Welcome to the thermal world
„ Thermal analysis is a quick means to get to
Thermal Analysis
Acknowledgement:
Prof. Christopher Y. Li
References
„ Thermal Analysis, by Bernhard
Wunderlich Academic Press 1990.
„ Calorimetry and Thermal Analysis of
Polymers, by V. B. F. Mathot, Hanser
1993.
know your samples
„ Easy to start
„ Oftentimes, details are neglected
„ Get to know the science
Molecules are friendly, willing to
communicate; all you need to do is
Listen!!!
Class Outline
„ Concept of thermal analysis
„ Differential Thermal Analysis (DTA) and
Differential Scanning Calorimetry (DSC)
„ Crystallization and Melting
„ Glass Transition
„ Thermogravimetric Analysis
„ Questions
 Concept of thermal analysis Concept of thermal analysis

Temperature Scale: Heat: The macroscopically observed heat has its

microscopic origin in molecular motion. Unit: J (m2kgs-2,
Newton: 1701, freezing point of water: 0, body, 12
1 cal = 4.184 J)
Fahrenheit: 1714, freezing point of water mixed with salt 0 ,
body 96, freezing point of water 32, boiling point of water 212
dQ = dU + pdV
Celsuis: 1742, freezing point of water 0, boiling point of water
Q heat, U internal energy, p pressure, V volume
100
H = U + pV H, enthalpy
Kelvin: 1848, Absolute zero is the temperature at which
Cp = dQ/dT =(∂H/∂T)p,n Heat capacity
molecular energy is a minimum, and it corresponds to a
temperature of -273.15° on the Celsius temperature scale.

Techniques of Thermal Analysis Leading Companies

„ Thermometry: temperature •Perkin Elmer Thermal Analysis Systems

http://www.perkin-elmer.com/thermal/index.html
„ Calorimetry: heat •TA Instruments Home Page
„ Differential Thermal Analysis http://www.tainst.com/
•METTLER TOLEDO Thermal Analysis Systems
„ Thermomechanical analysis (TMA): length http://www.mt.com/
•Rheometric Scientific Home Page http://www.rheosci.com/
and stress) •Haake http://polysort.com/haake/
„ Dilatometry: volume and pressure
•NETZSCH Instruments http://www.netzsch.com/ta/
„ Dynamic Mechanical Analysis (DMA) •SETARAM Instruments http://setaram.com/
•Instrument Specialists Inc. http://www.instrument-specialists.com/
„ Thermogravimetry (mass)
 Differential thermal analysis Differential Thermal Analysis (DTA)

„ In differential thermal analysis (DTA)

technique, the heat flow to the sample and
reference remains the same. When the
sample and reference are heated identically
phase changes and other thermal processes
cause a difference in temperature between
the sample and reference. Both DSC and DTA
provide similar information; DSC is the more
widely used of the two techniques.
DTA measures temperature difference

Differential Scanning Calorimetry

Differential scanning calorimetry (DSC)
„ Differential scanning calorimetry (DSC) is a technique in
which the difference in the amount of heat required to increase
the temperature of a sample and reference are measured as a
function of temperature. Both the sample and reference are
maintained at very nearly the same temperature throughout the
experiment. Generally, the temperature program for a DSC

Exothermal dQ/dT
analysis is designed such that the sample holder temperature
increases linearly as a function of time. The reference sample
should have a well-defined heat capacity over the range of
temperatures to be scanned. The basic principle underlying this
technique is that, when the sample undergoes a physical
transformation such as phase transitions, more (or less) heat Temperature
will need to flow to it than the reference to maintain both at the
same temperature. Whether more or less heat must flow to the
sample depends on whether the process is exothermic or
endothermic.
The DTA method applied to the measurement of heat is called DSC.
 Differential Scanning Calorimeter Differential Scanning Calorimetry

