JP2014074656A - Sample holder, sample chamber, and x-ray analyzer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sample holder, a sample chamber and an X-ray analyzer capable of preventing a sample from being exposed to air as much as possible.SOLUTION: A sample holder includes: a box part 12 in which a sample 5 is to be disposed; and a lid part 11 that moves in a lateral direction to open/close an opening of the box part 12. With the lid part 11 closing the opening, airtightness of the box part 12 is maintained. A sample stage 16 for placing a sheet-like sample 5 thereon is provided in the box part 12. The sample stage 16 moves up and down with the lid part 11 opening the opening. In a sample chamber of an X-ray analyzer, power is supplied to move the lid part 11 and the sample stage 16, and X-rays are radiated to the sample 5 from above to perform X-ray fluorescence analysis. The sample is disposed in the box part 12 in a decompressed atmosphere and the lid part 11 closes the opening, so that the sample 5 can be held in the sample holder, preventing air exposure. The lid part 11 opens the opening in the decompressed sample chamber, so that X-ray fluorescence analysis can be performed, preventing air exposure.

Description

  The present invention relates to a sample holder for holding a sample for X-ray analysis, a sample chamber in which a sample is placed during X-ray analysis, and an X-ray analysis apparatus.

  X-ray fluorescence analysis is an analysis technique in which a sample is irradiated with X-rays, fluorescent X-rays generated from the sample are detected, and qualitative analysis or quantitative analysis of elements contained in the sample is performed from the spectrum of fluorescent X-rays. In addition, fluorescent X-ray mapping is also performed to analyze the spatial distribution of elements contained in a sample by detecting the fluorescent X-ray while scanning the sample with X-rays concentrated on a minute part on the sample. . In addition, some X-ray analyzers include an airtight sample chamber, and the sample chamber is depressurized with the sample disposed therein, and the fluorescent X-ray is measured in a depressurized state. Patent Document 1 discloses a fluorescent X-ray analyzer that includes a sample chamber and can perform fluorescent X-ray mapping.

Japanese Patent No. 4041606

  Samples subject to X-ray fluorescence analysis should avoid exposure to air, such as samples that may be altered by exposure to air, or samples that may ignite by reacting with moisture in the air. Sample is present. For example, some of the electrode materials used in lithium ion batteries contain lithium and are one of the samples that should avoid air exposure. In conventional X-ray analyzers, air exposure can be avoided when the sample chamber in which the sample is placed is decompressed, but air exposure is avoided during sample preparation and when the sample is taken in and out of the sample chamber. I can't. For this reason, there exists a problem that it is difficult to perform the fluorescent X-ray analysis of the sample which should avoid air exposure.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide a sample holder, a sample chamber, and an X-ray analyzer capable of avoiding air exposure of the sample as much as possible. It is to provide.

  The sample holder according to the present invention is a portable sample holder that holds a sample, and has an opening on the upper side, a box part in which the sample is arranged, and a lid part for closing the opening. And an opening / closing means for opening and closing the opening portion with the lid portion, and the box portion and the lid portion are configured to maintain airtightness in the box portion with the lid portion closed. It is characterized by.

  The sample holder according to the present invention is characterized in that a sample stage on which a sample is placed is provided in the box part, and further a lifting means for raising and lowering the sample stage in a state where the lid part is opened.

  The sample holder according to the present invention is characterized in that the opening / closing means is an electric type, and further includes a connection part to which a power line is connected and supplies electric power from the power line to the opening / closing means.

  The sample holder according to the present invention is characterized in that the opening / closing means and the lifting / lowering means are electrically operated, and further comprising a connecting portion to which a power line is connected and supplying power from the power line to the opening / closing means and the lifting / lowering means. And

  The sample chamber according to the present invention is capable of disposing a sample therein, and the sample holder according to the present invention is disposed in the sample chamber provided with means for reducing the pressure inside or introducing any gas into the inside. And having a power line connected to the connection portion of the sample holder and supplying power to the connection portion.

