of the internal element is provided with a portion through which the X-ray can pass, the internal element Depending on how the elements are arranged, the progress of X-rays may be hindered, which may hinder X-ray measurement. In such a case, it is desirable to use the following second invention.

  The second X-ray and thermal analysis apparatus according to the present invention includes (1) an inner side container placing part on which a sample container containing a sample is placed, and (2) an opening containing the inner container placing part. A furnace body, (3) a partition wall containing the furnace body and provided with an opening, (4) an opening / closing lid for opening and closing the opening of the partition wall, and (5) a sample placed on the inner side container placing portion A thermal analysis measurement device that performs measurement for thermal analysis on the sample contained in the container; and (6) irradiating the sample contained in the sample container placed on the inner container placement unit with X-rays. An X-ray measuring device that detects secondary X-rays emitted from the sample by an X-ray detector, and (7) can be placed on the inner element mounting portion, and the inner element mounting The X-ray measuring apparatus can be removed from the X-ray measuring apparatus and is disposed at a position that blocks the X-ray path. (8) an outer side container mounting portion provided outside the partition wall for placing the sample container, and (9) an internal element provided outside the partition wall. An external element placement section for placing an element; (10) the sample container is transported between the internal container placement section and the external container placement section; and the internal element placement section (11) Controlling the operation of the opening / closing lid, the thermal analysis measuring device, the X-ray measuring device, and the transporting means. And (12) the sample container has a part capable of passing X-rays. (13) The control means includes (a) the internal element is placed on the internal element. In the state where the opening / closing lid closes the opening of the partition wall. And (b) the opening / closing lid opens the opening of the partition wall, and the internal element is placed on the external element mounting portion. (C) transporting the sample container between the outer container placing part and the inner container placing part through the opening of the partition wall and the opening of the furnace body between the outer container placing part and the inner container placing part. (14) When the transfer means (a) arranges the internal element on the internal element placement unit, the plurality of sample containers arranged on the external vessel placement unit are sequentially repeated. , A structure that does not block the X-ray passage of the internal element is aligned with the X-ray passage in the X-ray measurement apparatus, and (a) when the sample container is disposed on the inner-side container placement portion, The portion of the sample container through which X-rays can pass is the X-ray measurement. It is characterized by being aligned with the X-ray path in the fixed device.

  In the first X-ray and thermal analysis apparatus, it was not considered whether an internal element such as a lid obstructed the X-ray passage in the X-ray measurement apparatus. Whether or not the X-ray passage is blocked is included in the technical scope of the invention of claim 1. In the second X-ray and thermal analysis apparatus, the internal element is disposed at a position where the X-ray passage of the X-ray measurement apparatus is blocked in position, but the internal element of that portion does not block the X-ray ( That is, a portion through which X-rays can pass is provided.

  In the second X-ray and thermal analysis apparatus, when the conveying means places the sample container in the furnace, the part of the sample container that can pass the X-ray is automatically aligned with the X-ray passage of the X-ray measuring apparatus. This is the same as the first X-ray and thermal analyzer. In the second X-ray and thermal analysis apparatus, in addition to this, when the conveying means arranges the internal element on the internal element mounting portion in the partition wall, a structural portion that does not block the X-ray passage of the internal element is provided. The conveying means is automatically adapted to the X-ray path of the X-ray measuring device. Therefore, X-ray measurement can always be stably performed under normal conditions even when the operation of removing the internal element from the furnace or mounting it at a predetermined position in the furnace is repeated.

  In the second X-ray and thermal analyzer, the X-ray measuring apparatus has a structure in which the transport means does not block the X-ray path of the internal element when the internal element is arranged on the internal element mounting portion. The positional alignment with the X-ray path in FIG. 4 is because the positioning member for the internal element is provided in the external element mounting portion, and the transfer means does not rotate the internal element during transfer. Can be achieved. Although this configuration is a simple configuration, a very stable positioning effect can be obtained.

  In the second X-ray and thermal analyzer, the positioning member provided on the external element mounting portion may be a block member having a positioning plane, and the internal element is positioned by the block member. It can have a shape that fits in the plane. For example, a protruding portion can be provided on the outer element mounting portion side, and a shape portion that fits the protruding portion can be provided on the inner element side.

  In the second X-ray and thermal analysis apparatus, the internal element may be a furnace body cover that covers an opening of the furnace body. In this case, the structure of the furnace body cover that does not block the X-ray passage of the X-ray measurement apparatus is a structure in which a foil member formed by a member that can pass X-rays is partially provided on the furnace body cover. It can be. The furnace cover is a device that is frequently used in a thermal analysis measurement apparatus.

  In the first and second X-ray and thermal analysis apparatuses, when the transporting unit places the sample container on the inner-side container mounting portion, a portion through which the X-ray of the sample container can pass is the X Positioning to the X-ray path in the X-ray measuring apparatus means that a positioning member for the sample container is provided on the outer container mounting portion, and the transport means does not rotate the sample container during transport. , And can be achieved by. Although this configuration is a simple configuration, a very stable positioning effect can be obtained.

  In the first and second X-ray and thermal analyzers, the positioning member provided in the outer container mounting portion may be a concave portion similar to the sample container in plan view. According to this configuration, it becomes possible for the measurer to very easily perform the work of setting the sample container on the external container placing part prior to the start of the measurement. The planar shape of the sample container and the concave portion can be a rectangular shape such as a square shape or a rectangular shape.

    In the first and second X-ray and thermal analyzers, the portion of the sample container through which X-rays can pass is a portion where the height of a part of the side wall of the sample container is lower than the other part. It can be. This configuration is a configuration that does not complicate the structure of the sample container. Further, when the sample container is gripped by the gripping member, the higher side wall can be gripped, which is very convenient. .

  In the first and second X-ray and thermal analysis apparatuses, the opening / closing lid may be a plate-like member, and the opening / closing lid is further between a position where the opening of the partition wall is closed and a position where the opening is opened. It can be set as the structure which can be translated by. This configuration can be formed very small, and can be easily installed inside the partition even when the partition is small. It is desirable to provide a pad made of a material softer than metal on a portion of the opening / closing lid that covers the opening of the partition wall. Furthermore, it is desirable to provide a sealing member such as an O-ring at a portion that contacts the pad.

  In the first and second X-ray and thermal analysis apparatuses, it is desirable that the transport means can have a rod-shaped gripping member, and the gripping member can pass through the opening of the partition wall and the opening of the furnace body. With this configuration, it is not necessary to form the opening of the partition wall and the opening of the furnace body in a wide range, and the moving area of the conveying means can be limited to the narrowest possible range.

  In the first and second X-ray and thermal analyzers, the transport means can be configured by a three-axis rectilinear movement mechanism including a moving unit that reciprocates linearly in each of three axial directions orthogonal to each other. Since the three-axis linear movement mechanism moves linearly, it is easy to keep the angular positions of the sample container and the internal element constant. Thus, it is advantageous with respect to the present invention where it is desired to accurately maintain the angular position of the gripping member.

