Sample cell for fluorescent x-ray analysis, sample cell manufacturing method, and fluorescent x-ray analysis method

Abstract

To provide a sample cell for fluorescent X-ray analysis which is excellent in outside air shielding property and manufacturing easiness and has high measurement reproducibility.SOLUTION: The sample cell includes an inner-side unit and an outer-side unit, each of the inner-side unit and the outer-side unit includes a tubular body and an annular locking member fitted to an outer side of a film covering an opening of the tubular body, and the sample is disposed on a surface of the film covering the opening of the tubular body of the inner-side unit, the surface being on an inner side of the tubular body, the film is hermetically sealed inside the tubular body of the inner unit, and a surface of the film covering the opening of the tubular body of the inner unit on the outer side of the tubular body and a surface of the film covering the opening of the tubular body of the outer unit on the inner side of the tubular body are disposed so as to face each other, and the inner unit is hermetically sealed inside the tubular body of the outer unit.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a sample cell for X-ray fluorescence analysis, a method for producing the same, and a method for X-ray fluorescence analysis. [Background technology]

[0002] X-ray fluorescence analyzers are known as instruments for measuring the elemental composition and composition ratios of samples. In measurements using X-ray fluorescence analyzers, an appropriate jig (e.g., sample cell or sample holder) for placing the sample is generally selected depending on the properties and reactivity of the sample.

[0003] Some samples measured by X-ray fluorescence analysis can be adversely affected by exposure to the atmosphere, for example, by oxidation due to oxygen, moisture absorption, and hydrolysis due to water, which can cause changes in composition and crystalline structure through reactions with atmospheric components. Furthermore, some reactions can produce harmful substances. For example, sulfide solid electrolytes and polysulfides used in the electrode structure of next-generation solid-state batteries can react with moisture in the air to alter their properties and generate hydrogen sulfide, so they must be handled in a moisture-free inert gas atmosphere. Such samples must be sealed in a package or container to prevent exposure to the atmosphere before measurement.

[0004] When measuring powder samples, a known method is to press the sample into pellets to prevent the sample from scattering during measurement. When such samples need to be handled in an environment that is not exposed to the atmosphere, a known method is to use a sample package in which the pelletized sample is sealed in a vacuum-sealed, heat-sealed film (Non-Patent Document 1).

[0005] Another method for measuring powder samples is the loose powder method, in which the powder is used as is without being molded. A known method of X-ray fluorescence analysis using the loose powder method involves preparing a sample cell in which the sample is placed in a container whose non-measurement surface is covered with a filter or lid, and irradiating the sample with X-rays through a film surface in the sample cell that functions as an analysis window (Non-Patent Document 2). [Prior art documents] [Non-patent literature]

[0006] [Non-Patent Document 1] Rigaku Corporation "Component Analysis of Battery Materials Using Fluorescent X-rays and Measurement Methods Without Air Exposure" (Webinar, June 23, 2023) [Non-patent document 2] Rigaku Corporation "X-ray Fluorescence Analysis Sample Preparation Devices and Analysis Accessories Catalog" 32nd Edition (Published July 1, 2023) Summary of the Invention [Problem to be solved by the invention]

[0007] However, even in the case of a sample package prepared by vacuuming, a small amount of gas may remain inside the sample package. When performing X-ray fluorescence analysis by placing the sample package in a vacuum-evacuated, reduced-pressure atmosphere, the gas remaining inside the sample package expands, creating voids inside the sample package, which can cause undesired shifts in the sample position. In this case, even when measurements are performed on the sample under the same conditions, measurement reproducibility may deteriorate due to changes in the sample position over multiple measurements. Even when the environment for X-ray fluorescence analysis is changed from a reduced-pressure atmosphere to a helium atmosphere, helium molecules penetrate the film and into the sample package, expanding the internal space, which can lead to the same problem of sample misalignment due to the creation of voids.

[0008] Furthermore, if the sample is adversely affected by exposure to the atmosphere, the pressure molding of the sample and the preparation of the sample package must also be carried out in an environment that is not exposed to the atmosphere. In a glove box, which is generally used as a work environment that is not exposed to the atmosphere, the use of thick gloves makes it difficult to work, and it takes a lot of time to perform tasks such as heat welding of the film and vacuuming the inside of the welded film. In addition, there is a risk of problems such as vacuum leakage due to insufficient heat welding in the prepared sample package, resulting in a low yield in the preparation of the sample package.

[0009] Even when X-ray fluorescence analysis is performed in a vacuum using the loose powder method, the sample cell must be covered on the side opposite the measurement surface with a breathable filter or similar, which poses the problem that it cannot be used when it is necessary to keep the sample in an environment that is not exposed to the atmosphere.

