JP2020139834A - Thermoelectric property evaluation unit, thermoelectric property evaluation device, and thermoelectric property evaluation method - Google Patents

Thermoelectric property evaluation unit, thermoelectric property evaluation device, and thermoelectric property evaluation method Download PDF

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JP2020139834A
JP2020139834A JP2019035443A JP2019035443A JP2020139834A JP 2020139834 A JP2020139834 A JP 2020139834A JP 2019035443 A JP2019035443 A JP 2019035443A JP 2019035443 A JP2019035443 A JP 2019035443A JP 2020139834 A JP2020139834 A JP 2020139834A
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JP7323108B2 (en
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小川　清
Kiyoshi Ogawa
清 小川
崇宏 梶間
Takahiro Kajima
崇宏 梶間
良三 平松
Ryozo Hiramatsu
良三 平松
方星 長野
Hosei Nagano
方星 長野
匠 山崎
Takumi Yamazaki
匠 山崎
申　ウソク
Usoku Shin
申　　ウソク
彰宏 鶴田
Akihiro Tsuruta
彰宏 鶴田
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OZAWA KAGAKU KK
National Institute of Advanced Industrial Science and Technology AIST
Tokai National Higher Education and Research System NUC
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OZAWA KAGAKU KK
National Institute of Advanced Industrial Science and Technology AIST
Tokai National Higher Education and Research System NUC
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Abstract

To provide a thermoelectric property evaluation unit, a thermoelectric property evaluation device, and a thermoelectric property evaluation method, by which thermoelectric properties can be evaluated in the same measurement direction (heat flow direction) using the same evaluation sample, having a simple configuration, and capable of evaluating the thermoelectric properties in a short time with high accuracy.SOLUTION: An evaluation sample M is placed on a sample holder 30 having a heater 32, and four measurement probes 10 are brought into contact with the evaluation sample M at an appropriate pressure by using a contact pressure adjustment member 60. Thermoelectric properties including electrical resistivity, Seebeck coefficient, and thermal diffusivity in the same measurement direction (heat flow direction) in the same evaluation sample are evaluated in a short time by using a thermoelectric property evaluation device 2.SELECTED DRAWING: Figure 1

Description

本発明は、熱電材料の電気抵抗率、ゼーベック係数及び熱伝導率を測定する熱電特性評価ユニット、熱電特性評価装置及び熱電特性評価方法に関する。 The present invention relates to a thermoelectric characterization unit for measuring electrical resistivity, Seebeck coefficient and thermal conductivity of a thermoelectric material, a thermoelectric characterization device and a thermoelectric characterization method.

熱を電気に変える熱電変換材料は物質の両端に温度差を生じさせることで電圧が生じるゼーベック効果を利用している。熱を電力に直接変換できる「熱電変換」は、タービンのような可動部がなく、二酸化炭素などの排出もない環境にやさしい発電技術のひとつとして注目されている。 Thermoelectric conversion materials that convert heat into electricity utilize the Seebeck effect, which creates a voltage by creating a temperature difference between both ends of a substance. "Thermoelectric conversion," which can directly convert heat into electric power, is attracting attention as one of the environment-friendly power generation technologies that does not have moving parts like turbines and does not emit carbon dioxide.

熱電材料の性能は、一般的に性能指数Z =α2/ρκで定義される。ここで、αはゼーベック係数、ρは電気抵抗率、κは熱伝導率である。性能指数Zが大きな値ほど優れた熱電材料（発電性能が高い）であるが、性能指数Zはまた温度の関数であり、ある温度で最大値をとる。熱電性能や抵抗率、熱伝導率の微妙な調整を行って、材料を最適化する実験が多く試みられている。 The performance of thermoelectric materials is generally defined by the figure of merit Z = α2 / ρκ. Here, α is the Seebeck coefficient, ρ is the electrical resistivity, and κ is the thermal conductivity. The larger the figure of merit Z, the better the thermoelectric material (higher power generation performance), but the figure of merit Z is also a function of temperature and takes the maximum value at a certain temperature. Many experiments have been attempted to optimize materials by making fine adjustments to thermoelectric performance, resistivity, and thermal conductivity.

ゼーベック係数αや熱伝導率λは、熱電性能指数を決定する重要な因子である。すなわち、熱電材料の性能評価では、ある温度において、これらの物性値を定量的に決定する必要があり、一般的には、熱電能に関しては定常２端子法によって決定する。このような熱電材料である試料の性能評価は、当該試料上の２点に高精度に位置決めして、当該２点の電圧と温度を計測する必要がある。 The Seebeck coefficient α and the thermal conductivity λ are important factors that determine the thermoelectric figure of merit. That is, in the performance evaluation of thermoelectric materials, it is necessary to quantitatively determine these physical property values at a certain temperature, and in general, the thermoelectric power is determined by the stationary two-terminal method. In order to evaluate the performance of a sample such as a thermoelectric material, it is necessary to position the sample at two points on the sample with high accuracy and measure the voltage and temperature at the two points.

また、各熱電特性の測定装置において、当該特性の測定方向（面方向又は厚さ方向）が異なるため、特性が測定方向に依存する異方性のある試料の場合は、微細組織の方向と熱の流れる方向とを考慮して試料を用意する必要があり、測定の負荷が大きかった。 In addition, since the measurement direction (plane direction or thickness direction) of the characteristic is different in each thermoelectric characteristic measuring device, in the case of an anisotropic sample whose characteristic depends on the measurement direction, the direction of the microstructure and the heat. It was necessary to prepare the sample in consideration of the flow direction of the sample, and the measurement load was heavy.

同一試料で電気抵抗率、ゼーベック係数及び熱拡散率の測定を行う方法として、例えば、特許文献１には、ヒータを一端に配置した試料側面に２本の熱電対を接触させて熱拡散率を測定する方法を主とし、併せてゼーベック係数及び電気抵抗率を測定する方法が開示されている。 As a method of measuring the electrical resistivity, Seebeck coefficient, and thermal diffusivity of the same sample, for example, in Patent Document 1, two thermocouples are brought into contact with the side surface of a sample in which a heater is arranged at one end to determine the thermal diffusivity. Mainly the method of measuring, and also the method of measuring the Seebeck coefficient and the electrical resistivity is disclosed.

特開２０１６−２４１７４号公報Japanese Unexamined Patent Publication No. 2016-24174

上述のような従来の測定方法では、熱電対などの測定プローブと試料の接触が不安定で、熱電対を導電ペーストなどで試料に取り付ける方法、バネの力で押し付ける方法が用いられることが多い。これらの方法では、試料の準備に時間と手間が必要であり、バネの押し付け力の調整が難しく、測定中に接触不良による計測不良が発生する問題があった。 In the conventional measurement method as described above, the contact between the measurement probe such as a thermocouple and the sample is unstable, and a method of attaching the thermocouple to the sample with a conductive paste or the like or a method of pressing with a spring force is often used. With these methods, it takes time and effort to prepare the sample, it is difficult to adjust the pressing force of the spring, and there is a problem that measurement failure occurs due to poor contact during measurement.

そこで、本発明は、同一測定試料を用い、同一測定方向（熱流方向）で熱電特性を評価することができるとともに、簡単な構成であり、短時間で高精度な熱電特性評価を行うことができる熱電特性評価ユニット、熱電特性評価装置及び熱電特性評価方法を提供することを目的とする。 Therefore, according to the present invention, the thermoelectric characteristics can be evaluated in the same measurement direction (heat flow direction) using the same measurement sample, and the thermoelectric characteristics can be evaluated with high accuracy in a short time with a simple configuration. An object of the present invention is to provide a thermoelectric characteristic evaluation unit, a thermoelectric characteristic evaluation device, and a thermoelectric characteristic evaluation method.

上記目的を達成するため、請求項１に記載の発明では、熱電材料からなる被測定物の電気抵抗率、ゼーベック係数及び熱拡散率を評価する熱電特性評価ユニットであって、被測定物に接触し、被測定物からの電圧及び熱起電力を計測するための複数の測定プローブと、前記被測定物が前記測定プローブと接触する測定面と反対側から前記被測定物を保持する保持部材と、前記測定プローブをそれぞれ被測定物に押し当てるための押付け手段と、前記被測定物の一端部を定常加熱または周期加熱して前記被測定物の測定面方向に温度差を発生させるためのヒータと、を備え、前記測定プローブは、それぞれ絶縁体の支持管に熱電対を通して先端を計測部として突出させて構成されており、それぞれの前記測定プローブの計測部が前記被測定物に流れる電流または熱流に沿った方向に配置されている、という技術的手段を用いる。 In order to achieve the above object, the invention according to claim 1 is a thermoelectric property evaluation unit that evaluates the electric resistance, the Seebeck coefficient, and the thermal diffusion rate of the object to be measured, which is made of a thermoelectric material, and is in contact with the object to be measured. A plurality of measuring probes for measuring the voltage and thermoelectromotive force from the object to be measured, and a holding member for holding the object to be measured from the side opposite to the measurement surface where the object to be measured contacts the measuring probe. , A pressing means for pressing the measurement probe against the object to be measured, and a heater for constantly heating or periodically heating one end of the object to be measured to generate a temperature difference in the direction of the measurement surface of the object to be measured. Each of the measuring probes is configured by passing a thermocouple through a support tube of an insulator and projecting the tip as a measuring unit, and the measuring unit of each measuring probe is configured to have a current flowing through the object to be measured. The technical means of being arranged in the direction along the heat flow is used.