According to the X-ray and thermal analysis apparatus according to the present invention, the sample container can be transported between the inside of the furnace body and the outside of the furnace body by the transporting means through the opening of the furnace body and the opening of the partition wall. Measurements can be automatically and repeatedly performed while being exchanged by the conveying means.
Moreover, since the sample container has a part that can pass X-rays, X-ray measurement can be performed without any trouble by matching the part with the X-ray path of the X-ray measuring apparatus. Of course, thermal analysis measurement can be performed without any problem.
In addition, when the sample container is placed in the furnace, the transfer means automatically aligns the portion of the sample container that can pass X-rays with the X-ray passage of the X-ray measurement apparatus, so that a plurality of samples are automatically detected. Repeated X-ray measurements can be performed stably under certain conditions.

1 is a perspective view showing an embodiment of an X-ray and thermal analysis apparatus according to the present invention. It is a disassembled perspective view which shows the sample support unit which is the principal part of the apparatus of FIG. It is sectional drawing according to the DD line | wire of FIG. It is a perspective view which shows the DSC unit which is an internal structure of the structure shown in FIG. It is sectional drawing of the DSC unit shown in FIG. It is a disassembled perspective view which shows one Embodiment of a furnace body cover. It is a figure which shows one Embodiment of a holding member. It is a perspective view which shows one Embodiment of a sample container. It is a perspective view which shows one embodiment of each of an external container mounting part, an external cover mounting part, and an external lid mounting part. It is a block diagram which shows one Embodiment of the control system in the X-ray and thermal analyzer which concerns on this invention. It is a flowchart of the control implement | achieved by the control system of FIG.

  Hereinafter, an X-ray and thermal analysis apparatus according to the present invention will be described based on embodiments. Of course, the present invention is not limited to this embodiment.

  FIG. 1 shows an embodiment of an X-ray and thermal analysis apparatus according to the present invention. In the present embodiment, an X-ray diffractometer is exemplified as an apparatus for performing measurement for X-ray analysis (hereinafter referred to as an X-ray measurement apparatus), and an apparatus for performing measurement for thermal analysis (hereinafter referred to as a thermal analysis measurement apparatus). DSC (Differential Scanning Calorimetry) measuring device is illustrated as an example, but other devices can be used as necessary.

  For example, the X-ray measurement apparatus is an arbitrary apparatus that performs measurement using X-rays, and includes, for example, an X-ray scattering apparatus, a fluorescent X-ray apparatus, and the like in addition to the X-ray diffraction apparatus. The thermal analysis measurement apparatus is an arbitrary apparatus that performs measurement while changing the temperature of the sample. In addition to the DSC measurement apparatus, a DTA (Differential Thermal Analysis) measurement apparatus is also conceivable.

  An X-ray and thermal analysis apparatus 1 shown in FIG. 1 includes an X-ray diffraction apparatus 2 as an X-ray measurement apparatus, a DSC measurement apparatus 3 as a thermal analysis measurement apparatus, a sample transport apparatus 4, and a sample support unit 5. Have. The sample support unit 5 has a removable outer case 16.

(X-ray diffractometer)
The X-ray diffraction apparatus 2 includes a goniometer 6, an X-ray generation unit 7, and an X-ray detector 8. The goniometer 6 includes a support shaft 13 that extends forward from the center, a first arm 11 that extends leftward from the center, and a second arm 12 that extends from the center to the opposite side of the first arm 11. And have.

  The X-ray generator 7 is supported by the first arm 11. An X-ray source 9 for generating X-rays is provided in the X-ray generator 7. The X-ray source 9 generates X-rays including, for example, Cu (copper) characteristic X-rays.

  The X-ray detector 8 is supported by the second arm 12. The X-ray detector 8 is, for example, a zero-dimensional counter having no position resolution such as SC (Scintillation Counter), or the rotational movement direction of the X-ray detector 8 (that is, the arrow BB ′ direction). It is comprised by the semiconductor sensor etc. which are arranged in a line along.

  The support shaft 13 of the goniometer 6 is fixed so as not to rotate. Although described in detail later, the sample support unit 5 is fixedly supported by the support shaft 13 so as not to rotate. Instead of supporting the sample support unit 5 with the goniometer 6, it may be fixed on a separately provided table (not shown). When the sample support unit 5 is supported by the goniometer 6, the goniometer 6 may be distorted when the weight of the sample support unit 5 increases. If the sample support unit 5 is removed from the goniometer 6 and placed on the table, there is no need to worry about such distortion of the goniometer 6. The sample support unit 5 has a removable outer case 16. A partition wall 17 is provided inside the outer case 16. A standard substance 19 and a sample 18 to be measured are arranged inside the partition wall 17.

  The first arm 11 can rotate as indicated by an arrow A-A ′ about a center line of the support shaft 13 (which coincides with a sample axis to be described later). Therefore, the X-ray generator 7 can rotate in the same manner around the center line of the support shaft 13. The second arm 12 can rotate around the center line of the support shaft 13 as indicated by an arrow B-B ′. Therefore, the X-ray detector 8 can be similarly rotated about the center line of the support shaft 13.

  The goniometer 6 according to the present embodiment is a so-called θ-θ type goniometer in which the sample 18 is fixedly supported and the X-ray source 9 and the X-ray detector 8 are rotated in the opposite direction around the sample 18 at the same angular velocity. It is. Specifically, in FIG. 5, when a line extending through the X-ray irradiation surface of the sample 18 in the horizontal direction (direction passing through the paper surface of FIG. 5) is referred to as a sample axis ω, the line enters the sample 18 from the X-ray source 9. While changing the incident angle θ of the X-ray in a predetermined direction at a predetermined angular velocity about the sample axis ω, at the same time, the line at which the center of the X-ray inlet of the X-ray detector 8 looks at the center of the sample 18 and the sample 18 Is rotated in the opposite direction about the sample axis ω at the same angular velocity as the incident angle θ.

  The X-ray detector 8 rotates at the same angular velocity as the θ rotation of the X-ray source 9. However, the rotation of the X-ray detector 8 causes a diffraction angle 2θ in the sample 18 when the X-ray incident angle is θ. This is a rotation for capturing a diffraction line generated at (an angle twice as large as θ). Therefore, this rotation of the X-ray detector 8 is usually called a 2θ rotation.

  In FIG. 1, X-rays emitted from the X-ray source 9 enter a sample 18. Between the X-ray source 9 and the sample 18, a slit, a monochromator, an X-ray filter, and other X-ray optical elements are provided as necessary. These X-ray optical elements and the X-ray source 9 constitute an incident side X-ray optical system. On the other hand, when secondary X-rays, that is, diffraction lines in this embodiment, are generated from the sample 18, the diffraction lines are detected by the X-ray detector 8. The X-ray detector 8 outputs an electric signal corresponding to the intensity of the acquired X-ray. A slit, an attenuator and other X-ray optical elements are provided between the sample 18 and the X-ray detector 8 as necessary. These X-ray optical elements and the X-ray detector 8 constitute a light-receiving side X-ray optical system.