„ Parts:
ƒ Isolated Box w/ two Platinum sensors
pans Temperature Range:
ƒ Heating element and 110 K- 1000K
thermo couple Heating rate 0.1 –500k/min
(normally 0.5-50 K/min)
ƒ Liquid Nitrogen Noise is ± 4µw
ƒ Nitrogen Gas Sample volume: up to 75 mm3
ƒ Aluminum Pan
Sample heater Reference heater

Perkin-Elmer DSC 7

The conformation of a
Polymers are large molecules polyethylene macromolecule
Typical molecule:
Molecular weight: 500 cm
C20000H40002, MW = 280,000 (Magnification 2,000,000×)
Na: 23, CO2 44…. Contour Length 3,100 nm
Planar zig-zag conformation
PE Polyethylene ----(CH2)n--- molecular weight could
be as high as millions! Atomic model of a planar H HH HH H
zig-zag conformation 111°
bond C C C
angle
(Magnification 108 ×) C C C ~ 0.45 nm
rotation
H HH HH H
 Random conformation
of a macromolecular chain
Random coil conformation
A number of different
conformations
320,000 = 1010,000
Molecular Distribution
Molecular Distribution:
Mn = ∑ NXMX/ ∑ NX,
MW = ∑ NXMX2/ ∑ NXMX
MW/Mn = 1 ~ 10 or even more
Molecular weight distribution is a unique characteristic of
polymers.

Broad molecular weight distribution could broaden the

crystal melting Peak.

Classification of Polymers Crystallization and Melting

Disordered State → Crystallization → Crystalline State

Amorphous polymer
Atactic polystyrene, poly methyl methacrylate
Crystalline polymers Gibbs free energy change:
polyethylene, polyethylene terephthalate… ∆G = Gcrystal - Gmelt
∆G = ∆H - T∆S
Plastics, rubber, thermal-plastic elastomers, resin… At Tm:
∆G = ∆H - Tm∆S = 0
The “softness” depends on the glass transition
temperature for amorphous polymers. Tm = ∆H/∆S

Crystallization could also “harden” polymer

Typical melt-grown polyethylene spherulites
 The three macromolecular
conformations in condensed states Crystallization and melting

Lamellar crystals Extended chain: presents

and Clusters equilibrium crystals. melting
1. Produced by annealing:
Crystallinity e.g. polyethylene
concept polytetrafluoroethylene

Exothermal
the molecules are polychlorotrifluoroethylene
much larger than the 2. Produced by crystallization
crystals during polymerization:
e.g. polyoxymethylene
Chain folded
1. Fold length 5 -50 nm
polyphosphates, selenium
Crystallization
2. Best grown from dilute Glassy amorphous
solution 1. Random copolymers
3. Metastable lamellae 2. Atatic stereoisomers
because of the large fold e.g. PS, PMMA, PP
surface area 3.Quenched slow
crystallizing
molecules DSC heating curve of PEEK, Poly(oxy-1,4 phynyleneoxy-
e.g. PET, PC 1,4-phenylenecarbonyl-1,4-phenylene), heating rate 10 K/min
and others.

