Fluorescent x-ray analysis device, sample container, and analysis method

Abstract

An analysis device (100) (fluorescent X-ray analysis device) comprises: a sample stage (33) on which a sample is placed; an X-ray tube (51) (X-ray source) that irradiates the sample with primary X-rays; a detector (52) that detects fluorescent X-rays emitted from the sample in response to the irradiated primary X-rays; a control device (1) (analysis unit) that analyzes the fluorescent X-rays detected by the detector (52); and an agitating mechanism (2) that agitates the sample.

Description

X-ray fluorescence analyzer, sample container, and analysis method

[0001] The present invention relates to an X-ray fluorescence analyzer, a sample container, and an analysis method, and more particularly to an X-ray fluorescence analyzer that handles samples that may have heterogeneous components.

[0002] X-ray fluorescence analysis (XRF) is a technique for analyzing the constituent elements of a sample by irradiating the sample with X-rays and measuring the fluorescent X-rays emitted from the sample. XRF is broadly classified into energy dispersive X-ray spectroscopy (EDX) and wavelength dispersive X-ray spectroscopy (WDX) depending on the method of detecting the fluorescent X-rays.

[0003] Since each element in a fluorescent X-ray has its own specific energy, the type and content of elements that make up the sample can be determined by analyzing the energy and intensity of the fluorescent X-rays emitted from the sample using XRF.

[0004] Many methods have been developed for precisely analyzing elements contained in samples in XRF. Regarding an X-ray irradiation method, International Publication No. 2020 / 044399 (Patent Document 1) discloses a technique for reducing bias in the irradiation position of primary X-rays by rotating a gripper holding the sample around a rotation axis perpendicular to the analysis surface of the sample during primary X-ray irradiation. Regarding a fluorescent X-ray measurement method, Japanese Patent Application Laid-Open No. 2021-135160 (Patent Document 2) discloses a technique for enabling an X-ray analyzer to detect whether a sample to be analyzed is a liquid and, if a liquid is detected, to prohibit or stop operation of an exhaust device.

[0005] International Publication No. 2020 / 044399 Japanese Patent Application Laid-Open No. 2021-135160

[0006] As described above, improvements in primary X-ray irradiation methods and fluorescent X-ray measurement methods are expected to contribute to improving the accuracy of analysis of elements contained in a sample. However, depending on the condition of the sample itself, such as the sample's constituent components being non-uniform within the sample, it may be difficult to perform a precise analysis of the entire sample. Therefore, there is still a need for technology to improve the accuracy of elemental analysis.

[0007] The present disclosure has been made in view of the above circumstances, and its purpose is to improve the analytical accuracy of elements contained in a sample in an X-ray fluorescence analyzer.

[0008] A first aspect of the present disclosure is an X-ray fluorescence analysis apparatus comprising: a sample stage on which a sample is placed; an X-ray source that irradiates the sample with primary X-rays; a detector that detects fluorescent X-rays emitted from the sample in response to the irradiated primary X-rays; an analysis unit that analyzes the fluorescent X-rays detected by the detector; and a stirring mechanism that stirs the sample.

[0009] A second aspect of the present disclosure is a sample container for containing a sample to be analyzed by an X-ray fluorescence analyzer, wherein the X-ray fluorescence analyzer is equipped with a stirring mechanism, and the sample container is equipped with a baffle portion that improves the efficiency of stirring the sample by the stirring mechanism.

[0010] A third aspect of the present disclosure is a method for analyzing a sample using an X-ray fluorescence analyzer, comprising the steps of stirring the sample using the X-ray fluorescence analyzer, and irradiating the sample with X-rays to obtain X-ray fluorescence spectrum information of the sample.

[0011] According to the present disclosure, it is possible to improve the analytical accuracy of elements contained in a liquid sample in an X-ray fluorescence analyzer.

[0012] 1 is a schematic diagram showing the configuration of an analytical device according to an embodiment of the present disclosure; FIG. 2 is a flowchart showing a fluorescent X-ray measurement process performed by the analytical device; FIG. 3 is a flowchart of a subroutine of the measurement step of FIG. 2; FIG. 4 is a cross-sectional front view of the analytical device, showing a turret set on the sample stage; FIG. 5 is a plan view showing the turret as viewed along the Z-axis direction in FIG. 4; FIG. 6 is a cross-sectional front view of the analytical device, showing a sample spinner set on the sample stage; FIG. 7 is a perspective view of the sample spinner; FIG. 8 is a cross-sectional front view of a sample container, showing an embodiment of a stirring mechanism using a baffle portion provided in the sample container; and FIG. 9 is a plan view of the sample container as viewed from the Z-axis direction in FIG.

[0013] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are designated by the same reference numerals, and description thereof will not be repeated.

[0014] [Overall Configuration of X-Ray Fluorescence Analysis Apparatus] Fig. 1 is a schematic diagram showing the configuration of an analysis apparatus 100 according to an embodiment of the present disclosure. The analysis apparatus 100 irradiates a sample to be analyzed with X-rays and measures the fluorescent X-rays emitted from the sample to determine the types and amounts of elements contained in the sample. In one example, the analysis apparatus 100 is an EDX apparatus, but a WDX apparatus may be used instead of an EDX apparatus. The analysis apparatus 100 includes a control device 1, a stirring mechanism 2, a main body 3, a heating mechanism 6, a display device 16, and an input device 17.

[0015] The main body 3 includes a housing 31, a housing 32, and a sample stage 33. The housing 31 is placed on a first surface 34 of the sample stage 33. The housing 31 and the sample stage 33 form a sample chamber 4. The housing 32 is placed on a second surface 35 of the sample stage 33. The housing 32 and the sample stage 33 form a measurement chamber 5. The sample chamber 4 and the measurement chamber 5 are enclosed by the housing 31 and the housing 32 in an airtight manner.

[0016] 1, the direction perpendicular to the sample stage 33 is defined as the Z axis, and the plane parallel to the surface of the sample stage 33 is defined as the XY plane. In one embodiment, the analysis device 100 is used in a state where it is installed so that the Z axis is approximately parallel to the direction of gravity. In this case, the first surface 34 of the sample stage 33 is the so-called "sample stage upper surface," and the second surface 35 of the sample stage 33 is the so-called "sample stage lower surface."

[0017] An opening 36 is formed in the sample stage 33. When analyzing the sample S, the sample S is placed on the sample stage 33 so as to cover the opening 36. As a result, the analysis surface SA, which is the lower surface of the sample S, is exposed to the measurement chamber 5 through the opening 36.

[0018] In one embodiment, the sample S is a liquid and is held in a sample container C for holding the sample S. In this case, when analyzing the sample S, the sample S contained in the sample container C is placed on the first surface 34 so as to cover the opening 36.

