THERMAL ANALYSIS 1

Course Conducted By
Fatema-Tuz-Zahra
Department of MSE
KUET
Introduction
➢Measurement of property change as a function of temperature.
➢Changes in materials properties with temperature are considered as
thermal events.
➢Properties change include dimension, mass, phase change and
mechanical behavior.
➢We will discuss about the following thermal analysis techniques in this
lesson.
1) Thermogravimetry (TG)
2) Differential Thermal Analysis (DTA)
3) Differential Scanning Calorimetry (DSC)
 Thermal Events
➢Solid phase transformation: Solid phase transformation may occur for solids that have
different equilibrium crystalline phases in different temperature ranges. For example, pure iron
changes its crystal structure from body-centered cubic (BCC) to face-centered cubic (FCC) when
the temperature increases to 912 ◦C. (1st order)
➢Glass transition: Glass transition occurs in non-crystalline solids. With increasing
temperature, a rigid non-crystalline solid in a glass phase may change to a rubber-like solid. The
glass transition is referred to as a second-order phase transition.
➢Melting
➢Sublimation
➢Thermal Decomposition: Thermal decomposition is referred to as a change in a solid
containing more than one type of atom or molecule. With increasing temperature, the bonding
between atoms becomes so weak that certain constituents will be released from the solid into the
atmosphere and the remaining constituents will form a new type of solid. For example, solid
CaCO3 will decompose to form solid CaO and gaseous CO2 over a certain temperature range.
Instrumentation
Experimental Parameters
➢Sample dimension or, mass
➢Heating/cooling rates
➢Atmosphere surrounding the sample
➢Thermal and mechanical history of the sample
TA Techniques
Differential Thermal Analysis (DTA)
➢Objective: to examine thermal events in a sample by heating or
cooling without mass exchange with its surroundings.
➢The thermal events examined by DTA include solid-phase
transformation, glass transition, crystallization and
melting.
➢‘‘Differential’’ emphasizes that analysis is based on differences
between sample material and a reference material in which the
examined thermal events do not occur.
Differential Thermal Analysis (DTA)
➢Sample and reference symmetrically placed in the furnace.
➢Temperature difference measured using thermocouples.
➢The reference should have the following characteristics:
1) Doesn’t undergo thermal events over the operation temp. range
2) Doesn’t react with any component in the instrument
3) Has similar thermal conductivity and heat capacity to the sample
being examined.
➢The temperature difference between sample and reference (∆T)
should be zero when no thermal event occurs in the sample,
because of similar thermal conductivity and heat capacity
between the sample and reference.
➢When a thermal event occurs in the sample, nonzero ∆T will be
generated. ∆T will be negative if the thermal event is endothermic
(absorbing heat) or positive if the thermal even is exothermic
(releasing heat).
➢An endothermic event makes the sample temperature lower than
the reference temperature that follows the heating program
closely.
➢On the other hand, an exothermic event makes the sample
temperature higher than the reference temperature.
Differential Scanning Calorimetry (DSC)
➢A DSC instrument is designed to measure the heat-flow difference
between sample and reference.
➢There are two widely used DSC systems: the heat flux DSC and
the power-compensated DSC.
➢The heat flux DSC is also called ‘‘quantitative DTA’’ because it
measures the temperature difference directly and then converts
it to a heat-flow difference. This conversion is accomplished by
an algorithm in computer software installed in the system.
➢The power-compensated DSC directly measures the enthalpy
change of a sample during a thermal event.
➢In power-compensated DSC, there are two separate chambers to
contain the sample and reference.
➢Each chamber has its own individual heat element to control
temperature.
➢The instrument always maintains a thermal null state (∆T =0).
➢When a thermal event occurs in the sample, the power to the
heating element has to change in order to maintain the sample
temperature the same as that of the reference.
➢An endothermic event causes an increase in power to heat the
sample; an exothermic event causes a reduction in power to cool
the sample.
➢The amount of power change should equal the energy of heat flow
to compensate for the heat release or gain of the sample.
◦ In a DSC curve heat flow is plotted versus temperature.
◦ The heat flow has a unit of energy per unit time per unit mass, usually in units of
W/g.
◦ Commonly, heat flow into a sample is indicated as an upward feature of the DSC
curve.
◦ The DSC curves are commonly recorded over a temperature range by heating or
cooling a sample with a constant rate, similar to DTA curves.
Although DTA and DSC are similar in thermal event measurements
and instrumentation, they are different in the following aspects.
➢DTA is a qualitative technique because measured temperature
differences do not provide any quantitative data for energy.
➢In contrast, DSC is a quantitative technique because measured
heat flow provides enthalpy changes in the sample during a
thermal event.
➢DTA can operate over a wider temperature range than DSC. The
DTA can reach a temperature of greater than 1500°C, while the
power-compensated DSC is restricted to a maximum temperature
of about 750 °C.
➢This DTA feature is important for examining materials with high
melting temperature such as ceramics and some metals.
Temperature-Modulated Differential
Scanning Calorimetry
◦ In conventional DSC measurements, the enthalpy change of thermal events
in the sample is measured at a constant heating rate.
◦ This means the sample temperature change with time as written as
follows:

◦ Temperature-modulated differential scanning calorimetry (TMDSC) is an

advanced DSC technique in which the heating rate is modulated by
superimposing a cyclic heating rate on the constant rate; for example, a
sinusoidal temperature modulation is superimposed on the temperature
profile
◦ B is the amplitude of temperature modulation that is commonly in the range
of ±1 to ±10 K and ω=2π 𝑝−1 , in which p is the modulation period that is
commonly in the range 10–100 s.
◦ The constant heating profile to the sample can provide total heat-flow
information, while the sinusoidal heating profile gives information
corresponding to the rate of temperature change.
◦ Raw TMDSC data are rather complex compared with conventional DSC data.
◦ TMDSC data require deconvolution to generate standard DSC curves.
◦ At any moment of a DSC experiment, the heat flow can be expressed as a
differential equation:
◦ 𝐶𝑝 is the sample heat capacity. The first term on the right-hand side of Eq. represents the heat
flow of reversing thermal events and the second term represents the heat flow of nonreversing
thermal events.
◦ f (T,t) is also referred as to the kinetic component of heat flow.
◦ The main advantage of TMDSC is its ability to separate the reversing and nonreversing
thermal events. Reversing thermal events include glass transition and fusion (melting).
◦ Nonreversing thermal events include oxidation, curing, relaxation and cold
crystallization (glass–crystal transition below the melting temperature).
◦ Separating the reversing and nonreversing heat-flow components, TMDSC can
distinguish overlapping thermal events.
◦ Figure illustrates the example of using TMDSC to examine a poly(ethylene
terephthalate)–poly(acrylonitrile– butadiene–styrene) (PET–ABS) polymer blend.
◦ The first heating curve reveals the PET glass transition at 340 K, the PET cold
crystallization at 394 K, and PET fusion at 508 K (not shown).
◦ The ABS glass transition at 379 K cannot be observed in the first heating curve because
it is overlapped with the PET cold crystallization peak.
◦ The ABS glass transition can only be revealed by a second heating after the first heating
and cooling.
Experimental Aspects: Sample Requirements
◦ Samples for DTA or DSC should be in the form of dense powders or
small disks.
◦ Film, sheets, and membranes are often cut into disks fitting into the
sample pans.
◦ Large shear forces during cutting samples should be avoided because
the shear force may induce plastic deformation in a sample and that
can affect DTA and DSC curves.
◦ Low-mass samples are also preferred because a low-mass sample can
quickly reach temperature equilibrium throughout its volume.
◦ A large-mass sample will have undesirable internal temperature
gradient and this will affect the accuracy of the curve.
◦ Commercial DSC instruments are able to measure phase change in
microgram samples.
◦ In practice, the lower limit of sample size relates to the nature of the
sample materials. For composites and polymer blends, large sample size
of about 10mg may be required.
◦ DTA is usually operated in a high-temperature range. Platinum and gold
crucibles are commonly used as sample and reference holders.
◦ DSC is usually operated in a low-temperature range (<500 ◦C), and
thus aluminum pans are commonly used as sample and reference
holders.
◦ The pans often need to be sealed to avoid sample mass change due to
evaporation. A special press can be used to mechanically weld a lid and
a pan together.