Sample cell and fluorescent X-ray analysis method

Abstract

Provided are a sample cell and a fluorescent X-ray analysis method capable of accurately irradiating the surface of a sample with X-rays even when the sample has a property of volatilizing by heat. This sample cell is to be used in a fluorescent X-ray analysis device and comprises: a first resin film disposed on the side from which a primary X-ray is emitted; a second resin film disposed so as to face the first resin film with a sample therebetween; and a holding member that holds a positional relationship between the sample and the first resin film. The first resin film and the second resin film are at least partially bonded at the periphery of a region where the sample is disposed.

Description

Technical Field

[0001] The present invention relates to a sample cell and a fluorescent X-ray analysis method.

Background Art

[0002] As an apparatus for measuring elements contained in a sample and the concentration of the elements, a fluorescent X-ray analyzer is known. When performing measurement using a fluorescent X-ray analyzer, it is common to use a jig (for example, a sample cell or a sample holder) on which a sample is placed.

[0003] For example, Patent Document 1 below discloses a sample holder that fixes a sample at a predetermined position by a spring coil that presses a member on which the sample is placed from the back side. Further, Patent Document 2 below discloses a sample pack that is provided with a window material adhered to a flat surface around a recess filled with a sample and is attached to a sample holder. Further, Patent Document 3 below discloses a point of sandwiching a sample between a first film and a second film and vacuum-packing it.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] By the way, as described in Patent Document 2 and Patent Document 3, by using a sample cell in which a sample is hermetically sealed and an analysis window is provided in a portion irradiated with X-rays, the sample can be measured in a vacuum environment without being exposed to the atmosphere. However, when the sample has the property of volatilizing due to heat or when it is a porous sample containing pores inside, gas is generated inside the hermetically sealed sample cell, creating a space between the analysis window and the sample. Also, in the process of hermetically sealing the sample cell, a small amount of gas may remain inside the sample cell, creating a space between the analysis window and the sample. The occurrence of such a space may prevent X-rays from irradiating the sample surface, or even if X-rays are irradiated on the sample surface, the irradiation position may shift and the intensity of the fluorescent X-rays measured may decrease.

[0006] The present disclosure has been made in view of the above problems, and an object thereof is to provide a sample cell and a fluorescent X-ray analysis method capable of accurately irradiating X-rays to the measurement position on the sample surface even when gas is generated inside the sample cell or when the sample cell expands during measurement.

Means for Solving the Problems

[0007] (1) A sample cell according to one aspect of the present disclosure is a sample cell used in a fluorescent X-ray analyzer, and includes a first resin film disposed on the irradiation side of primary X-rays, a second resin film disposed opposite to the first resin film with the sample therebetween, and a holding member that holds the positional relationship between the sample and the first resin film, wherein at least a part of the periphery of the region where the sample is disposed is adhered between the first resin film and the second resin film.

[0008] (2) In the above aspect of the present disclosure, the holding member is a biasing member that biases the sample toward the first resin film side.

[0009] (3) In the above aspect of the present disclosure, the biasing member is a spring or a wave washer.

[0010] (4) In the above aspect of the present disclosure, the biasing member is formed of a porous material that expands and contracts.

[0011] (5) In the above aspect of the present disclosure, the porous material that expands and contracts is characterized by being sponge, silicone rubber, or urethane.

[0012] (6) In the above aspect of the present disclosure, the first resin film has an analysis window provided with holes and a thin film resin film disposed in the holes.

[0013] (7) In the above aspect of the present disclosure, the thin film resin film is any one of polyimide, polypropylene, and polyethylene.

[0014] (8) In the above aspect of the present disclosure, the first resin film and the second resin film are sealed so as to surround the sample, and the space between the first resin film and the second resin film is hermetically sealed.

[0015] (9) In the above aspect of the present disclosure, further, a linear openable and closable fastener is provided in a part of the region where the first resin film and the second resin film are adhered.

[0016] (10) In the above aspect of the present disclosure, the holding member is a suppressing member that suppresses an increase in internal air pressure.

[0017] (11) In the above aspect of the present disclosure, the suppressing member is a degassing member that degasses gas to the outside.