[0019] The user can select the conditions for stirring by the stirring mechanism 2 in the analyzer 100 based on the information on the "type of sample" and / or "properties of sample."

[0020] "Sample type" refers to the types and mixing ratios of substances that make up the sample. Specifically, the sample type includes, for example, at least one of the name and / or chemical formula of the solute substance, the name and / or chemical formula of the solvent substance, and the concentration of the solute. The sample may contain oil or fat. In this case, the components that make up the oil or fat itself (e.g., sulfur in mineral oil) may be analyzed, or additives added to the oil or fat may be analyzed using the oil or fat as a solvent.

[0021] "Sample properties" refer to the characteristics of the sample and the characteristics of the substances that make up the sample. Specifically, the sample characteristics are, for example, the viscosity of the sample. Furthermore, the characteristics of the substances that make up the sample include at least one of the ease of separation of the solute substance, the ease of precipitation of the solute substance, the ease of separation of the solvent substance, and the ease of solidification of the solvent substance.

[0022] The sample container C includes, for example, a cylindrical member made of resin and a thin resin film. The opening at the bottom of the cylindrical member is covered and closed with a film. The film is fixed to the sample container C using, for example, a ring-shaped fixing member. The film is made of a resin composed of carbon and hydrogen atoms, or carbon, hydrogen, and oxygen atoms, such as polypropylene or polyethylene terephthalate. Because the fluorescent X-rays emitted from these elements are weak, the film has little effect on the fluorescent X-ray analysis in EDX. Because the film is sufficiently thin, the heights of the first surface 34 of the sample stage 33 and the analysis surface SA in the Z-axis direction are approximately the same. Therefore, the film is not shown in the figures referenced in this specification. The sample container C may have a relief hole for liquid expansion and / or a liquid retainer.

[0023] An X-ray tube 51 and a detector 52 are disposed in the measurement chamber 5. The X-ray tube 51 generates X-rays and irradiates the sample S with them. The X-ray tube 51 includes a filament that emits thermions and a target that converts the thermions into predetermined primary X-rays and emits them. The detector 52 detects fluorescent X-rays emitted from the sample. The detector 52 is configured, for example, by a semiconductor detector including a Si element. Note that the detector 52 may also be configured by a semiconductor detector including an element in which a Si element is doped with a Li element.

[0024] The X-ray tube 51 and the detector 52 are installed on the wall of the measurement chamber 5. The primary X-rays emitted from the X-ray tube 51 are irradiated onto the sample S through the opening 36. The fluorescent X-rays generated from the sample S are incident on the detector 52, which measures the energy and amount of the fluorescent X-rays. More specifically, the energy of the fluorescent X-rays is generally represented by the wavelength of the fluorescent X-rays. The amount of the fluorescent X-rays is generally represented by the number of photons of the fluorescent X-rays per unit time, and is also called the intensity of the fluorescent X-rays. The detection result of the detector 52 is typically represented as an X-ray fluorescence spectrum, which shows the relationship between the energy and amount of the detected fluorescent X-rays.

[0025] The stirring mechanism 2 is a transport mechanism for moving the sample S between a position where the sample is waiting before measurement and an analysis position AP where the sample S is placed during analysis, and is also capable of stirring the sample S. The stirring mechanism 2 includes an X-axis rail 21, a Y-axis rail 22, a Z-axis rail 23, a moving body 24, an arm unit 25, and a gripper unit 26.

[0026] The X-axis rail 21 extends along the X-axis direction. The X-axis rail 21 is provided so as to be movable in the Y-axis direction by a Y-axis rail 22. The X-axis rail 21 runs on the Y-axis rail 22 by a drive source such as a motor.

[0027] The X-axis direction is any one horizontal direction, and the Y-axis direction is a direction perpendicular to the X-axis direction.

[0028] The Y-axis rail 22 extends along the Y-axis direction and guides the movement of the X-axis rail 21 in the Y-axis direction. The Y-axis rail 22 is provided on both ends of the X-axis rail 21 in the X-axis direction.

[0029] The Z-axis rail 23 extends along the Z-axis direction. The Z-axis direction is the up-down direction and is perpendicular to the X-axis and Y-axis directions. The Z-axis rail 23 is fixed to the moving body 24. The Z-axis rail 23 guides the movement of the arm unit 25 along the Z axis.

[0030] The moving body 24 is provided so as to be movable in the X-axis direction along the X-axis rail 21 as indicated by arrow 27. The moving body 24 is moved by a drive source such as a motor. The Z-axis rail 23 is fixed to the moving body 24. As a result, when the moving body 24 moves in the X-axis direction, the Z-axis rail 23 also moves along the X-axis direction.

[0031] The arm unit 25 is fixed to the Z-axis rail 23 and is provided so as to be movable in the Z-axis direction along the Z-axis rail 23 as indicated by arrow 28. The arm unit 25 is also provided so as to be rotatable about a rotation axis perpendicular to the analysis surface SA of the sample S as indicated by arrow 29. When the arm unit 25 rotates while gripping the sample S contained in the sample container C, the sample S is rotated and stirred.

[0032] The gripper 26 is provided at the tip (lower end) of the arm 25. The gripper 26 is provided so as to be able to grip the sample S contained in the sample container C. The gripper 26 is, for example, a robot arm.

[0033] The gripper 26 is provided so as to be movable in the X-axis, Y-axis, and Z-axis directions. More specifically, the gripper 26 moves along the X-axis direction together with the movable body 24 as the movable body 24 moves in the X-axis direction along the X-axis rail 21. The gripper 26 moves along the Y-axis direction together with the X-axis rail 21 as the X-axis rail 21 moves in the Y-axis direction along the Y-axis rail 22. The gripper 26 moves along the Z-axis direction together with the arm unit 25 as the arm unit 25 moves along the Z-axis rail 23.

[0034] As described above, the gripping portion 26 grips the sample S contained in the sample container C, enables the sample S to be moved between the standby position and the measurement position, and enables the sample S to be stirred by rotating the arm portion 25.

[0035] The gripper 26 is provided so as to be rotatable about a rotation axis perpendicular to the analysis surface SA of the sample S. Specifically, when the arm 25 rotates as described above, the gripper 26 rotates integrally with the arm 25. The direction of the rotation axis coincides with the Z-axis direction.

[0036] The control device 1 has, as its main components, a CPU (Central Processing Unit) 11, a ROM (Read Only Memory) 12, a RAM (Random Access Memory) 13, a HDD (Hard Disk Drive) 14, and an I / O (Input / Output) interface 15. The components are interconnected via a data bus. The control device 1 controls the stirring mechanism 2, the main body 3, and the heating mechanism 6. During measurement, the control device 1 also performs analysis (qualitative analysis and quantitative analysis) of various elements contained in the sample S contained in the sample container C based on the spectrum of fluorescent X-rays detected by the detector 52. The control device 1 can be, for example, a personal computer.

