JP2010286323A - Sample holder for x-ray diffraction measurement and method of measuring x-ray diffraction - Google Patents

Sample holder for x-ray diffraction measurement and method of measuring x-ray diffraction Download PDF

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JP2010286323A
JP2010286323A JP2009139592A JP2009139592A JP2010286323A JP 2010286323 A JP2010286323 A JP 2010286323A JP 2009139592 A JP2009139592 A JP 2009139592A JP 2009139592 A JP2009139592 A JP 2009139592A JP 2010286323 A JP2010286323 A JP 2010286323A
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sample
ray diffraction
diffraction measurement
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sample holder
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JP5448587B2 (en
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Toru Furusawa
透流 古沢
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Honda Motor Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a sample holder that is capable of performing high-temperature measurement and can be used repeatedly. <P>SOLUTION: As shown in Fig.(a), a heater 15 is loaded into a heater storage recess 21, and a lower lid 14 is placed on it before fixing by a second bolt 35, thus completing the sample holder 10 having a heater in a form shown by Fig.(b). Thus, since an X-ray transmission member 31 is made of a metal, no creases are generated and no deterioration results for repeated use and resistance against high-temperature. As a result, the sample holder that can perform high-temperature measurement and can be used repeatedly can be composed regardless of the use of an ordinary X-ray diffraction measuring device. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、大気暴露により変質しやすい化学物質のＸ線回析計測技術に関する。   The present invention relates to an X-ray diffraction measurement technique for chemical substances that are easily altered by exposure to the atmosphere.

物質の結晶構造を調べる技術として、Ｘ線回析計測法が知られている。このＸ線回析計測法では、試料にＸ線を照射するため、試料の保持が重要となる。試料を保持する試料ホルダの構造が各種提案されている（例えば、特許文献１（図１）、特許文献２（図３）参照。）。   An X-ray diffraction measurement method is known as a technique for examining a crystal structure of a substance. In this X-ray diffraction measurement method, since the sample is irradiated with X-rays, it is important to hold the sample. Various structures of sample holders for holding samples have been proposed (see, for example, Patent Document 1 (FIG. 1) and Patent Document 2 (FIG. 3)).

特許文献１を次図に基づいて説明する。
図８は従来の試料ホルダの断面図であり、試料台１０１と、この試料台１０１に取り外し可能に取り付けることができるホルダ本体１０２と、このホルダ本体１０２にねじ込みことで一体化できるプラグ１０３とを準備する。なお、フラグ１０３には保持ピン１０４が設けられ、ホルダ本体１０２には保持ピン１０４を覆う筒状の試料封入部１０５が一体的に設けられている。 Patent document 1 is demonstrated based on the following figure.
FIG. 8 is a cross-sectional view of a conventional sample holder. A sample stage 101, a holder body 102 that can be removably attached to the sample stage 101, and a plug 103 that can be integrated by screwing into the holder body 102 are shown. prepare. The flag 103 is provided with a holding pin 104, and the holder main body 102 is integrally provided with a cylindrical sample enclosure 105 that covers the holding pin 104.

試料台１０１と、ホルダ本体１０２と、プラグ１０３とを分離しておく。そして、グローブボックス内で、保持ピン１０４の先端に試料１０６を付着させる。次に、フラグ１０３をホルダ本体１０２にねじ込み、このホルダ本体１０２を試料台１０１に取付けることで、図の形態が完成する。そして、Ｘ線回析計測装置にかけ、コリメータ１０７からＸ線を試料１０６へ照射し、回析Ｘ線が顕微鏡１０８に至る。これで、試料１０６の結晶構造を計測することができる。   The sample stage 101, the holder main body 102, and the plug 103 are separated. Then, the sample 106 is attached to the tip of the holding pin 104 in the glove box. Next, the flag 103 is screwed into the holder main body 102, and the holder main body 102 is attached to the sample stage 101, thereby completing the form shown in the figure. Then, the sample 106 is irradiated with X-rays from the collimator 107 by applying to an X-ray diffraction measurement apparatus, and the diffraction X-rays reach the microscope 108. Thus, the crystal structure of the sample 106 can be measured.

しかし、試料１０６は、微細でかつ顕微鏡１０８で観察することができる透明な材料、例えばプラスチックやガラスに限られる。グローブボックス内での作業も細かい。
多量の試料を測定対象にでき、且つグローブボックス内での作業が簡便であることが望まれる。この要望に応えうる技術が、特許文献２に示されている。 However, the sample 106 is limited to a transparent material that is fine and can be observed with the microscope 108, such as plastic or glass. The work in the glove box is also fine.
It is desired that a large amount of samples can be measured and that the work in the glove box is simple. A technique capable of meeting this demand is disclosed in Patent Document 2.

特許文献２を次図に基づいて説明する。
図９は従来の別の試料ホルダの断面図であり、試料収納凹部１１１が設けられているホルダ本体１１２と、Ｘ線を透過するフィルム１１３と、リングパッキン１１４と、押さえリング１１５と、ビス１１６、１１６とを準備する。 Patent document 2 is demonstrated based on the following figure.
FIG. 9 is a cross-sectional view of another conventional sample holder, in which a holder main body 112 provided with a sample storage recess 111, an X-ray transmitting film 113, a ring packing 114, a pressing ring 115, and a screw 116 are shown. 116 are prepared.

