JP2591570B2 - Thermal analysis method and apparatus using temperature wave - Google Patents

Thermal analysis method and apparatus using temperature wave

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Publication number
JP2591570B2
JP2591570B2 JP4271471A JP27147192A JP2591570B2 JP 2591570 B2 JP2591570 B2 JP 2591570B2 JP 4271471 A JP4271471 A JP 4271471A JP 27147192 A JP27147192 A JP 27147192A JP 2591570 B2 JP2591570 B2 JP 2591570B2
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JP
Japan
Prior art keywords
sample
measured
temperature
thin film
thermal analysis
Prior art date
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JP4271471A
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Japanese (ja)
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JPH05223762A (en
Inventor
寿正 橋本
玲 宮本
公平 静
耕三 田中
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Mitsui Toatsu Chemicals Inc
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Mitsui Toatsu Chemicals Inc
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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は物質の熱分析方法および
これに用いられる装置に関し、特に、高分子化合物やセ
ラミックス等の難導電性物質の融点、ガラス転移点など
の熱分析を精度良く行う測定方法および装置と、熱分析
と同時に厚み方向の熱拡散率を測定する方法および装置
と、その熱拡散率測定方法より得られる熱拡散率の測定
値を用いて熱伝導率を求める熱伝導率の測定方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for thermal analysis of a substance and an apparatus used for the method, and more particularly to a method for accurately performing a thermal analysis on a melting point and a glass transition point of a poorly conductive substance such as a polymer compound and ceramics. Measuring method and apparatus, method and apparatus for measuring thermal diffusivity in the thickness direction simultaneously with thermal analysis, and thermal conductivity for obtaining thermal conductivity using measured values of thermal diffusivity obtained by the thermal diffusivity measuring method The measurement method.

【０００２】[0002]

【従来の技術】高分子化合物などの物質は、その温度を
変化させていくとある温度において、ガラス状態からゴ
ム状態への変化、固相から液相への変化、結晶構造の変
化などの転移を起こす。これらの転移温度は、高分子化
合物等の各種の物質の材料設計、製品設計を行う際の加
工条件、使用条件を決定する上で重要な物性値の一つで
ある。また、熱拡散率および熱伝導率も同様に、高分子
化合物等の各種の物質の材料設計、製品設計を行う際の
加工条件、使用条件を決定する上で重要な物性値の一つ
である。近年、コンピュ−タ化の発展にともない各種シ
ミュレ−ション・プログラムが数多く開発され、それら
を利用した材料設計、製品設計が頻繁に行われている。
例えば、加工製品や構造物の応力や変形を解析する構造
解析、熱移動現象を解析する熱伝導解析等は既に世の中
で広く活用されており、最近では射出成形における金型
内の樹脂挙動を解析する熱流動解析等も数多く利用され
てきている。それらのシミュレ−ション・プログラムの
解析精度は、プログラムの内容もさることながら、解析
に用いる物性値の精度により大きく左右される。従っ
て、それらの解析精度を向上させ、材料設計、製品設計
を的確に行う為に対象物質の高精度な物性測定が望まれ
ている。2. Description of the Related Art When a temperature of a substance such as a polymer compound is changed, at a certain temperature, a transition from a glassy state to a rubbery state, a change from a solid phase to a liquid phase, a change in a crystal structure, and the like. Cause These transition temperatures are one of the important physical property values in determining the material design of various substances such as a polymer compound and the processing conditions and the use conditions when designing products. Similarly, thermal diffusivity and thermal conductivity are also one of the important physical property values in determining material design of various substances such as polymer compounds, processing conditions when performing product design, and use conditions. . In recent years, with the development of computerization, many simulation programs have been developed, and material design and product design using them have been frequently performed.
For example, structural analysis, which analyzes the stress and deformation of processed products and structures, and heat conduction analysis, which analyzes heat transfer phenomena, have already been widely used in the world.Recently, analysis of resin behavior in a mold during injection molding has been performed. Thermal fluid analysis, etc., have been widely used. The analysis accuracy of these simulation programs is greatly affected not only by the contents of the program but also by the accuracy of the physical property values used in the analysis. Therefore, high-precision physical property measurement of a target substance is desired in order to improve their analysis accuracy and accurately perform material design and product design.

【０００３】実際に加工された製品は、室温下で使用さ
れるだけではなく、高温下で使用される場合が数多くあ
り、また、高分子材料等の多くは、加工する際に高温下
で溶融した後に室温まで冷却するという成形過程を経
る。このため、製品の実際の使用条件、加工条件を考慮
しての材料設計、製品設計を行なう場合や、実現象に基
づいた解析を行なう場合、対象となる物質の転移温度を
知ることが必要である。近年では、加工材料の複合形態
での利用が頻繁に行われるようになってきており、その
組合せは多岐にわたり複雑化してきている。そのよう
な、特殊な加工材料の開発、設計を行なうための物性を
測定するにあたり、大量の被測定試料を入手するのが困
難な場合が数多くある。また、物性値を素早く知り、そ
の結果を開発内容や設計内容に、時間的遅れ無く反映さ
せることが必要とされてきており、それらの結果、小量
の試料で迅速に物性測定を行うことが不可欠である。[0003] Actually processed products are used not only at room temperature but also at high temperatures in many cases, and many polymer materials and the like are melted at high temperatures during processing. After that, it goes through a molding process of cooling to room temperature. For this reason, it is necessary to know the transition temperature of the target substance when performing material design and product design in consideration of the actual use conditions and processing conditions of the product, or when performing analysis based on actual phenomena. is there. In recent years, processing materials have been frequently used in a composite form, and combinations thereof have become diverse and complicated. In measuring physical properties for developing and designing such special processing materials, it is often difficult to obtain a large amount of samples to be measured. In addition, it is necessary to know the physical property values quickly and reflect the results in development and design contents without time delay.As a result, it is possible to measure physical properties quickly with a small amount of sample. It is essential.

【０００４】転移温度は、物質を外部から一定の速度で
加熱または冷却して比熱、重量などの変化を検出する熱
分析により測定される。熱分析には、測定温度範囲内で
吸熱、発熱のない標準試料との温度差を測定する示差熱
重量分析や、温度差を絶えず打ち消すように熱量を供給
または除去する示差走査熱量計が最も広く用いられてい
る。これらの測定に際して被測定試料は、アルミニウム
やステンレス製の容器にいれられて、測定用の試料室内
で加熱、冷却される。[0004] The transition temperature is measured by thermal analysis in which a substance is heated or cooled from the outside at a constant rate and changes in specific heat, weight, etc. are detected. The most common types of thermal analysis are differential thermogravimetric analysis, which measures the temperature difference between a standard sample that does not absorb heat and heat generation within the measurement temperature range, and differential scanning calorimeter, which supplies or removes heat so that the temperature difference is constantly canceled. Used. At the time of these measurements, the sample to be measured is placed in an aluminum or stainless steel container and heated and cooled in the sample chamber for measurement.

【０００５】[0005]

【発明が解決しようとする課題】従来法である示差熱重
量分析、示差走査熱量計は、転移温度を正確に得るため
に、温度、熱量の高精度な測定が必要であり、また、試
料の形状や試料を容器にセットした時の状態により、加
熱、冷却時の熱伝導が変化して、測定精度が悪くなると
いった問題点がある。さらに、測定に際して、測定温度
範囲で熱的に変化しない標準物質が必要である。また、
従来の熱分析方法では、転移温度の測定と熱拡散率、熱
伝導率の測定を同時に行うことは非常に困難である。The conventional methods of differential thermogravimetric analysis and differential scanning calorimetry require high-precision measurement of temperature and calorie in order to accurately obtain a transition temperature. There is a problem that the heat conduction during heating and cooling changes depending on the shape and the state when the sample is set in the container, and the measurement accuracy deteriorates. Further, at the time of measurement, a standard material that does not thermally change in the measurement temperature range is required. Also,
With the conventional thermal analysis method, it is very difficult to simultaneously measure the transition temperature and the thermal diffusivity and thermal conductivity.

【０００６】[0006]

【課題を解決するための手段】すなわち、本発明は、薄
い被測定試料の熱分析方法であって、該薄い被測定試料
の両面に導電性の薄膜を形成あるいは密着させて、該薄
膜の一方に電流を流すことによってそのジュール熱によ
り発熱する交流熱源とし、他方の薄膜を温度によりその
抵抗値が変化することを利用する抵抗式温度計とした測
定系を用い、該被測定試料の前記交流熱源に所定の変調
周波数で変調を加えた交流電流を流して交流発熱させ、
該抵抗式温度計に該交流発熱に対応する温度変化を起こ
させるとともに、該被測定試料の温度をあるパターンで
変化せしめ、かくして得られた各測定温度における該温
度変化の位相と温度の関係または振幅と温度の関係、あ
るいは該交流熱源の温度変化と該抵抗式温度計により測
定された温度変化との位相差と該変調周波数との関係よ
り、該被測定試料の熱分析を行う被測定試料の熱分析方
法、であり、また両面に導電性薄膜を備えた薄い被測定
試料の熱分析を行う装置であって、一方の導電性薄膜に
一定振幅の変調を加えた交流電流を供給する交流電流発
生手段と、他方の導電性薄膜に所定の直流電流を供給す
る直流電流供給手段と、前記他方の導電性薄膜の抵抗値
の温度依存性に起因して変化する電圧を増幅するロック
イン増幅器とを有する温度波による熱分析装置、を要旨
とする。That is, the present invention relates to a thermal analysis method for a thin sample to be measured, wherein a conductive thin film is formed or adhered to both sides of the thin sample to be measured. A current source is used as an AC heat source that generates heat by Joule heat, and the other thin film uses a measurement system that is a resistance thermometer that utilizes the fact that its resistance value changes with temperature. An AC current modulated at a predetermined modulation frequency is supplied to the heat source to generate AC heat,
The resistance thermometer causes a temperature change corresponding to the AC heat generation, and the temperature of the sample to be measured is changed in a certain pattern, and the relationship between the phase and the temperature of the temperature change at each measurement temperature thus obtained or A sample to be subjected to thermal analysis of the sample to be measured based on a relationship between amplitude and temperature, or a relationship between the modulation frequency and a phase difference between a temperature change of the AC heat source and a temperature change measured by the resistance thermometer. An apparatus for performing a thermal analysis of a thin sample to be measured having a conductive thin film on both sides, wherein an alternating current is supplied to one of the conductive thin films by applying an alternating current having a constant amplitude modulation. Current generating means, DC current supplying means for supplying a predetermined DC current to the other conductive thin film, and a lock-in amplifier for amplifying a voltage that changes due to temperature dependence of the resistance value of the other conductive thin film With That thermal analyzer by temperature wave, and the gist.

【０００７】以下本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.

【０００８】本発明における被測定試料はフィルム、シ
ートまたは板状の難導電性の物質あるいは液体状または
液体状となしうる難導電性の物質であり、例えば、 Ｉ．フェノール、ユリア、メラミン、ポリエステル、エ
ポキシ、ポリウレタン、セルロース、ポ リスチレン、
ポリプロピレン、ポリエチレン、塩化ビニルデン、ポリ
アミド、ポリアセタール、ポリカーボネイト、ポリサル
ホン、ＡＢＳ、ポリフェニレンオキサイド、ポリエーテ
ルサルホン、ポリアリレート、アクリル、アクリルニト
リル、ポリアクリルニトリル、ポリエーテルエーテルケ
トン、ポリエーテルケトン、ポリイミド、ポリオレフィ
ン等の高分子化合物 II．シアニン、フタロシアニン、ナフタロシアニン、ニ
ッケル酢体、スピロ化合物、フェロセン、フルギド、イ
ミダゾール、ペリレン、フェナジン、フェノチアジン、
ポリエン、アゾ化合物、キノン、インジゴ、ジフェニル
メタン、トリフェニルメタン、ポリメチン、アクリジ
ン、アクリジノン、カルボスチリル、クマリン、ジフェ
ニルアミン、キナクリドン、キノフタロン、フェノサキ
ジン、フタロペリノン等の有機色素 III. 珪石、ダイアモンド、ざくろ石、コランダム、ル
ビー、サファイア、めのう、沸石、珪藻土、雲母、岩
塩、燐灰石、カオリン、チュモルチ石、珪線石、紅柱
石、藍晶石、苦灰石、月長石、大理石、蛇紋石、くじゃ
く石、ボーキサイト、ベンナイト、石英、カンラン石、
石膏、硫黄、重晶石、みょうばん石、蛍石、長石、滑
石、石綿、石灰石、ドロマイト、方解石、水晶、こは
く、スピネル、アレキサンドライト、エメラルド、トパ
ーズ、猫目石、ひすい、オパール等の鉱石 IV．石英ガラス、フッ化物ガラス、ソーダガラス、ソー
ダ石灰ガラス、バリウム・ストロンチウムガラス、鉛ガ
ラス、アルミノホウケイ酸ガラス、ホウケイ酸ガラス、
アルミノケイ酸塩ガラス、シリカガラス等のガラス Ｖ．Ａｌ2 Ｏ3 、ＭｇＡｌ2 Ｏ4 、ＢｅＯ、ＳｉＣ、Ａ
ＩＮ、ＭｇＯ、ＰＬＺＴ、Ｙ2 Ｏ3 、ＺｒＯ2 、ＴｉＯ
2 、ＣａＦ2 、ＧａＡｓ、ＰｂＯ、ＣａＯ、Ｌａ
2 Ｏ3 、Ｓｉ3 Ｎ4 、ａ−ＳｉＨ等のファインセラミッ
クス等である。The sample to be measured in the present invention is a film,
Sheet or plate-shaped non-conductive substance or liquid or
A non-conductive substance that can be made into a liquid state. Phenol, urea, melamine, polyester, d
Poxy, polyurethane, cellulose, polystyrene,
Polypropylene, polyethylene, vinyldene chloride, poly
Amide, polyacetal, polycarbonate, polysal
Hong, ABS, polyphenylene oxide, polyether
Lusulfone, polyarylate, acrylic, acrylic nitrite
Lil, polyacrylonitrile, polyetheretherke
Ton, polyetherketone, polyimide, polyolefin
II. Cyanine, phthalocyanine, naphthalocyanine, d
Hackel vinegar, spiro compound, ferrocene, fulgide, i
Midazole, perylene, phenazine, phenothiazine,
Polyene, azo compound, quinone, indigo, diphenyl
Methane, triphenylmethane, polymethine, acrizi
, Acridinone, carbostyril, coumarin, diphe
Nilamine, quinacridone, quinophthalone, phenosaki
Organic dyes such as gin, phthaloperinone, etc. III. Silica, diamond, garnet, corundum, ru
Bee, sapphire, agate, zeolite, diatomaceous earth, mica, rock
Salt, apatite, kaolin, tumorite, sillimanite, red pillar
Stones, kyanite, dolomite, feldspar, marble, serpentine, kuku
Stone, bauxite, benite, quartz, olivine,
Gypsum, sulfur, barite, alumite, fluorite, feldspar, slip
Stone, asbestos, limestone, dolomite, calcite, crystal, koha
, Spinel, alexandrite, emerald, topa
Ores such as beet, cat eye, jade, opal, etc. IV. Quartz glass, fluoride glass, soda glass, saw
Lime glass, barium strontium glass, lead gas
Glass, aluminoborosilicate glass, borosilicate glass,
Glasses such as aluminosilicate glass and silica glass AlTwoOThree, MgAlTwoOFour, BeO, SiC, A
IN, MgO, PLZT, YTwoOThree, ZrOTwo, TiO
Two, CaFTwo, GaAs, PbO, CaO, La
TwoOThree, SiThreeNFour, A-SiH and other fine ceramics
Etc.

【０００９】交流熱源に用いる導電性物質は、電流を流
すことでジュ−ル熱により発熱するもので、例えば、
金、銀、白金、銅、鉄、亜鉛、アンチモン、イリジウ
ム、クロメル、コンスタンタン、ニクロム、アルミニウ
ム、クローム、ニッケル、カ−ボン等である。抵抗式温
度計に用いる導電性薄膜は、温度により抵抗値が変化す
るもので、例えば、金、銀、白金、銅、鉄、亜鉛、アン
チモン、イリジウム、クロメル、コンスタンタン、ニク
ロム、アルミニウム、クローム、ニッケル、カ−ボン等
である。また、それらの交流熱源および抵抗式温度計に
用いる導電性薄膜は、被測定試料との界面が無視できる
程度に、その厚みは被測定試料に比べて充分薄く、その
熱容量は被測定試料に比べて充分小さく、被測定試料に
完全に密着しており、従って被測定試料の一方の面自体
が交流熱源の変調周波数で交流発熱し、他方の面の温度
変化の交流成分を直接測定していると考えられる。The conductive substance used for the AC heat source generates heat by Joule heat when an electric current is applied.
Gold, silver, platinum, copper, iron, zinc, antimony, iridium, chromel, constantan, nichrome, aluminum, chrome, nickel, carbon and the like. The conductive thin film used for the resistance thermometer changes its resistance depending on the temperature.For example, gold, silver, platinum, copper, iron, zinc, antimony, iridium, chromel, constantan, nichrome, aluminum, chrome, nickel , Carbon and the like. The thickness of the conductive thin film used for the AC heat source and the resistance thermometer is sufficiently thin compared to the sample to be measured so that the interface with the sample to be measured is negligible, and its heat capacity is smaller than that of the sample to be measured. Small enough to be in full contact with the sample under test, so that one surface of the sample under test itself generates AC heat at the modulation frequency of the AC heat source and directly measures the AC component of the temperature change on the other surface. it is conceivable that.

