JP2019220484A - Fixture of specimen holder - Google Patents

Abstract

To provide a fixture of a specimen holder for an aqueous solution specimen suitable for when analyzing a fluid inclusion in mineral.SOLUTION: A specimen holder 1 for infusing a standard sample solution, is fixed to a fixture 2, and is set to a laser ablation device. The specimen holder 1 comprises: a base part 11 positioned at a lower part 1B; and a cover part 12 positioned at an upper part 1A. The base part 11 and the cover part 12 are constructed by quartz glass. A plurality of columnar holes 13 directing to a bottom surface 11B from a top surface 11A is provided to an almost central part of the top surface 11A in the base part 11. The columnar holes 13 comprise a small diameter hole 14 of which the diameter is small, and a large diameter hole 15 of which the diameter is larger than that of the small diameter hole 14. The whole of columnar holes 13 has a columnar form, and cross area parallel to the top surface 11A, that is, an opening surface is approximately even in a depth direction.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a fixture for a sample holder used for measuring a standard sample solution, and particularly to a standard sample solution used when measuring a liquid inclusion of a mineral resource using a mass spectrometer connected to a laser ablation device. The present invention relates to a sample holder fixture suitable for measurement.

  It is known that minerals such as quartz formed with hot water such as geothermal activity include a fluid when the minerals are formed as inclusions. Fluid inclusions of these minerals include metal elements such as sodium (Na), potassium (K), silicon (Si), aluminum (Al), copper (Cu), zinc (Zn), and lead (Pb). Included, these elements are involved in deposit formation. If the chemical composition of such fluid inclusions can be obtained, it will be useful for elucidating mineral resources and geothermal resources, and fluid inclusions are being analyzed around the world. The size of fluid inclusions contained in minerals is very small, and their analysis is often performed using inductively coupled plasma mass spectrometry or laser Raman spectroscopy connected to a laser ablation device. When these analysis methods are used, it is necessary to measure a standard sample solution containing a certain contained substance and a certain amount of an element, and to prepare a calibration curve. Obtaining an accurate calibration curve enables more accurate analysis of fluid inclusions.

JP-A-10-325831

  2. Description of the Related Art Conventionally, a technique related to measurement of a standard sample in an ultrasonic deep wound inspection is known (see Patent Document 1). The standard sample in this conventional technique is an individual and is premised on nondestructive inspection. That is, a holder for a standard sample is formed of a thermoplastic resin, and particles for forming an artificial defect serving as a standard sample are held in the resin. By irradiating the artificial defect forming particles with ultrasonic waves, it is possible to measure the standard sample without breaking the holder.

  However, the standard sample targeted in the present invention is a liquid, and is premised on destructive measurement using a laser. If a liquid standard sample is injected into a conventional thermoplastic resin holder, the upper portion of the standard sample is covered with the resin. That is, the laser is applied to the resin, which is a material different from the mineral to be analyzed. A calibration curve based on such a measurement shows characteristics of the resin and is not suitable for analysis of minerals. That is, there is a problem that it is difficult to accurately analyze an analysis target.

  An object of the present invention is to provide a fixture for a sample holder for a standard sample solution that is suitable for analyzing fluid inclusions of minerals.

The present invention relates to a fixture for a sample holder for holding a standard sample solution used for analyzing fluid inclusions of minerals by a laser, wherein a first member capable of contacting at least an upper portion of the sample holder and an at least lower portion of the first member. A second member that can be brought into contact with the first member and a fastening member that connects the first member and the second member to each other; a first opening that exposes at least a part of the sample holder is provided in the first member; It is characterized by the following.
According to such a fixture, since the process from the injection of the standard sample solution to the sample holder to the fixation can be performed, the sample holder can be fixed without spilling the standard sample solution in the sample holder.

The first member includes a first space portion provided with a first space for holding the sample holder, and a first opening portion adjacent to the first space portion and provided with the first opening, The diameter of the first opening is smaller than the space, a first step is formed by the first opening and the first space, and the second member is provided with a second space for holding the sample holder. A second opening provided adjacent to the second space and provided with a second opening, wherein a diameter of the second opening is smaller than the second space; A second step portion is formed by the space, and the first space and the second space hold the sample holder, and an upper portion of the holder abuts on the first step portion, Or it may be characterized in that the lower portion of the holder to the second step portion abuts.
According to this fixture, by providing the second opening, the sample holder can be observed by the transmitted light through the second opening, and the laser and the sample holder can be easily positioned.

