Sample cell and method of fluorescence x-ray analysis

Abstract

Provided is a sample cell and a fluorescent X-ray analysis method capable of accurately irradiating an X-ray to a surface of a sample even when the sample has a property of being volatilized by heat. A sample cell for a fluorescent X-ray analysis device has a first resin film disposed on an irradiation side of a primary X-ray, a second resin film disposed opposite the first resin film with a sample interposed therebetween, and a holding member that holds a positional relationship between the sample and the first resin film, at least a portion of the first resin film and the second resin film around an area in which the sample is disposed being bonded.

Description

Technical Field

[0001] This invention relates to a sample cell and a fluorescence X-ray analysis method. Background Technology

[0002] Fluorescence X-ray analysis apparatuses are known as devices for determining the elements contained in a sample and their concentrations. When performing measurements using a fluorescence X-ray analysis apparatus, a fixture (e.g., a sample cell or sample holder) containing the sample is typically used.

[0003] For example, Patent Document 1 discloses a sample holder that fixes the sample in a predetermined position by pressing a spring coil of a component on which the sample is disposed from the back side. Furthermore, Patent Document 2 discloses a sample bag having a window material adhered to a flat surface around a recess filled with the sample and mounted on a sample holder. Moreover, Patent Document 3 discloses a viewpoint of holding the sample between a first film and a second film and vacuum packaging it.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 10-232208

[0007] Patent Document 2: Japanese Utility Model Application Publication No. 7-5047

[0008] Patent Document 3: Utility Model Registration No. 2524760 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, as described in Patent Documents 2 and 3, by using a sample cell that hermetically seals the sample and provides an analysis window in the portion irradiated by X-rays, measurements can be performed in a vacuum environment without exposing the sample to the atmosphere. However, in cases where the sample has properties that evaporate upon heating or is a porous sample containing internal pores, gas may be generated inside the hermetically sealed sample cell, creating a space between the analysis window and the sample. Furthermore, during the hermetically sealing of the sample cell, trace amounts of gas may sometimes remain inside the sample cell, creating another space between the analysis window and the sample. Due to this space, it is possible that X-rays cannot reach the sample surface, or even if X-rays do reach the sample surface, the intensity of the measured fluorescence X-rays may decrease due to the shift in the irradiation position.

[0011] This disclosure is made in view of the above-mentioned problems, and its purpose is to provide a sample cell and a fluorescence X-ray analysis method that can accurately irradiate X-rays onto the measurement position on the sample surface even when gas is generated in the sample cell during measurement or when the sample cell expands.

[0012] Technical solutions for solving the problem

[0013] (1) One aspect of the present disclosure is a sample cell for a fluorescence X-ray analysis apparatus, characterized in that it comprises: a first resin membrane disposed on the irradiation side of a primary X-ray; a second resin membrane disposed opposite to the first resin membrane with respect to the sample; and a holding member that holds the positional relationship between the sample and the first resin membrane, wherein at least a portion of the first resin membrane and the second resin membrane are bonded around the area where the sample is disposed.

[0014] (2) In the above-described manner of the present disclosure, the holding member is characterized in that the holding member is a force-applying member that applies force to the sample toward the first resin film side.

[0015] (3) In the above-described manner of this disclosure, the force-applying component is a spring or a wave washer.

[0016] (4) In the above-described manner of this disclosure, the force-applying component is formed of a stretchable porous material.

[0017] (5) In the above-described manner of this disclosure, the characteristic is that the stretchable porous material is a sponge, silicone rubber or polyurethane.

[0018] (6) In the above-described manner of the present disclosure, the first resin membrane is provided with a hole and has an analysis window in which a thin film resin membrane is disposed.

[0019] (7) In the above-described manner of this disclosure, the thin film resin film is any one of polyimide, polypropylene, and polyethylene.

[0020] (8) In the above-described manner of the present disclosure, the first resin film and the second resin film are sealed in such a manner that they surround the sample, and the space between the first resin film and the second resin film is airtightly sealed.

[0021] (9) In the above-described manner of the present disclosure, the feature is that a linear, openable fastener is further provided on a portion of the area where the first resin film and the second resin film are bonded.

[0022] (10) In the above-described manner of the present disclosure, the retaining member is characterized as a suppressing member that suppresses the rise of internal air pressure.

[0023] (11) In the above-described manner of the present disclosure, the suppressing component is a degassing component that degasses the gas to the outside.

