THERMAL ANALYSIS

Thermal methods of Analysis

 This is based on the concept of heating a sample
– followed by well-defined modified procedures,
such as : gravimetric analysis, differential
analysis and titrimetric analysis.
 Some property of a system is measured as a
function of temperature.
 Thermal spectra or Thermograms
Conti….

 Thermo grams characterize a single or multi

component system in terms of :
 Thermodynamic properties, and

 physicochemical reaction kinetics.

Thermal Analysis is widely used …

Other Polymers
13% 21%
Chemicals
9%

Textiles Pharma
4% 9%

Aerospace
4% Petrochem
8%
Metals
5%
Auto Ag/Food
5% Government Academic 8%
7% 7%
 Different Techniques
 Thermometric Titration (TT)

 Thermal Mechanical Analysis (TMA)

 Dynamic Mechanical Analysis (DMA)

 Differential Scanning Calorimetriy (DSC)

 Thermal Gravimetric Analysis (TGA)

 Differential Thermal Analysis (DTA)

 Temperature Programmed Desorption (TPD)

 Principle
 Sample is heated at a constant heating rate
 Sample’s Property Measured
 Wt TGA
 Size TMA
 Heat Flow DSC
 Temp. DTA
 Heat of mixing TT
 Tem. at which TPD
gas is desorbed
at the surface.
 What is DTA ?

 Involves the technique of recording the difference in

temperature between the Test and Reference material
time being constant for both.
 Hence the Differential Thermogram consists record of
difference in Temperatures.
 This is a comparison method

 Analytical method for recording the difference in

temperature (∆T) b/w a substance and an inert
reference material as a function of temperature
or time
 Any transformation – change in specific heat or
an enthaply of transition can be detected by DTA
 In DTA both test sample & an inert reference material
(alumina) – controlled heating or cooling programming
 If zero temperature difference b/w sample & reference
material – sample does not undergo any chemical or
physical change.
 If any reaction takes place temperature difference (∆T)
will occur b/w sample & reference material
 A DTA curve can be used as a finger print for
identification purposes, for example,
 in the study of clays where the structural similarity of
different forms renders diffraction experiments difficult
to interpret.
 ∆T VS Temp.
Sharp Endothermic – changes in crystallanity or fusion
Broad endotherms - dehydration reaction
Physical changes usually result in endothermic curves
Chemical reactions are exothermic
 Factors affecting DTA curve

A] Environmental factors
B] Instrumental factors
i] Sample holder
ii] Differential temperature sensing device
iii] Furnace characteristics
iv] Temperature- programmer controller
v] Thermal Regime
vi] Recorder
C] Sample factors
1] Physical
2] Chemical
 Instrumentation
 A differential thermal analyzer is composed of five
basic components, namely :
1} Furnace
2} Sample holder
3} temperature controller and recorder
4} thermocouple
5} Cooling device
 1} Furnace
 Tubular furnace is most commonly used because it
possess the desired characteristic for good
temperature regulation and programming.
 Dimension of the furnace is depends upon the
length of the uniform temperature zone desired.
  The choice of resistance material is depends on
the maximum temperature of the operation and
gaseous environment.
 Grooved muffled cores preferred.
2} Sample holder
o Should having low cost, ease of fabrication and
inertness towards the sample.
o Metallic material: nickel, stainless steel, platinum
o Non-metallic material: glass, vitreous silica or
sintered alumina.
o Most commonly the shape of holder is
cylindrical.
o The nature of physical constant between the
sample, thermocouple junction and the specimen
holder affect the DTA signals. So to maintain it, a
sample holder with dimples in which
thermocouple junctions are inserted
 3} Temperature controller and recorder

A] Temperature Controller
  In order to control temperature, the three basic elements
are required.

 These are sensor, control element and heater.

 The control element governs the rate of heat-input

required to match the heat loss from the system.