[0037] The CPU 11 performs overall control of the entire analysis device 100. The ROM 12 stores a program that describes the processing procedures of the analysis device 100 to be executed by the CPU 11. The RAM 13 can temporarily store data generated by the execution of the program by the CPU 11 and can function as a primary storage device. The HDD 14 is a non-volatile storage device in which data acquired by the analysis device 100 is saved. The control device 1 may have a semiconductor storage device such as a flash memory instead of or in addition to the HDD 14.

[0038] The I / O interface 15 is an interface for input to the stirring mechanism 2, main body 3, and display device 16, or for output from the main body 3 and input device 17. The I / O interface 15 is connected to the stirring mechanism 2, X-ray tube 51, detector 52, display device 16, and input device 17. The control device 1 controls the movement of the movable body 24 in each of the X-, Y-, and Z-axis directions, the movement of the gripper 26, the tube voltage, tube current, and irradiation time of the X-ray tube 51, the heating temperature and heating time by the heating mechanism 6, and the display on the display device 16, by transmitting control signals (commands) via the I / O interface 15.

[0039] The display device 16 is configured by, for example, a liquid crystal monitor, and displays the detection results of the fluorescent X-rays in accordance with commands from the CPU 11.

[0040] The input device 17 is configured by, for example, a keyboard and a mouse. The input device 17 receives instructions from the user for the control device 1 and the main body 3, and outputs the instructions to the CPU 11 via the I / O interface 15. Alternatively, a touch panel in which the display device 16 and the input device 17 are integrated may be used.

[0041] The heating mechanism 6 is, for example, composed of a heater, and adjusts the temperature inside the sample chamber 4. By heating the inside of the sample chamber 4, the viscosity of the sample S contained in the sample chamber 4 decreases, making it easier to stir. The heating temperature is preferably 50°C or less. In FIG. 1, the heating mechanism 6 is shown as heating the inside of the sample chamber 4, but the heating mechanism 6 may also be configured to heat only the sample S. For example, the heating mechanism 6 is installed so as to cover the sample container C, and as the heating mechanism 6 heats up, the sample container C in contact with the heating mechanism 6 is heated, and the sample S is heated.

[0042] X-ray fluorescence analysis is a useful analytical method for determining the elemental composition of a sample. Specifically, the type and amount of elements contained in the sample can be determined by irradiating the sample with primary X-rays and analyzing the fluorescent X-rays that are generated.

[0043] In analyzing a sample, the analytical accuracy and analytical sensitivity tend to be worse for the portion of the sample away from the analytical surface (SA in Figure 1) than for the portion closer to the analytical surface. This is because, to measure the portion away from the analytical surface, the primary X-rays and fluorescent X-rays must pass through the sample, during which the X-rays are absorbed by the sample, resulting in energy attenuation.

[0044] Therefore, if the sample is not homogeneous, it becomes difficult to accurately analyze the elemental composition of the entire sample. Therefore, when analyzing the elemental composition of the entire sample, it is important that the sample is mixed homogeneously. In conventional techniques, users have to manually mix the sample before performing X-ray fluorescence analysis to ensure that the sample is homogeneous.

[0045] However, if the solute of the sample is prone to precipitation or the solvent of the sample is prone to precipitation, precipitates or crystals may form during the X-ray fluorescence analysis, resulting in an imbalance in the components in the sample.

[0046] [Analytical Apparatus According to the Embodiment] In the analytical apparatus 100 according to the present embodiment, the stirring mechanism 2 stirs the sample during or immediately before the fluorescent X-ray analysis. This makes it possible to prevent the occurrence of imbalances in the sample components during the fluorescent X-ray analysis. The analytical apparatus 100 also has a heating mechanism 6 that warms the sample, which can stir even highly viscous samples and prevent the occurrence of imbalances in the sample components during the fluorescent X-ray analysis.

[0047] [Aspects of Sample Stirring] Next, an aspect of sample stirring will be described. Specific aspects of stirring will be described later.

[0048] Sample stirring refers to stirring the sample contained in a sample container by rotating and / or vibrating the sample container. Rotation refers to rotating the sample around a rotation axis. In sample rotation, the sample may be rotated around one rotation axis or multiple rotation axes. Rotation is defined by the rotation speed, rotation direction, and rotation time. At least one of these may be variable or may be changed in response to user input. The rotation speed and / or rotation direction may change during the rotation time. Vibration refers to shaking the sample up and down and / or left and right. The vibration mode may change periodically or aperiodically. The vibration is defined by the vibration direction, amplitude, speed, acceleration, and vibration time. At least one of these may be variable in response to user input. The parameters that define the rotation and / or vibration in the above-mentioned stirring are called stirring parameters. In sample measurement, a combination of the sample stirring parameters and the timing to start stirring the sample, or the timing to stop stirring the sample, together with these, is called a stirring pattern.

[0049] The stirring of the sample may be achieved by a stirring unit provided inside the sample container, which stirs the sample. For example, the stirring unit may include a propeller blade. The propeller blade rotates within the sample to stir the sample.

[0050] Furthermore, a baffle may be provided inside the sample container, and the baffle improves the efficiency of stirring the sample. Specifically, the baffle improves the efficiency of stirring the sample when the sample container containing the sample is rotated and / or vibrated to stir the sample. The baffle includes an uneven surface inside the sample container, and when the sample container rotates, the uneven surface formed inside the sample container generates turbulence, thereby stirring the sample more efficiently.

[0051] [Timing of Sample Stirring] Next, timing of sample stirring will be described.

[0052] The stirring of the sample may be performed once or multiple times for one fluorescent X-ray measurement. The stirring of the sample is started either before the start of the fluorescent X-ray measurement, simultaneously with the start of the fluorescent X-ray measurement, or during the fluorescent X-ray measurement.

[0053] The user can select the timing of sample stirring depending on the type and / or properties of the sample. For example, if the components contained in the sample become non-uniform within the sample before fluorescent X-ray measurement, it is desirable to start stirring the sample before starting fluorescent X-ray measurement or to stir the sample multiple times before starting fluorescent X-ray measurement. Furthermore, for example, if the components contained in the sample become non-uniform within the sample during fluorescent X-ray measurement, it is desirable to stir the sample during fluorescent X-ray measurement. Stirring the sample before and / or during fluorescent X-ray measurement can prevent the components contained in the sample from becoming non-uniform within the sample during fluorescent X-ray measurement.