[0018] (12) In the above aspect of the present disclosure, the suppressing member is formed of a porous material that absorbs gas.

[0019] (13) In the above aspect of the present disclosure, further, it is characterized by having a flat or dish-shaped flat plate member disposed in contact with the biasing member.

[0020] (14) A fluorescent X-ray analysis method according to another aspect of the present disclosure is a fluorescent X-ray analysis method using a sample cell having a first resin film and a second resin film, the method including the steps of arranging a holding member for holding the positional relationship between the sample and the first resin film, arranging the sample on the holding member, sealing the first resin film to the second resin film so as to surround the periphery of the sample while discharging the air between the first resin film and the second resin film to complete the pouch-shaped sample cell, and arranging the sample cell in a fluorescent X-ray analyzer to perform fluorescent X-ray analysis, wherein the first resin film is formed of a material that transmits fluorescent X-rays generated from the sample or has an analysis window that transmits fluorescent X-rays generated from the sample.

[0021] (15) In the above aspect of the present disclosure, the sample includes a configuration in which a positive electrode member, a separator, and a negative electrode member are arranged in this order, and a first conductive material and a second conductive material are arranged between the first resin film and the second resin film such that one end portion is located outside the end portions of the first resin film and the second resin film, and the other end portion of the first conductive material is electrically connected to one of the positive electrode member and the negative electrode member, and the other end portion of the second conductive material is electrically connected to the other of the positive electrode member and the negative electrode member, and an adhesive region excluding the injection port of the first resin film and the second resin film is adhered, and an electrolytic solution is injected from the injection port, and the adhesive region having the injection port is adhered, and a voltage or a load is applied to the first conductive material and the second conductive material.

Advantages of the Invention

[0022] According to the present disclosure, even when gas is generated in the sample cell during measurement or when the sample cell expands, X-rays can be accurately irradiated to the measurement position on the sample surface.

Brief Description of the Drawings

[0023]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Modes for Carrying Out the Invention

[0024] Hereinafter, preferred embodiments for carrying out the present invention (hereinafter referred to as embodiments) will be described. FIG. 1(a) is a plan view of the sample cell 100, and FIG. 1(b) is a bottom view of the sample cell 100. FIGS. 2(a) and 2(b) are diagrams showing the II-II cross section of FIGS. 1(a) and 1(b). The sample cell 100 according to the present embodiment is a sample cell 100 used in a fluorescence X-ray analyzer 300, and includes a first resin film 102, a second resin film 104, a holding member, and a flat plate member 204.

[0025] The first resin film 102 is disposed on the side irradiated with the primary X-rays. Specifically, for example, the first resin film 102 is a thin film formed of a resin such as an aluminum laminate, polypropylene, or 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. When analyzing light elements, the first resin film 102 may have an analysis window 108 provided with holes and having a thin film resin film 106 disposed in the holes. For example, the holes shown in FIG. 1 are provided in the central portion of the first resin film 102 and have a round shape. A very thin resin film 106 made of a resin such as polyimide is disposed in the holes provided in the first resin film 102 and functions as the analysis window 108 during measurement. Note that the shape of the first resin film 102, the presence or absence of holes, the position, and the shape are arbitrary. Further, when the first resin film 102 is formed of a material that transmits X-rays, the analysis window 108 (that is, the holes and the thin film resin film 106) may be omitted.

[0026] The second resin film 104 is disposed opposite to the first resin film 102 with the sample 206 interposed therebetween. Specifically, for example, the second resin film 104 is a film formed of the same material as the first resin film 102. The second resin film 104 may have holes (analysis window 108) similar to those of the first resin film 102, but the outer shape is preferably a shape corresponding to that of the first resin film 102. The sample 206 is, for example, plate-shaped, film-shaped, or powder-shaped.

[0027] The first resin film 102 and the second resin film 104 are adhered at least partially around the area where the sample 206 is placed. Specifically, the first resin film 102 and the second resin film 104 are adhered so as to 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 the adhesion area 110 shown by the dashed line in FIG. 1, the first resin film 102 and the second resin film 104 are heat-sealed. When the first resin film 102 and the second resin film 104 are made of materials that are difficult to heat-seal, they may be heat-sealed with a filamentous or tape-shaped thermoplastic resin interposed therebetween. Also, ultrasonic sealing may be used instead of heat-sealing.