[0024] (12) In the above-described manner of the present disclosure, the suppressing component is characterized in that it is formed of a porous material that absorbs gas.

[0025] (13) In the above-described manner of the present disclosure, the feature is that it further comprises a flat or disc-shaped plate component that is configured to contact the force-applying component.

[0026] (14) Another aspect of the present disclosure is a fluorescence X-ray analysis method using a sample cell having a first resin film and a second resin film, characterized by comprising: a step of configuring a holding member for maintaining the positional relationship between the sample and the first resin film; a step of configuring the sample on the holding member; a step of venting the air between the first resin film and the second resin film and sealing the first resin film on the second resin film in a manner that surrounds the sample, thereby completing the bag-shaped sample cell; and a step of configuring the sample cell in a fluorescence X-ray analysis apparatus and performing fluorescence X-ray analysis, wherein the first resin film is formed of a material that transmits fluorescence X-rays generated from the sample, or has an analysis window that transmits fluorescence X-rays generated from the sample.

[0027] (15) In the above-described manner of this disclosure, the sample includes a structure in which a positive electrode component, a separator, and a negative electrode component are sequentially disposed. The fluorescence X-ray analysis method further includes: disposing a first conductive material and a second conductive material between the first resin film and the second resin film, such that one end is located outside the ends of the first resin film and the second resin film; electrically connecting the other end of the first conductive material to one of the positive electrode component and the negative electrode component, and electrically connecting the other end of the second conductive material to the other of the positive electrode component and the negative electrode component; bonding an adhesive region other than the injection port of the first resin film and the second resin film; injecting electrolyte from the injection port; bonding the adhesive region having the injection port; and applying a voltage or load to the first conductive material and the second conductive material.

[0028] Invention Effects

[0029] According to this disclosure, even if gas is generated in the sample cell or the sample cell expands during the measurement, X-rays can be accurately irradiated at the measurement location on the sample surface. Attached Figure Description

[0030] Figure 1 These are the top and bottom views of the sample cell.

[0031] Figure 2 This is a cross-sectional view of the sample cell.

[0032] Figure 3 This is a diagram showing an overview of a fluorescence X-ray analysis apparatus equipped with a sample cell.

[0033] Figure 4 This is a flowchart illustrating a fluorescence X-ray analysis method using a sample cell.

[0034] Figure 5 This is a cross-sectional view of the sample cell in a modified example.

[0035] Figure 6 This is a cross-sectional view of the sample cell in a modified example.

[0036] Figure 7 These are the top view and cross-sectional view of the sample cell in the modified example.

[0037] Figure 8 These are the top view and cross-sectional view of the sample cell in the modified example.

[0038] Figure 9 This is a flowchart illustrating a fluorescence X-ray analysis method using a modified sample cell. Detailed Implementation

[0039] Hereinafter, preferred embodiments for carrying out the present invention (hereinafter referred to as implementation methods) will be described. Figure 1 (a) is a top view of sample cell 100. Figure 1 (b) is a bottom view of sample cell 100. Figure 2 (a) and Figure 2 (b) means Figure 1 (a) and Figure 1 (b) is a cross-sectional view of section II-II. The sample cell 100 of this embodiment is a sample cell 100 for a fluorescence X-ray analysis apparatus 300, having a first resin membrane 102, a second resin membrane 104, a holding member, and a plate member 204.

[0040] The first resin film 102 is disposed on the side irradiated by the primary X-ray. Specifically, for example, the first resin film 102 is a thin film formed of resins such as aluminum laminate, polypropylene, and polyester. The material of the first resin film 102 is preferably a thermoplastic resin. The shape of the first resin film 102 is, for example, rectangular. In the case of analyzing light elements, the first resin film 102 may also have pores and an analytical window 108 in which a thin film resin film 106 is disposed. For example, Figure 1The holes shown are located in the center of the first resin membrane 102 and are circular in shape. A very thin film resin membrane 106, made of resin such as polyimide, is disposed within the holes of the first resin membrane 102 and functions as an analytical window 108 during measurement. Furthermore, the shape of the first resin membrane 102, as well as the presence, location, and shape of the holes, are arbitrary. Additionally, if the first resin membrane 102 is formed of a material that transmits X-rays, the analytical window 108 (i.e., the holes and the thin film resin membrane 106) may be omitted.