[0054] [Position for Stirring the Sample] When the sample is stirred during X-ray fluorescence measurement, the sample is stirred while positioned at the X-ray fluorescence measurement position. In this case, the rotation and / or vibration mode is adjusted to stir the sample so that the analysis surface of the sample does not move away from the sample stage. For example, the sample S is stirred while the analysis surface SA of the sample S is in contact with the first surface 34 of the sample stage 33. When the sample is stirred before X-ray fluorescence measurement, the position for stirring the sample is not particularly limited. The sample may be stirred while positioned at the X-ray fluorescence measurement position, or may be stirred at a position different from the X-ray fluorescence measurement position.

[0055] The sample to be analyzed by the X-ray fluorescence analyzer is not limited to a liquid, but may also be a solid. In the case of a solid, the X-ray fluorescence measurement is performed without stirring. The analysis device 100 may use an acceleration sensor to determine whether the sample S is a liquid, and may stir the sample S if it is determined that the sample S is a liquid.

[0056] 2 is a flowchart showing the fluorescent X-ray measurement process performed by the analytical device 100. In one implementation example, this process is executed when an application for fluorescent X-ray measurement is launched.

[0057] 2, in S10, the control device 1 performs initial settings for fluorescent X-ray measurement. Items set in the initial settings include whether or not to use heating by the heating mechanism 6, and the heating temperature if heating is performed. The heating temperature may be set by the user, or the control device 1 may call up settings that have been previously saved in the HDD 14. There are no restrictions on the timing at which heating is started, but it is preferable that the temperature of the sample S be stabilized before the fluorescent X-ray measurement is started. Once the initial settings are complete, the control device 1 advances control to S12.

[0058] In S12, the control device 1 receives information about the fluorescent X-ray measurement. The information about the fluorescent X-ray measurement includes at least one of the fluorescent X-ray measurement time and the sample stirring pattern. The control device 1 may call up settings for the fluorescent X-ray measurement time and / or the sample stirring pattern that have been previously saved in the HDD 14 based on the type and / or properties of the sample input by the user. The control device 1 then proceeds to S14.

[0059] In S14, the control device 1 determines whether a measurement command has been issued by the user. The control device 1 repeats the control of S12 until it determines that a measurement command has been issued (NO in S12). When the control device 1 determines that a measurement command has been issued (YES in S12), the control proceeds to S16.

[0060] In S16, the control device 1 outputs an instruction to execute X-ray fluorescence measurement to the main body 3 based on the information on the X-ray fluorescence measurement received in S12. The main body 3, which has received the instruction to execute X-ray fluorescence measurement, starts the measurement. After the measurement is completed, the main body 3 sends the measurement results to the control device 1. After receiving the measurement results, the control device 1 ends the X-ray fluorescence measurement process.

[0061] Fig. 3 is a flowchart of the subroutine of S16 in Fig. 2. As shown in Fig. 3, in the control of S20, the stirring pattern included in the fluorescent X-ray measurement information received in S12 is read out.

[0062] In S22, the control device 1 determines whether the stirring pattern read out in S20 includes an instruction to stir before fluorescent X-ray measurement. If the control device 1 determines that stirring before fluorescent X-ray measurement has been instructed (YES in S22), the control device 1 proceeds to S24. If the control device 1 determines that stirring before fluorescent X-ray measurement has not been instructed (NO in S22), the control device 1 proceeds to S26.

[0063] In S24, the control device 1 sends an instruction to start stirring to the stirring mechanism 2. The stirring mechanism 2, which has received the instruction to start stirring, stirs the sample S based on the stirring pattern received in S20. The stirring started in S24 may end in S24, or may continue after S24. Furthermore, stirring may be started and ended multiple times in S24. Thereafter, the control device 1 advances the process to S26.

[0064] In S26, the control device 1 sends an instruction to start fluorescent X-ray measurement to the main body 3. Upon receiving the instruction to start fluorescent X-ray measurement, the main body 3 irradiates primary X-rays onto the sample S from the X-ray tube 51 and detects fluorescent X-rays emitted from the sample S with the detector 52. Thereafter, the control device 1 advances the process to S28.

[0065] In S28, the control device 1 determines whether the stirring pattern read out in S20 includes an instruction to stir simultaneously with the start of fluorescent X-ray measurement. If the control device 1 determines that stirring has been instructed simultaneously with the start of fluorescent X-ray measurement (YES in S28), the control proceeds to S30. If the control device 1 determines that stirring has not been instructed before fluorescent X-ray measurement (NO in S28), the control proceeds to S32.

[0066] In S30, the control device 1 sends an instruction to start stirring to the stirring mechanism 2. The stirring mechanism 2, which has received the instruction to start stirring, stirs the sample S based on the stirring pattern received in S20. The stirring started in S30 may end in S30, or may continue after S30. Furthermore, stirring may be started and ended multiple times in S30. Thereafter, the control device 1 advances the process to S32.

[0067] In S32, the control device 1 determines whether the stirring pattern read out in S20 includes an instruction to stir during fluorescent X-ray measurement. If the control device 1 determines that stirring has been instructed during fluorescent X-ray measurement (YES in S32), the control proceeds to S34. If the control device 1 determines that stirring has not been instructed before fluorescent X-ray measurement (NO in S32), the control device 1 ends the subroutine and returns control to the main routine.

[0068] In S34, the control device 1 sends an instruction to start stirring to the stirring mechanism 2. The stirring mechanism 2, which has received the instruction to start stirring, stirs the sample S based on the stirring pattern received in S20. The stirring started in S34 may end in S34, or may continue after S34. In addition, stirring may be started and ended multiple times in S34. Thereafter, the control device 1 ends the subroutine and returns control to the main routine.

[0069] The X-ray fluorescence analyzer according to the present embodiment described above is provided with a mechanism for stirring the sample, which prevents the concentration in the sample from becoming non-uniform during analysis, thereby improving the analytical sensitivity and analytical accuracy of elemental analysis of the entire sample.

[0070] Furthermore, since the X-ray fluorescence analyzer according to this embodiment is equipped with a mechanism for stirring the sample, even if components in the sample precipitate, the precipitate can be dispersed, thereby improving the analytical sensitivity and analytical accuracy of elemental analysis of samples in which components precipitate when left for a long period of time.

[0071] Furthermore, the X-ray fluorescence analyzer according to this embodiment is equipped with a heating mechanism, which allows the sample to be heated, thereby reducing the viscosity of the sample and improving the stirring efficiency of the sample.

[0072] [Examples] Specific examples according to the present disclosure will be described in detail below with reference to the drawings.

[0073] Example 1: Stirring of sample when transport mechanism is used as stirring mechanism Next, a description will be given of an example of stirring of a sample using the stirring mechanism 2. The stirring mechanism 2 stirs the sample S by rotating the gripper 26 while the gripper 26 grips the sample container C containing the sample S.

