JP5523805B2 - Sample cell assembly tool - Google Patents

Description

  The present invention relates to an instrument for assembling a sample cell for accommodating a sample for fluorescent X-ray analysis, and more particularly to a sample cell assembly for assembling a sample cell for accommodating a volatile sample in a sealed state.

  X-ray fluorescence analysis is an analysis technique in which primary X-rays are irradiated onto a sample, 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 fluorescent X-ray spectrum. . In X-ray fluorescence analysis, a sample is irradiated with primary X-rays, X-ray fluorescence generated from the sample irradiated with primary X-rays is detected with an X-ray detector, and the spectrum of the detected X-ray fluorescence is analyzed with an analyzer. To do. Such fluorescent X-ray analysis can be used for elemental analysis of a liquid sample. For example, elemental analysis of liquid fuel using fluorescent X-ray analysis is performed for the purpose of reducing harmful components contained in liquid fuel such as light oil. Patent Document 1 describes a fluorescent X-ray analyzer that performs fluorescent X-ray analysis of a liquid sample. When analyzing a volatile liquid sample such as liquid fuel, the sample is accommodated in a sealed sample cell in order to prevent the sample from being reduced and altered due to volatilization.

  Patent Document 2 discloses a sample cell that accommodates a liquid sample. The sample cell includes a sample cup, an X-ray transmission sheet that can transmit X-rays, and an outer frame that fits around the sample cup. When assembling the sample cell, inject the liquid sample into the sample cup with the upper surface opened, place an X-ray transmissive sheet on the upper surface of the sample cup, and sandwich the X-ray transmissive sheet between the outer frames of the sample cup. The outer frame is fitted from the upper side of the sample cup so as to fit. The X-ray transmission sheet is pulled from the center toward the periphery when the outer frame is fitted, and the peripheral portion is sandwiched between the outer periphery of the sample cup and the outer frame, thereby sealing the opening of the sample cup. To be stretched. When performing fluorescent X-ray analysis, the X-ray transmission sheet is used as the bottom surface of the sample cell, the primary X-rays are irradiated to the sample in the sample cell through the X-ray transmission sheet, and are transmitted through the X-ray transmission sheet and emitted. X-ray fluorescence is detected.

Japanese Patent Laid-Open No. 9-127028 JP-A-9-257664

  If you try to fill the sample cell with the liquid sample when assembling the sample cell, the liquid sample will overflow from the sample cell, so it cannot be filled. The sample cell is filled with the liquid sample and some air. Will be. When the liquid sample is a highly volatile liquid such as fuel, the liquid sample volatilizes in the sample cell with the passage of time, and the pressure in the sample cell increases. When the pressure in the sample cell rises, the X-ray transmission sheet that seals the sample cell expands. When the X-ray transmission sheet that transmits fluorescent X-rays from the sample expands, the distance between the sample and the detector that detects the fluorescent X-rays changes, and the intensity of the fluorescent X-rays detected by the detector changes. There is a problem that accurate elemental analysis cannot be performed.

  Conventionally, when the sample cell is assembled, an X-ray transmission sheet is placed in the opening of the sample cup after the liquid sample is injected, and an outer frame is fitted on the X-ray transmission sheet. The liquid sample may adhere to the X-ray transmission sheet. The portion of the X-ray transmission sheet to which the liquid sample has adhered becomes slippery when it comes into contact with the edge of the sample cup, and causes wrinkles when the X-ray transmission sheet is stretched. The X-ray transmission sheet becomes the bottom surface of the sample cell when performing fluorescent X-ray analysis. If wrinkles occur, the liquid sample may leak out, and the distance between the sample and the detector may fluctuate. There is a problem that accurate elemental analysis cannot be performed. Further, when the outer frame is fitted, the tension for pulling the X-ray transmission sheet in the peripheral direction is likely to be non-uniform, and the non-uniform tension causes wrinkles in the X-ray transmission sheet.

  The present invention has been made in view of such circumstances, and an object of the present invention is to make it possible to deform the sample cell so that parts other than the X-ray transmission sheet can be deformed so as to absorb an increase in pressure in the sample cell. An object of the present invention is to provide a sample cell assembly for assembling a sample cell so that expansion of the X-ray transmission sheet during fluorescent X-ray analysis can be prevented by assembling.

  Another object of the present invention is to provide a sample cell assembly tool capable of preventing the generation of wrinkles in the X-ray transmission sheet when the sample cell is assembled.

The sample cell assembly according to the present invention accommodates a sample in a sample cup, seals the opening of the sample cup containing the sample with an X-ray transmission sheet, and sandwiches the X-ray transmission sheet between the outer frames of the sample cup. In a sample cell assembly used for assembling a sample cell for fluorescent X-ray analysis by fitting the sample cup, it is a stage for placing the sample cup and placing the sample cup with the opening on the upper side When fitting the outer frame from the upper side to the positioning part for positioning the sample cup and the placed sample cup, the flat end surface on the lower side of the sample cup is pushed up toward the inside of the sample cup. It includes a sample cup mounting table having a protruding portion that is deformed into a convex shape.

