Sample holding device for X-ray analysis

Abstract

The present invention provides a sample holding device for X-ray analysis. The sample holding device for X-ray analysis holds a sample holder (10) filled with a sample on a base member (20), and an airtight member (30) is assembled to the base member (20) so as to surround the sample holder (10), thereby forming a sample holding structure in a closed space. A fitting portion (35) that is fitted into and assembled to the fitting portion (21) is formed in the airtight member (30).

Description

Technical Field

[0001] The present invention relates to an X-ray analysis sample holding device used for placing a sample on an X-ray analysis device, and particularly to an X-ray analysis sample holding device having a function of being able to transfer a sample and place it on an X-ray analysis device in a state where the sample is disposed in a sealed space. Background Art

[0002] Various X-ray analysis devices such as an X-ray diffractometer, an X-ray reflectivity measuring device, an X-ray small-angle scattering device, and a fluorescent X-ray analysis device generally use an instrument called a sample holder to place a sample and perform X-ray-based measurement analysis in the atmosphere. However, in the case of using an anaerobic substance that easily reacts with components in the atmosphere (oxygen, nitrogen, moisture, etc.) as a sample, it is necessary to perform measurement analysis by disposing the sample in a sealed space not in contact with the atmosphere.

[0003] Japanese Patent Laid-Open No. 11-6805 (Patent Document 1) discloses an airtight sample holder for an X-ray device having a structure suitable for such a use. That is, the airtight sample holder for an X-ray device disclosed in this Document 1 has the following structure: A sample is filled into a sample filling portion (3a) of a sample stage (3), and after the sample surface is leveled using a spatula or the like, a film (4) and a packing material (5) are sequentially assembled, and the film (4) and the packing material (5) are pressed against the sample stage (3) by a pressing tool and fixed to the sample stage (3) using a male screw (7). It should be noted that the reference numerals in parentheses are the reference numerals assigned to each structural element in Patent Document 1.

[0004] In the above prior art, although a male screw is used to fix the film and the packing material to the sample stage, the tightening operation of the male screw requires a tool such as a screwdriver. However, the above series of operations for holding the sample X in the airtight sample holder for an X-ray device are generally performed as follows: An inert gas is pre-filled into a sealed container called a glove-sealed operation box, and an operator operates each structural element of the airtight sample holder for an X-ray device disposed in the glove-sealed operation box from the outside through rubber gloves. At this time, it is very difficult to perform a delicate operation such as tightening the male screw using a tool from the outside through rubber gloves, which is the main reason for a significant decrease in work efficiency. Summary of the Invention

[0005] The present invention has been made in view of such circumstances, and an object thereof is to provide an X-ray analysis sample holding device that is easy to handle and can form a state in which a sample is disposed in a sealed space by a simple operation.

[0006] In order to achieve the above object, the sample holding device for X-ray analysis of the present invention includes: a sample holder having a sample filling portion for filling a sample; a base member for holding the sample holder; and an airtight member that is detachably assembled to the base member to cover the periphery of the sample holder held by the base member.

[0007] Moreover, an assembly portion for assembling the airtight member is formed on the base member, and a fitting portion that is fitted into the assembly portion is formed on the airtight member. A locking mechanism is provided between the assembly portion and the fitting portion. During the process of fitting the fitting portion into the assembly portion, the locking mechanism engages to prevent the airtight member from detaching from the base member.

[0008] With the sample holding device for X-ray analysis of the present invention configured in this way, by simply fitting the fitting portion of the airtight member into the assembly portion of the base member, a closed space can be formed around the sample filled in the sample filling portion. Thus, according to the sample holding device for X-ray analysis of the present invention, the handling is easy, and a state in which the sample is disposed in a closed space can be formed by a simple operation.

[0009] Furthermore, during the fitting operation, the locking mechanism functions to prevent the airtight member from detaching from the base member. Therefore, the possibility of air flowing into the hollow portion of the airtight member during transportation is reduced, and the periphery of the sample can be stably maintained in an airtight state.

[0010] The airtight member includes: a main body portion formed in a block shape with a hollow portion inside; and a fitting portion protruding from the lower surface of the main body portion. The lower end surface of the fitting portion is open and communicates with the hollow portion inside the main body portion. An X-ray transmission window is formed by cutting the main body portion, and an X-ray window material is formed around it so as to cover the X-ray transmission window. Moreover, an operation portion for the operator to grasp and perform the fitting operation is formed on the surface region of the main body portion where the X-ray transmission window is not formed.

[0011] The X-ray window material is preferably formed of any one of metal, artificial mineral, or polymer.