  An X-ray analysis apparatus according to the present invention includes a sample chamber according to the present invention, a means for irradiating a sample held by a sample holder disposed in the sample chamber with X-rays from above, and fluorescence X generated from the sample. Means for detecting a line.

  In the present invention, the sample holder includes a box portion in which the sample is disposed and a lid portion that opens and closes the opening portion of the box portion, and the hermeticity in the box portion is maintained when the lid portion is closed. . The sample can be held by the sample holder while avoiding air exposure by disposing the sample in the box portion in an atmosphere introduced with reduced pressure or an arbitrary gas and closing the lid portion.

  In the present invention, the position of the sample is adjusted so that the sample is placed at a position suitable for X-ray analysis by moving the sample table on which the sample is placed.

  In the present invention, the power supply for opening / closing the lid or raising / lowering the sample stage is supplied via the power line connected to the connection part of the sample holder, so that the sample chamber is in a decompressed state or not in the sample chamber. While maintaining a state in which a gas such as an active gas is introduced, the lid of the sample holder is opened in the sample chamber, and the sample held in the sample holder is irradiated with X-rays to perform fluorescent X-ray analysis.

  In the present invention, it is possible to avoid exposure of the sample to the air during sample preparation, during work for inserting and removing the sample holder with respect to the sample chamber, and during processing for fluorescent X-ray analysis. Therefore, the present invention has an excellent effect, for example, that it is possible to perform fluorescent X-ray analysis while avoiding air exposure as much as possible with respect to a sample that should avoid air exposure.

It is a schematic diagram which shows the structure of an X-ray analyzer. It is a typical perspective view of a sample holder. It is a typical perspective view of a sample holder. It is a typical perspective view of the sample holder which raised the sample stand. It is a block diagram which shows the electrical structure of a sample holder. It is a typical perspective view which shows the sample holder which connected the portable controller.

Hereinafter, the present invention will be specifically described with reference to the drawings showing embodiments thereof.
FIG. 1 is a schematic diagram showing a configuration of an X-ray analyzer. The X-ray analyzer includes an X-ray tube 31 that generates X-rays, an X-ray lens 32, an X-ray detector 33 that detects fluorescent X-rays, and a sample chamber 2 in which a sample 5 is disposed. The sample chamber 2 has a space in which a portable sample holder 1 that holds the sample 5 can be placed. In the sample chamber 2, a sample holder 1 can be placed, and a moving stage 21 that can move in the horizontal direction with the sample holder 1 placed thereon is provided.

  The X-ray lens 32 is an optical element that receives X-rays from the X-ray tube 31, reflects and focuses the incident X-rays inside, and emits the focused X-rays from the emission end. The X-ray lens 32 is, for example, a monocapillary made of a fine capillary that guides incident X-rays while totally reflecting them inside, or a polycapillary in which a large number of capillaries are bundled. Note that the X-ray lens 32 may have a form other than a monocapillary or a polycapillary, such as a form for focusing X-rays using a mirror. The X-ray lens 32 is provided in the sample chamber 2 so that the emission end is located inside the sample chamber 2 and faces the moving stage 21 from above. In a state where the sample holder 1 that holds the sample 5 is placed on the moving stage 21, the X-rays incident on the X-ray lens 32 from the X-ray tube 31 are focused by the X-ray lens 32, and the sample 5 from above. Is irradiated. In the portion of the sample 5 irradiated with X-rays, fluorescent X-rays are generated, and the generated fluorescent X-rays are detected by the X-ray detector 33. In FIG. 1, X-rays and fluorescent X-rays irradiated on the sample 5 are indicated by arrows.

  The X-ray detector 33 is provided at a position where the fluorescent X-ray can be detected in the sample chamber 2. The X-ray detector 33 has a configuration using a semiconductor element such as a Si element as a detection element, and outputs a signal proportional to the detected energy of the fluorescent X-ray. The X-ray detector 33 may have a form using a detection element other than the semiconductor detection element. Further, the X-ray detector 33 may be configured to detect fluorescent X-rays separately by wavelength, instead of detecting fluorescent X-rays separately by energy.