In the sample cell assembly according to the present invention, a cylindrical inner frame is fitted on the end face side of the sample cup, the end of the inner frame protrudes from the end face, and the positioning portion is on a plane. A column that is raised, the outer diameter of the column is a size that fits into the inner frame, the height of the column is smaller than the distance from the end of the inner frame to the end surface, and the protrusion is A projection protruding at the center of the upper surface of the cylinder.

  The sample cell assembly according to the present invention is separate from the sample cup mounting table, has a cylindrical shape, has both end faces parallel to each other and perpendicular to the axis, and has an inner diameter larger than the outer diameter of the sample cell. The height when mounted on the sample cup mounting table is higher than that of the sample cup. The sample cup mounting table is mounted so as to surround the sample cup, and an X-ray transmission sheet is mounted thereon. It further includes a sheet placing tool used for placing.

Sample cell assembly tool according to the present invention, the the sample cup mount and the sheet placement base is separate, a tubular shape, the inner diameter is the size that is fitted in the outer frame, the outer diameter Is smaller than the inner diameter of the sheet placing tool, and the height is higher than the outer frame, and the outer frame fitted inside from the upper side of the X-ray transmission sheet placed on the sheet placing tool is taken as a sample cup. It further includes an outer frame fitting tool used for fitting the outer frame to the sample cup by being pushed in toward it.

  In the present invention, when performing the work of sealing the opening with an X-ray transmission sheet with the opening of the sample cup on the upper side, the sample cup is mounted on the sample cup mounting table having the protrusions, thereby The end surface of the projection is deformed convex toward the inside.

  Further, in the present invention, when the X-ray transmission sheet is placed on the sample cup containing the sample, the sample cup on the sample cup mounting table is surrounded, and the sheet mounting tool that is taller than the sample cup is used. By placing the X-ray transmission sheet, the X-ray transmission sheet can be placed on the sample cup without contacting the sample.

  Further, in the present invention, when the outer frame is fitted to the sample cup in order to fix the X-ray transmission sheet, a cylindrical outer frame fitting tool that is fitted to the outer frame is used to Since the outer frame is fitted by inserting the outer frame from above the X-ray transmissive sheet placed on the outer frame, the outer frame fitting tool is guided by the inner wall of the sheet placing tool and the outer frame is inserted almost vertically, The X-ray transmission sheet spreads uniformly.

  In the present invention, the sample cell assembled using the sample cell assembly tool of the present invention is deformed in a convex shape inward in advance even when the fluid sample evaporates and the internal pressure rises. The end face of the sample cup that has been caused to deform outwardly does not expand the X-ray transmissive sheet through which the primary X-rays and fluorescent X-rays are transmitted. Accordingly, the intensity of the fluorescent X-ray does not change due to a factor other than the element distribution in the fluid sample, so that the elemental analysis of the fluid sample can be performed with high accuracy by the fluorescent X-ray analysis. Excellent effect.

It is a schematic diagram which shows the structure of a fluorescent X ray analyzer. It is sectional drawing which shows the structure of a sample cell and a cell holder. It is a disassembled perspective view which shows the structure of a sample cell. It is a disassembled perspective view which shows the structure of a cell holder. It is a perspective view which shows the structure of the sample cell assembly tool of this invention. It is explanatory drawing explaining the assembly method of a sample cell by a front view. It is explanatory drawing explaining the assembly method of a sample cell by a front view. It is explanatory drawing explaining the assembly method of a sample cell by a front view. It is explanatory drawing explaining the assembly method of a sample cell by a front view. It is explanatory drawing explaining the assembly method of a sample cell by a front view. It is the perspective view which turned the cell support member upside down. It is a perspective view which shows the cell holder assembly tool for assembling a cell holder. It is sectional drawing along the axis | shaft of a cell holder assembly tool. It is typical sectional drawing explaining the assembly method of the cell holder using a cell holder assembly tool. It is sectional drawing which shows the assembled cell holder. It is sectional drawing which shows the sample cell mounted on the cell holder. It is sectional drawing which shows the sample cell after a cup end surface deform | transforms with a raise of a pressure.

Hereinafter, the present invention will be specifically described with reference to the drawings showing embodiments thereof.
FIG. 1 is a schematic diagram showing the configuration of a fluorescent X-ray analyzer. The X-ray fluorescence analyzer includes a housing 5 formed in a box shape with a material that shields X-rays, and an upper portion of the housing 5 is configured to be a plane. An opening is formed in the center of the upper plane of the housing 5, and the cell holder 2 is mounted in a manner of being fitted into the opening. Then, a sample cell (fluorescent X-ray analysis sample cell) 1 containing a sample to be analyzed is placed on the cell holder 2. The X-ray fluorescence analyzer is provided with a cover 6 that covers a portion of the upper surface of the housing 5 including the opening, and the sample cell 1 placed on the cell holder 2 and the cell holder 2 is covered with the cover 6. Is called. The sample cell 1 is a cell for storing a fluid sample such as powder or liquid fuel, and is formed in a cup shape. The cell holder 2 is provided with an X-ray transmission sheet 22 capable of transmitting X-rays, and the lower surface of the sample cell 1 is constituted by the X-ray transmission sheet 12.