  The center line of the incident X-ray that exits from the X-ray source 9 and enters the sample 18 is the incident-side X-ray optical axis. The line where the center of the X-ray inlet of the X-ray detector 8 looks into the center of the sample 18 is the light receiving side X-ray optical axis. In the present embodiment, the incident side X-ray optical axis and the light receiving side X-ray optical axis continuous thereto are referred to as an X-ray optical axis X1. In addition, the X-ray optical axis may be referred to as an X-ray path.

(Sample support unit)
FIG. 2 shows the device housed in the outer case 16 of FIG. 1 with the outer case 16 removed. FIG. 3 shows the internal structure of the partition wall 17 according to the line DD in FIG. In these drawings, the partition wall 17 is constituted by a cylindrical heat transfer material 14 and a similarly cylindrical heat insulation material 15 covering the heat transfer material 14. The heat transfer material 14 is formed of a material that easily transfers heat, for example, a metal such as aluminum. A liquid passage 20 is provided in the wall of the heat transfer material 14. The heat insulating material 15 is formed of a material that is difficult to transmit heat as much as possible. Since the heat transfer material 14 and the heat insulating material 15 integrally form the partition wall 17, the heat transfer body 14 and the heat insulating material 15 may be referred to as the partition wall 17 in the following description. A DSC unit 30 which will be described in detail later is fixed to a shelf member 27 extending from the support shaft 13 of FIG. A partition wall 17 is detachably mounted on the DSC unit 30.

  An X-ray passing window 22 that is an incident X-ray passing portion is provided in a portion on the incident side X-ray optical system side of the side wall of the heat transfer material 14 constituting the partition wall 17. An X-ray passing window 23 which is an outgoing X-ray passing portion is provided on the side wall of the heat transfer material 14 opposite to the X-ray passing window 22. These windows are made of a material capable of transmitting X-rays and having high mechanical strength, for example, a polyimide film. An opening 24 leading to the internal space is provided on the upper wall of the heat transfer material 14 constituting the partition wall 17. The opening 24 is aligned with the opening 21 of the outer case 16 of FIG. Around the opening 24, an O (O) ring 25 which is a sealing member for sealing is provided.

  In FIG. 2, two upper and lower liquid passing ports 26 a and 26 b are provided in front of the side wall of the partition wall 17. The lower liquid passing port 26 a is a port for supplying a cooling liquid, for example, cooling water, to the inside of the wall of the heat transfer material 14 of the partition wall 17. The upper liquid passing port 26 b is a port for recovering the coolant from the inside of the partition wall 17. The cooling liquid supplied from the lower liquid passing port 26a as needed flows through the liquid flowing path 20 in FIG. 3 to cool the inside of the partition wall 17, and then is recovered from the upper liquid flowing port 26b in FIG.

  A stand 28, which is a gate-shaped member, is provided on the shelf member 27 adjacent to the partition wall 17, and an electric motor 31 is fixed to the lower portion of the upper plate 29 of the stand 28. An output shaft of the motor 31 passes through the upper plate 29, and a rotating plate 32 is mounted on the output shaft. The rotating plate 32 is driven by a motor 31 and rotates in one direction. Further, a pin 33 is provided at an appropriate position of the rotating plate 32. A roller 34 is rotatably provided on the pin 33.

  A guide case 36 that is rectangular in plan view is fixed to the upper wall of the partition wall 17 by bolts or other fastening means. The guide case 36 forms a flat space of an appropriate height between the upper wall of the partition wall 17. An open / close lid 39 is provided in the flat space. The open / close lid 39 is a rectangular plate member. A circular through hole 44 is formed in the upper plate of the guide case 36. The through hole 44 is aligned with the opening 24 in the upper wall of the partition wall 17.

  A long hole 41 extending in a direction parallel to the surface including the X-ray passage X1 is provided in a portion near the end surface of the opening / closing lid 39 on the support shaft 13 side (that is, the back side). A circular sealing pad 42 is provided in a portion near the end surface of the opening / closing lid 39 on the side away from the support shaft 13 (that is, the front side). The pad 42 is made of a synthetic resin that is relatively hard but softer than metal. The diameter of the pad 42 is larger than the diameter of the O-ring 25. The thickness of the pad 42 is larger than the thickness of the opening / closing lid 39. A circular through hole 43 is formed in the opening / closing lid 39 between the long hole 41 and the pad 42.

  The roller 34 of the pin 33 provided on the rotating plate 32 is fitted in the long hole 41 of the opening / closing lid 39. When the rotating plate 32 is driven and rotated by the motor 31, the pin 33 rotates about the motor output shaft. Then, the opening / closing lid 39 is pushed by the pin 33 and guided by the guide case 36, and slides in a direction perpendicular to the plane including the X-ray passage X1, as shown by an arrow C-C ', that is, reciprocates linearly.

  The rotating plate 32 moves in a fixed direction at every rotation angle of 180 ° between an angular position where the pin 33 is positioned closest to the X-ray path and an angular position where the pin 33 is positioned farthest from the X-ray path. Controlled to rotate. When the pin 33 is at a position farthest from the X-ray passage X1, the pad 42 of the opening / closing lid 39 covers the upper wall opening 24 of the partition wall 17. At this time, the pad 42 rides on the O-ring 25 in the guide case 36 as shown in FIG. 3 and is further pressed against the O-ring 25 by two pressing pins 46 provided on the upper plate of the guide case 36. It is done. Thereby, the opening 24 is sealed by the pad 42.

  A screw is provided on the outer peripheral surface of the pressing pin 46. Therefore, if the operator turns the pressing pin 46 with a finger, the pressing pin 46 can be moved with respect to the guide case 36. As a result, the pressing pin 46 is moved. The amount of protrusion of the leading end 46 into the internal space of the guide case 36 can be adjusted. By adjusting the protruding amount, the pressing force of the pad 42 to the O-ring 25 can be adjusted.

  When the pin 33 of the rotating plate 32 in FIG. 2 rotates and stops to the position closest to the X-ray path X1, the opening / closing lid 39 moves most forward. At this time, the through-hole 43 of the opening / closing lid 39 coincides with the upper wall opening 24 of the partition wall 17 in position. At this time, the inside of the partition wall 17 can be seen through the opening 43 of the opening / closing lid 39 and the upper wall opening 24 of the partition wall 17 through the opening 21 of the outer case 16 of FIG.

  FIG. 4 shows the DSC unit 30 with the partition wall 17 removed from the structure of FIG. FIG. 5 shows a cross-sectional structure of the DSC unit 30. A DSC unit 30 as shown in FIGS. 4 and 5 is accommodated in the partition wall 17 of FIG. The DSC unit 30 includes a cylindrical first support member 47 fixed to the shelf member 27, a second support member 48 fixed to the first support member 47 by screws or other fastening means, and a second support member. A furnace body 49 is fixed to the lower surface of the upper curved edge of 48 by screws or other fastening means and hangs down.

