WO2022004000A1 - 蛍光ｘ線分析装置 - Google Patents

蛍光ｘ線分析装置 Download PDF

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Publication number
WO2022004000A1
WO2022004000A1 PCT/JP2020/045375 JP2020045375W WO2022004000A1 WO 2022004000 A1 WO2022004000 A1 WO 2022004000A1 JP 2020045375 W JP2020045375 W JP 2020045375W WO 2022004000 A1 WO2022004000 A1 WO 2022004000A1
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WO
WIPO (PCT)
Prior art keywords
sample
detector
hole
rays
chamber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/045375
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English (en)
French (fr)
Japanese (ja)
Inventor
祐司 森久
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shimadzu Corp
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Shimadzu Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shimadzu Corp filed Critical Shimadzu Corp
Priority to JP2022533027A priority Critical patent/JP7380884B2/ja
Priority to US18/013,205 priority patent/US12292397B2/en
Priority to EP20943522.1A priority patent/EP4174479A4/en
Priority to CN202080102474.0A priority patent/CN115803612B/zh
Publication of WO2022004000A1 publication Critical patent/WO2022004000A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/30—Accessories, mechanical or electrical features
    • G01N2223/317—Accessories, mechanical or electrical features windows

Definitions

  • the present invention relates to a fluorescent X-ray analyzer.
  • the energy dispersive type fluorescent X-ray analyzer is a device that can analyze the type and concentration of the elements constituting the sample by irradiating the sample with X-rays and detecting the fluorescent X-rays generated from the surface of the sample.
  • a wide range of samples including solids and liquids can be analyzed non-destructively and easily.
  • Patent Document 1 A fluorescent X-ray analyzer for improving the substitution rate with helium gas in order to solve such a problem is disclosed in, for example, International Publication No. 2014/192173 (Patent Document 1). This document discloses that a first introduction pipe and a second introduction pipe for introducing helium gas are provided, and the helium gas accumulated in the introduction port and the detection port can be reliably replaced with the atmosphere.
  • Patent Document 1 is used to measure while supplying helium gas, which is an atmospheric gas, to the detection port, there is a problem that the consumption of helium gas increases.
  • an object of the present invention is to provide a fluorescent X-ray analyzer capable of reducing the consumption of gas constituting the measurement atmosphere. be.
  • the first aspect of the present invention is a sample chamber in which a sample is placed, a measurement chamber arranged adjacent to the sample in the sample chamber, an X-ray tube for irradiating the sample with X-rays, and reflection by the sample.
  • a detector for detecting X-rays is provided, and the detector is provided with a passage located in the measurement chamber through which the reflected X-rays pass and a hole connecting the passage and the outside of the detector.
  • the fluorescent X-ray analyzer includes a sample chamber in which a sample is placed, a measurement chamber arranged adjacent to the sample in the sample chamber, an X-ray tube for irradiating the sample with X-rays, and a sample.
  • the detector is provided with a detector for detecting the X-rays reflected by the detector, and the detector is provided with a passage located in the measurement chamber through which the reflected X-rays pass and a hole for connecting the passage and the outside of the detector. Therefore, since the detector is provided with a hole connecting the passage and the outside of the detector, even if gas is accumulated in the passage, this gas can be discharged through the hole. As a result, even if the gas constituting the atmosphere is not supplied during the measurement, the residual gas in the detector can be prevented and the consumption of the gas constituting the atmosphere can be reduced.
  • the hole may extend from the passage toward the outside of the detector so as to have a vertically downward component.
  • a light atmosphere gas such as helium gas
  • heavy air flows in a hole extending so as to have a vertically downward component, so that air can be smoothly discharged from the passage.
  • the hole may extend at its exit from the passage towards the outside of the detector and away from the X-ray tube. In this case, since the hole extends away from the X-ray tube near the outlet, it is possible to prevent scattered X-rays generated from the periphery of the X-ray tube from entering the detector from the exit of the hole.