[0010] An object of the present invention is to provide a sample cell for fluorescent X-ray analysis that is easy to fabricate, has excellent stable air-blocking properties, and has high measurement reproducibility. [Means for solving the problem]

[0011] In order to achieve the above object, the sample cell for X-ray fluorescence analysis of the present invention is a sample cell for X-ray fluorescence analysis consisting of an inner unit and an outer unit, wherein the inner unit and the outer unit each comprise a cylindrical body and an annular locking member that fits onto the outside of a film that covers the opening of the cylindrical body, and a sample is placed on the inner surface of the film that covers the opening of the cylindrical body of the inner unit and is hermetically sealed inside the cylindrical body of the inner unit, and the outer surface of the film that covers the opening of the cylindrical body of the inner unit is arranged so that it faces the inner surface of the cylindrical body of the outer unit, and the inner unit is hermetically sealed inside the cylindrical body of the outer unit.

[0012] In the sample cell for fluorescent X-ray analysis of the present invention, the insides of the inner unit and the outer unit are preferably filled with different or the same predetermined inert gases.

[0013] In the sample cell for fluorescent X-ray analysis of the present invention, the pressure inside the inner unit and the outer unit is preferably equal to the pressure of the atmospheric air.

[0014] In the sample cell for X-ray fluorescence analysis of the present invention, it is preferable that both ends of the cylindrical body of the inner unit and the cylindrical body of the outer unit are open, and that each of the openings is covered with a film clamped by an annular locking member that fits onto the outside of the cylindrical body of the inner unit or the cylindrical body of the outer unit.

[0015] In the sample cell for X-ray fluorescence analysis of the present invention, a member having a predetermined function can be placed between the outer surface of the cylindrical body of the film covering the opening at both ends of the cylindrical body of the inner unit opposite the opening covered by the film on which the sample is placed, and the inner surface of the cylindrical body of the film covering the opening of the cylindrical body of the outer unit opposite thereto.

[0016] In the sample cell for fluorescent X-ray analysis of the present invention, the member having a predetermined function may be an oxygen detector or a water vapor detector.

[0017] In the sample cell for fluorescent X-ray analysis of the present invention, the member having a predetermined function may be a light-shielding member that blocks external light from reaching the sample.

[0018] The sample cell for X-ray fluorescence analysis of the present invention can be provided with a film covering one or both of the openings of the cylindrical body of the inner unit, and a film covering one or both of the openings of the cylindrical body of the outer unit.

[0019] In the sample cell for X-ray fluorescence analysis of the present invention, the film covering one or both of the openings of the cylindrical body of the inner unit and the film covering one or both of the openings of the cylindrical body of the outer unit can be made of different materials and / or thicknesses.

[0020] In the sample cell for fluorescent X-ray analysis of the present invention, at least one of the films may have light-blocking properties, moisture absorption properties, or chemical resistance properties, or a combination thereof.

[0021] The method for producing a sample cell for fluorescent X-ray analysis of the present invention includes producing an inner unit and producing an outer unit, wherein producing the inner unit includes covering at least one opening of the first cylindrical body with a film sandwiched between a first cylindrical body and an annular locking member that fits on the outside of the first cylindrical body, placing a sample on the film on the inner surface of the first cylindrical body, and hermetically sealing the sample inside the first cylindrical body, and producing the outer unit includes covering at least one opening of the first cylindrical body with a film sandwiched between a second cylindrical body and an annular locking member that fits on the outside of the first cylindrical body, placing a sample on the film on the inner surface of the first cylindrical body, and hermetically sealing the sample inside the first cylindrical body. The method includes covering at least one opening of the second cylindrical body with a film sandwiched between the film and an annular locking member that fits onto the outside of the second cylindrical body, arranging the film of the inner unit and the film of the outer unit opposite each other, and hermetically sealing the inner unit inside the second cylindrical body, and it is preferable that the hermetically sealing the sample inside the first cylindrical body and the hermetically sealing the inner unit inside the second cylindrical body are performed under a pressure equal to atmospheric pressure and in a predetermined inert gas atmosphere.

[0022] In the X-ray fluorescence analysis method using the sample cell for X-ray fluorescence analysis of the present invention, it is preferable that the sample cell is placed under atmospheric pressure and the X-ray fluorescence analysis is carried out.