[0012] It may be that a holding groove for detachably holding the sample holder is formed in the base member, and a fitting convex portion that is fitted into the holding groove is formed in the sample holder. In addition, the sample filling portion of the sample holder is formed by a groove, and the opening surface of the groove is formed in a rectangular shape. The sample holding device for X-ray analysis has the following structure: by fitting the fitting convex portion of the sample holder into the holding groove of the base member while changing the orientation by 90° around the central axis, the long side or the short side of the rectangular shape of the opening surface of the groove is arranged in a direction orthogonal to the optical axis of the incident X-ray.

[0013] By having such a structure, for example, in X-ray analysis such as X-ray diffraction measurement in which X-rays are incident on the sample surface from a low angle, by arranging the short side of the opening surface of the groove (sample filling portion) in a direction orthogonal to the optical axis of the incident X-rays (in other words, arranging the long side of the opening surface parallel to the optical axis of the incident X-rays), a wide X-ray irradiation area in the optical axis direction of the incident X-rays can be ensured for the sample surface.

[0014] In addition, in X-ray analysis such as X-ray diffraction measurement in which X-rays are incident on the sample surface from a normal angle, by arranging the long side of the opening surface of the groove (sample filling portion) in a direction orthogonal to the optical axis of the incident X-rays, an X-ray irradiation region long in the width direction can be ensured for the sample surface, and high-intensity X-ray irradiation can be achieved.

[0015] Preferably, when assembled to the X-ray analysis device, the upper surface of the base member is arranged at the same height position as the X-ray irradiation position of the X-ray analysis device. When the sample holder is held on the base member, the opening surface of the groove is positioned so as to be in the same plane as the upper surface of the base member.

[0016] According to this structure, even when the sample holder is replaced, by appropriately fitting the fitting convex portion of the sample holder into the holding groove of the base member, the opening surface of the groove formed in the sample holder can be positioned in the same plane as the upper surface of the base member.

[0017] And by making the surface of the sample (sample surface) filled in the groove coincide with the opening surface of the groove, the sample surface is arranged in the same plane as the upper surface of the base member. In X-ray analysis, it is necessary to arrange the sample surface at the X-ray irradiation position set in the X-ray analysis device.

[0018] The upper surface of the base member serves as a reference surface when irradiating X-rays on the sample. When the base member is installed in the X-ray analysis device, this reference surface is positioned at the same height as the X-ray irradiation position. At this time, since the sample surface is also arranged at the same height position as the X-ray irradiation position, the positioning of the sample surface relative to the X-ray irradiation position (especially the positioning in the height direction) becomes easy.

[0019] In the hollow portion of the main body of the airtight member, a knife edge for shielding scattered X-rays incident from the X-ray transmission window is provided hanging down from the top surface downward.

[0020] By providing a knife edge in the hollow portion of the airtight member, the scattered X-rays generated when the incident X-rays pass through the X-ray window material pasted on the X-ray transmission window can be effectively shielded by the knife edge. Therefore, the noise of the X-ray measurement data caused by the incidence of scattered X-rays on the sample can be reduced, and high-precision measurement analysis can be achieved.

[0021] In addition, it is possible that the fitting portion of the base member is formed by a concave portion or a convex portion, and the fitting portion of the airtight member is formed in a cylindrical shape that can be fitted into the fitting portion. And a locking mechanism is provided between the surfaces of the fitting portion and the fitting portion where they are fitted to each other.

[0022] As described above, the sample holding device for X-ray analysis according to the present invention facilitates processing, and a state in which a sample is disposed in a sealed space can be formed by a simple operation. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is an exploded perspective view of the sample holding device for X-ray analysis according to an embodiment of the present invention.

[0024] Figure 2 is a perspective view showing the appearance of the sample holding device for X-ray analysis according to an embodiment of the present invention.

[0025] Figure 3A is a perspective view of the sample holder as viewed obliquely from above, Figure 3B is a top view of the sample holder, Figure 3C is a perspective view of another sample holder as viewed obliquely from above, Figure 3D is a top view of another sample holder, Figure 3E is a perspective view of the sample holder as viewed obliquely from below, Figure 3F is a bottom view of the sample holder.

[0026] Figure 4A is a perspective view showing the base member, Figure 4B is a top view showing the base member, Figure 4C is a top view of a state in which the sample holder is assembled to the base member.

[0027] Figure 5A is a front cross-sectional view showing a state in which X-rays are irradiated onto the sample surface of the sample filled on the sample holder from a low angle, Figure 5B is a top view thereof, Figure 5C is a perspective view thereof.

[0028] Figure 6A is a front cross-sectional view showing a state in which X-rays are irradiated onto the sample surface of the sample filled on the sample holder from a normal angle, Figure 6B is a top view thereof, Figure 6C is a perspective view thereof.