 The location of sensor with respect to the heater and

mode of heat transfer measure the time elapsed between
sensing and variation in heat input.
 Conti…

B] Temperature programming
 It transmits a certain time-based instruction to the
control unit.
 By this device one can achieve linearity in the rate of
heating or cooling it is driven in a non-linear fashion
using a special cam-drive.
 Heating rates of 10-20 o C / mints are employed.
C] Recorder
 The signals obtained from the sensors can be recorded
in which the signal trace is produced on paper or film,
by ink, heating stylus, electric writing or optical beam.
4} Thermocouple
 Thermocouples are the temperature sensors.

 It is made up from chromel p and alumel wires

are used to measure and control temperature
up to 1100 0C in air.

 For above 1100 0C one should use

thermocouple made from pure platinum &
platinum-rhodium alloy wires.
5} Cooling device

 It is separate from the temperature programmer

because it is independent from heating.
DTA Analyzer
 Methodology
o Insert a very thin thermocouple into a disposable
sample tube 2 mm in diameter and containing 0.1- 10
mg of sample,
o Another identical tube is either kept empty or filled
with a reference substance, such as quartz, sand,
alumina.
o The two tubes are simultaneously inserted into the
sample block and subsequently heated (or cooled) at
a uniform predetermined programmed rate
 Requirements
 DTA—A few of the vital aspects are :

 Pre-treatment of the specimen,

 Particle size and packing of the specimen,

 Dilution of the specimen,

 Nature of the inert diluent,

 Crystalline substances must be powdered, and sieved

through 100-mesh sieve

Cont…

Either to suppress an unwanted reaction (e.g.,

oxidation), or to explore the study of a reaction(e.g.,
gaseous reaction product)—the atmosphere should be
controlled adequately.
DTA Curve
 Heart of the analysis – heating block
 Identical pair of cavities for the sample, ref. material
 Whole unit is set in an oven- control pressure
 Thermocouple is place directly in contact with the
sample and another in contact with the reference
 Temp.of the block is raised, the temperature of the
sample & reference follow
 Zero temp. difference – no physical or chemical
change
 If any reaction – difference in ∆T
 Advantages:

 Instruments can be used at very high

temperatures.
 instruments are highly sensitive.
 flexibility in crucible volume/form.
 characteristic transition or reaction temperatures
can be accurately determined.
Disadvantage:
 uncertainty of heats of fusion, transition, or
reaction estimations is 20-50%.
 Applications
 Quantitative identification and purity
assessment of materials are accomplished by
comparing the DTA curve of sample to that of a
reference curve
 Impurities may be detected by depression of the
M.P
 Applications of DTA
 Physical Chemistry
1. Heat of a Reaction
2. Specific Heat of substance like Naphthalene.
3. Thermal Diffusivity of samples
 Analytical Chemistry
1. Identification of Products since no two
products have identical curves.
2. Determination of Melting point.
 Applications of
DTA
1. To construct phase diagrams and study phase transitions.
2. To find ∆H
Peak areas depend upon sample mass, m, enthalpy change ∆H of
the process, and geometric and conductivity factors such as heating
rate φ and particle size (included in a constant k for a certain
substance).

Usually the sample peak area is compared with a standard undergoing an

enthalpy change at a similar T (since the calibration constant depends on
T), under the same conditions,
e.g. indium MPt 156.4 C; ∆H fusion = 28.5 J g-1
3. To fingerprint substances

4. To determine M.Pt., B.Pt., decomposition temperatures of organic

compounds .
5. To characterize inorganic materials

The peak at 113°C corresponds to a solid-phase change from the rhombic to the
monoclinic form, while the peak at 124°C corresponds to the melting point of the
element.

Liquid sulphur is known to exist in at least three forms, and the peak at 179°C
apparently involves a transition among these.

The peak at 446°C corresponds to the boiling point of sulphur.

