Thermal Analysis

Week 4-5
Thermal Analysis

A group of techniques in which a physical property is

measured as a function of temperature, while the sample is
subjected to a controlled temperature programme

By heating, cooling or isothermal

Thermal Analysis
Thermal Analysis Techniques Thermal Analysis Techniques

DSC
Differential Scanning Calorimetry
DMA/TMA Other
Heat Flow 5%
15%

TGA
DSC
Thermogravimetric Analysis
50%
Mass
TGA
30%
TG/DTA
Thermogravimetric Analysis/Differential
Thermal Analysis
Mass & Heat Flow

TMA Research / Analytical 70%

Thermomechanical Analysis
Dimension
Routine / QC 20%

DMA
Dynamic Mechanical Analysis
Modulus
 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%
Our main topics

Differential Scanning Heat flow during Transitions

Calorimetric (DSC)

Weight Loss due to

Thermal Gravimetric decomposition

Analysis (TGA) Derivative Thermogravimetric

Analysis (DTG)

Differential Thermal Heat of Transitions

Analysis (DTA)
 Physics Theory
The temperature increase, T, of a body
which is heated is directly proportional to
m.C.T = Q the amount of heat absorbed, Q, and
inversely proportional to its mass, m, and
its heat capacity C to store heat.
T= Q/m.C
Consider the temperature increase of two
different samples of the same mass

m1 = m2
for which the same amount of heat was
given

Q1 = Q2
If their heat capacities are different

C1  C2
they do not experience the same
temperature increase, i.e.,

T1  T2
 Basic Principles
 Modern instrumentation used for thermal analysis
usually consists of the following parts:
 sample holder/compartment for the sample
 sensors to detect/measure a property of the sample and the
temperature
 an enclosure within which the experimental parameters
(temperature, speed, environment) may be controlled
 a computer to control data collection and processing

temperature sample
PC
control (furnace)
sensors
Differential Scanning Calorimetry (DSC)
 Most popular thermal technique
 DSC measures the heat absorbed or liberated during the
various transitions in the sample due to temperature
treatment
 Differential: sample relative to reference
 Scanning: temperature is ramped
 Calorimeter: measures heat
 DSC measurements are both qualitative and
quantitative and provide information about physical and
chemical changes involving:
 Endothermic processes – sample absorbs energy
 Exothermic processes – sample releases energy
 Changes in heat capacity
Principles of DSC Analysis
 Power Compensation DSC

 High resolution / high sensitivity research studies

 Absolute specific heat measurement
 Very sensitive to contamination of sample holders
 Heat Flux DSC

 Routine applications
 Near / at line testing in harsh environments
 Automated operation
 Cost-sensitive laboratories
DSC Analysis Applications
Desolvation –
Melting points – Glass transitions –
adsorbed and bound
crystalline materials amorphous materials
solvents

Purity determination Polymorphic

Heats of transitions – – contamination, transitions –
melting, crystallisation crystalline/amorphous polymorphs and
phase quantification pseudopolymorphs

Processing conditions Compatibility – Decomposition

– environmental interactions between kinetics – chemical
factors components and thermal stability
Principle Of DSC
Typical Features of a DSC Trace
^exo Exothermic upwards
Endothermic downwards

MELTING
CRYSTALLISATION
GLASS TRANSITION
DESOLVATION

20 H2O
mW
DECOMPOSITION

Y-axis – heat flow

X-axis – temperature (and time)

40 60 80 100 120 140 160 180 200 220 240 260 280 300
o
temperature [ C]
General DSC Trace Data

Oxidation
Heat Flow -> exothermic

Crystallisation Cross-Linking
(Cure)

Glass
Transition

Melting

Temperature
Karena saya ada meeting Asesor Royal Society of Chemistry
(RSC) Jam 11.00 (UK Time)/Jam 17.00 (WIB),

Kuliah hari ini sampai jam 17.00

 Polyethylene terephthalate (PET)

Polymer without weight change in this temperature range

Melting Point
^exo Onset = melting point (mp)