【００１０】被測定試料が固体状の場合、被測定試料の
両面に導電性薄膜を、 Ｉ．イオンを固体表面に照射することにより、固体を構
成する原子が飛び出す現象を利用して、表面上に吸着さ
せることにより薄膜を生成するスパッタ II．真空中で物質を蒸発させ、これを表面上に吸着させ
ることにより薄膜を生成する蒸着 III. 液体、半液体状態の物質を表面上に塗りつける塗
布 IV．同種あるいは異種物質からなる接着剤により、表面
を接合する接着 Ｖ．表面上に同種あるいは異種物質からなる接着剤を用
いずに、押しつけることによる圧着力で接合する圧着 VI．被測定試料を溶融後冷却固化することにより密着さ
せる融着 等により形成あるいは密着させるが、スパッタまたは、
蒸着による方法が最も好ましい。When the sample to be measured is solid, a conductive thin film is provided on both sides of the sample to be measured. Sputtering that forms a thin film by adsorbing it on the surface, utilizing the phenomenon that atoms constituting the solid fly out by irradiating ions to the surface of the solid. II. Vaporization in which a substance is evaporated in a vacuum and adsorbed on the surface to form a thin film. III. Application in which liquid or semi-liquid state substance is applied on the surface. IV. Adhesion of joining surfaces with an adhesive composed of the same or different materials. Crimping by bonding with pressing force without using an adhesive made of the same or different substance on the surface VI. The sample to be measured is melted and then solidified by cooling and solidification.
The method by vapor deposition is most preferred.

【００１１】スパッタにより被測定試料に導電性薄膜を
形成あるいは密着する場合は、例えば金を用いる場合、
被測定試料あるいは密着させる物質にポリエステル・フ
ィルム等でマスクを施した後、真空下において、１．２
ＫＶ、３．５ｍＡ程度の電圧および電流で、３０分程度
にわたり被測定試料上あるいは密着させる物質上に金を
吸着させ、厚さ１０〜５０００オングストローム、抵抗
値０．１Ω〜１０ＫΩ程度の導電性薄膜にするのが好ま
しい。When a conductive thin film is formed or adhered to a sample to be measured by sputtering, for example, when gold is used,
After applying a mask with a polyester film or the like to the sample to be measured or the substance to be adhered to,
At a voltage and a current of about 3.5 mA, gold is adsorbed on a sample to be measured or a substance to be adhered for about 30 minutes, and a conductive thin film having a thickness of 10 to 5000 angstroms and a resistance of about 0.1 Ω to 10 KΩ is applied. It is preferred that

【００１２】蒸着により被測定試料に導電性薄膜を形成
あるいは密着する場合は、例えば金を用いる場合、被測
定試料あるいは密着させる物質にポリエステル・フィル
ム等でマスクを施した後、真空下において金をその融点
以上まで通電加熱して蒸発させ、３０分程度にわたり被
測定試料上あるいは密着させる物質上に金を吸着させ、
厚さ１０〜５０００オングストローム、抵抗値０．１Ω
〜１０ＫΩ程度の導電性薄膜にするのが好ましい。When a conductive thin film is formed or adhered to a sample to be measured by vapor deposition, for example, when gold is used, a mask is applied to the sample to be measured or a substance to be adhered with a polyester film or the like, and then gold is applied under vacuum. Electricity heating up to the melting point or more to evaporate, and for about 30 minutes gold is adsorbed on the sample to be measured or on the substance to be adhered,
10-5000 angstrom thickness, 0.1Ω resistance
It is preferable to form a conductive thin film of about 10 to 10 KΩ.

【００１３】塗布により被測定試料に導電性薄膜を形成
あるいは密着する場合は、銀ペーストなどの導電性ペー
ストを被測定試料あるいは密着させる物質に、厚さ１０
〜５０００オングストローム、抵抗値０．１Ω〜１０Ｋ
Ω程度になるように均一に塗るのが好ましい。When a conductive thin film is formed or adhered to a sample to be measured by coating, a conductive paste such as a silver paste is applied to the sample to be measured or a substance to be adhered with a thickness of 10 μm.
Up to 5000 angstroms, resistance 0.1Ω to 10K
It is preferable to apply uniformly so as to be about Ω.

【００１４】接着により被測定試料に導電性薄膜を形成
あるいは密着する場合は、厚さ１０〜５０００オングス
トローム、抵抗値０．１Ω〜１０ＫΩ程度の銅箔、金箔
等の導電性薄膜に、接着剤を導電性薄膜と被測定試料あ
るいは密着させる物質との界面が無視できる程度に薄く
塗り、被測定試料に剥がれないように完全に密着させる
のが好ましい。When a conductive thin film is formed or adhered to the sample to be measured by bonding, an adhesive is applied to a conductive thin film such as a copper foil or a gold foil having a thickness of 10 to 5000 angstroms and a resistance of about 0.1 Ω to 10 KΩ. It is preferable that the interface between the conductive thin film and the sample to be measured or the substance to be adhered is thinly applied to a negligible extent, and the film is completely adhered to the sample to be measured so as not to peel off.

【００１５】圧着により被測定試料に導電性薄膜を形成
あるいは密着する場合は、厚さ１０〜５０００オングス
トローム、抵抗値０．１Ω〜１０ＫΩ程度の銅箔、金箔
等の導電性薄膜を、導電性薄膜と被測定試料との界面の
影響が無視できる圧着力以上の力で、被測定試料に押し
つけて完全に密着させるのが好ましい。When a conductive thin film is formed or brought into close contact with the sample to be measured by crimping, a conductive thin film such as a copper foil or a gold foil having a thickness of 10 to 5000 angstroms and a resistance of about 0.1 Ω to 10 KΩ is used. It is preferable that the sample is pressed against the sample to be measured and completely adhered thereto with a force equal to or greater than the crimping force where the influence of the interface between the sample and the sample can be ignored.

【００１６】融着により被測定試料に導電性薄膜を形成
する場合は、厚さ１０〜５０００オングストローム、抵
抗値０．１Ω〜１０ＫΩ程度のスパッタ膜、蒸着膜、銅
箔、金箔等の導電性薄膜を被測定試料に溶融させて密着
した後に冷却固化させることにより、導電性薄膜と被測
定試料との界面の影響が無視できる程度に完全に密着さ
せるのが好ましい。When a conductive thin film is formed on a sample to be measured by fusion, a conductive thin film such as a sputtered film having a thickness of 10 to 5000 angstroms and a resistance value of about 0.1 Ω to 10 KΩ, a deposited film, a copper foil, a gold foil or the like is used. Is preferably melted and adhered to the sample to be measured, and then cooled and solidified to completely adhere to the conductive thin film and the sample to be measured so that the influence of the interface is negligible.

【００１７】被測定試料が液体状の場合、導電性薄膜
を、 Ｉ．イオンを固体表面に照射することにより、固体を構
成する原子が飛び出す現象を利用して、表面上に吸着さ
せることにより薄膜を生成するスパッタ II．真空中で物質を蒸発させ、これを表面上に吸着させ
ることにより薄膜を生成する蒸着 III.液体、半液体状態の物質を表面上に塗りつける塗布 IV．同種あるいは異種物質からなる接着剤により、表面
を接合する接着 等によりガラス板等の上に形成させるが、スパッタまた
は、蒸着による方法が最も好ましい。When the sample to be measured is in a liquid state, the conductive thin film is formed by: Sputtering that forms a thin film by adsorbing it on the surface, utilizing the phenomenon that atoms constituting the solid fly out by irradiating ions to the surface of the solid. II. Vaporization in which a substance is evaporated in a vacuum and adsorbed on the surface to form a thin film. III. Application in which a liquid or semi-liquid state substance is applied on the surface. IV. It is formed on a glass plate or the like by bonding the surfaces together with an adhesive made of the same or different substance, but the method by sputtering or vapor deposition is most preferable.

【００１８】スパッタによりガラス板等に導電性薄膜を
形成する場合は、例えば金を用いる場合、ガラス板等に
ポリエステル・フィルム等でマスクを施した後、真空下
において、１．２ＫＶ、３．５ｍＡ程度の電圧および電
流で、３０分程度にわたりガラス板等の上に金を吸着さ
せ、厚さ１０〜５０００オングストローム、抵抗値０．
１Ω〜１０ＫΩ程度の導電性薄膜にするのが好ましい。
蒸着によりガラス板等に導電性薄膜を形成する場合は、
例えば金を用いる場合、をその融点以上まで通電加熱し
て蒸発させ、３０分程度にわたりガラス板等の上に金を
吸着させ、厚さ１０〜５０００オングストローム、抵抗
値０．１Ω〜１０ＫΩ程度の導電性薄膜にするのが好ま
しい。塗布によりガラス板等に導電性薄膜を形成する場
合は、銀ペースト等の導電性ペーストをガラス板等に、
厚さ１０〜５０００オングストローム、抵抗値０．１Ω
〜１０ＫΩ程度になるように均一に塗るのが好ましい。
接着によりガラス板等に導電性薄膜を形成する場合は、
厚さ１０〜５０００オングストローム、抵抗値０．１Ω
〜１０ＫΩ程度の銅箔、金箔等の導電性薄膜に、接着剤
を塗り、ガラス板等からはがれないように完全に密着さ
せるのが好ましい。When a conductive thin film is formed on a glass plate or the like by sputtering, for example, when gold is used, a mask is applied to the glass plate or the like with a polyester film or the like, and then 1.2 KV, 3.5 mA under vacuum. At a voltage and a current of about 30 minutes, gold is adsorbed on a glass plate or the like for about 30 minutes, the thickness is 10 to 5000 angstroms, and the resistance value is 0.
It is preferable to form a conductive thin film of about 1 Ω to 10 KΩ.
When forming a conductive thin film on a glass plate etc. by vapor deposition,
For example, when gold is used, it is heated to a temperature equal to or higher than its melting point to evaporate it, and the gold is adsorbed on a glass plate or the like for about 30 minutes, and has a thickness of 10 to 5000 angstroms and a resistance of about 0.1 Ω to 10 KΩ. It is preferable to use a conductive thin film. When a conductive thin film is formed on a glass plate or the like by coating, a conductive paste such as a silver paste is
10-5000 angstrom thickness, 0.1Ω resistance
It is preferable to apply evenly so as to be about 10 to 10 KΩ.
When forming a conductive thin film on a glass plate etc. by bonding,
10-5000 angstrom thickness, 0.1Ω resistance
It is preferable to apply an adhesive to a conductive thin film such as a copper foil or a gold foil having a thickness of about 10 to 10 KΩ so that the conductive thin film is completely adhered so as not to be separated from a glass plate or the like.

