JPH11201923A - Measuring method for specific heat and differential scanning calorimeter - Google Patents
Measuring method for specific heat and differential scanning calorimeterInfo
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- JPH11201923A JPH11201923A JP419298A JP419298A JPH11201923A JP H11201923 A JPH11201923 A JP H11201923A JP 419298 A JP419298 A JP 419298A JP 419298 A JP419298 A JP 419298A JP H11201923 A JPH11201923 A JP H11201923A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、試料の比熱を高精
度に測定することができる比熱測定方法及び示差走査熱
量計に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a specific heat measuring method and a differential scanning calorimeter capable of measuring a specific heat of a sample with high accuracy.
【０００２】[0002]
【従来の技術】物質の比熱の値を温度の関数として精密
に求めることが、物質の工学的な応用と、物性理論の両
方から要求されている。この物質の比熱を求めるものと
して、従来、図３に示す双子型示差走査熱量計（熱流束
型）が提案されている。2. Description of the Related Art It is required from both the engineering application of materials and the theory of physical properties to accurately determine the value of the specific heat of a material as a function of temperature. Conventionally, a twin-type differential scanning calorimeter (heat flux type) shown in FIG. 3 has been proposed to determine the specific heat of this substance.
【０００３】この示差走査熱量計は、図３に示すよう
に、外周に配置された電気炉（図示しない）により加熱
される均熱容器ａ内に、両端を均熱容器ａに熱的に接触
させて熱流計板である金属薄板ｂを設け、該金属薄板ｂ
の熱的に対称位置（Ｎｏ．１，Ｎｏ．２）に、試料用セ
ルｃ1 及び空セルｃ2 をそれぞれ配置し、金属薄板ｂ
の、該試料用セルｃ1 及び空セルｃ2 に対応する位置に
試料温度用熱電対ｄ1 及び空セル用熱電対ｄ2 をそれぞ
れ取り付けた構造を有しており、試料の比熱は、これを
用いて次のような方法によって求める。As shown in FIG. 3, this differential scanning calorimeter has both ends in thermal contact with a heat equalizing container a in a heat equalizing container a heated by an electric furnace (not shown) arranged on the outer periphery. Then, a metal sheet b, which is a heat flow meter plate, is provided.
The sample cell c 1 and the empty cell c 2 are respectively arranged at the thermally symmetric positions (No. 1 and No. 2) of the metal sheet b.
Of, each have a mounting structure sample temperature thermocouple d 1 and empty cell thermocouple d 2 a at a position corresponding to the sample cell c 1 and the air-cell c 2, the specific heat of the sample, this Is determined by the following method.
【０００４】この測定は、２回行なわれる。第１回目の
測定では、熱量計のＮｏ．１の位置に試料、Ｎｏ．２の
位置に空セルｃ2 を配置する。次に、第２回目の測定で
は、熱量計のＮｏ．１の位置に熱容量が既知の標準試
料、Ｎｏ．２の位置に空セルｃ2 を配置する。[0004] This measurement is performed twice. In the first measurement, the calorimeter No. No. 1 at the position of the sample. The empty cell c2 is arranged at the position of No. 2 . Next, in the second measurement, the No. A standard sample having a known heat capacity at the position of No. 1; The empty cell c2 is arranged at the position of No. 2 .
【０００５】 第１回目の測定。[0005] First measurement.
【０００６】金属薄板ｂの均熱容器ａ（熱源）からの熱
流束（Φ）は、熱源温度［Ｔh （Ｔh1、Ｔh2）］と試料
温度測定点の温度［Ｔm （Ｔm1、Ｔm2）］との間の温度
差を熱抵抗（Ｒ）で割ったものに等しい。[0006] heat flux from the soaking vessel a (heat source) of the sheet metal b ([Phi) is a heat source temperature [T h (T h1, T h2)] between the temperature of the sample temperature measuring point [T m (T m1, T m2 )] is equal to the temperature difference divided by the thermal resistance (R).
【０００７】 Φ＝（Ｔh ーＴm ）／Ｒ …（１） この熱流束により、熱容量がＣm （Ｃm1、Ｃm2）の試料
温度測定点の部分（試料セルを載せる位置の周辺）、熱
容量がＣ（Ｃ1 、Ｃ2 ）の空セル、熱容量がＣs の試料
は温度上昇し、その昇温速度がｄＴ／ｄｔ＝φとなる。
Ｎｏ．１のセルｃ1 については、 （Ｔh1ーＴm1）／Ｒ1 ＝φ1 （Ｃm1＋Ｃ1 ＋Ｃs ） …（２） Ｎｏ．２のセルｃ2 についても同様に、 （Ｔh2ーＴm2）／Ｒ2 ＝φ2 （Ｃm2＋Ｃ2 ） …（３） 理想的条件の下では、 Ｔh1＝Ｔh2 Ｒ1 ＝Ｒ2 ＝Ｒ(1) φ1 ＝φ2 ＝φ(1) Ｃm1＝Ｃm2＝Ｃm Ｃ1 ＝Ｃ2 …（４） この条件の下で、（２）、（３）式より、 （Ｔm2ーＴm1）／Ｒ(1) ＝φ(1) ・Ｃs …（５） ΔＴ(1) ＝Ｔm2ーＴm1＝Ｒ(1) ・Ｔ(1) ・Ｃs …（５´） ここで、添字の（１）は第１回目の測定を示す。[0007] [Phi = (T h over T m) / R ... (1 ) The heat flux, portions of the sample temperature measuring point heat capacity C m (C m1, C m2 ) ( near the position to place the sample cell) , empty cell heat capacity C (C 1, C 2) , the sample heat capacity C s temperature rises, the heating rate is dT / dt = φ.
No. No. 1 cell c 1 , ( Th 1 −T m1 ) / R 1 = φ 1 (C m1 + C 1 + C s ) (2) Similarly, the second cell c 2, (T h2 over T m2) / R 2 = Under φ 2 (C m2 + C 2 ) ... (3) ideal conditions, T h1 = T h2 R 1 = R 2 = R (1) φ 1 = φ 2 = φ (1) C m1 = C m2 = C m C 1 = C 2 (4) Under this condition, from the equations (2) and (3), m2 over T m1) / R (1) = φ (1) · C s ... (5) ΔT (1) = T m2 over T m1 = R (1) · T (1) · C s ... (5') Here, the subscript (1) indicates the first measurement.
【０００８】 第２回目の測定。[0008] Second measurement.