[0074] 1, the arm unit 25 is configured to be rotatable about a rotation axis perpendicular to the analysis surface SA of the sample S. Therefore, when the gripper 26 grips the sample container C containing the sample S, the arm unit 25 is rotated to rotate and stir the sample S. The rotation speed is approximately 10 to 1000 rpm. In this case, the sample S may be rotated either before or during the measurement of fluorescent X-rays.

[0075] Furthermore, the rotation axis of the arm unit 25 does not have to be perpendicular to the XY plane. The sample S may be stirred by rotating the arm unit 25 at an angle relative to the Z axis. Such rotation of the sample S is performed before measuring the fluorescent X-rays. This is because, if the sample is rotated around a rotation axis that is not perpendicular to the XY plane, the analysis surface SA may not be uniformly irradiated with the sample, making fluorescent X-ray analysis difficult.

[0076] Furthermore, as a modified example of this embodiment, the stirring mechanism 2 may stir the sample S by vibrating the gripping portion 26 while the gripping portion 26 is gripping the sample container C containing the sample S.

[0077] In this modified example, the arm 25 is configured to be vibrable along the Z-axis direction and / or along any one horizontal direction. Therefore, when the gripper 26 grips the sample container C containing the sample S, the arm 25 is vibrated to agitate the sample S. Note that it is desirable to vibrate the sample S along the Z-axis direction before measuring the fluorescent X-rays. This is because, if the analysis surface SA vibrates along the Z-axis direction, the analysis surface SA may not be exposed to the measurement chamber 5 through the opening 36, preventing stable irradiation of the sample S with primary X-rays and potentially affecting the fluorescent X-ray measurement.

[0078] Note that stirring of the sample S by rotating the arm unit 25 and stirring of the sample S by vibrating the arm unit 25 may be performed in combination. In this case, for example, the arm unit 25 is configured to be rotatable about a rotation axis perpendicular to the analysis surface SA of the sample S and to be vibrable along the Z-axis direction. With this configuration, before measuring the fluorescent X-rays of the sample S, the arm unit 25 can be vibrated while the gripper 26 is holding the sample container C containing the sample S, and during the fluorescent X-ray measurement of the sample S, the arm unit 25 can be rotated while the gripper 26 is holding the sample container C containing the sample S. Stirring the sample S by combining rotation and vibration can improve the stirring efficiency of a sample that is difficult to stir by stirring either by rotation or vibration alone.

[0079] Example 2: Stirring of a sample S using a turret as a stirring mechanism Next, an example of stirring a sample S using a turret installed on the sample stage 33 as a stirring mechanism will be described. The turret is a mechanism for continuously performing X-ray fluorescence analysis on multiple samples by placing multiple samples on it and rotating it to switch between samples to be analyzed. FIG. 4 is a front cross-sectional view of the analytical device 100, showing the turret 7 set on the sample stage 33. FIG. 4 shows the interior of the sample chamber 4 formed by the housing 31 and sample stage 33 of FIG. 1. FIG. 5 is a plan view of the turret 7 as viewed along the Z-axis direction in FIG. 4. For ease of explanation, the housing 31 is not shown in FIG. 5.

[0080] The turret 7 is arranged to be rotatable on the XY plane with the center of the turret 7 as the axis of rotation, as shown by the arrow 73 in Figure 5. The turret 7 is arranged on the first surface 34 of the sample stage 33. The turret 7 has a plurality of openings 71 (for example, 12 openings 71). A sample container C containing a sample S is placed in each opening 71 so as to cover the opening 71. The turret 7 can be rotated to switch the sample S to be analyzed. During measurement, the opening 71 in which the sample S to be analyzed is placed is positioned so as to overlap with the opening 36 at the bottom of the housing 31.

[0081] The turret used for the continuous analysis of multiple samples is capable of stirring the samples. Specifically, the sample S is stirred by rotating the turret 7 with a sample container C containing the sample S placed on it. The rotation speed is, for example, about 10 to 1000 rpm. The rotation direction is, for example, switched between clockwise and counterclockwise at regular time intervals, and the acceleration of the sample S is changed, causing the sample S to be stirred by the inertial force acting on the sample S.

[0082] Stirring by rotating the turret 7 may be performed before or during fluorescent X-ray analysis of the sample S. However, when stirring is performed during fluorescent X-ray analysis of the sample S, the sample S is rotated so that the analysis surface SA of the sample S overlaps the entire surface of the opening 36. In this case, the rotation direction, one of the parameters that defines the rotation, is controlled. This is to prevent the primary X-rays from irradiating the sample S with the primary X-rays, making fluorescent X-ray analysis impossible, if a portion of the analysis surface SA of the sample S to be analyzed is positioned outside the range of the opening 36, and to prevent a sample not to be analyzed placed in the opening 71 of the turret 7 from being irradiated with the primary X-rays, thereby affecting the measurement of the fluorescent X-rays of the sample S to be analyzed. For example, in FIG. 5 , when the turret 7 rotates clockwise, the opening 36 of the sample stage 33 is positioned outside the range of the opening 71 of the turret 7, resulting in a situation in which a portion of the analysis surface SA of the sample S to be analyzed is positioned outside the range of the opening 36. To prevent this from happening, the rotation direction must be switched to counterclockwise before the opening 36 of the sample stage 33 is positioned outside the range of the opening 71 of the turret 7 .

[0083] In addition, when multiple samples to be analyzed are placed on the turret 7, stirring the sample being analyzed also stirs the other samples placed on the turret 7. This allows multiple samples to be stirred simultaneously, thereby shortening the time required for stirring when measuring the fluorescent X-rays of multiple samples.

[0084] Furthermore, as a modification of this embodiment, the turret 7 may be configured to vibrate along the Z-axis direction while a sample container C containing the sample S is placed on the turret 7, thereby stirring the sample S.

[0085] In this modification, the turret 7 is arranged on the first surface 34 of the sample stage 33 so as to be vibrated in the Z-axis direction, as shown by the arrow 72 in Figure 4. Therefore, by vibrating the turret 7 with a sample container C containing the sample S placed thereon, the sample S can be stirred. Note that it is desirable to vibrate the sample S in the Z-axis direction before measuring the fluorescent X-rays. This is because, if the analysis surface SA is vibrating in the Z-axis direction, the analysis surface SA may not be exposed to the measurement chamber 5 through the opening 36, preventing stable irradiation of the sample S with primary X-rays and potentially affecting the fluorescent X-ray measurement.

[0086] Furthermore, stirring of the sample S by rotating the turret 7 and stirring of the sample S by vibrating the turret 7 may be performed in combination. In this case, for example, the turret 7 is configured to be rotatable around the center of the turret 7 as the rotation axis and to be vibrable along the Z-axis direction. With this configuration, before measuring the fluorescent X-rays of the sample S, the turret 7 vibrates while the sample S is placed in the opening 71 of the turret 7 to stir the sample S, and during the fluorescent X-ray measurement of the sample S, the turret rotates to stir the sample S. Stirring the sample S by combining rotation and vibration can improve the stirring efficiency of a sample that is difficult to stir by stirring either by rotation or vibration alone.