  According to the embodiment of the present invention, since the first opening is provided in the fixture, the upper portion of the sample holder can be exposed, and the laser can be directly applied to the sample holder through the first opening. Further, the sample holder can be fixed without spilling the standard sample solution in the sample holder. Therefore, accurate analysis of the analysis target is possible.

1 is a perspective view of a sample holder and a fixture according to an embodiment of the present invention. FIG. 2 is a sectional view taken along line II-II of FIG. 1. Explanatory drawing of a sample holder. FIG. 4 is an enlarged view of a portion surrounded by IV in FIG. 2.

  The surface of the object to be analyzed is irradiated with a laser by the laser ablation apparatus used in this embodiment, and at the same time, the elements contained in the object to be analyzed are sampled, and the sampled elements are measured by a mass spectrometer connected to the laser ablation apparatus. In this embodiment, it is an object to analyze minerals having fluid inclusions, and to analyze the types and amounts of elements contained in the fluid inclusions. Specifically, a part of the mineral is cut by irradiating it with a laser, the laser is directly irradiated on the fluid inclusions, and the fluid is gasified or turned into fine droplets, which are transported to the mass spectrometer. The content element is measured by this.

  In analyzing the elements of the fluid inclusions of the mineral, an arbitrary standard sample solution is measured, and a calibration curve is created from the measurement results. The amount of the element contained in the fluid inclusion can be specified by comparing the measurement result of the fluid inclusion with the calibration curve. Since the fluid inclusions are often contained in quartz among the minerals, in this embodiment, a mineral mainly composed of quartz is selected.

  Referring to FIGS. 1 and 2, a sample holder 1 for injecting a standard sample solution is fixed to a fixture 2 and set on a laser ablation device (not shown).

  Referring also to FIG. 3, the sample holder 1 includes a base part 11 and a cover part 12, and the base part 11 forms a lower part 1 </ b> B and the cover part 12 forms an upper part 1 </ b> A. The base part 11 and the cover part 12 are formed of the same quartz glass as the main constituent elements of the mineral to be analyzed. The base 11 has a cylindrical shape, a diameter of about 15 mm, and a thickness of about 8 mm. The base portion 11 is provided with a plurality of columnar holes 13 extending from the upper surface 11A to the lower surface 11B at a substantially central portion of the upper surface 11A. In this embodiment, the columnar hole 13 includes a small diameter hole 14 having a small diameter and a large diameter hole 15 having a larger diameter than the small diameter hole 14.

Referring to FIG. 4, small-diameter hole 14 and large-diameter hole 15 include opening surfaces 14A and 15A located on upper surface 11A, and bottom surfaces 14B and 15B opposed thereto, respectively. , Bottom surfaces 14B and 15B each have a circular shape. In the small-diameter hole 14, the area of the opening surface 14A and the area of the bottom surface 14B are substantially equal and substantially parallel. Therefore, the small-diameter hole 14 has a columnar shape as a whole, and its center line extends vertically. The cross-sectional area parallel to the upper surface 11A, that is, the opening surface 14A is substantially equal in the depth direction. Similarly, also in the large-diameter hole 15, the area of the opening surface 15A and the bottom surface 15B are substantially equal and substantially parallel. Therefore, the large-diameter hole 15 has a columnar shape as a whole, and its center line extends vertically. The cross-sectional area parallel to the upper surface 11A, that is, the opening surface 15A is substantially equal in the depth direction.

  In this embodiment, the diameter of the small diameter hole 14 is about 20 μm and the depth is about 40 μm. The diameter of the large-diameter hole 15 is about 150 μm, and the depth is about 80 μm. In addition, the diameter and the depth of the columnar hole 13 are not limited to the dimensions exemplified here, and can be appropriately changed. It can be changed according to the type of laser used for analysis. In addition, by making the diameter of the columnar hole 13 circular, it is possible to cope with the irradiation of a substantially circular laser.

