JPH1019815A - Thermal analysis and x-ray measuring device - Google Patents
Thermal analysis and x-ray measuring deviceInfo
- Publication number
- JPH1019815A JPH1019815A JP8195385A JP19538596A JPH1019815A JP H1019815 A JPH1019815 A JP H1019815A JP 8195385 A JP8195385 A JP 8195385A JP 19538596 A JP19538596 A JP 19538596A JP H1019815 A JPH1019815 A JP H1019815A
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- sample
- ray
- thermal analysis
- measurement
- temperature
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- Analysing Materials By The Use Of Radiation (AREA)
- Investigating Or Analyzing Materials Using Thermal Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、熱分析測定及びＸ
線測定の両方の測定を行うことができる熱分析及びＸ線
測定装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to a thermal analysis and X-ray measurement device capable of performing both measurements of X-ray measurement.
【０００２】[0002]
【従来の技術】熱分析というのは、試料の温度を変化さ
せたときのその試料の性質の温度依存症を測定すること
である。具体的な分析方法としては非常に多種類の方法
があるが、代表的なものをあげれば、例えば、示差熱分
析（ＤＴＡ：Differential Thermal Analysis）や、示
差走査熱量測定（ＤＳＣ：Differential Scanning Calo
rimetry）等がある。2. Description of the Related Art Thermal analysis is the measurement of the temperature dependence of the properties of a sample when the temperature of the sample is changed. There are a wide variety of specific analysis methods, and typical examples include, for example, differential thermal analysis (DTA) and differential scanning calorimetry (DSC).
rimetry).
【０００３】ＤＴＡというのは、試料と標準物質とを同
時に加熱して、反応の際に両者間に現れた温度差から試
料に発生した熱変化を知る方法である。ＤＳＣというの
は、試料内に発生した熱変化を、それを補償するのに必
要な熱量として求めるものであり、具体的には、試料と
標準物質との間に温度差が生じたら、いずれか一方に供
給する単位時間当たりの熱量を増やしたり、減らしたり
して、等速昇温、等速冷却あるいは等温の状態を保つよ
うに温度コントロールし、そのときに増やしたり、減ら
したりした熱量を測定するものである。ＤＴＡは、試料
の熱変化を温度差の形で間接的に測定するものであっ
て、例えば、転移熱すなわち潜熱は測定できないが、Ｄ
ＳＣはその転移熱も測定できる。[0003] DTA is a method of heating a sample and a standard material at the same time, and knowing a thermal change generated in the sample from a temperature difference appearing between the two during the reaction. DSC is to determine the heat change generated in the sample as the amount of heat required to compensate for it. Specifically, if a temperature difference occurs between the sample and the standard, any DSC Increase or decrease the amount of heat supplied per unit time to one side, control the temperature so that the temperature rises, cools, or maintains the isothermal state, and measure the amount of heat that was increased or decreased at that time Is what you do. DTA measures indirectly the thermal change of a sample in the form of a temperature difference. For example, the transition heat or latent heat cannot be measured.
SC can also measure its heat of transition.
【０００４】一方、Ｘ線測定というのは、試料にＸ線を
照射してその試料で回折又は反射するＸ線を検出してそ
の試料の性質を測定することである。このＸ線測定の具
体的な分析手法としても非常に多種類の方法があるが、
例えばＸ線回折測定、Ｘ線反射率測定がある。On the other hand, X-ray measurement means irradiating a sample with X-rays, detecting X-rays diffracted or reflected by the sample, and measuring the properties of the sample. There are a wide variety of specific analysis methods for this X-ray measurement,
For example, there are X-ray diffraction measurement and X-ray reflectance measurement.
【０００５】Ｘ線回折測定というのは、試料で回折した
Ｘ線を検出する測定であり、Ｘ線反射率測定というの
は、試料で反射したＸ線を検出する測定である。一般に
は、試料に入射するＸ線の入射角度が大きい場合に、Ｘ
線が試料で回折することが多い。そして、Ｘ線入射角度
が小さい場合に、Ｘ線が試料で反射することが多い。[0005] X-ray diffraction measurement is a measurement for detecting X-rays diffracted by a sample, and X-ray reflectivity measurement is a measurement for detecting X-rays reflected by a sample. Generally, when the incident angle of the X-ray incident on the sample is large, X
Lines often diffract at the sample. When the X-ray incidence angle is small, the X-ray is often reflected by the sample.
【０００６】従来、産業界においては、熱分析について
はそれ専用の測定装置を使ってその測定を行い、Ｘ線測
定についてはそれ専用の測定装置を使ってその測定を行
うというのが一般的であった。しかしながら、少ない例
ではあるが、熱分析及びＸ線測定の両方を１つの測定装
置によって行うようにしたものも提案されている。例え
ば、図５及び図６に示すように、円筒形状のヒータ５１
又は５２の内部に試料５３及び標準物質５４を配置し、
試料５３及び標準物質５４の両方をヒータ５１，５２に
よって加熱しながら、試料５３にＸ線Ｒを照射してＸ線
測定を行い、一方、熱電対５５によって試料５３及び標
準物質５４の温度を検出して熱分析を行うようにした装
置が知られている。Heretofore, in the industry, it has been common practice to measure thermal analysis using a dedicated measuring device, and to perform X-ray measurement using a dedicated measuring device. there were. However, although few examples have been proposed, both thermal analysis and X-ray measurement are performed by one measuring device. For example, as shown in FIG. 5 and FIG.