【０００９】Ｎｏ．１のセルｃ1 に、熱容量が既知の標
準試料を入れ、Ｎｏ．２のセルは空とする。上と同じよ
うに、理想的条件下では、（２）、（３）、（５）式と
同様に、（６）（７）（８）式が成り立つ。標準試料の
熱容量をＣr とする。No. A standard sample having a known heat capacity was placed in the cell c 1 of No. 1; Cell 2 is empty. Similarly to the above, under ideal conditions, the equations (6), (7), and (8) hold as in the equations (2), (3), and (5). Let the heat capacity of the standard sample be Cr.
【００１０】 （Ｔh1ーＴm1）／Ｒ1 ＝φ1 （Ｃm1＋Ｃ1 ＋Ｃr ） …（６） （Ｔh2ーＴm2）／Ｒ2 ＝φ2 （Ｃm2＋Ｃ2 ） …（７） （Ｔm2ーＴm1）／Ｒ(2) ＝φ(2) ・Ｃr …（８） ΔＴ(2) ＝Ｔm2ーＴm1＝Ｒ(2) ・φ(2) ・Ｃr …（８´） ここで、添字の（２）は第２回目の測定を示す。[0010] (T h1 over T m1) / R 1 = φ 1 (C m1 + C 1 + C r) ... (6) (T h2 over T m2) / R 2 = φ 2 (C m2 + C 2) ... (7 (T m2 −T m1 ) / R (2) = φ (2) · C r (8) ΔT (2) = T m2 −T m1 = R (2) · φ (2) · C r ( 8 ') Here, the subscript (2) indicates the second measurement.
【００１１】 上記の２回の測定結果から、試料の熱
容量が求められる。From the results of the two measurements, the heat capacity of the sample is determined.
【００１２】（５´）と（８´）式より、 ΔＴ(1) ／ΔＴ(2) ・Ｒ(2) ／Ｒ(1) ＝φ(1) ／φ(2) ・Ｃs ／Ｃr …（９） ２回の測定で、次の理想的条件を仮定する。From the equations (5 ′) and (8 ′), ΔT (1) / ΔT (2) · R (2) / R (1) = φ (1) / φ (2) · C s / C r (9) The following ideal conditions are assumed in two measurements.
【００１３】 Ｒ(2) ＝Ｒ(1) φ(1) ＝φ(2) …（１０） したがって、（９）式は、 ΔＴ(1) ／ΔＴ(2) ＝Ｃs ／Ｃr …（１１） Ｃs ＝Ｃr ・ΔＴ(1) ／ΔＴ(2) …（１２） ΔＴ(1) 、ΔＴ(2) はいずれも測定できる数値であるか
ら、（１２）式により試料の熱容量Ｃs を求めることが
できる。R (2) = R (1) φ (1) = φ (2) (10) Therefore, the expression (9) is represented by ΔT (1) / ΔT (2) = C s / C r ( 11) C s = C r · ΔT (1) / ΔT (2) (12) Since both ΔT (1) and ΔT (2) are numerical values that can be measured, the heat capacity C s of the sample is obtained by the equation (12). Can be requested.
【００１４】（４）式のＲ1 ＝Ｒ2 の理想条件が満たさ
れない場合がある。この場合は、第３回目の測定を行
う。第３回目の測定は、Ｎｏ．１、Ｎｏ．２の両セルと
も空セルで行う。この測定の場合のＮｏ．１とＮｏ．２
の温度差をΔＴ(3) とすると、Ｒ1 ＝Ｒ2 でない場合に
も次式でＣs が求められる。The ideal condition of R 1 = R 2 in equation (4) may not be satisfied. In this case, the third measurement is performed. In the third measurement, No. 1, No. Both cells 2 are performed with empty cells. No. in this measurement. 1 and No. 2
Is given by ΔT (3) , C s can be obtained by the following equation even when R 1 = R 2 is not satisfied.
【００１５】 Ｃs ＝Ｃr ・（ΔＴ(1) −ΔＴ(3) ）／（ΔＴ(2) −ΔＴ(3) ） …（１２´） 第３回目の測定は、同一測定条件の場合には省略するこ
とができる。しかし、試料の比熱を求めるには、最低２
回の測定をしなければならない。C s = C r · (ΔT (1) −ΔT (3) ) / (ΔT (2) −ΔT (3) ) (12 ′) The third measurement is performed under the same measurement conditions. Can be omitted. However, to determine the specific heat of the sample, at least 2
You have to take the measurement several times.
【００１６】[0016]
【発明が解決しようとする課題】前述した従来の双子型
示差走査熱量計による比熱測定においては、理想的条件
として示した（４）式の中で、Ｔh1＝Ｔh2としたが、こ
れは、Ｎｏ．１とＮｏ．２の位置の温度分布が均一であ
ることを意味する。しかし、実際には、両者の間には、
多少の温度差が生じ、（５）（８）式に誤差を伴うとみ
なければならない。In the specific heat measurement by the conventional twin type differential scanning calorimeter described above, Th1 = Th2 in the equation (4) shown as an ideal condition. , No. 1 and No. This means that the temperature distribution at the position 2 is uniform. However, in practice,
It is necessary to consider that a slight temperature difference occurs and the equations (5) and (8) involve errors.
【００１７】特に、試料温度が高温度になれば、温度制
御の揺らぎと共にこの傾向が増大する。In particular, when the sample temperature becomes high, this tendency increases with the fluctuation of the temperature control.
【００１８】更に、（１０）式も実際には誤差を伴う。
試料の測定と標準試料の測定の２回の測定を全く同一の
条件とする（１０）式は理想上の仮定で、実際は等しく
なく、誤差を生ずる。Further, equation (10) actually involves an error.
Equation (10), in which the measurement of the sample and the measurement of the standard sample are performed in exactly the same condition, is an ideal assumption, which is not actually equal and causes an error.
【００１９】実際に上記熱量計を用いて比熱を測定する
と、室温付近で±５％、５００℃以上では、±８％のば
らつきを生ずる。特に１０００℃以上では±１０％以上
のばらつきを生ずる。When the specific heat is actually measured using the above calorimeter, a variation of ± 5% occurs near room temperature, and a variation of ± 8% occurs above 500 ° C. Particularly, at a temperature of 1000 ° C. or more, a variation of ± 10% or more occurs.
【００２０】したがって、室温から高温度の広い範囲に
おいて、示差走査熱量計を用いて精密な比熱を測定する
ためには、 ａ．熱量計の面内の温度分布の存在に対する対応策。Therefore, in order to accurately measure specific heat using a differential scanning calorimeter in a wide range from room temperature to high temperature, a. Countermeasures for the presence of temperature distribution in the plane of the calorimeter.
【００２１】ｂ．２回の測定ではなく、１回の測定で、
試料と標準試料の測定を可能にする方法。B. One measurement, not two measurements,
A method that allows measurement of samples and standard samples.
【００２２】の２つの問題点を解決しなければならな
い。The two problems must be solved.
