Analyzing & Testing

DSC - Method, Terms and Application –

A Brief Overview
DSC 214 Polyma
Training Course
Tautii Magheraus, August 8-9, 2018
Alexander Spengler, NETZSCH Gerätebau Selb, Germany
Thermal Analysis (TA)

Thermo-
Differential Thermo- mechanical Dielectric
Scanning gravimetric Analysis Analysis
Calorimetry Analysis (TMA) (DEA)
(DSC, DTA) (TGA) Dilatometry (DIL)
Dynamic-
Mechanical
Analysis (DMA)

Thermal effects Mass changes Dimensional Dielectr. constant

from physical due to changes, (permittivity),
and chemical evaporation, deformations, loss factor,
processes (phase decomposition viscoelastic conductivity,
transitions, and interaction properties, resisitivity
reactions); with the transitions, (ion viscosity);
specific heat atmosphere density cure index (degr.
of cross-linking)

Evolved Gas Analysis

(EGA – MS, FTIR)
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DSC-Instruments
Differences
DSC 214 Polyma
Temperature range:
-170 °C to 600 °C
Heating/cooling rate:
0,001 to 500 K/min
Automatic sample changer (ASC)
for 20 samples
DSC 404 F1/F3 Pegasus®
Temperature range:
-150 °C to 2000 °C
Heating/cooling rate:
0,001 to 50 K/min
Vacuum (10-4 mbar)
Automatic sample changer (ASC)
for 20 samples
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Cooling options

liquid / gaseous nitrogen cooling

(LN2/GN2) with 26/60l-Container Compressed air cooling
–180/150 ... 600 °C

Intracooler
-40/70/80 … 600 °C

Compressor
RT … 600 °C

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DSC is Based on Heat-Flow Principle

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Differential Scanning Calorimetry (DSC)

ASTM E 473 – 85:

reference sample

Differential Scanning
Calorimetry (DSC) is a
technique in which the temperature and
heat flow sensor

difference in energy heat flow

thermal resistance
heating and cooling
inputs into a substance
and a reference materials measured as a function of
temperature while the substance and reference is
subjected to a controlled-temperature program.

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 Dynamic Heat flow Differential Dynamic Performance
Calorimetry Differential Calorimetry

TR = reference temperature TR = reference temperature

TP = sample temperature TP = sample temperature
QOR = heat flow from the furnace to the PR = heat output of the reference furnace
reference
PP = heat output of the sample furnace
QOP = heat flow from the furnace to the
sample

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Thermocouples according to ITS 90 and IEC 584-1

Thermocouple (+) (-) Thermovoltage in µV Application temperature Remark

Part Part (Reference temperature 0°C)

at at at
100°C 500°C 1000°C

K Ni-Cr Ni-Al 42 43 39 0 …1100°C Suitable for oxidizing

(Chromel) (Alumel) atmosphere

T Cu CuNi 46 - - -185 … 300°C Suitable for high humidity

(Konsta ntan)

J Fe CuNi 54 56 59 20 … 700°C Can be used in reducing

atmsophere

N NiCrSi NiSi 30 38 39 0 … 1100°C Very stable signal

(Nicrosil)

E NiCr CuNi 68 81 - -200 … 800°C

-200...800°C Highest thermovoltage
per °C

R Pt13Rh Platin 8 11 13 0 … 1600°C High oxidation and

- corrosion
Platin - resistance
13%Rhodium

S Pt10Rh Platin 8 9 11 0 … 1550°C

Platin -
10%Rhodium

B Pt30Rh Pt6Rh 1 5 9 0 ... 1600°

Platin - Platin -
30%Rhodium 6%Rhodiu m

Type E and type S thermocouples are the most often used ones.

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Thermocouples

The thermocouple tolerance windows given by standards (e.g. DIN

EN 60584-2 and IEC 584-2) are too large for precise TG and DSC-
measurements.
e.g. type E (NiCr/CuNi), class 1, 375°C – 800°C
+/- 0,004 (t)
by 600°C (+/- 2.4°C)
e.g. type E (NiCr/CuNi), class 2, 333°C – 900°C
+/- 0,0075 (t)
by 600°C (+/- 4.5°C)

Calibration necessary

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Various Transitions – DSC

Transition Peak direction

endothermic exothermic
Melting x -
Crystallization - x
Evaporation x -
Sublimation x -
Adsorption - x
Absorption x -
Desorption x -
Magnetic transition. x -
(Curie point)
Liquid crystal transitions x -
Glass transition No peak, but step in
endothermic direction