  The second support member 48 has a double cylindrical structure having an inner cylindrical portion and an outer cylindrical portion. The materials and functions of the first support member 47, the second support member 48, and the furnace body 49 are described in detail in Japanese Patent Application Laid-Open No. 2001-050913. The furnace body 49 has a substantially cylindrical shape, and a heater wire 51 as a heating means is wound around the outer periphery thereof. The heater wire 51 generates heat when energized. Energization of the heater wire 51 is controlled by the temperature control device 55.

  The interior of the upper portion of the furnace body 49 is a space 52, and the space 52 has an opening 53 that leads to the outside. A part of the furnace body 49 forming the space 52 on the X-ray incident side is cut out to form a lateral hole 54a. Further, a part of the furnace body 49 at a portion facing the horizontal hole 54a is also cut away to form a horizontal hole 54b. The horizontal hole 54a functions as an incident X-ray passing part for allowing X-rays incident on the inside of the furnace body, and the other lateral hole 54b functions as an X-ray exiting from the furnace body and an outgoing X-ray passing part for allowing the X-rays to pass through. .

  The space 52 is provided with a heat sensitive plate 56 as an inner container placement portion. Then, one side of the heat sensitive plate 56 functions as an inner container placing portion for placing a sample container 57 in which a part of the upper surface accommodates the sample 18, and the other side of the heat sensitive plate 56 contains the standard material 19. It functions as an internal container placement portion for placing the accommodated sample container 57. These regions of the heat sensitive plate 56 may have a flat plate shape or a dish shape so that the sample container 57 can be placed in a stable state. The temperature measuring points of the thermocouples 58 are fixed to the lower surfaces of the portions of the heat sensitive plates 56 corresponding to the heat sensitive points on which the sample containers are placed by welding or other fixing methods. The DSC measuring apparatus 3 in FIG. 1 is connected to the thermocouple 58.

  A guide ring member 59 is fixed to the upper surface of the second support member 48 so that it cannot be easily removed. A step portion 61 is formed on the guide ring member 59. The upper periphery of the furnace body 49 is covered with a furnace body cover 62. The furnace body cover 62 is attached to and detached from the furnace body 49 while being guided by the guide ring member 59. The furnace body cover 62 is mainly used for so-called soaking so as to make the temperature distribution in the space 52 in the furnace body 49 uniform.

  As shown in FIG. 6, the furnace body cover 62 includes an inner cover 63, a foil member 64, an outer cover 65, and a knob 66. The inner cover 63 and the outer cover 65 are made of metal such as stainless steel, for example. The foil member 64 is made of a material that can pass X-rays, for example, a polyimide film.

  Two locations on the diameter of the inner cover 63 are cut out to form openings 72. The opening 72 is formed from the upper surface to the side surface of the inner cover 63. The foil member 64 is formed in a substantially rectangular shape having a width wider than the width of the opening 72 of the inner cover 63. The foil member 64 covers both openings 72 of the inner cover 63 by being bent. The outer cover 65 is also formed with an opening 73 having substantially the same shape as the opening 72 of the inner cover 63.

  The inner diameter of the outer cover 65 is at least larger than the thickness of the foil member 64 than the outer diameter of the inner cover 63. Thus, the foil member 64 can be sandwiched by closely fitting the outer cover 65 to the outside of the inner cover 63 with the foil member 64 interposed therebetween. In this case, the outer cover 65 is fitted to the outside of the inner cover 63 so that the opening 72 of the inner cover 63 and the opening 73 of the outer cover 65 coincide with each other in position.

  A female screw 68 is cut at the center of the inner cover 63. Through holes 69, 70, and 71 are provided in the central portions of the foil member 64, the outer cover 65, and the knob 66, respectively. The screw 74 is passed through the through holes 71, 70, 69 of the knob 66, the outer cover 65, and the foil member 64, and is fastened to the female screw 68 of the inner cover 63, whereby a furnace as a single unit as shown in FIG. The body cover 62 is assembled.

  In the furnace body cover 62, the two portions of the foil members 64 that are exposed to the outside from the two openings 73 of the outer cover 65 function as an incident X-ray passage portion or an emission X-ray passage portion, respectively. As shown in FIG. 5, the furnace body cover 62 is placed on the top of the furnace body 49 including the opening 53 of the space 52 in the furnace body 49. At this time, the portions of the two foil members 64 of the furnace body cover 62 are positioned to coincide with the incident side lateral hole 54a and the emission side lateral hole 54b of the furnace body 49 (so as to face each other). A furnace body cover 62 is put on the furnace body 49.

  As a result, in FIG. 5, incident X-rays are irradiated to the sample 18 at an incident angle θ through the incident-side foil member 64 of the furnace body cover 62 and the incident-side lateral hole 54 a of the furnace body 49. The incident angle θ is normally changed continuously or stepwise at a predetermined angular velocity. When diffraction lines are generated from the sample 18 at a diffraction angle 2θ, the diffraction lines are taken into the X-ray detector 8 through the emission side lateral hole 54b of the furnace body 49 and the emission side foil member 64 of the furnace body cover 62. It is.

  In FIG. 6, a knob 66 is a portion that is gripped when the entire furnace body cover 62 is lifted by a gripping member to be described later. The knob 66 is formed by a gripped portion 76 and a flange 77 protruding in the radial direction of the gripped portion 76. The planar cross-sectional shape of the gripped portion 76 is formed in a rectangular shape (that is, a square shape or a rectangular shape). That is, the gripped portion 76 is formed in a prismatic shape such as a cubic shape or a rectangular parallelepiped shape. The gripped member 76 is gripped by the gripping member as will be described later, but by forming the gripped member 76 into a prismatic shape as described above and gripping the square-shaped gripped member 76 by the gripping member, It is possible to prevent the furnace body cover 62 held by the holding member from rotating about its own central axis X2.

  In FIG. 5, a lid 78 is placed on the step portion 61 of the guide ring member 59. The lid 78 has a disk shape as shown in FIG. A knob 79 is provided at the center of the lid 78. Similar to the knob 66 of the furnace body cover 62, the knob 79 is formed by a gripped portion 79a and a flange 79b. Since the furnace body cover 62 has to consider the direction (angular position) with respect to the X-ray passage X1, the gripped portion 76 is formed in a prismatic shape. On the other hand, since the lid 78 is a simple disk, it is not necessary to consider the direction with respect to the X-ray path X1. Therefore, unlike the gripped portion 76 of the furnace body cover 62, the gripped portion 79 a of the lid 78 is formed in a cylindrical shape. However, the gripped portion 79a of the lid 78 may be formed in a prismatic shape. Similarly to the furnace body cover 62, the lid 78 is used to equalize the space 52 in the furnace body 49. In some cases, the lid 78 may not be used.

(DSC measuring device)
In FIG. 5, the DSC measurement device 3 calculates the difference in the amount of heat flowing into the sample 18 and the standard material 19 based on the temperature information of the sample 18 and the temperature information of the standard material 19 transmitted by the thermocouple 58. The standard material 19 is a material whose characteristics do not change with temperature change, and the sample 18 changes its characteristics according to the temperature change according to its own characteristics. For example, when the temperature rises to a predetermined temperature, the sample 18 undergoes phase transformation and the inflow heat quantity changes. The DSC measuring device 3 measures the change in the calorific value of the sample 18 with respect to the standard substance over time.