  A hollow measurement chamber 51 is formed inside the housing 5, and the housing 5 includes an X-ray tube 3 that emits primary X-rays into the measurement chamber 51 and an X-ray detector 4. I have. The X-ray tube 3 is disposed at a position where primary X-rays are emitted toward the opening of the housing 5. When performing fluorescent X-ray analysis, since the cell holder 2 and the sample cell 1 are arranged at the position of the opening of the housing 5, primary X-rays generated from the X-ray tube 3 are X-rays of the cell holder 2. The sample passes through the transmission sheet 22 and the X-ray transmission sheet 12 of the sample cell 1 and is irradiated to the sample in the sample cell 1. The sample in the sample cell 1 irradiated with the primary X-rays generates fluorescent X-rays, and the fluorescent X-rays pass through the X-ray transmitting sheet 12 and the X-ray transmitting sheet 22 of the cell holder 2 and are emitted into the measurement chamber 51. Is done. The X-ray detector 4 is disposed at a position where fluorescent X-rays generated from the sample in the sample cell 1 can be detected. The path through which the primary X-rays irradiated by the X-ray tube 3 and the fluorescent X-rays detected by the X-ray detector 4 pass is indicated by broken-line arrows in FIG.

  An openable / closable shutter (not shown) is provided at the radiation port that emits primary X-rays of the X-ray tube 3. The X-ray tube 3 is configured to always generate X-rays in order to stabilize the output of primary X-rays, and the X-ray tube 3 emits primary X-rays when the shutter is opened. The X-ray detector 4 has a configuration using a proportional counter as a detection element, and outputs an electrical signal proportional to the energy of fluorescent X-rays incident on the proportional counter. Note that the X-ray detector 4 may have a form using a detection element other than a proportional counter, such as a semiconductor detection element, as the detection element. The X-ray detector 4 is connected to a signal analysis unit (not shown) configured using a microcomputer or the like. The signal analyzer receives the electrical signal output from the X-ray detector 4, counts the intensity and number of each electrical signal corresponding to the energy of the fluorescent X-ray, and the relationship between the fluorescent X-ray energy and the count number, That is, a process of acquiring a fluorescent X-ray spectrum is performed. The signal analysis unit may be configured to further perform qualitative analysis or quantitative analysis of the element that has generated fluorescent X-rays based on the acquired spectrum of fluorescent X-rays.

  In a state where the cell holder 2 is attached to the opening of the housing 5, the measurement chamber 51 in the housing 5 becomes a sealed space by the cell holder 2. The housing 5 is connected to the measurement chamber 51, and a supply port 52 for supplying gas into the measurement chamber 51 is formed. A gas pipe (not shown) that supplies gas is connected to the supply port 52. When performing fluorescent X-ray analysis, a gas such as helium gas or nitrogen gas is supplied from the supply port 52 into the measurement chamber 51, and the air in the measurement chamber 51 is replaced by the gas. In FIG. 1, the supplied gas is indicated by a solid arrow. The X-ray tube 3 is attached to the housing 5 via a metal foil 31 for sealing so as not to directly touch the gas substituted for the air in the measurement chamber 51. Depending on the sample to be analyzed, a primary filter may be used to reduce the background of each spectrum of fluorescent X-rays, and primary X-rays from the X-ray tube 3 may be irradiated after passing through the primary filter. In this case, a primary filter may be used instead of the metal foil 31 for sealing.

  Further, when the sample cell 1 is placed on the cell holder 2, a space is generated between the X-ray transmission sheet 22 of the cell holder 2 and the X-ray transmission sheet 12 of the sample cell 1. The X-ray fluorescence analyzer includes a supply mechanism (not shown) for supplying gas to the space between the X-ray transmission sheet 22 and the X-ray transmission sheet 12. By the function of this supply mechanism, the air in the space between the X-ray transmission sheet 22 and the X-ray transmission sheet 12 is also replaced with a gas such as helium gas or nitrogen gas.

  FIG. 2 is a cross-sectional view illustrating the configuration of the sample cell 1 and the cell holder 2, and FIG. 3 is an exploded perspective view illustrating the configuration of the sample cell 1. The sample cell 1 includes a cell inner frame 10, a sample cup 11, a cell outer frame 13, and an X-ray transmission sheet 12. The cell inner frame 10 has a cylindrical shape and is formed of plastic such as polyethylene or metal. At the upper end portion of the cell inner frame 10, a flange portion 10 a is provided over the entire circumference of the outer peripheral surface. Further, a groove 10b is formed on the outer peripheral surface of the cell inner frame 10 at a central position in the axial direction over the entire circumference, and an annular protrusion 10c is formed on the inner peripheral surface of the cell inner frame 10 over the entire circumference. Is protruding.

  The sample cup 11 is formed by bending a sheet such as a soft plastic film. The sample cup 11 has a cup end surface 111 at one end, a cylindrical sample storage portion 112 having an opening at the other end, and an opening of the sample storage portion 112, and an outer peripheral surface of the sample storage portion 112. A cylindrical enclosure 113 provided so as to surround the outer peripheral surface of the sample storage unit 112 at a predetermined interval from the outer periphery, and a flange 114 provided at the end of the enclosure 113 over the entire circumference of the outer peripheral surface. Have. As will be described later, the cup end surface 111 can be deformed toward the inside of the sample cell 1.