[0028] Note that the area to be heat-sealed is not limited to the adhesion area 110 shown in FIG. 1, and may be other positions as long as the sample 206 is surrounded so that the sample 206 does not come out of the sample cell 100 during measurement. Also, the heat-sealing may be performed in two or more steps instead of one step. For example, among the four sides of the rectangular dashed line portion shown in FIG. 1, three sides may be heat-sealed first, and the remaining one side may be heat-sealed after the sample 206 is placed.

[0029] Furthermore, the first resin film 102 and the second resin film 104 may be integrally formed (by a single film). In this case, among the single folded film, the side irradiated with the primary X-ray corresponds to the first resin film 102, and the opposite side corresponds to the second resin film 104. Also, a linear openable and closable fastener may be provided in a part of the area where the first resin film 102 and the second resin film 104 are adhered. Specifically, one side of the adhesion area 110 may not be heat-sealed, and a rail fastener may be provided in this area. By providing an openable and closable fastener, the sample 206 can be easily exchanged.

[0030] The holding member holds the positional relationship between the sample and the first resin film. Specifically, for example, the holding member is a biasing member that biases the sample 206 toward the first resin film 102. The biasing member is disposed between the second resin film 104 and the flat member 204, and biases the flat member 204 toward the first resin film 102. For example, the biasing member shown in FIGS. 2(a) and 2(b) is a wave washer 202. In the case of a configuration in which the flat member 204 is omitted, the biasing member is disposed between the second resin film 104 and the sample 206. In the present embodiment, the case where the holding member is mainly a biasing member will be mainly described.

[0031] The flat member 204 is a flat or dish-shaped member disposed in contact with the biasing member. The sample 206 is placed between the flat member 204 and the first resin film 102. The flat member 204 preferably has a shape larger than that of the biasing member. Also, when the sample 206 has a fixed shape, the flat member 204 may be omitted. In this case, the sample 206 is placed in contact with the biasing member.

[0032] When the sample cell 100 is irradiated with the primary X-ray for a long time, the temperature of the sample 206 rises, and there is a risk that the sample 206 will volatilize due to heat. According to the sample cell 100 according to the present embodiment, even if gas is generated in the sample cell 100 due to thermal volatilization, the biasing member biases the sample 206 toward the first resin film 102, so that the sample 206 can be placed in contact with the back surface of the first resin film 102. That is, 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 thermal volatilization, and to accurately irradiate the primary X-ray at the measurement position.

[0033] The present disclosure is particularly effective in wavelength-dispersive X-ray fluorescence spectrometers with high-intensity irradiated X-rays among X-ray fluorescence spectrometers, but is also effective when measuring samples that are likely to generate gas using an energy-dispersive X-ray fluorescence spectrometer or when the measurement time is long. The gas generated from the sample 206 is, for example, a gas volatilized from the sample 206. In addition, there are also samples 206 that contain pores inside and have the property that the gas in the internal pores is discharged to the outside of the sample 206 by heating or the like (hereinafter referred to as porous samples). In such a case, the gas generated from the sample 206 is the gas discharged from the internal pores of the porous sample to the outside of the sample 206. Further, the X-ray fluorescence spectrometer may be any of an upper-surface irradiation type, a lower-surface irradiation type, and a side-surface irradiation type. FIG. 3 is a diagram showing an outline of an upper-surface irradiation type wavelength-dispersive X-ray fluorescence spectrometer 300 in which a sample cell 100 is arranged below an X-ray source 302. As shown in FIG. 3, the wavelength-dispersive X-ray fluorescence spectrometer 300 includes an X-ray source 302, a sample stage 304, a spectroscopic element 306, and a detector 310.

[0034] The sample stage 304 has the sample cell 100 arranged thereon. Further, a holder mask 312 is arranged on the sample cell 100. The holder mask 312 is provided with an opening, and when the sample cell 100 has an analysis window 108, the holder mask 312 is arranged such that the opening is located at the analysis window 108 of the sample cell 100. The 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 the primary X-rays.