[0041] The second resin membrane 104 is disposed opposite the first resin membrane 102, with the sample 206 in between. Specifically, for example, the second resin membrane 104 is a membrane formed of the same material as the first resin membrane 102. The second resin membrane 104 may also have pores (analytical windows 108) like the first resin membrane 102, but its shape is preferably a shape corresponding to that of the first resin membrane 102. The sample 206 is, for example, in plate, film, or powder form.

[0042] At least a portion of the first resin film 102 and the second resin film 104 are bonded together around the area where the sample 206 is placed. Specifically, the first resin film 102 and the second resin film 104 are bonded together in such a way that they surround the sample 206, and the space between the first resin film 102 and the second resin film 104 is hermetically sealed. For example, in Figure 1 In the bonding area 110 shown by the dashed line, the first resin film 102 and the second resin film 104 are heat-fused together. If the first resin film 102 and the second resin film 104 are materials that are difficult to heat-fuse, heat-fusion can also be performed by sandwiching filamentous or strip-shaped thermoplastic resin. Alternatively, ultrasonic welding can be used instead of heat-fusion.

[0043] Furthermore, the area of ​​heat fusion is not limited to Figure 1 The bonding area 110 shown can also surround other locations of the sample 206 in a manner that prevents the sample 206 from extending outside the sample cell 100 during measurement. Furthermore, heat fusion can be performed in two or more steps instead of a single operation. For example, it can also be done in… Figure 1 Of the four sides of the rectangular shape shown by the dashed line, three sides are first heat-fused together, and after the sample 206 is placed, the remaining side is heat-fused together.

[0044] Furthermore, the first resin film 102 and the second resin film 104 can also be formed integrally (from a single film). In this case, in the bent single film, the side irradiated by the primary X-ray corresponds to the first resin film 102, and the opposite side corresponds to the second resin film 104. Additionally, a linear, closable fastener can be provided on a portion of the area where the first resin film 102 and the second resin film 104 are bonded. Specifically, one side of the bonding area 110 can be non-thermally bonded, and a track fastener can be provided in this area. By providing closable fasteners, the sample 206 can be easily replaced.

[0045] The retaining component maintains the positional relationship between the sample and the first resin film. Specifically, for example, the retaining component is a force-applying component that applies force to the sample 206 towards the first resin film 102. The force-applying component is disposed between the second resin film 104 and the flat plate component 204, applying force to the flat plate component 204 towards the first resin film 102. For example, Figure 2 (a) and Figure 2 The force-applying component shown in (b) is the wave washer 202. In the case where the flat plate component 204 is omitted, the force-applying component is disposed between the second resin film 104 and the sample 206. In this embodiment, the case where the holding component is the force-applying component will be mainly described.

[0046] The flat plate component 204 is a flat or disc-shaped component configured to contact the force-applying component. The sample 206 is placed between the flat plate component 204 and the first resin film 102. Preferably, the flat plate component 204 is larger than the force-applying component. Alternatively, if the sample 206 has a fixed shape, the flat plate component 204 may be omitted. In this case, the sample 206 contacts and is placed on the force-applying component.

[0047] If the sample cell 100 is irradiated with primary X-rays for an extended period, the temperature of the sample 206 will rise, and the sample 206 may volatilize due to heat. According to the sample cell 100 of this embodiment, even if gas is generated within the sample cell 100 due to heat volatilization, the sample 206 can be pressed against the first resin film 102 by the force-applying member, thus placing the sample 206 in contact with the back surface of the first resin film 102. In other words, it is possible to prevent the irradiation position of the primary X-rays from deviating from the measurement position of the sample 206 due to heat volatilization, and to accurately irradiate the measurement position with primary X-rays.

[0048] This disclosure is particularly effective in fluorescence X-ray analysis apparatuses, especially wavelength dispersive fluorescence X-ray analysis apparatuses that irradiate with high intensity X-rays. However, it is also effective when using energy dispersive fluorescence X-ray analysis apparatuses to analyze samples that easily generate gases or when the measurement time is long. The gas generated from sample 206 is, for example, gas that evaporates from sample 206. Furthermore, sample 206 may contain internal pores, and the gas in these internal pores has the property of being discharged to the outside of sample 206 by heating or the like (hereinafter referred to as a porous sample). In this case, the gas generated from sample 206 is gas that is discharged to the outside of sample 206 through the internal pores of the porous sample. Furthermore, the fluorescence X-ray analysis apparatus can be any type of top-irradiation, bottom-irradiation, or side-irradiation apparatus. Figure 3 This is a schematic diagram showing an upward-illuminated wavelength dispersive fluorescence X-ray analysis device 300 in which the sample cell 100 is positioned below the X-ray source 302. (See diagram below.) Figure 3 As shown, the wavelength dispersive fluorescence X-ray analysis device 300 includes an X-ray source 302, a sample stage 304, a spectrophotometer 306, and a detector 310.

[0049] A sample cell 100 is disposed on the sample stage 304. Furthermore, a retainer mask 312 is disposed on the sample cell 100. The retainer mask 312 has an opening, and when the sample cell 100 has an analysis window 108, the retainer mask 312 is positioned such that the opening is located at the analysis window 108 of the sample cell 100. An X-ray source 302 irradiates the surface of the sample 206 with primary X-rays. Fluorescent X-rays are emitted from the sample 206 irradiated with primary X-rays.

[0050] The spectrometer 306 disperses the fluorescent X-rays. Specifically, for example, the spectrometer 306 disperses only the fluorescent X-rays of a specific wavelength that satisfy the Bragg condition from the multiple wavelengths of fluorescent X-rays generated from the sample 206. The incident angle between the direction of propagation of the fluorescent X-rays generated from the sample 206 and the surface of the spectrometer is set as θ.

[0051] Detector 310 is, for example, a scintillation counter. Detector 310 measures the intensity of fluorescent X-rays and outputs a pulse signal with a peak value corresponding to the energy of the measured fluorescent X-rays.

[0052] The spectrometer 306 and detector 310 maintain a constant angular relationship and rotate via a goniometer (not shown). Specifically, the spectrometer rotates the spectrometer so that the incident angle θ of the fluorescent X-rays relative to the surface of the spectrometer 306 varies within a specified range. Secondary X-rays are diffracted by the spectrometer 306 and emit fluorescent X-rays satisfying the Bragg condition (i.e., fluorescent X-rays with an exit angle of θ). The detector 310 moves via the goniometer to the position where the fluorescent X-rays exiting from the spectrometer 306 at an exit angle θ are incident.

[0053] By counting the pulse signals output from detector 310 based on peak values, the wavelength dispersive fluorescence X-ray analyzer 300 obtains a spectrum representing the relationship between the intensity and energy of fluorescent X-rays. Based on this spectrum, the elements contained in sample 206 are analyzed. When analyzing only specific elements, the wavelength dispersive fluorescence X-ray analyzer 300 may also be without a goniometer, and the positions of the spectrometer 306 and detector 310 may be fixed.

[0054] As described above, by using the sample cell 100 of this embodiment, even when measuring samples that easily generate gases (e.g., gases volatilized from the sample or gases expelled from pores inside a porous sample) using a wavelength dispersive fluorescence X-ray analyzer 300 or an energy dispersive fluorescence X-ray analyzer with high X-ray intensity for extended periods, primary X-rays can be accurately irradiated onto the measurement position. Furthermore, during thermal fusion processing, gas may sometimes remain in the sample cell 100. In such cases, the residual gas expands during measurement, potentially causing a shift in the measurement position. By using the sample cell 100 of this embodiment, not only can gas generated from the sample 206 be prevented, but also gas remaining in the sample cell 100 during thermal fusion processing can prevent shifts in the measurement position.

[0055] Next, refer to Figure 4 The fluorescence X-ray analysis method using the sample cell 100 of this embodiment will be described. First, a plate component 204 is arranged on a flat surface, and a carbon ribbon is arranged on the plate component 204. Then, a sample 206 (e.g., a powdered sample) is placed on the carbon ribbon (S402). Furthermore, the carbon ribbon is arranged to prevent the detection of fluorescence X-rays caused by elements contained in the plate component 204, and may be omitted depending on the material of the plate component 204.

[0056] Next, a wave-shaped washer 202 is disposed on the second resin film 104 as a force-applying component. Then, the aforementioned flat plate component 204 (S404) is disposed on the wave-shaped washer 202.

[0057] Next, a first resin film 102, on which a thin film resin film 106 of polyimide is pre-attached at the location of the hole, is disposed on a second resin film 104 having a flat plate component 204. Then, the air between the first resin film 102 and the second resin film 104 is expelled, and the first resin film 102 is heat-fused to the second resin film 104 in a manner that surrounds the sample 206. Thus, the bag-shaped sample cell 100 is completed (S406). The heat-fusion process is performed, for example, inside a glove box.

[0058] Next, the sample cell 100 is placed in the up-illuminated wavelength dispersive fluorescence X-ray analyzer 300, and fluorescence X-ray analysis is performed (S408).