  The outer diameter of the sample storage portion 112 is smaller than the inner diameter of the cell inner frame 10, and the inner diameter of the surrounding portion 113 is substantially equal to the outer diameter of the cell inner frame 10. Further, the height (length in the vertical direction) of the cell inner frame 10 excluding the flange portion 10 a is slightly shorter than the height of the space between the sample storage portion 112 and the enclosure portion 113. Therefore, the cell inner frame 10 can be inserted into the space between the sample storage portion 112 and the enclosure portion 113 from the upper side until the flange portion 10a of the cell inner frame 10 contacts the flange portion 114 of the sample cup 11. . When the cell inner frame 10 is inserted into the sample cup 11, the cell inner frame 10 is fitted into the surrounding portion 113 of the sample cup 11, and the inner peripheral surface of the cell inner frame 10 and the outer peripheral surface of the sample accommodating portion 112 of the sample cup 11. There is a gap between the two.

  The X-ray transmissive sheet 12 is a substantially circular thin sheet having a diameter sufficiently larger than the outer diameter of the sample cup 11, and is formed of a substance that does not pass a fluid sample such as liquid fuel and transmits X-rays. . The X-ray transmission sheet 12 is manufactured by a polyester sheet, for example. The X-ray transmission sheet 12 seals the inside of the sample cup 11 by covering the opening of the sample cup 11 in which the sample is accommodated, and forms the bottom surface of the sample cup 11 (that is, the sample cell 1).

  The cell outer frame 13 has a cylindrical shape and is formed of plastic such as polyethylene or metal. The inner diameter of the cell outer frame 13 is slightly larger than the outer diameter of the sample cup 11, and the sample cup 11 with the cell inner frame 10 inserted between the sample storage portion 112 and the enclosure portion 113 is inserted into the cell outer frame 13. It can be inserted and fitted from the opening side. At this time, the outer edge of the X-ray transmission sheet 12 is placed on the outer peripheral surface of the sample cup 11 by fitting the sample cup 11 in the cell outer frame 13 with the opening of the sample cup 11 covered with the X-ray transmission sheet 12. And the inner peripheral surface of the cell outer frame 13. Therefore, the X-ray transmission sheet 12 is firmly fixed as the bottom surface of the sample cell 1 so that the fluid sample in the sample cup 11 does not spill out from the opening.

  The upper end portion of the cell outer frame 13 is provided with a flange portion 13a over the entire circumference of the outer peripheral surface. The flange portion 13a includes the fitted cell inner frame 10 and the sample cup 11 with the respective flange portions 10a and 10a. Support at 114. Further, on the inner peripheral surface of the cell outer frame 13, a protrusion 13b is provided over the circumference at a position corresponding to the groove 10b provided on the outer peripheral surface of the cell inner frame 10, and this protrusion 13b is The groove portion 10b of the cell inner frame 10 fitted in the cell outer frame 13 is engaged with the enclosure portion 113 of the sample cup 11 and the X-ray transmission sheet 12 sandwiched therebetween. As a result, the sample cup 11 and the X-ray transmission sheet 12 are firmly sandwiched between the cell inner frame 10 and the cell outer frame 13.

  FIG. 4 is an exploded perspective view showing the configuration of the cell holder 2. The cell holder 2 includes a cell support member 21 and an X-ray transmission sheet 22. The cell support member 21 is made of metal such as copper or aluminum, and is provided with a disc-shaped bottom plate portion 213 having an opening 216 formed in the center at one end of a cylinder having a peripheral wall portion 212 and a flange at the other end. The portion 211 is provided. The inner diameter of the peripheral wall portion 213 is larger than the outer diameter of the cylindrical portion of the cell outer frame 13 of the sample cell 1, and the height of the peripheral wall portion 213 is sufficiently lower than the height of the sample cell 1 in the axial direction.

  In addition, the cell support member 21 is provided on the inner edge portion of the bottom plate portion 213 (peripheral portion of the opening portion 216), and protrudes obliquely upward toward the inside of the opening portion 216 over the entire circumference of the opening portion 216. have. That is, the support portion 214 has a cylindrical shape (substantially frustoconical shape) whose diameter is reduced upward, and an annular horizontal and smooth support plane 215 is formed at the protruding end portion (upper end portion) of the support portion 214. . The outer diameter of the support plane 215 is smaller than the diameter of the opening of the sample cup 11 of the sample cell 1. In addition, although the illustrated support portion 214 has a cylindrical shape whose diameter is reduced upward, the support portion 214 is not limited thereto, and the support portion 214 may be formed substantially vertically.

  The X-ray transmission sheet 22 has a substantially circular thin sheet shape having a diameter larger than the outer diameter of the cell support member 21 and is the same as the X-ray transmission sheet 12 of the sample cell 1. The X-ray transmission sheet 22 is attached to the cell support member 21 by being applied to the bottom surface of the cell support member 21 and fixed from the outside by an annular elastic member such as an O-ring by a method described later. The X-ray transmission sheet 22 attached to the cell support member 21 covers and closes the opening 216. The cell holder 2 is assembled by attaching the X-ray transmission sheet 22 to the cell support member 21. By attaching the assembled cell holder 2 to the opening of the housing 5 using a bolt or the like, the measurement chamber 51 of the fluorescent X-ray analyzer is sealed.

