Sample container, X-ray fluorescence analyzer, and measurement method

Abstract

To provide a sample container capable of safely measuring a liquid sample in an X-ray fluorescence analyzer.SOLUTION: The sample vessel 100 is a sample vessel for an X-ray fluorescence spectrometer, and accommodates a liquid sample S, and includes a first vessel 10 having a first opening 4a and a second opening 4b, an analysis film 20 blocking the first opening 4a and transmitting X-rays, and a protective film 44 transmitting X-rays. The apparatus includes a protection vessel (40) covering the analysis film (20) and a pressure adjustment valve (60) adjusting the pressure in the first vessel (10), wherein the first vessel (10) has a first space (2a) facing the first opening (4a), a second space (2b) facing the second opening (4b), and a connection hole (2c) connecting the first space (2a) and the second space (2b), and the cross-sectional area of the connection hole (2c) is smaller than the area of the first opening (4a).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a sample container, a fluorescent X-ray analyzer, and a measurement method.

Background Art

[0002] A fluorescent X-ray analyzer can perform qualitative analysis, quantitative analysis and the like by irradiating a sample with primary X-rays from an X-ray tube and detecting secondary X-rays emitted from the sample with a detector.

[0003] In fluorescent X-ray analysis, when analyzing light elements in a liquid, the measurement is performed by replacing the inside of the sample chamber with helium gas. However, in order to replace the sample chamber with helium gas, a mechanism for performing helium replacement on the sample chamber is required. Furthermore, equipment for managing high-pressure helium gas is required.

[0004] In contrast, Patent Document 1 discloses a sample container that can maintain the internal pressure of the container in a sample chamber in a vacuum atmosphere at a pressure higher than the boiling pressure of a liquid sample and lower than the pressure at which the analysis film breaks. By using this sample container, measurement can be performed with the sample chamber of the fluorescent X-ray analyzer set to a vacuum atmosphere, and light elements in the liquid sample can be measured without replacing the sample chamber with helium.

[0005] In the sample container disclosed in Patent Document 1, the opening of a cylindrical sample cup is closed with an analysis film, and a liquid sample is stored in the sample cup. By increasing the area of the opening of the sample cup, the X-ray irradiation region can be enlarged.

[0006] When the area of the opening of the sample cup is increased, the analysis film is likely to break due to the pressure difference between the inside and the outside of the container. Therefore, the sample container disclosed in Patent Document 1 is provided with a protective container having a protective film that transmits X-rays, and even if the analysis film breaks and the liquid sample leaks out, the liquid sample can be received by the protective container. This can prevent the liquid sample from splashing onto the fluorescent X-ray analyzer. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2024-000191 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] However, in the sample container disclosed in Patent Document 1, when the analytical film is damaged due to the pressure difference between the inside and outside of the container, the liquid sample or gas inside the container may be forcefully ejected, causing the protective film to be damaged. [Means for solving the problem]

[0009] One embodiment of the sample container according to the present invention is: A sample container for an X-ray fluorescence analyzer, A first container having a first opening and a second opening, which contains a liquid sample. The first opening is blocked by an analytical film that allows X-rays to pass through, A protective container having an X-ray-transmitting protective film, which covers the analytical film, A pressure regulating valve for adjusting the pressure inside the first container, Includes, The first container has a first space facing the first opening, a second space facing the second opening, and a connecting hole connecting the first space and the second space. The cross-sectional area of ​​the connection hole is smaller than the area of ​​the first opening.

[0010] In such a sample container, the cross-sectional area of ​​the connection hole is smaller than the area of ​​the first opening, thus limiting the flow rate of liquid samples and gases from the second space to the first space. Therefore, in such a sample container, the possibility of damage to the protective film when the analytical film is damaged is reduced. This allows for safe measurement of liquid samples in an X-ray fluorescence analyzer.

[0011] One embodiment of the X-ray fluorescence analyzer according to the present invention is: The above sample container and, A sample chamber that houses the aforementioned sample container and can be maintained in a vacuum atmosphere, Includes, In the sample chamber under a vacuum atmosphere, the liquid sample contained in the sample container is irradiated with X-rays to perform the measurement.

[0012] In this type of X-ray fluorescence analyzer, liquid samples are measured using the sample container described above, allowing for safe measurement of liquid samples. Furthermore, since this type of X-ray fluorescence analyzer can measure samples in a vacuum atmosphere in the sample chamber, light elements in liquid samples can be measured without replacing the sample chamber with helium.

[0013] One aspect of the measurement method according to the present invention is: A first container having a first opening and a second opening, which contains a liquid sample. The first opening is blocked by an analytical film that allows X-rays to pass through, A protective container having an X-ray-transmitting protective film, which covers the analytical film, A pressure regulating valve for adjusting the pressure inside the first container, Includes, The first container has a first space facing the first opening, a second space facing the second opening, and a connecting hole connecting the first space and the second space. A measurement method using a sample container, wherein the cross-sectional area of ​​the connection hole is smaller than the area of ​​the first opening, The steps include: placing the liquid sample into the sample container; The process involves introducing the aforementioned sample container into the sample chamber of the X-ray fluorescence analyzer, A step of reducing the pressure in the sample chamber to create a vacuum atmosphere in the sample chamber, In the sample chamber under a vacuum atmosphere, the liquid sample contained in the sample container is irradiated with X-rays through the analytical film and the protective film, and the fluorescent X-rays emitted from the liquid sample are detected. Includes.

[0014] In such a measurement method, since the liquid sample is measured using the aforementioned sample container, the liquid sample can be measured safely. In addition, since the measurement can be performed with the sample chamber kept in a vacuum atmosphere, light elements in the liquid sample can be measured without replacing the inside of the sample chamber with helium. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] [Figure 1] FIG. 1 is a cross-sectional view schematically illustrating a sample container according to a first embodiment. [Figure 2] A cross-sectional view schematically illustrating a first container. [Figure 3] A diagram for explaining a pressure regulating valve. [Figure 4] A diagram illustrating an example of the configuration of an X-ray fluorescence analyzer. [Figure 5] A flowchart illustrating an example of a measurement method using the sample container. [Figure 6] A diagram for explaining each step of the measurement method using the sample container. [Figure 7] A diagram for explaining each step of the measurement method using the sample container. [Figure 8] A diagram for explaining each step of the measurement method using the sample container. [Figure 9] A diagram for explaining each step of the measurement method using the sample container. [Figure 10] A diagram for explaining each step of the measurement method using the sample container. [Figure 11] A diagram schematically illustrating the state of the sample container in the sample chamber under vacuum. [Figure 12] A diagram for explaining the X-ray fluorescence analyzer in a state where the analysis film is damaged. [Figure 13] A cross-sectional view schematically illustrating a sample container according to a second embodiment. [Figure 14] A cross-sectional view schematically illustrating a first container. [Figure 15] A cross-sectional view schematically illustrating a sample container according to a third embodiment. DETAILED DESCRIPTION OF EMBODIMENTS

[0016] Preferred embodiments of the present invention will be described in detail below with reference to the drawings. The embodiments described below are not intended to unduly limit the scope of the present invention as described in the claims. Furthermore, not all of the configurations described below are necessarily essential components of the present invention.