  A plurality of columnar holes 13 can be provided as in this embodiment, or only one location can be provided. When a plurality of columnar holes 13 are provided, for example, by injecting the same type of standard sample solution into the columnar holes 13, there is no need to inject the standard sample solution into the sample holder 1 each time, thus simplifying the operation. Can be achieved. Further, columnar holes 13 having different diameters may be provided, or a plurality of columnar holes 13 having the same diameter may be provided. For example, when the diameter of the laser is different due to the analysis, the provision of the columnar holes 13 having different diameters allows the selection of the columnar holes 13 corresponding to the laser, and the analysis with higher accuracy is possible.

  The columnar hole 13 may be provided to penetrate from the upper surface 11A to the lower surface 11B. When the columnar hole 13 penetrates, a plate or the like for closing the lower surface 11B is separately provided. When a plate or the like is provided in this manner, the bottom surface of the columnar hole 13 is defined by the plate or the like. The columnar holes 13 as described above can be formed by cutting the base portion 11 by, for example, laser processing.

  The cover part 12 is cylindrical and has a diameter of about 15 mm and a thickness of about 0.2 mm. By laminating the cover portion 12 on the upper surface 11A of the base portion 11, the opening surface 14A of the small-diameter hole 14 and the opening surface 15A of the large-diameter hole 15 can be closed.

  Referring again to FIGS. 1 and 2, the fixture 2 includes a first member 21 and a second member 22, and the first member 21 can abut on the upper portion 1 </ b> A of the sample holder 1, and the second member Reference numeral 22 can contact the lower part 1B of the sample holder 1. The first member 21 and the second member 22 can be made of, for example, stainless steel.

  The first member 21 is in contact with the upper portion 1A side, has a first opening 23 having a first opening 23A smaller than the diameter of the sample holder 1 at the center thereof, and has a larger diameter than the first opening 23. And a first space portion 24 having a first space 24A at the center thereof. The diameter of the first space 24A is slightly larger than the diameter of the sample holder 1, and forms a holding space for the sample holder 1 together with a second space 26A described later. In addition, a first step 23B is provided between the first opening 23A and the first space 24A, and the first step 23B can be brought into contact with the upper portion 1A of the sample holder 1. The first opening 23 and the first space 24 are formed of separate members and are each a ring-shaped plate-like member. The first member 21 is configured by stacking them.

  In this embodiment, the outer diameters of the first opening 23 and the first space 24 are each about 25 mm. The diameter of the first opening 23A is about 10 mm, and the dimension in the thickness direction is about 1 mm. The diameter of the first space 24A is about 16 mm, and the dimension in the thickness direction is about 4 mm. The dimension of the first opening 23 in the thickness direction is preferably as small as possible. This is because when the fixture 2 is placed on the laser ablation device, the distance between the laser and the sample holder 1 is made as close as possible to facilitate focusing.

  The second member 22 is in contact with the lower portion 1B, and has a second opening 25 having a second opening 25A smaller than the diameter of the sample holder 1 at the center thereof, and a second opening 25 having a diameter larger than the second opening 25. And a second space portion 26 having a space 26A at a central portion thereof. The diameter of the second space 26A is slightly larger than that of the sample holder 1, and forms a holding space for the sample holder 1 together with the first space 24A. A second step 25B is provided between the second opening 25A and the second space 26A, and the second step 25B can be brought into contact with the lower portion 1B of the sample holder 1. The second opening 25 and the second space 26 are formed integrally.

  The outer diameter of the second opening 25 and the second space 26 is about 25 mm, the diameter of the second opening 25A is about 10 mm, and the dimension in the thickness direction is about 2 mm. The diameter of the second space 26A is about 16 mm, and the dimension in the thickness direction is about 3 mm.

  The sum of the size of the first space portion 24 in the thickness direction and the size of the second space portion 26 in the thickness direction is smaller than the size of the sample holder 1 in the thickness direction.

  In the above configuration, the first member 21 and the second member 22 of the fixture are combined so that the first space portion 24 and the second space portion 26 face each other, and the sample holder is inserted into the cavity formed by the first space portion 24 and the second space portion 26. 1 can be stored.