  Next, the sample cell assembly of the present invention for assembling the sample cell 1 will be described. FIG. 5 is a perspective view showing the configuration of the sample cell assembly of the present invention. The sample cell assembly tool includes a sample cup mounting table 71 that supports the sample cup 11 when the sample cell 1 is assembled, a sheet mounting tool 72 that supports the X-ray transmission sheet 12, and a cell outer frame 13 fitted into the sample cup 11. And an outer frame fitting tool 73 used for matching. The sample cup mounting table 71, the sheet mounting tool 72, and the outer frame fitting tool 73 are all formed of a metal such as brass or aluminum. The sheet placing tool 72 may be made of resin.

  The sample cup mounting table 71 has a cylindrical portion (positioning portion) 712 provided on the upper surface of a flat plate portion 711 formed in a flat plate shape, and a protrusion (push-up portion) 713 formed on the top surface of the cylindrical portion 712. It has a configuration. The width of the flat plate portion 711 is large enough to place the sample cell 1 and the sheet placing tool 72. The outer diameter of the cylindrical portion 712 is slightly smaller than the inner diameter of the flange portion 10a of the cell inner frame 10, and the sample cup 11 fitted with the cell inner frame 10 is placed on the sample cup mounting table 71 with the opening facing up. Sometimes, the flange portion 10a of the cell inner frame 10 is fitted to the cylindrical portion 712 so that the sample cup 11 can be positioned. The height of the cylindrical part 712 is formed lower than the height of the flange part 10a of the cell inner frame 10. The protruding portion 713 is provided at the approximate center of the top surface of the cylindrical portion 712. The height of the projecting portion 713 is slightly higher than the height of the flange portion 10a of the cell inner frame 10 with the height combined with the cylindrical portion 712, and the sample cup 11 fitted with the cell inner frame 10 faces the opening. When placed on the sample cup mounting table 71, the cup end surface 111 of the sample cup 1 is pushed by the protrusion 713 and deformed. Note that the sample cup mounting table 71 may have a shape in which a groove corresponding to the shape of the flange portion 10 a of the cell inner frame 10 is formed in place of the cylindrical portion 712 for positioning the sample cup 11.

  The sheet placing tool 72 is configured in a cylindrical shape with both ends opened. The inner diameter of the sheet placing tool 72 is larger than the outer diameter of the flange 13 a of the cell outer frame 13 and the outer diameter of the flange 114 of the sample cup 11, and smaller than the outer diameter of the X-ray transmission sheet 12. . The outer diameter of the sheet placing tool 72 is large enough to place the X-ray transmissive sheet 12 on the upper surface of the sheet placing tool 72. The outer diameter of the sheet placing tool 72 may be a shape other than a circle such as a polygon. The height of the sheet placing tool 72 is formed higher than the sample cup 11 fitted with the cell inner frame 10. That is, when the sample cup 11 fitted with the cell inner frame 10 is placed on the sample cup placement table 71 and further the sheet placement tool 72 is placed, the sample cup placement table 71 surrounds the sample cup 11 and is high. Even higher. Further, both end surfaces of the sheet placing tool 72 are parallel and orthogonal to the axis so that the X-ray transmission sheet 12 can be placed on the sheet placing tool 72 placed on the sample cup placing table 71. The sample cup mounting table 71 may have a shape in which a cylindrical portion or a groove for positioning the sheet mounting tool 72 is further formed when the sheet mounting tool 72 is mounted.

  The outer frame fitting tool 73 is configured in a cylindrical shape with both ends opened. The inner diameter of the outer frame fitting tool 73 is smaller than the outer diameter of the flange portion 13a of the cell outer frame 13, slightly larger than the outer diameter of other portions of the cell outer frame 13, and the cell from the opposite side to the flange portion 13a. It is formed in a size that allows the cell outer frame 13 to be fitted by inserting the outer frame 13. The outer diameter of the outer frame fitting tool 73 is smaller than the inner diameter of the sheet placing tool 72 and is formed in a size that can be inserted into the sheet placing tool 72. The height of the outer frame fitting tool 73 is higher than that of the cell outer frame 13. The outer frame fitting tool 73 may have a shape having a collar so that it can be easily held, and the cell outer frame 13 can be easily removed after the cell outer frame 13 is fitted to the sample cup 11. A slit may be formed in part.

  Next, a method for assembling the sample cell 1 using the sample cell assembly tool of the present invention will be described. 6-10 is explanatory drawing explaining the assembly method of the sample cell 1 by a front view. First, as shown in FIG. 6A, the sample cup 11 is put on the cell inner frame 10 with the flange portion 10a on the lower side from above. In this state, the cup end surface 111 is on the lower side, and the cell inner frame 10 is fitted to the sample cup 11. Next, as shown in FIG. 6B, the sample cup 11 fitted with the cell inner frame 10 is placed on the cylindrical portion 712 of the sample cup mounting table 71 with the cup end surface 111 facing down. Place.

