Thermal Analysis

Differential Scanning Calorimetry (DSC)

Principle DSC measures the differences in heat flow into a substance and a reference as a function of sample temperature while both are subjected to a controlled temperature program DSC provides access to accurate thermodynamic data as well as information regarding reactivity and phase transformations DSC types DSC is the most sophisticated and advanced of the thermal methods. There are two principal types: power compensated DSC heat-flux DSC Power Compensated DSC-principles Temperature difference is maintained zero, i.e., T = 0, by supplying heat into the sample or reference according to heat emission or absorption Electrical power is proportional to heat change in the sample i.e., P = I2.R

Power Compensated DSC-principles Rate of change of power input is plotted against average S & R temperature x-axis (abscissa) is temperature and the y-axis (ordinate) is difference in power input (which is proportional to the heat change i.e., enthalpy) Instrumentation

Furnace and sample holder

How does it work? Small, flat samples are contained in shallow pans, with the aim of making a good thermal contact between sample, pan and heat flux plate. Symmetrical heating of the cell, and therefore S and R, is achieved by constructing the furnace from a metal of high thermal conductivity for example, silver Sample and reference material are heated by separate heaters in two independent furnaces The furnaces are imbedded in a large temperature-controlled heat sink Sample holders are above the furnaces Pt resistance thermometers are imbedded in the furnaces to monitor the temperatures of sample and reference continuously There is provision for establishing gas flow through the cell, to sweep away volatiles, provide the required atmosphere, and to assist in heat transfer. Control of the furnace, signal acquisition, and data storage and analysis are handled by a computer. Two control circuits are used to obtain differential thermograms One for average temperature control One for T control S and R temp. signals are fed into a differential amplifier via a comparator circuit that determines which is greater The amplifier output then adjusts the power input to the two furnaces in such a way that their temperatures are kept identical Throughout the experiment, S and R are isothermal

A signal proportional to difference in power input to the S and R furnaces is transmitted to the data da acquisition system The power differences are plotted as a function of the sample temperature and its unit is milli Watts (mW) Heat flux DSC

How does it work? S and R are heated by a single heater Differential heat flow into the S and R pans is monitored by chromel disk/constantan thermocouple Differential heat flow in to S and R pans is directly proportional to the difference in output of the two thermocouple junctions Sample temp. is estimated by chromel/alumel junction under the sample disk junctio Purge gases Typical purge gases are air/N2 He is useful for efficient heat transfer and removal of volatiles. Ar is preferred as an inert purge when examining samples that can react with nitrogen. The experiment can also be carried out under a vacuum or under high pressure.

Crucibles Choice of crucible is critical. Thermal properties of crucible. Reactive properties with samples. Catalytic behaviour with samples.

Aluminum: inexpensive, low temp Copper: used as catalyst (testing polymers) Gold: higher temp, expensive Platinum: still higher temp, expensive. Alumina (Al2O3): very high temp Sapphire: crystalline alumina, more chemically resistant than amorphous Al2O3. DSC thermograms

S glass transition Ex exothermic reaction En endothermic reaction

Enthalpy changes The DSC curve may show an exothermic or endothermic peak The enthalpy changes associated with the events occurring are given by the area under the peaks. Peaks may be characterized by: Position (i.e., start, end, extrapolated onset and peak temperatures) Size (related to the amount of material and energy of the reaction) Shape (which can be related to the kinetics of the process) Some possible processes giving enthalpic peaks Process Solid-solid transition Crystallization Melting Vaporisation Sublimation Adsorption Desorption Desolvation (drying) Decomposition Solid-solid reaction Solid-liquid reaction Solid-gas reaction * * * * * * * * * * * Exotherm * * * * * Endotherm *

Curing Polymerization Catalytic reactions

* * *

Measurement of H of thermal transitions H

Calibration of DSC Temperature calibration is carried out by running standard materials, usually very pure metals with accurately known melting points.

Energy calibration may be carried out by using either known heats of fusion for metals, commonly indium, or known heat capacities.

Effect of heating rate

Heat flow (mW) Exo Endo

Temperature (0 C)
Slower heating rates will more accurately depict the onset temperature of transformation Two transformations which are very close in temperature range may be more distinctly seen as separate peaks, whereas they may be mistaken for a single transformation under a rapid heating rate single

Applications of DSC in materials analysis

Polymer characterization

Here is the DSC curve for a polymeric material such as high density polyethylene (HDPE). We see three phase transition temperatures: glass transition temperature (Tg), crystallization temperature (Tc), and the melting temperature (Tm)

Polymer characterization Tg may be used to identify polymers The amount or effectiveness of a plasticizer may be judged by how much it reduces Tg or affects the shape of the transition. Examination of the transitions in polymer blends gives information as to their compatibility. Curing reactions result in an increase in Tg and measurements can be used to monitor the extent of cure.

Polymer characterization

exo

Polymer A

endo

Polymer B

Blend of A+B

Thermogram of the blend shows two distinct Tg. Therefore, the components of this blend are immiscible in each other Tg also varies with chain length for a related group of polymers. Additional features occurring in the glass transition region, often a superimposed endothermic peak, are related to the aging undergone by the material in the glassy state, and can sometimes obscure the transition, making precise temperature measurement difficult.

Analysis of explosives Ammonium perchlorate is an important component of high explosives. The stability of this material is critical to their safe handling. Mechanism of decomposition was investigated.

Literature values for Ea 37 - 260 kJ/mol with different mechanisms proposed. This work clarified the mechanism and identified the activation energy as 115 kJ/mol. Analysis of lubricants An important test in the automotive industry is to determine the stability of lubricating oils at elevated temperatures and pressures. This will impact its utility as a lubricant in motors. In this case, the oil is brought to a high operating temperature and held there under an oxygen atmosphere.

At some point, the oil begins to oxidize and then quickly decomposes exothermically. Note how the synthetic oil synth has a much longer oxidation induction time (OIT) than does the mineral oil. Guidelines for interpreting data It is better to have some idea of what transitions to look for and why. For example: 1. What type of sample is it? 2. What type of transitions can it undergo? 3. What would any changes appear as? 4. What is the temperature range of interest? 5. What data are available from complimentary techniques, e.g. TGA? 6. Has there been any previous analysis?

Then examine the data: 1. Is the event an endotherm or exotherm? 2. Is the event repeatable on a fresh sample or on a reheat? 3. What happens on cooling? 4. Is the event the same in a sealed and unsealed pan? 5. Is the transition sharp or gradual, large or small? 6. Does the event look real? Thermal events are not normally excessively sharp. ok

Text book D. A. Skoog et al., Principles of instrumental analysis, fifth edition, Harcourt Publishers, 2001. Reference R. F. Speyer, Thermal analysis of materials, Marcel Dekker, 1994.