(Sample transport device)
In FIG. 1, the sample transport device 4 is provided at a position in front of the sample support unit 5. The sample transport device 4 is supported in a fixed state by an appropriate support device (not shown). The sample transport device 4 includes a table 83 on which a sample to be measured or a sample that has been measured is placed, a back-and-forth moving unit 82X that supports the gripping member 81, a left-right moving unit 82Y, and a vertical moving unit 82Z. have. The holding member 81 is formed of a rod-shaped member. Each unit has a drive source capable of controlling an operation amount such as a pulse motor and a servo motor.

  The front-rear moving unit 82X is driven by a power source and can move back and forth in the front-rear direction X. The left and right moving unit 82Y is driven by a power source and can move back and forth in the left and right direction Y perpendicular to the X direction. The vertical movement unit 82Z is driven by a power source and can move back and forth in the Z direction perpendicular to both the front-rear direction X and the left-right direction Y. As described above, the gripping member 81 can freely move between the table 83 and the opening 21 of the outer case 16 by appropriately moving the gripping member 81 in the three-dimensional directions of XYZ.

  When the gripping member 81 moves to the opening 21 of the outer case 16, the opening 24 of the partition wall 17 is open in FIG. 3, the lid 78 and the furnace body cover 62 are removed, and the opening 53 of the furnace body 49 is removed. If the gripping member 81 is in the open state, the gripping member 81 is moved downward in the Z direction in FIG. 1, so that the gripping member 81 is moved to the opening 21 of the exterior case 16, the opening 24 of the partition wall 17, and the furnace body. It can be inserted into the internal space 52 of the furnace body 49 through the opening 53 of 49. Further, the gripping member 81 can be conveyed to the outside through the reverse path.

  As shown in FIG. 7A, a gripping tip 84 is fixed to the tip of the gripping member 81 with a screw 86. The gripping tip 84 has a generally prismatic shape, and a square groove 87 is formed in the horizontal direction at the tip. The width h in the vertical direction of these grooves 87 is set wider than both the thickness of the flange 77 of the knob 66 of the furnace body cover 62 and the thickness of the flange 79b of the knob 79 of the lid 78 shown in FIG. ing. Thereby, the flanges 77 and 79 b can enter the groove 87 of the gripping member 81.

  The upper ends of the pair of gripping members 81 facing each other are rotatably supported by a shaft 88 as shown in FIG. 7B inside the front / rear moving unit 82X of FIG. The pair of gripping members 81 are urged so as to rotate and move in the direction of contraction as shown by an arrow E by an elastic force of an elastic member (not shown), for example, a spring. A wedge-shaped member 89 is provided between the gripping members 81. If the wedge-shaped member 89 is driven by a pulse motor, servo motor, or the like 90 and moved in a direction to interrupt between the pair of gripping members 81, the gripping member 81 can be opened. On the other hand, if the wedge member 89 is moved away from the gripping member 81, the pair of gripping members 81 can be closed by the elastic force of the spring.

  In FIG. 5, the sample container 57 placed on the heat sensitive plate 56 in the furnace body 49 has a rectangular shape (square shape or rectangular shape) in plan view as shown in FIG. 8, and a pair of opposite sides of the sample container 57. The wall heights 93 and 93 are higher than the wall heights of the adjacent opposite sides 94 and 94. A sample to be measured (reference numeral 18 in FIG. 5) or a standard substance (reference numeral 19 in FIG. 5) is placed on the bottom wall 95. Samples are in various forms such as solid, powder, and liquid.

  The lower wall 94 of the sample container 57 is set to a height that does not interfere with the X-rays incident on the sample 18 and the X-rays emitted from the sample 18 along the X-ray path X1 in FIG. In particular, even when the incident angle θ of incident X-rays to the sample 18 and the diffraction angle 2θ of diffraction lines emitted from the sample 18 are small, the wall 94 is set so as not to obstruct the progress of X-rays. The higher wall 93 of the sample container 57 is formed high so that the gripping tip 84 of FIG.

  In FIG. 1, the table 83 is a place for placing the external cover placement portion 91 as an external element placement portion, which is a place for placing the furnace body cover 62 of FIG. 4, and a lid 78 of FIG. 4. An external lid placing portion 92 as a certain external element placing portion and two pallets 96 as places for placing the sample container 57 in FIG. 8 are provided. There may be one pallet 96. As shown in FIG. 9, the pallet 96 is a single plate-like member, and can be moved in and out by parallel movement as indicated by an arrow F while being guided by a guide 97. The illustrated position is stored in a predetermined position, and the pallet 96 cannot be inserted further forward by the action of a stopper (not illustrated).

  Each pallet 96 is formed with a plurality of concave portions 98 as a rectangular outer side container placement portion in plan view. One pallet 96 is provided with two rows of concave portions 98. The group of recesses 98 in one row includes six recesses 98. The planar shape of each recess 98 is similar to the planar shape of the sample container 57 in FIG. 8 and is slightly larger than the sample container 57. Accordingly, the entire sample container 57 can be placed in the recess 98, and when so placed, the sample container 57 is positioned so that it cannot be moved by the side wall of the recess 98. That is, the side wall of the recess 98 functions as a positioning structure for restricting the movement of the side walls 93 and 94 of the sample container 57.

  The recesses 98 are formed in a total of 6 × 4 rows = 24. And the address is attached | subjected to those recessed parts 98. FIG. In the present embodiment, numerals 1 to 24 are given. In the case where the plurality of recesses 98 can be easily identified, it is not always necessary to add numbers. In this embodiment, the arrangement is such that the sample container 57 containing the reference material 19 is placed in the first and second recesses 98 and the sample container 57 containing the sample 18 is placed in the third to 24th recesses 98. ing.

  Further, the pair of gripping members 81 are provided side by side in the longitudinal direction of the pallet 96. Accordingly, the sample container 57 placed in the recess 98 is arranged such that the high wall 93 (see FIG. 8) is perpendicular to the longitudinal direction of the pallet 96. This arrangement is achieved when the measurer places the sample container 57 on the pallet 96. When the measurer performs the work of placing the sample container 57 on the pallet 96, it is convenient to remove the pallet 96 from the guide 97 and bring it to a place where the work can be easily performed.

  The positioning block member 99 is fixed to the outer cover mounting portion 91 so as not to be easily removed. For example, it is fixed by bolting, adhesion or the like. This block member 99 has two convex portions 101 provided at intervals. As shown in FIG. 6, these convex portions 101 have a shape in which an edge wall forming the opening 72 of the inner cover 63 of the furnace body cover 62 fits. Therefore, if the furnace body cover 62 is carried to the outer cover mounting portion 91 of FIG. 9 and the furnace body cover 62 is placed on the block member 99, the convex portion 101 automatically fits into the opening 72, and the furnace body cover 62 angular positions are automatically positioned.