【００２３】従来、前記ｂの問題解決の方法が提案され
た。Conventionally, a method for solving the above problem b has been proposed.
【００２４】それは、Ｂ．Ｗｕｎｄｅｒｌｉｃｈによる
トリプルセル方式の示差走査熱量計［Ｂ．Ｗｕｎｄｅｒ
ｌｉｃｈ著、Ｊ．Ｔｈｅｒｍａｌ Ａｎａｌ．，32，P.
1949-1955 （1987）］である。It is described in B. Wunderlich triple cell differential scanning calorimeter [B. Wunder
lich, J.L. Thermal Anal. , 32, P.
1949-1955 (1987)].
【００２５】図４はその示差走査熱量計の原理図を示
す。FIG. 4 shows the principle of the differential scanning calorimeter.
【００２６】同一面上の熱流束計の上に、３等配の位置
に基準試料、標準試料及び試料を配置して、基準試料ー
試料間の温度差と、基準試料と標準試料間の温度差をそ
れぞれ同時に測定すれば、１回の測定で済む。A reference sample, a standard sample, and a sample are arranged at three equally distributed positions on a heat flux meter on the same surface, and a temperature difference between the reference sample and the sample, and a temperature difference between the reference sample and the standard sample are measured. If the differences are measured simultaneously, only one measurement is required.
【００２７】この熱量計による測定方法について説明す
る。The measurement method using this calorimeter will be described.
【００２８】Ｎｏ．１のセルｃ1 は空セル（基準試料）
とし、Ｎｏ．２のセルｃ2 には試料を、Ｎｏ．３のセル
ｃ3 には標準試料を入れて、一定速度で加熱する。各セ
ルについて、上記（２）式と同様な式が成り立つ。No. 1 cell c 1 is an empty cell (reference sample)
No. Samples The second cell c 2, No. A standard sample is placed in the cell c3 of No. 3 and heated at a constant rate. For each cell, a formula similar to the above formula (2) holds.
【００２９】 （Ｔh1ーＴm1）／Ｒ1 ＝φ1 （Ｃm1＋Ｃ） …（１３） （Ｔh2ーＴm2）／Ｒ2 ＝φ2 （Ｃm2＋Ｃ＋Ｃs ） …（１４） （Ｔh3ーＴm3）／Ｒ3 ＝φ3 （Ｃm3＋Ｃ＋Ｃr ） …（１５） ここで、Ｔh1＝Ｔh2＝Ｔh3＝Ｔh Ｒ1 ＝Ｒ2 ＝Ｒ3
＝Ｒ φ1 ＝φ2 ＝φ3 ＝φ Ｃm1＝Ｃm2＝Ｃm3＝Ｃm と理想条件を仮定すると、（１４）式ー（１３）式及び
（１５）式ー（１３）式により Ｔm2ーＴm1＝Ｒ・φ・Ｃs ＝ΔＴ21 …（１６） Ｔm3ーＴm1＝Ｒ・φ・Ｃr ＝ΔＴ31 …（１７） （１６）（１７）式より ΔＴ21／ΔＴ31＝Ｃs ／Ｃr （１８） したがって、 Ｃs ＝Ｃr ・ΔＴ21／ΔＴ31 （１９） により、Ｎｏ．２とＮｏ．１の温度差及びＮｏ．３とＮ
ｏ．１の温度差を測定すれば、試料の熱容量を求めるこ
とができる。[0029] (T h1 over T m1) / R 1 = φ 1 (C m1 + C) ... (13) (T h2 over T m2) / R 2 = φ 2 (C m2 + C + C s) ... (14) (T h3 over T m3) / R 3 = φ 3 (C m3 + C + C r) ... (15) where, T h1 = T h2 = T h3 = T h R 1 = R 2 = R 3
= R φ 1 = φ 2 = φ 3 = φ C m1 = C m2 = C m3 = C m Assuming the ideal conditions of (14)-(13) and (15)-(13) T m2 −T m1 = R · φ · C s = ΔT 21 (16) T m3 −T m1 = R · φ · C r = ΔT 31 (17) (16) From the expressions (16) and (17), ΔT 21 / ΔT 31 = C s / C r (18) Therefore, C s = C r · ΔT 21 / ΔT 31 (19). 2 and No. No. 1 temperature difference and No. 1 3 and N
o. By measuring the temperature difference of 1, the heat capacity of the sample can be obtained.
【００３０】このトリプルセル方法により、ただ１回の
測定で試料の熱容量を求め得たが、上記のａ．の問題点
については未解決である。Ｔh1＝Ｔh2＝Ｔh3の仮定は、
試料周辺の温度の不均一がある場合には成り立たない。
この現象は、特に５００℃以上の高温度域では顕著とな
り、測定のばらつきが大きくなり、±３％以内の誤差範
囲の精密な比熱測定は不可能となっている。According to the triple cell method, the heat capacity of the sample was obtained by only one measurement. The problem of has not been resolved. Assumption of T h1 = T h2 = T h3 is,
This is not feasible when the temperature around the sample is uneven.
This phenomenon is particularly remarkable in a high temperature range of 500 ° C. or more, and the variation of the measurement becomes large, so that precise measurement of specific heat within an error range of ± 3% is impossible.
【００３１】このように、従来の技術は、５００℃〜６
００℃より高温度では、高精度で試料の比熱を測定する
ことができない。As described above, the conventional technology is used at 500 ° C. to 6 ° C.
At a temperature higher than 00 ° C., the specific heat of the sample cannot be measured with high accuracy.
【００３２】本発明は、上述した従来の問題点に鑑み、
試料周辺の温度が不均一である場合でも、高温度域にお
ける比熱を高精度に測定することができる比熱測定方法
及び示差走査熱量計を提供することを課題とする。The present invention has been made in view of the above-mentioned conventional problems,
It is an object of the present invention to provide a specific heat measurement method and a differential scanning calorimeter capable of measuring the specific heat in a high temperature range with high accuracy even when the temperature around the sample is not uniform.