請求項２に記載の発明では、請求項１に記載の熱電特性評価ユニットにおいて、前記ヒータは、前記保持部材に、前記被測定物の一端部で接触可能に配置されている、という技術的手段を用いる。 In the invention according to claim 2, in the thermoelectric characteristic evaluation unit according to claim 1, the heater is arranged so as to be in contact with the holding member at one end of the object to be measured. Is used.

請求項３に記載の発明では、請求項１または請求項２に記載の熱電特性評価ユニットにおいて、前記押付け手段は、プッシュロッド機構を備え、前記測定プローブにそれぞれ取り付けられた接触圧調整部材と、前記接触圧調整部材を介して前記複数の測定プローブを前記被測定物に向かって対して直線駆動する駆動手段と、を備え、前記接触圧調整部材は、各測定プローブにおいて、前記計測部が前記被測定物に接触した後は、前記駆動手段による変位を吸収するとともに当該計測部による前記被測定物に対する押付け力を発生させる、という技術的手段を用いる。 In the invention according to claim 3, in the thermoelectric characteristic evaluation unit according to claim 1 or 2, the pressing means includes a push rod mechanism, and a contact pressure adjusting member attached to the measuring probe, respectively. The contact pressure adjusting member includes a driving means for linearly driving the plurality of measuring probes toward the object to be measured via the contact pressure adjusting member, and the contact pressure adjusting member has the measuring unit in each measuring probe. After contacting the object to be measured, a technical means is used in which the displacement caused by the driving means is absorbed and the pressing force of the measuring unit against the object to be measured is generated.

請求項４に記載の発明では、請求項１ないし請求項３のいずれか１つに記載の熱電特性評価ユニットと、当該熱電特性評価ユニットを制御し当該熱電特性評価ユニットから送出される信号に基づいて前記被測定物の電気抵抗率、ゼーベック係数及び熱拡散率を測定する制御手段と、を備えた、という技術的手段を用いる。 The invention according to claim 4 is based on the thermoelectric characteristic evaluation unit according to any one of claims 1 to 3 and a signal transmitted from the thermoelectric characteristic evaluation unit by controlling the thermoelectric characteristic evaluation unit. The technical means of providing the control means for measuring the electrical resistivity, Seebeck coefficient and thermal diffusion rate of the object to be measured is used.

請求項５に記載の発明では、請求項４に記載の熱電特性評価装置を用いた熱電特性評価方法であって、請求項４に記載の熱電特性評価装置を用いた熱電特性評価方法であって、前記熱電特性評価ユニットを用いて、被測定物に前記測定プローブをそれぞれ接触させる工程と、前記測定プローブにより被測定物に電流を流し、他の測定プローブにより計測された異なる２点間の電圧に基づいて電気抵抗率を算出する工程と、前記ヒータにより被測定物を定常加熱し、前記測定プローブにより測定される異なる２点間の温度差により発生する起電力に基づいてゼーベック係数を算出する工程と、前記ヒータにより被測定物を周期加熱し、前記測定プローブにより異なる２点の温度波形データをそれぞれ取得し、前記制御手段で生成した基準となる温度波形データを用いて異なる２点間の周期的な温度変化の位相差を演算し、当該周期的な温度変化の位相差の周波数依存性に基づいて周期的な温度変化の位相差周波数依存性に基づいて熱拡散率を算出する工程と、を備えた、という技術的手段を用いる。 The invention according to claim 5 is a thermoelectric characteristic evaluation method using the thermoelectric characteristic evaluation device according to claim 4, and is a thermoelectric characteristic evaluation method using the thermoelectric characteristic evaluation device according to claim 4. , The step of bringing the measurement probe into contact with the object to be measured by using the thermoelectric characteristic evaluation unit, and the voltage between two different points measured by the other measurement probes by passing a current through the object to be measured by the measurement probe. The Zeebeck coefficient is calculated based on the step of calculating the electric resistance based on the above and the electromotive force generated by the temperature difference between two different points measured by the measuring probe while constantly heating the object to be measured by the heater. In the process, the object to be measured is periodically heated by the heater, temperature waveform data of two different points are acquired by the measurement probe, and the reference temperature waveform data generated by the control means is used between the two different points. A process of calculating the phase difference of a periodic temperature change and calculating the thermal diffusion rate based on the phase difference frequency dependence of the periodic temperature change based on the frequency dependence of the phase difference of the periodic temperature change. The technical means of providing, is used.

請求項１に記載の発明によれば、一つの測定装置で、同一測定試料を用い、同一測定方向（熱流方向）で３つの熱電特性を評価することができる。押付け手段により、測定プローブを評価試料に対して適切な圧力で確実に接触させることができるので、良好な接触状態で測定を行うことができ、測定精度及び再現性を向上させることができる。 According to the invention of claim 1, it is possible to evaluate three thermoelectric characteristics in the same measurement direction (heat flow direction) by using the same measurement sample with one measuring device. Since the measuring probe can be reliably brought into contact with the evaluation sample at an appropriate pressure by the pressing means, the measurement can be performed in a good contact state, and the measurement accuracy and reproducibility can be improved.

請求項２に記載の発明のようにヒータを配置することにより、ヒータが十分に評価試料に熱を供給できるような接触状態にすることができるので、良好な加熱を行うことができ、測定精度及び再現性を向上させることができる。また、熱拡散率測定において、ヒータを評価試料の裏面から加熱するように配置することにより、温度波が安定するので測定精度及び再現性を向上させることができる。 By arranging the heater as in the invention of claim 2, the heater can be in a contact state so as to sufficiently supply heat to the evaluation sample, so that good heating can be performed and the measurement accuracy can be improved. And the reproducibility can be improved. Further, in the thermal diffusivity measurement, by arranging the heater so as to heat from the back surface of the evaluation sample, the temperature wave is stabilized, so that the measurement accuracy and reproducibility can be improved.

請求項３に記載の発明によれば、各測定プローブを個別に操作するのではなく、駆動手段の操作により、すべての測定プローブを評価試料に対して適切な圧力で確実に接触させることができる。 According to the third aspect of the present invention, all the measuring probes can be surely brought into contact with the evaluation sample at an appropriate pressure by operating the driving means instead of operating each measuring probe individually. ..

請求項４に記載の発明のように、熱電特性評価ユニットと制御手段とを備えた熱電特性評価装置を構成することができる。 As in the invention of claim 4, a thermoelectric characteristic evaluation device including a thermoelectric characteristic evaluation unit and control means can be configured.

請求項５に記載の発明のように、請求項４に記載の熱電特性評価装置を用いて、電気抵抗率、ゼーベック係数及び熱拡散率を短時間で順次測定することができる。特に、熱拡散率測定において、熱拡散率を測定する時間が大幅に短縮される。また、測定に必要な機器構成を簡略化することができる。 As in the invention of claim 5, the electrical resistivity, Seebeck coefficient, and thermal diffusivity can be sequentially measured in a short time by using the thermoelectric characteristic evaluation device according to claim 4. In particular, in the thermal diffusivity measurement, the time for measuring the thermal diffusivity is significantly shortened. In addition, the equipment configuration required for measurement can be simplified.

熱電特性評価ユニットの全体側面図である。なお、以下の説明において、図１の上方を「上」、下方を「下」とする。It is an overall side view of a thermoelectric characteristic evaluation unit. In the following description, the upper part of FIG. 1 is referred to as “upper” and the lower part is referred to as “lower”. 図１の熱電特性評価ユニットを上方から見た全体平面図である。FIG. 5 is an overall plan view of the thermoelectric characteristic evaluation unit of FIG. 1 as viewed from above. 試料ホルダ近傍の構造を示す側面図である。It is a side view which shows the structure in the vicinity of a sample holder. 測定プローブが所定の評価試料に接触する状態を模式的に示した説明図である。It is explanatory drawing which shows typically the state which the measurement probe comes into contact with a predetermined evaluation sample. 試料ホルダの概略構成を示す説明図である。It is explanatory drawing which shows the schematic structure of the sample holder. 試料ホルダを測定プローブ側から見たときの構成を示す平面説明図である。It is a plane explanatory view which shows the structure when the sample holder is seen from the measurement probe side. 支持手段及び接触圧調整手段の構成を説明するための説明図である。図７（Ａ）は、上方から見た説明図であり、図７（Ｂ）は側面から見た説明図である。It is explanatory drawing for demonstrating the structure of the support means and contact pressure adjusting means. FIG. 7 (A) is an explanatory view seen from above, and FIG. 7 (B) is an explanatory view seen from the side surface. 熱電特性評価装置の構成を示すブロック図である。It is a block diagram which shows the structure of the thermoelectric characteristic evaluation apparatus. 電気抵抗率の測定原理を示す説明図である。It is explanatory drawing which shows the measurement principle of electrical resistivity. ゼーベック係数の測定原理を示す説明図である。It is explanatory drawing which shows the measurement principle of a Seebeck coefficient. 熱拡散率の測定原理を示す説明図である。It is explanatory drawing which shows the measurement principle of a thermal diffusivity. 熱拡散率測定における信号処理方法を示す説明図である。It is explanatory drawing which shows the signal processing method in thermal diffusivity measurement. 加熱周波数を変化させて熱換算率測定を行った結果を示す説明図である。It is explanatory drawing which shows the result of having performed the heat conversion rate measurement by changing the heating frequency.

（熱電特性評価ユニット）
本発明の熱電特性評価ユニットについて、図１−７を参照して説明する。 (Thermoelectric characterization unit)
The thermoelectric characterization unit of the present invention will be described with reference to FIGS. 1-7.

