Article No : b06_001
Thermal Analysis and Calorimetry
STEPHEN B. WARRINGTON, Formerly Anasys, IPTME, Loughborough University, Loughborough, United Kingdom
Gu€NTHER W. H. Ho€HNE, Formerly Polymer Technology (SKT), Eindhoven University of Technology, Eindhoven, The Netherlands
1. Thermal Analysis...... 415 2.2. Methods of Calorimetry...... 424 1.1. General Introduction ...... 415 2.2.1. Compensation of the Thermal Effects.... 425 1.1.1. Definitions ...... 415 2.2.2. Measurement of a Temperature Difference 425 1.1.2. Sources of Information ...... 416 2.2.3. Temperature Modulation ...... 426 1.2. Thermogravimetry...... 416 2.3. Calorimeters ...... 427 1.2.1. Introduction ...... 416 2.3.1. Static Calorimeters ...... 427 1.2.2. Instrumentation ...... 416 2.3.1.1. Isothermal Calorimeters ...... 427 1.2.3. Factors Affecting a TG Curve ...... 417 2.3.1.2. Isoperibolic Calorimeters ...... 428 1.2.4. Applications ...... 417 2.3.1.3. Adiabatic Calorimeters ...... 430 1.3. Differential Thermal Analysis and 2.3.2. Scanning Calorimeters ...... 430 Differential Scanning Calorimetry..... 418 2.3.2.1. Differential-Temperature Scanning 1.3.1. Introduction ...... 418 Calorimeters ...... 431 2.3.2.2. Power-Compensated Scanning Calorimeters 432 1.3.2. Instrumentation ...... 419 2.3.2.3. Temperature-Modulated 1.3.3. Applications ...... 419 Scanning Calorimeters ...... 432 1.3.4. Modulated-Temperature DSC (MT-DSC) . 421 2.3.3. Chip-Calorimeters ...... 433 1.4. Simultaneous Techniques...... 421 2.4. Applications of Calorimetry...... 433 1.4.1. Introduction ...... 421 2.4.1. Determination of Thermodynamic Functions 433 1.4.2. Applications ...... 421 2.4.2. Determination of Heats of Mixing ...... 434 1.5. Evolved Gas Analysis...... 422 2.4.3. Combustion Calorimetry ...... 435 1.6. Mechanical Methods ...... 422 2.4.4. Reaction Calorimetry...... 436 1.7. Less Common Techniques ...... 423 2.4.5. Safety Studies ...... 437 2. Calorimetry ...... 424 References ...... 438 2.1. Introduction ...... 424
1. Thermal Analysis within the field of thermal analysis as it is usually understood. The present chapter will 1.1. General Introduction be restricted to major techniques. Since all materials respond to heat in some way, TA 1.1.1. Definitions has been applied to almost every field of science, with a strong emphasis on solving Thermal analysis (TA) has been defined as ‘‘a group problems in materials science and engineering, of techniques in which a physical property of a as well as fundamental chemical investiga- substance and/or its reaction products is measured tions. TA is applicable whenever the primary as a function of temperature while the substance is interest is in determining the effect of heat subjected to a controlled temperature programme’’ upon a material, but the techniques can also be [1]. The formal definition is usually extended to used as a means of probing a system to obtain include isothermal studies, in which the property of other types of information, such as composition. interest is measured as a function of time. The following list summarizes quantities sub- The definition is a broad one, and covers ject to investigation and the corresponding ther- many methods that are not considered to fall mal analysis techniques: