JP5435389B2 - Sample container for glow discharge optical emission spectrometry and glow discharge optical emission spectrometer equipped with the same - Google Patents

Description

  The present invention relates to a sample container used for glow discharge optical emission spectrometry for analyzing generated light while sputtering a sample, and a glow discharge optical emission spectrometer equipped with the same.

  When a direct current or high frequency high voltage is applied between two electrodes in an argon (Ar) atmosphere with a gas pressure of about 500 to 1300 Pa, glow discharge occurs and Ar ions are generated. The generated Ar ions are accelerated by a high electric field, collide with the cathode surface, and knock out the substances present there. Although this phenomenon is called sputtering, the sputtered particles (atoms, molecules, ions) are excited in the plasma and emit light of a wavelength specific to the element when returning to the ground state. An analysis method for identifying elements by spectroscopically analyzing the emitted light is called a glow discharge emission spectroscopy method.

  As a glow discharge tube in an analyzer embodying the above-described glow discharge emission spectroscopic analysis method, a hollow anode type grim glow discharge tube 1 as shown in FIG. 5 is generally used. In the Grimm glow discharge tube 1, a support block 2 (a support portion with which the sample 5 is brought into contact and is a cathode at the same time in this example) and an anode block 3 are joined via an insulating portion 4. . The anode block 3 has an argon gas supply hole 3a and first and second vacuum exhaust holes 3b and 3c which are decompression means, and the inside V of the tube is an argon rare gas atmosphere (500 to 1300 Pa). Yes. The anode block 3 has a hollow anode tube 3d. The anode tube 3d passes through the insulating portion 4 and is close to the surface (measurement surface) 5a of the sample 5. The sample 5 is pressed in an airtight state against the support block 2 through an O-ring 6 that is a seal member. Further, the support block 2 and the insulating portion 4 may be integrated and may be all formed of an insulator. The anode tube 3d has a cylindrical shape, and its distal end surface is perpendicular to the cylindrical axis. Although not shown, a plurality of anode tubes having different inner diameters and / or outer diameters can be exchanged depending on the sample. Sometimes.

  The grim glow discharge tube 1 generates a glow discharge by applying a high voltage between an anode block 3 and a support block 2 by a power supply unit 9 serving as a power feeding means, and a sample 5 through a support block 2 generally made of copper. The sample 5 is sputtered by applying a negative voltage to the surface 5a and causing the argon cations generated by the occurrence of glow discharge to collide with the surface 5a of the sample 5. Further, the coolant K is introduced into the jacket 2b from the coolant introduction path 2a of the support block 2 and fed to the coolant discharge path 2c, and the sample 5 and the hollow anode tube are passed through the support block 2 and the support block 2. 3d is being cooled. In the Grimm glow discharge tube 1, the anode tube 3d is directed downward in the vertical direction. However, as in the Grimm glow discharge tube 10 in the embodiment of the present invention to be described later, the anode tube 3d may be in the horizontal direction. (FIG. 1).

  By the way, in the above-mentioned glow discharge emission spectroscopic analyzer, the surface 5 a of the sample 5 is vacuum-sealed with the O-ring 6 embedded in the support block 2 and pressed against the support block 2, and the hollow anode tube 3 d is formed by the sample 5. The inner space of the supporting block 2 to be accommodated is closed and the inner space is evacuated. Until then, the sample 5 is exposed to air. Therefore, a sample such as a lithium ion battery material that requires handling in an inert gas atmosphere cannot be analyzed. Therefore, a glow discharge emission spectroscopic analysis of a transfer vessel (see transfer vessel device (12) of Patent Document 1, page 35, lines 3 to 6 of Patent Document 2, etc.) used for transporting such samples in a wide range of technical fields. There is an example in which a sample is sealed in a sample container that is applied to an apparatus and in an inert gas atmosphere, and the entire sample container is transported to an analyzer to perform glow discharge emission spectroscopic analysis (Patent Document 3). According to this example, it is possible to carry out glow discharge emission spectroscopic analysis by transporting the sample to the analyzer without exposing it to the air.

  However, for example, a sample that is a material of a lithium ion battery not only requires handling in an inert gas atmosphere, but is also fragile, so that pressing should be avoided. In the example of Patent Document 3, the sample is analyzed through an O-ring. Since the sample is pressed against the sample holder (corresponding to the support block described above), the sample may be peeled off or damaged, and accurate analysis cannot be performed.