熱電特性評価ユニット１は、測定プローブ１０と、被測定物である評価試料Ｍを保持する試料ホルダ３０と、測定プローブ１０を所定の配置に支持する支持手段４０と、測定プローブ１０を評価試料Ｍに対して直線駆動する駆動手段５０と、測定プローブ１０の先端の計測部が評価試料Ｍの評価面に接触する状態を調整する接触圧調整手段（以下、接触圧調整部材６０）と、を備えている。ここで、支持手段４０、駆動手段５０及び接触圧調整部材６０が、複数の測定プローブ１０の計測部をそれぞれ評価試料Ｍに押し当てて接触させるための押付け手段を構成する。評価試料Ｍとして、熱電材料からなる板状の試料を用いることができる。 The thermoelectric characteristic evaluation unit 1 uses the measurement probe 10, the sample holder 30 that holds the evaluation sample M as the object to be measured, the support means 40 that supports the measurement probe 10 in a predetermined arrangement, and the measurement probe 10 as the evaluation sample M. A drive means 50 for linearly driving the measurement probe 10 and a contact pressure adjusting means (hereinafter referred to as a contact pressure adjusting member 60) for adjusting a state in which the measuring unit at the tip of the measuring probe 10 is in contact with the evaluation surface of the evaluation sample M are provided. ing. Here, the supporting means 40, the driving means 50, and the contact pressure adjusting member 60 form a pressing means for pressing the measuring portions of the plurality of measuring probes 10 against the evaluation sample M to bring them into contact with each other. As the evaluation sample M, a plate-shaped sample made of a thermoelectric material can be used.

測定プローブ１０として、第１測定プローブ１１、第２測定プローブ１２、第３測定プローブ１３及び第４測定プローブ１４を用いる。測定プローブ１０は、室温〜１０００℃までの測定が可能で、真空雰囲気下で使用可能な構成とすることが好ましい。 As the measurement probe 10, the first measurement probe 11, the second measurement probe 12, the third measurement probe 13 and the fourth measurement probe 14 are used. The measuring probe 10 is preferably configured so that it can measure from room temperature to 1000 ° C. and can be used in a vacuum atmosphere.

第１測定プローブ１１は、熱電対１５と、支持管１６と、を備え、支持管１６は熱電対１５の先端の計測部１５ａが露出するように内装して固定している。 The first measurement probe 11 includes a thermocouple 15 and a support tube 16, and the support tube 16 is internally fixed so that the measurement unit 15a at the tip of the thermocouple 15 is exposed.

第２測定プローブ１２は、熱電対１７と、支持管１８と、を備え、支持管１８は熱電対１７の先端の計測部１７ａが露出するように内装して固定している。 The second measurement probe 12 includes a thermocouple 17 and a support tube 18, and the support tube 18 is internally fixed so that the measurement unit 17a at the tip of the thermocouple 17 is exposed.

第３測定プローブ１３は、第２測定プローブ１２と同様の構成であり、熱電対１９と、支持管２０と、を備え、支持管２０は熱電対１９の先端の計測部１９ａが露出するように内装して固定している。 The third measurement probe 13 has the same configuration as the second measurement probe 12, and includes a thermocouple 19 and a support tube 20, so that the support tube 20 exposes the measurement unit 19a at the tip of the thermocouple 19. It is interior and fixed.

第４測定プローブ１４は、第１測定プローブ１１と同様の構成であり、熱電対２１と、支持管２２と、を備え、支持管２２は熱電対２１の先端の計測部２１ａが露出するように内装して固定している。 The fourth measurement probe 14 has the same configuration as the first measurement probe 11, and includes a thermocouple 21 and a support tube 22 so that the support tube 22 exposes the measurement unit 21a at the tip of the thermocouple 21. It is interior and fixed.

第１測定プローブ１１、第２測定プローブ１２、第３測定プローブ１３及び第４測定プローブ１４は、後述する支持手段４０により平行に等間隔で配置されている。 The first measurement probe 11, the second measurement probe 12, the third measurement probe 13, and the fourth measurement probe 14 are arranged in parallel at equal intervals by the support means 40 described later.

支持管１６、１８、２０、２２は、耐熱性が高い絶縁材料により形成されており、例えば、アルミナ管などを好適に用いることができる。 The support tubes 16, 18, 20, and 22 are formed of an insulating material having high heat resistance, and for example, an alumina tube or the like can be preferably used.

高温での測定を勘案すると、熱電対１５、１７、１９、２１は、Ｒ熱電対を好適に用いることができる。 Considering the measurement at a high temperature, R thermocouples can be preferably used as the thermocouples 15, 17, 19, and 21.

第１測定プローブ１１、第２測定プローブ１２、第３測定プローブ１３及び第４測定プローブ１４の各先端の計測部１１ａ、１２ａ、１３ａ、１４ａは、探針プローブとして評価試料Ｍに直接接触される。そのため、良好な接触状態を得ることができ、また、熱容量が大き過ぎないように形成される。通常、熱電対の先端部は球状であるが、計測部１１ａ、１２ａ、１３ａ、１４ａは、評価試料Ｍとの接触部が平面となるように形成されている。これにより、評価試料Ｍに対する計測部１１ａ、１２ａ、１３ａ、１４ａの接触面積を増大させることができるので、測定精度を向上させることができる。 The measurement units 11a, 12a, 13a, 14a at the tips of the first measurement probe 11, the second measurement probe 12, the third measurement probe 13, and the fourth measurement probe 14 are in direct contact with the evaluation sample M as probe probes. .. Therefore, a good contact state can be obtained, and the heat capacity is not too large. Normally, the tip of the thermocouple is spherical, but the measuring units 11a, 12a, 13a, and 14a are formed so that the contact portion with the evaluation sample M is flat. As a result, the contact area of the measuring units 11a, 12a, 13a, and 14a with respect to the evaluation sample M can be increased, so that the measurement accuracy can be improved.

試料ホルダ３０は、評価試料Ｍを測定プローブ１０に対向して保持する保持部材３１と、評価試料Ｍに温度勾配を生じさせるように構成されたヒータ３２と、を備えている。 The sample holder 30 includes a holding member 31 that holds the evaluation sample M facing the measurement probe 10, and a heater 32 that is configured to cause a temperature gradient in the evaluation sample M.

保持部材３１は、評価試料Ｍの裏面を支持して保持するブロック状の部材であり、熱電特性評価ユニット１を電気炉などの加熱手段に取り付けるためのフランジ部７０から延設されるホルダシャフト３３により、保持された評価試料Ｍが測定プローブ１０の各先端の計測部に対向するように配置されている。 The holding member 31 is a block-shaped member that supports and holds the back surface of the evaluation sample M, and is a holder shaft 33 extending from a flange portion 70 for attaching the thermoelectric characteristic evaluation unit 1 to a heating means such as an electric furnace. Therefore, the held evaluation sample M is arranged so as to face the measurement unit at each tip of the measurement probe 10.

保持部材３１は、熱拡散率の測定において評価試料Ｍ中に印加される温度波に対する影響を小さくするために低熱伝導材料による形成することが好ましい。また、機械的な強度を保ちながら気孔率を高くするなど、保持部材３１を介した測定誤差の要因となる熱の漏洩を効率よく防ぐことが好ましい。 The holding member 31 is preferably formed of a low thermal conductive material in order to reduce the influence on the temperature wave applied to the evaluation sample M in the measurement of the thermal diffusivity. Further, it is preferable to efficiently prevent heat leakage that causes a measurement error through the holding member 31, such as increasing the porosity while maintaining the mechanical strength.

ヒータ３２は、熱物性（ゼーベック係数、熱拡散率）を測定するために評価試料Ｍを一端から加熱する定常加熱及び周期加熱可能に構成された加熱源である。 The heater 32 is a heating source configured to be capable of steady heating and periodic heating in which the evaluation sample M is heated from one end in order to measure the thermal properties (Seebeck coefficient, thermal diffusivity).

ヒータ３２は、保持部材３１で保持した評価試料Ｍを一端部近傍の裏面から加熱可能なように保持部材３１に埋め込まれて配置されている。本実施形態では、第１測定プローブ１１により押付けされる位置に対応して配置されている。つまり、第１測定プローブ１１が評価試料Ｍに接触する位置の裏面側で評価試料Ｍに接触する位置に配置されている。 The heater 32 is arranged so as to be embedded in the holding member 31 so that the evaluation sample M held by the holding member 31 can be heated from the back surface near one end. In this embodiment, it is arranged corresponding to the position pressed by the first measurement probe 11. That is, the first measurement probe 11 is arranged at a position that contacts the evaluation sample M on the back surface side of the position where the first measurement probe 11 contacts the evaluation sample M.

支持手段４０は、測定プローブ１０の他端をそれぞれ支持する支持部材４１と、測定プローブ１０を案内するプローブガイド４２と、を備えている。 The support means 40 includes a support member 41 that supports the other end of the measurement probe 10, and a probe guide 42 that guides the measurement probe 10.

支持手段４０は、評価試料Ｍの面方向でヒータ３２から離間する方向に、第１測定プローブ１１、第２測定プローブ１２、第３測定プローブ１３、第４測定プローブ１４の順に所定の取付間隔で配置する。 The support means 40 has a predetermined mounting interval in the order of the first measurement probe 11, the second measurement probe 12, the third measurement probe 13, and the fourth measurement probe 14 in the plane direction of the evaluation sample M and away from the heater 32. Deploy.