[0059] The above steps are just one example and can be modified as appropriate. For example, the order of steps in S402 and S404 is different.

[0060] Furthermore, the heat fusion process can be performed in multiple stages. Specifically, for example, firstly, an adhesive or similar agent is used to adhere the polyimide film resin film 106 to the location of the pores in the first resin film 102. Then, with the outer edges of the first resin film 102 and the second resin film 104 aligned, heat fusion is performed without surrounding the area where the sample 206 is placed. For example, only... Figure 1 The rectangular shape shown (dashed line portion) is heat-fused to three of its four sides. Next, the sample 206, plate component 204, and force-applying component are placed in the area where no heat fusion was performed (e.g., the area of ​​the remaining side). Then, the air between the first resin film 102 and the second resin film 104 is expelled, and a seal is formed around the area where the sample 206 is placed (e.g., the area of ​​the remaining side) using either heat fusion or a track fastener. Based on the above steps, by pre-preparing the first resin film 102 and the second resin film 104, which are heat-fused only in certain areas, the actual measurement process can be performed easily.

[0061] Next, refer to Figure 5 and Figure 6 Modifications to the above-described embodiments will be described. Figure 5 Modification 1 shown in (a) and Figure 5 In variation 2 shown in (b), the force-applying component differs from the embodiment described above. Specifically, Figure 5 In the modified example 1 shown in (a), the force-applying component is a spring 502. Alternatively, the force-applying component may also be formed of a stretchable porous material. Figure 5In Modification 2 shown in (b), the force-applying component is a sponge 504, which is a stretchable porous material. While a force is applied towards the first resin film 102 and the second resin film 104 in a direction opposite to them, thermal fusion is performed on the spring 502 or the sponge 504 (step S406 described above). That is, at the moment the sample cell 100 is completed, the spring 502 or the sponge 504 is in a compressed state. Therefore, if gas is generated in the sample cell 100 during measurement, the sample 206 can be forced towards the first resin film 102. Thus, similar to the embodiment described above, the primary X-ray can be accurately irradiated at the measurement location. Furthermore, the stretchable porous material can be any component other than a sponge, as long as it can force the sample 206 towards the first resin film 102. For example, the stretchable porous material can be silicone rubber or polyurethane, etc.

[0062] Figure 6 Modification 3 shown in (a) and Figure 6 Modification 4 shown in (b) differs from the above embodiment in that the retaining member is a suppressing member that suppresses the rise in gas pressure inside the sample cell 100. Specifically, for example, the retaining member may also be a suppressing member formed of a porous material that absorbs gas. Figure 6 In Modification 3 shown in (a), the sample cell 100 includes a porous ceramic 602 for absorbing gas, which replaces the force-applying component. The porous material for absorbing gas can be a porous polymer. In the event of gas generation within the vacuum-maintained sample cell 100 during measurement, or in the event of residual gas within the sample cell 100, the gas is absorbed into the tiny pores inside the porous ceramic 602. Therefore, since the expansion of the sample cell 100 can be suppressed, it is possible to prevent the irradiation position of the primary X-ray from shifting from the measurement position of the sample 206 due to gas generated by thermal volatilization or residual gas. Figure 6 The sample cell 100 shown in (a) does not contain a force-applying component, but a force-applying component may be provided above or below the porous ceramic 602.

[0063] Figure 6 The sample cell 100 in Modification 4 shown in (b) includes a degassing component 604, which serves as a holding member to degas the gas to the outside. The degassing component 604 is, for example, a check valve. In the event that gas is generated within the sample cell 100 during measurement, or in the event that gas remains within the sample cell 100, the degassing component 604 discharges the gas to the outside of the sample cell 100. Therefore, since the expansion of the sample cell 100 can be suppressed, it is possible to prevent the irradiation position of the primary X-ray from shifting from the measurement position of the sample 206 due to gas generated by thermal evaporation or residual gas. Figure 6 As shown in (b), the sample cell 100 may include a force-applying component in addition to the degassing component 604, or the force-applying component may be omitted.