グローブボックス内で、試料収納凹部１１１へ試料１１７を載せる。次に、フィルム１１３を被せ、このフィルム１１３の縁をリングパッキン１１４及び押さえリング１１５で軽く押さえる。続いて、ビス１１６、１１６で押さえリング１１５をホルダ本体１１２に固定する。フィルム１１３で密封された試料１１７を、Ｘ線回析計測装置にかけることで、多量の試料を測定することができる。   In the glove box, the sample 117 is placed in the sample storage recess 111. Next, the film 113 is covered, and the edge of the film 113 is lightly pressed by the ring packing 114 and the pressing ring 115. Subsequently, the holding ring 115 is fixed to the holder body 112 with screws 116 and 116. A large amount of samples can be measured by applying the sample 117 sealed with the film 113 to an X-ray diffraction measurement apparatus.

しかし、フィルム１１３は繰り返して使用すると、皺が寄り、亀裂が入る。そのため、フィルムの交換頻度が高まり、計測コストが嵩む。
また、近年、高温における試料の結晶構造を調べる必要がでてきた。例えば、燃料電池の構成材料などがそうである。常温計測を前提とした特許文献１及び２の技術では、高温計測が困難である。対策として、仮に、Ｘ線回析計測装置を恒温槽仕様にすると、Ｘ線回析計測装置が極めて高価なものとなる。 However, when the film 113 is used repeatedly, the wrinkles are shifted and cracks are generated. Therefore, the replacement frequency of the film increases and the measurement cost increases.
In recent years, it has become necessary to examine the crystal structure of a sample at a high temperature. For example, it is the constituent material of a fuel cell. With the techniques of Patent Documents 1 and 2 on the premise of normal temperature measurement, high temperature measurement is difficult. As a countermeasure, if the X-ray diffraction measurement device is set to a thermostatic bath specification, the X-ray diffraction measurement device becomes extremely expensive.

そこで、普通のＸ線回析計測装置を用いるにも拘わらず高温測定が可能であり且つ繰り返して使用することができる試料ホルダが必要となる。   Therefore, there is a need for a sample holder that can perform high-temperature measurement and can be used repeatedly despite using an ordinary X-ray diffraction measurement apparatus.

特開平５−３０７０１２号公報Japanese Patent Laid-Open No. 5-307012 特開平１１−６８０５号公報Japanese Patent Laid-Open No. 11-6805

本発明は、普通のＸ線回析計測装置を用いるにも拘わらず高温測定が可能であり且つ繰り返して使用することができる試料ホルダ及びその使用方法を提供することを課題とする。   An object of the present invention is to provide a sample holder that can perform high-temperature measurement and can be used repeatedly despite the use of an ordinary X-ray diffraction measurement apparatus, and a method for using the sample holder.

請求項１に係る発明は、Ｘ線回析計測用の試料ホルダであって、
化学物質などの試料を載せる試料載せ部を有するホルダ本体、このホルダ本体に被せることができ且つ試料と対向する上面にＸ線透過部材を備えた上蓋、この上蓋と前記ホルダ本体との間に気密シール用ガスケットを備えていることを特徴とする。 The invention according to claim 1 is a sample holder for X-ray diffraction measurement,
A holder main body having a sample mounting portion for placing a sample such as a chemical substance, an upper lid that can be placed on the holder main body and provided with an X-ray transmitting member on the upper surface facing the sample, and an airtight gap between the upper lid and the holder main body A sealing gasket is provided.

請求項２に係る発明では、請求項１記載のＸ線回析計測用の試料ホルダは、研究者がグローブボックスなどの不活性ガス雰囲気の筐体に搬入搬出可能な大きさ及び重さの物であって、前記筐体内で前記試料載せ部へ試料の充填作業が行え不活性ガスを封入することができて、前記筐体の外へ出しても試料の大気暴露による変質を防ぐことができることを特徴とする。   In the invention according to claim 2, the sample holder for X-ray diffraction measurement according to claim 1 is an object of a size and weight that allows a researcher to carry in and out of the case in an inert gas atmosphere such as a glove box. In this case, the sample mounting portion can be filled with the sample in the case, and an inert gas can be sealed, and even if the sample is moved out of the case, the sample can be prevented from being deteriorated by exposure to the atmosphere. It is characterized by.

請求項３に係る発明では、試料載せ部は、前記Ｘ線透過部材に沿って延びており、作業中に試料がずれることがなく且つＸ線回析計測に必要な初期の試料表面状態が保持できる浅い凹部であることを特徴とする。   In the invention according to claim 3, the sample mounting portion extends along the X-ray transmitting member so that the sample does not shift during the operation and the initial sample surface state necessary for X-ray diffraction measurement is maintained. It is a shallow concave part that can be formed.

請求項４に係る発明では、Ｘ線透過部材は、ベリリウム又はベリリウム合金製であることを特徴とする。   The invention according to claim 4 is characterized in that the X-ray transmitting member is made of beryllium or a beryllium alloy.