Or placing a sample 53 and a standard substance 54 inside 52,
While heating both the sample 53 and the standard material 54 by the heaters 51 and 52, the sample 53 is irradiated with X-rays R to perform X-ray measurement, while the thermocouple 55 detects the temperature of the sample 53 and the standard material 54. There is known an apparatus for performing thermal analysis.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、図５及
び図６に示すような従来の熱分析及びＸ線測定装置にお
いては、０℃以下の温度に関する測定や、試料温度を急
速に加熱冷却するような測定を行うことができなかっ
た。また、図５に示すように高さの高いヒータ５１を用
いる場合には、Ｘ線Ｒを試料５３へ低角度で入射させる
ことができないという問題がある。一方、図６に示すよ
うな高さの低いヒータ５２を用いる場合には、Ｘ線Ｒを
低角度から試料５３へ入射することができるものの、ヒ
ータ５２による試料室Ｈ内の温度分布が極端に悪くなる
という問題が発生する。However, in the conventional thermal analysis and X-ray measuring apparatus as shown in FIGS. 5 and 6, measurement relating to a temperature of 0 ° C. or less and rapid heating and cooling of the sample temperature are performed. Measurement could not be performed. Further, when a high heater 51 is used as shown in FIG. 5, there is a problem that X-rays R cannot be incident on the sample 53 at a low angle. On the other hand, when the heater 52 having a low height as shown in FIG. 6 is used, although the X-ray R can be incident on the sample 53 from a low angle, the temperature distribution in the sample chamber H by the heater 52 is extremely low. The problem of getting worse occurs.
【０００８】本発明は、上記の問題点を解消するために
なされたものであって、熱分析及びＸ線測定の両方の測
定を１つの測定装置によって行う場合に、試料を均一な
温度分布で加熱でき、しかも試料に対して低角度からＸ
線を入射できるようにすることを第１の目的とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problem, and when both a thermal analysis and an X-ray measurement are performed by a single measuring apparatus, a sample is formed with a uniform temperature distribution. Can be heated, and X from a low angle to the sample
A first object is to enable the incidence of a line.
【０００９】また、熱分析及びＸ線測定の両方の測定を
１つの測定装置によって行う場合に、０℃以下の温度に
関する測定や、試料温度を急速に加熱冷却するような測
定を行うことができるようにすることを第２の目的とす
る。Further, when both the thermal analysis and the X-ray measurement are performed by one measuring device, it is possible to perform a measurement relating to a temperature of 0 ° C. or less and a measurement such as heating and cooling the sample temperature rapidly. The second object is to do so.
【００１０】[0010]
【課題を解決するための手段】上記第１の目的を達成す
るため、本発明に係る熱分析及びＸ線測定装置は、熱分
析測定系及びＸ線測定系の両測定系を備え、さらに、試
料のＸ線照射面の裏側であってその試料に接触又は近接
する位置にヒータを設けたことを特徴としている。In order to achieve the first object, a thermal analysis and X-ray measuring apparatus according to the present invention comprises both a thermal analysis measuring system and an X-ray measuring system, A heater is provided on the back side of the X-ray irradiation surface of the sample and at a position in contact with or close to the sample.
【００１１】また、上記第２の目的を達成するため、本
発明に係る熱分析及びＸ線測定装置は、熱分析測定系及
びＸ線測定系の両測定系を備え、さらに、試料を加熱す
る試料加熱手段と、試料を冷却するための試料冷却手段
とを有することを特徴としている。In order to achieve the second object, the thermal analysis and X-ray measuring apparatus according to the present invention comprises both a thermal analysis measuring system and an X-ray measuring system, and further heats the sample. It is characterized by having a sample heating means and a sample cooling means for cooling the sample.
【００１２】上記試料冷却手段の構成は特定のものに限
定されないが、望ましくは、試料のまわりに冷媒タンク
を設け、その冷媒タンク内に液体窒素を貯留する。ま
た、冷媒タンク内に液体窒素その他の寒剤を流すように
することもできる。また、試料冷却手段の別の構成とし
て、試料のまわりに螺旋状の冷媒パイプを設け、液体窒
素その他の寒剤をその冷媒パイプを通して循環させるこ
ともできる。Although the structure of the sample cooling means is not limited to a specific one, preferably, a refrigerant tank is provided around the sample, and liquid nitrogen is stored in the refrigerant tank. In addition, liquid nitrogen or other cryogens may be allowed to flow in the refrigerant tank. Further, as another configuration of the sample cooling means, a spiral refrigerant pipe may be provided around the sample, and liquid nitrogen and other cryogens may be circulated through the refrigerant pipe.