  On the other hand, for a sample that does not have a large outer diameter that can be joined to the entire circumference of the O-ring or a sample that has a non-planar surface, the sample is accommodated in the sample stage and the sample stage is pressed against the analyzer via the O-ring. Thus, there are inventions that do not press the sample (see FIG. 2 of Patent Document 4, FIG. 6 of Patent Document 5, etc.), but these inventions are made because the inner space of the support block cannot be closed on the sample surface. This is not because the sample is fragile and may be peeled off or damaged when pressed. Further, no consideration is given to the case where the sample needs to be handled in an inert gas atmosphere.

Japanese Patent Laid-Open No. 1-158329 International Publication No. 02/082569 Pamphlet JP 2010-197308 A No. 8-6288 JP-A-7-146238

  Therefore, in the conventional technique, accurate glow discharge emission spectroscopic analysis cannot be performed on a sample that requires handling in an inert gas atmosphere and that may be peeled off or damaged when pressed.

  The present invention has been made in view of the above-mentioned conventional problems, and requires accurate glow discharge emission spectrometry analysis for a sample that requires handling in an inert gas atmosphere and that may be peeled off or damaged when pressed. An object of the present invention is to provide a sample container and a glow discharge emission spectroscopic analysis apparatus including the sample container.

  In order to achieve the above object, the sample container of the present invention is a sample container that contains a sample and holds the sample so as to face the anode tube of the glow discharge optical emission spectrometer, and has a through hole formed therein. A container body having a bottom part, a side part provided around the bottom part, and a detachable attachment part for attaching to a glow discharge optical emission spectrometer so as to close an opening surrounded by an open end of the side part; A sample holder that is inserted in the hole so as to be able to advance and retreat, a sample is attached to the recessed portion of the tip portion, and an outer periphery of the recessed portion has a contact portion with a glow discharge optical emission spectrometer, and the opening of the recessed portion And a shutter for opening and closing. The mounting portion is attached to the glow discharge optical emission spectrometer, and the sample holding portion is pressed to the glow discharge optical emission spectrometer through the seal member in a state where the opening of the recessed portion is opened by the shutter. When the abutting portion comes into contact with the glow discharge emission spectrometer, the sample faces the anode tube of the glow discharge emission spectrometer without contacting the seal member.

  According to the sample container of the present invention, the sample can be sealed and transported to the glow discharge emission spectroscopic analyzer in the state where the internal space of the recessed portion of the sample holding portion to which the sample is attached is in an inert gas atmosphere, and the sample holding Since the sample is pressed against the analyzer through the seal member, the sample is not in contact with the seal member and faces the anode tube of the analyzer, so that the sample is not exposed to air or pressed. Therefore, accurate glow discharge emission spectroscopic analysis can be performed on a sample that requires handling in an inert gas atmosphere and that may be peeled off or damaged when pressed.

  The glow discharge optical emission spectrometer of the present invention comprises an anode block having an anode tube, a support block having an inner space for housing the anode tube, a decompression means for evacuating the inner space of the support block, Introducing means for introducing an inert gas into the inner space, the sample container of the present invention, and a container side decompression for evacuating the container side space between the sample container and the support block attached to the support block Means, a container-side introduction means for introducing an inert gas into the container-side space, and a power supply means for generating a glow discharge by applying a voltage between the anode block and the sample holder of the sample container. ing.

  Since the glow discharge emission spectroscopic analysis apparatus of the present invention includes the sample container of the present invention, the same effects as the sample container can be obtained.

It is sectional drawing which shows the grim glow discharge tube and sample container in the glow discharge emission-spectral-analysis apparatus which is one Embodiment of this invention. It is sectional drawing which shows the state before attachment to the analyzer of the sample container. It is a schematic block diagram of the analyzer. It is sectional drawing which shows the state before the attachment to the analyzer of the modification of the sample container. It is sectional drawing which shows the grim glow discharge tube in the conventional glow discharge emission-spectral-analysis apparatus.