(Measurement operation)
FIG. 10 shows a block diagram of the control system of the X-ray and thermal analysis apparatus 1 of FIG. FIG. 11 shows a flowchart showing the flow of control. Hereinafter, the measurement operation of this embodiment will be described with reference to these drawings. 10, the X-ray diffraction apparatus 2, the DSC measurement apparatus 3, and the sample transport apparatus 4 are the same as the devices indicated by the same reference numerals in FIG.

  The display 102 is configured by a flat panel display such as a liquid crystal display device. The input device 103 includes a keyboard, a mouse, and the like. The control device 104 includes a computer having a CPU (Central Processing Unit) 105, a ROM (Read Only Memory) 106, a RAM (Random Access Memory) 107, and a memory 108. Each device is connected to each other by a bus line 109.

  The memory 108 is configured by a storage medium having an arbitrary configuration such as a mechanical memory or a semiconductor memory. Further, the memory 108 may be formed not only by one storage medium but also by several storage media. In the memory 108, an X-ray measurement program 111 for causing the X-ray diffraction device 2 to perform X-ray diffraction measurement, a DSC measurement program 112 for causing the DSC measurement device 3 to perform DSC measurement, and the sample transport device 4. And a sample exchange program 113 for performing a sample exchange process.

  Further, the memory 108 includes a measurement data file 114 that is an area for storing data (sometimes referred to as raw data) obtained by the measurement by the X-ray diffraction apparatus 2 and the measurement by the DSC measurement apparatus 3, and the raw data An analysis data file 115, which is an area for storing analysis data obtained by applying analysis, is provided. The analysis data is, for example, peak search processing or background processing.

  When the control system is activated, the device is first initialized in step S1 of FIG. Specifically, the opening / closing lid 39 of FIG. 2 is moved in the direction of the arrow C ′, and the upper opening 24 of the partition wall 17 is closed by the pad 42. 1 is placed at a predetermined standby position. In FIG. 3, the furnace body cover 62 and the lid 78 are set by the measurer at a position covering the furnace body 49. If the furnace cover 62 or the like is placed at a position covering the furnace body 49 after the previous measurement, the measurer does not need to set the furnace cover 62 or the like again.

  The measurer prepares a standard material in the sample container 57 and one or more samples to be measured individually in the sample container 57. Then, the measurer puts the sample container 57 containing the standard substance into one or both of the first and second recesses 98 in FIG. Further, the measurer sets the sample container 57 containing the sample in any of the 3rd to 24th recesses. Then, the measurer operates the input device 103 of FIG. 10 to indicate the address of the concave portion 98 in which the sample container 57 containing the standard substance is placed, and further, the concave portion 98 in which the sample container 57 containing the sample is placed. Specify the street address.

  In step S2, the CPU reads the above-described data regarding the sample input by the measurer. If the measurement person gives an instruction to start measurement (YES in step S3), the opening / closing lid 39 in FIG. 2 is moved in step S4, and the opening 24 of the partition wall 17 is opened.

  Next, a lid removal process is executed in step S5. That is, the gripping member 81 of FIG. 1 is transported by the moving units 82X, 82Y, and 82Z and is transported from the initial standby position on the table 83 to a position above the upper opening 21 of the outer case 16 of the sample support unit 5. Further, the gripping member 81 is lowered to the knob 79 of the lid 78 shown in FIG. 3, and further opens and closes to grip the knob 79. At this time, the lateral groove 87 of the gripping tip 84 in FIG. 7A is fitted into the flange 79b (FIG. 5) of the knob 79.

  Next, the gripping member 81 is lifted upward and taken out of the opening 21 of the outer case 16 of FIG. The gripping member 81 further moves to the external lid placement portion 92 of the table 83 and further moves to open to put the lid 78 into the external lid placement portion 92. Thereby, the lid removing process in step S5 is completed.

  Next, a furnace cover removal process is executed in step S6. That is, in FIG. 1, the gripping member 81 is again conveyed to the opening 21 of the outer case 16, and further lowered to the knob 66 of the furnace body cover 49 in FIG. 3. Further, the gripping member 81 opens and closes and grips the knob 77 (FIG. 5). At this time, the lateral groove 87 of the gripping tip 84 in FIG. 7A is fitted into the flange 77 of the knob 66.

  Next, the gripping member 81 is lifted upward and taken out of the opening 21 of the outer case 16 of FIG. The gripping member 81 further moves to the outer cover placement portion 91 of the table 83, and further moves to open to put the furnace body cover 62 into the outer cover placement portion 91. At this time, the furnace body cover 62 is always positioned in a fixed state by the block member 99 of FIG. Thus, the furnace cover removal process in step S6 is completed.

Next, a standard substance arrangement process is performed in step S7. Specifically, in FIG. 9, the gripping member 81 is carried to the first or second recess 98 where the standard substance 19 is placed, and the gripping member 81 is opened and closed to move the standard substance 19. The accommodated sample container 57 is gripped at the high wall 93 (FIG. 8). Since the wall 93 is high, the gripping is performed without failure.

  Next, the gripping member 81 is transported from above the table 83 to a position above the opening 21 of the outer case 16 in FIG. 1, and further lowered to the placement position of the standard material on the heat sensitive plate 56 inside the furnace body 49 in FIG. The sample container 57 containing the standard substance is placed at that position. Thereby, the arrangement process of the standard substance in step S7 ends.

  When the sample container 57 is transported, the sample container 57 is positioned by the recess 98 in FIG. 9 and is always placed in a certain direction. Therefore, the sample container 57 placed on the heat sensitive plate 56 by the gripping member 81. Is always in a certain direction. Specifically, the sample container 57 is always set in the direction in which the low wall 94 is placed corresponding to the X-ray path X1.

  Next, sample placement processing is performed in step S8. Specifically, in FIG. 9, the gripping member 81 is carried to the concave portion 98 of the address where the sample 18 is put, and the gripping member 81 is opened and closed to move the sample container 57 containing the sample 18. Is securely gripped at the high wall 93 (FIG. 8).

  Next, the holding member 81 is carried from the table 83 to a position above the opening 21 of the outer case 16 in FIG. 1, and further lowered to the sample placement position of the heat sensitive plate 56 inside the furnace body 49 in FIG. The sample container 57 containing the sample is placed at that position. Thereby, the sample arrangement process in step S8 ends.

  When the sample container 57 is transported, the sample container 57 is positioned by the concave portion 98 of FIG. 9 and is always placed in a certain direction. Therefore, the sample container 57 placed on the heat sensitive plate 56 by the gripping member 81 is Always in a certain direction. Specifically, the sample container 57 is always set in the direction in which the low wall 94 is placed corresponding to the X-ray path X1. Therefore, when X-ray measurement is performed in FIG. 5, the wall of the sample container 57 does not obstruct the progress of the X-ray.

  Next, in step S6, the furnace body cover 62 taken out to the outer cover mounting portion 91 in FIG. 9 is set to a position that again covers the furnace body 49 in FIG. At this time, the furnace body cover 62 placed on the outer cover mounting portion 91 of FIG. 9 was always positioned in a fixed direction by the block member 99. Then, the groove 87 of the gripping tip 84 of the gripping member 81 (FIG. 7A) fits into the flange 77 of the knob 66 of the furnace body cover 62 (FIG. 6), and the tip surface of the tip 84 is the prism of the knob 66. Since the gripped portion 76 having the shape is sandwiched, the furnace body cover 62 does not rotate while being conveyed by the gripping member 81.