[0029] Figure 7A is a perspective view showing the airtight member, Figure 7B is a perspective view showing a state in which the X-ray transmission window of the airtight member is covered with an X-ray window material, Figure 7C is a perspective view of the fitting portion of the airtight member as viewed obliquely from below, Figure 7D is a front view showing an enlarged view of the locking mechanism of the airtight member.

[0030] Figure 8 It is a diagram showing the process before arranging a sample to the X-ray irradiation position of an X-ray analysis apparatus, using the sample holding apparatus according to an embodiment of the present invention.

[0031] Figure 9 It is a coordinate diagram showing the experimental results of testing the airtight holding ability of the X-ray analysis sample holding apparatus according to an embodiment of the present invention.

[0032] Figure 10A It is a perspective view of an airtight member in an X-ray analysis sample holding apparatus according to another embodiment of the present invention. Figure 10B It is a perspective view of the X-ray analysis sample holding apparatus. Figure 10C It is a left side view of the X-ray analysis sample holding apparatus.

[0033] Figure 11A It is a perspective view of an X-ray analysis sample holding apparatus according to another embodiment of the present invention. Figure 11B It is a left side view of the X-ray analysis sample holding apparatus. Figure 11C It is a front view of the X-ray analysis sample holding apparatus.

[0034] Figure 12 It is a diagram showing an experimental example for verifying the effect of a knife edge. Detailed Embodiments

[0035] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0036] Figure 1 It is an exploded perspective view of the X-ray analysis sample holding apparatus according to this embodiment. Figure 2 It is a perspective view showing the appearance of the apparatus.

[0037] As Figure 1 shown, the X-ray analysis sample holding apparatus according to this embodiment includes structural elements such as a sample holder 10, a base member 20, and an airtight member 30. And, the sample holder 10 filled with a sample is held by the base member 20, and the airtight member 30 is assembled to the base member 20 so as to surround the periphery of the sample holder 10, thereby forming Figure 2 a sample holding structure in a closed space as shown.

[0038] Figures 3A - 3F It is a diagram showing the sample holder.

[0039] As shown in these diagrams, the sample holder 10 has a sample filling portion 12 formed on the upper surface of a cylindrical holder body 11, and a sample to be analyzed is filled into the sample filling portion 12.

[0040] The stent main body 11 can be formed of, for example, metallic materials such as aluminum alloy and stainless steel, or non-metallic materials such as glass. However, when selecting the material for forming the stent main body 11, it is preferable to avoid materials that chemically react with the filled sample, and materials similar to the sample that emit diffracted X-rays under diffraction conditions. Moreover, a material obtained by cutting a single crystal of silicon in an orientation that does not satisfy the diffraction conditions of X-rays (X-ray non-reflective material) can also be used to form the stent main body 11. By using such an X-ray non-reflective material, for example, it is possible to reduce the mixing of noise into the X-ray measurement data.

[0041] In the present embodiment, the sample filling portion 12 is formed by a shallow groove 12. The sample filled in the groove 12 is preferably leveled on its surface (sample surface) using a spatula or the like to become a plane flush with the opening surface of the groove 12. However, the shape of the sample filling portion 12 is not limited to a shallow groove.

[0042] The groove (sample filling portion) 12 can have its opening surface formed into various shapes. For example, the opening surface of the groove 12 can be formed into Figure 3A , Figure 3B a rectangle as shown or Figure 3C , Figure 3D a circle as shown.

[0043] Regarding the sample stent 10, it is preferable to prepare in advance a plurality of types of stents in which the above-described various materials and the shape of the opening surface of the groove 12 are arbitrarily combined, and they can be appropriately selected and used according to the sample to be analyzed or the content of the X-ray analysis.

[0044] As Figure 3E , Figure 3F shown, in the sample stent 10, a fitting convex portion 13 is formed to protrude downward from the central portion of the bottom surface of the stent main body 11. The fitting convex portion 13 has a shape in which a square convex portion 13a having a square cross-section at the base that is in contact with the bottom surface of the stent main body 11 and a cylindrical core portion 13b further protrudes from the central portion of its bottom surface.

[0045] Even in the case where a plurality of types of sample stents 10 having different materials and the shape of the opening surface of the groove 12 are prepared as described above, it is preferable to make the shape of the fitting convex portion 13 common and maintain the interchangeability with respect to the base member 20.

[0046] Figures 4A - 4C FIG. is a view showing the base member.

