| 1 Introduction |
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1 | (8) |
| 2 Types of Differential Scanning Calorimeters and Modes of Operation |
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9 | (22) |
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10 | (7) |
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2.1.1 Heat Flux DSC with Disk-Type Measuring System |
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10 | (3) |
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2.1.2 Heat Flux DSC with Turret-Type Measuring System |
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13 | (1) |
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2.1.3 Heat Flux DSC with Cylinder-Type Measuring System |
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14 | (3) |
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2.2 Power Compensation DSC |
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17 | (8) |
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17 | (5) |
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2.2.2 Special Power Compensating DSC |
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22 | (3) |
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2.3 DSC with Combined Heat Flux and Power Compensation Measuring System |
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25 | (1) |
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25 | (6) |
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2.4.1 Constant Heating Rate |
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26 | (1) |
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2.4.2 Variable Heating Rate (Modulated Temperature) |
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27 | (4) |
| 3 Theoretical Fundamentals of Differential Scanning Calorimeters |
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31 | (34) |
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31 | (17) |
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3.2 Power Compensation DSC |
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48 | (2) |
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3.3 Temperature-Modulated DSC (TMDSC) |
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50 | (15) |
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3.3.1 The Temperature-Modulated Method |
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51 | (1) |
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3.3.2 Influences of the Sample |
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52 | (5) |
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3.3.3 Influences of Heat Transport |
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57 | (6) |
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63 | (2) |
| 4 Calibration of Differential Scanning Calorimeters |
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65 | (50) |
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4.1 Aspects of Quality Assurance |
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66 | (1) |
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4.2 Basic Aspects of Calibration |
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66 | (3) |
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4.3 Temperature Calibration |
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69 | (17) |
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4.3.1 Temperature Calibration on Heating |
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69 | (15) |
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4.3.2 Temperature Calibration on Cooling |
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84 | (2) |
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86 | (11) |
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4.4.1 Heat Flow Rate Calibration |
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87 | (3) |
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4.4.2 Heat (Peak Area) Calibration |
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90 | (2) |
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4.4.3 Examples of Caloric Calibration |
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92 | (5) |
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4.4.4 Caloric Calibration in Cooling Mode |
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97 | (1) |
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4.5 Conclusions Regarding the Calibration of DSCs |
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97 | (1) |
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4.6 Reference Materials for DSC Calibration |
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98 | (9) |
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4.6.1 Reference Materials for Temperature Calibration |
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99 | (2) |
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4.6.2 Reference Materials for Heat Flow Rate Calibration |
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101 | (6) |
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4.6.3 Reference Materials for Heat (Peak Area) Calibration |
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107 | (1) |
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4.7 Additional Calibration in Temperature-Modulated Mode of Operation |
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107 | (8) |
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4.7.1 Calibration of Magnitude |
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113 | (1) |
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4.7.2 Calibration of Phase |
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113 | (2) |
| 5 DSC Curves and Further Evaluation |
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115 | (32) |
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5.1 Characteristic Terms of DSC Curves |
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116 | (2) |
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5.2 Parameters Influencing the DSC Curve |
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118 | (1) |
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5.3 Further Evaluation of DSC Curves |
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119 | (7) |
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5.3.1 Determination of the Real Sample Heat Flow Rate |
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119 | (2) |
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5.3.2 The Baseline and the Determination of Peak Areas (Enthalpy Differences) |
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121 | (5) |
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5.4 Desmearing of the DSC Curve |
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126 | (14) |
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5.4.1 Correction of the Temperature and Heat Flow Rate Indicated |
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128 | (1) |
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5.4.2 Subtraction of the Zeroline |
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129 | (1) |
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5.4.3 Calculation of the True Heat Flow Rate into the Sample |
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129 | (4) |
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5.4.4 Advanced Desmearing |
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133 | (7) |
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5.4.5 Further Calculations |
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140 | (1) |
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140 | (5) |
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5.5.1 Reversing and Non-Reversing Heat Capacity |
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141 | (2) |
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5.5.2 Complex Heat Capacity |
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143 | (2) |
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5.5.3 Curves from Step-Scan Evaluation |
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145 | (1) |
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5.6 Interpretation an Presentation of Results |
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145 | (2) |
| 6 Applications of Differential Scanning Calorimetry |
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147 | (98) |
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6.1 Measurement of the Heat Capacity |
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147 | (15) |
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6.1.1 "Classical" Three-Step Procedure |
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148 | (5) |
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6.1.2 The "Absolute" Dual Step Method |
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153 | (1) |
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6.1.3 General Precautions for the Minimization of Errors and their Estimation |
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154 | (1) |
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6.1.4 Procedure of Small Temperature Steps |
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155 | (4) |
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6.1.5 The Temperature-Modulated Method |
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159 | (1) |
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6.1.6 Typical Applications of Heat Capacity Measurements |
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160 | (2) |
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6.2 Determination of Heats of Reaction |
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162 | (6) |
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6.3 Kinetic Investigations |
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168 | (32) |
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6.3.1 Introduction and Definitions |
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168 | (5) |
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6.3.2 Experimental Prerequisites for a Reliable Kinetic Analysis |
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173 | (2) |
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6.3.3 Selection of the Measuring Conditions - Isothermal or Non-Isothermal Reaction Mode |
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175 | (5) |
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6.3.4 Activation of the Sample by UV Irradiation |
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180 | (3) |
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6.3.5 Different Strategies of Kinetic Evaluation |
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183 | (6) |
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6.3.6 Selected Examples and Possible Predictions |
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189 | (11) |
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6.4 The Glass Transition Process |
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200 | (19) |
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6.4.1 The Phenomenology of the Glass Transition |
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200 | (1) |
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6.4.2 The Nature of the Glass Transition and Consequences for DSC Measurements |
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201 | (2) |
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6.4.3 Definition and Determination of the Glass Transition Temperature Tg |
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203 | (9) |
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6.4.4 Applications of Glass Transition Measurements |
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212 | (5) |
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6.4.5 The Dynamic Glass Process, an Example |
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217 | (2) |
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6.5 Characterization of Substances, the Phase Behavior |
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219 | (11) |
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6.5.1 Applications in Biology and Food Science |
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219 | (2) |
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6.5.2 Applications in Pharmacy |
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221 | (3) |
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224 | (4) |
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6.5.4 Porosity Measurements |
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228 | (2) |
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6.6 Determination of Phase Diagrams |
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230 | (2) |
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6.7 Safety Aspects and Characterization of High-Energetic Materials |
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232 | (1) |
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6.8 Characterization of Polymers |
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233 | (8) |
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6.8.1 Effects of Origin and Thermal History |
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234 | (2) |
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6.8.2 Determination of the Degree of Crystallinity |
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236 | (2) |
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6.8.3 Advanced Characterization with the TMDSC Method |
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238 | (3) |
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6.9 Purity Determination of Chemicals |
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241 | (4) |
| 7 Evaluation of the Performance of a Differential Scanning Calorimeter |
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245 | (14) |
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7.1 Characterization of the Complete Instrument |
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245 | (1) |
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7.2 Characterization of the Measuring System |
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245 | (6) |
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7.3 Characterization of the Results of a Measurement: Uncertainty Determination |
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251 | (6) |
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253 | (1) |
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253 | (4) |
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257 | (2) |
| Appendix 1 |
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259 | (4) |
| Appendix 2 |
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263 | (18) |
| References |
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281 | (10) |
| Subject Index |
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291 | |
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