[0087] Example 3: Stirring of sample S using a sample spinner as a stirring mechanism Next, an example of stirring the sample S using a sample spinner installed on the sample stage 33 as a stirring mechanism will be described. The sample spinner is a mechanism for reducing bias in the irradiation position of primary X-rays by rotating around the center of the sample container C as the rotation axis at the analysis position AP during fluorescent X-ray measurement. Figure 6 is a cross-sectional front view of the analysis device 100, showing the sample spinner 8 installed on the sample stage 33. Figure 6 shows the interior of the sample chamber 4 formed by the housing 31 and sample stage 33 of Figure 1. Figure 7 is a perspective view of the sample spinner 8. For ease of explanation, the front of the housing 31 and the sample container C are not shown in Figure 7.

[0088] The sample spinner 8 has an opening 81 formed therein for allowing the primary X-rays and fluorescent X-rays to pass through. The sample spinner 8 is placed on the sample stage 33 so that the analysis surface SA is exposed from the opening 36 at the bottom of the housing 31. A sample container C containing a sample S is placed on the sample spinner 8 so as to cover the opening 81.

[0089] 7, the sample spinner 8 is installed so as to be rotatable about a rotation axis perpendicular to the analysis surface SA of the sample S. When measuring the fluorescent X-rays of the sample S, the sample container C containing the sample S is rotated at 10 to 100 rpm while placed on the sample spinner 8, thereby preventing bias in the portion of the sample S that is irradiated with the primary X-rays. During measurement, the sample S to be analyzed rotates about a rotation axis perpendicular to the analysis surface SA of the sample S with the analysis surface SA exposed through the opening 36 at the bottom of the housing 31.

[0090] The above-described sample spinner can also be rotated to stir the sample. Specifically, the sample S is stirred by rotating the sample spinner 8 while the sample container C containing the sample S is placed therein. The rotation speed for such stirring is approximately 100 to 1000 rpm. As described above, the sample spinner 8 can also be rotated to reduce bias in the X-ray irradiation position on the sample S. However, when rotating for the purpose of stirring, the sample spinner 8 is characterized by rotating at a higher speed than when rotating for the purpose of reducing bias in the X-ray irradiation position. Furthermore, for example, the sample spinner 8 may be switched between clockwise and counterclockwise at regular time intervals, changing the acceleration of the sample S and thereby stirring the sample S due to the inertial force acting on the sample S. Stirring by rotating the sample spinner 8 may be performed before or during the fluorescent X-ray analysis of the sample S.

[0091] As a modification of this embodiment, the sample S may be stirred by vibrating the sample spinner 8 in the Z-axis direction while the sample container C containing the sample S is placed.

[0092] In this modified example, as shown by arrow 82 in Figure 6, the sample spinner 8 is arranged on the first surface 34 of the sample stage 33 so as to be vibrated along the Z-axis direction. Therefore, when a sample container C containing a sample S is placed at the measurement position, the sample S can be stirred by vibrating the sample spinner 8. Note that it is desirable to vibrate the sample S along the Z-axis direction before measuring the fluorescent X-rays. This is because, if the analysis surface SA is vibrating along the Z-axis direction, the analysis surface SA may not be exposed to the measurement chamber 5 through the opening 36, making it impossible to stably irradiate the sample S with primary X-rays, which may affect the fluorescent X-ray measurement.

[0093] Note that stirring of the sample S by rotation of the sample spinner 8 and stirring of the sample S by vibration of the sample spinner 8 may be performed in combination. In this case, for example, the sample spinner 8 is configured to be rotatable around the center of the placed sample container C as the rotation axis and to be vibrated along the Z-axis direction. With this configuration, before measuring the fluorescent X-rays of the sample S, the sample S can be stirred by vibrating the sample spinner 8 with the sample S placed on the sample spinner 8, and during the fluorescent X-ray measurement of the sample S, the sample S can be stirred by rotating the sample spinner 8. Stirring the sample S by combining vibration and rotation can improve the stirring efficiency of a sample that is difficult to stir by stirring either by vibration or rotation alone.

[0094] Furthermore, a modified example is also conceivable in which the sample spinner 8 described in Example 3 is disposed in the opening 71 of the turret 7 described in Example 2. In this case, the sample can be stirred by the rotation and / or vibration of the turret 7 and the sample spinner 8, thereby improving the efficiency of stirring the sample.

[0095] Example 4: Agitation of sample when sample container is provided with baffle Next, an example of agitation of sample when the sample container C is provided with a baffle for improving the efficiency of agitation of the sample S will be described.

[0096] Fig. 8 is a front cross-sectional view of the sample container C showing an embodiment of a stirring mechanism using a baffle unit 93 provided in the sample container C. Fig. 9 is a plan view of the sample container C as seen from the Z-axis direction in Fig. 8. For ease of explanation, the sample S and the lid of the sample container C are not shown in Fig. 9.

[0097] 8, the sample container C includes a baffle portion 93. The sample container C is configured such that when the sample container C is rotated to stir the sample S, the baffle portion 93 improves stirring efficiency.

[0098] A plurality of baffles 93 (for example, two) are attached and fixed to the inner wall of the sample container C. For example, when the sample S is rotated by the gripper 26 (FIG. 1), the turret 7 (FIG. 4), and the sample spinner 8 (FIG. 6), the baffle 93 generates turbulence in the sample S, thereby improving the stirring efficiency of the sample S.

[0099] Contamination of the sample can be prevented by disposing of the sample container C having the baffle portion 93. The sample container C may also be reused.

[0100] The baffle 93 provided inside the sample container C is configured so as not to affect the measurement of fluorescent X-rays. For example, the baffle 93 is made of a material that does not affect the measurement of fluorescent X-rays from the sample S, or is placed in a position where it does not affect the measurement of fluorescent X-rays from the sample S. Specifically, the material is made of a resin such as polypropylene or polyethylene terephthalate, which has almost no effect on the analysis of the sample S even when irradiated with primary X-rays. The position where the baffle 93 is placed is selected so that it does not affect the irradiation of primary X-rays and the measurement of fluorescent X-rays. Specifically, in FIG. 8 , the baffle 93 is desirably placed above the analysis surface SA of the sample S in the Z-axis direction.

[0101] The stirring of the sample is not limited to the above-described embodiment, and any configuration capable of stirring a liquid sample can be applied to the present disclosure.

[0102] Aspects It will be understood by those skilled in the art that the exemplary embodiments described above are examples of the following aspects.