[0017] 1. First Embodiment 1.1. Sample container First, the sample container according to the first embodiment will be described with reference to the drawings. Figure 1 is a schematic cross-sectional view of the sample container 100 according to the first embodiment. Figure 1 shows the state in which the second container 50 is attached to the first container 10. Figure 2 is a schematic cross-sectional view of the first container 10.

[0018] Sample container 100 is a sample container for a fluorescent X-ray analyzer. Sample container 100 is a container for measuring a liquid sample S in a vacuum atmosphere sample chamber.

[0019] As shown in Figures 1 and 2, the sample container 100 includes a first container 10, an analytical film 20, a porous film 30, a protective container 40, a second container 50, a pressure regulating valve 60, and a leak valve 70.

[0020] The first container 10 contains the liquid sample S to be measured. The liquid sample S to be measured is, for example, food such as drinking water, cleaning solutions such as organic solvents, alcohol such as ethanol, oil, plating solution, electrolyte used in batteries, liquid fertilizer, water for water quality testing, etc. The first container 10 has a first space 2a, a second space 2b, and a connecting hole 2c that connects the first space 2a and the second space 2b. The first container 10 has a first opening 4a that is sealed with an analytical film 20 and a second opening 4b that is sealed with a porous film 30.

[0021] The first container 10 includes a sample cup 12 and a damper 14 (an example of a partitioning member). The sample cup 12 is, for example, cylindrical. The damper 14 is placed inside the sample cup 12. The damper 14 is a partitioning member that divides the space inside the sample cup 12. By partitioning the space 2 inside the sample cup 12 with the damper 14, a first space 2a, a second space 2b, and a connecting hole 2c are formed.

[0022] The first space 2a faces the first opening 4a. The first space 2a is filled with the amount of liquid sample S required for measurement. The height H of the first space 2a, that is, the distance between the first opening 4a and the connection hole 2c, is greater than the analysis depth for X-ray fluorescence analysis. The height H of the first space 2a is, for example, about 1 mm to 3 mm. This allows the first space 2a to be filled with the liquid sample S to the depth required for measurement.

[0023] The first space 2a has a tapered portion 3a whose cross-sectional area decreases towards the tip. The shape of the tapered portion 3a is a frustoconical shape. The tip of the tapered portion 3a is connected to the connecting hole 2c. In the illustrated example, the first space 2a has a tapered portion 3a and a cylindrical portion 3b, with the tip of the tapered portion 3a connected to the connecting hole 2c and the rear end of the tapered portion 3a connected to one end of the cylindrical portion 3b. The other end of the cylindrical portion 3b forms the first opening 4a. The cross-sectional area of ​​the cylindrical portion 3b is larger than the cross-sectional area of ​​the connecting hole 2c.

[0024] The second space 2b faces the second opening 4b. The second space 2b functions as a buffer tank for containing the liquid sample S to be supplied to the first space 2a. The volume of the second space 2b is, for example, larger than the volume of the first space 2a. Although not shown in the figures, the volume of the second space 2b may be smaller than the volume of the first space 2a, or the volume of the second space 2b may be the same as the volume of the first space 2a. Here, when the analytical film 20 expands outward due to the pressure difference between the first container 10 and the sample chamber, the volume of the first space 2a increases. Therefore, the volume of the second space 2b should be such that it can be filled with enough buffer solution to replenish the first space 2a with the liquid sample S by the amount of the volume of the first space 2a that has increased due to the expansion of the analytical film 20.

[0025] The second space 2b has a tapered portion 5a whose cross-sectional area decreases towards its tip. The shape of the tapered portion 5a is a frustoconical shape. The tip of the tapered portion 5a is connected to the connecting hole 2c. In the illustrated example, the second space 2b has a tapered portion 5a and a cylindrical portion 5b, with the tip of the tapered portion 5a connected to the connecting hole 2c and the rear end of the tapered portion 5a connected to one end of the cylindrical portion 5b. The other end of the cylindrical portion 5b forms the second opening 4b. The cross-sectional area of ​​the cylindrical portion 5b is larger than the cross-sectional area of ​​the connecting hole 2c.

[0026] The connecting hole 2c connects the first space 2a and the second space 2b. The cross-sectional area of ​​the connecting hole 2c is smaller than the area of ​​the first opening 4a. Also, the cross-sectional area of ​​the connecting hole 2c is smaller than the area of ​​the second opening 4b. For example, if the connecting hole 2c is cylindrical, the cross-sectional area of ​​the connecting hole 2c is the area of ​​the plane perpendicular to the central axis of the cylinder. The connecting hole 2c serves as a flow path for supplying the liquid sample S from the second space 2b to the first space 2a. The cross-sectional area of ​​the connecting hole 2c corresponds to the cross-sectional area of ​​the flow path. The connecting hole 2c narrows the flow path of the liquid sample S from the second space 2b to the first space 2a. The connecting hole 2c functions as an orifice.

[0027] The first opening 4a is located on the bottom side of the sample container 100, and the second opening 4b is located on the top side of the sample container 100. The first opening 4a is the bottom opening of the damper 14, and the second opening 4b is the top opening of the damper 14. The shape of the first opening 4a is, for example, a circle. The shape of the second opening 4b is, for example, a circle.

[0028] The diameter of the first opening 4a is, for example, about 20 mm. The diameter of the second opening 4b is, for example, smaller than the diameter of the first opening 4a. The diameter of the connecting hole 2c is, for example, about 2 mm.

[0029] A groove 15 is provided around the damper 14. An O-ring 90 is fitted into the groove 15. The O-ring 90 seals the gap between the damper 14 and the sample cup 12. The groove 15 may be made deeper to increase the compression allowance of the O-ring 90. This increases the tolerance range of the gap between the sample cup 12 and the damper 14.