  • the hole may extend in an L shape. In this case, by forming an L-shaped hole along the detector, it is possible to easily form a hole that can prevent the intrusion of X-rays.
  • FIG. 1 is a cross-sectional view of the fluorescent X-ray analyzer 1 according to the embodiment.
  • the fluorescent X-ray analyzer 1 has a shielding wall 10 that defines a sample chamber 11 and a measuring chamber 12, an X-ray tube 20 attached to the shielding wall 10, and an opposite side of the X-ray tube 20. It has a detector 30 attached to a shielding wall 10 in the above.
  • the shielding wall 10 has a function of shielding X-rays so that the X-rays generated from the X-ray tube 20 and radiated into the measuring chamber 12 and the sample chamber 11 do not leak to the outside.
  • the sample chamber 11 and the measurement chamber 12 are surrounded by the shielding wall 10.
  • the sample chamber 11 and the measuring chamber 12 are separated from each other by a partition wall 13.
  • a plurality of ventilation passages 14 are provided in the partition wall 13. Since the ventilation path 14 communicates the sample chamber 11 and the measurement chamber 12, the pressure is the same between the sample chamber 11 and the measurement chamber 12.
  • sample 41 is arranged in the sample chamber 11.
  • Sample 41 may be either solid or liquid.
  • a thin film (not shown) is provided on the bottom surface of the case 40. The sample 41 is placed on this film. When the sample 41 is a solid, it may be a large mass or a powder.
  • the measurement chamber 12 is provided at the lower part of the sample chamber 11.
  • the X-ray tube 20 generated at the X-ray generation point 22 of the X-ray tube 20 in which the X-ray tube 20 for irradiating the sample 41 with the X-ray tube 20 is attached to the outside of the shielding wall 10 includes a band path filter and a primary collimator (not shown). After passing, the lower surface 42 of the sample 41 is irradiated.
  • the rotary pump 110 and the valve 120 It is possible to adjust the pressure in the sample chamber 11 and the measurement chamber 12 by the rotary pump 110 and the valve 120. Specifically, when the valve 120 is opened to drive the rotary pump 110, the sample chamber 11 and the measurement chamber 12 can be evacuated by the action of the rotary pump 110.
  • the pressure of helium in the sample chamber 11 and the measuring chamber 12 can be adjusted by the helium cylinder 130 and the valve 140. Specifically, by opening the valve 140 and supplying helium gas from the helium cylinder 130, the sample chamber 11 and the measurement chamber 12 can have a helium gas atmosphere.
  • the detector 30 has a case 31.
  • the tip of the case 31 is inserted into the measuring chamber 12, and the other parts are not inserted into the measuring chamber 12.
  • FIG. 2 is a diagram showing a tip portion of the detector 30.
  • the case 31 of the detector 30 has a cylindrical shape.
  • a secondary collimator 32 which is a detector cap, is provided at the tip of the case 31.
  • the secondary collimator 32 is provided with a passage 36 for transmitting the X-rays reflected by the sample 41.
  • the X-ray 23 is reflected by the sample 41 in principle, but is also reflected by a portion other than the sample 41. Since the X-rays reflected by other than the sample reflect the physical properties of the reflected substance, if they are put in the detector 30, the correct physical properties of the sample 41 cannot be specified.
  • a secondary collimator 32 having a passage 36 extending in the axial direction is provided at the tip of the case 31.
  • the inner diameter and length of the passage 36 are adjusted so that only the X-rays 23 reflected by the lower surface 42 of the sample 41 can pass through the passage 36.
  • a window member 34 made of, for example, beryllium is provided at the tip of the case 31.
  • the window member 34 transmits X-rays without attenuating them, and has a function of separating the inside of the case 31 and the measurement chamber 12.
  • a light receiving element 35 made of a semiconductor is provided inside the case 31, for example.
  • the light receiving element 35 is a semiconductor
  • a pair of electrons and holes is generated when X-rays pass through the light receiving element 35, and the current and voltage generated by the pair are measured to determine the physical characteristics of the sample based on the X-rays. Can be identified.
