Thermal analysis

techniques

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Thermal analysis techniques
Plastic materials are tested throughout their life:

 Monomer / Reactants
 Polymer / Raw Material & Additives
 Product / Design
 Product / Research & Development
 Processing / Quality Control
 Product / End of Life

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Thermal Methods

 Thermal methods are based upon the measurement of

the dynamic relationship between temperature and
some property of the system such as mass and heat
absorbed or evolved by/from it.

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Thermal analysis
ANALYTICAL TECHNIQUES
 Differential Scanning Calorimetry (DSC)※
 Dynamic Mechanical Thermal Analysis (DMTA)
 Thermogravimetric Analysis (TGA) ※
 Differential Thermal Analysis (DTA) ※
 Melt Flow Rheology (MFI)

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Basic Principle
 Sample is heated at a constant heating rate
 Sample’s Property Measured

◦ Wt TGA
◦ Heat Flow DSC
◦ Temp DTA

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Thermogravimetric Analysis

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definitions
“…. a technique in which the mass of a substance is
measured as a function of temperature, while the
substance is subjected to a controlled temperature
programme.”

“Controlled temperature programme” can mean:

• heating and/or cooling at a linear rate
• isothermal measurements
• combinations of heating, cooling and isothermal stages
• other, more modern approaches, in which the temperature
profile is modified according to the behaviour of the
sample.

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 TG is inherently quantitative, and therefore
an extremely powerful thermal technique, but
gives no direct chemical information. The
ability to analyse the volatile products during
a weight loss is of great value.

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 Instrumentation

 The essential components of the equipment used,

 a thermobalance,
 furnace,
 temperature programmer,
 sample holder,
 an enclosure for establishing the required atmosphere,
 and a means of recording and displaying the data.
 Balance sensitivity is usually around one microgram,
with a total capacity of a few hundred milligrams. A
typical operating range for the furnace is ambient to
1000°C, with heating rates up to 100°C/min

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 The quality of the furnace atmosphere
deserves careful attention, particularly the
ability to establish an inert (oxygen-free)
atmosphere,
 it is useful to be able to quickly change the
nature of the atmosphere.
 Compatibility between the materials of
construction and the sample and its
decomposition products, and the gaseous
atmosphere, must be considered.
 Sample holder materials commonly available
include aluminium, platinum, silica, and
alumina.
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instrumentation
GAS IN BALANCE
WEIGHT
CONTROLLER
GAS-TIGHT
ENCLOSURE

SAMPLE

HEATER
SAMPLE TEMP.

POWER FURNACE TEMP.

TEMPERATURE PROGRAMMER

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balance/furnace configurations

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 Calcium Oxalate Decomposition

 1st Step CaC2O4•H2O (s) CaC2O4 (s) + H2O (g)

Calcium Oxalate Monohydrate Calcium Oxalate
Loss will occur between 113 and 207°C.

 2nd Step CaC2O4 (s) CaCO3 (s) + CO (g)

Calcium Oxalate Calcium Carbonate

Loss will occur between 405 and 523C.

 3rd Step CaCO3 (s) CaO (s) + CO2 (g)

Calcium Carbonate Calcium Oxide
Loss will occur between 626 and 793C.
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example curve

Mass (%) in green, rate of mass loss (%/°C) in blue.

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 The plot also shows the derivative of the TG
curve, or the DTG curve, which is often useful in
revealing extra detail, such as the small event
around 400°C, which would not have been seen
on the TG curve itself.

 The DTG curve is sometimes used to determine

inflection points on the TG curve, to provide
reference points for weight change
measurements in systems.

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 TG has been applied extensively to studying
analytical precipitates for gravimetric
analysis.
 One example is that of calcium oxalate

monohydrate, as shown in the plot.

 This material has become popular for

demonstrating thermobalance performance,

as it gives three distinct weight losses over a
wide temperature range.

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Determination of the degradation temperature

 The degradation temperature is the temperature at

which a plastic reverts to its original component(s).
This is also known as the ceiling temperature.
 There are two TGA techniques to determine the
degradation temperature of a plastic.
 The first is called the isothermal method and is
based on setting the sample on a temperature that
is between 50 and 150C above its melting
temperature and letting the instrument measure the
weight loss with time.
 This is one technique used to determine physical
aging of a sample under extreme conditions
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APPLICATIONS
 Determination of the degradation temperature
 Physical Aging
 Moisture Determination
 Determination of Filler/Additive Content
 Determination of Different Types of Plastics in

one Sample

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 The second technique is based on running the
sample under an increasing temperature pattern
while measuring the weight loss.
 This is known as a non-isothermal degradation

test. This technique is used when the

decomposition temperature of the sample is not
known.

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21
Physical Aging
 It is often essential to know the lifetime
performance of a plastic. The TGA can
provide an accelerated testing to predict
lifetime performance.

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Determination of Filler/Additive
Content
 In most industrial applications, plastics do not
possess the properties needed, thus the use of
additives and fillers.
 The procedure to determine the content of
additives/fillers is to run the sample to and above
its decomposition temperature.
 Most additives will decompose at temperatures
below the material’s decomposition temperature,
while most fillers will still be present after the
sample has decomposed.
 The typical heating rate is between 15 and 30
C/min.