これにより、測定プローブ１０は、評価試料Ｍに流れる電流または熱流に沿った方位に配置されることになり、各物性を同じ方向で測定できる。 As a result, the measurement probe 10 is arranged in an orientation along the current or heat flow flowing through the evaluation sample M, and each physical property can be measured in the same direction.

支持部材４１ａは第１測定プローブ１１の端部を支持し、支持部材４１ｂは第２測定プローブ１２の端部を支持し、支持部材４１ｃは第３測定プローブ１３の端部を支持し、支持部材４１ｄは第４測定プローブ１４の端部を支持する。 The support member 41a supports the end of the first measurement probe 11, the support member 41b supports the end of the second measurement probe 12, and the support member 41c supports the end of the third measurement probe 13. 41d supports the end of the fourth measurement probe 14.

ホルダシャフト３３には、第１測定プローブ１１、第２測定プローブ１２、第３測定プローブ１３及び第４測定プローブ１４を挿通して、位置決め及び前進、後退時のガイドを行うプローブガイド４２が取り付けられている。ここで、ホルダシャフト３３及びプローブガイド４２は耐熱性の観点から石英で形成することが好ましい。 A probe guide 42 is attached to the holder shaft 33 by inserting a first measurement probe 11, a second measurement probe 12, a third measurement probe 13 and a fourth measurement probe 14 to guide positioning, forward movement, and backward movement. ing. Here, the holder shaft 33 and the probe guide 42 are preferably made of quartz from the viewpoint of heat resistance.

駆動手段５０は、直線駆動を行う駆動装置５１と、駆動装置５１により測定プローブ１０の直線駆動を行うための駆動部材５２と、を備えている。 The driving means 50 includes a driving device 51 for linearly driving the measurement probe 10 and a driving member 52 for linearly driving the measurement probe 10 with the driving device 51.

駆動装置５１は、駆動部５１ａと、駆動シャフト５１ｂと、を備えており、駆動シャフト５１ｂの先端に駆動部材５２が取り付けられている。また、支持部材４１の一端を前後方向へ案内する溝部をそれぞれ有するガイド部材５３が設けられている。 The drive device 51 includes a drive unit 51a and a drive shaft 51b, and a drive member 52 is attached to the tip of the drive shaft 51b. Further, a guide member 53 having a groove portion for guiding one end of the support member 41 in the front-rear direction is provided.

本実施形態では、駆動装置５１として、ダイヤルの回動を直線駆動に変換するダイヤルゲージを用いたが、直線駆動を行うことができる駆動装置であれば各種装置を採用することができる。 In the present embodiment, a dial gauge that converts the rotation of the dial into a linear drive is used as the drive device 51, but various devices can be adopted as long as the drive device can perform linear drive.

また、駆動部材５２には、測定プローブ１０の先端の計測部が評価試料Ｍに接触する状態を調整する接触圧調整部材６０が取り付けられている。 Further, a contact pressure adjusting member 60 for adjusting a state in which the measuring unit at the tip of the measuring probe 10 is in contact with the evaluation sample M is attached to the driving member 52.

接触圧調整部材６０は、ばねを内装したシリンダ状の部材であり、一方から押付けしたときに、内装したばねが縮んで全長が短くなるとともに押付け方向と逆方向に付勢するプッシュロッド機構を有する。 The contact pressure adjusting member 60 is a cylinder-shaped member having a spring inside, and has a push rod mechanism that contracts the built-in spring to shorten the total length and urges the member in the direction opposite to the pressing direction when pressed from one side. ..

接触圧調整部材６０は、各測定プローブ１０と押付け方向が平行となるようにそれぞれの支持部材４１に接続されている。 The contact pressure adjusting member 60 is connected to each support member 41 so that the pressing direction is parallel to each measurement probe 10.

第１測定プローブ１１には支持部材４１ａを介して接触圧調整部材６０ａが、第２測定プローブ１２には支持部材４１ｂを介して接触圧調整部材６０ｂが、第３測定プローブ１３には支持部材４１ｃを介して接触圧調整部材６０ｃが、第４測定プローブ１４には支持部材４１ｄを介して接触圧調整部材６０ｄが、それぞれ接続されている。 The first measurement probe 11 has a contact pressure adjusting member 60a via a support member 41a, the second measurement probe 12 has a contact pressure adjusting member 60b via a support member 41b, and the third measurement probe 13 has a support member 41c. The contact pressure adjusting member 60c is connected to the fourth measurement probe 14 via the support member 41d, and the contact pressure adjusting member 60d is connected to the fourth measurement probe 14 via the support member 41d.

測定プローブ１０を直線駆動し、評価試料Ｍに各測定プローブ１０の先端の計測部を接触させる方法を説明する。 A method of linearly driving the measurement probe 10 and bringing the measurement unit at the tip of each measurement probe 10 into contact with the evaluation sample M will be described.

まず、評価試料Ｍから各測定プローブ１０の先端の計測部が離間した状態で駆動装置５１を操作し、駆動部材５２を評価試料Ｍに向かって前進させる。 First, the drive device 51 is operated with the measurement unit at the tip of each measurement probe 10 separated from the evaluation sample M, and the drive member 52 is advanced toward the evaluation sample M.

駆動部材５２が評価試料Ｍに向かって前進すると、接触圧調整部材６０及び支持部材４１を介して第１測定プローブ１１、第２測定プローブ１２、第３測定プローブ１３及び第４測定プローブ１４が同時に評価試料Ｍに対して前進する。 When the driving member 52 advances toward the evaluation sample M, the first measurement probe 11, the second measurement probe 12, the third measurement probe 13 and the fourth measurement probe 14 simultaneously move through the contact pressure adjusting member 60 and the support member 41. Advance with respect to the evaluation sample M.

このとき、第１測定プローブ１１、第２測定プローブ１２、第３測定プローブ１３及び第４測定プローブ１４は、プローブガイド４２に案内されて前進するので、所定の間隔など位置決めされた状態で前進する。 At this time, since the first measurement probe 11, the second measurement probe 12, the third measurement probe 13 and the fourth measurement probe 14 are guided by the probe guide 42 and move forward, they move forward in a positioned state such as a predetermined interval. ..

第１測定プローブ１１、第２測定プローブ１２、第３測定プローブ１３及び第４測定プローブ１４の先端の計測部が評価試料Ｍに接触すると、接触圧調整部材６０が作動する。 When the measurement unit at the tip of the first measurement probe 11, the second measurement probe 12, the third measurement probe 13 and the fourth measurement probe 14 comes into contact with the evaluation sample M, the contact pressure adjusting member 60 operates.

測定プローブ１０の先端の計測部が評価試料Ｍに接触した後でも、接触圧調整部材６０に内装されたばねが変位可能な距離だけ支持部材４１を移動させ、駆動手段５０による変位を吸収することができる。このとき、測定プローブ１０の先端の計測部は適切な押付け力で評価試料Ｍを押付けすることになる。 Even after the measuring unit at the tip of the measuring probe 10 comes into contact with the evaluation sample M, the support member 41 can be moved by a displaceable distance by the spring built in the contact pressure adjusting member 60 to absorb the displacement caused by the driving means 50. it can. At this time, the measuring unit at the tip of the measuring probe 10 presses the evaluation sample M with an appropriate pressing force.

接触圧調整部材６０は、第１測定プローブ１１、第２測定プローブ１２、第３測定プローブ１３及び第４測定プローブ１４にそれぞれ設けられているので、個別の測定プローブ１０毎に上記の動作が行われる。これにより、一部の測定プローブ１０の先端の計測部しか評価試料Ｍに接触していなかった場合も、更に駆動部材５２の直線駆動により支持部材４１を評価試料Ｍに接近させることにより、すべての測定プローブ１０の先端の計測部を適切な押付け力で評価試料Ｍに確実に接触させることができる。このように、各測定プローブ１０を個別に操作するのではなく、駆動手段５０の操作により、すべての測定プローブ１０を評価試料Ｍに対して確実に接触させることができる。 Since the contact pressure adjusting member 60 is provided on each of the first measurement probe 11, the second measurement probe 12, the third measurement probe 13, and the fourth measurement probe 14, the above operation is performed for each individual measurement probe 10. Be told. As a result, even when only the measuring portion at the tip of a part of the measuring probes 10 is in contact with the evaluation sample M, the support member 41 is further brought closer to the evaluation sample M by the linear drive of the driving member 52, so that all of them are brought into contact with the evaluation sample M. The measuring unit at the tip of the measuring probe 10 can be reliably brought into contact with the evaluation sample M with an appropriate pressing force. In this way, all the measurement probes 10 can be reliably brought into contact with the evaluation sample M by operating the driving means 50, instead of operating each measurement probe 10 individually.

上記の構成により、第１測定プローブ１１、第２測定プローブ１２、第３測定プローブ１３及び第４測定プローブ１４の先端の計測部の正確な位置決めを行い、銀ペーストなどを用いることなく、評価試料Ｍに対して適切な圧力で確実に接触させることができる。これにより、熱電物性測定を測定プローブ１０の良好な接触状態で行うことができるので、測定精度及び再現性を向上させることができる。 With the above configuration, the measurement unit at the tip of the first measurement probe 11, the second measurement probe 12, the third measurement probe 13 and the fourth measurement probe 14 is accurately positioned, and the evaluation sample is evaluated without using silver paste or the like. It can be reliably contacted with M at an appropriate pressure. As a result, the thermoelectric property measurement can be performed in a good contact state of the measurement probe 10, so that the measurement accuracy and reproducibility can be improved.