[0023] The sample cell for X-ray fluorescence analysis of the present invention is easy to fabricate, and by holding the sample in a double-layered sample cell, it can more reliably block out the outside air and protect the sample. Furthermore, it has high reproducibility in repeated measurements. [Brief explanation of the drawings]

[0024] [Figure 1] FIG. 2 is a longitudinal cross-sectional view of a sample cell according to an embodiment of the present invention. [Figure 2] FIG. 2 is a vertical cross-sectional view showing an inner unit of the sample cell. [Figure 3] FIG. 2 is a vertical cross-sectional view showing an outer unit of the sample cell. [Figure 4] 10 is a flowchart showing a fluorescent X-ray analysis method using the sample cell. [Figure 5A] 10A and 10B are perspective views showing the procedure for producing the sample cell. [Figure 5B] 10A and 10B are perspective views showing the procedure for producing the sample cell. [Figure 5C] 10A and 10B are perspective views showing the procedure for producing the sample cell. [Figure 5D] 10A and 10B are perspective views showing the procedure for producing the sample cell. [Figure 5E] 10A and 10B are perspective views showing the procedure for producing the sample cell. [Figure 5F] 10A and 10B are perspective views showing the procedure for producing the sample cell. [Figure 5G] 10A and 10B are perspective views showing the procedure for producing the sample cell. [Figure 5H] 10A and 10B are perspective views showing the procedure for producing the sample cell. [Figure 6] FIG. 2 is a diagram showing an outline of an X-ray fluorescence analyzer in which the sample cell is placed. [Figure 7] FIG. 10 is a longitudinal sectional view of a sample cell according to another embodiment of the present invention. [Figure 8] FIG. 10 is a longitudinal cross-sectional view of a sample cell according to yet another embodiment of the present invention. [Figure 9] FIG. 10 is a longitudinal cross-sectional view of a sample cell according to yet another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0025] A preferred embodiment of the present invention will now be described with reference to the drawings. As shown in Fig. 1, the sample cell 10 for X-ray fluorescence analysis of the present invention is a double-structured container, and is composed of an inner unit 30 that hermetically seals the sample 20, as shown in Fig. 2, and an outer unit 40 that hermetically seals the inner unit 30, as shown in Fig. 3.

[0026] <Inner unit> 2, the inner unit 30 includes a tubular body 31 and locking members 34 and 35. The tubular body 31 has a cylindrical shape with both ends open. The tubular body 31 and the locking members 34 and 35 are made of, for example, polypropylene, but may also be made of other resin materials or metal materials.

[0027] Films 32, 33 are placed over the openings of the cylindrical body 31 so as to cover them from the outside. In this state, locking members 34, 35 are fitted onto both ends of the cylindrical body 31 from the outside, and the films 32, 33 are sandwiched and fixed between the inner diameter surfaces of the locking members 34, 35 and the outer diameter surface of the cylindrical body 31. The locking members 34, 35 have an annular shape, and their inner diameter surfaces are cylindrical surfaces that fit into the outer diameter surface of the cylindrical body 31. The inner diameters of the annular locking members 34, 35 are approximately equal to the outer diameter of the cylindrical body 31, but there is a gap between them and the outer diameter of the cylindrical body 31 so that the films can be sandwiched between them.

[0028] The clamped films 32 and 33 are pulled toward the center of the axial direction of the cylindrical body 31 by the locking members 34 and 35 fitted to the cylindrical body 31. As a result, they are positioned to cover the opening of the cylindrical body 31 under tension, and the films 32 and 33 are in contact with the axial end faces of the cylindrical body 31, forming no gaps. Furthermore, any radial gaps that may occur between the cylindrical body 31 and the locking members 34 and 35 are filled by the films 32 and 33 clamped therebetween. As a result, the interior 36 of the cylindrical body 31 is sealed from the outside air by the films 32 and 33 covering the opening of the cylindrical body 31. The interior 36 of the cylindrical body 31 is filled with a predetermined inert gas corresponding to the reactivity of the sample 20, and the internal pressure is 1 atmosphere. The predetermined inert gas is, for example, dry argon gas.

[0029] The outer diameter surface of the cylindrical body 31 may not be a simple cylindrical surface, but may have a radially uneven shape at the position where the locking members 34, 35 are fitted, so that the locking members 34, 35 are stably positioned. By having the inner diameter surfaces of the locking members 34, 35 have a shape that corresponds to the uneven shape of the cylindrical body 31, the locking members 34, 35 are more stably positioned relative to the cylindrical body 31, and the films 32, 33 sandwiched between them can also stably cover the opening of the cylindrical body 31. This more reliably seals the interior 36 of the cylindrical body 31. In this case, when the locking members 34, 35 are fitted into the cylindrical body 31, a force may be applied to the locking members 34, 35 so as to push them toward the axial center of the cylindrical body 31, temporarily elastically deforming the locking members 34, 35, the cylindrical body 31, or both, so that the uneven shapes fit together.

[0030] <Sample> The sample 20 to be subjected to X-ray fluorescence analysis is placed inside the cylindrical body 31 of the inner unit 30. The sample 20 is introduced into the cylindrical body 31 from one opening of the cylindrical body 31 and placed on the inner surface of the cylindrical body 31 of the inner unit 30, on which the film 33 is placed so as to cover the other opening of the cylindrical body 31. The sample 20 is used in a powder state that is not pressed. In this embodiment, the sample 20 is a sulfide solid electrolyte powder that can react with moisture in the air when exposed to the air. The powder sample is subjected to pretreatment such as pulverization and drying, as necessary.

[0031] <Film> The material and thickness of the films 32 and 33 are selected so that they have gas barrier properties, i.e., the ability to hermetically seal the interior of the cylindrical body 31 and prevent the intrusion of gas molecules from the outside. In addition, the films 32 and 33 are preferably flexible so that they can be easily sandwiched between the locking members 34 and 35 and the cylindrical body 31. Furthermore, the film 33 on which the sample 20 is placed is preferably selected so that the primary X-rays irradiated onto the sample 20 and the secondary X-rays generated by the sample 20 in fluorescent X-ray analysis are not attenuated when passing through the film 33, and sufficient intensity is maintained for measurement.

[0032] In this embodiment, the films 32 and 33 in the inner unit 30 are made of polypropylene and have a thickness of 6 μm. As described above, the film 33 on which the sample 20 is placed is preferably X-ray transparent. Other specific film materials include, but are not limited to, Mylar, polyimide, propylene, and ultrapolyester.

[0033] It is preferable that film 32 covering the opening on the opposite side to the opening of cylindrical body 31 covered by film 33 has particularly high gas barrier properties, and other specific film materials include, but are not limited to, barrier nylon, polyester film, vinyl alcohol polymer film, biaxially oriented polypropylene, polyvinyl fluoride (PVF), tetrafluoroethylene-hexafluoropropylene copolymer film, transparent vapor-deposited polyester, polyvinylidene fluoride (PVDF), vinylidene chloride-coated biaxially oriented polypropylene, hybrid film of EVAL and nylon film, and laminate film with a five-layer structure of nylon, polyethylene, aluminum foil, polyethylene, and polyethylene.

[0034] Furthermore, in addition to gas barrier properties, the films 32 and 33 may have other functions, such as light-blocking properties, moisture absorption properties, chemical resistance, heat resistance, cold resistance, impact resistance, and moisture resistance. This allows the sample 20 to be more reliably and effectively sealed and maintain its ideal properties. For example, if the film has light-blocking properties, it can prevent the sample from being adversely affected by external light, particularly light with wavelengths in the ultraviolet region, causing deterioration of the sample. A film with light-blocking properties may be realized by the film itself being made of a light-blocking material, or by coating the film with a light-blocking paint. If the film has moisture absorption properties, moisture in the air is absorbed by the films 32 and 33 covering the cylindrical body 31 of the inner unit 30 before penetrating the interior of the inner unit 30 where the sample 20 is placed. This prevents the sample 20 from being exposed to moisture, thereby preventing deterioration of the sample 20. If the films 32, 33 are chemical resistant, it is possible to reduce the risk that undesirable substances such as volatile chemical substances will react with the films 32, 33, reducing the gas barrier properties of the films 32, 33 and making it impossible to maintain a sealed state.

[0035] <Outer unit> The outer unit 40 has a similar configuration to the inner unit 30. As shown in Fig. 3, the outer unit 40 includes a cylindrical body 41 having openings at both ends and penetrating therethrough, and annular locking members 44, 45. Films 42, 43 are arranged in the openings of the cylindrical body 41 so as to cover the respective openings, and the films 42, 43 are sandwiched and fixed between the cylindrical body 41 and the annular locking members 44, 45 that fit into the cylindrical body 41.

[0036] The inner unit 30 is disposed inside the cylindrical body 41 and is hermetically sealed by the films 42 and 43. As shown in Fig. 1, the inner unit 30 is disposed such that the outer surface of the film 33 covering the opening of the cylindrical body 31, on which the sample 20 is disposed, faces the inner surface of the film 43 of the outer unit 40 covering the opening of the cylindrical body 41.

[0037] The interior 46 of the cylindrical body 41 is filled with a predetermined inert gas. In this embodiment, the predetermined inert gas is dry argon gas. The internal pressure is 1 atmosphere. The inert gas filled in the cylindrical body 31 of the inner unit 30 and the cylindrical body 41 of the outer unit 40 may be the same gas species or different gas species.

[0038] The cylindrical body 41 and the locking members 44, 45 of the outer unit 40 are made of, for example, polypropylene, but the material and thickness can be changed, similar to the cylindrical body 31 and the locking members 34, 35 of the inner unit 30. The films 42, 43 arranged to cover the opening of the cylindrical body 41 are gas barrier films, for example, made of 6 μm-thick polypropylene. However, similar to the films 32, 33 arranged to cover the opening of the cylindrical body 31 of the inner unit 30, other materials can be selected. In particular, the film 43 arranged opposite the film 33 on which the sample is placed on the inner surface of the cylindrical body 31 preferably has X-ray transparency, similar to the film 33. The film 42 arranged to cover the opening on the opposite side of the opening of the cylindrical body 41 covered by the film 43 preferably has high gas barrier properties, similar to the film 32. The films 42, 43 do not need to be made of the same material as the films 32, 33, respectively, and may be made of different materials.

[0039] Thus, the sample 20 is held inside the sample cell 10, which has a double structure consisting of the inner unit 30 and the outer unit 40, and is doubly sealed by the films 32, 33 and 42, 43. While a single-walled container has insufficient gas barrier properties, the use of a double-walled sample cell as in this embodiment more reliably prevents outside air from entering by the double-walled films. Even if one film is damaged, the other film blocks the outside air, preventing the sample 20 from being exposed to the atmosphere. This more reliably protects the sample 20. Furthermore, for example, by using different materials and / or thicknesses for the films 32, 33 covering the opening of the inner unit 30 and the films 42, 43 covering the opening of the outer unit 40, the sample cell 10 can be provided with a combination of functions that a film can have in addition to the gas barrier properties exemplified above, such as light-blocking properties, moisture absorption properties, chemical resistance, heat resistance, cold resistance, impact resistance, and moisture resistance.

[0040] Next, with reference to FIG. 4, FIGS. 5A to 5H, and FIG. 6, a method for fabricating the sample cell 10 according to the present embodiment shown in FIGS. 1 to 3 (steps S61 to S66 in FIG. 4) and a method for X-ray fluorescence analysis using the sample cell 10 (steps S67 to S68 in FIG. 4) will be described.

[0041] The sample cell 10 is fabricated in a glove box filled with an inert gas. The inert gas is, for example, argon gas, and the gas pressure is 1 atmosphere. As a result, the interior of the sample cell 10 to be fabricated is filled with argon gas at 1 atmosphere, and the sample 20 hermetically sealed inside the sample cell 10 is placed under an inert gas atmosphere. Note that, depending on the type of inert gas selected, other devices or environments may be used instead of a glove box. For example, when dry air is selected, the sample cell 10 is fabricated in a dry room.

[0042] In fabricating the sample cell 10, the inner unit 30 is first fabricated by steps S61 to S63, which will be described below. As shown in FIG. 5A, a film 33 is placed to cover one opening of the cylindrical body 31. In this state, as shown in FIG. 5B, an annular locking member 35 is fitted to the outside of the cylindrical body 31, and the film 33 is sandwiched between the outer surface of the cylindrical body 31 and the inner surface of the locking member 35 (step S61). The locking member 35 is fitted so as to slide from one end of the cylindrical body 31 toward the axial center, pulling the film 33 toward the axial center of the cylindrical body 31. The film 33 is tightly positioned against the end face of the cylindrical body 31 in a taut state under tension, with no gap between them, and is fixed by the locking member 35. This operation is also the same when covering the opening of the cylindrical body with a film and sandwiching the film between the cylindrical body and the locking member in the following steps.

[0043] Next, as shown in Fig. 5C, the sample 20 is inserted into the cylindrical body 31 from the other opening of the cylindrical body 31 that is not yet covered with the film, and the sample 20 is placed on the inner surface 33A of the cylindrical body of the film 33 (step S62). In Fig. 5C, the set of the cylindrical body 31, the film 33, and the locking member 35 is in a state in which it is turned upside down from the state in which step S61 is completed. It is preferable that the powder sample 20 is placed by applying a force to compress it so that it is evenly placed over the entire surface of the film surface 33A.

[0044] Next, as shown in Fig. 5D, film 32 is placed so as to cover the other opening of cylindrical body 31. In this state, as shown in Fig. 5E, an annular locking member 34 is fitted onto the outside of cylindrical body 31, and film 32 is sandwiched between the outer peripheral surface of cylindrical body 31 and the inner peripheral surface of locking member 34 (step S63). As a result, sample 20 is placed in an inert atmosphere, which is the environment in which inner unit 30 is fabricated, and is hermetically sealed inside cylindrical body 31 of inner unit 30.

[0045] Next, the outer unit 40 is fabricated by steps S64 to S66 in FIG. 4. The outer unit 40 includes a cylindrical body 41 and annular locking members 44, 45. Fabrication of the outer unit 40 is also performed in a glove box, similar to the fabrication of the inner unit 30. If the inert gas sealed inside the inner unit 30 is the same as the inert gas sealed inside the outer unit 40, step S64, which will be described below, can be performed in parallel with steps S61 to S63 described above, without any order. On the other hand, if the inert gas sealed inside the outer unit 40 is a different gas species from the inert gas sealed inside the inner unit 30, it is necessary to replace the gas inside the glove box after fabrication of the inner unit 30 is completed. In this case, step S64 described below is performed after fabrication of the inner unit 30 is completed by step S63.