Glass Transition Phase Transitions

„ A material’s glass transition temperature, Tg, is the temperature First-order phase transitions (in Ehrenfest
below which molecules have little relative mobility. Tg is usually classification) exhibit a discontinuity in the first derivative of
applicable to wholly or partially amorphous phases such as the free energy with a thermodynamic variable. The various
glasses and polymers. For inorganic or mineral glasses, such as solid/liquid/gas transitions are classified as first-order
common glass, it is the mid-point of a temperature range in
which they gradually become more viscous and change from transitions because they involve a discontinuous change in
being liquid to solid. Thermoplastic (non-crosslinked) polymers density (which is the first derivative of the free energy with
are more complex because, in addition to melting point, Tm, respect to chemical potential.)
above which all their crystalline structure disappears, such
plastics have a second, lower Tg below which they become rigid First order transition:
and brittle, and can crack and shatter under stress.
(∂∆G/∂T) = -∆S ≠ 0, (∂2∆G/∂T2) ≠ 0
„ Above Tg, the secondary, non-covalent bonds between the
polymer chains become weak in comparison to thermal motion,
and the polymer becomes rubbery and capable of elastic or Crystallization and melting
plastic deformation without fracture. This behavior is one of the
things which make most plastics useful.
 Phase Transitions
Second-order phase transitions have a discontinuity in a
second derivative of the free energy. These include the
ferromagnetic phase transition in materials such as iron,
where the magnetization, which is the first derivative of the
free energy with the applied magnetic field strength,
increases continuously from zero as the temperature is
lowered below the Curie temperature.
Glass Transition
In certain crystallizable materials, fast cooling can take the material
pass the freezing point and the liquid apparently “solidifies” without
Crystallizing and without a discontinuity in quantities such as the volume.
There is a change in the slope of the volume/temperature curve.
liquid
Glass transition

Volume
Second order transition: glass
(∂∆G/∂T) = -∆S = 0, (∂2∆G/∂T2) ≠ 0
crystal

Glass transition is a “quasi” second order transition. Temperature

Paul C. Painter and Michael L. Coleman,
Fundamentals of polymer science, Technomic: Lancaster PA, 1994

How to observe Tg Differential Scanning Calorimetry

2
PET
Melting
1.5
ENDOTHERMIC
1 Glass Transition

Heat Flow (W/gm)

Exothermal

Exothermal

0.5

0
0 50 100 150 200 250 300 350
-0.5

Temperature -1

EXOTHERMIC Crystallization
-1.5
Temperature (C)
Experimental curves on heating after cooling at 0.0084 K/min (1), 0.2 K/min (2)
0.52 K/min (3), 1.1 K/min (4), 2.5 K/min (5), 5 K/min (6), and 30 K/min (7). Sample: Polyethylene terephthalate (PET)
Temperature increase rate: 20°C/min
Temperature range: 30°C - 300°C
 Thermogravimetric Analysis Thermogravimetric Analysis
„ Thermogravimetric Analysis or TGA is a type of Thermogravimetric analysis
testing that is performed on samples to determine (TGA) device,
changes in weight in relation to change in Setaram TG-DTA 92 B type;
temperature. Such analysis relies upon a high degree the cooling water pipe is not
of precision in three measurements: weight, represented
temperature, and temperature change. As many
weight loss curves look similar, the weight loss curve
may require transformation before results may be
interpreted. A derivative weight loss curve depicts at
what point weight loss is most apparent. Again,
interpretation is limited without further modifications
and deconvolution of the overlapping peaks may be
required.

TGA of a series of Polymers TGA of SWCNT

C+O2=CO2
Oxidation of Oxidation of catalyst
amorphous carbon

http://www.msel.nist.gov/Nanotube2/
 Thermogravimetric Analysis
Determining the CNT contents in Polymer nanocomposites
Pure PAN nanofiber
Kinetic studies
The kinetic reaction mechanism can be determined from the
Arrhenius equation,
K=A exp (-Ea/RT),
where Ea is the activation energy; R is the universal gas
constant; A is the pre-exponential factor; T is the absolute
temperature; and K is the reaction rate constant.
The above equation upon log transformation can be rewritten
as
lnK= lnA - Ea/RT
The activation energy can be determined from the slope of the
above plot, and the intercept value would yield the pre-
exponential factor.
PAN nanofiber with CNT

Arrhenius plot Applications of TGA

„ Oxidation
„ Decomposition of organic matter
„ Explosives (ignition temperature)
„ Curing of polymers
„ Evaporation of solvents
Determination of kinetic mechanism for volatilization of „ Kinetics and activation energy
triacetin, diethyl phthalate, and glycerin from Arrhenius plots. measurements
The Ea values are 66.45, 65.12, and 67.54 kJ/mol