【００３３】[0033]
【課題を解決するための手段】上記の課題を解決するた
めに、本発明の比熱測定方法は、請求項１に記載のよう
に、試料及び標準試料を配置する第１の熱流計板の下方
に、該試料及び標準試料とそれぞれ対称する位置に２個
の基準試料を配置する第２の熱流計板を設け、第１の熱
流計板の端部と第２の熱流計板の端部を互いに接触させ
た状態で熱源に熱的に接触させた構造を有する熱流束型
示差走査熱量計を用い、熱源を一定の温度変化速度で加
熱する過程において、第１の熱流計板に配置した試料と
第２の熱流計板に配置した基準試料の温度差及び第１の
熱流計板に配置した標準試料と第２の熱流計板に配置し
た基準試料の温度差を同時に測定し、これらの測定値と
標準試料の既知の比熱値とから試料の比熱の値を求める
ことを特徴とする。また、本発明の示差走査熱量計は、
請求項２に記載のように、双子型の熱流束型示差走査熱
量計であって、試料用セル及び標準試料用セルを配置し
た第１の熱流計板と、その下方に配設し前記試料用セル
及び標準試料用セルとそれぞれ対称する位置に基準試料
としての２個の空セルを配置した第２の熱流計板と、第
１の熱流計板の、試料用セル及び標準試料用セルにそれ
ぞれ対応する位置に取り付けられた２個の温度センサ
と、第２の熱流計板の、２個の空セルにそれぞれ対応す
る位置に取り付けられた２個の温度センサを具備し、前
記第１の熱流計板の端部と第２の熱流計板の端部を互い
に接触させた状態で熱源に熱的に接触させたことを特徴
とする。In order to solve the above-mentioned problems, a specific heat measuring method according to the present invention, as described in claim 1, has a structure in which a sample and a standard sample are arranged below a first heat flow meter plate. A second heat flow meter plate for arranging two reference samples at positions symmetrical to the sample and the standard sample respectively, and connecting an end of the first heat flow meter plate and an end of the second heat flow meter plate to each other. In the process of heating the heat source at a constant temperature change rate using a heat flux type differential scanning calorimeter having a structure in which the heat source is in thermal contact with the heat source in a state where the heat source is in contact with each other, the sample placed on the first heat flow meter plate The temperature difference between the reference sample placed on the second heat flow meter and the reference sample placed on the second heat flow meter and the reference sample placed on the second heat flow meter are measured simultaneously. The value of the specific heat of the sample is determined from the value and the known specific heat value of the standard sample. Further, the differential scanning calorimeter of the present invention,
3. A twin heat flux type differential scanning calorimeter according to claim 2, wherein the first heat flow meter plate in which a sample cell and a standard sample cell are disposed, and the sample is disposed below the first heat flow plate. The second heat flow meter plate in which two empty cells as reference samples are arranged at positions symmetrical to the cell for measurement and the cell for standard sample, respectively, the sample cell and the standard sample cell of the first heat flow meter plate The first heat flow meter plate includes two temperature sensors mounted at corresponding positions, and two temperature sensors mounted at positions respectively corresponding to the two empty cells of the second heat flow meter plate, The end of the heat flow meter plate and the end of the second heat flow meter plate are brought into thermal contact with the heat source in a state where they are in contact with each other.
【００３４】前記熱流束型示差走査熱量計を用いた比熱
測定方法を、図１を参照して説明すると、先ず、試料を
入れたＮｏ．１のセルについて、上述の（２）式と同様
の式が得られる。A specific heat measuring method using the heat flux type differential scanning calorimeter will be described with reference to FIG. An expression similar to the above expression (2) is obtained for one cell.
【００３５】 （Ｔh1ーＴm1）／Ｒ1 ＝φ1 （Ｃm1＋Ｃ1 ＋Ｃs ） …（２０） 符号は、従来の技術の項で説明したのに対応する意味を
有する。[0035] (T h1 over T m1) / R 1 = φ 1 (C m1 + C 1 + C s) ... (20) code has a corresponding meaning to as described in the background section.
【００３６】Ｎｏ．３のセルについても同様に、 （Ｔh3ーＴm3）／Ｒ3 ＝φ3 （Ｃm3＋Ｃ3 ） …（２１） 今、熱量計の面内に温度の不均一があったとしても、Ｔ
h1とＴh3とは同一位置にあり、熱的に接触しているか
ら、Ｔh1＝Ｔh3と考えてよい。No. Similarly, the third cell, (T h3 over T m3) / R 3 = φ 3 (C m3 + C 3) ... (21) Now, even if nonuniformity of temperature in the plane of the calorimeter, T
Since h1 and Th3 are at the same position and are in thermal contact, it may be considered that Th1 = Th3 .
【００３７】上記の（４）式と同様に次の理想的条件を
仮定する。The following ideal conditions are assumed in the same manner as in the above equation (4).
【００３８】 Ｒ1 ＝Ｒ3 ＝Ｒ13 φ1 ＝φ3 ＝φ13 Ｃm1＝Ｃm3＝Ｃm13 Ｃ1 ＝Ｃ3 ＝Ｃ13 …（２２） （２０）、（２１）、（２２）式より （Ｔm3ーＴm1）／Ｒ13＝φ13・Ｃs …（２３） Ｎｏ．２とＮｏ．４のセルについても、同様にＲ2 ＝Ｒ
4 ＝Ｒ24 φ2 ＝φ4 ＝φ24 Ｃm2＝Ｃm4＝Ｃm24 Ｃ2 ＝Ｃ4 ＝Ｃ24 と仮定して （Ｔm4ーＴm2）／Ｒ24＝φ24・Ｃr …（２４） 理想的条件として、 Ｒ13＝Ｒ24 φ13＝φ24 …（２５） とすると、（２３）（２４）（２５）式より （Ｔm3ーＴm1）／（Ｔm4ーＴm2）＝Ｃs ／Ｃr …（２６） または、 Ｃｓ＝Ｃｒ・（Ｔm3ーＴm1）／（Ｔm4ーＴm2） …（２７） 測定により、（Ｔm3ーＴm1）／（Ｔm4ーＴm2）が求めら
れるから、ただ１回の測定だけで、試料の熱容量を決定
することができる。R 1 = R 3 = R 13 φ 1 = φ 3 = φ 13 C m1 = C m3 = C m13 C 1 = C 3 = C 13 (22) (20), (21), (22) from the formula (T m3 over T m1) / R 13 = φ 13 · C s ... (23) No. 2 and No. Similarly, for the cell No. 4, R 2 = R
4 = R 24 φ 2 = φ 4 = φ 24 C m2 = C m4 = C m24 C 2 = C 4 = C 24 assuming (T m4 over T m2) / R 24 = φ 24 · C r ... ( 24) As an ideal condition, if R 13 = R 24 φ 13 = φ 24 (25), then (T m3 −T m1 ) / (T m4 −T m2 ) from equations (23), (24) and (25). = C s / C r (26) or Cs = Cr · (T m3 −T m1 ) / (T m4 −T m2 ) (27) According to the measurement, (T m3 −T m1 ) / (T m4 − Since T m2 ) is determined, the heat capacity of the sample can be determined with only one measurement.
【００３９】また、この方法では、熱量計の面内に温度
の不均一があっても、Ｔh1とＴh3は等しいから、結果に
は影響を与えず、高精度の比熱を測定することができ
る。Further, according to this method, even if the temperature of the calorimeter is non-uniform, Th1 and Th3 are equal, so that the result is not affected and the specific heat can be measured with high accuracy. it can.