  The first member 21 and the second member 22 of the fixture 2 are connected to each other by a first fastening member 27. In this embodiment, three first fastening members 27 are provided, and the distance between them is equal on the upper surface of the fixture 2. Specifically, a screw can be used as the first fastening member 27. The first member 21 into which the first fastening member 27 is inserted is provided with a through hole larger than the diameter of the screw, and the second member 22 is formed with a screw hole. The screw used as the first fastening member 27 has a length that penetrates the first member 21 and enables the second member 22 to be screwed.

  In this embodiment, the first opening 23 and the first space 24 of the first member 21 are formed of different members, and are connected to each other by the second fastening member 28. A screw can be used as the second fastening member 28, and its length is such that it reaches the first space portion 24 through the first opening 23. Therefore, the length of the second fastening member 28 is shorter than the length of the first fastening member 27. Three second fastening members 28 are provided, are arranged between the first fastening members 27 on the upper surface of the fixture 2, and have the same separation dimension.

  In the above configuration, the base 11 of the sample holder 1 is fitted into the second space 26A of the second member 22 of the fixture 2. The base 11 is supported by the second step 25B. A standard sample solution is injected into the columnar holes 13 of the base 11 supported by the second member 22, and the columnar holes 13 are covered with the cover 12. At this time, the cover 12 is placed on the base 11 so that air does not enter the columnar holes 13. Next, the first member 21 is placed on the second member 22 so that the second space portion 26 and the first space portion 24 face each other. In the first member 21, the first opening 23 and the first space 24 are connected in advance by the second fastening member 28. When the first member 21 is placed on the cover portion 12 in this manner, the first step portion 23B comes into contact with the cover portion 12. After the first member 21 is placed on the second member 22, they are connected to each other by the first fastening member 27.

In the fixing device 2 as described above, since the process from the injection of the standard sample solution to the fixing of the cover portion 12 can be performed without moving the base portion 11, the standard sample solution is prevented from being spilled by the movement of the base portion 11. be able to.
By tightening the first fastening member 27, the first member 21 and the second member 22 can be connected. Therefore, the sample holder 1 arranged between the first member 21 and the second member 22 can be reliably supported.

  In this embodiment, the sum of the dimensions of the first space portion 24 and the second space portion 26 in the thickness direction is smaller than the size of the sample holder 1 in the thickness direction. Therefore, by appropriately tightening the first fastening member 27 and pressing the first member 21 and the second member 22 and the sample holder 1 against each other, the play of the sample holder 1 in the thickness direction can be suppressed. Further, since the sample holder 1 can be pressed into the thickness direction, the base portion 11 and the cover portion 12 can be brought into close contact with each other. In the sample holder 1 held by the fixture 2 as described above, the columnar holes 13 provided at the center of the holder 2 correspond to the openings 23A, 24A, 25A, 26A provided at the center of the fixture 2. Placed in

The sample holder 1 held by the fixture 2 as described above can be applied to analysis using a laser ablation device.
In the laser ablation device used in this embodiment, a sample is held in a sample chamber and analyzed. The sample chamber is connected to a high-frequency inductively coupled plasma mass spectrometer (ICP-MS device) or an ICP emission spectrometer (ICP-AES device) by a gas introduction system. Helium (He) gas, argon (Ar) gas, or nitrogen gas flows as a carrier gas in the sample chamber, and fine particles, gas, and fine droplets ablated by a laser are subjected to ICP-MS or ICP- It is supplied to an AES device and a chemical analysis is performed.

  The sample holder 1 held by the fixture 2 is set in the sample chamber of the laser ablation device, and the laser is focused on the upper surface of the cover section 12 of the sample holder 1 to start ablation. At this time, the fixture 2 is positioned so that the laser beam corresponds to any one of the columnar holes 13. Since the first opening 23A is provided in the fixture 2, the upper portion 1A of the sample holder 1 can be exposed, and the laser can be directly applied to the sample holder 1 via the first opening 23A. In addition, by providing the second opening 25A, the columnar hole 13 can be observed by the transmitted light from the lower portion 1B, and the alignment between the laser and the columnar hole 13 is facilitated.

  The laser excavates the cover portion 12 within the set focal range, and penetrates the cover portion 12 to irradiate the standard sample solution held in the columnar hole 13. The standard sample solution is vaporized or formed into fine droplets by a laser, introduced into an ICP-MS device or an ICP-AES device together with a carrier gas in the sample chamber, and subjected to chemical analysis.