【００１９】被測定試料が液体状の場合、前記いずれか
の方法によりガラス板等に形成された２枚の導電性薄膜
で、液体状の被測定試料をはさみ、導電性薄膜と被測定
試料との界面の影響が無視できる程度に完全に密着させ
る。When the sample to be measured is in a liquid state, the liquid sample to be measured is sandwiched between two conductive thin films formed on a glass plate or the like by any one of the above methods, and the conductive thin film and the sample to be measured are separated. Are completely adhered to such an extent that the influence of the interface is negligible.

【００２０】以下、本発明の基本的構成とその特徴を図
面を参照して説明する。図１は被測定試料が固体状の場
合で、１は被測定試料で、厚みの上限は２０００μｍ以
下、好ましくは１５００μｍ以下、さらに好ましくは１
０００μｍ以下であり、厚みの下限は両面に形成された
導電性薄膜の熱容量が無視できる範囲で、０．０１μｍ
以上、好ましくは０．１μｍ以上、さらに好ましくは１
μｍ以上のフィルム又はシ−トもしくは板状のものであ
る。また、被測定試料１は高分子化合物、セラミックス
等の難導電性物質で、その抵抗率が１×１０4 Ω・ｃｍ
以上、好ましくは１×１０6 Ω・ｃｍ以上、さらに好ま
しくは１×１０7 Ω・ｃｍ以上であり、抵抗率の上限に
ついてはいくら大きくてもかまわないが、例えば１×１
０21Ω・ｃｍ以下、好ましくは１×１０22Ω・ｃｍ以
下、さらに好ましくは１０23Ω・ｃｍ以下である。Hereinafter, the basic structure and features of the present invention will be described with reference to the drawings. FIG. 1 shows a case where the sample to be measured is solid. Reference numeral 1 denotes a sample to be measured. The upper limit of the thickness is 2000 μm or less, preferably 1500 μm or less, and more preferably 1 μm or less.
000 μm or less, and the lower limit of the thickness is 0.01 μm in a range where the heat capacity of the conductive thin film formed on both surfaces can be ignored.
Or more, preferably 0.1 μm or more, more preferably 1 μm or more.
It is a film or sheet or plate having a thickness of at least μm. The sample 1 to be measured is a poorly conductive substance such as a polymer compound or ceramics, and has a resistivity of 1 × 10 4 Ω · cm.
As described above, the resistivity is preferably 1 × 10 6 Ω · cm or more, more preferably 1 × 10 7 Ω · cm or more, and the upper limit of the resistivity may be any value.
0 21 Ω · cm or less, preferably 1 × 10 22 Ω · cm or less, more preferably 10 23 Ω · cm or less.

【００２１】２は変調を加えた電流により被測定試料の
一面を交流加熱するための交流熱源となる導電性薄膜
で、その抵抗値は０．０１Ω〜１００ＫΩ、好ましくは
０．０５Ω〜５０ＫΩ、さらに好ましくは０．１Ω〜１
０ＫΩである。交流熱源となる導電性薄膜は、被測定試
料と交流熱源の界面が無視できる程度に被測定試料に完
全に密着しており、その厚みは被測定試料に比べて充分
薄く、例えば５００００オングストロ−ム以下、好まし
くは１００００オングストロ−ム以下、さらに好ましく
は５０００オングストロ−ム以下で、厚みの下限は交流
電流が通電可能であればいくらでも良いが、例えば１オ
ングストローム以上、好ましくは５オングストローム以
上、さらに好ましくは１０オングストローム以上であ
る。Reference numeral 2 denotes a conductive thin film serving as an AC heat source for AC-heating one surface of the sample to be measured by a modulated current, and has a resistance value of 0.01 Ω to 100 KΩ, preferably 0.05 Ω to 50 KΩ, and Preferably 0.1Ω to 1
0 KΩ. The conductive thin film serving as the AC heat source is completely adhered to the sample to be measured so that the interface between the sample and the AC heat source is negligible, and its thickness is sufficiently smaller than the sample to be measured, for example, 50,000 angstroms. Or less, preferably 10,000 angstroms or less, more preferably 5000 angstroms or less, and the lower limit of the thickness is not particularly limited as long as an alternating current can be passed, but is, for example, 1 angstroms or more, preferably 5 angstroms or more, and more preferably 10 Å or more.

【００２２】３は交流熱源と反対の面の温度変化の交流
成分を測定するための抵抗式温度計となる導電性薄膜
で、その抵抗値は０．０１Ω〜１００ＫΩ、好ましくは
０．０５Ω〜５０ＫΩ、さらに好ましくは０．１Ω〜１
０ＫΩである。抵抗式温度計となる導電性薄膜は、被測
定試料と抵抗式温度計の界面が無視できる程度に被測定
試料に完全に密着しており、その厚みは被測定試料に比
べて充分薄く、例えば５００００オングストロ−ム以
下、好ましくは１００００オングストロ−ム以下、さら
に好ましくは５０００オングストロ−ム以下で、厚みの
下限は直流電流を通電し抵抗値の温度依存性に起因して
起こる電圧の変化を読み取ることが可能であればいくら
でも良いが、例えば１オングストローム以上、好ましく
は５オングストローム以上、さらに好ましくは１０オン
グストローム以上である。Reference numeral 3 denotes a conductive thin film serving as a resistance thermometer for measuring an AC component of a temperature change on a surface opposite to the AC heat source, and has a resistance value of 0.01 Ω to 100 KΩ, preferably 0.05 Ω to 50 KΩ. , More preferably 0.1 Ω to 1
0 KΩ. The conductive thin film that becomes the resistance thermometer is completely adhered to the measurement sample so that the interface between the measurement sample and the resistance thermometer can be ignored, and its thickness is sufficiently thin compared to the measurement sample. 50,000 angstrom or less, preferably 10,000 angstrom or less, more preferably 5,000 angstrom or less, and the lower limit of the thickness is to apply a direct current to read the voltage change caused by the temperature dependence of the resistance value. Any number is possible as long as it is possible, for example, 1 Å or more, preferably 5 Å or more, more preferably 10 Å or more.

【００２３】図２は被測定試料が液体状の場合で、１は
被測定試料で４のスペーサにより保持されており、その
厚みの上限は２０００μｍ以下、好ましくは１５００μ
ｍ以下、さらに好ましくは１０００μｍ以下であり、厚
みの下限は両面に形成された導電性薄膜の熱容量が無視
できる範囲で、０．０１μｍ以上、好ましくは０．１μ
ｍ以上、さらに好ましくは１μｍ以上の液体状のもので
ある。また、被測定試料１は高分子化合物、有機色素等
の難導電性物質で、その抵抗率が１×１０4 Ω・ｃｍ以
上、好ましくは１×１０6 Ω・ｃｍ以上、さらに好まし
くは１×１０7Ω・ｃｍ以上であり、抵抗率の上限につ
いてはいくら大きくてもかまわないが、例えば１×１０
21Ω・ｃｍ以下、好ましくは１×１０22Ω・ｃｍ以下、
さらに好ましくは１０23Ω・ｃｍ以下である。FIG. 2 shows a case where the sample to be measured is in a liquid state. Reference numeral 1 denotes a sample to be measured, which is held by spacers 4. The upper limit of the thickness is 2000 μm or less, preferably 1500 μm.
m or less, more preferably 1000 μm or less, and the lower limit of the thickness is 0.01 μm or more, preferably 0.1 μm, in a range where the heat capacity of the conductive thin film formed on both surfaces can be ignored.
m, more preferably 1 μm or more. The sample 1 to be measured is a poorly conductive substance such as a polymer compound or an organic dye, and has a resistivity of 1 × 10 4 Ω · cm or more, preferably 1 × 10 6 Ω · cm or more, and more preferably 1 × 10 6 Ω · cm or more. It is 10 7 Ω · cm or more, and the upper limit of the resistivity may be any value.
21 Ω · cm or less, preferably 1 × 10 22 Ω · cm or less,
More preferably, it is 10 23 Ω · cm or less.

【００２４】２は変調を加えた電流により被測定試料の
一面を交流加熱するための交流熱源となる導電性薄膜
で、その抵抗値は０．０１Ω〜１００ＫΩ、好ましくは
０．０５Ω〜５０ＫΩ、さらに好ましくは０．１Ω〜１
０ＫΩである。交流熱源となる導電性薄膜はガラス板５
の上に形成され、被測定試料と交流熱源の界面が無視で
きる程度に被測定試料に完全に密着しており、その厚み
は被測定試料に比べて充分薄く、例えば５００００オン
グストロ−ム以下、好ましくは１００００オングストロ
−ム以下、さらに好ましくは５０００オングストロ−ム
以下で、厚みの下限は交流電流が通電可能であればいく
らでも良いが、例えば１オングストローム以上、好まし
くは５オングストローム以上、さらに好ましくは１０オ
ングストローム以上である。Reference numeral 2 denotes a conductive thin film serving as an AC heat source for AC-heating one surface of the sample to be measured by a modulated current, and has a resistance of 0.01 Ω to 100 KΩ, preferably 0.05 Ω to 50 KΩ. Preferably 0.1Ω to 1
0 KΩ. The conductive thin film serving as the AC heat source is a glass plate 5.
Is formed on the sample, and the interface between the sample and the AC heat source is completely adhered to the sample to the extent that it can be ignored, and the thickness thereof is sufficiently thinner than the sample to be measured, for example, 50,000 angstroms or less, preferably Is not more than 10,000 angstroms, more preferably not more than 5000 angstroms, and the lower limit of the thickness is not particularly limited as long as an alternating current can be passed. It is.

【００２５】３は交流熱源と反対の面の温度変化の交流
成分を測定するための抵抗式温度計となる導電性薄膜
で、その抵抗値は０．０１Ω〜１００ＫΩ、好ましくは
０．０５Ω〜５０ＫΩ、さらに好ましくは０．１Ω〜１
０ＫΩである。抵抗式温度計となる導電性薄膜はガラス
板５の上に形成され、被測定試料と抵抗式温度計の界面
が無視できる程度に被測定試料に完全に密着しており、
その厚みは被測定試料に比べて充分薄く、例えば５００
００オングストロ−ム以下、好ましくは１００００オン
グストロ−ム以下、さらに好ましくは５０００オングス
トロ−ム以下で、厚みの下限は直流電流を通電し抵抗値
の温度依存性に起因して起こる電圧の変化を読み取るこ
とが可能であればいくらでも良いが、例えば１オングス
トローム以上、好ましくは５オングストローム以上、さ
らに好ましくは１０オングストローム以上である。Reference numeral 3 denotes a conductive thin film serving as a resistance thermometer for measuring an AC component of a temperature change on a surface opposite to the AC heat source, and has a resistance value of 0.01 to 100 KΩ, preferably 0.05 to 50 KΩ. , More preferably 0.1 Ω to 1
0 KΩ. The conductive thin film serving as the resistance thermometer is formed on the glass plate 5 and is completely adhered to the sample to be measured so that the interface between the sample and the resistance thermometer can be ignored.
Its thickness is sufficiently thin compared to the sample to be measured, for example, 500
The thickness is lower than 00 Å, preferably lower than 10,000 Å, more preferably lower than 5,000 Å, and the lower limit of the thickness is to apply a direct current to read the voltage change caused by the temperature dependence of the resistance value. Any number is possible as long as it is possible, for example, 1 Å or more, preferably 5 Å or more, more preferably 10 Å or more.

【００２６】なお、試料が液体状のもの、または液体と
しうるものの場合、試料の調製法は例えば、図２(a) の
ごとく行う。まず二枚のガラス板５を準備し、金または
銀等をスパッタまたは蒸着等により試料の大きさに略等
しい導電性薄膜２または３をそれぞれ形成する。なお、
図のごとく、導電性薄膜に通電するため、スペーサの外
へ薄膜の一部を延出させてリード線として使用する。こ
の導電性薄膜の上に、スペーサを設置する。スペーサは
液体状の試料をスペーサ内部に保持する作用を有すると
ともに、スペーサにより液状試料の厚みが決定される。
かかるスペーサは、難導電性物質であれば、特に限定は
無いが、通常、０．１〜２０００μm 程度の高分子フィ
ルムが好ましい。スペーサは液体状試料の流動性に応じ
て、枠型、コの字型、二の字型等適宜選択する。When the sample is in a liquid state or can be made into a liquid state, the sample is prepared, for example, as shown in FIG. 2 (a). First, two glass plates 5 are prepared, and conductive thin films 2 or 3 each having a size substantially equal to the size of the sample are formed by sputtering or vapor deposition of gold, silver, or the like. In addition,
As shown in the figure, a part of the thin film is extended out of the spacer and used as a lead wire in order to supply electricity to the conductive thin film. A spacer is provided on the conductive thin film. The spacer has a function of holding the liquid sample inside the spacer, and the thickness of the liquid sample is determined by the spacer.
The spacer is not particularly limited as long as it is a non-conductive substance, but is preferably a polymer film having a thickness of about 0.1 to 2000 μm. The spacer is appropriately selected depending on the fluidity of the liquid sample, such as a frame, a U-shape, or a two-shape.

【００２７】図２では、枠型のものを示す。斯くして、
設置したスペーサの枠部と導電性薄膜の表面とで形成さ
れる空間部に液体状の被測定試料を注入する。この上部
に同様に導電性薄膜を形成した別のガラス板５を、該導
電性薄膜を試料に向けるようにして図２(b) のように重
ねる。斯くして、液体状の試料は、スペーサを介して対
向する二枚のガラス板間に(言い換えれば対向する二枚
の導電性薄膜間に )薄膜状に封入され、被測定試料ユニ
ットを形成する。すなわち、このユニット内で、液体状
試料と二枚の導電性薄膜は完全に密着固定されている。
なお、取扱上、このユニット全体を適当な封止剤で封止
し、例えばエポキシ樹脂封止剤内に封入して完全に固着
することがさらに好ましい。FIG. 2 shows a frame type. Thus,
A liquid sample to be measured is injected into a space formed between the frame portion of the installed spacer and the surface of the conductive thin film. Another glass plate 5 on which a conductive thin film is formed in the same manner as above is stacked as shown in FIG. 2B so that the conductive thin film faces the sample. In this way, the liquid sample is sealed in a thin film shape between the two glass plates facing each other via the spacer (in other words, between the two conductive thin films facing each other) to form a sample unit to be measured. . That is, in this unit, the liquid sample and the two conductive thin films are completely adhered and fixed.
For handling, it is more preferable that the entire unit is sealed with an appropriate sealing agent, and is sealed in an epoxy resin sealing agent and completely fixed.

【００２８】図３、図４に示されるごとく、交流熱源２
は交流電流発生器（ファンクション・シンセサイザ−
等）６により変調された交流電流を通電され、そのジュ
ール熱により交流加熱される。抵抗式温度計３は７の直
流電源（電池等）により一定電圧の直流電圧が流され、
その抵抗値の温度依存性によって変化する電圧を７のロ
ックイン増幅器で増幅し、温度変化の交流成分を測定す
る。９のロックイン増幅器は、図３のようにダミー抵抗
８と並列に組み込まれるか、または、図４のように抵抗
式温度計３と並列に組み込まれ、温度変化の交流成分を
測定する。１１は加熱冷却用のセルで、温度コントロー
ラ１２によりあるパターンに従って例えば昇温または降
温することにより被測定試料はセル内で雰囲気温度を連
続的に変化させられる。すなわち、被測定試料板の温度
は、このような被測定試料板の温度を連続的に昇温また
は降温する手段により、連続的に昇温または降温させら
れる。実際的には、被測定試料板の温度はセル雰囲気温
度と同じとしてよい。As shown in FIGS. 3 and 4, the AC heat source 2
Is an AC current generator (function synthesizer)
Etc.), an AC current modulated by 6 is applied, and the AC current is heated by Joule heat. A constant DC voltage is applied to the resistance thermometer 3 by a DC power supply (battery or the like) 7.
The voltage that changes due to the temperature dependence of the resistance value is amplified by a lock-in amplifier 7 and the AC component of the temperature change is measured. The lock-in amplifier 9 is incorporated in parallel with the dummy resistor 8 as shown in FIG. 3, or is incorporated in parallel with the resistance thermometer 3 as shown in FIG. 4, and measures an AC component of a temperature change. Reference numeral 11 denotes a heating / cooling cell. The temperature of the sample to be measured can be continuously changed in the cell by, for example, raising or lowering the temperature according to a certain pattern by the temperature controller 12. That is, the temperature of the sample plate to be measured is continuously raised or lowered by means for continuously increasing or decreasing the temperature of the sample plate to be measured. In practice, the temperature of the sample plate to be measured may be the same as the cell ambient temperature.