[0035] The spectroscopic element 306 spectroscopically analyzes the fluorescent X-rays. Specifically, for example, the spectroscopic element 306 spectroscopically analyzes only the fluorescent X-rays of a specific wavelength that satisfy the Bragg conditional equation among the fluorescent X-rays of a plurality of wavelengths generated from the sample 206. Let the incident angle formed between the direction in which the fluorescent X-rays generated from the sample 206 travel and the surface of the spectroscopic element be θ.

[0036] The detector 310 is, for example, a scintillation counter. The detector 310 measures the intensity of the fluorescent X-rays and outputs a pulse signal having a pulse height value corresponding to the energy of the measured fluorescent X-rays.

[0037] The spectroscopic element 306 and the detector 310 rotate while maintaining a certain angular relationship by means of a goniometer (not shown). Specifically, the spectroscopic element 306 rotates by means of a goniometer so that the incident angle θ of the fluorescent X-ray with respect to the surface of the spectroscopic element 306 changes within a predetermined range. The secondary X-ray is diffracted by the spectroscopic element 306, and a fluorescent X-ray (i.e., the fluorescent X-ray with the emission angle θ) that satisfies the Bragg's conditional formula is emitted from the spectroscopic element 306. The detector 310 moves to a position where the fluorescent X-ray emitted at the emission angle θ from the spectroscopic element 306 is incident by means of a goniometer.

[0038] By counting the pulse signal output from the detector 310 according to the pulse height value, the wavelength-dispersive fluorescent X-ray analyzer 300 obtains a spectrum representing the relationship between the intensity and energy of the fluorescent X-ray. Based on the spectrum, an analysis of the elements contained in the sample 206 is performed. When only a specific element is analyzed, the wavelength-dispersive fluorescent X-ray analyzer 300 does not have a goniometer, and the positions of the spectroscopic element 306 and the detector 310 may be fixed.

[0039] As described above, by using the sample cell 100 according to the present embodiment, even when measuring a sample in which gas (for example, gas volatilized from the sample or gas discharged from the pores inside the porous sample) is likely to be generated for a long time using a wavelength-dispersive fluorescent X-ray analyzer 300 with a high intensity of irradiated X-ray or an energy-dispersive fluorescent X-ray analyzer, the primary X-ray can be accurately irradiated to the measurement position. Also, when performing the heat fusion treatment, gas may remain in the sample cell 100. In this case, the remaining gas may expand during measurement, and there is a risk that the measurement position may shift. By using the sample cell 100 according to the present embodiment, it is possible to prevent the measurement position from shifting not only due to the gas generated from the sample 206 but also due to the gas remaining in the sample cell 100 during the heat fusion treatment.

[0040] Next, while referring to FIG. 4, a fluorescence X-ray analysis method using the sample cell 100 according to this embodiment will be described. First, the flat plate member 204 is placed on a flat surface, and a carbon tape is placed on the flat plate member 204. Then, a sample 206 (for example, a powdery sample) is placed on the carbon tape (S402). Note that the carbon tape is arranged to prevent fluorescence X-rays caused by the elements contained in the flat plate member 204 from being detected, and may be omitted depending on the material of the flat plate member 204.

[0041] Next, a wave washer 202 is arranged as a biasing member on the second resin film 104. Then, the flat plate member 204 is arranged on the wave washer 202 (S404).

[0042] Next, a first resin film 102 with a polyimide thin film resin film 106 pre-attached at the hole positions is arranged on the second resin film 104 on which the flat plate member 204 is arranged. Then, while exhausting the air between the first resin film 102 and the second resin film 104, the first resin film 102 is heat-sealed to the second resin film 104 so as to surround the sample 206. Thereby, the pouch-type sample cell 100 is completed (S406). The heat-sealing process is performed, for example, in a glove box.

[0043] Next, the sample cell 100 is arranged in an upper surface irradiation type wavelength dispersive fluorescence X-ray analyzer 300, and fluorescence X-ray analysis is performed (S408).