【００１３】試料のＸ線照射面の裏側であってその試料
に接触又は近接する位置にヒータを設けた構成の熱分析
及びＸ線測定装置では、図６に示すような高さの低い円
筒状ヒータを用いた従来の装置に比べて、試料を均一な
温度分布で加熱することができ、しかも、図５に示すよ
うな高さの高い円筒状ヒータを用いた従来の装置に比べ
て、試料に対するＸ線の入射角度を低角度側へ広げるこ
とができる。つまり、Ｘ線測定における測角範囲を広く
維持すること及び試料の温度分布を均一に維持すること
の両方の要求を同時に達成できる。[0013] In a thermal analysis and X-ray measurement apparatus having a heater provided on the back side of an X-ray irradiation surface of a sample and at a position in contact with or close to the sample, a cylindrical shape having a low height as shown in FIG. A sample can be heated with a uniform temperature distribution as compared with a conventional apparatus using a heater, and the sample can be heated as compared with a conventional apparatus using a cylindrical heater having a high height as shown in FIG. The incident angle of X-rays to the beam can be widened toward the lower angle side. That is, both requirements of maintaining a wide angle measurement range in X-ray measurement and maintaining a uniform temperature distribution of the sample can be simultaneously achieved.
【００１４】試料加熱手段及び試料冷却手段の両手段を
備えた構造の熱分析及びＸ線測定装置では、試料を高温
にしたいときには試料加熱手段を用い、試料を０℃以下
にしたいときには試料冷却手段を用い、また、試料温度
を高温から急速に冷却したいときには試料加熱手段及び
試料冷却手段の両方を用いる。In a thermal analysis and X-ray measuring apparatus having a structure provided with both a sample heating means and a sample cooling means, the sample heating means is used when the sample is to be heated to a high temperature, and the sample cooling means is used when the sample is to be kept at 0 ° C. or lower. When it is desired to rapidly cool the sample temperature from a high temperature, both the sample heating means and the sample cooling means are used.
【００１５】[0015]
（第１実施形態）図１は、本発明に係る熱分析及びＸ線
測定装置の一実施形態を示している。この装置は、円筒
状のブロック部材２と、ブロック部材２の中心部に形成
した凹状の試料室Ｈと、試料室Ｈの上部を気密に覆う円
弧状のカバー６と、そして試料室Ｈのまわりを取り囲む
ようにブロック部材２の内部に形成したリング状の冷媒
タンク７とを有している。(First Embodiment) FIG. 1 shows an embodiment of a thermal analysis and X-ray measurement apparatus according to the present invention. The apparatus comprises a cylindrical block member 2, a concave sample chamber H formed at the center of the block member 2, an arc-shaped cover 6 for hermetically covering the upper part of the sample chamber H, and a periphery of the sample chamber H. And a ring-shaped refrigerant tank 7 formed inside the block member 2 so as to surround the same.
【００１６】試料室Ｈの内部には、２本の支持棒８ａ及
び８ｂが立てられ、それらの支持棒の上端に試料皿９ａ
及び９ｂが設けられている。一方の試料皿９ａの上には
試料３が載せられ、他方の試料皿９ｂの上には標準物質
４が載せられている。標準物質４としては、温度変化し
ても性質に変化のない材料、すなわち熱的に安定な材料
が用いられる。試料３の直下、すなわち試料３のＸ線照
射面の裏側であってその試料３に接触又は近接する位置
には、上下２段にわたってヒータ１ａが設けられる。ま
た、標準物質４の直下にもヒータ１ｂが上下２段にわた
って設けられる。Inside the sample chamber H, two support rods 8a and 8b are set up, and a sample plate 9a is provided at the upper end of the support rods.
And 9b are provided. The sample 3 is placed on one sample dish 9a, and the standard substance 4 is placed on the other sample dish 9b. As the standard substance 4, a material whose properties do not change even when the temperature changes, that is, a thermally stable material is used. Immediately below the sample 3, that is, on the back side of the X-ray irradiation surface of the sample 3 and at a position in contact with or close to the sample 3, a heater 1 a is provided in two upper and lower stages. Further, a heater 1b is provided immediately below the standard substance 4 in two vertical stages.
【００１７】カバー６は、図２に示すように、上から見
ると長方形状に形成され、その中央部にはＸ線透過窓１
０が設けられている。試料室Ｈ内が比較的低温、例えば
５００℃程度までしか上がらない場合は、例えばステン
レスや真鍮によってカバー６を形成する。また、試料室
Ｈが比較的高温、例えば１５００℃程度まで上がる場合
は、例えばアルミナによってカバー６を形成する。ま
た、Ｘ線透過窓１０は、気密性を保持でき、さらにＸ線
を透過できる材料、例えば、ベリリウム（Ｂｅ）やニッ
ケル等によって形成する。As shown in FIG. 2, the cover 6 is formed in a rectangular shape when viewed from above, and has an X-ray transmission window 1 at the center thereof.