MELTING

20
mW

Heat of fusion (melting) =

integration of peak

40 60 80 100 120 140 160 180 200 220 240 260 280 300
o
temperature [ C]
DSC scan of a crystalline material – one polymorphic form
Polymorphic Forms
^exo
TRANSITION

STABLE
METASTABLE
FORM
FORM

20
mW

40 60 80 100 120 140 160 180 200 220 240 260 280 300
o
temperature [ C]

DSC scan of a crystalline material – polymorphic transition

Pseudopolymorphism
^exo
MELTING

DEHYDRATION

20
mW

40 60 80 100 120 140 160 180 200 220 240 260 280 300
o
temperature [ C]
DSC scan of a hydrate
Amorphous Material

DEHYDRATION
Midpoint = glass transition (Tg)

GLASS TRANSITION
1 mW

40 60 80 100 120 140 160 180 200 220 240 260 280 300
temperature [°C]

Polyvinylpyrrolidone (PVP) co-processed with hydroflumethiazide

 Source: TA Instruments, Cassel RB,
Purity Determination and DSC Tzero™ Technology

Purity Determination of Drug

Purity of phenacetin drug

 DSC analysis of a poly ethylene terephthalate (PET)
sample quenched from the melt.
Compatibility Studies (Compound Mix)

Source: Schmitt E et al.

Thermochim Acta 2001, 380 , 175 – 183
Blank Slide
Graphene Oxide/PMMA
 THERMAL GRAVIMETRIC
ANALYSIS

Record mass change during heating /cooling

Thermogravimetric Analysis (TGA)
 A technique measuring the balance
variation in mass of a sample
undergoing temperature
scanning in a controlled sample
atmosphere
 Thermobalance allows for
monitoring sample weight as a
function of temperature
 The sample hangs from the
balance inside the furnace and
the balance is thermally purge gas
furnace
isolated from the furnace
 GAS IN BALANCE
WEIGHT
CONTROLLER
GAS-TIGHT
ENCLOSURE

SAMPLE

HEATER
SAMPLE TEMP.

POWER FURNACE TEMP.

TEMPERATURE PROGRAMMER
TGA Analysis Applicationa
Desolvation/dehydration – adsorbed and bound solvents,
stoichiometry of hydrates and solvates

Decomposition – chemical and thermal stability

Compatibility – interactions between components

Examples of TGA Curves

2
mg

0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
o
temperature [ C]
TGA curves of crystalline and amorphous substance
TGA Data of Calcium Oxalate Hydrate
TGA CaC2O4.xH2O data
Lactose monohydrate

^exo

20
mW 2
mg

0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340
o
temperature [ C]
DSC and TGA scans of lactose monohydrate
DTA and TGA

20.0
０．１ｍｇ シュウ酸カルシウム
0,1 mg CaC2O4
20.00
0.0

-20.0 15.00

DTA uV
TG %

-40.0 10.00

-60.0 5.00

-80.0 0.00

-100.0
0.0 200.0 400.0 600.0 800.0
温度 ℃
 TGA

• Constant Heating
Rate
– Initial Temp
– Final Temp
– Heating Rate (°C/min)
• Data
– Weight vs Time
– Weight vs Temp.
• Differential This Data
(DTG)
TG/DTA
Automated Stepwise Temperature Control

Sample: CuSO4･5H2O
TG/DTA
TG-GC-MS Data of PVC Film

50℃ ～ 200℃

200℃

300℃
MS Spectrum
310℃
300℃ ～ 310℃

TG / DTA
 Effect of heating rate

10 mg samples of PTFE, heated at 2.5, 5, 10 and 20 °C/min in nitrogen

Analysis of composite

TGA trace sampel komposit polyurethane dan polyphosphazene

 DTA
• Sample and Reference Placed in Heater
• Constant Heating Rate
– Initial Temp
– Final Temp
– Heating Rate (°C/min)
• Data
– Temp of Sample vs Time (or Temp)
– Temp of Reference vs Time (or Temp)
– Reference should be inert, e.g. nothing but latent heat
• Measures
– Heat of crystallization
– Glass Transition Temperature
 polymer stability studies

a = PVC, b= nylon-6, c = LDPE, d= PTFE

Composition of PV Acetate
TGA-MS of PVC