Differential Scanning Calorimetry

theoretical background

Galina Kubyshkina

Elektromaterial Lendava d.d., Slovenia

Crystalline materials
Typical features

presence of a unit (cell),

which is periodically repeated
in space
regular structure (lattice)
have short and long range
ordering
anisotropy of properties
have certain melting and
crystallization temperature

Figure 1. Examples of different crystal lattices

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Amorphous materials
Typical features

do not have lattice

irregular structure
have short range ordering
only
isotropy of properties
do not have certain
melting (crystallization)
temperature
exhibit glass transition Figure 2. Polymorphism: crystalline
and amorphous structure of SiO2

3
 Materials and their transitions
Phase transitions

A phase transition is the transformation of a thermodynamic system from one

phase to another

phase transitions

first order second order

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 Materials and their transitions
Melting and crystallization

Melting temperature - the temperature under which solid crystalline body has
transition to liquid state

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Materials and their transitions
Glass transition

amorphous solids

glassy state rubber state

Tg

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Materials and their transitions
Rate effect: physical aging

g
in
ol
co

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Aging
Physical and chemical

AGING

chemical physical

leads to modification of polymer chain chemistry remains unchanged,

(chemical reaction) but the local packing of the chains alters
(dimensional changes)

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 Materials and their transitions
Glass transition, melting, crystallization

crystal region
amorphous
region

amorphous material crystalline material

glass transition (Tg) melting (Tm), crystallization (Tc)

Figure 3. Polymer structure

Semicrystalline material
Tg, Tm, Tc

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Materials and their transitions
The task

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Standards used
ISO and ASTM Standards

International standard ISO 11357: Plastics – Differential scanning

calorimetry, prepared by Technical Committee ISO/TC 61, Plastics,
Subcommittee SC 5, Physical-chemical properties (7 parts)

ASTM D3417-99 ASTM E1356-98 ASTM E537-98 ASTM E698-99

ASTM E793-95 ASTM D3895-98 ASTM D5028-96 ASTM E928-01
ASTM D4591-97 ASTM E1858-00 ASTM E1269-01
ASTM D3418-99 ASTM E2009-99 ASTM E2070-00
ASTM E794-98 ASTM E2046-99 ASTM E2041-99

www.iso.ch
www.astm.org

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Thermal Analysis - definition
* International Confederation for Thermal Analysis and Calorimetry (ICTAC)

Thermal analysis* – a group of techniques in which a property of the

sample is monitored against time or temperature
while the temperature of the sample, in a specified
atmosphere, is programmed.

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 Classification of Thermal Analysis methods
By a property under studying

temperature magnetic deformation

temperature heat mass
difference properties mechanical properties

the heating/cooling thermomagneti thermomechanical analysis

curves analysis DTA calorimetry DSC TG TG analysis
c analysis dynamic mechanical analysis

modulated force TMA

dynamic force TMA
static force TMA

dilatometry

DMA
optical electrical acoustic
pressure
properties properties properties

thermomanometri thermooptical thermoelectrical thermoacousti

c analysis analysis analysis c analysis
thermoluminescence analysis

thermorefractometric analysis
thermospectrometric analysis

Thermally simulated sound

thermophotometric analysis

thermomicrometric analysis

Dielectric thermal analysis

thermoacoustic analysis
thermoelectrical analysis
Thermally simulated

Alternating current
current analysis

13 analysis
 DSC theoretical background
Exothermic and endothermic processes

According to the classification, calorimetry is a technique for determining the quantity of heat
that is either absorbed or released by a substance undergoing a physical or a chemical
change. Such a change alters the internal energy of the substance. At constant pressure, the
internal energy is known as enthalpy, H.

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DSC theoretical background
Enthalpy change between two states

∆H - the change of enthalpy between two states

∆H = ∫ Cp· dT Cp - specific heat capacity − the quantity of
energy needed to change the temperature of
1g of material by 1°C at constant pressure
T. - temperature
hard to measure
Q - heat flux - the quantity of heat transferred per
unit time and mass
υ - heating rate
.
measure Q instead of cp

.
The formula clearly shows the relationship between the most
important influential factors, namely, the heating rate and
mass

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 DSC theoretical background
DSC measuring principle

The investigated specimen and the reference

specimen are heated (cooled) individually

“Zero equilibrium” principle is realized:

should be permanently provided ∆T=0

The heaters automatically adapt to the

temperature changes between the
investigated specimen and the reference
specimen by supplying additional power

The difference between the power applied to

the investigated specimen and into the
reference specimen is measured as a
function of temperature and/or time

Figure 4.Scheme of a power-compensation DSC

The difference in thermal power ∆P is the
change in heat flux ∆Q relative to the
reference specimen thermal power PR

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 Sample crucibles (vessels)
Factors affecting the choice of a crucible

sample-crucible match use conditions

used method
sample (DSC, DTA, TGA…)
Requirements for materials:
sample material temperature range

crucible material atmosphere

Should be inert to the sample in the
crucible volume other conditions temperature range used
(heating rate, pressure)

Should not exhibit any physical

crucibles transitions in the temperature range
aluminum gold platinum steel used

The melting point should be

sufficiently high
copper glass sapphire alumina

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 DSC calibration
Standard reference material

Standard reference material – a material for which one or more of the thermal properties are sufficiently
homogeneous and well established to be used for the calibration of DSC
apparatus, for the assessment of a measurement method or for assigning
values of materials.