【００４０】以上の測定方法では、Ｒ1 、Ｒ2 、Ｒ3 、
Ｒ4 が等しいと仮定したが、等しくない場合でも比熱を
測定することができる。In the above measuring method, R 1 , R 2 , R 3 ,
Although it was assumed that R 4 are equal, it is possible to measure the specific heat, even if not equal.
【００４１】この場合には、３回の測定が必要である。In this case, three measurements are required.
【００４２】第１回目の測定では、すべてのセルを空セ
ルで測定する。（２１）式と同様な式の４式を得る。In the first measurement, all cells are measured with empty cells. The following four equations, which are similar to the equation (21), are obtained.
【００４３】 （Ｔh1ーＴm1）／Ｒ1 ＝φ1 （Ｃm ＋Ｃ） …（２８） （Ｔh3ーＴm3）／Ｒ3 ＝φ3 （Ｃm ＋Ｃ） …（２９） （Ｔh2ーＴm2）／Ｒ2 ＝φ2 （Ｃm ＋Ｃ） …（３０） （Ｔh4ーＴm4）／Ｒ4 ＝φ4 （Ｃm ＋Ｃ） …（３１） ここで、Ｔh1＝Ｔh3 Ｔh2＝Ｔh4であるから、（２
８）（２９）式より（２８）式−（２９）式 Ｔm3−Ｔm1＝Ｒ1 φ1 （Ｃm ＋Ｃ）−Ｒ3 φ3 （Ｃm ＋
Ｃ） φ1 ＝φ3 ＝φと仮定する。[0043] (T h1 over T m1) / R 1 = φ 1 (C m + C) ... (28) (T h3 over T m3) / R 3 = φ 3 (C m + C) ... (29) (T h2 −T m2 ) / R 2 = φ 2 (C m + C) (30) ( Th 4 −T m4 ) / R 4 = φ 4 (C m + C) (31) where Th 1 = Th 3 T Since h2 = Th4 , (2
8) (29) from equation (28) - (29) T m3 -T m1 = R 1 φ 1 (C m + C) -R 3 φ 3 (C m +
C) Assume φ 1 = φ 3 = φ.
【００４４】Ｔm3−Ｔm1＝（Ｒ1 −Ｒ3 ）φ（Ｃm ＋
Ｃ）＝（Ｒ1 −Ｒ3 ）／Ｒ1 ・Ｒ1 ・φ（Ｃm ＋Ｃ） （２８）式より Ｔm3−Ｔm1＝（Ｒ1 −Ｒ3 ）／Ｒ1 ・（Ｔh1ーＴm1） Ｔm3ーＴm1＝（１ーＲ3 ／Ｒ1 ）（Ｔh1ーＴm1）＝ΔＴ31(1) …（３２） ここで、ΔＴ31(1) は、（Ｔm3−Ｔm1）の第１回目の温
度差測定値を示す。T m3 −T m1 = (R 1 −R 3 ) φ (C m +
C) = (R 1 -R 3 ) / R 1 · R 1 · φ (C m + C) From equation (28), T m3 -T m1 = (R 1 -R 3 ) / R 1 · ( Th 1 -T m1) T m3 over T m1 = (1 over R 3 / R 1) (T h1 over T m1) = ΔT 31 (1 ) ... (32) where, ΔT 31 (1) is, (T m3 -T m1 3) shows the first measured value of the temperature difference.
【００４５】（３０）（３１）式より Ｔm4ーＴm2＝（１ーＲ4 ／Ｒ2 ）（Ｔh2ーＴm2）＝ΔＴ42(1) …（３３） 第２回目の測定では、Ｎｏ．１のセルに試料を、Ｎｏ．
２のセルに比熱が既知の標準試料を、Ｎｏ．３のセルと
Ｎｏ．４のセルは空セルとして測定すると、（２８）〜
（３１）式と同様に、（３４）〜（３７）式が得られ
る。From equations (30) and (31), T m4 −T m2 = (1−R 4 / R 2 ) ( Th 2 −T m2 ) = ΔT 42 (1) (33) In the second measurement, No. Sample No. 1 was placed in the cell No. 1;
A standard sample having a known specific heat was placed in the cell of No. 2; No. 3 cell and No. 3 When the cell of No. 4 is measured as an empty cell, (28)-
Expressions (34) to (37) are obtained in the same manner as Expression (31).
【００４６】 （Ｔh1ーＴm1）／Ｒ1 ＝φ1 （Ｃm ＋Ｃ＋Ｃs ） …（３４） （Ｔh3ーＴm3）／Ｒ3 ＝φ3 （Ｃm ＋Ｃ） …（３５） （Ｔh2ーＴm2）／Ｒ2 ＝φ2 （Ｃm ＋Ｃ＋Ｃr ） …（３６） （Ｔh4ーＴm4）／Ｒ4 ＝φ4 （Ｃm ＋Ｃ） …（３７） ここで、Ｔh1＝Ｔh3 Ｔh2＝Ｔm4 であるから、（３
４）（３５）式より Ｔm3ーＴm1＝（１ーＲ3 ／Ｒ1 ）（Ｔh1ーＴm1）＋Ｒ3 φ1 Ｃs …（３８） 同様に、（３６）（３７）式より Ｔm4ーＴm2＝ΔＴ42(2) ＝（１ーＲ4 ／Ｒ2 ）（Ｔh2ーＴm2）＋Ｒ4 φ2 Ｃr …（３９） （３２）（３８）式より Ｔm3ーＴm1＝ΔＴ31(2) ＝ΔＴ31(1) ＋Ｒ3 φ1 Ｃs …（４０） （３３）（３９）式より Ｔm4ーＴm2＝ΔＴ42(2) ＝ΔＴ42(1) ＋Ｒ4 φ2 Ｃr …（４１） （４０）（４１）式より Ｃs ＝Ｃr ・( ΔＴ31(2) ーΔＴ31(1) ）／（ΔＴ42(2) ーΔＴ42(1) ）・ Ｒ4 ／Ｒ3 …（４２） Ｒ4 ／Ｒ3 は、Ｎｏ．１のセルとＮｏ．２のセルの両方
に標準試料を入れた測定より求めることができる。ΔＴ
31とΔＴ42の第３回目の測定値をΔＴ31(3) 、ΔＴ
42(3) とすると、 Ｒ4 ／Ｒ3 ＝（ΔＴ42(3) −ΔＴ42(1) ）／（ΔＴ31(3) −ΔＴ31(1) ） …（４２´） したがって、 Ｃs ＝Ｃr ・（ΔＴ31(2) ーΔＴ31(1) ）／（ΔＴ42(2) ーΔＴ42(1) ） ・（ΔＴ42(3) −ΔＴ42(1) ）／（ΔＴ31(3) −ΔＴ31(1) ） …（４２”） になる。[0046] (T h1 over T m1) / R 1 = φ 1 (C m + C + C s) ... (34) (T h3 over T m3) / R 3 = φ 3 (C m + C) ... (35) (T h2 over T m2) / R 2 = φ 2 (C m + C + C r) ... (36) (T h4 over T m4) / R 4 = φ 4 (C m + C) ... (37) where, T h1 = T because it is h3 T h2 = T m4, ( 3
4) (35) than the T m3 over T m1 = (1 over R 3 / R 1) (T h1 over T m1) + R 3 φ 1 C s ... (38) Similarly, from (36) (37) Equation T m4 −T m2 = ΔT 42 (2) = (1−R 4 / R 2 ) ( Th 2 −T m2 ) + R 4 φ 2 Cr (39) From the equations (32) and (38), T m3 −T m1 = ΔT 31 (2) = ΔT 31 (1) + R 3 φ 1 C s ... (40) (33) (39) T m4 over from the equation T m2 = ΔT 42 (2) = ΔT 42 (1) + R 4 φ 2 C r ... (41) (40) From equation (41), C s = C r · (ΔT 31 (2) -ΔT 31 (1) ) / (ΔT 42 (2) -ΔT 42 (1) ) ・R 4 / R 3 (42) R 4 / R 3 is the No. No. 1 cell and No. 1 It can be determined from a measurement in which a standard sample is put in both cells. ΔT
The third measured values of 31 and ΔT 42 are ΔT 31 (3) , ΔT