[0064] Furthermore, the sample 206 inside the sample cell 100 can contain not only samples composed solely of the objects to be analyzed, but also additional components that are not objects to be analyzed. For example, the sample 206 may include a positive electrode component 702, a separator 704, and a negative electrode component 706. The sample cell 100 can also be sealed with the terminals (the ends of the conductive material described later) of the positive electrode component 702 and the negative electrode component 706 led out from the sample cell 100, and these terminals can be connected to a charging and discharging device, allowing the sample cell 100 to function as a battery unit (rechargeable battery) and to perform measurements. Specifically, in Figure 7 (a) to Figure 7 Modification 5 shown in (c) and Figure 8 (a) to Figure 8 In Modification 6 shown in (c), sample 206 together with the first resin film 102 and the second resin film 104 constitutes a battery cell. Hereinafter, the positive electrode component 702 and the negative electrode component 706, or both of them combined, are also referred to as electrode components. Figure 7 (a) is a top view of sample cell 100 of modified example 5. Figure 7 (b) means Figure 7 (a) Schematic diagram of section VII-VII, Figure 7 (c) represents Figure 7 (a) Schematic diagram of section VII'-VII'. Figure 8 (a) is a top view of the sample cell 100 of modified example 6. Figure 8 (b) means Figure 8 (a) A diagram of section VIII-VIII. Figure 8 (c) represents Figure 8 (a) A diagram of section VIII'-VIII'.

[0065] Sample 206 in Modifications 5 and 6 includes a structure in which a positive electrode component 702, a separator 704, and a negative electrode component 706 are arranged sequentially. Specifically, the positive electrode component 702 has a structure in which a positive electrode active material of about 100 micrometers, such as a metal oxide, is coated on a metal foil that serves as a current collector. The separator 704 is a component that isolates the positive electrode component 702 and the negative electrode component 706 and ensures ion conductivity between the positive electrode component 702 and the negative electrode component 706. The negative electrode component 706 has a structure in which a negative electrode active material of about 100 micrometers, such as graphite, is coated on a metal foil that serves as a current collector. Furthermore, an electrolyte 712 is filled between the first resin film 102 and the second resin film 104.

[0066] The sample cell 100 of Modification 5 has an analytical window 108, but the sample cell 100 of Modification 6 differs from that of Modification 5 in that it does not have an analytical window 108. Modification 5 and Modification 6 are the same in all aspects except for the presence or absence of the analytical window 108. Furthermore, not limited to Modification 5, the analytical window 108 may also be omitted in the sample cells 100 shown in the above embodiments and Modifications 1 to 4.

[0067] Figure 9 This is a flowchart illustrating the fluorescence X-ray analysis method using the sample cell 100 of Modified Example 5. In the case where the sample cell 100 has a structure with an analysis window 108, a thin polyimide resin film 106 is pre-attached to the first resin film 102 at the location of the hole.

[0068] First, a portion of the bonding area 110 is bonded together with the conductive material (S902). Specifically, for example, as shown in... Figure 7 As shown in (a), conductive material is sandwiched between one side (or two sides) of the first resin film 102 and the second resin film 104, and the bonding area 110, including one to three sides of the side containing the conductive material, is thermally fused together. When using the integrally formed first resin film 102 and second resin film 104, the bent portion corresponds to the first resin film 102, and the other portion corresponds to the second resin film 104. In S902, the bonding area is preferably two adjacent sides.

[0069] For example, the first conductive material 708 and the second conductive material 710 are disposed between the first resin film 102 and the second resin film 104, such that one end is located on one side of the first resin film 102. Figure 7 The outer side of the upper edge in (a). At this time, the first conductive material 708 is configured such that when the sample 206 is configured, its other end is located in contact with the positive electrode component 702 (or the negative electrode component 706). In addition, the second conductive material 710 is configured such that its other end is located in contact with the negative electrode component 706 (or the positive electrode component 702). The first conductive material 708 and the second conductive material 710 are thermally bonded in the areas that overlap with the bonding area 110, respectively, by an adhesive sealant (not shown) in a state separated by the first resin film 102 and the second resin film 104.

[0070] In addition, such as Figure 7As shown in (a), the first conductive material 708 and the second conductive material 710 can be arranged on the same side in a manner that does not overlap when viewed from above, or they can be arranged such that one end of each is located outside a different side. Furthermore, if the first conductive material 708 and the second conductive material 710 are electrically separated, they can also be arranged in a position that overlaps when viewed from above. Moreover, the first conductive material 708 and the second conductive material 710 can be formed of any conductive material.

[0071] Next, a sample 206 and a force-applying component are positioned between the first resin membrane 102 and the second resin membrane 104 (S904). Specifically, for example, through step S902, the first resin membrane 102 and the second resin membrane 104 are bonded together on adjacent sides. The sample 206 and the force-applying component are placed from the unbonded portion of the first resin membrane 102 and the second resin membrane 104. The sample 206 includes a structure in which a positive electrode component 702, a separator 704, and a negative electrode component 706 are arranged in sequence.