[0030] The analytical film 20 is a film that transmits X-rays. The analytical film 20 is an organic film such as a prolene film or a mylar film. The thickness of a prolene film used as the analytical film 20 is, for example, about 4 μm. The thickness of a mylar film used as the analytical film 20 is, for example, about 1.5 μm. The thickness and material of the analytical film 20 can be changed depending on the type of liquid sample S to be measured, the element to be measured, the purpose of the measurement, the diameter of the sample cup 12, etc.

[0031] The porous film 30 can be, for example, a polypropylene film, a nonwoven fabric, or the like. A film used as a separator for lithium-ion batteries may also be used as the porous film 30. By covering the second opening 4b with the porous film 30, it is possible to prevent the liquid sample S from adhering to the second container 50, etc., when the liquid sample S boils or splashes.

[0032] The porous film 30 is fixed to the second opening 4b of the damper 14 by the cap 80. For example, the inner surface of the cap 80 has female threads, and the outer surface of the damper 14 has male threads, and the cap 80 is attached to the damper 14 by fitting the male and female threads together. At this time, by sandwiching the porous film 30 between the cap 80 and the damper 14, the porous film 30 can be fixed in a state where it closes the second opening 4b. The cap 80 has a through hole 82 that communicates with the second opening 4b.

[0033] The protective container 40 covers the analytical film 20. The protective container 40 includes a protective cup 42 and a protective film 44. The protective cup 42 is cylindrical. The opening at the bottom of the protective cup 42 is sealed by the protective film 44. The first opening 4a of the sample cup 12, which is sealed by the analytical film 20, is located inside the protective cup 42. Therefore, even if the analytical film 20 is damaged and the liquid sample S leaks out, it can be caught in the protective container 40.

[0034] The protective film 44 is an X-ray transparent film. The material of the protective film 44 is, for example, the same as the material of the analytical film 20. Since the bottom of the protective container 40 is made of the protective film 44, in the X-ray fluorescence analyzer, primary X-rays are transmitted through the protective film 44 and the analytical film 20 and irradiated onto the liquid sample S. Secondary X-rays are transmitted through the analytical film 20 and the protective film 44 and detected by the detector.

[0035] Although not shown in the diagram, the protective cup 42 has a vent hole that serves as a gas pathway connecting the inside and outside of the protective cup 42. Therefore, even if the sample chamber of the X-ray fluorescence analyzer is evacuated and the pressure changes from atmospheric pressure to a vacuum, the pressure inside and outside the protective cup 42 can be made the same. Consequently, the possibility of damage to the protective film 44 can be reduced.

[0036] The second container 50 is equipped with a pressure adjustment valve 60 for adjusting the pressure in the space 2 inside the first container 10. The second container 50 is also equipped with a leak valve 70. The space 6 inside the second container 50 is in communication with the space 2 inside the first container 10. In the sample container 100, the pressure in the space 2 inside the first container 10 is adjusted by adjusting the pressure in the space 6 inside the second container 50.

[0037] The second container 50 is a resealable container. The second container 50 includes a base 52, a support member 54, and a lid 56.

[0038] The base 52 is provided with an opening 53 into which the first container 10 can be inserted. An O-ring 92 is fitted to the bottom of the opening 53, and the gap between the first container 10 and the base 52 is airtightly sealed by the O-ring 92. The space 6 inside the second container 50 is the space enclosed by the base 52 and the lid 56. A through hole 52a is provided at the bottom of the opening 53 of the base 52, which communicates with the space 6 enclosed by the base 52 and the lid 56.

[0039] The support member 54 supports the first container 10. The support member 54 is attached to the base 52. For example, a female thread is formed on the inner surface of the base 52, and a male thread is formed on the outer surface of the support member 54, and the support member 54 is attached to the base 52 by fitting the male thread and the female thread together. At this time, the first container 10 is supported from below by the support member 54. Then, the first container 10 is pressed against the O-ring 92. This allows the gap between the first container 10 and the base 52 to be airtightly sealed. In addition, the gap between the support member 54 and the first container 10 is airtightly sealed by the O-ring 94.

[0040] An opening is provided at the bottom of the protective cup 42, into which the support member 54 is inserted. A protective film 44 is sandwiched between the support member 54 and the protective cup 42. As a result, the opening at the bottom of the protective cup 42 is closed by the protective film 44. Therefore, the protective film 44 is positioned below the analytical film 20. In other words, the analytical film 20 overlaps the protective film 44.

[0041] A pressure regulating valve 60 and a leak valve 70 are attached to the lid 56. In the vacuum atmosphere of the X-ray fluorescence analyzer's sample chamber, the pressure regulating valve 60 maintains a constant pressure in the space 6 inside the first container 10. For example, the pressure inside the first container 10 is maintained at more than 600 Pascals but less than atmospheric pressure.

[0042] The lid 56 is attached to the base 52. The gap between the base 52 and the lid 56 is airtightly sealed with an O-ring 96. The base 52 and the lid 56 form a space 6. Space 6 communicates with the second space 2b, the connection hole 2c, and the first space 2a through through holes 52a and 82. Therefore, the pressure in the first space 2a, the second space 2b, and the connection hole 2c can be adjusted by adjusting the pressure in space 6 within the second container 50.

[0043] The pressure regulating valve 60 operates in the vacuum atmosphere of the X-ray fluorescence analyzer's sample chamber so that the pressure difference between the inside and outside of the second container 50 becomes the set pressure. Here, the pressure outside the second container 50 is the pressure inside the sample chamber.

[0044] The pressure regulating valve 60 opens when the pressure in the space 6 inside the second container 50 is higher than the pressure outside the second container 50, and the pressure difference between the inside and outside of the second container 50 is higher than the set pressure. The pressure regulating valve 60 also closes when the pressure in the space 6 inside the second container 50 is higher than the pressure outside the second container 50, and the pressure difference between the inside and outside of the second container 50 is less than or equal to the set pressure, and the pressure inside the second container 50 is less than or equal to the pressure outside the second container 50. The set pressure of the pressure regulating valve 60 is variable.

[0045] In the vacuum atmosphere of the X-ray fluorescence analyzer's sample chamber, the pressure regulating valve 60 maintains a constant pressure in the space 6 within the second container 50. Consequently, the pressure in the space 2 within the first container 10 also remains constant. For example, the pressure in the space 2 within the first container 10 is maintained between 600 Pascals and atmospheric pressure.