6. To quantitatively analyze polymer mixtures

This is a thermogram of a physical mixture of seven commercial

polymers. Each peak corresponds to the characteristic melting point
of one of the components. Poly tetrafluoroethylene (PTFE) has an
additional low temperature peak, which arises from a crystalline
transition. Clearly, differential thermal methods can be useful for
qualitative analysis of polymer mixtures.
7. To characterize polymers

Schematic DTA thermal curves for the totally amorphous polymer structure and
the semi crystalline polymer structure. Both show Tg ; only the semi-crystalline
polymer has a crystallization exotherm.
Cont…

 Quantitative analysis of Compounds

 Determination of Structural and Chemical
changes occurring during heat treatments.
 Quality Control of Cement, glass, textiles, soils,
explosives and resins.
DIFFERENTIAL SCANNING
CALORIMETRY
Definitions

• A calorimeter measures the heat into or out of a

sample.
• A differential calorimeter measures the heat of a
sample relative to a reference.
• A differential scanning calorimeter does all of the
above and heats the sample with a linear temperature
ramp.
• Endothermic heat flows into the sample.
• Exothermic heat flows out of the sample.
DSC: The Technique

• Differential Scanning Calorimetry (DSC) measures the

temperatures and heat flows associated with transitions in
materials as a function of time and temperature in a
controlled atmosphere.

• These measurements provide quantitative and qualitative

information about physical and chemical changes that
involve endothermic or exothermic processes, or changes
in heat capacity.
 Conventional DSC
Sample Empty

Metal Metal Metal Metal

1 2 1 2
Sample Reference
Temperature Temperature

Temperature
Difference =
Heat Flow

•A “linear” heating profile even for isothermal methods

 Thermal Analysis
Differential Scanning Calorimetry (DSC)
What can DSC measure?
•Glass transitions
•Melting and boiling points
•Crystallisation time and temperature
•Percent crystallinity
•Heats of fusion and reactions
•Specific heat capacity
•Oxidative/thermal stability
•Rate and degree of cure
•Reaction kinetics
•Purity
 Principle

 The sample and reference are maintained at the same

temperature, even during a thermal event in the
sample

 The energy required to maintain zero temperature

difference between the sample and the reference is
measured

 During a thermal event in the sample, the system will

transfer heat to or from the sample pan to maintain the
same temperature in reference and sample pans
 Procedure
 There are two pans, In sample pan, polymer is added,
while the other, reference or standard substance is
added

 Each pan sits on top of heaters which are controlled by

a computer

 The computer turns on heaters, and let them heat the

two pans at a specific rate, usually 10oC/min.

 The computer makes absolutely sure that the heating

rate stays exactly the same throughout the experiment
 DSC

 Measure Transitions:
 Glass Transition Temperature (Tg)
 Melting Temperature (Tm)
 Crystallization Temperature (Tc)
 Think First………Heat Later

1. Does the sample contain volatile components?

- 2 to 3% water/solvent can lower the glass
transition temperature (Tg) by up to
100oC.
- Evaporation creates endothermic peaks in
standard (non-hermetic) DSC pans and
can be suppressed with use of hermetic
DSC pans.
2. At what temperature does the sample
decompose?

 Set the upper limit of the DSC experiment

based on decomposition temperature (TGA).
No meaningful DSC data can be obtained once
decomposition results in a 5% weight loss.

 Decomposition affect: the quality of the

baseline due to both endothermic and
exothermic heat flow, the quality of the
baseline for future experiments and can affect
the useful lifetime of the DSC cell due to
corrosion.
Differential Scanning Calorimetry Instrument

 Two basic types of DSC instruments:

power compensation DSC And heat-flux DSC
 individual
heaters controller DP
Power Compensation DSC

introduced in the early sample reference

pan pan
1960s.