【００２９】ロックイン増幅器９は同期整流回路とも呼
ばれ、交流電源発生器６からの参照交流波と検出波との
積をとり直流分を得るものである。所定の等価帯域幅を
有し、選択性を持つため、必要とする周波数以外のノイ
ズはほぼ完全に除去される。このロックイン増幅器９の
出力はデータ処理装置（例えば、パーソナルコンピュー
タ）１０に入力され、熱分析が行われる。その原理は以
下のとおりである。ジュール熱によって起きる発熱は電
流の正負を問わずそのピーク点において最大となるた
め、温度の変化周期は通電された交流電流の周期の２倍
となる。従って、交流熱源２に振幅ＶH0、周波数ω／２
の交流電圧を加えると、試料表面は周波数ω（＝２π
ｆ）で加熱される。試料表面の単位面積あたりに発生す
るジュール熱ｑは、時間ｔの関数として、式(1) [ 数1
]The lock-in amplifier 9 is also called a synchronous rectification circuit, and obtains a DC component by multiplying a reference AC wave from the AC power generator 6 and a detection wave. Since it has a predetermined equivalent bandwidth and has selectivity, noise other than the required frequency is almost completely removed. The output of the lock-in amplifier 9 is input to a data processing device (for example, a personal computer) 10 where thermal analysis is performed. The principle is as follows. Since the heat generated by Joule heat is maximum at the peak point regardless of whether the current is positive or negative, the temperature change cycle is twice the cycle of the supplied alternating current. Therefore, the amplitude V H0 and the frequency ω / 2 are applied to the AC heat source 2.
Is applied, the sample surface has a frequency ω (= 2π
Heated in f). The Joule heat q generated per unit area of the sample surface is expressed by the following equation (1) as a function of time t.
]

【００３０】[0030]

【数１】 により表される。ここでＲHは交流熱源の抵抗、Ｓは加
熱面の面積である。被測定試料１は難導電性物質である
が、その厚さが極めて薄いため、交流熱源２のジュール
熱による熱エネルギーは厚さ方向の熱伝導のみにより伝
熱され、反対面の抵抗式温度計３で交流熱源２の変調周
波数に依存する周期的な温度変化を引き起こす。被測定
試料１の厚みをｄ、熱拡散率をα、λを熱伝導率、抵抗
式温度計３の熱拡散率をαs、熱伝導率をλsとするとそ
の変動温度は、式(2) [ 数2 ] となる。(Equation 1) Is represented by Here, RH is the resistance of the AC heat source, and S is the area of the heating surface. The sample 1 to be measured is a poorly conductive material, but since its thickness is extremely thin, heat energy due to Joule heat of the AC heat source 2 is transferred only by heat conduction in the thickness direction, and a resistance thermometer on the opposite surface. 3 causes a periodic temperature change depending on the modulation frequency of the AC heat source 2. Assuming that the thickness of the sample 1 to be measured is d, the thermal diffusivity is α, λ is thermal conductivity, the thermal diffusivity of the resistance thermometer 3 is α s , and the thermal conductivity is λ s , the fluctuation temperature is expressed by the following equation (2). ) [Equation 2].

【００３１】[0031]

【数２】 ただし、(Equation 2) However,

【００３２】[0032]

【数３】 ここで、熱拡散長μs ＝１／ｋを定義して、試料の厚さ
が熱拡散長より大きい場合（ｄ＞μs ）、(2) 式の温度
変化は、式(3) [ 数4 ] となる。(Equation 3) Here, when the thermal diffusion length μ s = 1 / k is defined and the thickness of the sample is larger than the thermal diffusion length (d> μ s ), the temperature change of the expression (2) is expressed by the expression (3) 4].

【００３３】[0033]

【数４】 交流熱源２と抵抗式温度計３の温度変化の位相差に着目
すると、式(4) [ 数5 ](Equation 4) Focusing on the phase difference of the temperature change between the AC heat source 2 and the resistance thermometer 3, Equation (4)

【００３４】[0034]

【数５】 となる。ここで、△θは被測定試料１の熱拡散による位
相遅れである。抵抗式温度計３の温度変化の振幅に着目
すると、式(5) [ 数6 ](Equation 5) Becomes Here, Δθ is a phase delay due to thermal diffusion of the sample 1 to be measured. Focusing on the amplitude of the temperature change of the resistance thermometer 3, Equation (5) [Equation 6]

【００３５】[0035]

【数６】 となる。ここでＡは振幅の強度である。(Equation 6) Becomes Here, A is the amplitude intensity.

【００３６】従って（４）式、（５）式よりより、交流
熱源の変調周波数ｆを一定にして、厚さｄ一定の被測定
試料について、交流熱源と裏面における温度変化との位
相差Δθまたは、裏面における温度変化の振幅Ａを測定
することにより、熱拡散率αの変化に応じた位相差Δθ
または振幅Ａの変化が得られる。たとえば、図７は結晶
性高分子についての代表的な温度Ｔと位相差Δθの関係
を示すが、位相差の温度による微分値（ΔΔθ／ΔＴ）
が急変している点（Ｔｍ）が融点と一致する。同様に、
図８は結晶性高分子についての代表的な温度Ｔと振幅Ａ
の関係を示すが、振幅の温度による微分値（ΔＡ／Δ
Ｔ）が急変している点（Ｔｍ）が融点と一致する。した
がって、被測定試料の雰囲気温度をあるパターンで、通
常は一定速度で昇温、降温することにより、熱拡散率の
温度依存性に伴う位相差または振幅の変化より、相転
移、ガラス転移などの転移温度を求めることができる。Therefore, according to the equations (4) and (5), the phase difference Δθ between the AC heat source and the temperature change on the back surface of the sample to be measured having a constant thickness d and the modulation frequency f of the AC heat source is constant. By measuring the amplitude A of the temperature change on the back surface, the phase difference Δθ according to the change in the thermal diffusivity α is obtained.
Alternatively, a change in the amplitude A is obtained. For example, FIG. 7 shows a relationship between a representative temperature T and a phase difference Δθ for a crystalline polymer, and a differential value (ΔΔθ / ΔT) of the phase difference with temperature is shown.
Point (Tm) coincides with the melting point. Similarly,
FIG. 8 shows a typical temperature T and amplitude A for a crystalline polymer.
, The differential value of the amplitude with temperature (ΔA / Δ
The point (Tm) where T) changes suddenly coincides with the melting point. Therefore, by raising and lowering the ambient temperature of the sample to be measured in a certain pattern, usually at a constant rate, the change in phase difference or amplitude due to the temperature dependence of the thermal diffusivity causes the phase transition, glass transition, etc. The transition temperature can be determined.

【００３７】この測定に適した変調周波数の下限は、熱
拡散長（μs ＝（2 α/ ω）1/2 ）が被測定試料の厚み
ｄ以下になる周波数であり、上限は抵抗式温度計により
測定される温度振幅がノイズより充分大きい範囲であ
る。被測定試料が厚さ１００μｍの高分子フィルムの場
合その測定に最適な変調周波数は、０．０１Ｈｚから１
０００Hz、好ましくは０．５Ｈｚから７００Hz、さらに
好ましくは０．１Ｈｚから５００Hzの間である。The lower limit of the modulation frequency suitable for this measurement is a frequency at which the thermal diffusion length (μ s = (2α / ω) 1/2 ) is equal to or less than the thickness d of the sample to be measured, and the upper limit is the resistance type temperature. The range in which the temperature amplitude measured by the meter is sufficiently larger than the noise. When the sample to be measured is a polymer film having a thickness of 100 μm, the optimum modulation frequency for the measurement is 0.01 Hz to 1 Hz.
000 Hz, preferably between 0.5 Hz and 700 Hz, more preferably between 0.1 Hz and 500 Hz.

【００３８】図５に示すように、これらの装置は全てパ
ーソナルコンピュータで制御され、測定結果も自動的に
処理され、一括して自動化された測定システムとするの
が好ましい。被測定試料の雰囲気温度は、温度コントロ
ーラにより自動的に変更される。ロックイン増幅器によ
る測定値は、パーソナルコンピュータに送られて、あら
かじめ決められた雰囲気温度範囲での測定終了後にそれ
らの測定値はフロッピー・ディスクへ保存される。As shown in FIG. 5, it is preferable that these devices are all controlled by a personal computer, the measurement results are automatically processed, and the measurement system is collectively automated. The ambient temperature of the sample to be measured is automatically changed by the temperature controller. The measured values by the lock-in amplifier are sent to a personal computer, and after the measurement in a predetermined ambient temperature range is completed, the measured values are stored on a floppy disk.

【００３９】また、（４）式より厚みｄが既知の被測定
試料に関して、測定する変調周波数における交流熱源２
と抵抗式温度計３との温度波の交流成分の位相差Δθを
測定することにより、熱拡散率αを同時に求めることが
できる。Further, with respect to the sample to be measured whose thickness d is known from the equation (4), the AC heat source 2 at the modulation frequency to be measured is used.
By measuring the phase difference Δθ of the AC component of the temperature wave between the resistance thermometer 3 and the resistance thermometer 3, the thermal diffusivity α can be obtained at the same time.