請求項５に係る発明では、請求項１〜４のいずれか１項記載のＸ線回析計測用の試料ホルダは、前記試料を加熱するヒータを内蔵すると共に加熱時における前記試料の近傍の温度を計測する測温手段を備えていることを特徴とする。   In the invention which concerns on Claim 5, the sample holder for X-ray diffraction measurement of any one of Claims 1-4 incorporates the heater which heats the said sample, and is the temperature of the vicinity of the said sample at the time of heating It is characterized by comprising a temperature measuring means for measuring.

請求項６に係る発明は、請求項１〜５のいずれか１項記載のＸ線回析計測用の試料ホルダを、Ｘ線回析計測装置に設置し、不活性ガス雰囲気の気密を保持した前記試料を加熱し高温時の結晶構造変化をその場でＸ線回析計測することを特徴とする。   According to a sixth aspect of the present invention, the sample holder for X-ray diffraction measurement according to any one of the first to fifth aspects is installed in an X-ray diffraction measurement device, and the airtightness of an inert gas atmosphere is maintained. The sample is heated, and the crystal structure change at high temperature is measured in situ by X-ray diffraction.

請求項１に係る発明では、気密シール用ガスケットにより、ホルダ本体と上蓋との間の気密性を確保することができ、試料載せ部に試料と共に不活性ガスを封じ込めることができる。結果、試料が大気暴露で変質することを防ぐことが可能となる。
また、Ｘ線透過部材に金属を使用すれば、高温での測定が可能になると共に繰り返しの使用が可能となる。 In the invention which concerns on Claim 1, the airtight seal gasket can ensure the airtightness between the holder main body and the upper lid, and the sample mounting part can contain the inert gas together with the sample. As a result, it becomes possible to prevent the sample from being altered by exposure to the atmosphere.
In addition, if a metal is used for the X-ray transmitting member, measurement at a high temperature is possible and repeated use is possible.

請求項２に係る発明では、試料ホルダは、研究者がグローブボックスなどの不活性ガス雰囲気の筐体に搬入搬出可能な大きさ及び重さの物であって、筐体内で試料載せ部へ試料の充填作業が行え不活性ガスを封入することができて、筐体の外へ出しても試料の大気暴露による変質を防ぐことができる。   In the invention according to claim 2, the sample holder is of a size and weight that allows a researcher to carry in and out of the case in an inert gas atmosphere, such as a glove box. Thus, the inert gas can be sealed and the sample can be prevented from being altered by exposure to the atmosphere even if it is moved out of the casing.

請求項３に係る発明では、試料載せ部は、Ｘ線透過部材に沿って延びた浅い凹部であり、作業中に試料がずれることがなく且つＸ線回析計測に必要な初期の試料表面状態が保持できる。   In the invention according to claim 3, the sample mounting portion is a shallow concave portion extending along the X-ray transmitting member, so that the sample does not shift during operation and is an initial sample surface state necessary for X-ray diffraction measurement. Can hold.

請求項４に係る発明では、Ｘ線透過部材は、ベリリウム又はベリリウム合金製である。
ベリリウム又はベリリウム合金は、Ｘ線透過率が極めて高い金属である。金属であるため、耐熱温度が高いため高温での使用が可能であり、機械的強度が高く、劣化しにくいといった利点がある。 In the invention according to claim 4, the X-ray transmitting member is made of beryllium or a beryllium alloy.
Beryllium or a beryllium alloy is a metal having an extremely high X-ray transmittance. Since it is a metal, it has the advantage that it can be used at high temperatures because of its high heat-resistant temperature, has high mechanical strength, and is difficult to deteriorate.

請求項５に係る発明では、請求項１〜４のいずれか１項記載のＸ線回析計測用の試料ホルダは、前記試料を加熱するヒータを内蔵すると共に加熱時における前記試料の近傍の温度を計測する測温手段を備えているため、高温でのＸ線回析計測が可能となる。しかも、ヒータを試料ホルダに内蔵したため、Ｘ線回析計測装置にヒータを備える必要が無い。
すなわち、普通のＸ線回析計測装置を用いるにも拘わらず高温測定が可能である。 In the invention which concerns on Claim 5, the sample holder for X-ray diffraction measurement of any one of Claims 1-4 incorporates the heater which heats the said sample, and is the temperature of the vicinity of the said sample at the time of heating Therefore, X-ray diffraction measurement at a high temperature is possible. In addition, since the heater is built in the sample holder, it is not necessary to provide a heater in the X-ray diffraction measurement apparatus.
That is, high temperature measurement is possible despite using an ordinary X-ray diffraction measurement device.