[0047] The base member 20 can be made of a metal material such as aluminum alloy or stainless steel, for example. A stepped recess with a circular cross-section is formed by digging downward from the upper surface of the base member 20. A part of the stepped recess constitutes an assembly portion 21 for assembling the airtight member 30. That is, the inner bottom surface of the stepped recess is processed into a flat surface, and the inner bottom surface constitutes the bottom surface 21a of the assembly portion 21. In addition, the inner peripheral surface from the inner bottom surface to the intermediate stepped portion constitutes a fitting surface 22 that fits with a fitting portion 35 of the airtight member 30 described later. Moreover, a locking pin 23 protruding radially inward (i.e., in the central axis direction within the stepped recess) is provided at the intermediate portion of the fitting surface 22.

[0048] In addition, a holding groove 24 is formed by further digging downward the central portion of the inner bottom surface of the stepped recess formed in the base member 20. By fitting the fitting convex portion 13 of the sample holder 10 described above into the holding groove 24, the sample holder 10 is held on the base member 20 without looseness. It should be noted that the holding groove 24 is provided for the fitting convex portion 13 to be detachably fitted. Thereby, multiple types of sample holders 10 can be held on the base member 20 with appropriate replacement.

[0049] The holding groove 24 is also formed in a stepped shape. A square convex portion 13a formed on the fitting convex portion 13 of the sample holder 10 is fitted into the upper region 24a of the holding groove 24 from the upper end opening surface to the intermediate stepped portion, and a core portion 13b formed on the fitting convex portion 13 of the sample holder 10 is fitted into the lower region 24b from the intermediate stepped portion to the inner bottom surface of the holding groove 24. The lower region 24b of the holding groove 24 is formed with a circular cross-section corresponding to the cylindrical shape of the core portion 13b of the fitting convex portion 13, and the core portion 13 of the fitting convex portion 13 is fitted on its inner peripheral surface.

[0050] On the other hand, as Figure 4A shown, the upper region 24a of the holding groove 24 has four side surfaces S1, S2, S3, and S4 on the inner wall that are in contact with the respective sides of the square convex portion 13a formed on the fitting convex portion 13 of the sample holder 10. Thereby, the square convex portion 13a formed on the fitting convex portion 13 of the sample holder 10 can be fitted into the upper region 24a of the holding groove 24 with a 90° change in orientation around its central axis.

[0051] In addition, the base member 20 for holding the sample holder 10 is installed in the X-ray analysis device 200 as described later. And X-rays are irradiated onto the sample filled in the groove 12 of the sample holder 10.

[0052] Here, as Figure 3A 、 Figure 3BAs shown, in the sample holder 10 with a rectangular opening surface formed in the groove 12, when the square projection 13a of the fitting projection 13 is inserted into the upper region 24a of the holding groove 24 of the base member 20, the long side or the short side of the opening surface of the groove 12 is arranged in a direction orthogonal to the optical axis of the incident X-ray.

[0053] For example, in X-ray diffraction measurement, when the incident angle of the X-ray with respect to the sample surface is set to a low angle (for example, set to θ = 1° or less in the 2θ scan with a fixed incident angle θ, and set the start angle of θ to around 2° in the θ / 2θ scan without a fixed incident angle), as Figures 5A - 5C shown, by arranging the short side 12a of the opening surface of the groove 12 in a direction orthogonal to the optical axis O of the incident X-ray a (in other words, arranging the long side 12b of the opening surface parallel to the optical axis O of the incident X-ray a), a wide X-ray irradiation area of the incident X-ray a in the direction of the optical axis O can be ensured for the sample surface.

[0054] In addition, in X-ray diffraction measurement, when the incident angle of the X-ray with respect to the sample surface is set to a normal angle, as Figures 6A - 6C shown, by arranging the long side 12b of the opening surface of the groove 12 in a direction orthogonal to the optical axis O of the incident X-ray a, an X-ray irradiation region long in the width direction can be ensured for the sample surface, and high-intensity X-ray irradiation can be achieved.

[0055] Return Figure 4C , on the side wall of the base member 20, cutout portions 25 communicating with the stepped recesses forming the fitting portion 21 are formed at two opposed positions. These cutout portions 25 form a sweeping portion that opens the bottom surface 21a of the fitting portion 21 to the outside from the side of the base member 20, and it is possible to easily sweep out the sample etc. that has fallen on the bottom surface 21a of the fitting portion 21 when filling the sample holder 10 held by the base member 20 with the sample from this cutout portion 25 to the outside.

[0056] Figures 7A - 7D It is a diagram showing an airtight member.

[0057] The airtight member 30 includes: a main body portion 31 formed in a box shape with a hollow portion inside; a fitting portion 35 formed to protrude from the lower surface of the main body portion 31.