[0044] The above procedure is an example and may be changed as appropriate. For example, the steps of S402 and S404 may be in any order.

[0045] Also, the heat-sealing procedure may be performed in multiple steps. Specifically, for example, first, a polyimide thin-film resin film 106 is attached to the positions of the holes in the first resin film 102 using an adhesive or the like. Then, heat-sealing is performed in such a manner that it does not surround the region where the sample 206 is placed in a state where the outer edges of the first resin film 102 and the second resin film 104 are aligned. For example, heat-sealing is performed only at the positions of three sides out of the four sides of the rectangular dashed-line portion shown in FIG. 1. Next, the sample 206, the flat plate member 204, and the biasing member are arranged from the location where heat-sealing has not been performed (for example, the region of the remaining one side). Then, while discharging the air between the first resin film 102 and the second resin film 104, heat-sealing or sealing with a rail fastener is performed so as to surround the region where the sample 206 is placed (for example, the region of the remaining one side). According to the above procedure, by preparing in advance the first resin film 102 and the second resin film 104 that are heat-sealed only in a certain region, the procedure for actual measurement can be simplified.

[0046] Next, a modified example of the above embodiment will be described with reference to FIGS. 5 and 6. In Modified Example 1 shown in FIG. 5(a) and Modified Example 2 shown in FIG. 5(b), the biasing member is different from that in the above embodiment. Specifically, the biasing member in Modified Example 1 shown in FIG. 5(a) is a spring 502. Further, the biasing member may be formed of a porous material that expands and contracts. The biasing member in Modified Example 2 shown in FIG. 5(b) is a sponge 504 which is a porous material that expands and contracts. Heat fusion is performed (step S406 above) in a state where a force is applied to the spring 502 or the sponge 504 in a direction in which the first resin film 102 side and the second resin film 104 face each other. That is, when the sample cell 100 is completed, the spring 502 or the sponge 504 is in a compressed state. Therefore, when gas is generated in the sample cell 100 during measurement, the sample 206 can be biased toward the first resin film 102 side. Thereby, similarly to the above embodiment, the primary X-ray can be accurately irradiated to the measurement position. Note that the porous material that expands and contracts may be a member other than the sponge as long as it can bias the sample 206 toward the first resin film 102 side. For example, the porous material that expands and contracts may be silicone rubber, urethane, or the like.

[0047] Modified Example 3 shown in FIG. 6(a) and Modified Example 4 shown in FIG. 6(b) are different from the above embodiment in that the holding member is a suppressing member that suppresses an increase in the internal air pressure of the sample cell 100. Specifically, for example, the holding member may be a suppressing member formed of a porous material that absorbs gas. The sample cell 100 in Modified Example 3 shown in FIG. 6(a) includes a porous ceramic 602 that absorbs gas provided instead of the biasing member. The porous material that absorbs gas may be a porous polymer. When gas is generated in the sample cell 100 maintained in a vacuum during measurement or when gas remains in the sample cell 100, the gas is absorbed into the minute cavity portions 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 and the measurement position of the sample 206 from shifting due to the gas generated by thermal volatilization or the remaining gas. The sample cell 100 shown in FIG. 6(a) does not include a biasing member, but a biasing member may be provided above or below the porous ceramic 602.

[0048] In the sample cell 100 in Modification 4 shown in FIG. 6(b), as a holding member, it includes a degassing member 604 that degasses gas to the outside. The degassing member 604 is, for example, a check valve. When gas is generated in the sample cell 100 during measurement or when gas remains in the sample cell 100, the degassing member 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 and the measurement position of the sample 206 from shifting due to the gas generated by thermal volatilization or the remaining gas. As shown in FIG. 6(b), the sample cell 100 may include a biasing member in addition to the degassing member 604, or the biasing member may be omitted.