請求項６に係る発明は、請求項１〜５のいずれか１項記載のＸ線回析計測用の試料ホルダを、Ｘ線回析計測装置に設置し、不活性ガス雰囲気の気密を保持した試料を加熱し高温時の結晶構造変化をその場でＸ線回析計測することを特徴とする。
請求項６によれば、普通の汎用のＸ線回析計測装置を用いるにも拘わらず、試料が大気暴露により変質することを防ぐことが可能となり、且つ試料加熱高温時の結晶構造変化をその場で計測することが可能となり、且つ容易に試料交換作業ができ、運搬時に試料の表面状態を保つことが可能であるＸ線回析計測方法が提供される。 According to a sixth aspect of the present invention, the sample holder for X-ray diffraction measurement according to any one of the first to fifth aspects is installed in an X-ray diffraction measurement device, and the airtightness of an inert gas atmosphere is maintained. It is characterized in that the sample is heated and the crystal structure change at high temperature is measured in situ by X-ray diffraction.
According to claim 6, it is possible to prevent the sample from being deteriorated by exposure to the atmosphere despite the use of an ordinary general-purpose X-ray diffraction measurement device, and the crystal structure change at the time of heating the sample is high. An X-ray diffraction measurement method is provided that can be measured in the field, can be easily replaced, and can maintain the surface state of the sample during transportation.

本発明に係る試料ホルダの分解図である。It is an exploded view of the sample holder which concerns on this invention. 本発明の試料封入工程を説明する図である。It is a figure explaining the sample enclosure process of this invention. ヒータの取付要領を説明する図である。It is a figure explaining the attachment point of a heater. 本発明の試料ホルダをＸ線回析計測装置に取り付ける際に用いるアタッチメントの説明図である。It is explanatory drawing of the attachment used when attaching the sample holder of this invention to an X-ray diffraction measurement apparatus. 本発明のＸ線回析工程を説明する図である。It is a figure explaining the X-ray diffraction process of this invention. 温度曲線の例を説明する図である。It is a figure explaining the example of a temperature curve. ベリリウムの回析強度を調べたグラフ図である。It is the graph which investigated the diffraction intensity of beryllium. 従来の試料ホルダの断面図である。It is sectional drawing of the conventional sample holder. 従来の別の試料ホルダの断面図である。It is sectional drawing of another conventional sample holder.

本発明の実施の形態を添付図に基づいて以下に説明する。   Embodiments of the present invention will be described below with reference to the accompanying drawings.

本発明の実施例を図面に基づいて説明する。
図１に示されるように、試料ホルダ１０は、上方に開いた凹状の試料載せ部１１を有するホルダ本体１２と、このホルダ本体１２の上面に被せる上蓋１３と、ホルダ本体１２の下面に当てる下蓋１４と、ヒータ１５とを主要素とする。次に、各要素について詳しく説明する。 Embodiments of the present invention will be described with reference to the drawings.
As shown in FIG. 1, the sample holder 10 includes a holder main body 12 having a concave sample mounting portion 11 that opens upward, an upper lid 13 that covers the upper surface of the holder main body 12, and a lower surface that contacts the lower surface of the holder main body 12. The lid 14 and the heater 15 are the main elements. Next, each element will be described in detail.

試料載せ部１１は、Ｘ線透過部材３１に沿って延びており、図２（ｂ）に示されるように、作業中に試料がずれることがなく且つＸ線回析計測に必要な初期の試料表面状態が保持できる浅い凹部である。   The sample mounting portion 11 extends along the X-ray transmitting member 31, and as shown in FIG. 2B, the sample does not shift during the operation and is an initial sample necessary for X-ray diffraction measurement. It is a shallow recess that can maintain the surface state.

ホルダ本体１２は、円柱などの柱部１６と、この柱部１６の下部から水平に張り出したフランジ部１７と、このフランジ部１７に設けたガスケット溝１８及び第１雌ねじ部１９、１９と、柱部１６の底の中央に設けたヒータ収納凹部２１と、柱部１６の底に且つヒータ収納凹部２１の周囲に上向きに設けた第２雌ねじ部２２及び測温手段２３を装入する測温手段挿入穴２４とからなり、柱部１６の上部に試料載せ部１１が設けられ、ガスケット溝１８に気密シール用ガスケット２５が嵌められている。測温手段２３は、熱電対が好適であるが、測温抵抗体など他の手段であってもよい。   The holder main body 12 includes a column portion 16 such as a column, a flange portion 17 projecting horizontally from a lower portion of the column portion 16, a gasket groove 18 and first female screw portions 19 and 19 provided in the flange portion 17, and a column. The heater housing recess 21 provided in the center of the bottom of the portion 16, the temperature measuring means for inserting the second female screw portion 22 and the temperature measuring means 23 provided on the bottom of the column portion 16 and around the heater housing recess 21. The sample mounting part 11 is provided on the upper part of the column part 16, and an airtight seal gasket 25 is fitted in the gasket groove 18. The temperature measuring means 23 is preferably a thermocouple, but may be other means such as a resistance temperature detector.