[0046] In manufacturing the outer unit 40, first, as shown in FIG. 5E, a film 43 is placed so as to cover one opening of the cylindrical body 41. In this state, as shown in FIG. 5F, an annular locking member 45 is fitted onto the outside of the cylindrical body 41, and the film 43 is sandwiched between the outer surface of the cylindrical body 41 and the inner surface of the locking member 45 (step S64).

[0047] Next, as shown in Fig. 5G, the inner unit 30 is inserted into the other opening of the cylindrical body 41 that is not yet covered with the film, and is placed inside the cylindrical body 41 (step S65). In Fig. 5G, the set of the cylindrical body 41, the film 43, and the locking member 45 is in a state in which it is turned upside down from the state in which step S64 is completed, and the inner unit 30 is in a state in which step S63 is completed, with the sample 20 placed on the lower side inside the cylindrical body 31 of the inner unit 30. Inside the cylindrical body 41, the outer surface of the film 33 covering the opening of the cylindrical body 31 of the inner unit 30 is placed opposite the inner surface of the film 43 covering the opening of the cylindrical body 41.

[0048] 5H, film 42 is placed so as to cover the other opening of cylindrical body 41, and annular locking member 44 is fitted to the outside of cylindrical body 41, and film 42 is sandwiched between the outer peripheral surface of cylindrical body 41 and the inner peripheral surface of locking member 44 (step S66). Through the above steps, the production of outer unit 40 is completed.

[0049] In this embodiment, as described above, step S64 can be performed in parallel with steps S61 to S63, but the order of the other steps can also be changed or they can be performed in parallel to the extent that the desired sample cell 10 can be produced.

[0050] Steps S61 and S64, which are steps before the sample 20 is placed in the inner unit 30 or the outer unit 40, may be performed outside the argon glove box (or in another environment, for example, outside the dry room in the case of a dry room). In this case, work can be performed in any environment, such as an atmospheric environment, which can further improve workability.

[0051] Next, a method for performing X-ray fluorescence analysis using the fabricated sample cell 10 will be described. In preparation for performing X-ray fluorescence analysis using the X-ray fluorescence analyzer 70 shown in FIG. 6, the sample cell 10 is set in a sample holder and placed on an automatic sample changer provided in the X-ray fluorescence analyzer 70. The sample holder with the sample cell 10 set in it is then carried by the automatic sample changer to a sample stage 81 in a sample chamber 80 (step S67). In this embodiment, the sample cell 10 is placed with the sample 20 facing downward, and primary X-rays 92 irradiating the sample 20 are irradiated from below the sample cell 10. The X-ray fluorescence analyzer 70 includes a sample chamber 80 and a spectroscopic chamber 90, each chamber being isolated by a partition wall 82 and a vacuum shutter 83.

[0052] Finally, in step S68, X-ray fluorescence analysis is performed on the sample 20. During analysis, the sample chamber 80 is maintained at atmospheric pressure, and the spectroscopic chamber 90 is evacuated to maintain a vacuum atmosphere. The vacuum shutter 83, which separates the sample chamber 80 from the spectroscopic chamber 90, is movable and is closed when the spectroscopic chamber 90 is evacuated, and is opened when analysis is performed. Even when the vacuum shutter 83 is open, the sample chamber 80 and the spectroscopic chamber 90 are isolated while being maintained at different pressures by the partition 82. The partition 82 is equipped with a partition film (not shown) that is transparent to X-rays, which allows measurement to be performed by irradiating X-rays from the spectroscopic chamber 90 to the sample chamber 80 with the sample chamber 80 at atmospheric pressure and the spectroscopic chamber 90 at vacuum pressure.

[0053] Analysis is performed by irradiating primary X-rays 92 onto a sample 20 placed in a sample cell 10 of the present invention and measuring the intensity of secondary X-rays 93, such as fluorescent X-rays, generated from the sample 20. The spectroscopic chamber 90 includes an X-ray tube 91, a slit 94, a spectroscopic element 95, and a detector 96. Primary X-rays 92 are irradiated from the X-ray tube 91 toward the sample 20 in the sample chamber 80. As described above, the partition wall 83 separating the spectroscopic chamber 90 from the sample chamber 80 is X-ray transparent. Secondary X-rays 93 are generated from the sample 20 irradiated with the primary X-rays 92. The generated secondary X-rays 93 pass through a slit 94, which limits the direction of transmission, and are dispersed by the spectroscopic element 95. The dispersed secondary X-rays are detected by the detector 96. The spectroscopic element 95 and the detector 96 are positioned at an angle that allows X-rays of the desired wavelength to be obtained, thereby obtaining the intensity of X-rays of a specific wavelength.