  • the secondary collimator 32 is provided with a hole 33 for connecting the passage 36 and the outside of the detector 30.
  • the hole 33 is formed by cutting the secondary collimator 32 with a drill, for example.
  • the hole 33 may be composed of, for example, a pipe.
  • the valve 140 When introducing helium gas lighter than air into the sample chamber 11 and the measuring chamber 12 in an air atmosphere, the valve 140 is opened to supply the helium gas from the helium cylinder 130 to the sample chamber 11 and the measuring chamber 12. In this case, helium gas is introduced into the removal from the sample chamber 11 existing in the upper part, and then the measurement chamber 12 is filled with helium gas. Normally, when the layer of helium gas is lowered to the height of the secondary collimator 32, the helium gas should enter the secondary collimator 32 from the passage 36.
  • FIG. 3 is a cross-sectional view of the detector of the comparative example shown for explaining the air reservoir 39. Since the air is heavier than the helium gas, the air does not escape from the passage while the air remains between the secondary collimator 32 and the window member 34. That is, the air pool 39 shown in FIG. 3 is generated. If nothing is done, an air layer will exist immediately before the window member 34. X-rays with weak energy are attenuated by this air reservoir 39. The transmittance of the layer of air (20 ° C., 1 atm) having an optical path length of 1 mm for FK ⁇ rays (667 eV) is 29%.
  • the transmittance of the layer of helium gas (20 ° C., 1 atm) having an optical path length of 1 mm for FK ⁇ rays (667 eV) is 99.6%. Therefore, when performing fluorescent X-ray analysis in a helium gas atmosphere, it is necessary not to form this air reservoir 39.
  • the sample chamber 11 and the measurement chamber 12 are decompressed in advance to remove air, and then helium gas is introduced to remove air. Air does not collect inside the secondary collimator 32.
  • this method requires an exhaust pump. Since the analysis is performed in a helium gas atmosphere for a sample that dislikes a vacuum atmosphere such as a liquid sample, it is not possible to create a vacuum atmosphere in advance. In addition, it is difficult to install an exhaust system in terms of cost.
  • a nozzle of the secondary collimator 32 is provided and connected to a helium gas line, and the helium gas is vigorously flowed directly into the secondary collimator 32 to diffuse the air accumulated inside the secondary collimator 32.
  • the tip of the detector 30 is a place where various mechanisms are concentrated, and providing a nozzle in this portion has a problem that it becomes difficult to assemble and maintain the device.
  • a certain flow velocity and flow rate of helium are required, so that a larger amount of helium gas is consumed than originally intended, which causes a running cost.
  • a hole 33 for bleeding air is provided as shown in FIG.
  • the hole 33 is arranged from the passage 36 toward the outside of the detector 30 so as to have a vertically downward component indicated by an arrow 180.
  • FIG. 4 is a cross-sectional view of the tip portion of the detector 30 according to another embodiment.
  • the hole 33 of the detector 30 has a first portion 33a extending perpendicular to the longitudinal direction of the case 31 and a first portion 33a connected to the first portion 33a and extending in the longitudinal direction of the case 31. It has a second portion 33b.
  • the hole 33 is provided in an L shape.
  • the first portion 33a and the second portion 33b of the hole 33 are formed to have a vertically downward component along this direction so as to smooth the flow of air from the passage 36 to the outside of the detector 30.
  • the second portion 33b constituting the outlet of the hole 33 extends away from the X-ray tube 20 in the above-mentioned air flow direction.
  • the shape is such that scattered X-rays from the X-ray tube 20 are difficult to enter. As a result, it is possible to prevent the scattered X-rays from being detected by the detector 30 and improve the accuracy of the measurement.
  • FIG. 4 is a cross-sectional view of the tip portion of the detector 30 according to another embodiment.
  • the hole 33 of the detector 30 has a first portion 33a extending perpendicular to the longitudinal direction of the case 31 and a first portion 33a connected to the first portion 33a and extending in the longitudinal direction of the case 31. It has a second portion 33b.
  • the hole 33 is provided in an L shape.