[0072] At this time, with sample 206 on one side of the first resin membrane 102 and the force-applying component on one side of the second resin membrane 104, sample 206 and the force-applying component are placed between the first resin membrane 102 and the second resin membrane 104. The force-applying component is, for example, a wave-shaped washer 202. When the positive electrode component 702 is the object of analysis, the positive electrode component 702 is disposed on one side of the first resin membrane 102. On the other hand, when the negative electrode component 706 is the object of analysis, the negative electrode component 706 is disposed on one side of the first resin membrane 102.

[0073] Furthermore, in S904, the other end of the first conductive material 708 is positioned between one of the positive electrode component 702, the negative electrode component 706, and the first resin film 102 or the force-applying component. This other end of the first conductive material 708 is electrically connected to one of the electrode components. Similarly, the other end of the second conductive material 710 is positioned between the other end of the positive electrode component 702, the negative electrode component 706, and the second resin film 104 or the force-applying component. This other end of the second conductive material 710 is electrically connected to one of the electrode components. Furthermore, if the sample 206 is thin and cannot maintain a flat shape on the force-applying component, a flat plate component 204 may be positioned between the force-applying component and the sample 206. In this case, the conductive material is positioned to be held between the electrode component and the flat plate component 204.

[0074] Next, a portion of the bonding area 110 is bonded (S906). Specifically, the area of ​​the bonding area 110 other than the injection port is thermally fused. In this modified example 5, Figure 7The area on the right side of the bonding area 110 shown in (a) is heat-fused. This step is not required if the sample is prepared with the three sides bonded first (S906).

[0075] Next, electrolyte 712 is injected (S908). Through step S906, the first resin film 102 and the second resin film 104 form a bag-like structure where the three sides (left, top, and right) of the bonding area 110 are bonded together, with only the injection port open. In S908, electrolyte 712 is injected from the injection port ( Figure 7 Electrolyte 712 is injected into the lower region of the bonding area 110 shown in (a). Furthermore, Figure 7 (b) and Figure 7 (c) emphasizes that the sample cell 100 is in an expanded state, but the actual amount of electrolyte 712 may be less than that shown in the figure.

[0076] Next, the remaining area of ​​the bonding area 110 is bonded (S910). Specifically, for example, similar to S406, the air between the first resin film 102 and the second resin film 104 is expelled, and one side of the bonding area 110 with the injection port is bonded ( Figure 7 The lower region of the bonding area 110 shown in (a) is heat-fused. Thus, the bag-shaped sample cell 100 is completed.

[0077] Next, the sample cell 100 is arranged in the fluorescence X-ray analysis apparatus, and the conductive material is energized (S912). Specifically, for example, the sample cell 100 is arranged in an up-illuminated wavelength dispersive fluorescence X-ray analysis apparatus 300, and a voltage or load is applied to the first conductive material 708 and the second conductive material 710 to allow current to flow. In Modification 5, the sample cell 100 is a battery cell with charge and discharge functions. Therefore, when a voltage is applied to the first conductive material 708 and the second conductive material 710, the battery cell is in a charging state. On the other hand, when a load is applied to the first conductive material 708 and the second conductive material 710, the battery cell is in a discharging state.

[0078] Finally, the sample cell 100 is irradiated with primary X-rays, and fluorescence X-ray analysis is performed (S914). Specifically, if a voltage is applied to the first conductive material 708 and the second conductive material 710 in S912, elemental analysis can be performed on the positive electrode component 702 or the negative electrode component 706 in the charging state. Furthermore, if a load is applied to the first conductive material 708 and the second conductive material 710 in S912, elemental analysis can be performed on the positive electrode component 702 or the negative electrode component 706 in the discharging state. That is, the operation number of the battery cell can be measured.

[0079] During charging and discharging, battery cells sometimes generate bubbles inside the electrolyte 712. According to this modified example, even if bubbles are generated, the positive electrode component 702 or the negative electrode component 706 exerts force on the first resin film 102 side. Therefore, similar to the embodiment described above, primary X-rays can be accurately irradiated at the measurement location of the positive electrode component 702 or the negative electrode component 706.