[0054] In this way, using the X-ray fluorescence analyzer 70, the sample 20 placed in the sample cell 10 is irradiated with primary X-rays 91, and the intensity of secondary X-rays 93 generated from the sample 20 is measured with the detector 95, thereby performing X-ray fluorescence analysis of the sample 20.

[0055] As described above, the sample cell for X-ray fluorescence analysis of this embodiment allows the sample to be measured in an atmospheric environment while being hermetically sealed in an environment that is not exposed to the atmosphere. Furthermore, by holding the sample in a double-structure sample cell, the outside air can be more reliably shut out and the sample can be protected.

[0056] Furthermore, since undesired positional deviation of the sample due to gas remaining inside or entering the sample cell does not occur, the coefficient of variation of the X-ray intensity in multiple measurements can be reduced, improving the repeatability of measurements.

[0057] Furthermore, the sample can be sealed in the sample cell using a simple process that does not involve pre-processing such as pelletizing the sample, or processes that require complicated procedures and special tools, such as heat welding or vacuuming, thereby shortening the time required to prepare the sample specimen and improving workability.

[0058] Furthermore, because the environment in which the sample is sealed is not a vacuum, even powder samples can be prepared by the loose powder method, which does not require molding such as pelleting. This allows the powder to be placed on the film as is, ensuring a large measurement area and improving measurement strength.

[0059] <Other Examples> Next, a modification of the above embodiment will be described with reference to FIGS.

[0060] Variation 1 shown in FIG. 7 differs from the above embodiment in that oxygen detector paper 47 is disposed between films 32, 42 covering the openings of cylindrical bodies 31, 41 in sample cell 10 as a component with a predetermined function. Oxygen detector paper 47 detects the presence or absence of oxygen in the environment in which it is placed and displays the result. By disposing oxygen detector paper 47 between films 32, 42, i.e., on the outer surface of film 31 covering the opening of inner unit 31, the presence and amount of oxygen in the atmosphere at the location where inner unit 30 is placed can be monitored. Since sample 20 is disposed inside inner unit 30 via films 32, 33, monitoring the environment in which inner unit 30 is placed can monitor the environment inside inner unit 30, i.e., the environment in which sample 20 is placed. If oxygen detector paper 47 does not detect oxygen, oxidation of sample 20 due to oxygen entering from the outside has not occurred. Furthermore, it is considered that nitrogen has not entered along with the oxygen in the atmosphere, and therefore, it can be said that sample 20 has not been nitrided. In this way, the condition of the sample 20 inside the sample cell 10 can be ensured by the member having a predetermined function disposed between the films 32 and 42 .

[0061] In variant example 1, it is preferable that film 42 covering the opening of cylindrical body 41 of outer unit 40 is made of a transparent or translucent material so that the detection results displayed by oxygen detection paper 47 placed inside film 42 can be visually recognized.

[0062] Moisture detection paper may be placed as a component having a predetermined function in place of oxygen detection paper 47. When moisture detection paper is placed between films 32 and 42, it can detect the presence and amount of moisture in the atmosphere at the position where inner unit 30 is placed.

[0063] Modification 2 shown in FIG. 8 differs from Modification 1 in that the member having a predetermined function is a light-shielding member 48. The light-shielding member 48 is made of a material that does not transmit light, such as black film or metal foil. The light-shielding member 48 can prevent deterioration of the sample 20 placed inside the sample cell 10 due to adverse effects of light from outside the sample cell, for example, exposure to light with a wavelength in the ultraviolet region. The light-shielding member 48 is preferably disposed between the films covering the openings of the inner unit and the outer unit so as to cover the entire opening.

[0064] 9 differs from the above embodiment in that one of the openings of the outer unit 40 is closed using a closing lid 49 having a concave, bowl-like shape instead of the film 42 and the locking member 44. The closing lid 49 can hermetically seal the inside of the outer unit 40 by fitting the recess of the closing lid 49 into the outer peripheral surface of the cylindrical body 41. A member such as a film or an O-ring that further improves the sealing performance may be sandwiched between the closing lid 49 and the cylindrical body 41.

[0065] The shape of the closing lid 49 and the method of closing the opening with the closing lid 49 are not limited to the shape shown in Fig. 9 and the method described above. For example, the closing lid 49 may be threaded on the inside of a recess in the closing lid 49 and fixed by screws to the outer circumferential surface of the cylindrical body 41, which has corresponding threads, thereby hermetically sealing the inside of the cylindrical body 41. The closing lid 49 may be disk-shaped with a cylindrical protrusion in the center, and the side of the protrusion may fit into the inner circumferential surface of the cylindrical body 41 to close the opening of the cylindrical body 41.

[0066] According to such a sealing method using a closing lid, the sample cell can be hermetically sealed through a simple process.