0 is provided. When the inside of the sample chamber H rises only at a relatively low temperature, for example, about 500 ° C., the cover 6 is formed of, for example, stainless steel or brass. When the temperature of the sample chamber H rises to a relatively high temperature, for example, about 1500 ° C., the cover 6 is formed of, for example, alumina. The X-ray transmission window 10 is formed of a material that can maintain airtightness and transmit X-rays, such as beryllium (Be) and nickel.
【００１８】図１において、冷媒タンク７の内部には、
冷却媒体、例えば液化窒素（ＬＮ2）が貯留されてい
る。支持棒８ａ及び８ｂの内部には、それぞれ、試料３
の底面及び標準物質４の底面を測温点とする熱電対５ａ
及び５ｂが格納されている。In FIG. 1, inside the refrigerant tank 7,
A cooling medium, for example, liquefied nitrogen (LN 2 ) is stored. Samples 3 are provided inside the support rods 8a and 8b, respectively.
Thermocouple 5a whose bottom is the temperature measurement point and the bottom of the standard material 4
And 5b are stored.
【００１９】上記の試料支持系の上方にはＸ線測定系１
１が配設され、その下方には熱分折系１２が配設されて
いる。本実施形態の場合、Ｘ線測定系１１はθ−θ走査
形式のＸ線回折装置によって構成され、熱分析系１２は
示差走査熱量測定（ＤＳＣ）装置によって構成されてい
る。詳しく説明すれば、Ｘ線測定系１１は、Ｘ線源Ｆ
と、Ｘ線カウンタ１３と、Ｘ線強度演算回路１４と、そ
してＸ線回折記録計１５とによって構成されている。熱
分析系１２は、Ｔ及びΔＴ測定回路１６と、熱量補償回
路１７と、そして熱分析記録計１８とによって構成され
ている。An X-ray measuring system 1 is provided above the sample supporting system.
1 is disposed, and a thermal analysis system 12 is disposed below the reference numeral 1. In the case of the present embodiment, the X-ray measurement system 11 is configured by an X-ray diffractometer of a θ-θ scanning format, and the thermal analysis system 12 is configured by a differential scanning calorimeter (DSC). More specifically, the X-ray measurement system 11 includes an X-ray source F
, An X-ray counter 13, an X-ray intensity calculation circuit 14, and an X-ray diffraction recorder 15. The thermal analysis system 12 includes a T and ΔT measurement circuit 16, a calorific value compensation circuit 17, and a thermal analysis recorder 18.
【００２０】以下、上記構成により成る熱分析及びＸ線
測定装置の動作について説明する。試料室Ｈの内部は、
冷媒タンク７内のＬＮ2 によって一定の冷却能力で冷却
される。そして同時に、試料３及び標準物質４は、それ
ぞれに対応するヒータ１ａ及び１ｂによって等しい温度
に加熱される。ヒータ １ａ,１ｂはそれぞれ試料３及び
標準物質４に接触又は近接して設けられるので、試料３
及び標準物質４はそれらの全域にわたって均一に加熱さ
れて、均一に昇温する。試料室Ｈ内の昇温及び降温状態
は、温度コントローラを兼ねた熱量補償回路１７に予め
記憶されたプログラムに従って制御される。ＬＮ2 を用
いた冷却手段を設置してあるので、試料室Ｈの内部を０
℃以下に設定することもでき、また、一旦設定した高温
を急速に冷却することもできる。Hereinafter, the operation of the thermal analysis and X-ray measuring apparatus having the above configuration will be described. The inside of the sample chamber H is
The cooling is performed with a constant cooling capacity by LN 2 in the refrigerant tank 7. At the same time, the sample 3 and the standard substance 4 are heated to the same temperature by the corresponding heaters 1a and 1b. Since the heaters 1a and 1b are provided in contact with or close to the sample 3 and the standard material 4, respectively,
And the reference material 4 is uniformly heated over the entire region, and the temperature is uniformly increased. The temperature rise and fall in the sample chamber H are controlled according to a program stored in advance in the calorific value compensation circuit 17 also serving as a temperature controller. Since the cooling means using LN 2 is installed, the inside of the sample chamber H
The temperature can be set to not more than ℃, and the high temperature once set can be rapidly cooled.
【００２１】このように試料３及び標準物質４を温度制
御した状態で、以下の通りに、Ｘ線回折測定系１１によ
るＸ線回折測定及び熱分析系１２による示差走査熱量測
定（ＤＳＣ）が行われる。With the temperature of the sample 3 and the standard substance 4 controlled as described above, X-ray diffraction measurement by the X-ray diffraction measurement system 11 and differential scanning calorimetry (DSC) by the thermal analysis system 12 are performed as follows. Will be
【００２２】（Ｘ線回折測定）Ｘ線源Ｆが試料３を中心
として図の上下方向へ走査回転（いわゆるθ回転）し、
それに同期してＸ線カウンタ１３が、等しい速度で反対
方向へ試料３を中心として走査回転（いわゆるθ回転）
する。これらのθ回転の間、Ｘ線源Ｆから出たＸ線Ｒが
試料３に入射する。図示はしてないが、必要に応じて、
Ｘ線源Ｆから試料３に至るＸ線光路上にはＸ線Ｒの発散
を規制する発散規制スリットや、連続Ｘ線を単色化する
モノクロメータ等が配設される。(X-ray Diffraction Measurement) The X-ray source F scans and rotates (so-called θ rotation) in the vertical direction of FIG.
In synchronism therewith, the X-ray counter 13 rotates in the opposite direction at the same speed for scanning around the sample 3 (so-called θ rotation).
I do. During these θ rotations, the X-rays R emitted from the X-ray source F enter the sample 3. Although not shown, if necessary,
On the X-ray optical path from the X-ray source F to the sample 3, a divergence restricting slit for restricting the divergence of the X-ray R, a monochromator for monochromatic continuous X-rays, and the like are provided.
【００２３】試料３に入射するＸ線と試料３の結晶格子
面との間で、周知のブラッグ条件が満足されると、試料
３でＸ線が回折する。回折したＸ線は、Ｘ線カウンタ１
３の内部に取り込まれて電気的なパルス信号に変換され
て出力され、その出力パルスはＸ線強度演算回路１４に
送られる。図示はしていないが、必要に応じて、Ｘ線カ
ウンタ１３と試料３との間には、散乱Ｘ線がＸ線カウン
タ１３に入るのを防止する散乱線阻止スリットや、Ｘ線
カウンタ１３に向かう回折Ｘ線の断面形状を一定の大き
さに規制する受光スリット等が配設される。When the well-known Bragg condition is satisfied between the X-ray incident on the sample 3 and the crystal lattice plane of the sample 3, the X-ray is diffracted by the sample 3. The diffracted X-ray is the X-ray counter 1
3, is converted into an electric pulse signal and output, and the output pulse is sent to the X-ray intensity calculation circuit 14. Although not shown, if necessary, a scattered ray blocking slit for preventing scattered X-rays from entering the X-ray counter 13 and a X-ray counter 13 are provided between the X-ray counter 13 and the sample 3. A light receiving slit or the like for regulating the cross-sectional shape of the traveling diffracted X-ray to a certain size is provided.
【００２４】Ｘ線強度演算回路１４はＸ線強度、すなわ
ち単位時間当たりの出力パルス数（ｃｐｓ）を演算し
て、その結果を記録計１５へ送る。記録計１５は、入射
Ｘ線Ｒに対するＸ線カウンタ１３の回転角度、すなわち
２θ角度値に対する回折Ｘ線強度を求め、周知のＸ線回
折図形を作成する。このＸ線回折図形を検討することに
より、試料３を構成する物質の同定や、結晶構造の判定
や、その他種々の解析が行われる。The X-ray intensity calculation circuit 14 calculates the X-ray intensity, that is, the number of output pulses per unit time (cps), and sends the result to the recorder 15. The recorder 15 determines the rotation angle of the X-ray counter 13 with respect to the incident X-ray R, that is, the diffraction X-ray intensity with respect to the 2θ angle value, and creates a well-known X-ray diffraction pattern. By examining the X-ray diffraction pattern, identification of the substance constituting the sample 3, determination of the crystal structure, and other various analyzes are performed.
【００２５】（示差走査熱量測定）熱電対５ａによって
検出される試料３の表面温度及び熱電対５ｂによって検
出される標準物質４の表面温度は、Ｔ及びΔＴ測定回路
１６へ送られる。測定回路１６は、試料３及び標準物質
４の温度（Ｔ）を測定し、同時に両者の差（ΔＴ）を演
算する。演算結果は熱量補償回路１７へ送られる。熱量
補償回路１７は、ΔＴが０（ゼロ）でないとき、それを
補償してΔＴ＝０となるように、試料側ヒータ１ａ又は
標準物質側ヒータ１ｂのいずれかへの通電量を調節し、
そのときに供給した熱量を測定する。これにより、試料
３に発生する熱量変化が検出される。熱分析記録計１８
は、試料温度（Ｔ）と試料に発生した熱量変化との関係
を求めてグラフ上に表示する。このグラフを検討するこ
とにより、試料３の物理的持性、例えば転移点や融解点
等の温度依存性を測定する。(Differential Scanning Calorimetry) The surface temperature of the sample 3 detected by the thermocouple 5a and the surface temperature of the standard substance 4 detected by the thermocouple 5b are sent to the T and ΔT measuring circuit 16. The measurement circuit 16 measures the temperature (T) of the sample 3 and the standard substance 4 and simultaneously calculates the difference (ΔT) between them. The calculation result is sent to the calorie compensation circuit 17. When ΔT is not 0 (zero), the heat amount compensating circuit 17 adjusts the amount of current supplied to either the sample-side heater 1a or the standard-material-side heater 1b so that ΔT = 0 by compensating for ΔT,
The amount of heat supplied at that time is measured. Thus, a change in the amount of heat generated in the sample 3 is detected. Thermal analysis recorder 18
Indicates the relationship between the sample temperature (T) and the change in the amount of heat generated in the sample, and displays the relationship on a graph. By examining this graph, the physical durability of the sample 3, for example, the temperature dependence of the transition point, melting point, and the like is measured.