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Thermogravimetric Analysis (TGA)

% Polymer = 64.4%

% Carbon Black = 3.4%

% Glass Fibre = 32.2%

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Process Weight gain Weight loss

Ad- or absorption *

Desorption *

Dehydration/desolvation *

Sublimation *

Vaporization *

Decomposition *

Solid-solid reactions *

Solid-gas reactions * *

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 Temperature Amplifier m-T (Recorder)
sensor

Analytical Balance

Sample
Thermal Sample holder with
Insulation environment
control
Furnace

Microprocessor

TGA
controlled power
source

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Difference between DTA and DSC
 Differential Thermal Analysis (DTA)

• the temperature difference between a sample and an inert

reference material, ∆T = TS - TR, is measured as both are
subjected to identical heat treatments

 Differential Scanning Calorimetry (DSC)

• 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 differential

between the sample and the reference, dQ/dt, is measured

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 ∆T-Tr
DTA Amplifier Amplifier

Temperature Temperature
Sensor-1(Tr) Sensor-2(∆T)

Sample
holder with
Reference R S
R environme
holder
nt control
Furnace equipment

Microprocessor controlled power

source
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 Amplifier ∆H-T Recorder

Transducer
Temperature Temperature
Sensor-1 Amplifier
Sensor-2

DSC
R S
R

Secondary
Furnace power
source
supplied to
Microprocessor controlled power sample or
source reference to
make
∆T=0

Secondary power source 30

 Basic Principles of Thermal Analysis

Modern instrumentation used for thermal analysis usually consists of four parts:

1) sample/sample holder

2) sensors to detect/measure a property of the sample and the temperature

3) an enclosure within which the experimental parameters may be controlled

4) a computer to control data collection and processing

DTA power compensated DSC heat flux DSC

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 Differential Thermal Analysis

sample holder

• sample and reference cells (Al)

alumina block
sensors heating
coil

• Pt/Rh or chromel/alumel thermocouples

• one for the sample and one for the reference sample reference
• joined to differential temperature controller pan pan

furnace
inert gas
vacuum
• alumina block containing sample and reference
cells
Pt/Rh or chromel/alumel
temperature controller thermocouples

• controls for temperature program and furnace

atmosphere

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 Differential Thermal Analysis

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

DTA
disadvantages:

• uncertainty of heats of fusion, transition, or

reaction estimations is 20-50%

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 In DTA the heat absorbed or emitted by a system is
observed by measuring the temperature difference (∆T)
between that system (the sample) and an inert reference
material (often alumina), as the temperature of both is
increased at a constant rate (usually 5-10 °C/min).

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 Differential Scanning Calorimetry

• DSC differs fundamentally from DTA in that the sample and reference are both
maintained at the temperature predetermined by the program.

• 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

• two basic types of DSC instruments: power compensation and heat-flux

power compensation DSC

heat flux DSC
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The temperature increase, ∆T, of a body which is heated is
directly proportional to the amount of heat absorbed, ∆ Q,
and inversely proportional to its mass, m, and its capacity
C to store heat:
∆ T = ∆ Q/m C Eq. 1

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Consider the temperature increase of two different
samples of the same mass
m1 = m 2
for which the same amount of heat was given
∆ Q1 = ∆ Q2
If their heat capacities are different
C1 ≠ C 2
they do not experience the same temperature increase, i.e.,
∆ T1 ≠ ∆ T 2

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A greater heat flow (dQ/dt, where t is time) will always
flow into the sample whose heat capacity is higher, in
order that the steady-state heating rate be maintained.

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 Heat Capacity or Specific Heat is the amount of heat
required to change the temperature of a specific mass of
material (no transition in structure):
Heat Capacity = Specific Cp (J/g°C) x Sample Weight (g)

 Heat capacity is a measure of molecular motion. Heat

capacity increases as molecular motion increases.
Vibration – occurs below and above Tg
Rotation – polymer backbone and sidechains (in and
above Tg)
Translation – entire polymer molecule (above Tg)

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 Transitions in the structure of a material are
important because they result in changes in heat
capacity (molecular mobility) and other important
physical, and sometimes chemical, properties
 Thermodynamic property of material (vs. heat
flow). Heat flow is relative; whereas, the heat
capacity is absolute

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 True Heat Capacity (no transition) is
completely reversible; the material
releases the same amount of heat as
temperature is lowered from T2 to T1
 Specific Heat Capacity refers to a specific
mass and temperature change for a
material (J/g/°C)

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 For the same substance, Cp is dependent upon its
aggregation state, i.e., it is different for the liquid state
as compared to loose gaseous or to more compact solid
state.

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 A polymeric material has different heat capacities for
amorphous or crystalline morphologies. For amorphous
polymers, the heat capacity for the glassy state (i.e., below
glass transition, Tg, where only vibrations of atomic
groups occur) is different from that characterizing the
leathery (short range diffusional motion, i.e., of chain
segments), rubbery (retarded long-range motions), rubbery
flow (slippage of long-range entanglements) or liquid state.

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Melting of Indium

Extrapolated
0
Onset
Temperature 156.60°C
-5
28.50J/g
Heat of
Fusion Indium
Heat Flow (mW)

5.7mg
-10 10°C/min

For pure, low

-15
molecular weight
materials (mw<500
g/mol) use
-20
Extrapolated Onset as
Peak Temperature 157.01°C Melting Temperature
-25
150 155 160 165
Exo Up Temperature (°C) Universal V4.0B TA Instruments

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 Melting of PET
For polymers, use Peak as Melting Temperature
-1

-2 Extrapolated
Onset
Temperature
Heat Flow (mW)

-3

236.15°C
-4 52.19J/g
Heat of
-5
Fusion
PET
6.79mg
10°C/min
-6

Peak Temperature 249.70°C

-7
200 210 220 230 240 250 260 270
Exo Up Temperature (°C) Universal V4.0B TA Instruments

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