測定プローブ１０を評価試料Ｍから後退させるときは逆の操作を行えばよい。 When the measuring probe 10 is retracted from the evaluation sample M, the reverse operation may be performed.

（熱電特性評価装置）
図８に示すように、本発明の熱電特性評価装置２は、熱電特性評価ユニット１、熱電特性評価ユニット１を制御し熱電特性評価ユニット１から送出される信号に基づいて評価試料Ｍの電気抵抗率、ゼーベック係数及び熱拡散率を測定する制御手段１００と、評価試料Ｍを評価温度まで昇温する加熱手段２００と、を備えている。 (Thermoelectric characterization device)
As shown in FIG. 8, the thermoelectric characteristic evaluation device 2 of the present invention controls the thermoelectric characteristic evaluation unit 1 and the thermoelectric characteristic evaluation unit 1, and the electrical resistivity of the evaluation sample M based on the signal sent from the thermoelectric characteristic evaluation unit 1. It includes a control means 100 for measuring the rate, a Seebeck coefficient, and a thermal diffusion rate, and a heating means 200 for raising the temperature of the evaluation sample M to the evaluation temperature.

制御手段１００は、デジタルマルチメータ１１０と、直流電圧・電流発生器１１３と、ファンクションジェネレータ１１４と、ヒータ３２に制御電流を送出するヒータ加熱電源１１５と、パーソナルコンピュータなどの制御装置１１６と、を備えている。 The control means 100 includes a digital multimeter 110, a DC voltage / current generator 113, a function generator 114, a heater heating power supply 115 that sends a control current to the heater 32, and a control device 116 such as a personal computer. ing.

デジタルマルチメータ１１０は、各測定プローブ間から温度・電圧・抵抗測定を行う第１スイッチカード１１１及び電気抵抗率及び熱拡散率測定時の直流電流＆交流信号の供給回路制御を行う第２スイッチカード１１２を内蔵している。デジタルマルチメータ１１０は、ゼーベック係数測定時、第１測定プローブ１１、第４測定プローブ１４を用いて温度測定・起電力（電圧）の測定を行う。 The digital multimeter 110 includes a first switch card 111 that measures temperature, voltage, and resistance between each measurement probe, and a second switch card that controls the supply circuit of DC current and AC signals when measuring electrical resistance and thermal diffusion. It has a built-in 112. The digital multimeter 110 measures temperature and electromotive force (voltage) using the first measurement probe 11 and the fourth measurement probe 14 when measuring the Seebeck coefficient.

第１スイッチカード１１１には、第１測定プローブ１１、第２測定プローブ１２、第３測定プローブ１３及び第４測定プローブ１４と、制御装置１１６と、が接続されている。 The first measurement probe 11, the second measurement probe 12, the third measurement probe 13, the fourth measurement probe 14, and the control device 116 are connected to the first switch card 111.

第２スイッチカード１１２には、第１測定プローブ１１及び第４測定プローブ１４と、ヒータ加熱電源１１５と、直流電圧・電流発生器１１３と、ファンクションジェネレータ１１４と、制御装置１１６と、が接続されている。 The first measurement probe 11 and the fourth measurement probe 14, the heater heating power supply 115, the DC voltage / current generator 113, the function generator 114, and the control device 116 are connected to the second switch card 112. There is.

直流電圧・電流発生器１１３は、電気抵抗率測定時の直流電流印加及びゼーベック係数測定時の定常加熱用電流印加を行う。 The DC voltage / current generator 113 applies a DC current when measuring the electrical resistivity and applies a current for steady heating when measuring the Seebeck coefficient.

ファンクションジェネレータ１１４は、熱拡散率を測定時、ヒータ加熱電源からヒータ３２に周期加熱するための任意の周波数と波形を持つ交流電圧信号の生成を行う。 When measuring the thermal diffusivity, the function generator 114 generates an AC voltage signal having an arbitrary frequency and waveform for periodic heating from the heater heating power source to the heater 32.

直流電圧・電流発生器１１３と、ファンクションジェネレータ１１４と、は制御装置１１６に接続されている。 The DC voltage / current generator 113 and the function generator 114 are connected to the control device 116.

加熱手段２００としては、電気炉など通常の高温計測に用いる加熱手段を用いることができる。 As the heating means 200, a heating means used for ordinary high temperature measurement such as an electric furnace can be used.

熱電特性評価ユニット１には、フランジ部７０に試料室２１０を取り付けて設けることもできる。試料室２１０は、測定プローブ１０、試料ホルダ３０などを覆い、雰囲気制御が可能なチャンバとして形成されており、例えば、不活性雰囲気、真空雰囲気下での測定も可能である。ここで、真空状態で測定すると、評価試料Ｍからの熱の漏洩を抑制することができるので、測定精度を向上させることができる。 The thermoelectric characteristic evaluation unit 1 may be provided with the sample chamber 210 attached to the flange portion 70. The sample chamber 210 covers the measurement probe 10, the sample holder 30, and the like, and is formed as a chamber capable of controlling the atmosphere. For example, the measurement can be performed in an inert atmosphere or a vacuum atmosphere. Here, when the measurement is performed in a vacuum state, heat leakage from the evaluation sample M can be suppressed, so that the measurement accuracy can be improved.

（熱電特性評価方法）
熱電特性評価装置２を用いた電気抵抗率、ゼーベック係数及び熱拡散率の測定方法について説明する。 (Thermoelectric characterization method)
A method for measuring the electrical resistivity, Seebeck coefficient, and thermal diffusivity using the thermoelectric characteristic evaluation device 2 will be described.

まず、評価試料Ｍを一端近傍の裏面にヒータ３２が接触するように、試料ホルダ３０の保持部材３１に取り付ける。次に、熱電特性評価装置２を操作して、測定プローブ１０の先端の計測部を評価試料Ｍに接触させる。制御装置１１６により、オーミックコンタクトにより測定プローブ１０が良好な接触状態であることを確認してから加熱手段２００により測定温度まで昇温した後に、熱電特性の測定を開始する。 First, the evaluation sample M is attached to the holding member 31 of the sample holder 30 so that the heater 32 comes into contact with the back surface near one end. Next, the thermoelectric characteristic evaluation device 2 is operated to bring the measurement unit at the tip of the measurement probe 10 into contact with the evaluation sample M. After confirming that the measurement probe 10 is in a good contact state by ohmic contact by the control device 116, the temperature is raised to the measurement temperature by the heating means 200, and then the measurement of the thermoelectric characteristics is started.

制御装置１１６のソフトウェアにより測定の指示が実行されると、電気抵抗率、ゼーベック係数、熱拡散率の順に１回ずつ測定が実行され、測定データは制御装置１１６に保存される。 When the measurement instruction is executed by the software of the control device 116, the measurement is executed once in the order of the electrical resistivity, the Seebeck coefficient, and the heat diffusion rate, and the measurement data is stored in the control device 116.

本発明の熱物性評価方法によれば、熱電材料の開発で性能指数を求める上で必要な熱電物性である、電気抵抗率、ゼーベック係数及び熱拡散率を一の評価試料Ｍを用い、一の評価装置により評価することができる。 According to the thermoelectric property evaluation method of the present invention, the electrical resistivity, Seebeck coefficient, and thermoelectric property, which are the thermoelectric properties necessary for obtaining the figure of merit in the development of thermoelectric materials, are evaluated using one evaluation sample M. It can be evaluated by an evaluation device.

また、評価試料Ｍの同一面に接触させた測定プローブ１０により各物性の測定を行うので、同一方向の物性を測定することができる。 Further, since each physical property is measured by the measuring probe 10 in contact with the same surface of the evaluation sample M, the physical property in the same direction can be measured.

加熱手段２００により複数水準の温度を設定し測定を行うことにより、各物性の温度依存性を評価することができる。ここで、加熱手段２００により、測定温度を上昇させると、測定プローブ１０が膨張するが、接触圧調整部材６０によりその膨張分を吸収することができるので、測定プローブ１０より評価試料Ｍに過度の応力が負荷されることがなく、良好な接触状態を維持することができる。 The temperature dependence of each physical property can be evaluated by setting a plurality of levels of temperature by the heating means 200 and performing the measurement. Here, when the measurement temperature is raised by the heating means 200, the measurement probe 10 expands, but the expansion amount can be absorbed by the contact pressure adjusting member 60, so that the measurement probe 10 is excessive to the evaluation sample M. No stress is applied and a good contact state can be maintained.

電気抵抗率の測定には、主としてデジタルマルチメータ１１０、第１スイッチカード１１１、第２スイッチカード１１２、直流電圧・電流発生器１１３、制御装置１１６を使用する。測定原理を図９に示す。図中丸囲いの１−４は、それぞれ第１測定プローブ１１、第２測定プローブ１２、第３測定プローブ１３及び第４測定プローブ１４の接触点（測定点）を示す。図１０及び図１１においても同様である。 A digital multimeter 110, a first switch card 111, a second switch card 112, a DC voltage / current generator 113, and a control device 116 are mainly used for measuring the electrical resistivity. The measurement principle is shown in FIG. Circles 1-4 in the figure indicate contact points (measurement points) of the first measurement probe 11, the second measurement probe 12, the third measurement probe 13, and the fourth measurement probe 14, respectively. The same applies to FIGS. 10 and 11.