[0058] As Figure 7A shown, on the side surface of the main body portion 31, X-ray transmission windows 32 are formed by cutting two opposed positions. As Figure 7B shown, each of the above X-ray transmission windows 32 is covered with an X-ray window material 33, and the inside of the hollow portion of the airtight member 30 is kept in a sealed state. The X-ray window material 33 is pasted around the X-ray transmission window 32 ( Figure 7BThe area indicated by the middle shadow line), that is, it is pasted on the same surface as the surface forming the X-ray transmission window 32.

[0059] The X-ray window material 33 is preferably composed of a film-like material (including sheets, films, foils, etc. in addition to films) having a shielding property that allows X-rays to pass through but does not allow components in the atmosphere (oxygen, nitrogen, moisture, etc.) to pass through. By forming the X-ray window material 33 into a film shape, the X-ray transmission performance can be improved, and high-intensity X-rays can be irradiated onto the sample.

[0060] On the other hand, when the X-ray window material 33 is formed into a thin wall, when assembling the airtight member 30 to the base member 20, it may be damaged if the operator accidentally touches only the X-ray window material 33, resulting in a significant decrease in the shielding performance against components in the atmosphere.

[0061] In the present embodiment, by making the surface area of the main body portion 31 of the airtight member 30 where the X-ray transmission window 32 is not formed wide as the operation portion 34, a structure is formed in which it is difficult for the operator to accidentally touch the X-ray window material 33. That is, as Figure 7B shown, in the main body portion 31 formed in a box-shaped block shape, the two side surfaces where the X-ray transmission window 32 is not formed function as the operation portion 34. By the operator grasping these operation portions 34, the embedding operation of the airtight member 30 to the base member 20 can be easily and safely performed.

[0062] The material applied to the X-ray window material 33 is preferably appropriately selected according to the properties of the sample. For example, when the sample is a substance with a highly reactive property such as an alkali metal, beryllium or aluminum is suitable as the X-ray window material 33. However, since these materials are opaque, the inside of the airtight member 30 cannot be visually observed. In contrast, when a transparent polymer film is applied to the X-ray window material 33, the sample disposed inside the airtight member 30 can be visually observed.

[0063] As materials preferably used for the X-ray window material 33 having gas barrier properties, for example, the following substances can be cited.

[0064] That is, as metal materials, beryllium, aluminum, etc. are suitable for the X-ray window material 33. Moreover, as artificial minerals, graphite, vitreous carbon, diamond, SiN, quartz, sapphire, etc. are suitable for the X-ray window material 33. And, as polymer materials, polyethylene film (PE film), polyvinyl chloride film (PVC film), polyvinylidene chloride film (PVDC film), polyvinyl alcohol film (PVA film), polypropylene film (PP film), polycarbonate film (PC film), polystyrene film (PS film), polyacrylonitrile film (PAN film), ethylene-vinyl acetate copolymer film (EVA film), ethylene-vinyl alcohol copolymer film (EVOH film), polyetherimide (PEI), aromatic polyether ether ketone (PEEK), etc. are suitable for the X-ray window material 33.

[0065] It should be noted that the polymer material basically belongs to thermoplastic resin, and also includes fluororesin in which hydrogen is replaced by fluorine. Moreover, materials processed in multiple layers by co-extrusion method, etc., materials subjected to single evaporation coating or composite evaporation coating of aluminum, alumina, and silica, and materials subjected to surface treatment thereof are also suitable for the X-ray window material 33.

[0066] As Figure 7C shown, the fitting portion 35 is formed in a cylindrical shape (a cylindrical shape in this embodiment) that can be inserted into the fitting portion 21 formed in the base member 20. The outer peripheral surface 35a of the cylindrical fitting portion 35 is fitted to the fitting surface 22 of the fitting portion 21 formed in the base member 20.

[0067] The lower end opening surface of the fitting portion 35 communicates with the hollow portion in the main body portion 31 through the hollow portion of the fitting portion 35. When the fitting portion 35 is inserted into the fitting portion 21 of the base member 20, the sample holder 10 held by the base member 20 is received into the hollow portion of the main body portion 31 from the lower end opening surface.

[0068] A circumferential groove 37 for fitting the O-ring 36 is formed at the lower end edge of the fitting portion 35. The O-ring 36 fitted in the circumferential groove 37 is pressed against the bottom surface 21a of the fitting portion 21 formed in the base member 20, making the inside of the hollow portion of the airtight member 30 airtight. By covering the periphery of the sample holder 10 with the airtight member 30, the sample filled in the sample holder 10 can be isolated from the atmosphere.