  The X-ray detector 33 is connected to a signal processing unit 34 that processes the output signal. The signal processing unit 34 receives the signal output from the X-ray detector 33, counts the signal of each value, and the relationship between the X-ray fluorescence energy detected by the X-ray detector 33 and the count number, that is, the fluorescent X-ray. The process which acquires the spectrum of is performed. The X-ray tube 31 and the signal processing unit 34 are connected to a control device 4 that controls the operation of the X-ray analyzer. The control device 4 is configured by a computer including a calculation unit that performs a calculation, a storage unit that stores data and programs necessary for the calculation, an operation unit that receives an operation from a user, and a display unit that displays information. ing.

  The sample chamber 2 has a door (not shown) that can be opened and closed. When the door is opened, the sample holder 1 can be taken in and out. The sample chamber 2 has a configuration capable of maintaining the internal airtightness with the door closed. The X-ray analyzer includes an exhaust pump 23 communicating with the inside of the sample chamber 2. The exhaust pump 23 is a rotary pump, for example. By operating the exhaust pump 23 in a state where the door of the sample chamber 2 is closed, the inside of the sample chamber 2 can be decompressed. After the sample holder 1 is placed in the sample chamber 2, the sample holder 1 can be placed under a reduced pressure by reducing the pressure inside the sample chamber 2. Note that the X-ray analyzer may be in a form capable of introducing an arbitrary gas such as an inert gas into the sample chamber 2 whose pressure has been reduced.

  The moving stage 21 is configured to be able to move in the horizontal direction with the sample holder 1 placed thereon using a driving mechanism such as a stepping motor. It is desirable that the moving stage 21 can move in at least two directions within a horizontal plane. The moving stage 21 is connected to the control device 4. The control device 4 controls the movement of the moving stage 21 by controlling the operation of the moving stage 21 while the sample holder 1 is placed on the moving stage 21 and the sample 5 is irradiated with the X-rays. X-rays are sequentially irradiated to the respective portions on the sample 5, and the fluorescent X-rays generated at the respective portions on the sample 5 are sequentially detected by the X-ray detector 33. The signal processing unit 34 sequentially generates signals of the fluorescent X-rays generated in the respective portions on the sample 5 by sequentially performing signal processing. The signal processing unit 34 sequentially inputs data indicating the spectrum of the generated fluorescent X-rays to the control device 4. The control device 4 stores data indicating the spectrum of fluorescent X-rays, and associates the fluorescent X-ray spectrum generated in each part on the sample 5 with each part on the sample 5 to thereby distribute the fluorescent X-ray distribution. Ask for. As described above, the X-ray analyzer performs fluorescent X-ray mapping. Note that the X-ray analysis apparatus may have a form in which an apparatus that controls operations and an apparatus that performs information processing for obtaining the distribution of fluorescent X-rays are separated.

  2 and 3 are schematic perspective views of the sample holder 1. The sample holder 1 is portable and has a size that can be easily carried. The sample holder 1 includes a box part 12 having an upper side as an opening, and a lid part 11 for closing the box part 12 from the upper side. The lid part 11 can open and close the opening part of the box part 12, FIG. 2 shows a state where the lid part 11 is closed, and FIG. 3 shows a state where the lid part 11 is opened. The lid portion 11 and the box portion 12 are rectangular in plan view. A sealing member such as an O-ring is provided at a portion where the lid portion 11 and the box portion 12 are in contact with each other. The lid portion 11 and the box portion 12 are configured so that the airtightness in the box portion 12 is maintained in a state where the lid portion 11 is closed.

  The lid portion 11 rides on the support member 14, and can move in the lateral direction substantially in a horizontal plane by sliding with respect to the support member 14. Here, let the part located in the both sides with respect to the moving direction of the cover part 11 be a side part. Block-like members 111 are connected to both sides of the lid portion 11. A plurality of bar-shaped guide members 113 parallel to the moving direction of the lid portion 11 are provided on both side portions of the sample holder 1, and the guide members 113 penetrate the block-shaped member 111. Further, a feed screw shaft 112 parallel to the moving direction of the lid portion 11 passes through and is engaged with each block-shaped member 111. The two feed screw shafts 112 are connected to the motor 13 via a transmission mechanism including a belt. As the motor 13 rotates, the feed screw shaft 112 rotates in conjunction with it, and the block-shaped member 111 moves along the guide member 113 in accordance with the rotation of the feed screw shaft 112. By moving the block-shaped member 111, the lid portion 11 can move in the horizontal direction and open and close the opening of the box portion 12. Projections are provided on both side surfaces of the lid 11, and the support member 14 is externally fitted to a part of the projection from the lower side in a portion where the projection is located with the lid 11 closed. A groove 141 having a shape is formed. When the protruding part of the lid part 11 fits into the groove 141 and the lid part 11 sinks, the lid part 11 comes into close contact with the box part 12 in a closed state, and the inside of the box part 12 becomes airtight. The lid portion 11 may be in close contact with the box portion 12 by its own weight, or a member that biases the lid portion 11 so as to be in close contact with the box portion 12 may be provided.

  A sample stage 16 for spreading and placing the sheet-like sample 5 is provided in the box part 12. The size of the sheet-like sample 5 is, for example, 10 cm × 10 cm. The sample stage 16 has a flat plate shape that is wide in the lateral direction, and has a size that allows the sheet-like sample 5 to be spread and placed. The sample 5 is held on the sample holder 1 by being spread and placed on the sample stage 16. The sample holder 1 includes a moving mechanism that moves the sample table 16 up and down. FIG. 3 shows a state where the sample stage 16 is lowered. FIG. 4 is a schematic perspective view of the sample holder 1 with the sample stage 16 raised. The moving mechanism that raises and lowers the sample stage 16 includes a motor 15. The motor 15 is connected to the sample table 16 via a transmission mechanism (not shown), and the sample table 16 is moved up and down as the motor 15 rotates. The sample stage 16 can be raised to a height at which the sample 5 can be lifted to the focal position of the X-ray lens 32 with the sample holder 1 placed on the moving stage 21. Further, it is desirable that the sample stage 16 rises to a height at which the sample 5 is lifted to a position other than the sample stage 16 in the sample holder 1, for example, a position higher than the lid 11.

  FIG. 5 is a block diagram showing an electrical configuration of the sample holder 1. The sample holder 1 includes a connection portion 101 to which a power line outside the sample holder 1 is connected. The connection portion 101 is connected to motors 13 and 15. The connection unit 101 is a connection connector to which a power line is detachably connected. The power for operating the motors 13 and 15 is individually supplied from the power line connected to the connection unit 101, and the connection unit 101 supplies the power for operating the motor 13 to the motor 13 and operates the motor 15. Electric power for causing the motor 15 to be supplied. The motors 13 and 15 operate by being supplied with electric power, and the lid 11 is opened and closed and the sample stage 16 is raised and lowered. For example, the motors 13 and 15 are direct current motors, supplied with direct current, and by adjusting the direction of the direct current, the rotation direction of the motors 13 and 15 is controlled, and the direction in which the lid 11 and the sample stage 16 move. Is controlled.

  In the sample chamber 2, a power line 22 for connecting to the connection portion 101 of the sample holder 1 is provided. The user connects the power line 22 to the connection unit 101 in a state where the sample holder 1 is placed on the moving stage 21. The power line 22 is connected to the control device 4. The control device 4 controls the movement of the lid portion 11 and the sample stage 16 by performing a process of supplying power for operating the motors 13 and 15 to the connection portion 101 through the power line 22. The sample holder 1 further includes a control unit that controls the operation of the motors 13 and 15, and the control device 4 is a process for inputting a control signal for causing the control unit to perform desired control together with electric power to the sample holder 1. The form which performs is also possible.

  A portable controller can be connected to the connection unit 101. FIG. 6 is a schematic perspective view showing the sample holder 1 to which the portable controller 6 is connected. The controller 6 is portable and has a size that can be easily carried. The controller 6 includes a power line connected to the connection unit 101 and an operation unit that receives an operation from the user, and includes a power source for supplying power to the connection unit 101 therein. The controller 6 supplies power for operating the motors 13 and 15 to the connection unit 101 in accordance with an operation from the user while being connected to the connection unit 101. The user can open and close the lid 11 and raise and lower the sample stage 16 by operating the controller 6. The sample holder 1 may include a power source such as a secondary battery, and may be configured to receive a control signal and supply power from the internal power source to the motors 13 and 15 according to the control signal. Moreover, the sample holder 1 may be configured to receive a control signal by infrared communication. Further, the sample holder 1 may be configured such that the lid portion 11 and the sample stage 16 can be manually moved using an electromagnetic clutch or the like in a state where power is not supplied from the outside.

  The sample holder 1 is used when performing a fluorescent X-ray analysis of the sample 5 that should avoid air exposure. Such a sample 5 is prepared in an airtight chamber such as a glove box (not shown), for example. Further, for example, the sample 5 is transported in a hermetically sealed container and taken out from the hermetic container in the hermetic chamber. The inside of the hermetic chamber is in a reduced pressure state of about 100 Pa, for example, and exposure of the sample to air can be avoided. The sample holder 1 to which the controller 6 is connected is placed in the hermetic chamber, and the user operates the controller 6 to open the lid 11 and raise the sample table 16, so that the sheet is placed on the sample table 16. The sample 5 is spread and placed. Next, the user operates the controller 6 to lower the sample table 16 and close the lid 11. Since the lid portion 11 is closed while the airtight chamber is decompressed, the inside of the box portion 12 is in a decompressed state. In a form in which the lid 11 and the sample stage 16 can be moved manually, the user manually opens and closes the lid 11 and raises and lowers the sample stage 16. With the lid 11 closed, the user returns the inside of the hermetic chamber to normal pressure, removes the controller 6 from the sample holder 1, and removes the sample holder 1 from the hermetic chamber. Even when the outside of the sample holder 1 is at normal pressure, the box part 12 with the lid part 11 closed is airtight, so the inside of the box part 12 is kept in a reduced pressure state and is placed in the box part 12. Air exposure of sample 5 is avoided. It is also possible to work in a state where the hermetic chamber is filled with an inert gas.

  The sample holder 1 taken out from the hermetic chamber is transported to the sample chamber 2 of the X-ray analyzer. Even during transportation, the air exposure of the sample 5 is avoided due to the airtightness of the box 12. The user places the transported sample holder 1 on the moving stage 21 in the sample chamber 2, connects the power line 22 to the connection portion 101 of the sample holder 1, and closes the door of the sample chamber 2. Next, the user operates the exhaust pump 23 to decompress the inside of the sample chamber 2. The inside of the sample chamber 2 is depressurized to about 100 Pa, for example. In a state where the inside of the sample chamber 2 is depressurized, the control device 4 supplies electric power for operating the motor 13 to the sample holder 1 through the power line 22 and performs a process of opening the lid 11. Even when the lid 11 is open, the sample chamber 2 is depressurized, so that exposure of the sample 5 in the box 12 to air exposure can be avoided. The control device 4 further supplies power for operating the motor 15 to the sample holder 1 and performs a process of raising the sample stage 16. The sample 5 is held by being placed on the sample table 16. The control device 4 moves the moving stage 21 on which the sample holder 1 is placed, irradiates the sample 5 from above with the X-ray tube 31 through the X-ray lens 32, and is detected by the X-ray detector 33. Data indicating the spectrum of fluorescent X-rays is received, and fluorescent X-ray mapping processing is executed. In addition, after depressurizing the sample chamber 2 that has been depressurized, an inert gas may be introduced, and the fluorescent X-ray mapping process may be performed in an inert gas atmosphere.