デジタルマルチメータ１１０により第１測定プローブ１１の−側素線及び第４測定プローブ１４の−側素線に通電して評価試料Ｍの表面に電流を流し、第２測定プローブ１２の−側素線及び第３測定プローブ１３の−側素線間の電圧を測定する。そして、得られた測定データに基づいて下式により電気抵抗率ρeを算出する。ここで補正係数ｆ１は、試料厚さｔ[ｍ]およびヒータ・センサ間距離ｄ１、ｄ２[ｍ]に依存する値であり、補正係数ｆ２は、ヒータ・センサ間距離ｄ１、ｄ２[ｍ]及び試料の短手方向の長さｌ[ｍ]に依存する値である。 The-side wire of the first measurement probe 11 and the-side wire of the fourth measurement probe 14 are energized by the digital multimeter 110 to pass a current through the surface of the evaluation sample M, and the-side wire of the second measurement probe 12 is passed. And the voltage between the − side strands of the third measurement probe 13 is measured. Then, the electrical resistivity ρe is calculated by the following formula based on the obtained measurement data. Here, the correction coefficient f 1 is a value that depends on the sample thickness t [m] and the distances d 1 and d 2 [m] between the heaters and sensors, and the correction coefficient f 2 is the distance d 1 between the heaters and sensors. It is a value that depends on d 2 [m] and the length l [m] of the sample in the lateral direction.

Figure 2020139834
Figure 2020139834

ゼーベック係数の測定には、主としてデジタルマルチメータ１１０、第１スイッチカード１１１、第２スイッチカード１１２、直流電圧・電流発生器１１３、ヒータ加熱電源１１５、制御装置１１６を使用する。測定原理を図１０に示す。 A digital multimeter 110, a first switch card 111, a second switch card 112, a DC voltage / current generator 113, a heater heating power supply 115, and a control device 116 are mainly used for measuring the Seebeck coefficient. The measurement principle is shown in FIG.

直流電圧・電流発生器１１３によってヒータ加熱電源１１５を経由してヒータ３２に直流電圧を印加し、評価試料Ｍを定常加熱する。第１測定プローブ１１及び第４測定プローブ１４により、それぞれの接触部の温度差によって発生する起電力を測定する。そして、得られた測定データに基づいて下式によりゼーベック係数を算出する。 A DC voltage / current generator 113 applies a DC voltage to the heater 32 via the heater heating power supply 115 to constantly heat the evaluation sample M. The electromotive force generated by the temperature difference between the contact portions is measured by the first measurement probe 11 and the fourth measurement probe 14. Then, the Seebeck coefficient is calculated by the following formula based on the obtained measurement data.

Figure 2020139834
Figure 2020139834

熱拡散率の測定には、主としてデジタルマルチメータ１１０、第１スイッチカード１１１、第２スイッチカード１１２、ファンクションジェネレータ１１４、ヒータ加熱電源１１５、制御装置１１６を使用する。測定原理を図１１及び図１２に示す。 A digital multimeter 110, a first switch card 111, a second switch card 112, a function generator 114, a heater heating power supply 115, and a control device 116 are mainly used for measuring the thermal diffusivity. The measurement principle is shown in FIGS. 11 and 12.

まず、ファンクションジェネレータ１１４によりヒータ加熱電源１１５を経由してヒータ３２に周期的な電圧を印加することで、評価試料Ｍを周期加熱する。第２測定プローブ１２及び第３測定プローブ１３によりそれぞれの温度（温度２、温度３とする）を計測し、制御装置１１６に温度波形データを取り込む。そして、温度２、温度３の波形から、第２測定プローブ１２及び第３測定プローブ１３の温度応答の差（位相差）、及びこの位相差の周波数依存性を利用して熱拡散率ａを下式により算出する。 First, the evaluation sample M is periodically heated by applying a periodic voltage to the heater 32 via the heater heating power supply 115 by the function generator 114. The respective temperatures (temperature 2 and temperature 3) are measured by the second measurement probe 12 and the third measurement probe 13, and the temperature waveform data is taken into the control device 116. Then, from the waveforms of temperature 2 and temperature 3, the thermal diffusivity a is lowered by utilizing the difference in temperature response (phase difference) between the second measurement probe 12 and the third measurement probe 13 and the frequency dependence of this phase difference. Calculate by the formula.

Figure 2020139834
Figure 2020139834

ヒータ３２は、第１測定プローブ１１により評価試料Ｍが押付けられることにより、評価試料Ｍの裏面から一定の接触圧で押付けられる。これにより、ヒータ３２が十分に評価試料Ｍに熱を供給できるような接触状態にすることができるので、良好な加熱を行うことができ、測定精度及び再現性を向上させることができる。また、ヒータ３２を評価試料Ｍの裏面から加熱するように配置することにより、温度波が安定するので測定精度及び再現性を向上させることができる。 The heater 32 is pressed from the back surface of the evaluation sample M with a constant contact pressure by pressing the evaluation sample M by the first measurement probe 11. As a result, the heater 32 can be brought into a contact state so that heat can be sufficiently supplied to the evaluation sample M, so that good heating can be performed and the measurement accuracy and reproducibility can be improved. Further, by arranging the heater 32 so as to heat from the back surface of the evaluation sample M, the temperature wave is stabilized, so that the measurement accuracy and reproducibility can be improved.

熱拡散率の測定において、内側２つの第２測定プローブ１２及び第３測定プローブ１３を用いると、ヒータ３２からの温度波の振幅が得やすいとともに、評価試料Ｍの試料の厚さ方向の熱伝導を無視でき、面方向（熱流方向）のみの熱伝導として扱えることが可能な熱伝導の一次元性が保たれる位置で測定できるため、好適である。 When the inner two second measurement probes 12 and the third measurement probe 13 are used in the measurement of the thermal diffusivity, the amplitude of the temperature wave from the heater 32 can be easily obtained, and the heat conduction in the thickness direction of the sample of the evaluation sample M can be easily obtained. Is preferable because it can be measured at a position where one-dimensionality of heat conduction is maintained, which can be treated as heat conduction only in the plane direction (heat flow direction).

従来の周期加熱法では、レーザによる加熱で試料を加熱する場合、
・試料の光吸収の違いによる問題
・光の焦点を合わせるのが難しい
・装置構成が複雑となる
・高温環境下での計測において、評価試料の特定個所に正確にレーザを照射することが困難である
等の問題があった。 In the conventional periodic heating method, when the sample is heated by heating with a laser,
・ Problems due to the difference in light absorption of the sample ・ Difficult to focus the light ・ Complicated equipment configuration ・ In measurement in a high temperature environment, it is difficult to accurately irradiate a specific part of the evaluation sample with a laser There was a problem such as.

また、ヒータブロックを評価試料の片端に接触して加熱する方法では、ヒータの熱容量が大きいため、高い周波数での温度変化を発生させることが難しく、その結果、計測に用いられる周波数の範囲が狭く、計測可能な材料の熱拡散率の範囲が厳しく制限されるという問題があった。 In addition, in the method of heating the heater block by contacting one end of the evaluation sample, it is difficult to generate a temperature change at a high frequency because the heat capacity of the heater is large, and as a result, the frequency range used for measurement is narrow. There is a problem that the range of thermal diffusivity of measurable materials is severely limited.

ヒータ３２は、小型であり自身の熱容量が小さいとともに、ヒータ３２の発熱を熱伝導率の小さい保持部材３１で囲むことから、周期的な熱エネルギーを評価試料Ｍに効率よく伝搬することが可能である。これにより、高い周波数で試料の温度変化を発生させることができる。また、低周波の場合でも時差を減らすことができるため、測定精度を高めることができる。 Since the heater 32 is small and has a small heat capacity and surrounds the heat generated by the heater 32 with a holding member 31 having a low thermal conductivity, it is possible to efficiently propagate the periodic heat energy to the evaluation sample M. is there. As a result, the temperature change of the sample can be generated at a high frequency. Moreover, since the time difference can be reduced even in the case of a low frequency, the measurement accuracy can be improved.

以下に、本発明の熱拡散率の測定方法について詳説する。 The method for measuring the thermal diffusivity of the present invention will be described in detail below.

評価試料Ｍに対し、ヒータ３２により周期加熱を開始し、ヒータ３２から近い第２測定プローブ１２の温度波形データと、ヒータ３２から遠い第３測定プローブ１３の温度波形データをデジタルマルチメータ１１０により計測し、制御装置１１６に２つの波形データを取り込む。 Periodic heating is started by the heater 32 for the evaluation sample M, and the temperature waveform data of the second measurement probe 12 near the heater 32 and the temperature waveform data of the third measurement probe 13 far from the heater 32 are measured by the digital multimeter 110. Then, the two waveform data are taken into the control device 116.

測定信号に対して、測定信号と同位相信号および測定信号と90°位相シフトした信号をそれぞれ掛算し、測定信号と等しい周波数成分を検出する。得られたそれぞれ検出信号をローパスフィルタに通すことで求められる、測定信号の同位相成分Xと測定信号の直交成分Yから、基準となる信号（制御装置１１６で生成した基準となる温度波形データ）に対する測定信号の位相差θは、θ＝arctan(Y/X) から得られる。 The measurement signal is multiplied by a signal having the same phase as the measurement signal and a signal having a phase shift of 90 ° from the measurement signal to detect a frequency component equal to the measurement signal. A reference signal (reference temperature waveform data generated by the control device 116) from the in-phase component X of the measurement signal and the orthogonal component Y of the measurement signal obtained by passing each of the obtained detection signals through a low-pass filter. The phase difference θ of the measurement signal with respect to is obtained from θ = arctan (Y / X).