[0067] The sample cell of the present invention is particularly effective in wavelength dispersive X-ray fluorescence analyzers, but is not limited to this and may be used in energy dispersive X-ray fluorescence analyzers that are capable of measurement in the air atmosphere. [Explanation of symbols]

[0068] 10...Sample cell for X-ray fluorescence analysis 20...Sample 30...Inner unit 31...Cylindrical body 32, 33...Film 34,35...Locking member 40...Outer unit 41...Cylindrical body 42, 43...Film 44,45...Locking member 70...X-ray fluorescence analyzer 80...Sample chamber 90...Spectroscopy room

Claims

1. The inner unit and An X-ray fluorescence analysis sample cell comprising: an outer unit; The inner unit and the outer unit each include: A cylindrical body; an annular locking member that fits onto the outside of the film that covers the opening of the cylindrical body; Equipped with a sample is placed on an inner surface of the film covering the opening of the cylindrical body of the inner unit, and is hermetically sealed inside the cylindrical body of the inner unit; A sample cell for X-ray fluorescence analysis in which the outer surface of the cylindrical body of the inner unit and the inner surface of the cylindrical body of the outer unit are arranged to face each other, and the inner unit is hermetically sealed inside the cylindrical body of the outer unit.

2. 2. The sample cell for X-ray fluorescence analysis according to claim 1, A sample cell for X-ray fluorescence analysis, wherein the insides of the inner unit and the outer unit are filled with different or the same predetermined inert gas.

3. 2. The sample cell for X-ray fluorescence analysis according to claim 1, A sample cell for X-ray fluorescence analysis, wherein the pressure inside the inner unit and the outer unit is equal to the pressure of the atmospheric air.

4. 2. The sample cell for X-ray fluorescence analysis according to claim 1, Both ends of the cylindrical body of the inner unit and the cylindrical body of the outer unit are open, A sample cell for X-ray fluorescence analysis, wherein each of the openings is covered with a film that is clamped by an annular locking member that fits onto the outside of the cylindrical body of the inner unit or the cylindrical body of the outer unit.

5. 5. The sample cell for X-ray fluorescence analysis according to claim 4, A sample cell for X-ray fluorescence analysis in which a member having a predetermined function is placed between the outer surface of the cylindrical body of the film covering the opening on the opposite side of the opening covered by the film on which the sample is placed, and the inner surface of the cylindrical body of the outer unit that covers the opening opposite thereto.

6. 6. The sample cell for X-ray fluorescence analysis according to claim 5, A sample cell for fluorescent X-ray analysis, wherein the member having a predetermined function is an oxygen detector or a water vapor detector.

7. 6. The sample cell for X-ray fluorescence analysis according to claim 5, A sample cell for fluorescent X-ray analysis, wherein the member having a predetermined function is a light-shielding member that blocks light from outside the sample.

8. The sample cell for X-ray fluorescence analysis according to any one of claims 1 to 7, The sample cell for X-ray fluorescence analysis further comprises: a film covering one or both of the openings of the cylindrical body of the inner unit; a film covering one or both of the openings of the cylindrical body of the outer unit.

9. 9. The sample cell for X-ray fluorescence analysis according to claim 8, A sample cell for X-ray fluorescence analysis, in which a film covering one or both of the openings of the cylindrical body of the inner unit and a film covering one or both of the openings of the cylindrical body of the outer unit are made of different materials and / or thicknesses.

10. 9. The sample cell for X-ray fluorescence analysis according to claim 8, A sample cell for X-ray fluorescence analysis, wherein at least one of the films has light-blocking properties, moisture absorption properties, chemical resistance properties, or a combination thereof.

11. A method for preparing a sample cell for X-ray fluorescence analysis, comprising the steps of: The method for preparing a sample cell for X-ray fluorescence analysis comprises: making an inner unit; and creating an outer unit; Creating the inner unit comprises: covering at least one opening of the first cylindrical body with a film sandwiched between the first cylindrical body and an annular locking member fitted to the outside of the first cylindrical body; placing a sample on an inner surface of the first cylinder of the film; hermetically sealing the sample inside the first cylindrical body; Including, Creating the outer unit comprises: covering at least one opening of the second cylindrical body with a film sandwiched between the second cylindrical body and an annular locking member fitted to the outside of the second cylindrical body; disposing the film of the inner unit and the film of the outer unit facing each other; hermetically sealing the inner unit within the second cylindrical body; Including, A method for preparing a sample cell for X-ray fluorescence analysis, wherein the sample is hermetically sealed inside the first cylindrical body and the inner unit is hermetically sealed inside the second cylindrical body under a pressure equal to atmospheric pressure and in a predetermined inert gas atmosphere.

12. 11. A method for X-ray fluorescence analysis, comprising: performing X-ray fluorescence analysis on the sample placed in the sample cell for X-ray fluorescence analysis according to claim 1 under atmospheric pressure.

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