[0046] The leak valve 70 is a valve for returning the pressure inside the second container 50 to atmospheric pressure. The leak valve 70 opens, for example, when the pressure outside the second container 50 is higher than the pressure inside the second container 50. The leak valve 70 also closes, for example, when the pressure outside the first container 10 is less than or equal to the pressure inside the first container 10.

[0047] Figure 3 is a diagram illustrating the pressure regulating valve 60. The pressure regulating valve 60 includes a valve 62 and a spring 64. The pressure regulating valve 60 uses the valve 62 and the spring 64 to regulate the pressure inside the second container 50.

[0048] When both the inside and outside of the second container 50 are at atmospheric pressure, the valve 62 of the pressure regulating valve 60 is closed by the force F2 of the spring 64. When the sample chamber of the X-ray fluorescence analyzer is evacuated and the pressure outside the second container 50 decreases, the pressure inside the second container 50 becomes higher than the pressure outside the second container 50, and the pressure difference between the inside and outside of the second container 50 becomes higher than the set pressure, the spring 64 The force F4 applied to valve 62 due to the pressure difference between the inside and outside of the second container 50 becomes greater than the force F2 that closes valve 62. As a result, valve 62 opens, and the inside and outside of the second container 50 become connected.

[0049] When valve 62 opens, the pressure in the space 6 inside the second container 50 decreases, and when the pressure difference between the inside and outside of the second container 50 falls below the set pressure, the force F2 that spring 64 exerts to close valve 62 becomes greater than the force F4 exerted on valve 62 by the pressure difference between the inside and outside of the second container 50. As a result, valve 62 closes.

[0050] In this way, by opening and closing the valve 62 in accordance with the pressure difference between the inside and outside of the second container 50, the pressure in the space 6 inside the second container 50 can be kept constant. Furthermore, the set pressure can be changed by adjusting the force F2 that the spring 64 exerts to close the valve 62 by changing the length of the spring 64.

[0051] Although not shown in the diagram, if the pressure in the space 6 inside the second container 50 is less than or equal to the pressure outside the second container 50, the force F4 applied to the valve 62 due to the pressure difference between the inside and outside of the second container 50 becomes a closing force for the valve 62, and the valve 62 remains closed.

[0052] The leak valve 70 has a configuration similar to, for example, the pressure regulating valve 60, and uses a spring to open and close the valve in accordance with the pressure difference between the inside and outside of the second container 50.

[0053] 1.2. X-ray fluorescence analyzer Figure 4 shows an example of the configuration of the X-ray fluorescence analyzer 200.

[0054] The X-ray fluorescence analyzer 200 is a device for performing analysis using the X-ray fluorescence analysis method. X-ray fluorescence analysis is a method of analyzing a liquid sample S by irradiating the liquid sample S with primary X-rays and detecting the secondary X-rays emitted from the liquid sample S as a result of the primary X-ray irradiation.

[0055] As shown in Figure 4, the X-ray fluorescence analyzer 200 includes a sample container 100, an X-ray tube 202, a filter 203, a primary X-ray collimator 204, a support plate 205, a secondary X-ray collimator 206, and a detector 207.

[0056] The sample container 100 is housed in the sample chamber 208 of the X-ray fluorescence analyzer 200. The sample chamber 208 houses, for example, a filter 203, a primary X-ray collimator 204, a support plate 205, and a secondary X-ray collimator 206. The sample chamber 208 may also house an X-ray tube 202 and a detector 207. Although not shown in the figures, the X-ray fluorescence analyzer 200 is equipped with a vacuum pump for evacuating the sample chamber 208.

[0057] When measuring a liquid sample S using the sample container 100, the sample chamber 208 is subjected to a vacuum atmosphere at a predetermined pressure. During measurement, the sample chamber 208 is maintained at a constant pressure by a vacuum pump. In the vacuum atmosphere of the sample chamber 208, the pressure inside the first container 10 is maintained at a pressure higher than the pressure in the sample chamber 208 (the predetermined pressure). In the vacuum atmosphere of the sample chamber 208, the pressure inside the first container 10 is maintained by the pressure adjustment valve 60 at a pressure higher than the boiling pressure of the liquid sample S and lower than the pressure at which the analytical film 20 breaks.

[0058] The X-ray tube 202 generates primary X-rays. The tube voltage and tube current in the X-ray tube 202 are set according to the material of the liquid sample S and the element to be analyzed. The tube voltage is the voltage applied to the X-ray tube 202. The tube current is the current flowing through the X-ray tube 202.

[0059] The filter 203 allows X-rays generated in the X-ray tube 202 to pass through. By irradiating the liquid sample S with X-rays through the filter 203, some of the continuous X-rays and characteristic X-rays can be absorbed by the filter 203, and these components can be removed. This allows for, for example, P / The peak-to-background ratio (B ratio) can be improved. The X-ray fluorescence analyzer 200 is equipped with multiple filters 203, each of which reduces different energy bands. Depending on the element being measured, the filter 203 used for measurement is selected from the multiple filters 203.

[0060] The primary X-ray collimator 204 limits the irradiation area of ​​the X-rays irradiated onto the liquid sample S. The size of the irradiation area can be selected using the primary X-ray collimator 204. The size of the irradiation area is selected according to the area of ​​the first aperture 4a. By increasing the area of ​​the first aperture 4a, the area of ​​the irradiation area can be increased. This improves the sensitivity of the measurement.

[0061] The support plate 205 supports the sample container 100. An opening is formed in the support plate 205, and primary X-rays are irradiated onto the sample container 100 through this opening. The primary X-rays pass through the protective film 44 and the analytical film 20 and irradiate the liquid sample S. When the liquid sample S is irradiated with primary X-rays, secondary X-rays are emitted from the liquid sample S. The secondary X-rays emitted from the liquid sample S pass through the analytical film 20 and the protective film 44 and are emitted from the opening in the support plate 205.

[0062] The secondary X-ray collimator 206 limits the acquisition area of ​​secondary X-rays emitted from the liquid sample S. By using the secondary X-ray collimator 206, the desired secondary X-rays can be efficiently detected. Here, secondary X-rays refer to X-rays emitted from a sample when it is irradiated with primary X-rays. Secondary X-rays include fluorescent X-rays and scattered X-rays. Scattered X-rays are X-rays emitted by the scattering of atoms and electrons when a sample is irradiated with primary X-rays. Fluorescent X-rays are X-rays emitted when inner-shell electrons of atoms are excited when a sample is irradiated with primary X-rays, and outer-shell electrons are transferred to the resulting vacancies.