上蓋１３は、柱部１６に嵌る円筒などの筒部２７と、この筒部２７の下部から水平に張り出したフランジ部２８と、このフランジ部２８に設けた第１ボルト穴２９、２９と、筒部２７の上部に渡し、ろう付けされたＸ線透過部材３１とからなる。
このＸ線透過部材３１の材質は、耐久性から金属とし、金属の中でベリリウム（金属ベリリウム）やベリリウム合金が好適である。その理由は後述する。
第１ボルト３２は、第１ボルト穴２９を介して、第１雌ねじ部１９へねじ込むことができる。 The upper lid 13 includes a cylindrical portion 27 such as a cylinder that fits into the column portion 16, a flange portion 28 that projects horizontally from the lower portion of the cylindrical portion 27, first bolt holes 29 and 29 provided in the flange portion 28, It consists of an X-ray transmitting member 31 that is passed to the upper part of the part 27 and brazed.
The material of the X-ray transmitting member 31 is a metal for durability, and beryllium (metal beryllium) or a beryllium alloy is preferable among the metals. The reason will be described later.
The first bolt 32 can be screwed into the first female screw portion 19 through the first bolt hole 29.

下蓋１４は、第２ボルト穴３３及び測温手段通孔３４とを備えた円板等の板である。
第２ボルト３５は、第２ボルト穴３３を介して、第２雌ねじ部２２へねじ込むことができる。 The lower lid 14 is a plate such as a disk provided with a second bolt hole 33 and a temperature measuring means through hole 34.
The second bolt 35 can be screwed into the second female screw portion 22 via the second bolt hole 33.

次に、試料の準備について説明するが、試料は大気暴露が許されないため、不活性ガス雰囲気例えばグローブボックス内で以下の作業を行う。   Next, preparation of the sample will be described. Since the sample is not allowed to be exposed to the atmosphere, the following operation is performed in an inert gas atmosphere, for example, a glove box.

先ず、図２（ａ）に示すように、試料瓶４６から所定量の試料４８を試料載せ部１１へ移す。次に、（ｂ）に示すように、上蓋１３を被せ、第１ボルト３２、３２で、ホルダ本体１２へ上蓋１３を固定する。
これで、（ｃ）に示す試料ホルダ１０Ｂが完成する。フランジ部１７とフランジ部２８との間の隙間は、気密シール用ガスケット２５でシールされている。そのため、この形態で、大気に晒しても、試料４８が変質する心配はない。 First, as shown in FIG. 2A, a predetermined amount of the sample 48 is transferred from the sample bottle 46 to the sample mounting unit 11. Next, as shown in (b), the upper lid 13 is covered, and the upper lid 13 is fixed to the holder body 12 with the first bolts 32 and 32.
Thus, the sample holder 10B shown in (c) is completed. A gap between the flange portion 17 and the flange portion 28 is sealed with an airtight sealing gasket 25. Therefore, in this form, there is no fear that the sample 48 will be altered even when exposed to the atmosphere.

続いて、図３（ａ）に示すように、ヒータ収納凹部２１へヒータ１５を入れ、下蓋１４を被せ、第２ボルト３５で固定する。これで、（ｂ）に示す形態のヒータ付き試料ホルダ１０が完成する。   Subsequently, as shown in FIG. 3A, the heater 15 is put into the heater housing recess 21, the lower lid 14 is put on, and fixed with the second bolt 35. Thereby, the sample holder 10 with a heater of the form shown to (b) is completed.

すなわち、気密シール用ガスケット２５により、ホルダ本体１２と上蓋１３との間の気密性を確保することができ、試料載せ部２１に試料４８と共に不活性ガスを封じ込めることができる。結果、試料４８が大気暴露で変質することを防ぐことが可能となる。   That is, the airtight seal gasket 25 can ensure airtightness between the holder main body 12 and the upper lid 13, and the sample mounting portion 21 can contain the inert gas together with the sample 48. As a result, it is possible to prevent the sample 48 from being altered by exposure to the atmosphere.

さらに、試料ホルダ１０は、研究者がグローブボックスなどの不活性ガス雰囲気の筐体に搬入搬出可能な大きさ及び重さの物であって、筐体内で試料載せ部へ試料の充填作業が行え不活性ガスを封入することができて、筐体の外へ出しても試料の大気暴露による変質を防ぐことができる。   Furthermore, the sample holder 10 has a size and weight that allows a researcher to carry in and out of a housing in an inert gas atmosphere such as a glove box, and the sample holder can be filled with the sample in the housing. An inert gas can be sealed, and even if the sample is taken out of the housing, the sample can be prevented from being deteriorated by exposure to the atmosphere.

図２（ｃ）に示す試料ホルダ１０Ｂや図３（ｂ）に示すヒータ付き試料ホルダ１０の形態で、グローブボックスから取り出す。
取り出した試料ホルダ１０Ｂ又は１０を、Ｘ線回析計測装置へセットすることは差し支えないが、好ましくは、次に述べるアタッチメントを用いてＸ線回析計測装置へセットする。 The sample holder 10B shown in FIG. 2 (c) and the sample holder 10 with a heater shown in FIG. 3 (b) are taken out from the glove box.
The sample holder 10B or 10 thus taken out may be set in the X-ray diffraction measurement apparatus, but is preferably set in the X-ray diffraction measurement apparatus using an attachment described below.