[0103] (Item 1) In one aspect, the fluorescent X-ray analysis apparatus may include a sample stage on which a sample is placed, an X-ray source that irradiates the sample with primary X-rays, a detector that detects fluorescent X-rays emitted from the sample in response to the irradiated primary X-rays, an analysis unit that analyzes the fluorescent X-rays detected by the detector, and a stirring mechanism that stirs the sample.

[0104] According to the X-ray fluorescence analyzer described in paragraph 1, by stirring the sample, the concentration bias of the substances that make up the sample is reduced, and a technology is provided for improving the analytical accuracy of the elements contained in the sample.

[0105] (Item 2) In the fluorescent X-ray analyzer described in item 1, the stirring mechanism may stir the sample while the sample is being irradiated with the primary X-rays.

[0106] According to the X-ray fluorescence analyzer described in paragraph 2, the sample is stirred while being irradiated with primary X-rays, thereby reducing the bias in the concentrations of the substances that make up the sample, and providing a technology for improving the analytical accuracy of the elements contained in the sample.

[0107] (Item 3) In the fluorescent X-ray analyzer according to item 1 or 2, the stirring mechanism may stir the sample before the sample is irradiated with the primary X-rays.

[0108] According to the X-ray fluorescence analyzer described in paragraph 3, the sample is stirred before being irradiated with primary X-rays, thereby reducing the concentration bias of the substances that make up the sample, and providing a technology for improving the analytical accuracy of the elements contained in the sample.

[0109] (4) In the X-ray fluorescence analyzer described in any one of paragraphs 1 to 3, the stirring mechanism may stir the sample by vibrating it, and at least one of the direction, amplitude, speed, acceleration, and vibration time of the vibration may be variable.

[0110] According to the X-ray fluorescence analyzer described in paragraph 4, the sample is agitated by vibration, thereby reducing the concentration bias of the substances that make up the sample, and a technology is provided for improving the analytical accuracy of the elements contained in the sample.

[0111] (5) In the X-ray fluorescence analyzer described in any one of paragraphs 1 to 4, the stirring mechanism may stir the sample by vibrating it, and at least one of the direction, amplitude, speed, acceleration, and vibration time of the vibration may be variable depending on at least one of the type and properties of the sample.

[0112] According to the X-ray fluorescence analyzer described in paragraph 5, the sample is agitated by vibration, thereby reducing the concentration bias of the substances that make up the sample, and a technology is provided for improving the analytical accuracy of the elements contained in the sample.

[0113] (Item 6) In the fluorescent X-ray analyzer described in any one of Items 1 to 5, the stirring mechanism may stir the sample by rotating it, and at least one of the rotation speed, rotation direction, and rotation time of the rotation may be variable.

[0114] According to the X-ray fluorescence analyzer described in paragraph 6, the sample is stirred by rotation, which reduces the concentration bias of the substances that make up the sample, and provides a technology for improving the analytical accuracy of the elements contained in the sample.

[0115] (7) In the X-ray fluorescence analyzer described in any one of paragraphs 1 to 6, the stirring mechanism may stir the sample by rotating it, and at least one of the rotation speed, direction, and time of the rotation may be variable depending on at least one of the type and properties of the sample.

[0116] According to the X-ray fluorescence analyzer described in paragraph 7, the sample is stirred by rotation, which reduces the concentration bias of the substances that make up the sample, and provides a technology for improving the analytical accuracy of the elements contained in the sample.

[0117] (Item 8) In the X-ray fluorescence analyzer described in Item 5 or Item 7, the type of sample may include at least one of the name of a substance that is a solute of the sample, the chemical formula of the substance that is a solute of the sample, the name of a substance that is a solvent of the sample, the chemical formula of the substance that is a solvent of the sample, and the concentration of the substance that is a solute of the sample.

[0118] The X-ray fluorescence analyzer described in paragraph 8 provides a technique for changing the vibration pattern in accordance with at least one piece of information among the name of the substance that is the solute of the sample, the chemical formula of the substance that is the solute of the sample, the name of the substance that is the solvent of the sample, the chemical formula of the substance that is the solvent of the sample, and the concentration of the substance that is the solute of the sample.

[0119] (Item 9) In the X-ray fluorescence analyzer described in Item 5 or Item 7, the properties of the sample may include at least one of the viscosity of the sample, the ease of separation of a substance that is a solute of the sample, the ease of precipitation of a substance that is a solute of the sample, the ease of separation of a substance that is a solvent of the sample, and the ease of precipitation of a substance that is a solvent of the sample.

[0120] The X-ray fluorescence analyzer described in paragraph 9 provides a technique for changing the vibration pattern in accordance with at least one piece of information among the viscosity of the sample, the ease of separation of the solute substance of the sample, the ease of precipitation of the solute substance of the sample, the ease of separation of the solvent substance of the sample, and the ease of precipitation of the solvent substance of the sample.

[0121] (Item 10) In the fluorescent X-ray analyzer described in any one of Items 1 to 9, the stirring mechanism may include a gripping portion that grips the sample, and the gripping portion may stir the sample by vibrating or rotating the sample gripped by the gripping portion.

[0122] According to the X-ray fluorescence analyzer described in paragraph 10, the sample is stirred by vibration or rotation using the gripping part, thereby reducing the bias in the concentration of the substances that make up the sample, and providing a technology for improving the analytical accuracy of the elements contained in the sample.

[0123] (Item 11) In the fluorescent X-ray analyzer described in any one of Items 1 to 10, the stirring mechanism may be disposed on the sample stage, and may stir the sample by vibrating or rotating the sample.

[0124] According to the X-ray fluorescence analyzer described in paragraph 11, the sample is stirred by vibration or rotation using a stirring mechanism arranged on the sample stage, thereby reducing bias in the concentrations of the substances that make up the sample and providing a technology for improving the analytical accuracy of the elements contained in the sample.

[0125] (Item 12) The fluorescent X-ray analyzer according to any one of items 1 to 11 may further include a heating mechanism for heating the sample.

[0126] According to the X-ray fluorescence analyzer described in paragraph 12, the sample is heated by the heating mechanism, thereby improving the stirring efficiency of the stirring mechanism, reducing bias in the concentrations of the substances that make up the sample, and providing a technology for improving the analytical accuracy of the elements contained in the sample.

[0127] (Item 13) In the X-ray fluorescence analyzer described in any one of Items 1 to 12, the sample may be contained in a sample container, and the sample container may be provided with a baffle portion that improves the efficiency of stirring the sample by the stirring mechanism.

[0128] According to the X-ray fluorescence analyzer described in paragraph 13, the baffle provided in the sample container improves the stirring efficiency of the sample, reducing the concentration bias of the substances that make up the sample, and providing a technology for improving the analytical accuracy of the elements contained in the sample.