[0069] The structure of fitting the O-ring 36 to the fitting portion 35 of the airtight member 30 has the following effects compared with the structure of arranging the O-ring 36 on the side of the fitting portion 21 of the base member 20. That is, when the sample holder 10 filled with the sample is assembled to the fitting portion 21 of the base member 20, even if the sample spills onto the bottom surface 21a of the fitting portion 21, it is impossible to contaminate the O-ring 36 fitted to the fitting portion 35 of the airtight member 30. The sample spilled onto the bottom surface 21a of the fitting portion 21 can be swept out from the cutout portion 25 before assembling the airtight member 30 to the base member 20.

[0070] In addition, a locking mechanism is provided between the surfaces (the fitting surface 22 of the fitting portion 21 and the outer peripheral surface 35a of the fitting portion 35) where the fitting portion 21 of the base member 20 and the fitting portion 35 of the airtight member 30 are fitted. This locking mechanism engages during the process of inserting the fitting portion 35 into the fitting portion 21, preventing the airtight member 30 from detaching from the base member 20.

[0071] In this embodiment, by the locking pin 23 provided on the fitting surface 22 of the fitting portion 21 of the base member 20 (refer to Figure 1 , Figure 4A)and an L-shaped groove 38 formed on the outer peripheral surface 35a of the fitting portion 35 of the airtight member 30 (see Figure 1 , Figure 7C ) constitute a locking mechanism. The L-shaped groove 38 opens at the lower end of the fitting portion 35, and a terminal portion 38a is formed at a position where it extends axially along the fitting portion 35 and then bends circumferentially.

[0072] That is, as Figure 7D shown, when the fitting portion 35 of the airtight member 30 is inserted into the fitting portion 21 of the base member 20, the locking pin 23 is engaged with the L-shaped groove 38, and then the fitting portion 35 is rotated about the central axis, so that the locking pin 23 abuts against the terminal portion 38a of the L-shaped groove 38. At this time, the O-ring 36 is pressed against the bottom surface 21a of the fitting portion 21 formed on the base member 20 to form an airtight state.

[0073] Here, the operator can confirm that the airtight state is properly formed by the collision sound when the locking pin 23 abuts against the terminal portion 38a of the L-shaped groove 38. And in the state where the locking pin 23 abuts against the terminal portion 38a of the L-shaped groove 38, since the axial movement of the fitting portion 35 relative to the fitting portion 21 of the base member 20 is blocked, the airtight member 30 cannot be detached from the base member 20.

[0074] Through this series of insertion operations, the locking mechanism of the present embodiment constitutes an interlocking locking mechanism, which can interlockingly prevent the detachment of the airtight member 30 from the base member 20 and form an airtight state.

[0075] Figure 8 is a view showing the process before arranging the sample at the X-ray irradiation position of the X-ray analysis device using the sample holding device for X-ray analysis of the present embodiment.

[0076] The operation of inserting and holding the sample holder 10 into the base member 20 can be performed outside the glove-sealed operation box 100.

[0077] The base member 20 holding the sample holder 10, the airtight member 30, and the sample are housed in the glove-sealed operation box 100. Then, the operator wears the rubber gloves 101 provided on the glove-sealed operation box 100 and performs the processing inside the glove-sealed operation box 100 through the rubber gloves 101.

[0078] Inside the glove-sealed operation box 100, first, the sample is filled into the groove 12 of the sample holder 10, and then the surface (sample surface) is scraped flat with a spatula or the like to be flush with the opening surface of the groove 12.

[0079] Next, the airtight member 30 is assembled to the base member 20. At this time, the operation portion 34 of the airtight member 30 is grasped, and the airtight member 30 is inserted into the base member 20. Since the operation portion 34 is ensured in a wide area on the side surface of the airtight member 30, its operation can be easily performed.

[0080] By assembling the airtight member 30 to the base member 20, a sample is placed inside the hollow portion of the airtight member 30 in an airtight state. The X-ray analysis sample holding device 1 assembled with each member is moved to the front chamber (transfer box) 102 connected to the glove-sealed operation box 100, and the X-ray analysis sample holding device 1 is taken out to the outside through the front chamber 102. Then, the X-ray analysis sample holding device 1 is installed on the X-ray analysis device 200.

[0081] Even if the X-ray analysis sample holding device 1 is moved in the atmosphere, since the sample is separated from the atmosphere by the airtight member 30, there is no possibility of a chemical reaction between the sample and the components in the atmosphere.

[0082] Here, when performing X-ray analysis, it is necessary to arrange the sample surface at the X-ray irradiation position 201 provided in the X-ray analysis device 200. The X-ray irradiation position 201 is preset in the X-ray analysis device 200. Usually, the X-ray irradiation position 201 is the central position of the goniometer provided in the X-ray analysis device 200. A slit with a narrow width of about 0.05 mm is arranged at this central position so that the beam passes through the slit from the X-ray source and is incident on the X-ray detector, thereby positioning the central position of the goniometer at the X-ray irradiation position. In the X-ray analysis device 200, a sample support portion 202 for inserting and supporting a general sample holder is provided at the central position of the goniometer.