  • the first portion 33a and the second portion 33b of the hole 33 are formed to have a vertically downward component along this direction so as to smooth the flow of air from the passage 36 to the outside of the detector 30.
  • the second portion 33b constituting the outlet of the hole 33 extends away from the X-ray tube 20 in the above-mentioned air flow direction.
  • the length of the second portion 33b can be increased as long as the conductance of the entire hole 33 does not deteriorate.
  • the hole 33 may have a curved shape as well as an L-shape.
  • the shape is such that scattered X-rays from the X-ray tube 20 are difficult to enter.
  • the larger the aspect ratio of the hole 33 the length / inner diameter of the hole 33), the more difficult it is for scattered X-rays to enter. Therefore, it is preferable to increase the aspect ratio as much as possible.
  • FIG. 5 is a cross-sectional view of the tip portion of the detector 30 according to still another embodiment. As shown in FIG. 5, in this embodiment, not only the hole 33 is provided on the lower side of the tip of the secondary collimator 32, but also the hole 133 is provided on the upper side, which is shown in FIG. It is different from the secondary collimator 32.
  • the helium gas in the secondary collimator 32 can be easily discharged. Specifically, when the measurement is completed in the helium gas atmosphere and then the atmosphere is changed, the helium gas is light, so that the helium remaining inside the secondary collimator 32 is difficult to escape at the upper part of the window member 34. This helium can have some effect on the measurement.
  • the presence of the hole 133 makes it possible to easily remove helium gas from the upper part of the window member 34 and the inside of the secondary collimator 32.
  • the two holes 33 and 133 are provided, but it is not always necessary to provide the two holes 33 and 133, and only the holes 133 may be provided.
  • the embodiments shown here can be variously modified.
  • the sample 41 is arranged above the X-ray tube 20 and the detector 30, but the sample 41 may be provided below the X-ray tube 20 and the detector 30.
  • the X-rays emitted from the X-ray tube 20 are reflected on the upper surface of the sample 41, and the reflected X-rays are detected by the detector 30.
  • the fluorescent X-ray analyzer irradiates the sample with a sample chamber in which the sample is placed, a measurement chamber arranged adjacent to the sample in the sample chamber, and the sample.
  • the detector includes an X-ray tube and a detector for detecting the X-rays reflected by the sample, and the detector includes a passage through which the reflected X-rays pass located in the measurement chamber, and the passage and the detector. A hole for connecting to the outside is provided.
  • the detector is provided with a hole for connecting the passage and the outside of the detector, even if gas is accumulated in the passage, this gas is provided. Can be discharged through the hole. As a result, it is not necessary to continuously supply the gas constituting the atmosphere during the measurement, and it is possible to reduce the gas consumption.
  • the hole may extend from the passage toward the outside of the detector so as to have a vertically downward component.
  • the hole is directed from the passage toward the outside of the detector so as to be away from the X-ray tube as shown in FIG. It may have a second portion extending at the exit.
  • the fluorescent X-ray analyzer since the hole extends away from the X-ray tube near the outlet, it is possible to prevent scattered X-rays generated from the periphery of the X-ray tube from entering through the exit of the hole. ..
  • the holes may extend in an L shape.
  • the fluorescent X-ray analyzer According to the fluorescent X-ray analyzer according to the fourth item, by forming an L-shaped hole along the detector, it is possible to easily form a hole capable of preventing the intrusion of X-rays.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
PCT/JP2020/045375 2020-06-30 2020-12-07 蛍光ｘ線分析装置 Ceased WO2022004000A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2022533027A JP7380884B2 (ja) 2020-06-30 2020-12-07 蛍光ｘ線分析装置
US18/013,205 US12292397B2 (en) 2020-06-30 2020-12-07 X-ray fluorescence analyzer
EP20943522.1A EP4174479A4 (en) 2020-06-30 2020-12-07 X-RAY FLUORESCENCE ANALYSIS DEVICE
CN202080102474.0A CN115803612B (zh) 2020-06-30 2020-12-07 荧光x射线分析装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-112575 2020-06-30
JP2020112575 2020-06-30