  As described above, the furnace body cover 62 placed at a position covering the furnace body 49 in FIG. 5 always has a fixed orientation with respect to the X-ray passage X1, specifically, the foil member 64 which is an X-ray passage member is provided. The orientation is always set on the X-ray path X1. Next, the lid 78 taken out to the external lid placing portion 92 in FIG. 9 in step S5 is set again on the step portion 61 of the guide ring member 59 in FIG. 5 by the gripping member 81 in step S10. Thereafter, an instruction to perform X-ray diffraction measurement and DSC measurement is given in step S11.

  In response to this instruction, a predetermined X-ray diffraction measurement is performed by the X-ray diffractometer 2 of FIGS. 1 and 10, and at the same time, a predetermined DSC measurement is performed by the DSC measurement apparatus 3, respectively. DSC data is obtained. In step S12, these data are stored in the measurement data file 114 of the memory 108 in FIG. When the necessary analysis is performed, the analysis data obtained as a result is stored in the analysis data file 115.

  When the measurer gives an instruction to display the measurement result on the screen of the display 102 in FIG. 10 (YES in step S13), in step S14, for example, by an image generation program stored in the memory 108 The image display data is generated based on the measurement data, and the image display data is supplied to an image display driver built in the display 102 or provided externally, and the measurement data is displayed on the screen. To do.

  When the predetermined measurement is completed for one sample (YES in step S15), the opening / closing lid 39 of FIG. 2 is operated to open the upper opening 24 of the partition wall 17 in step S16, and then the step In S17, the lid 78 of FIG. 5 is taken out to the external lid mounting portion 92 on the table 83 by the sample transport device 4 of FIG. Further, in step S18, the furnace cover 62 shown in FIG. 5 is taken out to the external cover mounting portion 91 on the table 83 by the sample transport device 4 shown in FIG. Next, in step S19, the sample container 57 containing the sample for which the measurement has been completed is taken out from the position on the heat sensitive plate 56 in FIG. 5 and transported to the concave portion 98 at the original address in the pallet 96 in FIG.

  The above processing is repeated until all the samples provided on the pallet 96 in FIG. 9 are finished (NO in step S20, step S21). When the measurement for all the samples is completed (YES in step S20), the sample container 57 containing the reference material 19 is removed in step S22 from the heat sensitive plate 56 in FIG. 5 after the sample container containing the sample is taken out in step S19. It takes out outside and returns to the original recessed part 98 in the pallet 96 of FIG.

  Next, the furnace body cover 62 taken out to the outer cover mounting portion 91 of FIG. 9 in step S18 is returned into the furnace body 49 of FIG. 5 in step S23. Further, in step S17, the lid 78 taken out in the external lid placing portion 92 in FIG. 9 is returned to the inside of the furnace body 49 in FIG. 5 in step S24. Further, in step S25, the upper opening 24 of the partition wall 17 in FIG. In step S26, the gripping member 81 shown in FIG. 1 is set at a predetermined standby position on the table 83, and the control is terminated.

  As described above, according to the present embodiment, the furnace body cover 62 having the foil member 64 shown in FIG. Even when X-ray measurement and DSC measurement are repeated, the block member 99 (FIG. 9) and the opening 72 (FIG. 6) fitted to the outer cover mounting portion 91 and the furnace body cover 62 of FIG. ) And the position of the furnace cover 62 with respect to the X-ray passage X1 is always positioned at a fixed position. Therefore, accurate X-ray diffraction measurement and DSC measurement for a plurality of samples are repeatedly and automatically repeated. It became possible to do.

  In the field of drug discovery, it is required to analyze the molecular properties of a very large number of samples by X-ray diffraction measurement and to analyze the thermal characteristics by DSC measurement. Conventionally, it is very difficult to carry out removal / removal of a furnace cover partially having an X-ray passage part such as a foil member while maintaining a constant positional relationship with respect to the X-ray passage, Actually, automatic measurement was not possible. On the other hand, according to the present embodiment, it becomes possible to automatically and continuously measure a large number of samples without bothering the measurer, and the development of drug discovery can be greatly advanced. It has become possible.

(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, the θ-θ type goniometer is exemplified in the above embodiment, but the present invention can also be applied to a θ-2θ type goniometer. The [theta] -2 [theta] goniometer is a method in which an X-ray generator is fixedly arranged, the sample is rotated by [theta] in a predetermined direction, and the X-ray detector is rotated in the same direction as [theta] rotation at twice the angular velocity.

  In the above embodiment, when the measurement is started, the furnace body cover 62 and the lid 78 are set by the measurer at a position covering the furnace body 49 in FIG. Instead, at the start of the measurement, the program can be started by placing the furnace body cover 62 on the outer cover placing portion 91 and placing the lid 78 on the outer lid placing portion 92 in FIG. In this case, step S5 (cover removal process) and step S6 (furnace cover removal process) in FIG. 11 are unnecessary, and step S23 (furnace cover setting process) and step S24 (lid setting process) are unnecessary. It is.

  In the above embodiment, the partition wall 17 is formed by the double cylindrical structure of the heat transfer material 14 and the heat insulating material 15. However, the partition wall 17 is a member for isolating the DSC unit 30 from the outside, and does not necessarily have a double structure. A single cylinder structure or a triple or more cylinder structure may be used. In the embodiment, the liquid passage 20 is used, but the liquid passage may not be used.

1. 1. X-ray and thermal analyzer, 2. X-ray diffractometer (X-ray measuring device) 3. DSC measurement device (thermal analysis measurement device) 4. Sample transport device; 5. Sample support unit 6. Goniometer, X-ray generation unit, 8. X-ray detector, 9. X-ray source 11. First arm, 12. Second arm, 13. Support shaft, 14. 15. heat transfer material; Insulation, 16. Outer case, 17. Partition, 18. Sample, 19. Reference material 20. Fluid passage, 21. Opening, 22. X-ray passing window (incident X-ray passing part), 23. X-ray passing window (outgoing X-ray passing part), 24. Opening, 25. O-ring, 26a, 26b. Fluid flow port, 27. Shelf member, 28. Stand, 29. Upper plate, 30. DSC unit 31. Electric motor, 32. Rotating plate, 33. Pin, 34. Laura, 36. Guide case, 39. Opening and closing lid, 41. Long hole, 42. Pad, 43. Through hole, 44. Through hole, 46. Pressing pin, 47. First support member, 48. The second support member, 49. Furnace body, 51. Heater wire, 52. Space, 53. Opening, 54a. Incident side lateral hole (incident X-ray passage part), 54b. Exit side lateral hole (exit X-ray passage part), 55. Temperature controller, 56. 56. Thermal plate (inner side container mounting part) Sample container, 58. Thermocouple, 59. Guide ring member 61. Step, 62. Furnace cover (inner vessel), 63. Inner cover, 64. Foil member, 65. Outer cover, 66. Knob, 68. Female thread, 69, 70, 71. Through-holes, 72, 73. Opening, 74. Screws, 76. The gripped portion, 77. Flange, 78. Lid (inner element), 79. Knob, 79a. Gripped portion, 79b. Flange, 81. Gripping member, 82X. Forward / backward moving unit, 82Y. Left and right moving unit, 82Z. Vertical movement unit, 83. Table, 84. Chip for gripping, 86. Screws, 87. Groove, 88. Shaft, 89. Wedge-shaped member, 90. 91. Pulse motor, servo motor, etc. 92. External cover placement part (external element placement part) 93. External lid placement part (external element placement part) Opposite side (high), 94. Opposite side (low), 95. Bottom wall, 96. Palette, 97. Guide, 98. Recessed part (outer side container mounting part), 99. Block member, 101. Convex part, 104. Control device, 108. Memory 109. Bus line