[0063] Detector 207 detects secondary X-rays emitted from the liquid sample S. Detector 207 is, for example, a semiconductor detector. Detector 207 is, for example, an energy-dispersive X-ray detector. Alternatively, detector 207 may be a wavelength-dispersive X-ray detector.

[0064] In the X-ray fluorescence analyzer 200, the sample chamber 208 is in a vacuum atmosphere, allowing for highly sensitive detection of light elements in the liquid sample S.

[0065] 1.3. Measurement method Figure 5 is a flowchart illustrating an example of a measurement method using the sample container 100. Figures 6 to 10 are diagrams illustrating each step of the measurement method using the sample container 100.

[0066] First, the liquid sample S is filled into the sample container 100 (step S100).

[0067] For example, from several sample cups 12 of different diameters, the optimal sample cup 12 is selected according to the type of liquid sample S to be measured, the element to be measured, and the purpose of the measurement. Next, the optimal analytical film 20 is selected according to the type of liquid sample S to be measured, the element to be measured, the purpose of the measurement, and the diameter of the sample cup 12.

[0068] Next, as shown in Figure 6, attach the analytical film 20 to the sample cup 12 and seal the bottom of the sample cup 12 with the analytical film 20. Then, pour the liquid sample S into the sample cup 12.

[0069] Next, as shown in Figure 7, the support member 54 is attached to the sample cup 12.

[0070] Next, prepare the damper 14 as shown in Figure 8. First, put O into the groove 15 of the damper 14. Next, the ring 90 is attached. Then, the second opening 4b of the damper 14 is sealed with the porous film 30. Specifically, the porous film 30 is placed on the second opening 4b of the damper 14, and with the porous film 30 sandwiched between the cap 80 and the damper 14, the cap 80 is attached to the damper 14. This seals the second opening 4b with the porous film 30.

[0071] Next, as shown in Figure 9, the damper 14 is placed in the sample cup 12 filled with the liquid sample S. When the damper 14 is pushed in through the opening at the top of the sample cup 12, the liquid sample S and the gas inside the sample cup 12 flow into the first space 2a through the first opening 4a of the damper 14. Furthermore, when the damper 14 is pushed further into the sample cup 12, the liquid sample S and gas that have flowed into the first space 2a flow into the second space 2b through the connection hole 2c. At this time, the liquid sample S and gas in the first space 2a are collected at the connection hole 2c by the tapered portion 3a. Therefore, the possibility of air bubbles remaining in the first space 2a can be reduced. When the damper 14 is pushed into the sample cup 12, some of the gas guided into the second space 2b is discharged outside the sample container 100 through the porous film 30.

[0072] As shown in Figure 10, the damper 14 is pushed in until it contacts the bottom of the sample cup 12, i.e., the analytical film 20. This closes the first opening 4a with the analytical film 20. The first space 2a is filled with the liquid sample S, and the second space 2b is filled with the buffer liquid sample S. In this way, by pushing the damper 14 into the sample cup 12, the space 2 inside the sample cup 12 can be divided into the first space 2a, the second space 2b, and the connecting hole 2c.

[0073] Next, as shown in Figure 1, the second container 50 is attached to the first container 10. This connects the space 2 inside the first container 10 and the space 6 inside the second container 50 through the through hole 52a in the base 52.

[0074] In this way, the liquid sample S can be filled into the sample container 100. In the above example, the damper 14 was pressed into the sample cup 12 after the liquid sample S was placed in the sample cup 12, but it is also possible to place the damper 14 into the sample cup 12 first and then place the liquid sample S into the sample cup 12.

[0075] Next, adjust the pressure regulating valve 60 (step S102).

[0076] The pressure adjustment valve 60 is set so that, in a vacuum atmosphere of the sample chamber 208 at a predetermined pressure, the pressure inside the first container 10 is higher than the boiling pressure of the liquid sample S and lower than the pressure at which the analytical film 20 breaks. Therefore, the set pressure is determined according to the vapor pressure of the liquid sample S, the area of ​​the first opening 4a, the pressure in the sample chamber 208, and so on.

[0077] Next, the sample container 100 containing the liquid sample S is introduced into the sample chamber 208 of the X-ray fluorescence analyzer 200 (step S104). Although not shown in the diagram, the lid of the sample chamber is opened to introduce the sample container 100 into the sample chamber 208.

[0078] Next, the sample chamber 208 is evacuated to create a vacuum atmosphere at a predetermined pressure (step S106).

[0079] The sample chamber 208 is evacuated to a pressure (predetermined pressure) at which the X-rays of light elements emitted from the liquid sample S can be detected by the detector 207. At this time, the pressure inside the first container 10 also decreases along with the decrease in pressure in the sample chamber 208, but the pressure difference between the first container 10 and the sample chamber 208 is maintained at the set pressure by the operation of the pressure adjustment valve 60. The pressure inside the first container 10 is maintained at a pressure higher than the boiling pressure of the liquid sample S and lower than the pressure at which the analytical film 20 breaks.

[0080] Next, the liquid sample S is subjected to measurement by X-ray fluorescence analysis (step S108).

[0081] Measurement begins when the pressure in the sample chamber 208 becomes constant at a predetermined pressure. Specifically, primary X-rays generated in the X-ray tube 202 are irradiated onto the liquid sample S in the first container 10 via the filter 203 and the primary X-ray collimator 204. The primary X-rays pass through the protective film 44 and the analytical film 20 and irradiate the liquid sample S. Secondary X-rays emitted from the liquid sample S as a result of the primary X-ray irradiation pass through the analytical film 20 and the protective film 44 and are detected by the detector 207 via the secondary X-ray collimator 206.

[0082] As described above, since the pressure inside the first container 10 is higher than the pressure at which the liquid sample S boils, the liquid sample S can be measured without boiling. Also, since the pressure inside the first container 10 is lower than the pressure at which the analytical film 20 breaks, the possibility of the analytical film 20 breaking can be reduced. Furthermore, since the sample chamber 208 can be kept under vacuum, the attenuation of secondary X-rays emitted from the liquid sample S can be reduced. Therefore, for example, light elements can be measured with high sensitivity.

[0083] After the measurement is complete, the sample chamber 208 is vented to bring it back to atmospheric pressure (step S110).