[0129] (Item 14) In one aspect, the sample container is a sample container that contains a sample to be analyzed by an X-ray fluorescence analyzer, and the X-ray fluorescence analyzer may be equipped with a stirring mechanism, and the sample container may be equipped with a baffle portion that improves the efficiency of stirring the sample by the stirring mechanism.

[0130] According to the sample container described in paragraph 14, the baffle portion provided in the sample container improves the stirring efficiency of the sample, reducing the bias in the concentration of the substances that make up the sample, and providing a technology for improving the analytical accuracy of the elements contained in the sample.

[0131] (Item 15) In one aspect, a method for analyzing a sample using an X-ray fluorescence analyzer may include a step of stirring the sample using the X-ray fluorescence analyzer, and a step of irradiating the sample with X-rays and acquiring X-ray fluorescence spectrum information of the sample.

[0132] According to the analytical method described in paragraph 15, by stirring the sample, the concentration bias of the substances that make up the sample is reduced, and a technique is provided for improving the analytical accuracy of the elements contained in the sample.

[0133] (Item 16) In the analysis method according to item 15, the stirring step may be performed during the acquisition step.

[0134] According to the analytical method described in paragraph 16, the sample is stirred while acquiring information on the fluorescent X-ray spectrum emitted from the sample, thereby reducing bias in the concentrations of the substances that make up the sample and providing a technology for improving the analytical accuracy of the elements contained in the sample.

[0135] (Item 17) In the analysis method according to item 15 or 16, the stirring step may be performed immediately before the acquisition step is started.

[0136] According to the analytical method described in paragraph 17, the sample is stirred before acquiring information on the fluorescent X-ray spectrum emitted from the sample, thereby reducing bias in the concentrations of the substances that make up the sample and providing a technology for improving the analytical accuracy of the elements contained in the sample.

[0137] (Item 18) The analytical method according to any one of items 15 to 17 may further include a step of heating the sample.

[0138] According to the analytical method described in paragraph 18, the sample is heated by the heating mechanism, thereby improving the stirring efficiency of the stirring mechanism, reducing bias in the concentrations of the substances that make up the sample, and providing a technology for improving the analytical accuracy of the elements contained in the sample.

[0139] The embodiments disclosed herein should be considered to be illustrative in all respects and not restrictive. The scope of the present invention is defined by the claims, not by the above description, and is intended to include all modifications within the meaning and scope of the claims.

[0140] 1 Control device, 2 Stirring mechanism, 3 Main body, 4 Sample chamber, 5 Measurement chamber, 6 Heating mechanism, 7 Turret, 8 Sample spinner, 9 Stirring section, 11 CPU, 12 ROM, 13 RAM, 14 HDD, 15 I / O interface, 16 Display device, 17 Input device, 21 X-axis rail, 22 Y-axis rail, 23 Z-axis rail, 24 Moving body, 25 Arm section, 26 Grip section, 31, 32 Housing, 33 Sample stage, 34 First surface, 35 Second surface, 36, 71, 81 Opening, 51 X-ray tube, 52 Detector, 93 Baffle section, 100 Analysis device, AP Analysis position, C Sample container, S Sample, SA Analysis surface.

Claims

1. A sample stand on which the sample is placed, An X-ray source for irradiating the aforementioned sample with primary X-rays, A detector that detects fluorescent X-rays emitted from the sample by the irradiated primary X-rays, An analysis unit for analyzing the fluorescent X-rays detected by the detector, The system comprises a stirring mechanism for stirring the sample, The detector is an X-ray fluorescence analyzer that detects the fluorescent X-rays emitted from the sample by the primary X-rays irradiated during stirring by the stirring mechanism.

2. The X-ray fluorescence analyzer according to claim 1, wherein the stirring mechanism stirs the sample before the primary X-rays are irradiated onto the sample.

3. The stirring mechanism stirs the sample by vibrating it. The X-ray fluorescence analyzer according to claim 1 or claim 2, wherein at least one of the direction, amplitude, velocity, acceleration, and duration of the vibration is variable.

4. The stirring mechanism stirs the sample by vibrating it. The X-ray fluorescence analyzer according to claim 1, wherein at least one of the direction, amplitude, velocity, acceleration, and duration of the vibration is variable according to at least one of the type and properties of the sample.

5. The stirring mechanism stirs the sample by rotating it. The fluorescent X-ray analyzer according to claim 1 or claim 2, wherein at least one of the rotational speed, rotational direction, and rotational time of the rotation is variable.

6. The stirring mechanism stirs the sample by rotating it. The X-ray fluorescence analyzer according to claim 1, wherein at least one of the rotational speed, rotational direction, and rotational time of the rotation is variable according to at least one of the type and properties of the sample.

7. The X-ray fluorescence analyzer according to claim 4 or claim 6, wherein the type includes at least one of the following: the name of the substance that is the solute of the sample, the chemical formula of the substance that is the solute of the sample, the name of the substance that is the solvent of the sample, the chemical formula of the substance that is the solvent of the sample, and the concentration of the substance that is the solute of the sample.

8. The X-ray fluorescence analyzer according to claim 4 or claim 6, wherein the properties include at least one of the viscosity of the sample, the ease of separation of the solute substance of the sample, the ease of precipitation of the solute substance of the sample, the ease of separation of the solvent substance of the sample, and the ease of precipitation of the solvent substance of the sample.

9. The stirring mechanism includes a gripping section for gripping the sample, The X-ray fluorescence analyzer according to claim 1 or claim 2, wherein the gripping portion agitates the sample held by the gripping portion by vibrating or rotating the sample.

10. The stirring mechanism is placed on the sample stage, The X-ray fluorescence analyzer according to claim 1 or claim 2, wherein the stirring mechanism stirs the sample by vibrating or rotating the sample.

11. The fluorescent X-ray analyzer according to claim 1 or claim 2, further comprising a heating mechanism for heating the sample.

12. The sample is contained in a sample container. The X-ray fluorescence analyzer according to claim 1 or claim 2, wherein the sample container is provided with a baffle section to improve the efficiency of stirring the sample by the stirring mechanism.

13. A sample container for containing a sample to be analyzed by an X-ray fluorescence analyzer, The aforementioned X-ray fluorescence analyzer is equipped with a stirring mechanism, The sample container is a sample container equipped with a baffle section that improves the efficiency of stirring the sample by the stirring mechanism.

14. A method for analyzing a sample using an X-ray fluorescence analyzer, The step of the sample being stirred by the X-ray fluorescence analyzer, The procedure includes the step of irradiating the sample with X-rays and obtaining fluorescence X-ray spectral information of the sample, The analytical method comprising the step of detecting fluorescent X-rays emitted from the sample by the X-rays irradiated during stirring.

15. The analytical method according to claim 14, further comprising the step of heating the sample.