上記の位相差θについて、ヒータ３２から近い第２測定プローブ１２で得られる位相差をθ1、ヒータ３２から遠い第３測定プローブ１３で得られる位相差をθ2とすると、２点間の位相差はθ2-θ1で得られる。 Regarding the above phase difference θ, if the phase difference obtained by the second measurement probe 12 near the heater 32 is θ1 and the phase difference obtained by the third measurement probe 13 far from the heater 32 is θ2, the phase difference between the two points is Obtained by θ2-θ1.

指定した周波数域での計測において上記手順を繰り返し行い、測定を終了する。そして、制御装置１１６に記録された値から、各周波数毎の第２測定プローブ１２及び第３測定プローブ１３間の位相差を算出し、（周波数）１／２ に対する位相差のプロットから最小２乗法を用いて導出した一次の近似式の傾きから熱拡散率を得る。 The above procedure is repeated in the measurement in the specified frequency range, and the measurement is completed. Then, the phase difference between the second measurement probe 12 and the third measurement probe 13 for each frequency is calculated from the value recorded in the control device 116, and the least squares method is obtained from the plot of the phase difference with respect to (frequency) 1/2 . The thermal diffusivity is obtained from the slope of the first-order approximate expression derived using.

従来の熱拡散率測定では、以下の方法で測定を行っていた。 In the conventional thermal diffusivity measurement, the measurement is performed by the following method.

評価試料をヒータで周期加熱し、ヒータに近い熱物性計測プローブとヒータへ供給されるファンクションジェネレータの変調電圧との位相差と振幅をロックインアンプで計測し、計測される位相差、設定した位相差安定条件を充足したときに、その位相差の値を記録する。次に、ロックインアンプへ入力される値をヒータに近い熱物性計測プローブから遠い熱物性計測プローブへ切り替え、同様の計測を行い、位相差の値を記録する。そして、記録された値から、各周波数毎の熱物性計測プローブ２点間の位相差を算出し、（周波数）１／２ に対する位相差のプロットから最小二乗法を用いて導出した一次の近似式の傾きから熱拡散率を得る。（例えば、I.Hatta, K.Fujii, A.Sakakibara, F.Takahashi, Y.Hamada and Y.Kaneda: Jpn. J. Appl. Phys., 38 (1999) 2988.） The evaluation sample is periodically heated with a heater, and the phase difference and amplitude between the thermophysical property measurement probe close to the heater and the modulation voltage of the function generator supplied to the heater are measured with a lock-in amplifier, and the measured phase difference is set. When the phase difference stabilization condition is satisfied, the value of the phase difference is recorded. Next, the value input to the lock-in amplifier is switched from the thermophysical property measuring probe near the heater to the thermophysical property measuring probe far away, the same measurement is performed, and the phase difference value is recorded. Then, the phase difference between the two thermophysical property measurement probes for each frequency is calculated from the recorded value, and a linear approximation formula derived from the plot of the phase difference for (frequency) 1/2 using the least squares method. The thermal diffusivity is obtained from the slope of. (For example, I.Hatta, K.Fujii, A.Sakakibara, F.Takahashi, Y.Hamada and Y.Kaneda: Jpn. J. Appl. Phys., 38 (1999) 2988.)

熱電材料では信号強度が小さいため、従来の熱拡散率測定では、ロックインに時間がかかり測定時間が長くなるという欠点があった。 Since the signal strength of the thermoelectric material is small, the conventional thermal diffusivity measurement has a drawback that the lock-in takes time and the measurement time becomes long.

本発明の熱拡散率測定によれば、第２測定プローブ１２の温度波形データと第３測定プローブ１３の温度波形データを制御装置１１６に２つの波形データを取り込んだ後に、制御装置１１６内部で生成した信号波形を用いて演算処理を行うため、評価試料Ｍからの信号強度が小さくても測定が可能であり、従来の測定法のようにロックインするまで待機する必要がなく、ロックインアンプを用いた場合より熱拡散率を測定する時間が大幅に短縮される。また、測定に必要な機器構成を簡略化することができる。 According to the thermal diffusivity measurement of the present invention, the temperature waveform data of the second measurement probe 12 and the temperature waveform data of the third measurement probe 13 are generated inside the control device 116 after the two waveform data are taken into the control device 116. Since the arithmetic processing is performed using the generated signal waveform, measurement is possible even if the signal strength from the evaluation sample M is small, and there is no need to wait until lock-in unlike the conventional measurement method, and the lock-in amplifier is used. The time to measure the thermal diffusivity is significantly shorter than when it is used. In addition, the equipment configuration required for measurement can be simplified.

ヒータ３２は、保持部材３１表面に評価試料Ｍを載置可能な平面状の部材を介して設置することもできる。 The heater 32 can also be installed on the surface of the holding member 31 via a flat member on which the evaluation sample M can be placed.

ヒータ３２は、評価試料Ｍの測定面側から一端部に接触可能に、例えば、プッシュロッド型のヒータを測定面側から押し当てる構造として、構成することもできる。 The heater 32 can be configured so as to be able to contact one end of the evaluation sample M from the measurement surface side, for example, as a structure in which a push rod type heater is pressed from the measurement surface side.

ヒータ３２に代えて、評価試料Ｍの一端を冷却して温度差を生じさせる冷却ユニットを採用することもできる。 Instead of the heater 32, a cooling unit that cools one end of the evaluation sample M to generate a temperature difference can also be adopted.

（実施形態の効果）
本発明の熱電特性評価ユニット１、熱電特性評価装置２及び熱電特性評価方法によれば、一つの測定装置で、同一評価試料Ｍを用い、同一測定方向（熱流方向）で電気抵抗率、ゼーベック係数及び熱拡散率を測定することができる。接触圧調整部材６０により、測定プローブ１０を評価試料Ｍに対して適切な圧力で確実に接触させることができるので、測定精度及び再現性を向上させることができる。 (Effect of embodiment)
According to the thermoelectric characteristic evaluation unit 1, the thermoelectric characteristic evaluation device 2, and the thermoelectric characteristic evaluation method of the present invention, the same evaluation sample M is used in one measuring device, and the electrical resistivity and Seebeck coefficient are used in the same measurement direction (heat flow direction). And the heat diffusivity can be measured. Since the contact pressure adjusting member 60 can reliably contact the measurement probe 10 with the evaluation sample M at an appropriate pressure, the measurement accuracy and reproducibility can be improved.

熱電特性評価装置２を用いて、電気抵抗率、ゼーベック係数及び熱拡散率を短時間で順次測定することができる。特に、熱拡散率測定において、ロックインアンプを用いた場合より測定時間を大幅に短縮することができるとともに、測定に必要な機器構成を簡略化することができる。 The electrical resistivity, Seebeck coefficient, and thermal diffusivity can be sequentially measured in a short time by using the thermoelectric characteristic evaluation device 2. In particular, in thermal diffusivity measurement, the measurement time can be significantly shortened as compared with the case of using a lock-in amplifier, and the equipment configuration required for measurement can be simplified.

熱拡散率の測定可能周波数について検討した。薄板状の熱電変換素子（ビスマステルルＢｉ２Ｔｅ３）について、大気中の室温下にて熱拡散率測定を行った。（数３）に基づき、加熱周波数fを０．０１〜１．０[Ｈｚ]の範囲で、センサ間距離ｄ２−ｄ１を３[ｍｍ]にて、位相遅れの差φ２−φ１[ｄｅｇ]を測定した。また、ヒータのパワーは約０．３７[Ｗ]に設定した。図１３に熱拡散率測定結果例を示す。横軸は加熱周波数の平方根ｆ１／２[Ｈｚ１／２]、縦軸は位相遅れの差φ２−φ１[ｄｅｇ]を表している。この結果から、最小２乗法により算出した一次の近似直線の傾きが（数３）の分母式（（φ２−φ１）/ｆ１／２））に値するので、熱拡散率を求めることができる。 The measurable frequency of thermal diffusivity was examined. The thermal diffusivity of a thin plate-shaped thermoelectric conversion element (bismuth tellurium Bi 2 Te 3 ) was measured at room temperature in the atmosphere. Based on (Equation 3), the heating frequency f is in the range of 0.01 to 1.0 [Hz], the distance between sensors d 2 − d 1 is 3 [mm], and the phase delay difference φ 2 − φ 1 [Deg] was measured. The power of the heater was set to about 0.37 [W]. FIG. 13 shows an example of the thermal diffusivity measurement result. The horizontal axis represents the square root f 1/2 [Hz 1/2 ] of the heating frequency, and the vertical axis represents the phase lag difference φ 2 − φ 1 [deg]. From this result, the minimum square method primary slope of the approximate line calculated by deserves (number 3) in the denominator equation ((φ 2 -φ 1) / f 1/2)), it is determined thermal diffusivity it can.