[0084] By venting the sample chamber 208, the pressure in the sample chamber 208 increases, and the operation of the leak valve 70 also increases the pressure inside the first container 10. As a result, damage to the analytical film 20 can be prevented, and the pressure inside the first container 10 can be brought to atmospheric pressure.

[0085] Through the above steps, the liquid sample S can be measured.

[0086] Figure 11 is a schematic diagram showing the state of the sample container 100 inside the vacuum-sealed sample chamber 208.

[0087] The sample chamber 208 is under vacuum, and the pressure inside the first container 10 is a low vacuum, higher than the pressure inside the sample chamber 208. Therefore, the analytical film 20 expands outward due to the pressure difference between the first container 10 and the sample chamber 208. As the analytical film 20 expands outward, the volume of the first space 2a increases. At this time, the liquid sample S contained in the second space 2b flows into the first space 2a through the connection hole 2c. In this way, the sample container 100 can supply the liquid sample S from the second space 2b to the first space 2a when the analytical film 20 expands and the volume of the first space 2a increases. Therefore, even if the volume of the first space 2a changes, the sample container 100 can fill the first space 2a with the amount of liquid sample S required for measurement.

[0088] Figure 12 illustrates the X-ray fluorescence analyzer 200 in a damaged state of the analytical film 20.

[0089] As shown in Figure 12, even if the analytical film 20 is damaged due to the pressure difference between the first container 10 and the sample chamber 208, the liquid sample S can still be received by the protective container 40. Therefore, even if the analytical film 20 is damaged, it is possible to prevent the liquid sample S from flowing out of the sample container 100.

[0090] Furthermore, in the sample container 100, if the analytical film 20 is damaged, the pressure difference between the first container 10 and the sample chamber 208 causes the liquid sample S and gas inside the sample container 100 to be forcefully ejected, reducing the possibility of damage to the protective film 44.

[0091] In the sample container 100, the liquid sample S and gas in the second space 2b flow into the first space 2a through the connection hole 2c. Since the connection hole 2c narrows the flow path of the liquid sample S and gas from the second space 2b to the first space 2a, the flow rate of the liquid sample S and gas from the second space 2b to the first space 2a can be limited by the connection hole 2c. Therefore, when the analytical film 20 is damaged, it is possible to prevent the liquid sample S and gas in the second space 2b from flowing forcefully into the first space 2a due to the pressure difference between the first container 10 and the sample chamber 208. This reduces the possibility of the protective film 44 being damaged when the analytical film 20 is damaged.

[0092] 1.4. Effects The sample container 100 includes a first container 10 that contains a liquid sample S and has a first opening 4a and a second opening 4b, a protective container 40 that covers the analytical film 20 and has an X-ray-transmitting analytical film 20 that closes the first opening 4a, and an X-ray-transmitting protective film 44, and a pressure adjustment valve 60 that adjusts the pressure inside the first container 10. In the sample container 100, the first container 10 has a first space 2a facing the first opening 4a, a second space 2b facing the second opening 4b, and a connecting hole 2c that connects the first space 2a and the second space 2b. In the sample container 100, the cross-sectional area of ​​the connecting hole 2c is smaller than the area of ​​the first opening 4a.

[0093] Thus, in the sample container 100, the cross-sectional area of ​​the connection hole 2c is smaller than the area of ​​the first opening 4a. Therefore, in the sample container 100, the flow rate of the liquid sample S and gas flowing from the second space 2b to the first space 2a can be limited compared to, for example, the case where the cross-sectional area of ​​the connection hole 2c is greater than or equal to the area of ​​the first opening 4a. Consequently, in the sample container 100, the possibility of the protective film 44 being damaged when the analytical film 20 is damaged can be reduced. This allows for the safe measurement of the liquid sample S in the X-ray fluorescence analyzer.

[0094] Furthermore, in the sample container 100, the second space 2b functions as a buffer tank for containing the liquid sample S to be supplied to the first space 2a. For example, in the sample container 100, as shown in Figure 10, if the analytical film 20 expands due to the pressure difference between the first container 10 and the sample chamber 208, and the volume of the first space 2a increases, the liquid sample S is supplied from the second space 2b to the first space 2a. This reduces the possibility of air bubbles entering the first space 2a or a shortage of liquid sample S in the first space 2a.

[0095] In the sample container 100, the cross-sectional area of ​​the connection hole 2c is smaller than the area of ​​the second opening 4b. Therefore, in the sample container 100, the volume of the second space 2b facing the second opening 4b can be increased. Consequently, in the sample container 100, the capacity of the buffer tank that contains the liquid sample S to be supplied to the first space 2a can be increased. Furthermore, in the sample container 100, the flow rate of the liquid sample S and gas flowing from the second space 2b to the first space 2a can be limited.

[0096] In the sample container 100, the connection hole 2c narrows the flow path of the liquid sample S from the second space 2b to the first space 2a. Therefore, in the sample container 100, the flow rate of the liquid sample S and gas flowing from the second space 2b to the first space 2a can be limited by the connection hole 2c.

[0097] In the sample container 100, the first space 2a has a tapered portion 3a whose cross-sectional area decreases towards the tip, and the tip of the tapered portion 3a is connected to the connecting hole 2c. Therefore, the possibility of air bubbles entering the first space 2a can be reduced in the sample container 100.

[0098] In the sample container 100, the volume of the second space 2b is larger than the volume of the first space 2a. Therefore, in the sample container 100, the capacity of the buffer tank that contains the liquid sample S to be supplied to the first space 2a can be increased.

[0099] The sample container 100 includes a porous film 30 that seals the second opening 4b. Therefore, by sealing the second opening 4b with the porous film 30, the sample container 100 can prevent the liquid sample S from adhering to the second container 50 or the like when the liquid sample S boils or splashes.

[0100] In the sample container 100, the pressure regulating valve 60 maintains a constant pressure difference between the inside and outside of the first container 10 in a vacuum atmosphere. Therefore, the possibility of damage to the analytical film 20 can be reduced in the sample container 100.

[0101] In the sample container 100, the pressure adjustment valve 60 opens when the pressure inside the first container 10 is greater than the external pressure and the pressure difference between the inside and outside of the first container 10 is greater than the set pressure, and closes when the pressure inside the first container 10 is greater than the external pressure and the pressure difference between the inside and outside of the first container 10 is less than or equal to the set pressure, and the set pressure is variable. Therefore, in the sample container 100, the set pressure can be changed according to the diameter of the first opening 4a and the strength (thickness and material) of the analytical film 20. Thus, in the sample container 100, measurements can be performed using first containers 10 of various diameters and analytical films 20 of various types.