アタッチメント５０は、図４（ａ）に示すように、平坦なベース５１と、このベース５１から立ち上げた筒体５２と、この筒体５２に収納すると共にベース５１に載せたコイルスプリング５３と、このコイルスプリング５３の上部に載せた昇降板５４と、筒体５２の上部外周から水平に外方へ突出させたピン５５、５５と、これらのピン５５、５５に係合する傾斜溝５６を有するリング蓋５７とからなる。リング蓋５７には、Ｘ線通過用開口部５８が設けられている。   As shown in FIG. 4A, the attachment 50 includes a flat base 51, a cylinder 52 raised from the base 51, a coil spring 53 housed in the cylinder 52 and mounted on the base 51, The elevating plate 54 mounted on the upper portion of the coil spring 53, pins 55 and 55 projecting horizontally outward from the outer periphery of the upper portion of the cylindrical body 52, and inclined grooves 56 engaged with these pins 55 and 55 are provided. And a ring lid 57. The ring lid 57 is provided with an X-ray passage opening 58.

そして、昇降板５４に試料ホルダ１０を載せ、上からリング蓋５７を取り付ける。次に、（ｂ）に示すように、測温手段２３を挿入する。
試料ホルダ１０を含むアタッチメント５０を、図５に示すＸ線回析計測装置６０にセットする。 Then, the sample holder 10 is placed on the lifting plate 54, and the ring lid 57 is attached from above. Next, as shown in (b), the temperature measuring means 23 is inserted.
The attachment 50 including the sample holder 10 is set in the X-ray diffraction measurement apparatus 60 shown in FIG.

次に、ヒータ１５に通電する。温度制御部６１は、測温手段２３で得た温度情報に基づいてヒータ出力を制御し、試料４８が所定の温度になるように、加熱する。
所定の温度に達したら、Ｘ線回析計測装置６０のＸ線照射部６２からＸ線６３を発射し、試料４８に当て、受線部６４でＸ線を受ける。受けたＸ線は、演算部６５で解析される。 Next, the heater 15 is energized. The temperature control unit 61 controls the heater output based on the temperature information obtained by the temperature measuring means 23 and heats the sample 48 so as to reach a predetermined temperature.
When the temperature reaches a predetermined temperature, X-rays 63 are emitted from the X-ray irradiation unit 62 of the X-ray diffraction measurement device 60, hit the sample 48, and receive X-rays at the receiving unit 64. The received X-ray is analyzed by the arithmetic unit 65.

加熱及びその後の冷却は任意に設定することができる。例えば、図６に示すように、加熱、保温後に、１°／分程度の冷却速度で徐冷する曲線Ａや、加熱、保温後に、１７°／分程度の冷却速度で急冷する曲線Ｂを実施することができる。   Heating and subsequent cooling can be arbitrarily set. For example, as shown in FIG. 6, a curve A that gradually cools at a cooling rate of about 1 ° / min after heating and holding, and a curve B that rapidly cools at a cooling rate of about 17 ° / min after heating and holding are performed. can do.

図５に示すＸ線回析計測装置６０自体には、ヒータ等の加熱手段は不要である。仮に、Ｘ線回析計測装置６０を全体的に加熱しようとすると、大容量のヒータが必要となる。この点、本発明によれば、試料４８の近傍にヒータ１５を配置するため、ヒータ１５の容量は小さくなる。   The X-ray diffraction measurement apparatus 60 shown in FIG. 5 does not require a heating means such as a heater. If the X-ray diffraction measurement device 60 is to be heated as a whole, a large-capacity heater is required. In this regard, according to the present invention, since the heater 15 is disposed in the vicinity of the sample 48, the capacity of the heater 15 is reduced.

すなわち、試料ホルダを、Ｘ線回析計測装置６０に設置し、不活性ガス雰囲気の気密を保持した試料を加熱し高温時の結晶構造変化をその場でＸ線回析計測することができる。
普通の汎用のＸ線回析計測装置を用いるにも拘わらず、試料が大気暴露により変質することを防ぐことが可能となり、且つ試料加熱高温時の結晶構造変化をその場で計測することが可能となり、且つ容易に試料交換作業ができ、運搬時に試料の表面状態を保つことが可能であるＸ線回析計測方法が提供される。 That is, the sample holder can be installed in the X-ray diffraction measurement device 60, and the sample maintaining the airtightness of the inert gas atmosphere can be heated to measure the crystal structure change at high temperature on the spot.
Despite the use of a general-purpose X-ray diffraction measurement device, it is possible to prevent the sample from being altered by exposure to the atmosphere, and it is possible to measure the crystal structure change at high temperatures when the sample is heated. Thus, there is provided an X-ray diffraction measurement method capable of easily exchanging a sample and maintaining the surface state of the sample during transportation.

また、計測後に、図２（ｃ）、（ｂ）、（ａ）の順で、ホルダ本体１２から上蓋１３を外し、使用済みの試料４８を除去する。そして、図２（ａ）、（ｂ）、（ｃ）の手順で試料収納凹部１１に新しい試料４８を入れ、試料ホルダ１０Ｂを完成させて、次の計測を行う。   Further, after the measurement, the upper lid 13 is removed from the holder body 12 in the order of FIGS. 2C, 2B, and 2A, and the used sample 48 is removed. 2A, 2B, and 2C, a new sample 48 is put into the sample storage recess 11, the sample holder 10B is completed, and the next measurement is performed.