  FIG. 7A shows a cross-sectional view of the sample cup 11 placed on the sample cup placement table 71. The cylindrical portion 712 of the sample cup mounting table 71 is fitted into the cell inner frame 10 and the sample cup 11 is positioned. Further, the cup end surface 111 of the sample cup 11 is pressed by the protrusion 713 and is deformed to be convex toward the inside of the sample cup 11. Next, as shown in FIG. 7A, the liquid sample S is injected into the sample cup 11. FIG. 7B shows a cross-sectional view of the sample cup 11 after the liquid sample S is injected. The liquid sample S is injected to a position slightly lower than the upper end of the sample cup 11 in order to prevent overflowing from the sample cup 11.

After injecting the liquid sample S, as shown in FIG. 8A, the sheet placing tool 72 is placed on the sample cup placing table 71 so as to be covered from the upper side of the sample cup 11. In FIG. 8A, the inner surface of the sheet placing tool 72 is indicated by a broken line. In a state where the sheet placing tool 72 is placed on the sample cup placing table 71, the sample cup 11 is surrounded by the sheet placing tool 72. As shown in FIG. Covered by the sheet placement tool 72. In FIG. 8B, the inner surface of the sheet placing tool 72 and the sample cup 11 and the cell inner frame 10 hidden by the sample cup placing table 71 are indicated by broken lines. The liquid sample S may be injected into the sample cup 11 after the sheet placing tool 72 is placed on the sample cup placing table 71. Next, as shown in FIG. 8B, the X-ray transmission sheet 12 is placed on the sheet placement tool 72 . In this state, the X-ray transmissive sheet 12 is placed on the sheet placing tool 72 higher than the sample cup 11, and therefore does not contact the liquid sample S in the sample cup 11.

Furthermore, as shown to Fig.9 (a), the outer frame fitting tool 73 is covered on the cell outer frame 13 which made the collar part 13a the lower side from the upper side. In this state, the cell outer frame 13 is fitted in the outer frame fitting tool 73. Next, as shown in FIG. 9B, the outer frame fitting tool 73 into which the cell outer frame 13 is fitted is pushed from above the sheet placing tool 72 on which the X-ray transmission sheet 12 is placed. The cell outer frame 13 is pushed by the outer frame fitting tool 73 while being guided by the inner wall of the sheet placing tool 72. The X-ray transmission sheet 12 is pushed by the cell outer frame 13 and comes into contact with the edge of the opening of the sample cup 11. The cell outer frame 13 is lowered while the X-ray transmission sheet 12 is sandwiched between the cell cup 13 and the cell outer frame 13, and stops when the protrusion 13 b is engaged with the groove 10 b of the cell inner frame 10.

  FIG. 10A shows a cross-sectional view in a state where the cell outer frame 13 is pushed. The cell outer frame 13 is externally fitted to the cell inner frame 10 with the sample cup 11 and the X-ray transmission sheet 12 therebetween, and the sample cup 11 and the X-ray transmission sheet 12 are between the cell inner frame 10 and the cell outer frame 13. Sandwiched between. Further, the X-ray transmission sheet 12 pushed down by the cell outer frame 13 covers and closes the opening of the sample cup 11. When the cell outer frame 13 is pushed in, the X-ray transmission sheet 12 is pulled in the surrounding direction, and the cell outer frame 13 is guided by the inner wall of the sheet placing tool 72 and the outer frame fitting tool 73 and pushed almost vertically. Therefore, the tension | tensile_strength which pulls the X-ray permeable sheet 12 to the circumference direction becomes uniform. Accordingly, the X-ray transmissive sheet 12 is unlikely to be wrinkled, and the X-ray transmissive sheet 12 is stretched so as to seal the sample cup 11. Further, the X-ray transmission sheet 12 does not contact the liquid sample S nor the edge of the opening of the sample cup 11 until just before being stretched, so that the liquid sample S is X-rayed before the assembly of the sample cell 1 is completed. Wrinkles are not generated when the X-ray transmission sheet 12 is stretched due to the adhesion to the transmission sheet 12. Further, when the cell outer frame 13 is pushed in, the entire sample cell 1 is pushed downward, and the cup end surface 111 is reliably deformed by the protrusion 713 of the sample cup mounting table 71. Since the height of the outer frame fitting tool 73 is higher than that of the cell outer frame 13, the upper end of the outer frame fitting tool 73 is the upper end of the sheet placing tool 72 even when the cell outer frame 13 is fitted to the sample cup 11. The cell outer frame 13 can be reliably pushed in by pushing the outer frame fitting tool 73 from above.

  Next, the outer frame fitting tool 73 and the sheet mounting tool 72 are removed, and the sample cell 1 is detached from the sample cup mounting table 71, thereby assembling the sample cell 1 as shown in the sectional view of FIG. Ends. Since the upper end of the outer frame fitting tool 73 protrudes from the upper end of the sheet placing tool 72, it is easy to remove the outer frame fitting tool 73. The assembled sample cell 1 has the liquid sample S sealed inside, and the cup end surface 111 is deformed so as to protrude inward.