  In the ICP-MS device or the IPC-AES device, by monitoring the value of silicon which is a component of the quartz glass constituting the base portion 11 in the mass spectrometer, the laser cut the cover portion 12, and It is possible to detect that it has arrived and that it has reached the bottom of the columnar hole 13 of the base portion 11. The analysis may be completed before the laser reaches the bottom of the columnar hole 13.

  The columnar holes 13 extend in the vertical direction, and have substantially the same cross-sectional area from the opening surface to the bottom surface. Therefore, even if the base portion 11 around the columnar hole 13 is cut by the laser irradiated vertically, the amount of the quartz glass cut is constant over time, and the amount of the standard sample solution is also constant over time. Therefore, it is easy to calculate and correct these ratios. However, if the cross-sectional areas of the columnar holes 13 are not equal, the cut amount of the quartz glass is not constant, and it is not possible to calculate the ratio with the measured standard sample solution. Therefore, in such a case, it is difficult to create an accurate calibration curve.

  In this embodiment, the dimension in the thickness direction of the cover portion 12 can be about 0.1 mm to 0.5 mm. However, it is not limited to this dimension and can be changed as appropriate. However, if the thickness of the cover portion 12 is too thin, handling becomes difficult, and if it is too thick, there is a problem that it takes too much time for cutting. Therefore, it is necessary that the thickness of the cover portion 12 is easy to handle and that the cutting does not take too much time.

  The size of the columnar hole 13 in the depth direction can be about 10 μm to 100 μm, and a size corresponding to the size of the fluid inclusion to be analyzed can be selected. Further, the diameter of the columnar hole 13 can be about 20 to 150 μm. Desirably, the diameter is obtained by adding about 5 μm to the diameter of the laser to be irradiated. If the diameter of the columnar hole 13 becomes unreasonably large, the size of the fluid inclusion to be analyzed is far from that of the fluid inclusion, and the characteristics when the standard sample is measured and the characteristics when the analysis target are measured will be different. If the diameter of the columnar hole 13 is smaller than about 20 μm, there is a possibility that it becomes difficult to inject the standard sample solution.

  Although quartz glass is used for the base portion 11 and the cover portion 12, it is not limited to this. For example, olivine or corundum can be used as the mineral. In such a case, the sample holder 1 is made of the same material as the main constituent element of each mineral. Thus, by using the same material as the main constituent elements, the characteristics at the time of measuring the standard sample solution and the characteristics at the time of measuring the object to be analyzed can be approximated, and more accurate analysis results can be obtained.

  In this embodiment, the sample holder 1 and the fixture 2 are applied to a laser ablation apparatus, but the present invention can also be applied to a laser Raman spectrometer.

DESCRIPTION OF SYMBOLS 1 Sample holder 2 Fixture 11 Base part 12 Cover part 11A Upper surface 11B Lower surface 13 Column-shaped hole 21 1st member 22 2nd member 23 1st opening 23A 1st opening 23B 1st step part 24 1st space part 24A 1st space 25 second opening 25A second opening 25B second step 26 second space 26A second space 28 first fastening member (fastening member)

Claims (2)

A fixture for a sample holder for holding a standard sample solution used for analyzing fluid inclusions of minerals by laser,
A first member capable of contacting at least an upper portion of the sample holder, a second member capable of contacting at least a lower portion, and a fastening member for connecting the first member and the second member to each other,
A fixture for a sample holder, wherein the first member is provided with a first opening exposing at least a part of the sample holder. The first member includes a first space portion provided with a first space for holding the sample holder, and a first opening portion adjacent to the first space portion and provided with the first opening, The diameter of the first opening is smaller than the space, and the first step and the first space form a first step portion,
The second member includes a second space portion provided with a second space for holding the sample holder, and a second opening portion adjacent to the second space portion and provided with a second opening, The diameter of the second opening is smaller than the second space, and the second opening and the space form a second step,
The sample holder is held by the first space and the second space, and an upper portion of the holder abuts on the first step portion, and a lower portion of the holder abuts on the second step portion. The fixture for a sample holder according to claim 1.

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