The choice depends on the temperature range we work

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 DSC measurement
Reference specimen

Reference specimen – a known specimen which is usually thermally inactive over the
temperature and time range of interest

Generally an empty pan identical

to the one with sample is used

Figure 5.Scheme of a power-compensation DSC

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Result of DSC measurement
DSC curve

melting peak

glass transition region

1-st scan heating

2-nd scan heating

cooling

crystallization peak

Figure 6. DSC curve as a function of time (left) and temperature (right)

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 DSC applications
Characteristic temperatures of transitions determination

* according to ISO 11357

h/2

Figure 7. DSC curves in the region of a phase transition and the corresponding characteristic temperatures

The temperatures Tmg, Tpm and Tpc are taken as glass transition temperature,
melting temperature and temperature of crystallization respectively.

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DSC applications
Enthalpy of transitions determination

* according to ISO 11357

The area of a DSC peak can be used to

estimate the enthalpy of transition, ∆H.

Figure 8. Enthalpy of transition estimation

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 DSC applications
Enthalpy of transitions determination: problem

Endo.

Considered to have
zero error

Main problem: extrapolation of the baseline in the peak region

To determine the baseline generally a straight line is used.

However, such approach too formal and has lack of theory.

The influence of changes in the

(!!!) sample's heat capacity or heat
transfer characteristics is not taken
into consideration.

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 Factors affecting on the result of DSC measurement

sample calibration sample pan experiment conditions

sample mass baseline calibration pan material temperature range

mechanical history standard reference material pan geometry heating/cooling rate

thermal history temperature calibration pan volume start/end temperature

contact area enthalpy calibration pan cover holding time

behavior during pan deformation № of heating scan

the experiment reference material during packing
and the experiment
sample geometry environmental conditions results interpretation
sample shape atmosphere pressure purge gas baseline determination

impurities temperature type of purge gas extrapolation of

temperature
water uptake humidity flow characteristics

factors

input output
material DSC measurement vary

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DSC advantages

wide range of temperatures

programmed heating/cooling rates
sensitivity
any material may be tested
any form of material may be tested
piece
fiber
powder
film
liquid
etc
small amount of material is needed
does not take much time
clearness of results

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DSC disadvantages

can not really control the rate of experiment (can check with
thermocouple)
dependent on too many parameters
very sensitive to any changes
the result depends a lot from the operator
the procedure of standard parameters evaluation is not
described precise and has lack of thermodynamic background

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 DSC use for structure analysis
Indirect method of structure modification observation

Figure 9. Morphology of Monomodal and bimodal PA6

Monomodal PA6

Bimodal PA6

Figure 11. Melt-crystallization exotherms and

subsequent melting endotherms for monomodal and
Figure 10. Corresponding molecular mass distribution
bimodal PA6 materials prepared by the same
technology

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DSC use in quality control

Thermal characteristics measurement

characteristic temperatures of transitions
enthalpy of transition measurement
specific heat capacity measurement

Identification of material

Crystallinity

Purity control

Any chemical / physical transition revealing

Stability control

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DSC use in quality control
Thermal characteristics of raw material control

polymer
Thermal characteristics measurement
(to fit the requirements of technology)
Identification of polymer
Useful for recycled polymers

additives
Temperature characteristics measurement

prepared raw materials

Thermal characteristics measurement
(to fit the requirements of technology)
Identification of polymer
Useful for recycled polymers

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DSC use in quality control
Crystallinity estimation

The properties of polymers are critically affected by their crystallinity: the more
crystalline – the more rigid, strong, brittle it is.

Determined as: measured

from reference literature

May be useful for polymer identification
Endo.

Tm = 167°C Practical example:

∆Hm = 173J/g
Tm = 167°C PP

∆Hm 173
Heat flow

W= ⋅ 100 = ⋅ 100 = 84%

∆Hm0 207 too high

More likely it is POM

Temperature

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 DSC use in quality control
Purity estimation

The melting of a pure material takes place

over a narrow range. The result is sharp
melting peak on DSC curve at a
temperature characteristic of this
material.

Impurities cause gradient of temperature

in the sample. As a result the melting
peak broadens and melting temperature
shifts.

Figure 12. DSC curves of a substance at three purity levels.

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 Degradation of polymer
Characteristic temperatures of transitions determination

time, years
Polymers are very sensitive to degradation
reactions occurring both during the processing
and during use.

Dominating degradation processes: Result:

oxydation color change

thermal oxidation properties change
photo-oxidation

To prevent degradation process stabilizers are added.

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 DSC use in quality control
Oxidation stability estimation

Information about the stability of

materials can be obtained from the
analysis of decomposition reactions.
Isothermal measurement
One widely used standard test
method is the measurement of the
Endo.

Tm oxidation induction time

oxidation induction time, OIT.

The differences in stability toward

oxidation between materials can
Heat flow

N2 / O2 switch
be clearly seen.
These measurements also allow
thermally, mechanically or
Time
chemically stressed material to
be distinguished from fresh
Figure 13. OIT measurement
material.

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