When 42 (3), R 4 / R 3 = (ΔT 42 (3) -ΔT 42 (1)) / (ΔT 31 (3) -ΔT 31 (1)) ... (42') Thus, C s = C r · (ΔT 31 (2 ) over ΔT 31 (1)) / ( ΔT 42 (2) over ΔT 42 (1)) · ( ΔT 42 (3) -ΔT 42 (1)) / (ΔT 31 (3 ) −ΔT 31 (1) ) (42 ″).
【００４７】この場合にも、熱量計の面内に温度の不均
一があってもＴh1とＴh3は等しいから、結果には影響を
与えず、高精度の比熱を測定することができる。Also in this case, even if the temperature of the calorimeter is non-uniform, Th1 and Th3 are equal. Therefore, the result is not affected, and the specific heat can be measured with high accuracy.
【００４８】[0048]
【発明の実施の形態】本発明の実施の形態を図面を参照
して説明する。Embodiments of the present invention will be described with reference to the drawings.
【００４９】図１は本発明実施の双子型の熱流束型示差
走査熱量計１例の概略線図を示す。FIG. 1 is a schematic diagram showing an example of a twin heat flux type differential scanning calorimeter according to the present invention.
【００５０】同図において、１及び２は、いずれも熱流
計板（実際は感温板と呼ばれる）である第１及び第２の
金属薄板、３は、第１の金属薄板１上のＮｏ．１の位置
に置かれた試料（比熱が未知）を入れるセル、４は、第
１の金属薄板１上のＮｏ．２の位置に置かれた標準試料
（比熱が既知）を入れるセルであり、５及び６は、いず
れも第２の金属薄板２上のＮｏ．３及びＮｏ．４に置か
れた空セルである。In the drawing, reference numerals 1 and 2 denote first and second thin metal plates, both of which are heat flow meter plates (actually called temperature sensing plates), and reference numeral 3 denotes No. 1 on the first thin metal plate 1. The cell 4 in which the sample (specific heat is unknown) placed in the position of No. 1 is placed. 2 is a cell in which a standard sample (specific heat is known) placed in the position of No. 2 is provided. 3 and No. 3 4 is an empty cell.
【００５１】第１の金属薄板１上のセル３（Ｎｏ．１の
位置）とセル４（Ｎｏ．２の位置）の下方の対称位置
に、空セル５（Ｎｏ．３の位置）と空セル６（Ｎｏ．４
の位置）を第２の金属薄板２上に配置し、第１及び第２
の金属薄板１及び２の両端を均熱容器７に熱的及び電気
的に良好に接触させた構造になっている。第１及び第２
の金属薄板１及び２上のＮｏ．１、Ｎｏ．２、Ｎｏ．
３、及びＮｏ．４の位置は、いずれも均熱容器７との間
の熱抵抗が同じになる位置にある。８は試料温度用熱電
対、９は標準試料温度用熱電対、１０及び１１は、いず
れも空セル温度用熱電対で、それぞれ第１及び第２の金
属薄板１及び２に取り付けられている。An empty cell 5 (the position of No. 3) and an empty cell 5 are located symmetrically below the cell 3 (the position of No. 1) and the cell 4 (the position of No. 2) on the first metal sheet 1. 6 (No. 4)
Is positioned on the second metal sheet 2 and the first and second
The structure is such that both ends of the metal thin plates 1 and 2 are brought into good thermal and electrical contact with the heat equalizing vessel 7. First and second
No. on metal sheets 1 and 2 1, No. 2, No.
3, and No. 3 The position 4 is a position where the thermal resistance between the heat equalizing container 7 and the heat equalizing container 7 becomes the same. 8 is a thermocouple for sample temperature, 9 is a thermocouple for standard sample temperature, and 10 and 11 are thermocouples for empty cell temperature, which are attached to the first and second thin metal plates 1 and 2, respectively.
【００５２】図面では、均熱容器７の外周に設ける電気
炉や、試料温度用熱電対８、標準試料温度用熱電対９及
び空セル温度用熱電対１０、１１にそれぞれ接続される
直流増幅器等や、前記試料の比熱を算出するマイクロコ
ンピュータ、表示器等は、いずれも周知のものであるの
で省略した。In the drawing, an electric furnace provided on the outer periphery of the heat equalizing vessel 7, a DC amplifier connected to the sample temperature thermocouple 8, the standard sample temperature thermocouple 9, and the empty cell temperature thermocouples 10 and 11, etc. Also, a microcomputer for calculating the specific heat of the sample, a display device, and the like are well known and are omitted.
【００５３】図２は、前記熱流束計の金属薄板の他例を
図２に示す。FIG. 2 shows another example of the thin metal plate of the heat flux meter.
【００５４】同図において、金属薄板１（２）は、セル
３、４（５，６）を載置する部分がその周囲に明けられ
た孔１２により形成されたブリッジ１３を介して金属薄
板端部に接続されており、この構成によると、熱抵抗Ｒ
が大となり、同じ熱流束に対して温度差を大きくするこ
とができ、換言すると、熱流計板としての感度が向上す
る。In the figure, the metal sheet 1 (2) is connected to the ends of the metal sheet via bridges 13 formed by holes 12 formed around the cells 3, 4 (5, 6). Section, and according to this configuration, the thermal resistance R
And the temperature difference can be increased for the same heat flux, in other words, the sensitivity as a heat flow meter plate is improved.