Claims (11)

An inner side container placing part in which a sample container containing a sample is placed;
A furnace body that accommodates the inner side container placement section and has an opening;
A partition wall containing the furnace body and provided with an opening;
An opening and closing lid for opening and closing the opening of the partition;
A thermal analysis measurement device that performs measurement for thermal analysis on a sample contained in a sample container placed on the inner side container placement unit;
An X-ray measurement device that detects secondary X-rays emitted from the sample when the sample contained in the sample container placed on the inner side container placement unit is irradiated with X-rays by an X-ray detector;
An inner element that can be placed on and removed from the inner element mounting portion in the partition; and
An outer side container placing part for placing the sample container provided outside the partition;
An outer side element placing portion for placing the inner element provided outside the partition;
The sample container is transported between the inner side container placing part and the outer side container placing part, and further, the inner element is placed between the inner side element placing part and the outer side element placing part. Conveying means for conveying;
Control means for controlling the operation of the opening / closing lid, the thermal analysis measurement device, the X-ray measurement device, and the transport means,
The sample container has in part a portion that can pass X-rays,
The control means includes
In the state where the internal element is placed on the internal element mounting portion and the opening / closing lid closes the opening of the partition wall, measurement is performed using the thermal analysis measurement device and / or the X-ray measurement device. Further, in the state where the opening / closing lid opens the opening of the partition wall and the internal element is placed on the external element mounting portion, the external container mounting portion and the internal container mounting portion The sample container is conveyed through the opening of the partition wall and the opening of the furnace body by the conveying means,
Repeatedly sequentially for a plurality of sample containers arranged on the outer container mounting part,
The conveying means is
When the sample container is disposed on the inner container mounting portion, the X-ray and the X-ray passage in the X-ray measurement apparatus are positioned in alignment with a portion through which the X-ray of the sample container can pass Thermal analyzer. An inner side container placing part in which a sample container containing a sample is placed;
A furnace body that accommodates the inner vessel mounting portion and has an opening;
A partition wall containing the furnace body and provided with an opening;
An opening and closing lid for opening and closing the opening of the partition;
A thermal analysis measurement device that performs measurement for thermal analysis on a sample contained in a sample container placed on the inner side container placement unit;
An X-ray measurement device that detects secondary X-rays emitted from the sample when the sample contained in the sample container placed on the inner side container placement unit is irradiated with X-rays by an X-ray detector;
The X-ray can be placed on the inner element mounting portion, can be removed from the inner element mounting portion, and is disposed at a position that blocks an X-ray path in the X-ray measuring apparatus. An internal element having a structure that does not block the passageway;
An outer side container placing part for placing the sample container provided outside the partition;
An outer side element placing portion for placing the inner element provided outside the partition;
The sample container is transported between the inner side container placing part and the outer side container placing part, and further, the inner element is placed between the inner side element placing part and the outer side element placing part. Conveying means for conveying;
Control means for controlling the operation of the opening / closing lid, the thermal analysis measurement device, the X-ray measurement device, and the transport means,
The sample container has in part a portion that can pass X-rays,
The control means includes
In the state where the internal element is placed on the internal element mounting portion and the opening / closing lid closes the opening of the partition wall, measurement is performed using the thermal analysis measurement device and / or the X-ray measurement device. Further, in the state where the opening / closing lid opens the opening of the partition wall and the internal element is placed on the external element mounting portion, the external container mounting portion and the internal container mounting portion The sample container is conveyed through the opening of the partition wall and the opening of the furnace body by the conveying means,
Repeatedly sequentially for a plurality of sample containers arranged on the outer container mounting part,
The conveying means is
When arranging the internal element on the internal element mounting portion, a structure that does not block the X-ray path of the internal element is aligned with the X-ray path in the X-ray measurement device, and
When the sample container is disposed on the inner container mounting portion, the X-ray and the X-ray passage in the X-ray measurement apparatus are positioned in alignment with a portion through which the X-ray of the sample container can pass Thermal analyzer. When the conveying means arranges the internal element on the internal element mounting portion, the structure that does not obstruct the X-ray path of the internal element is aligned with the X-ray path in the X-ray measurement apparatus,
3. The outer element mounting portion is provided with a positioning member for the inner element, and the transfer means does not rotate the inner element during transfer. X-ray and thermal analysis equipment. The positioning member provided in the external element mounting portion is a block member having a positioning plane,
4. The X-ray and thermal analysis apparatus according to claim 2, wherein the internal element has a shape that fits into a positioning plane of the block member. The internal element is a furnace cover that covers an opening of the furnace body,
The structure that does not block the X-ray passage in the X-ray measurement apparatus in the furnace body cover is a structure in which a foil member formed by a member that can pass X-rays is partially provided in the furnace body cover. The X-ray and thermal analysis apparatus according to any one of claims 2 to 4, wherein the X-ray and thermal analysis apparatus is characterized. When the transporting means arranges the sample container on the inner side container placing portion, the part of the sample container that can pass X-rays is aligned with the X-ray passage in the X-ray measurement apparatus,
2. The method according to claim 1, wherein a positioning member for the sample container is provided on the outer container mounting portion, and the transport means does not rotate the sample container during transport. The X-ray and thermal analysis apparatus according to claim 5.   The X-ray and thermal analysis apparatus according to claim 6, wherein the positioning member provided in the external container mounting portion is a concave portion similar to the sample container in plan view.   8. The part of the sample container through which X-rays can pass is a part where the height of a part of the side wall of the sample container is lower than the other part. The X-ray and thermal analyzer according to one. 9. The opening / closing lid is a plate-like member, and the opening / closing lid is movable in parallel between a position where the opening of the partition wall is closed and a position where the opening is opened. serial mounting X-ray and thermal analysis apparatus to One.
It said conveying means has a gripping member of the rod-like gripping member X of the mounting serial to any one of claims 1 to 9, characterized in that can pass through the aperture of the aperture and the furnace body of the partition wall Wire and thermal analysis equipment.
It said conveying means, placing serial to any one of claims 1 to 10, characterized in that a three-axis linear movement mechanism having a moving portion which reciprocates linearly moves each of the three axes directions perpendicular to each other X-ray and thermal analysis equipment.

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