  Hereinafter, a glow discharge optical emission spectrometer according to an embodiment of the present invention will be described with reference to the drawings. In this analyzer, as shown in FIG. 3, the light L emitted from the Grimm glow discharge tube 10 that generates light having a wavelength specific to the element by sputtering using glow discharge and transmitted through the window plate 13 is The light enters the spectroscope 15. The spectroscope 15 measures the incident slit 14, the diffraction grating 16 that diffracts the light L incident from the incident slit 14 at different diffraction angles according to the wavelength, the exit slit 17 that passes the diffracted light, and the intensity of the diffracted light. A photomultiplier tube 18 is provided. Alternatively, a CCD spectroscope in which a CCD element is arranged at the position of the exit slit 17 may be used.

  FIG. 1 is a cross-sectional view showing a grim glow discharge tube 10 and a sample container 11 in the analyzer of FIG. This analyzer is an anode block 3 having an anode tube 3d, a support block 22 having an inner space V for housing the anode tube 3d, and a decompression means for evacuating the inner space V of the support block 22. The first and second vacuum exhaust holes 3b and 3c, the argon gas supply hole 3a which is an introduction means for introducing an inert gas into the inner space V, the sample container 11, the anode block 3, and the sample holder of the sample container 11 And a power supply unit 29 that is a power supply unit that generates glow discharge by applying a voltage between the power supply unit 21 and the power supply unit 21.

  Further, this analyzer introduces an inert gas into the container-side space S, and a container-side decompression means for evacuating the container-side space S between the sample container 11 and the support block 22 attached to the support block 22. A container-side intake / exhaust hole 25 is provided as a container-side introducing means. The container-side intake / exhaust hole 25 is connected to a valve 26 that switches between an argon gas supply path 25a and a vacuum exhaust path 25b. Instead of using the switching valve, a container-side exhaust hole as the container-side decompression means and an argon gas supply hole as the container-side introduction means may be provided separately. In FIG. 1, the same components as those in FIG.

  FIG. 2 is a cross-sectional view showing a state before the sample container 11 of FIG. 1 is attached to the analyzer. This sample container 11 contains a sample 12 that needs to be handled in an inert gas atmosphere, such as a lithium ion battery material, and may be peeled off or damaged when pressed. The sample container 11 holds the sample 12 so as to face the anode tube 3d of the apparatus (FIG. 1). First, a bottom portion 19b in which a through-hole 19a is formed, a side portion 19c provided around the bottom portion 19b, And the container main body 19 which has the attachment part 19d which can be attached or detached for attaching to a glow discharge emission-spectral-analysis apparatus so that the opening which the open end of the side part 19c surrounds may be plugged up is provided.

  The bottom portion 19b has a disk shape, for example, and a through hole 19a is formed in the periphery thereof, and the side portion 19c has a cylindrical shape, for example. The mounting portion 19d is provided with a plurality of through holes (not shown) in the axial direction (left and right direction in FIG. 2), and screw holes (not shown) are provided at corresponding portions of the support block 22 (FIG. 1). When the bolt 23 (FIG. 1) is screwed through the through-hole of the attachment portion 19d, the sample container 11 is detachably attached to the glow discharge optical emission spectrometer. In addition, since a circumferential groove is provided on the surface of the mounting portion 19d facing the glow discharge emission spectroscopic analyzer and the O-ring 7C as a seal member is fitted, the sample container 11 has a glow discharge emission spectroscopy. Airtightly attached to the analyzer.

  The sample container 11 is inserted in the through-hole 19a so as to be able to advance and retreat, the sample 12 is attached to the recessed portion 21a at the tip portion, and a contact portion with the glow discharge optical emission spectrometer on the outer periphery of the recessed portion 21a. A sample holder 21 having 21b is provided. In this example, the through-hole 19a is composed of a large-diameter portion on the inner side (right side of the paper surface of FIG. 2) and a small-diameter portion on the outer side (left side of the paper surface of FIG. 2), and the sample holding portion 21 is, for example, a stepped circle made of brass It is columnar and consists of an inner large-diameter portion and an outer small-diameter portion corresponding to the large-diameter portion and small-diameter portion of the through-hole 19a. The small-diameter portion is airtightly and slidable through a seal member (not shown) to the bottom portion 19b. By being attached, it is penetrated by the through-hole 19a so that it can advance and retract in the axial direction. The large-diameter portion, that is, the distal end portion of the sample holding portion 21 is a support for a glow discharge emission spectroscopic analyzer in which a sample 12 is attached to the recessed bottom surface by adhesion, for example, and a ring-shaped protrusion is formed on the outer periphery of the recessed portion 21a. It comprises a contact portion 21b to the block 22 (FIG. 1). A circumferential groove is provided in the contact portion 21b so as to surround the recessed portion 21a, and an O-ring 7A as a seal member is fitted therein. Yes. The projecting dimension of the contact portion 21b from the bottom surface of the recessed portion 21a is appropriately determined according to the thickness of the sample 12.