  Next, a cell holder assembly tool for assembling the cell holder 2 and a method for assembling the cell holder 2 using the cell holder assembly tool will be described. The cell holder 2 is assembled by mounting the X-ray transmission sheet 22 after turning the cell support member 21 upside down. FIG. 11 is a perspective view in which the cell support member 21 is turned upside down. The cell support member 21 has an annular bottom surface 217 corresponding to the back surface of the bottom plate portion 213, and a circumferential groove 218 that makes a round around the opening 216 is formed on the wall surface of the peripheral wall portion 212. In order to assemble the cell holder 2, the X-ray transmission sheet 22 may be fixed by adjusting the X-ray transmission sheet 22 so as to close the opening 216 and fitting an annular elastic member such as an O-ring into the circumferential groove 218. . However, when the X-ray transmissive sheet 22 is fixed by an annular elastic member such as an O-ring, the X-ray transmissive sheet 22 is likely to be wrinkled. A cell holder assembly that can be mounted is required.

  FIG. 12 is a perspective view showing a cell holder assembly for assembling the cell holder 2. The cell holder assembly 8 is made of a material such as metal or resin and is formed in a cylindrical shape as a whole. The cell holder assembly 8 is formed in a tapered shape so that the outer diameter monotonously decreases from the middle in the axial direction toward the top surface, and further, the outer diameter from the middle in the axial direction toward the bottom surface. Is formed in a tapered shape so as to monotonously decrease. That is, the outer diameter of the cell holder assembly 8 gradually increases from the top surface side to the bottom surface side, and after reaching the maximum at one end, gradually decreases from the middle. FIG. 13 is a cross-sectional view taken along the axis of the cell holder assembly 8. An annular projecting portion 82 projecting in a direction perpendicular to the bottom surface 81 is formed on the peripheral edge of the bottom surface 81 of the cell holder assembly 8. The inner diameter of the annular protrusion 82 is a size that fits around the peripheral wall 212 of the cell support member 21. Further, the height of the annular projecting portion 82 is smaller than the distance from the bottom surface 217 of the cell support member 21 to the circumferential groove 218.

  FIG. 14 is a schematic cross-sectional view illustrating a method for assembling the cell holder 2 using the cell holder assembling tool 8. As shown in FIG. 14A, first, the X-ray transmission sheet 22 is placed on the bottom surface 217 with respect to the cell support member 21 with the bottom surface 217 facing upward, and the cell holder assembly 8 is further placed thereon. To do. In a state where the cell holder assembly 8 is placed, the bottom surface 81 of the cell holder assembly 8 abuts on the bottom surface 217 of the cell support member 21 with the X-ray transmission sheet 22 interposed therebetween. The annular protrusion 82 is fitted on the peripheral wall 212 of the cell support member 21 with the X-ray transmission sheet 22 interposed therebetween.

  In a state where the cell holder assembly 8 is placed on the cell support member 21, the O-ring 23 is fitted into the cell holder assembly 8 from the top surface side. The diameter of the O-ring 23 is sized to fit into the circumferential groove 218 of the cell support member 21. Next, as indicated by white arrows in FIG. 14B, the O-ring 23 is gradually shifted from the top surface side toward the bottom surface 81. The top surface of the cell holder assembly 8 has the smallest outer diameter, and the outer diameter increases as the O-ring 23 is shifted, so that the O-ring 23 spreads out evenly. Further, the O-ring 23 is further moved, and the O-ring 23 is moved further below the annular projecting portion 82. Since the outer diameter of the cell holder assembly 8 is gradually reduced from the middle, the O-ring 23 is easily moved by elasticity. Further, since the annular protrusion 82 is fitted on the peripheral wall portion 212 of the cell support member 21, the O-ring 23 is reliably moved from the cell holder assembly 8 to the cell support member 21 by shifting the position. By moving the O-ring 23 further downward along the peripheral wall portion 212, the O-ring 23 fits into the circumferential groove 218 of the cell support member 21 and fixes the X-ray transmission sheet 22 to the cell support member 21. . Thereafter, the cell holder assembly 8 is removed to complete the assembly of the cell holder 2.

  FIG. 15 is a cross-sectional view showing the assembled cell holder 2. The X-ray transmission sheet 22 placed on the bottom surface 217 of the cell support member 21 is fixed by an O-ring 23 fitted in the circumferential groove 218. When the O-ring 23 moves along the peripheral wall portion 212, the X-ray transmission sheet 22 is pulled uniformly in the peripheral direction and is stretched so as to close the opening 216.

  The assembled cell holder 2 is turned upside down, the X-ray transmission sheet 22 is turned down, and the cell holder 2 is attached to the opening of the housing 5 using bolts or the like. By attaching the cell holder 2, the measurement chamber 51 of the fluorescent X-ray analyzer is sealed. Further, the assembled sample cell 1 is turned upside down, and the sample cell 1 is placed on the cell holder 2 with the X-ray transmission sheet 12 as a bottom surface and the cup end surface 111 as an upper side. FIG. 16 is a cross-sectional view showing the sample cell 1 placed on the cell holder 2. The sample cell 1 is placed on the cell holder 2 so that the X-ray transmission sheet 12 is the bottom surface and the X-ray transmission sheet 12 is in contact with the support plane 215 of the cell support member 21. In the sample cell 1, a liquid sample S and some air are enclosed. In a state where the sample cell 1 is placed on the cell holder 2, primary X-rays are irradiated from the X-ray tube 3, and fluorescent X-ray analysis is performed. The primary X-rays from the X-ray tube 3 are irradiated from the lower side of the diagram shown in FIG. 16, the primary X-rays pass through the X-ray transmission sheets 22 and 12, and are irradiated to the fluid sample S in the sample cell 1, The fluorescent X-rays generated from the fluid sample S are transmitted through the X-ray transmission sheets 12 and 22 and emitted.