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WO2022004000A1 true WO2022004000A1 (ja) 2022-01-06

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PCT/JP2020/045375 Ceased WO2022004000A1 (ja) 2020-06-30 2020-12-07 蛍光ｘ線分析装置

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US (1) US12292397B2 (https=)
EP (1) EP4174479A4 (https=)
JP (1) JP7380884B2 (https=)
CN (1) CN115803612B (https=)
WO (1) WO2022004000A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4296658A1 (en) * 2022-06-20 2023-12-27 Jeol Ltd. Sample container and measuring method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10160691A (ja) * 1996-11-29 1998-06-19 Shimadzu Corp 蛍光ｘ線分析装置
JPH10221047A (ja) * 1997-02-03 1998-08-21 Jeol Ltd 蛍光ｘ線膜厚分析装置及び方法
JP2005098906A (ja) * 2003-09-26 2005-04-14 Rigaku Industrial Co 雰囲気置換機能を備えたｘ線分析装置
US20050129174A1 (en) * 2003-12-01 2005-06-16 Heikki Sipila Measurement arrangement for X-ray fluoresence analysis
WO2014192173A1 (ja) 2013-05-27 2014-12-04 株式会社島津製作所 蛍光ｘ線分析装置
CN109239117A (zh) * 2018-10-26 2019-01-18 钢研纳克检测技术股份有限公司 直接测定样品中痕量铝、硅、磷、硫、氯含量的分析装置及方法
JP2020085826A (ja) * 2018-11-30 2020-06-04 株式会社島津製作所 蛍光ｘ線分析システム、蛍光ｘ線分析装置および蛍光ｘ線分析方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3629539B2 (ja) * 2002-03-04 2005-03-16 理学電機工業株式会社 蛍光ｘ線分析装置
JP3726161B2 (ja) * 2003-03-28 2005-12-14 理学電機工業株式会社 蛍光ｘ線分析装置
DE102004019030A1 (de) * 2004-04-17 2005-11-03 Katz, Elisabeth Vorrichtung für die Elementanalyse
DE08155628T1 (de) * 2008-05-05 2010-04-29 Oxford Instruments Analytical Oy Röntgenfluoreszenzanalysator mit gasgefüllter Kammer
JP6081260B2 (ja) * 2013-03-28 2017-02-15 株式会社日立ハイテクサイエンス 蛍光ｘ線分析装置
CN203824942U (zh) * 2014-05-14 2014-09-10 苏州三值精密仪器有限公司 一种x荧光光谱仪测试油品中有害元素的充氦气装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10160691A (ja) * 1996-11-29 1998-06-19 Shimadzu Corp 蛍光ｘ線分析装置
JPH10221047A (ja) * 1997-02-03 1998-08-21 Jeol Ltd 蛍光ｘ線膜厚分析装置及び方法
JP2005098906A (ja) * 2003-09-26 2005-04-14 Rigaku Industrial Co 雰囲気置換機能を備えたｘ線分析装置
US20050129174A1 (en) * 2003-12-01 2005-06-16 Heikki Sipila Measurement arrangement for X-ray fluoresence analysis
WO2014192173A1 (ja) 2013-05-27 2014-12-04 株式会社島津製作所 蛍光ｘ線分析装置
CN109239117A (zh) * 2018-10-26 2019-01-18 钢研纳克检测技术股份有限公司 直接测定样品中痕量铝、硅、磷、硫、氯含量的分析装置及方法
JP2020085826A (ja) * 2018-11-30 2020-06-04 株式会社島津製作所 蛍光ｘ線分析システム、蛍光ｘ線分析装置および蛍光ｘ線分析方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4174479A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4296658A1 (en) * 2022-06-20 2023-12-27 Jeol Ltd. Sample container and measuring method
US12436120B2 (en) 2022-06-20 2025-10-07 Jeol Ltd. Sample container and measuring method

Also Published As

Publication number Publication date
CN115803612B (zh) 2026-02-27
JPWO2022004000A1 (https=) 2022-01-06
US20230296541A1 (en) 2023-09-21
US12292397B2 (en) 2025-05-06
CN115803612A (zh) 2023-03-14
EP4174479A4 (en) 2024-08-14
EP4174479A1 (en) 2023-05-03
JP7380884B2 (ja) 2023-11-15

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