【００５５】前記の双子型の熱流束型示差走査熱量計を
用いて試料の比熱は次の方法により測定する。The specific heat of the sample is measured by the following method using the twin-type heat flux type differential scanning calorimeter.
【００５６】空セル温度用熱電対１０の出力と試料温度
用熱電対８の出力との差値及び空セル温度用熱電対１１
の出力と標準試料温度用熱電対９の出力との差値を、マ
イクロコンピュータに入力し、コンピュータによりこれ
らの差値及び標準試料の比熱値を前記（２７）式に代入
して試料の比熱を算出する。The difference between the output of the thermocouple for empty cell temperature 10 and the output of the thermocouple for sample temperature 8 and the thermocouple for empty cell temperature 11
And the difference between the output of the standard sample temperature thermocouple 9 and the output of the standard sample temperature thermocouple 9 are input to a microcomputer. calculate.
【００５７】前記の比熱測定方法では、Ｎｏ．１、Ｎ
ｏ．２、Ｎｏ．３、及びＮｏ．４の位置は、いずれも均
熱容器７との間の熱抵抗が同じになる位置に設定された
が、熱抵抗が相違する位置に設定してもよく、その場合
には、Ｎｏ．１のセルに試料を、Ｎｏ．２のセルに比熱
が既知の標準試料を、Ｎｏ．３のセル及びＮｏ．４のセ
ルを空セルとした場合と、Ｎｏ．１、Ｎｏ．２、Ｎｏ．
３、及びＮｏ．４のセルのすべてを空セルにした場合
の、それぞれの空セル温度用熱電対１０の出力と試料温
度用熱電対８の出力との差値と、空セル温度用熱電対１
１の出力と標準試料温度用熱電対９の出力との差値を求
めると共に、Ｎｏ．１とＮｏ．２の両方のセルに標準試
料を入れ、前記（３６）式よりＮｏ．３及びＮｏ．４の
位置と均熱容器７間の熱抵抗Ｒ3 、Ｒ4 を求め、以上の
差値、Ｒ4 ／Ｒ3 及び標準試料の比熱値を前記（４２）
式より代入することにより試料の比熱を算出する。In the above specific heat measurement method, 1, N
o. 2, No. 3, and No. 3 The position of No. 4 was set at a position where the thermal resistance between the heat equalizing container 7 was the same, but the position of the thermal resistance may be different. Sample No. 1 was placed in the cell No. 1; A standard sample having a known specific heat was placed in the cell of No. 2; 3 and No. 3 cell. No. 4 cell is an empty cell; 1, No. 2, No.
3, and No. 3 In the case where all of the cells 4 are empty cells, the difference between the output of the thermocouple 10 for the empty cell temperature and the output of the thermocouple 8 for the sample temperature, and the thermocouple 1 for the empty cell temperature
1 and the output of the standard sample temperature thermocouple 9, and 1 and No. The reference sample was placed in both cells of No. 2 and No. 2 was obtained from the formula (36). 3 and No. 3 The thermal resistances R 3 and R 4 between the position 4 and the heat equalizing vessel 7 were determined, and the above-mentioned difference value, R 4 / R 3 and the specific heat value of the standard sample were determined in the above (42).
The specific heat of the sample is calculated by substituting from the equation.
【００５８】以上の３回の測定は、毎回行う必要はな
い。同一の試料セルを用いて同一測定条件（例えば、加
熱速度、雰囲気、測定温度範囲など）の下で測定すれ
ば、すでにΔＴ31(1) 、ΔＴ42(1) 、ΔＴ31(3) 、ΔＴ
42(3) は求められているので、ただ１回の測定のみで、
ΔＴ31(2) 、ΔＴ42(2) を求めれば、試料の比熱を求め
ることができる。The above three measurements need not be performed every time. If measurement is performed using the same sample cell under the same measurement conditions (for example, heating rate, atmosphere, measurement temperature range, etc.), ΔT 31 (1) , ΔT 42 (1) , ΔT 31 (3) , ΔT
Since 42 (3) is required, only one measurement is required.
By determining ΔT 31 (2) and ΔT 42 (2) , the specific heat of the sample can be determined.
【００５９】尚、本発明の双子型示差走査熱量計は、単
なる熱分析として用いる場合には、２つの試料を同時に
同一条件で測定できるから、試料の熱的同定、比較など
に有効に利用できる。When the twin-type differential scanning calorimeter of the present invention is used for simple thermal analysis, two samples can be measured simultaneously under the same conditions, and therefore can be effectively used for thermal identification and comparison of the samples. .
【００６０】[0060]
【発明の効果】本発明は、試料周辺の温度が不均一であ
る場合でも、高温度域における比熱を高精度に測定する
ことができる。また、従来の測定方法と比較して測定回
数を少なく且つ高温度域における比熱を高精度に測定す
ることもできる。According to the present invention, the specific heat in a high temperature range can be measured with high accuracy even when the temperature around the sample is not uniform. In addition, the number of measurements can be reduced as compared with the conventional measurement method, and the specific heat in a high temperature range can be measured with high accuracy.
【図１】（Ａ）及び（Ｂ）は、本発明実施の示差走査熱
量計の概略構成を示す切断正面図及び切断平面図。FIGS. 1A and 1B are a cut front view and a cut plan view showing a schematic configuration of a differential scanning calorimeter according to an embodiment of the present invention.
【図２】（Ａ）及び（Ｂ）は、本発明実施の示差走査熱
量計に用いる熱流計板の他例の平面図及び断面図。FIGS. 2A and 2B are a plan view and a cross-sectional view of another example of a heat flow meter plate used for the differential scanning calorimeter according to the present invention.
【図３】（Ａ）及び（Ｂ）は、従来の示差走査熱量計の
概略構成を示す切断正面図及び切断平面図。FIGS. 3A and 3B are a cut front view and a cut plan view showing a schematic configuration of a conventional differential scanning calorimeter.
【図４】 従来の示差走査熱量計の他例の原理説明図。FIG. 4 is a diagram illustrating the principle of another example of a conventional differential scanning calorimeter.