また、Ｘ線透過部材３１が金属であるため、皺が寄ったり劣化する心配が無く、繰り返し使用することができると共に高温にも耐える。
したがって、本発明によれば、普通のＸ線回析計測装置を用いるにも拘わらず高温測定が可能であり且つ繰り返して使用することができる試料ホルダが提供される。 Further, since the X-ray transmitting member 31 is made of metal, there is no fear of wrinkles or deterioration, and it can be used repeatedly and can withstand high temperatures.
Therefore, according to the present invention, there is provided a sample holder that can perform high temperature measurement and can be used repeatedly even though an ordinary X-ray diffraction measurement apparatus is used.

次に、ベリリウム又はベリリウム合金について説明する。
Ｘ線透過部材３１が無い状態（図２（ａ）の形態）で、標準試料についてＸ線回析計測を行い、図７（ａ）の比較例を得た。３箇所に大きなピークが認められる。
Ｘ線透過部材３１が有る状態（図２（ｃ）の形態）で、標準試料についてＸ線回析計測を行い、図７（ｂ）の実施例を得た。３箇所に大きなピークが認められる。回析強度は３０％程度低減したが、図７（ａ）と同一の２θにおいて、大きなピークが認められる。
したがって、標準試料を用いて透過部材の有無によるピーク強度の補正を行うことにより、回析計測の信頼性は、実施例は比較例に遜色ないと言える。 Next, beryllium or beryllium alloy will be described.
In a state where there is no X-ray transmitting member 31 (in the form of FIG. 2A), X-ray diffraction measurement was performed on the standard sample to obtain a comparative example of FIG. 7A. Large peaks are observed at three locations.
X-ray diffraction measurement was performed on the standard sample in the state where the X-ray transmitting member 31 was present (in the form of FIG. 2C), and the example of FIG. 7B was obtained. Large peaks are observed at three locations. Although the diffraction intensity is reduced by about 30%, a large peak is observed at the same 2θ as in FIG.
Therefore, it can be said that the reliability of the diffraction measurement is comparable to that of the comparative example by correcting the peak intensity depending on the presence or absence of the transmission member using the standard sample.

尚、Ｘ線透過部材３１は、Ｘ線が透過する金属で構成される部材であれば、金属の材質は問わない。   The X-ray transmitting member 31 may be made of any metal material as long as it is a member made of a metal that transmits X-rays.

本発明は、大気暴露により変質しやすい化学物質の高温でのＸ線回析計測技術に好適である。   The present invention is suitable for an X-ray diffraction measurement technique at a high temperature of a chemical substance that is easily altered by exposure to the atmosphere.

１０、１０Ｂ…試料ホルダ、１１…試料載せ部、１２…ホルダ本体、１３…上蓋、１５…ヒータ、２３…測温手段、２５…気密シール用ガスケット、３１…Ｘ線透過部材、３７…グローブボックス、４５…不活性ガス供給源、６０…Ｘ線回析計測装置。   DESCRIPTION OF SYMBOLS 10, 10B ... Sample holder, 11 ... Sample mounting part, 12 ... Holder main body, 13 ... Upper lid, 15 ... Heater, 23 ... Temperature measuring means, 25 ... Gastight seal gasket, 31 ... X-ray transmissive member, 37 ... Glove box 45 ... inert gas supply source, 60 ... X-ray diffraction measurement device.

Claims (6)