[0080] In Modifications 5 and 6, examples are shown where the retaining member is a force-applying member; however, the retaining member can be a restraining member, or the retaining member can include both a force-applying member and a restraining member. Furthermore, the bonding sequence of the bonding areas 110 shown in S902 to S910 is one example, and other sequences are also possible as long as a battery cell can be formed.

[0081] Explanation of reference numerals in the attached figures

[0082] 100 Sample cell, 102 First resin membrane, 104 Second resin membrane, 106 Thin film resin membrane, 108 Analysis window, 110 Bonding area, 202 Waveform gasket, 204 Flat plate component, 206 Sample, 300 Wavelength dispersive fluorescence X-ray analysis device, 302 X-ray source, 304 Sample stage, 306 Spectrometer element, 310 Detector, 312 Holder mask, 502 Spring, 504 Sponge, 602 Porous ceramic, 604 Degassing component, 702 Positive electrode component, 704 Separator, 706 Negative electrode component, 708 First conductive material, 710 Second conductive material, 712 Electrolyte.

Claims

1. A sample cell for a fluorescence X-ray analysis apparatus, characterized in that, have: The first resin film is disposed on the side irradiated by the primary X-ray; A second resin membrane, disposed opposite to the first resin membrane with respect to the sample in between; and A retaining component that maintains the positional relationship between the sample and the first resin film. At least a portion of the first resin film and the second resin film are bonded together around the area where the sample is disposed. The retaining component is disposed between the first resin film and the second resin film.

2. The sample cell according to claim 1, characterized in that, The holding component is a force-applying component that applies force to the sample toward the first resin film.

3. The sample cell according to claim 2, characterized in that, The force-applying component is a spring or a wave washer.

4. The sample cell according to claim 2, characterized in that, The force-applying component is formed of a stretchable porous material.

5. The sample cell according to claim 4, characterized in that, The expandable porous material is a sponge, silicone rubber, or polyurethane.

6. The sample cell according to claim 1 or 2, characterized in that, The first resin membrane has pores and an analysis window in which a thin film resin membrane is disposed.

7. The sample cell according to claim 6, characterized in that, The thin film resin film is any one of polyimide, polypropylene, and polyethylene.

8. The sample cell according to claim 1 or 2, characterized in that, The first resin film and the second resin film are sealed in such a way that they surround the sample. The space between the first resin film and the second resin film is airtightly sealed.

9. The sample cell according to claim 1 or 2, characterized in that, A portion of the area where the first resin film and the second resin film are bonded also has a linear, closable fastener.

10. The sample cell according to claim 1, characterized in that, The retaining component is a suppressing component that inhibits the rise of internal air pressure.

11. The sample cell according to claim 10, characterized in that, The suppression component is a degassing component that degasses the gas to the outside.

12. The sample cell according to claim 10, characterized in that, The suppression component is formed of a porous material that absorbs gas.

13. The sample cell according to claim 1 or 2, characterized in that, It also has a flat or disc-shaped plate component configured to contact the retaining component.

14. A fluorescence X-ray analysis method, using a sample cell having a first resin membrane and a second resin membrane, characterized in that, include: The step of configuring a holding component for maintaining the positional relationship between the sample and the first resin film; The step of placing the sample on the holding component; The air between the first resin membrane and the second resin membrane is expelled, and the first resin membrane is sealed on the second resin membrane in such a way that it surrounds the sample, thus completing the step of making the bag-shaped sample cell; as well as The steps involve configuring the sample cell in a fluorescence X-ray analysis device and performing fluorescence X-ray analysis. The first resin film is formed of a material that transmits fluorescent X-rays generated from the sample, or has an analytical window that transmits fluorescent X-rays generated from the sample. The retaining component is disposed between the first resin film and the second resin film.

15. The fluorescence X-ray analysis method according to claim 14, characterized in that, The sample comprises a structure consisting of a positive electrode component, a separator, and a negative electrode component arranged sequentially. The fluorescence X-ray analysis method further includes: The step of disposing a first conductive material and a second conductive material between the first resin film and the second resin film, such that one end is located outside the ends of the first resin film and the second resin film; The steps are as follows: electrically connecting the other end of the first conductive material to one of the positive electrode component and the negative electrode component, and electrically connecting the other end of the second conductive material to the other of the positive electrode component and the negative electrode component; The step of bonding the bonding area other than the injection ports of the first resin film and the second resin film; The step of injecting electrolyte from the injection port; The step of bonding the bonding area having the injection port; and The step of applying voltage or load to the first conductive material and the second conductive material.

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