【００４０】熱拡散率を熱伝導率との関係式で表すと、
熱伝導率をλ、比熱をＣｐ、密度をρとして、式(6) [
数7 ]When the thermal diffusivity is represented by a relational expression with the thermal conductivity,
Assuming that λ is the thermal conductivity, Cp is the specific heat, and ρ is the density, equation (6)
Equation 7]

【００４１】[0041]

【数７】α＝λ／（Ｃｐ・ρ） ……… (6) となり、変形すると、式(7) [ 数8 ](7) α = λ / (Cp · ρ) (6) When transformed, equation (7) [Equation 8]

【００４２】[0042]

【数８】λ＝α・Ｃｐ・ρ ……… (7) となる。従って、他の測定方法により測定された比熱と
密度の測定値を得ることで、本発明による熱拡散率の測
定値と合わせて、（７）式より熱伝導率を求めることが
できる。比熱は示差走査熱量計、断熱型熱量計等で測定
することができ、密度は体積膨張計、Ｐ−Ｖ−Ｔ測定装
置等で測定することができ、それらの測定値を熱伝導率
を求めるために用いる。Λ = α · Cp · ρ (7) Therefore, by obtaining the measured values of the specific heat and the density measured by another measuring method, the thermal conductivity can be obtained from the equation (7) together with the measured value of the thermal diffusivity according to the present invention. The specific heat can be measured by a differential scanning calorimeter, an adiabatic calorimeter, etc., the density can be measured by a volume dilatometer, a PVT measuring device, etc., and the measured values are used to determine the thermal conductivity. Used for

【００４３】[0043]

【作用】このように本発明は、被測定試料の片面を交流
加熱したときの加熱面と加熱面に対向する他方の面との
温度変化の位相差および、他方の面の温度変化の振幅が
熱拡散率の雰囲気温度依存性により変化することを利用
して、微小な被測定試料に微小な導電性薄膜を形成し、
交流電流を導電性薄膜に通電することによってそのジュ
ール熱により発熱させ被測定試料の片面を交流加熱し、
加熱面に対向する他方の面の温度変化を電気的に測定す
ることにより熱分析を行う。As described above, according to the present invention, the phase difference of the temperature change between the heated surface and the other surface opposite to the heated surface when one surface of the sample to be measured is subjected to AC heating, and the amplitude of the temperature change on the other surface are reduced. Utilizing the fact that the thermal diffusivity changes depending on the ambient temperature, a minute conductive thin film is formed on a minute sample to be measured.
An AC current is applied to the conductive thin film to generate heat by the Joule heat, and one side of the sample to be measured is AC-heated,
Thermal analysis is performed by electrically measuring the temperature change on the other surface facing the heated surface.

【００４４】[0044]

【実施例】本発明の実施例を図面を参照して説明する。An embodiment of the present invention will be described with reference to the drawings.

【００４５】被測定試料には、厚さ５５μｍ、大きさが
１５ｍｍ×１０ｍｍの炭素数２３のｎ−アルカンに、２
枚のスライド・ガラスにそれぞれスパッタした交流熱源
および抵抗式温度計を密着させたものを用いた。交流熱
源は５００オングストローム、抵抗式温度計は８００オ
ングストロームの厚みに、ポリエステル・フィルムによ
り７ｍｍ×４ｍｍにマスクして、それぞれに金をスパッ
タした。The sample to be measured includes 55 μm thick, 15 mm × 10 mm size n-alkane having 23 carbon atoms, and 2
A spattered AC heat source and a resistance thermometer were used in close contact with a single slide glass. The AC heat source was 500 angstroms, the resistance thermometer was 800 angstroms thick, and 7 mm x 4 mm was masked with a polyester film, and gold was sputtered on each.

【００４６】昇温速度０．２℃／分で位相差と振幅を同
時に測定した結果より、図９に抵抗式温度計の交流成分
の位相差の温度による変化を、図１０に振幅の温度によ
る変化を示す。図のように位相差および振幅は、ほぼ同
じ温度で急激な変化を示し、この温度は示差走査熱量計
により測定された固相−固相転移温度および融点と一致
する。From the result of simultaneous measurement of the phase difference and the amplitude at a heating rate of 0.2 ° C./min, FIG. 9 shows the change in the phase difference of the AC component of the resistance thermometer with temperature, and FIG. Indicates a change. As shown, the phase difference and amplitude show a sharp change at about the same temperature, which is consistent with the solid-solid transition temperature and melting point measured by a differential scanning calorimeter.

【００４７】また、厚さ１４８μｍ、大きさ１８ｍｍ×
１８ｍｍのガラス板に、交流熱源は５００オングストロ
ーム、抵抗式温度計は８００オングストロームの厚み
に、ポリエステル・フィルムにより１０ｍｍ×３ｍｍに
マスクして、それぞれに金をスパッタした試料による、
交流熱源と抵抗式温度計の交流成分の出力との位相差の
周波数の平方根による変化を図６に示す。Δθが４５°
（π／４）の点は外挿値であるが、先に述べた（４）式
に従い、４５°（π／４）の点を通る直線関係が得られ
る。この関係より、熱分析を行うと同時に熱拡散率を求
めることができる。Further, the thickness is 148 μm, the size is 18 mm ×
An 18 mm glass plate, an AC heat source of 500 Å and a resistance thermometer of 800 Å in thickness were masked to a size of 10 mm × 3 mm with a polyester film, and gold was sputtered on each.
FIG. 6 shows a change in the phase difference between the AC heat source and the output of the AC component of the resistance thermometer due to the square root of the frequency. Δθ is 45 °
Although the point of (π / 4) is an extrapolated value, a linear relationship passing through the point of 45 ° (π / 4) is obtained according to the above-described equation (4). From this relationship, the thermal diffusivity can be determined at the same time as performing the thermal analysis.

【００４８】このように、本発明により物質の転移温度
を精度良く捉えることができ、高温下での製品設計など
を的確に行うことができる。また、各種シミュレーショ
ン・プログラムを利用していく上で、実際の加工温度、
使用温度でのより精度良い解析を行うことができる。As described above, according to the present invention, the transition temperature of a substance can be accurately grasped, and product design at a high temperature can be accurately performed. In using various simulation programs, the actual processing temperature,
More accurate analysis can be performed at the operating temperature.

【００４９】[0049]

【発明の効果】以上説明したように本発明によれば、以
下の効果が得られ、高分子化合物やセラミックス等の各
種材料の開発、製品設計およびシミュレーションによる
解析等の分野に好適に適用することが可能である。本発
明によると、温度の交流成分の位相差を測定することに
より熱分析を行うため、温度の絶対値が問題にならず、
誤差の少ない精度良い測定ができる。さらに、被測定試
料が微量かつ薄肉であり、微小な導電性薄膜を被測定試
料に直接形成あるいは密着する単純な構造なので、装置
の小型化、測定の高速化が可能となる。また、熱分析を
行うと同時に熱拡散率、熱伝導率の測定が可能なので、
従来の測定に比べてより多くの情報を得ることができ
る。交流熱源および抵抗式温度計となる導電性薄膜はス
パッタ等により被測定試料に完全に密着して形成され、
接触界面を無視できるほどに薄いため、被測定試料と熱
源、温度計との間の熱損失が問題にならない。As described above, according to the present invention, the following effects can be obtained, and the present invention can be suitably applied to the fields of development of various materials such as polymer compounds and ceramics, product design and analysis by simulation. Is possible. According to the present invention, since the thermal analysis is performed by measuring the phase difference of the AC component of the temperature, the absolute value of the temperature does not matter,
High accuracy measurement with few errors. Further, since the sample to be measured has a small amount and a small thickness, and has a simple structure in which a minute conductive thin film is directly formed or adhered to the sample to be measured, it is possible to reduce the size of the apparatus and increase the speed of measurement. In addition, thermal diffusivity and thermal conductivity can be measured at the same time as performing thermal analysis.
More information can be obtained compared to conventional measurement. The conductive thin film that becomes the AC heat source and the resistance thermometer is formed in close contact with the sample to be measured by sputtering or the like,
Since the contact interface is so thin that it can be ignored, heat loss between the sample to be measured, the heat source and the thermometer does not matter.

【図面の簡単な説明】[Brief description of the drawings]

【図１】固体状の被測定試料の説明図FIG. 1 is an explanatory view of a solid sample to be measured.

【図２】液体状の被測定試料ユニット調製の説明図FIG. 2 is an explanatory view of preparing a liquid sample unit to be measured.

【図３】 測定装置の説明図FIG. 3 is an explanatory view of a measuring device.

【図４】測定装置の説明図FIG. 4 is an explanatory view of a measuring device.

【図５】測定装置の自動化例を示すフロー図FIG. 5 is a flowchart showing an example of automation of a measuring device.

【図６】ガラスにおける位相差と周波数の平方根との関
係の測定例を示す図FIG. 6 is a diagram showing a measurement example of the relationship between the phase difference and the square root of the frequency in glass.

【図７】 結晶性高分子の代表的な温度と位相差の関係
模式図FIG. 7 is a schematic diagram showing a relationship between a typical temperature and a phase difference of a crystalline polymer.

【図８】結晶性高分子の代表的な温度と振幅の関係模式
図FIG. 8 is a schematic diagram showing the relationship between temperature and amplitude of a typical crystalline polymer.

【図９】炭素数２３のｎ−アルカンの位相差の温度によ
る変化測定例FIG. 9 is a measurement example of a change in phase difference of n-alkane having 23 carbon atoms with temperature.

【図１０】炭素数２３のｎ−アルカンの振幅の温度によ
る変化測定例FIG. 10 shows an example of measuring the change in amplitude of n-alkane having 23 carbon atoms with temperature.