[0049] Also, the sample 206 inside the sample cell 100 may include not only those composed only of the object of elemental analysis but also additional components that are not the object of elemental analysis. For example, the sample 206 may include a positive electrode member 702, a separator 704, and a negative electrode member 706. With the terminals of the positive electrode member 702 and the negative electrode member 706 (the ends of the conductive material described later) drawn out from the sample cell 100, the sample cell 100 is sealed, and the terminals are connected to a charge and discharge device to measure while the sample cell 100 functions as a battery cell ( Store battery). Specifically, in Modification 5 shown in FIGS. 7(a) to 7(c) and Modification 6 shown in FIGS. 8(a) to 8(c), the sample 206 constitutes a battery cell together with the first resin film 102 and the second resin film 104. Hereinafter, one or both of the positive electrode member 702 and the negative electrode member 706 are also collectively referred to as an electrode member. FIG. 7(a) is a plan view of the sample cell 100 of Modification 5. FIG. 7(b) is a view showing a cross section taken along line VII-VII of FIG. 7(a), and FIG. 7(c) is a view showing a cross section taken along line VII'-VII' of FIG. 7(a). FIG. 8(a) is a plan view of the sample cell 100 of Modification 6. FIG. 8(b) is a view showing a cross section taken along line VIII-VIII of FIG. 8(a), and FIG. 8(c) is a view showing a cross section taken along line VIII'-VIII' of FIG. 8(a).

[0050] In Modification 5 and Modification 6, the sample 206 includes a configuration in which the positive electrode member 702, the separator 704, and the negative electrode member 706 are arranged in this order. Specifically, the positive electrode member 702 has a structure in which a positive electrode active material such as a noble metal oxide is coated to a thickness of about 100 micrometers on a metal foil serving as a current collector. The separator 704 is a member that separates the positive electrode member 702 and the negative electrode member 706 and ensures ionic conductivity between the positive electrode member 702 and the negative electrode member 706. The negative electrode member 706 has a structure in which a negative electrode active material such as graphite is coated to a thickness of about 100 micrometers on a metal foil serving as a current collector. Further, an electrolytic solution 712 is filled between the first resin film 102 and the second resin film 104.

[0051] The sample cell 100 of Modification 5 has an analysis window 108, and is different from the sample cell 100 of Modification 5 in that the sample cell 100 of Modification 6 does not have an analysis window 108. Modification 5 and Modification 6 are the same in points other than the presence or absence of the analysis window 108. Note that, not limited to Modification 5, the analysis window 108 may also be omitted in the sample cell 100 shown in the above-described embodiment and Modifications 1 to 4.

[0052] FIG. 9 is a flowchart showing a fluorescent X-ray analysis method using the sample cell 100 according to Modification 5. When the sample cell 100 is configured to have an analysis window 108, it is assumed that a thin film resin film 106 of polyimide is previously attached to the position of the hole in the first resin film 102.

[0053] First, a part of the adhesion region 110 is adhered together with the conductive material (S902). Specifically, for example, as shown in FIG. 7(a), 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 adhesion region 110 of one to three sides including the side sandwiching the conductive material is heat-sealed. When using the integrally formed first resin film 102 and second resin film 104, one bent portion corresponds to the first resin film 102 and the other bent portion corresponds to the second resin film 104. The region adhered in S902 is preferably two adjacent sides.

[0054] 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 portion thereof is located outside the end portion of one side (the upper side in FIG. 7(a)) of the first resin film 102. At this time, the first conductive material 708 is disposed such that when the sample 206 is disposed, the other end portion thereof comes into contact with the positive electrode member 702 (or the negative electrode member 706). Further, the second conductive material 710 is disposed such that the other end portion thereof comes into contact with the negative electrode member 706 (or the positive electrode member 702). The first conductive material 708 and the second conductive material 710 are heat-sealed in a state of being sandwiched between the first resin film 102 and the second resin film 104 by an adhesive sealing material (not shown) in a region overlapping with the adhesion region 110, respectively.

[0055] Note that the first conductive material 708 and the second conductive material 710 may be disposed on the same side so as not to overlap in plan view as shown in FIG. 7(a), or may be disposed such that one end portion of each is located outside different sides. Further, if the first conductive material 708 and the second conductive material 710 are electrically separated, the first conductive material 708 and the second conductive material 710 may be disposed at overlapping positions in plan view. Furthermore, the first conductive material 708 and the second conductive material 710 may be formed of any material as long as it is a conductive material.