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Various Transitions – DSC

Transition Peak direction

endothermic exothermic
Chemisorption - x
Desolvation x -
Dehydration x -
Thermal decomposition x -
Oxidative decomposition - x
Combustion - x
Solid solid transition x x
Polymerisation - x

Curing - x
Redox reaction Can be exothermic or
endothermic

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DSC – depending on structure

amorphous:
glass transition, decomposition

semi-crystalline:
glass transition, melting, crystallization,
phase transition

crystalline:
melting, crystallization, phase transition

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DSC - melting curves ….

exo

Melting with decomposition

Melting with oxidative

decomposition

Plastics (semi-crystalline)

Sample with impurity

(eutectic melting)

Pure substance (e.g. metal)

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Limits in interpretation of a DSC curve …

DSC /(mW/mg)

0.70 exo
Peak
DSC- curve
Phase transition?
0.60
Mass change?

0.50

0.40

0.30 peak
? ?
0.20

100 200 300 400 500 600 700 800

Temperatur /°C

Measurement of a clay sample in DSC mode

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Signal Generation

TF TR The DSC signal is the difference

TS between the sample temperature and
the reference temperature.
Temperature [°C]

Depending on the fact if TS is

subtracted from TR or vice versa
the melting peak is displayed
tb
upwards or downwards.
tm tp Time [min]

All effects which are consuming heat are endothermic, all effects which are
producing heat are exothermic.

The area under the DSC peak is proportional to the transition enthalpy (heat).

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Peak Area

µV/mW
µV mW
µVs J

sensitivity
calibration

t t

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DSC 204 F1 – Cross-Section

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How does a DSC Curve look like?

DSC /(uV/mg) Temp. /°C

 exo DSC 204 F1 Phoenix
Sample mass: 14.95 mg
7 Crucible: Al, pierced lid
Atmosphere: N2, 40 ml/min 160.0
Heating rate: 10 K/min
6
140.0
[1] 110105_cal_019.sd3
5 DSC
120.0
Temp.
4
100.0
3
80.0
2
60.0
1
40.0

0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0

Time /min

Measurement on indium

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What Information we can get from DSC?

Peaks:

 Melting (for crystalline or partially crystalline materials)

 Crystallization
 Phase transformations (structural changes)
 Reactions (like curing)
 Magnetic transitions (e.g. Curie point)
 Specific heat (cp)
 Evaporation
 Dehydration (evolvement of solvents)
 Decomposition

Steps:

 Glass transition (for amorphous materials)

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Amorphous – Semi-crystalline

Source:
J. Weiß, TRW
NETZSCH-
polymer seminar,
Nurrenberg, 2006

Semi-crystalline state
Amorphous state
Long-range order is realized in
No long-range order
varying degree

Molecules are already disordered in the solid state. Therefore no

energy is necessary to break up the lattice structure;
During heating increase of translation and rotation movement in small
subdomains (approx. 100 atoms).

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Glass Transition as Material Property

Tg midpoint: glass transition temperature at cp/2

low Tg  better cold flexibility

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Typical Measurement Parameters - DSC

 Crucibles with lid

 Crucible material with high thermal conductivity (like Al, Pt etc.) preferred,
but compatibility with sample is important
 5 to 30 K/min heating rate (standard heating rate: 10 K/min)
 For polymer measurements two heating segments are required
 Typical flow rate (depending on the instrument and measurement goal):
20 – 50 ml/min
 Identical measurement conditions for all measurements within a series of tests
 In most cases the reference crucible is empty
 DSC measurement is usually just a sample measurement without correction
 Correction curve is only necessary for cp determination or for very small effects

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Standards for DSC/DTA
General:

ASTM E 473: Standard Definition of Terms Relating to Thermal

Analysis
ASTM E 474: Evaluation of Temperature Scale for Differential
Thermal Analysis
ASTM E 793: Heats of Fusion and Crystallization by Differential
Scanning Calorimetry
ASTM E 794: Melting and Crystallization Temperatures by Thermal
Analysis
ASTM E 967: Temperature Calibration of Differential Scanning
Calorimetry and Differential Thermal Analyzers
ASTM E 968: Heat Flow Calibration of Differential Scanning
Calorimeters
DIN 51 005: Thermal Analysis (TA); Terms (in German)
DIN 51 004: Determination of Melting Temperatures of
crystalline Materials with Differential Thermal Analysis
(in German)
DIN 51 007: Differential Thermal Analysis (DTA); Basics (in German)

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