  Furthermore, the sample container 11 includes a shutter 20 that opens and closes the opening of the recessed portion 21a, and the large-diameter opening of the through hole 19a formed in the bottom 19b of the container body 19 so as to cooperate with the shutter 20. That is, a circumferential groove is provided in the bottom portion 19b so as to surround the inner opening, and an O-ring 7B as a seal member is fitted. The shutter 20 includes a rotary shaft 20b that is airtightly and rotatably attached to a through-hole provided in the axial direction, for example, at the center of the bottom portion 19b via a seal member (not shown), and a through-hole 19a that passes through an O-ring 7B. A shutter plate 20a having a dimension and shape that can seal the inner opening, that is, the opening of the recessed portion 21a, for example, a fan-shaped end having a narrow width, which is fixed to the inner end of the rotating shaft 20b, and a rotation It consists of a rod-shaped handle 20c extending in the direction orthogonal to the rotating shaft 20b from the outer end of the shaft 20b.

  The rotating shaft 20b is provided with a pin-shaped protrusion 20d protruding in the radial direction. On the other hand, a cylindrical cam member 24 through which the rotating shaft 20b passes is attached to the outside of the bottom portion 19b, and the cam member 24 is formed with a cam groove 24a which is a spiral cutout. A protrusion 20d of the rotary shaft 20b is engaged with 24a. With such a configuration, when the operator holds the handle 20c and rotates the rotary shaft 20b by 180 degrees, the opening of the recessed portion 21a can be opened and closed, and the rotary shaft 20b is closed in a direction to close the opening of the recessed portion 21a. When rotating, the rotating shaft 20b moves outward in the axial direction, whereby the shutter plate 20a is pressed against the O-ring 7B. In FIG. 2, the shutter plate 20a in a state where the opening of the recessed portion 21a is open is indicated by a two-dot chain line, and the shutter plate 20a in a closed state is indicated by a solid line.

  As shown in FIG. 1, the sample container 11 is attached to the support block 22 of the glow discharge emission spectroscopic analyzer by the attaching portion 19d, and the pressing of the notch portion 21a is not shown in the state where the opening of the recessed portion 21a is opened by the shutter 20. The sample holding part 21 is pressed against the support block 22 via the seal member 7A by means or an operator, and the contact part 21b comes into contact with the support block 22, so that the sample 12 is not in contact with the seal member 7A. Without being pressed by anything, it faces the anode tube 3d of the glow discharge optical emission spectrometer with an appropriate gap.

  The glow discharge optical emission spectrometer equipped with the sample container 11 is used in the following procedure. First, as shown by a two-dot chain line in FIG. 2, the sample container 11 is placed in a chamber of an inert gas atmosphere such as nitrogen or argon while the opening of the recessed portion 21a is open, and the recessed portion of the sample holding portion 21 is placed. The sample 12 prepared in the same chamber is attached to the bottom surface of the insertion portion 21a by, for example, adhesion, the handle 20c is rotated to move the shutter plate 20a, and the opening of the depression portion 21a is closed as indicated by a solid line. As a result, the sample 12 is sealed in an inert gas atmosphere, so the sample container 11 is taken out of the chamber and transported to the glow discharge emission spectroscopic analyzer, and attached to the support block 22 with bolts 23 as shown in FIG.

  Next, the container-side space S (the shutter plate 20a closed at this time as shown by the solid line in FIG. 2 and the support block 22) is formed by the container-side intake / exhaust holes 25 that the Grimm glow discharge tube 10 has in the support block 22. The space in the sample container 11 between) and the inner space V of the support block 22 communicating with the container side space S are evacuated. Next, the handle 20c is rotated to move the shutter plate 20a, the opening of the recessed portion 21a is opened as shown in FIG. 1, and the small diameter portion of the sample holding portion 21 is pushed inward, so that the seal member 7A is interposed. By pressing the support block 22, the contact portion 21 b is brought into contact with the support block 22. As a result, the sample 12 is not in contact with the seal member 7A and faces the anode tube 3d with an appropriate gap without being pressed by anything.

  Next, while the evacuation by the container side intake / exhaust hole 25 is continued, the inner space V of the support block 22 is evacuated by the first and second vacuum exhaust holes 3b and 3c, and the container side space S (in this case, FIG. When the inner space V) and the inner space V are sufficiently depressurized as shown in FIG. 1, the container-side intake / exhaust holes 25 and the first and second vacuum exhaust holes 3b, 3c After the evacuation is completed, the inner space V and the container-side space S are brought into an argon atmosphere by the argon gas supply hole 3a and the container-side intake / exhaust hole 25. Then, a voltage is applied between the anode block 3 and the sample holder 21 by the power supply unit 29 to generate glow discharge, and analysis is started.

  In the sample container 11, as in the modification shown in FIG. 4, the through-hole 19 a consists of only a small diameter part, and the circumferential groove and the O-ring 7 </ b> B (FIG. 2) are not provided in the bottom part 19 b. The O-ring 7A fitted in the groove of the portion 21b may have a function of opening and closing the opening of the recessed portion 21a in cooperation with the shutter 20.

  According to the glow discharge optical emission spectrometer equipped with the sample container 11 as described above, the sample 12 attached to the sample holder 21 can be sealed in an inert gas atmosphere and conveyed to the analyzer, and the sample can be held. When the portion 21 is pressed against the support block 22 of the analyzer through the seal member 7A, the sample 12 faces the anode tube 3d in a non-contact manner with the seal member 7A, so that the sample 12 is exposed to air. Therefore, accurate glow discharge emission spectroscopic analysis can be performed on the sample 12 which is not pressed and therefore needs to be handled in an inert gas atmosphere and may be peeled off or damaged when pressed. Note that the sample container 11 removed from the glow discharge optical emission spectrometer is a single embodiment of the present invention.

3 Anode block 3a introduction means (argon gas supply hole)
3b, 3c Pressure reducing means (vacuum exhaust hole)
3d Anode tube 7A Seal member (O-ring)
DESCRIPTION OF SYMBOLS 11 Sample container 12 Sample 19 Container main body 19a Through-hole 19b Bottom part 19c Side part 19d Mounting part 20 Shutter 21 Sample holding part 21a Recessed part 21b Contact part 22 Support block 25 Container side decompression means, container side introduction means 29 Power supply means (power supply Part)
S Container side space V Inner space

Claims (2)

A sample container that contains a sample and holds the sample so as to face the anode tube of a glow discharge optical emission spectrometer,
A bottom portion in which a through-hole is formed, a side portion provided around the bottom portion, and a detachable attachment portion for attaching to the glow discharge optical emission spectrometer so as to close an opening surrounded by an open end of the side portion. A container body;
A sample holding part that is inserted in the through hole so as to be able to advance and retreat, a sample is attached to the recessed part of the tip part, and a peripheral part of the recessed part has a contact part with a glow discharge optical emission spectrometer.
A shutter for opening and closing the opening of the recessed portion,
The sample holder is pressed against the glow discharge emission spectroscopic analyzer through a seal member in a state where the attachment portion is attached to the glow discharge emission spectrometer and the opening of the recessed portion is opened by the shutter. A sample container in which the contact portion is in contact with the glow discharge optical emission spectrometer, so that the sample faces the anode tube of the glow discharge optical emission spectrometer without contacting the seal member. An anode block having an anode tube;
A support block having an inner space for accommodating the anode tube;
Decompression means for evacuating the inner space of the support block;
Introducing means for introducing an inert gas into the inner space;
A sample container according to claim 1;
Container-side decompression means for evacuating the container-side space between the sample container and the support block attached to the support block;
Container-side introduction means for introducing an inert gas into the container-side space;
A glow discharge emission spectroscopic analysis apparatus comprising: a power feeding unit that applies a voltage between the anode block and a sample holding portion of the sample container to generate glow discharge.

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