[0056] Next, the sample 206 and the biasing member are disposed between the first resin film 102 and the second resin film 104 (S904). Specifically, for example, by the step of S902, the first resin film 102 and the second resin film 104 are in a state where two adjacent sides are adhered. The sample 206 and the biasing member are inserted from the non-adhered portion of the first resin film 102 and the second resin film 104. The sample 206 includes a configuration in which the positive electrode member 702, the separator 704, and the negative electrode member 706 are disposed in this order.

[0057] At this time, the sample 206 and the biasing member are placed between the first resin film 102 and the second resin film 104 such that the sample 206 is located on the side of the first resin film 102 and the biasing member is located on the side of the second resin film 104. The biasing member is, for example, a wave washer 202. When the positive electrode member 702 is the analysis target, the positive electrode member 702 is arranged on the side of the first resin film 102. On the other hand, when the negative electrode member 706 is the analysis target, the negative electrode member 706 is arranged on the side of the first resin film 102.

[0058] Also, in S904, the other end of the first conductive material 708 is arranged so as to be sandwiched between one of the positive electrode member 702 and the negative electrode member 706, and the first resin film 102 or the biasing member. Also, the other end of the first conductive material 708 and one of the electrode members are electrically connected. Also, the other end of the second conductive material 710 is arranged so as to be sandwiched between the other of the positive electrode member 702 and the negative electrode member 706, and the second resin film 104 or the biasing member. Also, the other end of the second conductive material 710 and one of the electrode members are electrically connected. In addition, when the sample 206 is thin and cannot maintain a flat shape on the biasing member, a flat plate member 204 may be arranged between the biasing member and the sample 206. In this case, the conductive material is arranged so as to be sandwiched between the electrode member and the flat plate member 204.

[0059] Next, a part of the adhesion region 110 is adhered (S906). Specifically, the region of the adhesion region 110 excluding the injection port is heat-sealed. In this Modification 5, the right region of the adhesion region 110 shown in Fig. 7(a) is heat-sealed. When the sample is arranged in a state where three sides are adhered first, this step (S906) is unnecessary.

[0060] Next, an electrolytic solution 712 is injected (S908). By the process of S906, the first resin film 102 and the second resin film 104 are adhered in the regions of three sides of the adhesion region 110 (left side, upper side, right side), forming a bag shape with only the injection port open. In S908, the electrolytic solution 712 is injected from the injection port (the lower region of the adhesion region 110 shown in FIG. 7(a)). Note that FIGS. 7(b) and 7(c) are described emphasizing the state where the sample cell 100 is inflated, but the actual amount of the electrolytic solution 712 may be less than the amount shown in the figures.

[0061] Next, the remaining region of the adhesion region 110 is adhered (S910). Specifically, for example, similar to S406, while discharging the air between the first resin film 102 and the second resin film 104, one side of the adhesion region 110 provided with the injection port (the lower region of the adhesion region 110 shown in FIG. 7(a)) is heat-sealed. Thereby, the pouch-type sample cell 100 is completed.

[0062] Next, the sample cell 100 is placed in a fluorescent X-ray analyzer and current is passed through the conductive materials (S912). Specifically, for example, the sample cell 100 is placed in a wavelength-dispersive fluorescent X-ray analyzer 300 of the upper surface irradiation type, and a voltage or a load is applied to the first conductive material 708 and the second conductive material 710 to pass a current. The sample cell 100 in Modification 5 is a battery cell having a charge / discharge function. 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.

[0063] Finally, the sample cell 100 is irradiated with primary X-rays to perform X-ray fluorescence analysis (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 member 702 or the negative electrode member 706 in a state where the charging function is being exerted. Also, 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 member 702 or the negative electrode member 706 in a state where the discharging function is being exerted. That is, in-situ measurement of the battery cell can be performed.

[0064] In the battery cell that performs charge and discharge, bubbles may be generated inside the electrolyte 712. According to this modification, even if bubbles are generated, the positive electrode member 702 or the negative electrode member 706 is biased toward the first resin film 102 side. Therefore, similar to the above-described embodiment, the primary X-rays can be accurately irradiated to the measurement position of the positive electrode member 702 or the negative electrode member 706.