【符号の説明】[Explanation of symbols]

１ 被測定試料 ２ 交流熱源（導電性薄膜） ３ 抵抗式温度計（導電性薄膜） ４ スペーサ ５ ガラス板 ６ 交流電流発生器（ファンクション・シンセサイザ
ー） ７ 直流電源（電池） ８ ダミー抵抗 ９ ロックイン増幅器 １０ データ処理装置 １１ 被測定試料加熱冷却用セル １２ 温度コントローラDESCRIPTION OF SYMBOLS 1 Sample to be measured 2 AC heat source (conductive thin film) 3 Resistance thermometer (conductive thin film) 4 Spacer 5 Glass plate 6 AC current generator (function synthesizer) 7 DC power supply (battery) 8 Dummy resistor 9 Lock-in amplifier Reference Signs List 10 Data processing device 11 Cell for heating and cooling sample under measurement 12 Temperature controller

───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−201149（ＪＰ，Ａ) 特開 平３−156351（ＪＰ，Ａ) ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-201149 (JP, A) JP-A-3-156351 (JP, A)

Claims (11)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 薄い被測定試料の熱分析方法であって、
該薄い被測定試料の両面に導電性の薄膜を形成あるいは
密着させて、該薄膜の一方に電流を流すことによってそ
のジュール熱により発熱する交流熱源とし、他方の薄膜
を温度によりその抵抗値が変化することを利用する抵抗
式温度計とした測定系を用い、該被測定試料の前記交流
熱源に所定の変調周波数で変調を加えた交流電流を流し
て交流発熱させ、該抵抗式温度計に該交流発熱に対応す
る交流状温度変化を起こさせるとともに、該被測定試料
の測定雰囲気温度を昇温や降温のごとき交流以外の設定
したパターンで連続的に変化せしめながら該変調周波数
に対応して交流発熱させた交流状温度変化を検出し、か
くして得られた各設定した測定雰囲気温度における該交
流状の温度変化の位相と該交流状の温度変化の振幅との
関係、あるいは該交流熱源の温度変化と該抵抗式温度計
により測定された温度変化との位相差と該変調周波数と
の関係より、該被測定試料の熱分析を行う被測定試料の
熱分析方法。1. A thermal analysis method for a thin sample to be measured,
An electrically conductive thin film is formed or adhered to both surfaces of the thin sample to be measured, and an electric current is applied to one of the thin films to form an AC heat source that generates heat by Joule heat. Using a measurement system as a resistance thermometer utilizing the above, an AC current modulated at a predetermined modulation frequency is passed through the AC heat source of the sample to be measured to generate AC heat, and the resistance thermometer is heated. In addition to causing an AC-like temperature change corresponding to the AC heat generation, setting the measurement atmosphere temperature of the sample to be measured to a setting other than AC such as raising or lowering the temperature.
The modulation frequency while continuously changing the modulation frequency
The exchange in the measurement atmosphere temperature was each set to detect an AC-like temperature changes obtained by alternating heating correspondingly, thus resulting in
Relationship between the amplitude of the temperature change phase and the alternating-like temperature change in Nagarejo, or the relationship between the phase difference and the modulation frequency of the change in temperature measured by the temperature change and the resistance thermometer of the AC heat source A method for thermal analysis of a sample to be measured, wherein the thermal analysis of the sample to be measured is performed. 【請求項２】 被測定試料が固体または液体から選択さ
れる難導電物質からなる請求項１記載の温度波による熱
分析方法。2. The thermal analysis method according to claim 1, wherein the sample to be measured is made of a poorly conductive material selected from a solid or a liquid. 【請求項３】 液体状の被測定試料が高分子化合物、有
機色素から選択される難導電性物質である請求項２記載
の温度波による熱分析方法。3. The thermal analysis method according to claim 2, wherein the liquid sample to be measured is a poorly conductive substance selected from a polymer compound and an organic dye. 【請求項４】 固体状の被測定試料が高分子化合物、有
機色素、鉱石、ガラス、セラミックスから選択される難
導電性物質である請求項２記載の温度波による熱分析方
法。4. The thermal analysis method according to claim 2, wherein the solid sample to be measured is a non-conductive substance selected from a polymer compound, an organic dye, ore, glass, and ceramics. 【請求項５】 交流熱源となる導電性薄膜が、ジュール
熱により発熱する導電性物質からなる請求項１記載の温
度波による熱分析方法。5. The thermal analysis method according to claim 1, wherein the conductive thin film serving as an AC heat source is made of a conductive substance that generates heat by Joule heat. 【請求項６】 抵抗式温度計となる導電性薄膜が、温度
により抵抗の変化する導電性物質からなる請求項１記載
の温度波による熱分析方法。6. The thermal analysis method according to claim 1, wherein the conductive thin film serving as a resistance thermometer is made of a conductive substance whose resistance changes with temperature. 【請求項７】 交流熱源および抵抗式温度計となる導電
性薄膜を、スパッタ、蒸着、塗布、接着、圧着、融着の
うちのいずれかより選択される方法により形成する請求
項１記載の温度波による熱分析方法。7. The temperature according to claim 1, wherein the conductive thin film serving as an AC heat source and a resistance thermometer is formed by a method selected from sputtering, vapor deposition, coating, adhesion, pressure bonding, and fusion. Thermal analysis method using waves. 【請求項８】 被測定試料を加熱または冷却することに
より、被測定試料の測定温度を所望の温度に変えて、熱
測定を行う請求項１記載の温度波による熱分析方法。8. The thermal analysis method according to claim 1, wherein the heat measurement is performed by heating or cooling the sample to be measured to change the measurement temperature of the sample to a desired temperature. 【請求項９】 被測定試料の温度を変化させる過程にお
いて、前記交流熱源の温度変化と前記抵抗式温度計によ
り測定された温度変化との位相差と、前記変調周波数と
の相関関係から、該被測定試料の厚み方向の熱拡散率を
同時に測定する請求項１記載の温度波による熱分析方
法。9. In the step of changing the temperature of the sample to be measured, a phase difference between a temperature change of the AC heat source and a temperature change measured by the resistance thermometer, and a correlation between the modulation frequency and the phase difference are obtained. 2. The thermal analysis method according to claim 1, wherein the thermal diffusivity in the thickness direction of the sample to be measured is simultaneously measured. 【請求項１０】 請求項９記載の方法により得られた被
測定試料の熱拡散率と、該被測定試料の比熱および密度
の測定値から、熱伝導率を求める該被測定試料の熱伝導
率の測定方法。10. The thermal conductivity of a sample to be measured, wherein the thermal conductivity is obtained from the thermal diffusivity of the sample to be measured obtained by the method according to claim 9 and the measured values of specific heat and density of the sample to be measured. Measurement method. 【請求項１１】 両面に導電性薄膜を備えた薄い被測定
試料の熱分析を行う装置であって、 一方の導電性薄膜に一定振幅の変調を加えた交流電流を
供給する交流電流発生手段と、 他方の導電性薄膜に所定の直流電流を供給する直流電流
供給手段と、 前記他方の導電性薄膜の抵抗値の温度依存性に起因して
変化する交流状電圧を増幅するロックイン増幅器と、 被測定試料を収納するセルと、 該被測定試料を収納したセル内の被測定試料部を加熱ま
たは冷却する手段とを備え、該加熱冷却手段によりセル
内の該被測定試料の測定雰囲気温度を昇温または降温の
ごとく交流以外の設定したパターンで変化せしめなが
ら、上記変調周波数に対応する交流状温度変化を増幅検
出し、かくして得られた各設定した測定雰囲気温度にお
ける該交流状の温度変化の位相と該交流状の温度変化の
振幅との関係、あるいは該交流熱源の温度変化と該抵抗
式温度計により測定された温度変化との位相差と該変調
周波数との関係より、該被測定試料の熱分析を行うよう
にした温度波による熱分析装置。11. An apparatus for performing a thermal analysis of a thin sample to be measured having a conductive thin film on both sides, comprising: an AC current generating means for supplying an AC current obtained by modulating one conductive thin film with a constant amplitude. A DC current supply means for supplying a predetermined DC current to the other conductive thin film; a lock-in amplifier for amplifying an AC-like voltage that changes due to the temperature dependence of the resistance value of the other conductive thin film; comprising a cell for containing a sample to be measured, and means for heating or cooling the sample to be measured of the cell housing the該被measurement sample cell by heating the cooling means
The該被measurement atmosphere temperature of the measurement sample of the inner raised or lowered
As long allowed to change at the set pattern of non-AC
Amplify the AC-like temperature change corresponding to the above modulation frequency.
Out, thus obtained relationship between the amplitude of the temperature change phase and the alternator like in the AC-like temperature change in the measurement atmosphere temperature was each set or measured by the temperature change and the resistance thermometer of the AC heat source A thermal analysis apparatus using a temperature wave for performing thermal analysis of the sample to be measured based on a relationship between a phase difference from the temperature change and the modulation frequency.
JP4271471A 1991-11-01 1992-10-09 Thermal analysis method and apparatus using temperature wave Expired - Fee Related JP2591570B2 (en)

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JP3-287666 1991-11-01
JP4271471A JP2591570B2 (en) 1991-11-01 1992-10-09 Thermal analysis method and apparatus using temperature wave

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