【００２６】以上のように、本実施例の熱分析及びＸ線
測定装置によれば、１つの試料３に対してＸ線測定及び
熱分析の２種類の測定を同時に行うことができる。As described above, according to the thermal analysis and X-ray measurement apparatus of the present embodiment, two types of measurement, X-ray measurement and thermal analysis, can be simultaneously performed on one sample 3.
【００２７】（第２実施形態）図４は、本発明に係る熱
分析及びＸ線測定装置の他の実施形態を示している。こ
の熱分析及びＸ線測定装置が図１に示した装置と異なる
点は、熱分析系２２として、示差走査熱量測定（ＤＳ
Ｃ）装置に代えて示差熱分析（ＤＴＡ）装置を用いた点
である。(Second Embodiment) FIG. 4 shows another embodiment of the thermal analysis and X-ray measuring apparatus according to the present invention. This thermal analysis and X-ray measurement apparatus is different from the apparatus shown in FIG. 1 in that a differential scanning calorimeter (DS
C) A point that a differential thermal analysis (DTA) device was used instead of the device.
【００２８】このＤＴＡ装置は、Ｔ及びΔＴ測定回路１
６と、熱分析記録計１８と、そして温度コントローラ２
７とを有している。温度コントローラ２７は予め決めら
れたプログラムに従って、試料側ヒータ１ａ及び標準物
質側ヒータ１ｂへの通電を制御する。熱分析記録計１８
は、試料３と標準物質４との間の温度差（ΔＴ）と、試
料３の温度変化（Ｔ）との関係を求めてグラフ上に表示
する。This DTA device has a T and ΔT measuring circuit 1
6, thermal analysis recorder 18, and temperature controller 2
7 are provided. The temperature controller 27 controls energization to the sample-side heater 1a and the standard-material-side heater 1b according to a predetermined program. Thermal analysis recorder 18
Indicates the relationship between the temperature difference (ΔT) between the sample 3 and the standard substance 4 and the temperature change (T) of the sample 3 and displays the relationship on a graph.
【００２９】以上、好ましい実施例をあげて本発明を説
明したが、本発明はその実施例に限られることなく、請
求の範囲に記載した技術的範囲内で種々に改変できる。
例えば、ＬＮ2 を冷媒タンク７内に貯留するのではなく
て、常時その冷媒タンク７を通過させて流すようにする
こともできる。また図３に示すように、冷媒タンク７に
替えて、図の上方から見て螺旋状の冷媒パイプ１９を試
料室Ｈのまわりに配設しこの冷媒パイプ１９の上端吸入
口２０から導入したＬＮ2 を下端排出口２１から排出す
るように構成しても良い。Although the present invention has been described with reference to the preferred embodiments, the present invention is not limited to the embodiments but can be variously modified within the technical scope described in the claims.
For example, instead of storing LN 2 in the refrigerant tank 7, the LN 2 may always flow through the refrigerant tank 7. As shown in FIG. 3, a helical refrigerant pipe 19 is disposed around the sample chamber H when viewed from above in place of the refrigerant tank 7, and LN introduced from an upper end inlet 20 of the refrigerant pipe 19 is provided. 2 may be configured to be discharged from the lower end discharge port 21.
【００３０】熱分析系は上記説明で例示したＤＳＣ及び
ＤＴＡ以外の任意の熱分析系を適用できる。Ｘ線測定系
は上記説明で例示したＸ線回折装置以外に、Ｘ線反射率
測定装置や、蛍光Ｘ線装置等といったその他の任意のＸ
線装置を適用できる。As the thermal analysis system, any thermal analysis system other than the DSC and DTA exemplified in the above description can be applied. The X-ray measuring system is not limited to the X-ray diffractometer exemplified in the above description, but may be any other X-ray reflectometer, fluorescent X-ray apparatus, or any other X-ray measuring apparatus.
Wire device can be applied.
【００３１】[0031]
【発明の効果】請求項１記載の熱分析及びＸ線測定装置
によれば、試料を均一な温度分布で加熱でき、しかも試
料に対して低角度からＸ線を入射できる。すなわち、試
料を均一に加熱するという要求と、Ｘ線装置の測角範囲
を広く維持するという要求の２つの要求を同時に満足で
きる。According to the thermal analysis and X-ray measuring apparatus of the first aspect, the sample can be heated with a uniform temperature distribution, and the X-ray can be incident on the sample from a low angle. That is, two requirements, that is, a requirement to uniformly heat the sample and a requirement to maintain a wide angle measurement range of the X-ray apparatus can be satisfied at the same time.