熱電変換素子は一般的に熱伝導率が小さいため、加熱周波数ｆが大きいほど熱電対で検出される温度波の振幅は小さくなりやすく、位相遅れの差φ２−φ１を正しく検出できなくなる。図１３から、本実施例では加熱周波数fが約０．０２５〜０．２２Ｈｚの領域において、加熱周波数の平方根ｆ１／２[Ｈｚ１／２]と位相遅れの差φ２−φ１[ｄｅｇ]の間に一次の相関性が確認されたことから、この範囲内で熱拡散率を算出した。その結果、熱拡散率ａ＝１．８３ｍｍ２／ｓと見積もられ、一般的な熱電材料で測定可能であることが確認された。また測定する材料の熱伝導率やヒータのパワー等によっても測定可能な周波数は変化するため、適切な条件を適宜設定する必要がある。 Since the thermoelectric conversion element is generally low thermal conductivity, the amplitude of the temperature wave detected by the thermocouple larger the heating frequency f tends decreased, can not be correctly detected difference phi 2 -.phi 1 phase delay. From FIG. 13, in this embodiment, in the region where the heating frequency f is about 0.025 to 0.22 Hz, the difference between the square root f 1/2 [Hz 1/2 ] of the heating frequency and the phase delay φ 2 − φ 1 [deg ], A first-order correlation was confirmed, so the thermal diffusivity was calculated within this range. As a result, it was estimated that the thermal diffusivity a = 1.83 mm 2 / s, and it was confirmed that it can be measured with a general thermoelectric material. In addition, since the measurable frequency changes depending on the thermal conductivity of the material to be measured, the power of the heater, etc., it is necessary to appropriately set appropriate conditions.

１…熱電特性評価ユニット
２…熱電特性評価装置
３…制御手段
１０…測定プローブ
１１…第１測定プローブ
１２…第２測定プローブ
１３…第３測定プローブ
１４…第４測定プローブ
１５…第１熱電対
１５ａ…計測部
１６…第１支持管
１７…第２熱電対
１７ａ…計測部
１８…第２支持管
１９…第３熱電対
１９ａ…計測部
２０…第３支持管
２１…第４熱電対
２１ａ…計測部
２２…第４支持管
３０…試料ホルダ
３１…保持部材
３２…ヒータ
３３…ホルダシャフト
４０…支持手段
４１…支持部材
４１ａ、４１ｂ、４１ｃ、４１ｄ…支持部材
４２…プローブガイド
５０…駆動手段
５１…駆動装置
５１ａ…駆動部
５１ｂ…駆動シャフト
５２…駆動部材
５３…ガイド部材
６０…接触圧調整部材
６０ａ、６０ｂ、６０ｃ、６０ｄ…接触圧調整部材
７０…フランジ部
１００…制御手段
１１０…デジタルマルチメータ
１１１…第１スイッチカード
１１２…第２スイッチカード
１１３…直流電圧・電流発生器
１１４…ファンクションジェネレータ
１１５…ヒータ加熱電源
１１６…制御装置
２００…加熱手段
２１０…試料室
Ｍ…評価試料 1 ... Thermoelectric characteristic evaluation unit 2 ... Thermoelectric characteristic evaluation device 3 ... Control means 10 ... Measurement probe 11 ... First measurement probe 12 ... Second measurement probe 13 ... Third measurement probe 14 ... Fourth measurement probe 15 ... First thermocouple 15a ... Measuring unit 16 ... First support tube 17 ... Second thermocouple 17a ... Measuring unit 18 ... Second support tube 19 ... Third thermocouple 19a ... Measuring unit 20 ... Third support tube 21 ... Fourth thermocouple 21a ... Measuring unit 22 ... 4th support tube 30 ... Sample holder 31 ... Holding member 32 ... Heater 33 ... Holder shaft 40 ... Support means 41 ... Support members 41a, 41b, 41c, 41d ... Support member 42 ... Probe guide 50 ... Drive means 51 ... Drive device 51a ... Drive unit 51b ... Drive shaft 52 ... Drive member 53 ... Guide member 60 ... Contact pressure adjusting member 60a, 60b, 60c, 60d ... Contact pressure adjusting member 70 ... Flange portion 100 ... Control means 110 ... Digital multimeter 111 ... 1st switch card 112 ... 2nd switch card 113 ... DC voltage / current generator 114 ... Function generator 115 ... Heater heating power supply 116 ... Control device 200 ... Heating means 210 ... Sample room M ... Evaluation sample

Claims (5)

熱電材料からなる被測定物の電気抵抗率、ゼーベック係数及び熱拡散率を評価する熱電特性評価ユニットであって、
被測定物に接触し、被測定物からの電圧及び熱起電力を計測するための複数の測定プローブと、
前記被測定物が前記測定プローブと接触する測定面と反対側から前記被測定物を保持する保持部材と、
前記測定プローブをそれぞれ被測定物に押し当てるための押付け手段と、
前記被測定物の一端部を定常加熱または周期加熱して前記被測定物の測定面方向に温度差を発生させるためのヒータと、
を備え、
前記測定プローブは、それぞれ絶縁体の支持管に熱電対を通して先端を計測部として突出させて構成されており、それぞれの前記測定プローブの計測部が前記被測定物に流れる電流または熱流に沿った方向に配置されていることを特徴とする熱電特性評価ユニット。 A thermoelectric characterization unit that evaluates the electrical resistivity, Seebeck coefficient, and thermal diffusivity of an object to be measured made of thermoelectric material.
Multiple measuring probes for contacting the object under test and measuring the voltage and thermoelectromotive force from the object under test.
A holding member that holds the object to be measured from the side opposite to the measurement surface where the object to be measured comes into contact with the measurement probe.
Pressing means for pressing the measurement probe against the object to be measured, and
A heater for constantly heating or periodically heating one end of the object to be measured to generate a temperature difference in the direction of the measurement surface of the object to be measured.
With
Each of the measurement probes is configured by passing a thermocouple through an insulator support tube and projecting the tip as a measurement unit, and the direction in which the measurement unit of each measurement probe is along the current or heat flow flowing through the object to be measured. A thermoelectric characteristic evaluation unit characterized by being arranged in. 前記ヒータは、前記保持部材に、前記被測定物の一端部で接触可能に配置されていることを特徴とする請求項１に記載の熱電特性評価ユニット。 The thermoelectric characteristic evaluation unit according to claim 1, wherein the heater is arranged so as to be in contact with the holding member at one end of the object to be measured. 前記押付け手段は、
プッシュロッド機構を備え、前記測定プローブにそれぞれ取り付けられた接触圧調整部材と、
前記接触圧調整部材を介して前記複数の測定プローブを前記被測定物に向かって対して直線駆動する駆動手段と、を備え、
前記接触圧調整部材は、各測定プローブにおいて、前記計測部が前記被測定物に接触した後は、前記駆動手段による変位を吸収するとともに当該計測部による前記被測定物に対する押付け力を発生させることを特徴とする請求項１または請求項２に記載の熱電特性評価ユニット。 The pressing means
A contact pressure adjusting member equipped with a push rod mechanism and attached to each of the measuring probes,
A driving means for linearly driving the plurality of measuring probes toward the object to be measured via the contact pressure adjusting member is provided.
In each measurement probe, the contact pressure adjusting member absorbs the displacement caused by the driving means and generates a pressing force against the object to be measured by the measuring unit after the measuring unit comes into contact with the object to be measured. The thermoelectric characteristic evaluation unit according to claim 1 or 2. 請求項１ないし請求項３のいずれか１つに記載の熱電特性評価ユニットと、
当該熱電特性評価ユニットを制御し当該熱電特性評価ユニットから送出される信号に基づいて前記被測定物の電気抵抗率、ゼーベック係数及び熱拡散率を測定する制御手段と、
を備えたことを特徴とする熱電特性評価装置。 The thermoelectric characterization unit according to any one of claims 1 to 3,
A control means that controls the thermoelectric characteristic evaluation unit and measures the electrical resistivity, Seebeck coefficient, and thermal diffusivity of the object to be measured based on the signal sent from the thermoelectric characteristic evaluation unit.
A thermoelectric characterization device characterized by being equipped with. 請求項４に記載の熱電特性評価装置を用いた熱電特性評価方法であって、
前記熱電特性評価ユニットを用いて、被測定物に前記測定プローブをそれぞれ接触させる工程と、
前記測定プローブにより被測定物に電流を流し、他の測定プローブにより計測された異なる２点間の電圧に基づいて電気抵抗率を算出する工程と、
前記ヒータにより被測定物を定常加熱し、前記測定プローブにより測定される異なる２点間の温度差により発生する起電力に基づいてゼーベック係数を算出する工程と、
前記ヒータにより被測定物を周期加熱し、前記測定プローブにより異なる２点の温度波形データをそれぞれ取得し、前記制御手段で生成した基準となる温度波形データを用いて異なる２点間の周期的な温度変化の位相差を演算し、当該周期的な温度変化の位相差の周波数依存性に基づいて周期的な温度変化の位相差の周波数依存性に基づいて熱拡散率を算出する工程と、を備えたことを特徴とする熱電特性評価方法。 A thermoelectric characteristic evaluation method using the thermoelectric characteristic evaluation device according to claim 4.
The step of bringing the measurement probe into contact with the object to be measured using the thermoelectric characterization unit, and
A step of passing a current through the object to be measured by the measuring probe and calculating the electrical resistivity based on the voltage between two different points measured by another measuring probe.
A step of constantly heating the object to be measured by the heater and calculating the Seebeck coefficient based on the electromotive force generated by the temperature difference between two different points measured by the measuring probe.
The object to be measured is periodically heated by the heater, temperature waveform data of two different points are acquired by the measurement probe, and the reference temperature waveform data generated by the control means is used to periodically heat the object to be measured. The process of calculating the phase difference of the temperature change and calculating the thermal diffusion rate based on the frequency dependence of the phase difference of the periodic temperature change based on the frequency dependence of the phase difference of the periodic temperature change. A thermoelectric characteristic evaluation method characterized by being provided.
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