1. Sample holder
Aluminum or Platinum pans inert gas inert gas
vacuum vacuum

2. Sensors thermocouple
DT = 0
Platinum resistance
thermocouples
Separate sensors and heaters for the sample and reference

3. Furnace
Separate blocks for sample and reference cells

4. Temperature controller
Supply the differential thermal power to the heaters to maintain the
temperature of the sample and reference at the program value
 heating
coil

Heat Flux DSC

1. Sample and reference holders sample reference
pan pan
Al or Pt pans placed on constantan disc
constantan
Sample and reference holders are
chromel/alumel
connected by a low-resistance wires
heat flow path
inert gas
vacuum thermocouples Chromel
2. Sensors
• Chromel® (an alloy made of 90% nickel and 10% chromium)-constantan area
thermocouples (differential heat flow)
• Chromel®-alumel (an alloy consisting of approximately 95% nickel, 2%
manganese, 2% aluminium and 1% silicon) thermocouples (sample temperature)
Thermocouple is a junction between two different metals that
produces a voltage due to a temperature difference
3. Furnace
• One block for both sample and reference cells
4. Temperature controller
• The temperature difference between the sample and reference is converted to
differential thermal power, which is supplied to the heaters to maintain the
temperature of the sample and reference at the program value
 DSC Curve

 The result of a DSC experiment is a curve of heat

flux versus temperature or versus time.

 This curve can be used to calculate enthalpies of

transitions, which is done by integrating the peak
corresponding to a given transition. The enthalpy
of transition can be expressed using equation:
 ΔH = KA
 Where,
ΔH is the enthalpy of transition,
K is the calorimetric constant,
A is the area under the peak.

The calorimetric constant varies from instrument to

instrument, and can be determined by analyzing a well-
characterized material of known enthalpies of transition.

Area under the peak is directly proportional to heat absorbed

or evolved by the reaction,

Height of the peak is directly proportional to rate of the

reaction
 Factors affecting DSC curve
Two types of factors effect the DSC curve
1-Instrumental factors

a- Furnace heating rate

b- Recording or chart speed
c- Furnace atmosphere
d- Geometry of sample holder/location of sensors
e- Sensitivity of the recoding system
f-Composition of sample containers
 2-Sample characteristics
a- Amount of sample
b- Nature of sample
c- Sample packing
d- Solubility of evolved gases in the
sample
e- Particle size
f- Heat of reaction
g- Thermal conductivity
 Determination of Heat Capacity
• DSC plot can be used to determine Heat
Capacity. Suppose a polymer is being heated.
When heating starts two pans, the computer will
plot the difference in heat output of the two
heaters against temperature that is plot of heat
absorbed by the polymer against temperature.
The plot will look like this at first.
 The heat flow is heat (q) supplied per unit time (t),
whereas,
 The heating rate of temperature increase (ΔT) per unit time

(t)
• By dividing heat flow (q/t) by the heating rate
(ΔT/t). It ends up with heat supplied divided by
the temperature increase, which is called heat
capacity.
When a certain amount of heat is transferred
to the sample, its temperature increases by
a certain amount, and the amount of heat it
takes to get a certain temperature increase
is called the heat capacity,

or Cp, it can be figured up from the DSC plot

DSC Thermogram

Oxidation
Heat Flow -> exothermic

Crystallisation Cross-Linking
(Cure)

Glass
Transition

Melting

Temperature
6
 The Glass Transition Temperature
On heating the polymer to a certain temperature,
plot will shift downward suddenly, like this:
 Crystallization
After glass transition, the polymers have a lot of
mobility. They wiggle and squirm, and never
stay in one position for very long time. But
when they reach the right temperature, they
will give off enough energy to move into very
ordered arrangements, which is called
crystals.
The temperature at the highest point in the
peak is usually considered to be the
polymer's crystallization temperature, or Tc
 Melting
If we heat our polymer past its Tc, eventually
we'll reach another thermal transition,
called melting. When we reach the
polymer's melting temperature, Tm, the
polymer crystals begin to fall apart, that is
they melt. It comes out of their ordered
arrangements, and begin to move around
freely that can be spotted on a DSC plot
This means that the little heater under the sample
pan has to put a lot of heat into the polymer in order
to both melt the crystals and keep the temperature
rising at the same rate as that of the reference pan.
This extra heat flow during melting shows up as a
big dip on DSC plot, like this:
 Putting It All Together
we saw a step in the plot when the polymer was heated
past its glass transition temperature. Then we saw a
big peak when the polymer reached its crystallization
temperature. Then finally we saw a big dip when the
polymer reached its melting temperature. To put
them all together, a whole plot will often look
something like this:
 Influence of Sample Mass
0