[0102] The sample container 100 includes a second container 50 equipped with a pressure adjustment valve 60, and the space 6 inside the second container 50 is in communication with the space 2 inside the first container 10. Therefore, in the sample container 100, the pressure in the space 2 inside the first container 10 can be adjusted by adjusting the pressure in the space 6 inside the second container 50.

[0103] The X-ray fluorescence analyzer 200 includes a sample container 100 and a sample chamber 208 that houses the sample container 100 and can be maintained in a vacuum atmosphere. In the X-ray fluorescence analyzer 200, measurements are performed by irradiating the liquid sample S contained in the sample container 100 with X-rays in the vacuum atmosphere of the sample chamber 208. In the sample container 100, the pressure inside the first container 10 can be adjusted by the pressure adjustment valve 60, so that in the vacuum atmosphere of the sample chamber 208, the pressure inside the first container 10 can be maintained at a level higher than the boiling pressure of the liquid sample S and lower than the pressure at which the analytical film 20 breaks. Therefore, by using the sample container 100, the X-ray fluorescence analyzer 200 can perform measurements in a vacuum atmosphere in the sample chamber 208. This makes it possible to measure light elements in the liquid sample S without replacing the sample chamber 208 with helium.

[0104] The measurement method using the sample container 100 includes the steps of: placing a liquid sample S into the sample container 100; introducing the sample container 100 into the sample chamber 208 of the X-ray fluorescence analyzer 200; reducing the pressure in the sample chamber 208 to create a vacuum atmosphere; and irradiating the liquid sample S contained in the sample container 100 with X-rays through the analytical film 20 and the protective film 44 in the vacuum atmosphere of the sample chamber 208, and detecting the fluorescent X-rays emitted from the liquid sample S. Therefore, the measurement method using the sample container 100 allows measurement to be performed in a vacuum atmosphere in the sample chamber 208. Furthermore, by using the sample container 100, the possibility of the protective film 44 being damaged when the analytical film 20 is damaged due to the pressure difference between the first container 10 and the sample chamber 208 can be reduced.

[0105] In a measurement method using a sample container 100, the step of placing a liquid sample S into the sample container 100 includes the steps of placing the liquid sample S into a sample cup 12 and placing a damper 14 into the sample cup 12 containing the liquid sample S to divide the space 2 inside the sample cup 12 into a first space 2a, a second space 2b, and a connecting hole 2c. Therefore, with the sample container 100, the liquid sample S can be easily filled into the sample container 100 having a first space 2a, a second space 2b, and a connecting hole 2c.

[0106] For example, when a liquid sample S is placed in a sample container having a first space 2a, a second space 2b, and a connecting hole 2c, it is difficult to fill the first space 2a with the liquid sample S because the connecting hole 2c is narrowed. Furthermore, because the connecting hole 2c is narrowed, air bubbles are easily trapped in the first space 2a. In contrast, by inserting the damper 14 after placing the liquid sample S into the container, the above problems do not occur.

[0107] 2. Second Embodiment Next, the sample container according to the second embodiment will be described with reference to the drawings. Figure 13 is a schematic cross-sectional view of the sample container 300 according to the second embodiment. Figure 14 is a schematic cross-sectional view of the first container 10 of the sample container 300. Hereinafter, in the sample container 300 according to the second embodiment, components having the same function as the components of the sample container 100 according to the first embodiment will be denoted by the same reference numerals, and their detailed descriptions will be omitted.

[0108] In the sample container 100 described above, the connecting hole 2c narrowed the flow path of the liquid sample S from the second space 2b to the first space 2a. In the sample container 100, the cross-sectional area of ​​the connecting hole 2c was smaller than the area of ​​the second opening 4b.

[0109] In contrast, in the sample container 300, the cross-sectional area of ​​the connection hole 2c is the same as the area of ​​the second opening 4b. In the sample container 300, the diameter of the connection hole 2c is the same as the diameter of the second space 2b, and the connection hole 2c does not narrow the flow path of the liquid sample S flowing from the second space 2b to the first space 2a.

[0110] In the sample container 300, as in the sample container 100, the cross-sectional area of ​​the connection hole 2c is smaller than the area of ​​the first opening 4a. Therefore, in the sample container 300, as in the sample container 100, the flow rate of the liquid sample S and gas flowing from the second space 2b to the first space 2a can be limited compared to, for example, the case where the cross-sectional area of ​​the connection hole 2c is greater than or equal to the area of ​​the first opening 4a. Consequently, in the sample container 300, as in the sample container 100, the possibility of the protective film 44 being damaged when the analytical film 20 is damaged can be reduced.

[0111] The measurement method using sample container 300 is the same as the measurement method using sample container 100, and therefore its explanation is omitted.

[0112] Sample container 300 can produce the same effects as sample container 100.

[0113] 3. Third Embodiment Next, the sample container according to the third embodiment will be described with reference to the drawings. Figure 15 is a schematic cross-sectional view showing the sample container 400 according to the third embodiment. Hereinafter, in the sample container 400 according to the third embodiment, components having the same function as the components of the sample container 100 according to the first embodiment will be denoted by the same reference numerals, and their detailed descriptions will be omitted.

[0114] As shown in Figures 1 and 2, the sample container 100 includes a sample cup 12 and a damper 14, and the damper 14 divides the space inside the sample cup 12 to form a first space 2a, a second space 2b, and a connecting hole 2c.

[0115] In contrast, in the sample container 400, as shown in Figure 15, the first container 10 includes a sample cup 402 having a first space 2a, a buffer tank 404 having a second space 2b, and a tube 406 having a connecting hole 2c that connects the sample cup 402 and the buffer tank 404.

[0116] A fixing member 410 for securing the tube 406 is housed inside the sample cup 402. The first space 2a is formed by placing the fixing member 410 into the sample cup 402. The buffer tank 404 is located outside the sample cup 402. That is, the second space 2b is the space outside the sample cup 402. The space inside the buffer tank 404 is in communication with the space 6 inside the second container 50.

[0117] The measurement method using sample container 400 is the same as the measurement method using sample container 100, and therefore its explanation is omitted.

[0118] Sample container 400 can produce the same effects as sample container 100.

[0119] 4. Variations It should be noted that the present invention is not limited to the embodiments described above, and various modifications can be implemented within the scope of the gist of the present invention.