  As described above in detail, in the present embodiment, the sample holder 1 holds the sample 5 while maintaining hermeticity, so that the sample holder 1 is prepared and the sample holder 1 is taken in and out of the sample chamber 2. , Exposure of sample 5 to air can be avoided. Moreover, the lid 11 of the sample holder 1 can be opened in the sample chamber 2 while maintaining the decompressed state of the sample chamber 2 by inputting electric power from the outside of the sample holder 1 to the connection unit 101. With the lid 11 opened in the decompressed sample chamber 2, the fluorescent X-ray analysis of the sample 5 can be executed while avoiding air exposure. As described above, by using the sample holder 1, it is possible to execute the fluorescent X-ray analysis on the sample 5 that should avoid air exposure while avoiding air exposure as much as possible.

  Moreover, the sample holder 1 opens and closes the cover part 11 by moving the cover part 11 to the horizontal direction. Compared with the method of moving the lid 11 in the vertical direction, the risk of the lid 11 coming into contact with the structure in the sample chamber 2 such as the X-ray lens 32 is reduced, and the structure in the sample chamber 2 or the sample holder 1 is reduced. Safe X-ray fluorescence analysis is possible without damaging. Further, the sample holder 1 adjusts the position of the sample 5 so that the sample holder 16 is placed at the focal position of the X-ray by the X-ray lens 32 by raising the sample table 16 with the lid portion 11 open. X-ray fluorescence analysis can be performed. Compared to the method of moving the X-ray lens 32 and the like, the position of the sample 5 can be easily adjusted by moving the sample table 16 up and down. In particular, by executing the fluorescent X-ray mapping in a state where the sample stage 16 is lifted to a position higher than the other part of the sample holder 1, the structure in the sample chamber 2 such as the X-ray lens 32 is changed to the sample. The risk of contact with the holder 1 is reduced, and the fluorescent X-ray mapping can be executed safely while avoiding damage.

  In the present embodiment, the sample 5 is scanned with the X-ray by moving the moving stage 21. However, the X-ray analyzer changes the X-ray direction by changing the direction of the focused X-ray. The sample 5 may be scanned with a line. Further, in the present embodiment, the form of performing the fluorescent X-ray mapping is shown, but the X-ray analyzer may be configured to perform the fluorescent X-ray analysis of the sample 5 without performing the X-ray scanning. Good. In addition, the X-ray analyzer may be in a form using a collimator or the like in addition to a monocapillary or polycapillary as the X-ray lens 32. The sample holder 1 is not only used for holding a sample 5 used for X-ray analysis, but also a sample used for analysis in which light other than X-rays is irradiated, such as a sample for Raman spectroscopy. It can also be used to hold

DESCRIPTION OF SYMBOLS 1 Sample holder 101 Connection part 11 Cover part 12 Box part 13, 15 Motor 16 Sample stand 2 Sample room 21 Moving stage 22 Power line 23 Exhaust pump 31 X-ray tube 32 X-ray lens 33 X-ray detector 34 Signal processing part 4 Control apparatus 5 Sample 6 Controller

Claims (6)

In a portable sample holder that holds a sample,
An opening on the upper side, and a box part in which the sample is arranged;
A lid for closing the opening;
Opening and closing means for opening and closing the opening by the lid,
The sample holder, wherein the box portion and the lid portion are configured to maintain airtightness in the box portion with the lid portion closed. In the box part, provided with a sample stage on which a sample is placed,
The sample holder according to claim 1, further comprising elevating means for elevating and lowering the sample stage in a state where the lid portion is open. The opening / closing means is electric,
The sample holder according to claim 1, further comprising a connection portion to which a power line is connected and supplies power from the power line to the opening / closing means. The opening / closing means and the lifting / lowering means are electrically operated,
The sample holder according to claim 2, further comprising a connection portion to which a power line is connected and supplies power from the power line to the opening / closing means and the lifting / lowering means. In the sample chamber equipped with a means for depressurizing the inside or introducing any gas into the inside, in which the sample can be arranged
It is possible to arrange the sample holder according to claim 3 or 4 inside,
A sample chamber comprising a power line connected to a connection portion of the sample holder and supplying power to the connection portion. A sample chamber according to claim 5;
Means for irradiating the sample held by the sample holder disposed in the sample chamber with X-rays from above;
An X-ray analyzer comprising: means for detecting fluorescent X-rays generated from the sample.

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