  When the X-ray fluorescence analysis is performed, the fluid sample S volatilizes with time, and when the pressure in the sample cell 1 increases, the cup end surface 111 is deformed as the pressure increases. FIG. 17 is a cross-sectional view showing the sample cell 1 after the cup end surface 111 is deformed as the pressure increases. The cup end surface 111 that has been deformed in advance toward the inside in advance deforms while expanding toward the outside of the sample cell 1 as the pressure in the sample cell 1 increases, whereby the volume inside the sample cell 1 is increased. Will increase. Since the increase in the pressure in the sample cell 1 is mitigated by increasing the internal volume of the sample cell 1, the X-ray transmission sheet 12 is prevented from expanding due to the increase in pressure.

  As described above, in the fluorescent X-ray analysis apparatus using the sample cell 1 assembled using the sample cell assembly of the present invention, the fluid sample S volatilizes in the sample cell 1 and the pressure in the sample cell 1 increases. Even in this case, the X-ray transmission sheet 12 that is a window portion through which primary X-rays and fluorescent X-rays are transmitted does not expand. Since the X-ray transmission sheet 12 that transmits the fluorescent X-rays does not expand, the distance between the fluid sample S and the X-ray detector 4 that detects the fluorescent X-rays does not fluctuate. The intensity of the fluorescent X-ray to be detected does not fluctuate. Accordingly, since the intensity of the fluorescent X-ray does not change due to factors other than the element distribution in the fluid sample S, the elemental analysis of the fluid sample S can be performed with high accuracy by the fluorescent X-ray analysis.

  Further, in the present invention, before the assembly of the sample cell 1 is completed, the liquid sample S adheres to the X-ray transmission sheet 12, so that wrinkles are generated in the X-ray transmission sheet 12 and the cell outer frame 13 is fitted. In this case, wrinkles are prevented from occurring in the X-ray transmission sheet 12 due to non-uniform tension pulling the X-ray transmission sheet 12. Therefore, the liquid sample S does not leak from the sample cell 1 due to generation of wrinkles in the X-ray transmission sheet 12. Further, since the distance between the liquid sample S and the X-ray detector 4 does not fluctuate due to the wrinkles of the X-ray transmission sheet 12, the elemental analysis of the fluid sample S can be performed with high accuracy by fluorescent X-ray analysis. It becomes.

DESCRIPTION OF SYMBOLS 1 Sample cell 10 Cell inner frame 11 Sample cup 111 Cup end surface 12 X-ray transmissive sheet 13 Cell outer frame 2 Cell holder 21 Cell support member 22 X-ray transmissive sheet 23 O-ring 3 X-ray tube 4 X-ray detector 71 Sample cup mounting base 713 Projection part 72 Sheet placing tool 73 Outer frame fitting tool 8 Cell holder assembly tool

Claims (4)

Fluorescent X-ray analysis by storing the sample in the sample cup, sealing the opening of the sample cup containing the sample with an X-ray transmission sheet, and fitting the outer frame to the sample cup with the X-ray transmission sheet in between In the sample cell assembly used when assembling the sample cell for
It is a stand for placing the sample cup,
A positioning part for positioning the sample cup when placing the sample cup with the opening on the upper side;
When the outer frame is fitted to the placed sample cup from above, the sample cup mounting table has a projection that pushes up the flat end surface on the lower side of the sample cup and deforms it toward the inside of the sample cup. A sample cell assembly characterized by comprising: A cylindrical inner frame is fitted on the end face side of the sample cup, and the end of the inner frame protrudes from the end face,
The positioning part is a cylinder raised on a plane,
The outer diameter of the column is a size that fits into the inner frame,
The height of the cylinder is smaller than the distance from the end of the inner frame to the end surface,
The sample cell assembly according to claim 1, wherein the protrusion is a protrusion protruding at the center of the upper surface of the cylinder. It is separate from the sample cup mounting table,
Cylindrical,
Both end faces are parallel and perpendicular to the axis,
The inner diameter is larger than the outer diameter of the sample cell,
The height when placed on the sample cup mounting table is higher than the sample cup,
The sheet cup further mounted on the sample cup mounting table so as to surround the sample cup and used for mounting an X-ray transmission sheet thereon. 3. The sample cell assembly according to 2. The sample cup mounting table and the sheet mounting tool are separate bodies,
Cylindrical,
The inner diameter is the size that is fitted in the outer frame,
The outer diameter is smaller than the inner diameter of the sheet placing tool,
The height is higher than the outer frame,
Used to fit the outer frame to the sample cup by pushing the outer frame fitted into the sample cup from the upper side of the X-ray transmission sheet placed on the sheet placing tool. The sample cell assembly according to claim 3, further comprising an outer frame fitting tool.

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