[0120] 4.1. First Variation In the first embodiment described above, the first container 10 includes a sample cup 12 and a damper 14, and by placing the damper 14 inside the sample cup 12, a first space 2a, a second space 2b, and a connection hole 2c are formed inside the sample cup 12. In contrast, for example, the sample cup 12 and the damper 14 may be integrally constructed. The same applies to the sample container 300 according to the second embodiment, in which the sample cup 12 and the damper 14 may be integrally constructed.

[0121] 4.2. Second Variation In the sample container 100 according to the first embodiment, the pressure regulating valve 60 maintains a constant pressure in the space 6 inside the second container 50 by using a spring 64 to open and close a valve 62 in accordance with the pressure difference between the inside and outside of the second container 50, as shown in Figure 3. However, the configuration of the pressure regulating valve 60 is not limited to this. Although not shown, for example, the pressure regulating valve 60 may use a weight instead of a spring 64 to open and close the valve 62 in accordance with the pressure difference between the inside and outside of the second container 50. For example, by using a weight to apply a force to close the valve, the pressure regulating valve 60 can be operated in the same way as when a spring 64 is used.

[0122] The embodiments and modifications described above are merely examples and are not limiting. For example, each embodiment and each modification can be combined as appropriate.

[0123] The present invention is not limited to the embodiments described above, and various further modifications are possible. For example, the present invention includes configurations that are substantially identical to those described in the embodiments. A substantially identical configuration is, for example, a configuration that has the same function, method, and result, or a configuration that has the same purpose and effect. The present invention also includes configurations in which non-essential parts of the configuration described in the embodiments are replaced. Furthermore, the present invention includes configurations that produce the same effects or achieve the same purpose as the configuration described in the embodiments. Furthermore, the present invention includes configurations that add known technology to the configuration described in the embodiments. [Explanation of Symbols]

[0124] 2...Space, 2a...First space, 2b...Second space, 2c...Connecting hole, 3a...Tapered section, 3b...Cylindrical section, 4a...First opening, 4b...Second opening, 5a...Tapered section, 5b...Cylindrical section, 6...Space, 10...First container, 12...Sample cup, 14...Damper, 15...Groove, 20...Analysis film, 30...Porous film, 40...Protective container, 42...Protective cup, 44...Protective film, 50...Second container, 52...Base, 52a...Through hole, 53...Opening, 54...Support member, 56...Lid, 60...Pressure adjustment valve, 62...Valve, 64...Spring, 70...Leak valve, 80...Cap, 82...Through hole, 90...O-ring, 92...O-ring, 94...O-ring, 96...O-ring G, 100...Sample container, 200...Fluorescent X-ray analyzer, 202...X-ray tube, 203...Filter, 204...Primary X-ray collimator, 205...Support plate, 206...Secondary X-ray collimator, 207...Detector, 208...Sample chamber, 300...Sample container, 400...Sample container, 402...Sample cup, 404...Buffer tank, 406...Tube, 410...Fixing member

Claims

1. A sample container for an X-ray fluorescence analyzer, A first container having a first opening and a second opening, which contains a liquid sample. The first opening is blocked by an analytical film that allows X-rays to pass through, A protective container having an X-ray-transmitting protective film, which covers the analytical film, A pressure regulating valve for adjusting the pressure inside the first container, Includes, The first container has a first space facing the first opening, a second space facing the second opening, and a connecting hole connecting the first space and the second space. A sample container in which the cross-sectional area of ​​the connection hole is smaller than the area of ​​the first opening.

2. In claim 1, A sample container in which the cross-sectional area of ​​the connection hole is smaller than the area of ​​the second opening.

3. In claim 1, The connection hole narrows the flow path of the liquid sample from the second space to the first space in the sample container.

4. In claim 1, The first space has a tapered portion in which the cross-sectional area decreases towards the tip. The tip of the tapered portion is connected to the connection hole, which is a sample container.

5. In claim 1, The first container is, Sample cup and The sample cup is divided into the first space, the second space, and the connection hole by a partitioning member, A sample container containing the sample.

6. In claim 1, A sample container in which the volume of the second space is greater than the volume of the first space.

7. In claim 1, A sample container comprising a porous film that seals the second opening.

8. In claim 1, The pressure regulating valve maintains a constant pressure difference between the inside and outside of the first container in a vacuum atmosphere.

9. In claim 1, The aforementioned pressure regulating valve is The opening occurs when the pressure inside the first container is greater than the pressure outside, and the pressure difference between the inside and outside of the first container is greater than the set pressure. The first container is closed when the pressure inside the first container is greater than the pressure outside, and the pressure difference between the inside and outside of the first container is less than or equal to the set pressure. The aforementioned set pressure is variable in the sample container.

10. In claim 1, The container includes a second container equipped with the aforementioned pressure regulating valve, The space inside the second container is in communication with the space inside the first container, and this is a sample container.

11. A sample container according to any one of claims 1 to 10, A sample chamber in which the aforementioned sample container is housed and which can be maintained in a vacuum atmosphere, Includes, A fluorescence X-ray analyzer that performs measurements by irradiating a liquid sample contained in a sample container with X-rays in a sample chamber under a vacuum atmosphere.

12. A first container having a first opening and a second opening, which contains a liquid sample. The first opening is blocked by an analytical film that allows X-rays to pass through, A protective container having an X-ray-transmitting protective film, which covers the analytical film, A pressure regulating valve for adjusting the pressure inside the first container, Includes, The first container has a first space facing the first opening, a second space facing the second opening, and a connecting hole connecting the first space and the second space. A measurement method using a sample container, wherein the cross-sectional area of ​​the connection hole is smaller than the area of ​​the first opening, The steps include: placing the liquid sample into the sample container; The process involves introducing the aforementioned sample container into the sample chamber of the X-ray fluorescence analyzer, A step of reducing the pressure in the sample chamber to create a vacuum atmosphere in the sample chamber, In the sample chamber under a vacuum atmosphere, the liquid sample contained in the sample container is irradiated with X-rays through the analytical film and the protective film, and the fluorescent X-rays emitted from the liquid sample are detected. Measurement methods, including those mentioned above.

13. In claim 12, The first container is, Sample cup and The sample cup is divided into the first space, the second space, and the connection hole by a partitioning member, Includes, The step of placing the liquid sample into the sample container is: The steps include: placing the liquid sample into the sample cup, The steps include: placing the partitioning member into the sample cup containing the liquid sample, thereby dividing the space within the sample cup into the first space, the second space, and the connection hole; Measurement methods, including those mentioned above.

Images