Ｘ線回析計測用の試料ホルダであって、
化学物質などの試料を載せる試料載せ部を有するホルダ本体、このホルダ本体に被せることができ且つ試料と対向する上面にＸ線透過部材を備えた上蓋、この上蓋と前記ホルダ本体との間に気密シール用ガスケットを備えていることを特徴とするＸ線回析計測用の試料ホルダ。 A sample holder for X-ray diffraction measurement,
A holder main body having a sample mounting portion for placing a sample such as a chemical substance, an upper lid that can be placed on the holder main body and provided with an X-ray transmitting member on the upper surface facing the sample, and an airtight gap between the upper lid and the holder main body A sample holder for X-ray diffraction measurement, comprising a sealing gasket. 請求項１記載のＸ線回析計測用の試料ホルダは、研究者がグローブボックスなどの不活性ガス雰囲気の筐体に搬入搬出可能な大きさ及び重さの物であって、前記筐体内で前記試料載せ部へ試料の充填作業が行え不活性ガスを封入することができて、前記筐体の外へ出しても試料の大気暴露による変質を防ぐことができることを特徴とするＸ線回析計測用の試料ホルダ。   The sample holder for X-ray diffraction measurement according to claim 1 is an object of a size and weight that allows a researcher to carry in and out of a housing in an inert gas atmosphere such as a glove box, X-ray diffraction characterized in that the sample can be filled in the sample mounting portion and can be filled with an inert gas, so that the sample can be prevented from being altered by exposure to the atmosphere even if it is moved out of the casing. Sample holder for measurement. 前記試料載せ部は、前記Ｘ線透過部材に沿って延びており、作業中に試料がずれることがなく且つＸ線回析計測に必要な初期の試料表面状態が保持できる浅い凹部であることを特徴とする請求項１又は請求項２記載のＸ線回析計測用の試料ホルダ。   The sample mounting portion extends along the X-ray transmitting member, and is a shallow recess that prevents the sample from shifting during operation and can maintain the initial sample surface state necessary for X-ray diffraction measurement. The sample holder for X-ray diffraction measurement according to claim 1 or 2, characterized in that 前記Ｘ線透過部材は、ベリリウム又はベリリウム合金製であることを特徴とする請求項１、請求項２又は請求項３記載のＸ線回析計測用の試料ホルダ。   The sample holder for X-ray diffraction measurement according to claim 1, 2, or 3, wherein the X-ray transmitting member is made of beryllium or a beryllium alloy. 請求項１〜４のいずれか１項記載のＸ線回析計測用の試料ホルダは、前記試料を加熱するヒータを内蔵すると共に加熱時における前記試料の近傍の温度を計測する測温手段を備えていることを特徴とするＸ線回析計測用の試料ホルダ。   The sample holder for X-ray diffraction measurement according to any one of claims 1 to 4, comprising a heater for heating the sample and temperature measuring means for measuring the temperature in the vicinity of the sample during heating. A sample holder for X-ray diffraction measurement, characterized in that 請求項１〜５のいずれか１項記載のＸ線回析計測用の試料ホルダを、Ｘ線回析計測装置に設置し、不活性ガス雰囲気の気密を保持した前記試料を加熱し高温時の結晶構造変化をその場でＸ線回析計測することを特徴とするＸ線回析計測方法。   The sample holder for X-ray diffraction measurement according to any one of claims 1 to 5 is installed in an X-ray diffraction measurement device, and the sample that maintains the airtightness of an inert gas atmosphere is heated to increase the temperature. An X-ray diffraction measurement method comprising measuring X-ray diffraction in situ on a crystal structure change.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017203663A (en) * 2016-05-10 2017-11-16 住友金属鉱山株式会社 X-ray diffraction measurement method
RU2650836C1 (en) * 2016-12-14 2018-04-17 федеральное государственное автономное образовательное учреждение высшего образования "Московский физико-технический институт (государственный университет)" Sample assembly block, intended for conducting combined measurements by x-ray structural analysis in a sliding bundle and additional physico-chemical methods of the study
CN111398009A (en) * 2019-01-02 2020-07-10 上海科技大学 In-situ temperature control table for in-situ high-pressure reaction tank and ultrahigh vacuum characterization and transfer
WO2021038943A1 (en) * 2019-08-27 2021-03-04 株式会社リガク Structure for battery analysis and x-ray diffraction device
CN113406128A (en) * 2021-07-23 2021-09-17 重庆大学 Temperature control accessory for X-ray diffractometer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61246656A (en) * 1985-04-02 1986-11-01 Natl Inst For Res In Inorg Mater Sample capsule for x ray defractometer
US5350923A (en) * 1992-02-06 1994-09-27 Northern Telecom Limited Apparatus for use with analytical measuring instruments using electromagnetic radiation analysis methods
JPH1019815A (en) * 1996-07-04 1998-01-23 Rigaku Corp Thermal analysis and x-ray measuring device
JPH116805A (en) * 1997-06-16 1999-01-12 Toho Titanium Co Ltd Airtight sample holder for x-ray device
JP2005257306A (en) * 2004-03-09 2005-09-22 Toyota Central Res & Dev Lab Inc X-ray analyzing sample container and sample container housing device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61246656A (en) * 1985-04-02 1986-11-01 Natl Inst For Res In Inorg Mater Sample capsule for x ray defractometer
US5350923A (en) * 1992-02-06 1994-09-27 Northern Telecom Limited Apparatus for use with analytical measuring instruments using electromagnetic radiation analysis methods
JPH1019815A (en) * 1996-07-04 1998-01-23 Rigaku Corp Thermal analysis and x-ray measuring device
JPH116805A (en) * 1997-06-16 1999-01-12 Toho Titanium Co Ltd Airtight sample holder for x-ray device
JP2005257306A (en) * 2004-03-09 2005-09-22 Toyota Central Res & Dev Lab Inc X-ray analyzing sample container and sample container housing device

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017203663A (en) * 2016-05-10 2017-11-16 住友金属鉱山株式会社 X-ray diffraction measurement method
RU2650836C1 (en) * 2016-12-14 2018-04-17 федеральное государственное автономное образовательное учреждение высшего образования "Московский физико-технический институт (государственный университет)" Sample assembly block, intended for conducting combined measurements by x-ray structural analysis in a sliding bundle and additional physico-chemical methods of the study
CN111398009A (en) * 2019-01-02 2020-07-10 上海科技大学 In-situ temperature control table for in-situ high-pressure reaction tank and ultrahigh vacuum characterization and transfer
WO2021038943A1 (en) * 2019-08-27 2021-03-04 株式会社リガク Structure for battery analysis and x-ray diffraction device
CN113406128A (en) * 2021-07-23 2021-09-17 重庆大学 Temperature control accessory for X-ray diffractometer
CN113406128B (en) * 2021-07-23 2022-11-11 重庆大学 Temperature control accessory for X-ray diffractometer

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