１…第１の熱流計板 ２…第２の熱流計板 ３〜６…セル ７…均熱容器 ８…試料温度用熱電対 ９…標準試料温度用熱電
対 １０、１１…空セル用熱電対DESCRIPTION OF SYMBOLS 1 ... 1st heat flow meter plate 2 ... 2nd heat flow meter plate 3-6 ... Cell 7 ... Soaking container 8 ... Thermocouple for sample temperature 9 ... Thermocouple for standard sample temperature 10, 11 ... Thermocouple for empty cell
Claims (2)
計板と、その下方に、該試料及び標準試料とそれぞれ対
称する位置に２個の基準試料を配置する第２の熱流計板
を設け、第１の熱流計板の端部と第２の熱流計板の端部
を互いに接触させた状態で熱源に熱的に接触させた構造
を有する熱流束型示差走査熱量計を用い、熱源を一定の
温度変化速度で加熱する過程において、第１の熱流計板
に配置した試料と第２の熱流計板に配置した基準試料の
温度差及び第１の熱流計板に配置した標準試料と第２の
熱流計板に配置した基準試料の温度差を同時に測定し、
これらの測定値と標準試料の既知の比熱値とから試料の
比熱の値を求めることを特徴とする比熱測定方法。1. A first heat flow meter plate on which a sample and a standard sample are disposed, and a second heat flow meter plate on which two reference samples are disposed at positions symmetrical to the sample and the standard sample, respectively. A heat flux type differential scanning calorimeter having a structure in which an end of the first heat flow meter plate and an end of the second heat flow meter plate are in contact with each other and in thermal contact with the heat source; In the process of heating at a constant temperature change rate, the temperature difference between the sample placed on the first heat flow meter plate and the reference sample placed on the second heat flow meter plate and the standard sample placed on the first heat flow meter plate Simultaneously measure the temperature difference of the reference sample placed on the second heat flow meter plate,
A specific heat measurement method, wherein a value of a specific heat of the sample is obtained from the measured value and a known specific heat value of the standard sample.
て、試料用セル及び標準試料用セルを配置した第１の熱
流計板と、その下方に配設し前記試料用セル及び標準試
料用セルとそれぞれ対称する位置に基準試料としての２
個の空セルを配置した第２の熱流計板と、第１の熱流計
板の、試料用セル及び標準試料用セルにそれぞれ対応す
る位置に取り付けられた２個の温度センサと、第２の熱
流計板の、２個の空セルにそれぞれ対応する位置に取り
付けられた２個の温度センサを具備し、前記第１の熱流
計板の端部と第２の熱流計板の端部を互いに接触させた
状態で熱源に熱的に接触させたことを特徴とする示差走
査熱量計。2. A twin type heat flux type differential scanning calorimeter, comprising: a first heat flow meter plate on which a sample cell and a standard sample cell are arranged; A reference sample is placed at a position symmetrical with the sample cell.
A second heat flow meter plate on which the empty cells are arranged; two temperature sensors mounted on the first heat flow meter plate at positions respectively corresponding to the sample cell and the standard sample cell; and The heat flow meter includes two temperature sensors mounted at positions corresponding to the two empty cells, respectively, wherein an end of the first heat flow meter and an end of the second heat flow meter are connected to each other. A differential scanning calorimeter characterized by being brought into thermal contact with a heat source in the contacted state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00419298A JP3953170B2 (en) | 1998-01-12 | 1998-01-12 | Specific heat measurement method and differential scanning calorimeter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00419298A JP3953170B2 (en) | 1998-01-12 | 1998-01-12 | Specific heat measurement method and differential scanning calorimeter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11201923A true JPH11201923A (en) | 1999-07-30 |
| JP3953170B2 JP3953170B2 (en) | 2007-08-08 |
Family
ID=11577844
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00419298A Expired - Fee Related JP3953170B2 (en) | 1998-01-12 | 1998-01-12 | Specific heat measurement method and differential scanning calorimeter |
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| Country | Link |
|---|---|
| JP (1) | JP3953170B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008157653A (en) * | 2006-12-21 | 2008-07-10 | Sii Nanotechnology Inc | Differential scanning calorimeter |
| KR101070998B1 (en) | 2008-12-12 | 2011-10-07 | 서울대학교산학협력단 | Heat capacity measurement device at high temperature |
| CN103323487A (en) * | 2013-06-07 | 2013-09-25 | 山东省计算中心 | Wall body local region volumetric specific heat capacity determination system and method |
| CN103940847A (en) * | 2014-04-15 | 2014-07-23 | 江苏大学 | Anisotropy film heat conductivity testing method and device based on heat flux sensors |
| CN110736764A (en) * | 2019-10-16 | 2020-01-31 | 杭州仰仪科技有限公司 | lithium battery specific heat capacity measuring method and device based on differential adiabatic tracing |
| RU2716472C1 (en) * | 2019-07-29 | 2020-03-11 | Российская Федерация, от имени которой выступает Федеральное агентство по техническому регулированию и метрологии (Росстандарт) | Method of measuring specific heat capacity of materials |
| CN117451217A (en) * | 2023-12-25 | 2024-01-26 | 中国空气动力研究与发展中心计算空气动力研究所 | Aerospace heat flow sensor and heat flow correction method based on double temperature difference compensation |
-
1998
- 1998-01-12 JP JP00419298A patent/JP3953170B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008157653A (en) * | 2006-12-21 | 2008-07-10 | Sii Nanotechnology Inc | Differential scanning calorimeter |
| KR101070998B1 (en) | 2008-12-12 | 2011-10-07 | 서울대학교산학협력단 | Heat capacity measurement device at high temperature |
| CN103323487A (en) * | 2013-06-07 | 2013-09-25 | 山东省计算中心 | Wall body local region volumetric specific heat capacity determination system and method |
| CN103940847A (en) * | 2014-04-15 | 2014-07-23 | 江苏大学 | Anisotropy film heat conductivity testing method and device based on heat flux sensors |
| RU2716472C1 (en) * | 2019-07-29 | 2020-03-11 | Российская Федерация, от имени которой выступает Федеральное агентство по техническому регулированию и метрологии (Росстандарт) | Method of measuring specific heat capacity of materials |
| CN110736764A (en) * | 2019-10-16 | 2020-01-31 | 杭州仰仪科技有限公司 | lithium battery specific heat capacity measuring method and device based on differential adiabatic tracing |
| CN110736764B (en) * | 2019-10-16 | 2022-05-17 | 杭州仰仪科技有限公司 | Lithium battery specific heat capacity measuring method and device based on differential adiabatic tracing |
| CN117451217A (en) * | 2023-12-25 | 2024-01-26 | 中国空气动力研究与发展中心计算空气动力研究所 | Aerospace heat flow sensor and heat flow correction method based on double temperature difference compensation |
| CN117451217B (en) * | 2023-12-25 | 2024-03-12 | 中国空气动力研究与发展中心计算空气动力研究所 | Aerospace heat flow sensor and heat flow correction method based on double temperature difference compensation |
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| Publication number | Publication date |
|---|---|
| JP3953170B2 (en) | 2007-08-08 |
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