【００３２】請求項２記載の熱分析及びＸ線測定装置に
よれば、熱分析及びＸ線測定の両方の測定を１つの測定
装置によって行う場合に、０℃以下の温度に関する測定
や、試料温度を急速に加熱冷却するような測定を行うこ
とができる。According to the thermal analysis and X-ray measuring apparatus of the second aspect, when both the thermal analysis and the X-ray measurement are performed by one measuring apparatus, the measurement relating to the temperature of 0 ° C. or less and the sample temperature Can be measured such that the sample is rapidly heated and cooled.
【００３３】請求項３記載の熱分析及びＸ線測定装置に
よれば、試料の均一加熱、Ｘ線装置の測角範囲の拡大、
０℃以下の試料温度に関する測定、そして試料温度の急
速加熱又は急速冷却といった全ての要求を満足できる。According to the thermal analysis and X-ray measurement apparatus of the third aspect, uniform heating of the sample, expansion of the angle measurement range of the X-ray apparatus,
All requirements such as measurement for sample temperatures below 0 ° C. and rapid heating or cooling of the sample temperature can be satisfied.
【００３４】請求項４又は請求項５記載の熱分析及びＸ
線測定装置によれば、簡単な構造で効率良く試料を冷却
できる。The thermal analysis according to claim 4 or 5, and X
According to the line measurement device, the sample can be efficiently cooled with a simple structure.
【００３５】[0035]
【図１】本発明に係る熱分析及びＸ線測定装置の一実施
形態を示す断面模式図である。FIG. 1 is a schematic sectional view showing an embodiment of a thermal analysis and X-ray measurement apparatus according to the present invention.
【図２】同熱分析及びＸ線測定装置の平面図である。FIG. 2 is a plan view of the thermal analysis and X-ray measurement apparatus.
【図３】本発明に係る熱分析及びＸ線測定装置の他の一
実施形態を示す断面図である。FIG. 3 is a sectional view showing another embodiment of the thermal analysis and X-ray measurement apparatus according to the present invention.
【図４】本発明に係る熱分析及びＸ線測定装置のさらに
他の一実施形態を示す断面図である。FIG. 4 is a sectional view showing still another embodiment of the thermal analysis and X-ray measurement apparatus according to the present invention.
【図５】従来の熱分析及びＸ線測定装置の一例を示す断
面図である。FIG. 5 is a cross-sectional view showing an example of a conventional thermal analysis and X-ray measurement device.
【図６】従来の熱分析及びＸ線測定装置の他の一例を示
す断面図である。FIG. 6 is a cross-sectional view showing another example of a conventional thermal analysis and X-ray measurement apparatus.
１ａ，１ｂ ヒータ ２ ブロック部材 ３ 試料 ４ 標準物質 ５ａ，５ｂ 熱電対 ６ カバー ７ 冷媒タンク ８ａ，８ｂ 支持棒 ９ａ，９ｂ 試料皿 １０ Ｘ線透過窓 １１ Ｘ線測定系 １２ 熱分析系 １３ Ｘ線カウンタ １９ 冷媒パイプ ２２ 熱分析系 Ｒ Ｘ線 Ｈ 試料室 Ｆ Ｘ線源 1a, 1b Heater 2 Block member 3 Sample 4 Standard substance 5a, 5b Thermocouple 6 Cover 7 Refrigerant tank 8a, 8b Support rod 9a, 9b Sample dish 10 X-ray transmission window 11 X-ray measurement system 12 Thermal analysis system 13 X-ray counter 19 Refrigerant pipe 22 Thermal analysis system R X-ray H Sample chamber F X-ray source
Claims (5)
の性質の温度依存性を測定する熱分析測定と、試料にＸ
線を照射してその試料で回折又は反射するＸ線を検出し
てその試料の性質を測定するＸ線測定との両方の測定を
行うことができる熱分析及びＸ線測定装置において、 試料のＸ線照射面の裏側であってその試料に接触又は近
接する位置にヒータを設けたことを特徴とする熱分析及
びＸ線測定装置。1. A thermoanalytical measurement for measuring the temperature dependence of the properties of a sample when the temperature of the sample is changed, and a X-ray
In a thermal analysis and X-ray measurement apparatus capable of performing both X-ray measurement of irradiating X-rays and detecting the X-ray diffracted or reflected by the sample and measuring the properties of the sample, A thermal analysis and X-ray measurement apparatus, characterized in that a heater is provided at a position on the back side of the radiation surface and in contact with or close to the sample.