Indium at Onset not

-2 10°C/minute influenced
Normalized Data 15mg by mass
10mg

4.0mg
-4
1.7mg
DSC Heat Flow (W/g)

1.0mg
0.6mg
-6
150 152 154 156 158 160 162 164 166
706 Temperature (°C)
Effect of Heating Rate
on Indium Melting Temperature

-1
Heat Flow (W/g)

-2
heating rates = 2, 5, 10, 20°C/min
-3

-4

-5
154 156 158 160 162 164 166 168 170
Temperature ( ° C)
6
DSC: Main Sources of Errors
•Calibration
•Contamination
•Sample preparation – how sample is loaded into a pan
•Residual solvents and moisture.
•Thermal lag
• Heating/Cooling rates
• Sample mass
•Processing errors
Sample Preparation : Shape
• Keep sample as thin as possible (to minimise thermal
gradients)
• Cover as much of the pan bottom as possible
• Samples should be cut rather than crushed to obtain a
thin sample (better and more uniform thermal contact
with pan)

99
Other DSC Techniques
Hyper-DSC
Based on principle that high heating rates give large broad
transitions.
•Heating rates typically 400-500oC/min
•Need very small sample sizes (~nanograms)

Good for:
•A quick overview of new sample
•Picking out minute transition

Poor for:
•Accuracy: transitions can be shifted by as much as 40oC
•Repeatabiliy: Very sensitive to thermal lag.
Other DSC Techniques
Modulated DSC

• Composite heating profile:

• Determines heat capacity and separates heat flow into that due to
reversible and non-reversible events.
62 62
Modulate +/- 0.42 °C every 40 seconds
Ramp 4.00 °C/min to 290.00 °C

Typicaly: 60 60

Heating rates: 0 - 50C

Modulated Temperature (°C)

58 58
Temperature (°C)

Modulation:
Period: 60 second 56 56

Amplitude: +/-10C
54 54

Note that temperature is not decreasing during

Modulation i.e. no cooling
52 52
13.0 13.5 14.0 14.5 15.0
Time (min)
Modulated DSC

Benefits
 Increased Sensitivity for Detecting Weak (Glass) Transitions
 Eliminates baseline curvature and drift
 Increased Resolution Without Loss of Sensitivity
 Two heating rates (average and instantaneous)
 Ability to Separate Complex Thermal Events and Transitions
Into Their Heat Capacity and Kinetic Components
 Ability to Measure Heat Capacity (Structure) Changes During
Reactions and Under Isothermal Conditions

Downside
 Slow data collection
Example MDSC

0.00 0.00

-0.02 -0.02 -0.02

-0.04 -0.04 -0.04

Nonrev Heat Flow (W/g)

Rev Heat Flow (W/g)

Heat Flow (W/g)

-0.06 -0.06 -0.06

-0.08 -0.08 -0.08

-0.10 -0.10 -0.10

-0.12 -0.12 -0.12

-0.14 -0.14
-50 0 50 100 150 200 250
ExoUp Temperature (°C) Universal V4.2ETA Instruments
Reversible Transitions
•Glass Transition
•Melting

Non-reversible
•Crystallisation
•Curing
•Oxidation/degradation
•Evaporation

Technical Group Talk

 Comparison of DSC & DTA

Aspect DSC DTA

1.Size of Sample 2-10 mg 50-20mg
2. Sensitivity A few joule/mol 0.5kJ/mol
3.Heating & Programmed Programmed
Cooling cycles Heating & Cooling heating
is possible.
4. Second order It can be observed It is not observed
phase transition with a sample of
200mg
5. Specfic heat Accurate Not accurate
measurement
 References
1. Instrumental Methods of Chemical Analysis-
By, G.R. Chatwal & S.K. Anand.
2. Instrumental methods of analysis; seventh
edition by Willard. Merritt, Dean Seffle.
3. www. wikipedia.com