[0083] The X-ray analysis sample holding device of the present embodiment is configured to insert and assemble the base member 20 into the sample support portion 202 of the X-ray analysis device 200. And pre-adjustment is performed so that when the base member 20 is inserted into the sample support portion 202, at the same time, the upper surface 20a of the base member 20 (refer to Figure 2 ) is arranged at the same height position as the X-ray irradiation position 201.

[0084] When the fitting convex portion 13 of the sample holder 10 is inserted and held in the holding groove 24 of the base member 20, the opening surface of the groove 12 forming the sample filling portion is positioned to be arranged on the same plane as the upper surface 20a of the base member 20. As described above, for the sample filled in the groove 12, its surface (sample surface) is scraped flat using a spatula or the like to be flush with the opening surface of the groove 12. Thus, the sample surface is arranged on the same plane as the upper surface 20a of the base member 20.

[0085] As described above, when the base member 20 is fixed to the X-ray analysis apparatus 200, the upper surface 20a of the base member 20 is positioned at the same height as the X-ray irradiation position 201 of the X-ray analysis apparatus 200. Therefore, the sample surface is also arranged at the same height as the X-ray irradiation position 201. Accordingly, the positioning of the sample surface relative to the X-ray irradiation position 201 (particularly the positioning in the height direction) becomes easy.

[0086] Figure 9 It is a coordinate diagram showing the experimental results of testing the airtight holding ability of the X-ray analysis sample holding device of the present embodiment.

[0087] Using Li 7 P 3 S 11 (sulfide glass-based electrolyte) as a sample, the same sample is assembled in a glove-sealed operation box under an argon atmosphere, and the periphery of the sample is made airtight by the airtight member 30. Then, the X-ray analysis sample holding device is taken out from the glove-sealed operation box and left in the atmosphere adjusted to 23°C for one day. Data A obtained by performing X-ray diffraction measurement on the sample immediately after taking it out from the glove-sealed operation box is compared with data B obtained by performing X-ray diffraction measurement on the sample after leaving it for one day, and substantially the same X-ray curve diagram (detection result) is obtained. If the atmospheric components or moisture invade the inside of the airtight member 30, they will react with the sample and cause a decrease in the peak intensity of the X-ray curve diagram. However, such a change was not confirmed from the above comparison results, and it can be seen that the periphery of the sample is kept airtight.

[0088] It should be noted that the present invention is not limited to the above-described embodiments, and various modifications or applications can be made as needed.

[0089] For example, in the above-described embodiment, a part of the stepped recess constitutes the fitting portion 21 for fitting the airtight member 30, but it may also be configured such that the fitting portion 21 is constituted by a convex portion or a rib, and the inner peripheral surface or the outer peripheral surface of the fitting portion 35 of the airtight member 30 formed in a cylindrical shape is fitted to the outer peripheral surface or the inner peripheral surface of the above convex portion or rib.

[0090] In addition, the airtight member 30 is not limited to the box-shaped block shape shown in the above-described embodiment, and may be constituted by various three-dimensional shapes capable of ensuring the operation portion 34 in a wide area.

[0091] For example Figure 10A 、 Figure 10BAs shown, the airtight member 30 can also be formed into an arched block shape. In the main body portion 31 of the airtight member 30, the X-ray transmission window 32 is formed into a semi-circular arc shape, and an X-ray window material 33 is pasted around the edge portion of the X-ray transmission window 32 so as to cover the X-ray transmission window 32.

[0092] The fitting portion 35 of the airtight member 30 is configured in the same manner as that of the Figure 7C , Figure 7D previously described embodiment shown.

[0093] For example Figure 10C as shown, in the X-ray diffraction measurement (thin film measurement method) in which the incident angle is fixed at a low angle and X-ray scanning (2θ scanning) is performed, if the box-shaped block-shaped airtight member 30 described above is used to measure a high angle 2θ, the diffracted rays from the sample may interfere with the edge portion (window frame portion) of the X-ray transmission window 32 of the main body portion 31 and cannot be detected by the X-ray detector. In contrast, in the airtight member 30 formed into an arched block shape, the diffracted rays from the sample are not blocked by the main body portion 31, and measurement up to a high angle region can be performed.

[0094] In addition, as Figures 11A - 11C shown, inside the hollow portion of the airtight member 30, a knife-edge 40 can also be provided hanging down from the top surface downward. The knife-edge 40 is a plate-like member formed of a material that blocks X-rays, and is configured to form an appropriate gap between the approximate center portion of the sample surface and the lower end edge of the knife-edge 40. The front surface of the knife-edge 40 is arranged along the optical axis of the incident X-rays, and the X-rays pass through the gap between the sample surface and the knife-edge 40 and irradiate the sample surface, and then the diffracted X-rays are reflected to the back side of the knife-edge 40.

[0095] When the incident X-rays pass through the X-ray window material 33, scattered X-rays sometimes occur. Since the scattered X-rays are blocked by the knife-edge 40, noise in the X-ray measurement data generated by the scattered X-rays can be reduced, and high-precision measurement analysis can be achieved.

[0096] Figure 12 is a diagram showing an experimental example for verifying the effect of the knife-edge 40.

[0097] Figure 12 The measurement data A shown is the measurement data obtained by performing X-ray diffraction measurement using an X-ray analysis sample holding device having the structure shown in Figure 2 without the knife-edge 40 provided. On the other hand, the measurement data B is the measurement data obtained by performing X-ray diffraction measurement using an X-ray analysis sample holding device having the structure shown in Figure 11A with the knife-edge 40 provided. Each X-ray analysis sample holding device has the same size and structure except for the knife-edge 40.

[0098] From the comparison of the above measurement data A and B, it can be seen that in the regions other than the scanning angles where the peak intensity of the diffracted X-rays appears, the noise generated by the scattered X-rays overlaps with the measurement data A. Therefore, in particular, the intensity of the diffracted X-rays measured in the low-angle region shows a value larger than that of the measurement data B.

Claims

1. A sample holding device for X-ray analysis, the sample holding device for X-ray analysis comprising: a sample holder having a sample filling portion for filling a sample; a base member for holding the sample holder; and an airtight member detachably assembled to the base member to cover the periphery of the sample holder held by the base member, the sample holding device for X-ray analysis being characterized in that, in the base member, an assembly portion for assembling the airtight member is formed by hollowing downward from the upper surface, a fitting portion that is fitted into the assembly portion is formed in the airtight member, and a locking mechanism is provided between the assembly portion and the fitting portion. During the process of fitting the fitting portion into the assembly portion, the locking mechanism engages to prevent the airtight member from detaching from the base member, furthermore, the airtight member comprises: a main body portion with a hollow portion inside; and the fitting portion formed to protrude from the lower surface of the main body portion, the lower end surface of the fitting portion is open and communicates with the hollow portion inside the main body portion, the main body portion is cut to form an X-ray transmission window, and an X-ray window material is formed around it so as to cover the X-ray transmission window, the main body portion is formed in a box-shaped block shape, the X-ray transmission window is formed on two opposed sides of the main body portion, operation portions for the operator to grasp and perform the fitting operation are formed on the other two opposed sides of the main body portion where the X-ray transmission window is not formed, the locking mechanism has the following structure: when the fitting portion of the airtight member is fitted into the assembly portion of the base member, the airtight member is prevented from detaching from the base member by rotating the fitting portion around the central axis, and a circumferential groove for fitting an O-ring is formed at the lower end edge of the fitting portion.

2. The sample holding device for X-ray analysis according to claim 1, characterized in that, the X-ray window material is formed of any one of metal, artificial mineral, and polymer.

3. The sample holding device for X-ray analysis according to claim 1, characterized in that, a holding groove for detachably holding the sample holder is formed in the base member, and a fitting convex portion that is fitted into the holding groove is formed in the sample holder, the sample filling portion of the sample holder is formed by a groove, and the opening surface of the groove is formed in a rectangular shape, the sample holding device for X-ray analysis has the following structure: by fitting the fitting convex portion of the sample holder into the holding groove of the base member while changing the orientation by 90° around the central axis, the long side or the short side of the rectangular shape of the opening surface of the groove is arranged in a direction orthogonal to the optical axis of the incident X-ray.

4. The sample holding device for X-ray analysis according to claim 3, characterized in that, when the base member is assembled to the X-ray analysis device, the upper surface of the base member is arranged at the same height position as the X-ray irradiation position of the X-ray analysis device, when the sample holder is held by the base member, the opening surface of the groove is positioned so as to be arranged in the same plane as the upper surface of the base member.

5. The sample holding device for X-ray analysis according to claim 1, wherein, in the hollow portion of the main body portion, a knife edge for shielding scattered X-rays incident from the X-ray transmission window is provided hanging downward from the top surface.

6. The sample holding device for X-ray analysis according to any one of claims 1 to 5, wherein, the fitting portion of the base member is formed by a concave portion or a convex portion, the fitting portion of the airtight member is formed in a cylindrical shape that can be fitted into the fitting portion, the locking mechanism is provided between the surfaces where the fitting portion and the fitting portion are fitted to each other.

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