の性質の温度依存性を測定する熱分析測定と、試料にＸ
線を照射してその試料で回折又は反射するＸ線を検出し
てその試料の性質を測定するＸ線測定との両方の測定を
行うことができる熱分析及びＸ線測定装置において、 試料を加熱する試料加熱手段と、試料を冷却するための
試料冷却手段とを有することを特徴とする熱分析及びＸ
線測定装置。2. A thermoanalytical measurement for measuring the temperature dependence of the properties of a sample when the temperature of the sample is changed, and X-ray
In a thermal analysis and X-ray measurement device capable of performing both X-ray measurement, which irradiates X-rays and detects X-rays diffracted or reflected by the sample and measures the properties of the sample, heating the sample Thermal analysis, comprising: a sample heating means for cooling the sample; and a sample cooling means for cooling the sample.
Line measuring device.
において、試料加熱手段は、試料のＸ線照射面の裏側で
あってその試料に接触又は近接する位置に配置したヒー
タを有することを特徴とする熱分析及びＸ線測定装置。3. The thermal analysis and X-ray measurement apparatus according to claim 2, wherein the sample heating means has a heater disposed at a position behind or in contact with or close to the sample, on the back side of the X-ray irradiation surface of the sample. A thermal analysis and X-ray measurement apparatus characterized by the above-mentioned.
Ｘ線測定装置において、試料冷却手段は、液体窒素を貯
留する冷媒タンクを有することを特徴とする熱分析及び
Ｘ線測定装置。4. The thermal analysis and X-ray measurement apparatus according to claim 2, wherein the sample cooling means has a refrigerant tank for storing liquid nitrogen.
Ｘ線測定装置において、試料冷却手段は、液体窒素を循
環させて流す螺旋状の冷媒パイプを有することを特徴と
する熱分析及びＸ線測定装置。5. The thermal analysis and X-ray measurement apparatus according to claim 2, wherein the sample cooling means has a helical refrigerant pipe for circulating and flowing liquid nitrogen. X-ray measurement device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19538596A JP3666831B2 (en) | 1996-07-04 | 1996-07-04 | Thermal analysis and X-ray measurement equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19538596A JP3666831B2 (en) | 1996-07-04 | 1996-07-04 | Thermal analysis and X-ray measurement equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1019815A true JPH1019815A (en) | 1998-01-23 |
| JP3666831B2 JP3666831B2 (en) | 2005-06-29 |
Family
ID=16340289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19538596A Expired - Fee Related JP3666831B2 (en) | 1996-07-04 | 1996-07-04 | Thermal analysis and X-ray measurement equipment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3666831B2 (en) |
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| EP1308417A2 (en) | 2001-11-02 | 2003-05-07 | Rigaku Corporation | Method and apparatus for producing metal oxide |
| JP2005221363A (en) * | 2004-02-05 | 2005-08-18 | Rigaku Corp | Sample support device for x-ray analysis, and x-ray analyzer |
| US6937695B2 (en) | 2002-10-02 | 2005-08-30 | Rigaku Corporation | Analyzing apparatus and analyzing method |
| JP2010048618A (en) * | 2008-08-20 | 2010-03-04 | Tokyo Institute Of Technology | Method for measuring phase transition conditions of sample to be subjected to phase transition, and measuring apparatus therefor |
| JP2010190807A (en) * | 2009-02-20 | 2010-09-02 | Sii Nanotechnology Inc | Differential scanning calorimeter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1308417A2 (en) | 2001-11-02 | 2003-05-07 | Rigaku Corporation | Method and apparatus for producing metal oxide |
| US6937695B2 (en) | 2002-10-02 | 2005-08-30 | Rigaku Corporation | Analyzing apparatus and analyzing method |
| JP2005221363A (en) * | 2004-02-05 | 2005-08-18 | Rigaku Corp | Sample support device for x-ray analysis, and x-ray analyzer |
| JP2010048618A (en) * | 2008-08-20 | 2010-03-04 | Tokyo Institute Of Technology | Method for measuring phase transition conditions of sample to be subjected to phase transition, and measuring apparatus therefor |
| JP2010190807A (en) * | 2009-02-20 | 2010-09-02 | Sii Nanotechnology Inc | Differential scanning calorimeter |
| JP2010203843A (en) * | 2009-03-02 | 2010-09-16 | Rigaku Corp | X-ray and thermal analyzer |
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| JP2012132697A (en) * | 2010-12-20 | 2012-07-12 | Rigaku Corp | X-ray diffraction and thermal analysis simultaneous measurement device |
| CN102519991A (en) * | 2011-12-20 | 2012-06-27 | 大连理工大学 | Natural gas hydrate heat transfer performance testing apparatus used in X-ray CT equipment |
| CN103487459A (en) * | 2013-10-15 | 2014-01-01 | 北京大学 | Test system and method for cooling performance of microscale liquid cooler |
| CN105181509A (en) * | 2015-08-07 | 2015-12-23 | 辽宁科技大学 | Method for detecting use performance of refractory material |
| CN109164128A (en) * | 2018-10-29 | 2019-01-08 | 中国科学院上海硅酸盐研究所 | A kind of furnace body for thermal-analysis instrumentation |
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|---|---|
| JP3666831B2 (en) | 2005-06-29 |
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