[0065] In Modification 5 and Modification 6, an example where the holding member is a biasing member has been described, but the holding member may be a suppressing member, or the holding member may include both a biasing member and a suppressing member. Also, the adhesion order of the adhesion regions 110 shown from S902 to S910 is an example, and other orders may be used as long as the battery cell can be formed.

Description of Reference Numerals

[0066] 100 Sample cell, 102 First resin film, 104 Second resin film, 106 Thin film resin film, 108 Analysis window, 110 Adhesion region, 202 Wave washer, 204 Flat plate member, 206 Sample, 300 Wavelength dispersive X-ray fluorescence analyzer, 302 X-ray source, 304 Sample stage, 306 Spectral element, 310 Detector, 312 Holder mask, 502 Spring, 504 Sponge, 602 Porous ceramic, 604 Degassing member, 702 Positive electrode member, 704 Separator, 706 Negative electrode member, 708 First conductive material, 710 Second conductive material, 712 Electrolyte.

Claims

1. A sample cell for use in an X-ray fluorescence analyzer, comprising: a first resin film disposed on an irradiation side of the primary X-ray; a second resin film disposed opposite the first resin film with a sample therebetween; a holding member for holding the positional relationship between the sample and the first resin film; having The first resin film and the second resin film are bonded to each other at least in a part of the periphery of a region in which the sample is placed. A sample cell comprising:

2. 2. The sample cell according to claim 1, wherein the holding member is a biasing member that biases the sample toward the first resin film.

3. 3. The sample cell of claim 2, wherein the biasing member is a spring or a wave washer.

4. 3. The sample cell according to claim 2, wherein the biasing member is formed of a porous material that expands and contracts.

5. 5. The sample cell according to claim 4, wherein the elastic porous material is a sponge, silicone rubber or urethane.

6. 3. The sample cell according to claim 1, wherein the first resin film has an analysis window in which a hole is provided and a thin resin film is disposed.

7. 7. The sample cell according to claim 6, wherein the thin resin film is made of any one of polyimide, polypropylene, and polyethylene.

8. the first resin film and the second resin film are sealed so as to surround the periphery of the sample, The space between the first resin film and the second resin film is hermetically sealed.

3. The sample cell according to claim 1 or 2.

9. 3. The sample cell according to claim 1, further comprising a linear fastener that can be opened and closed in a part of the area where the first resin film and the second resin film are bonded.

10. 2. The sample cell according to claim 1, wherein the holding member is a suppressing member that suppresses an increase in internal air pressure.

11. 11. The sample cell according to claim 10, wherein the suppression member is a degassing member that degasses gas to the outside.

12. 11. The sample cell of claim 10, wherein the suppression member is formed of a porous material that absorbs gas.

13. 3. The sample cell according to claim 1, further comprising a flat or dish-shaped plate member disposed in contact with the holding member.

14. 1. A method for fluorescent X-ray analysis using a sample cell having a first resin film and a second resin film, comprising: disposing a holding member for holding a positional relationship between a sample and the first resin film; placing a sample on the holding member; a step of sealing the first resin film to the second resin film so as to surround the periphery of the sample while discharging air between the first resin film and the second resin film, thereby completing the pouch-shaped sample cell; placing the sample cell in an X-ray fluorescence analyzer and performing X-ray fluorescence analysis; Including, A fluorescent X-ray analysis method, characterized in that the first resin film is formed of a material that transmits fluorescent X-rays generated from the sample, or has an analysis window that transmits fluorescent X-rays generated from the sample.

15. The sample includes a positive electrode member, a separator, and a negative electrode member arranged in this order, a 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 of the first conductive material is positioned outside 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 member and the negative electrode member, and electrically connecting the other end of the second conductive material to the other of the positive electrode member and the negative electrode member; a step of bonding the first resin film and the second resin film at bonding areas excluding an injection port; injecting an electrolyte solution through the injection port; bonding the bonding area with the inlet; applying a voltage or load to the first conductive material and the second conductive material; The method of claim 14, further comprising:

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