Differential Scanning Calorimetry
What is a DSC?
What is DSC?
Differential: measurement of the difference in heat flow
from sample and reference side
Scanning: the common operation mode is to run
temperature or time scans
Calorimeter: instrument to measure heat or heat flow.
Heat flow: a transmitted power measured in mW
1
DSC working principle
Ice Air
Ts Tr
Hot Plate
Heat the hot plate from -20 °C to 30 °C,
What will happen to the ice?
How do Ts and Tr react?
How do the Ts and Tr relate to each other?
2
DSC working principle
Temperature
Tr
Ts
Tf
Time
T =Ts-Tr
0
DSC raw signal
-0.5
Time
Tf or Tr
3
DSC working principle
T =Ts-Tr
0 DSC raw signal,
-0.5
Time
Φ=T/Rth
or Tr
Rth, thermal
Heat flow (mW) resistence of the
system
H DSC signal, Φ
-10
Time Peak integral H
Tf or Tr
4
Baseline slope
Heat flow Φ
(mW) Φ = m ⋅ cp ⋅
Where,
0
Φ m is the sample mass
cp is the specific heat capacity
Initial deflection
of the sample
β is the heating rate
-10
Time
or Tr
A normal DSC curve is not horizontal, its baseline shows a slope.
5
ICTA and Anti-ICTA
ICTAC (International Confederation for Thermal Analysis and Calorimetry)
Direction of DSC signal
ICTA (T=Ts-Tr) Anti-ICTA ( T=Tr-Ts)
endothermic downwards, endothermic upwards,
exothermic upwards. exothermic downwards.
mW
0
-10
-20
120 130 140 150 160 170 °C
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6
Endothermic and exothermic effects
Endothermic:
When the sample absorbs energy, the enthalpy change is said to be
endothermic. Processes such as melting and vaporization are endothermic.
Exothermic:
When the sample releases energy, the process is said to be exothermic.
Processes such as crystallization and oxidation are exothermic.
7
Exothermic effect
Temperature
Tr
Ts
Time
T =Ts-Tr
DSC raw signal
0
Time
or Tr
8
Schematic DSC curve of a polymer
exo
6
1 2
Heat flow
3 4 5
endo
Temperature
1. initial startup deflection; 2. glass transition;
3. crystallization; 4. melting; 5. vaporization; 6. decomposition.
9
What is melting and crystallization?
Melting of Indium: 156.6 °C, -28.6 J/g (endothermic)
crystalline amorphous
Crystallization of Indium: 153.5 °C, +28.6 J/g (exothermic)
10
Melting and Crystallization with DSC
^exo prod 1 13. 03.2006 13:58:29
mW
In: 6.18 mg Integral 194.27 mJ
20 10 K/min normalized 28.57 Jg^-1
Onset 153.43 °C
10
Integral -193.95 mJ
normalized -28.52 Jg^-1
Onset 156.58 °C
-10
140 145 150 155 160 165 °C
MSG2006: Marco S TAR
TA Re SW 9. 01
11
How to evaluate melting peaks
• Pure materials:
- onset (independent of heating rate)
- ∆Hf baseline: line, integral tangential
• Impure materials:
- peak temperature (depends on β)
- ∆Hf baseline: line, tangential right
- purity analysis for eutectic systems
(based on curve shape analysis)
• Polymers
- peak temperature (depends on β and m)
- ∆Hf baseline: line, spline, integral tangential
12
What is glass transition?
Glassy state Glass transition Rubbery state
amorphous solid, liquid (non polymers)
rigid, brittle rubber like (polymers)
Glass transition is cooperative molecular movement.
13
The glass transition with DSC
cp
1 dH
cp = ⋅
m dT
Temperature
exotherm Φ
Φ = m ⋅ cp ⋅ β
Temperature
14
Chemical reaction
A chemical reaction is a process that one or more substances
(reactants) are converted to one or more new chemical substances
(products) with different properties. e.g. oxidation, decomposition,
polymerization etc.
Chemical reactions always involve a change in energy. Depending on
whether the energy is absorbed or released during the process, they
can be endothermic or exothermic.
15
Chemical reaction
Homogeneous decomposition of dibenzoyl peroxide; peak temperature and
peak shape depend on heating rate; peak area is independent of heating rate.
16
Where to use DSC?
Polymers
Pharmaceuticals
Chemicals
Food
Cosmetics
Materials Processing
Additives Thermal treatment
Material
Plasticizers Mechanical stressing
Properties
Impurities Shaping
Fillers Storage and use
17
DSC
Resolution and Sensitivity
Multiple Thermocouples
increase sensitivity and
reduce noise
For Best Resolution:
Low signal time constant e.g
1.7 s
(20- L Al crucible, N2 gas)
High baseline stability using
chemically resistant ceramic
substrate and relatively inert
silver furnace
18
Sensor technology
S R
Temperature gradients on the sensor lead to
baseline deviation from zero
∆TSR
S
T0
R A single sensor temperature (T0) is measured.
Inhomogeneous temperature distribution of
∆TS0 ∆TR0 the sensor is not considered.
19
Sensor technology
S R
TS
TS TR
TS0 TR0
Inner ring of thermocouples measure TR and TS
Outer ring measures sensor temperatures at reference and
samples sides, TS0 and TR0
Thermocouples act as thermal resistence, R.
20
Sensor technology
N TS ,i − TS 0 ,i
S R ΦS0 =
TS i =1 Ri
N TR ,i − TR 0 ,i
TS TR Φ R0 =
i =1 Ri
TS0 TR0 dq
= Φ S 0 − Φ R0
dt
Heat flow on the sample and reference sides are separately
measured
N is the number of thermocouples (TC) per ring.
FRS5 sensor (56 TC): N = 14
HSS7 sensor (120 TC): N = 30
21
Noise and sensitivity
Lysozyme dissolved in 0.1 M HCl/glycine
buffer at pH = 3
Heating rate 3 K/min
Sample Mass around 105 mg Step 0.69 uW
1.7 % Lysozyme 0.1 % Lysozyme
5
100
uW
uW
Peak Height 137 uW Peak Height 6.5 uW
60 65 70 75 80 °C
50 60 70 80 90 °C 18 20 22 24 min
22
Noise and sensitivity
23
Resolution
24
Signal time constant
How long does the system take to equilibrate?
How fast does the signal come back to the baseline?
Small τSignal better resolution
τSignal = Rth⋅Cs, Cs = Cpan+ Csample+ Csensor
FRS5 sensor (Rth ≈ 0.04 K/mW) & Al40 µl (50 mg)
Cpan ≈ 50 mJ/K
Csample (10 mg, 1.5 J/gK) ≈ 15 mJ/K => τSignal ≈ 3 s
Csensor ≈ 10 mJ/K
FRS5 sensor (Rth ≈ 0.04 K/mW) & Al20 µl (20 mg)
Cpan ≈ 20 mJ/K => τSignal ≈ 1.8 s
25
Signal time constant
How to improve τSignal?
Cs can be strongly influenced by the choice of the pan.
Recommendations for better resolution:
-> Al20 ul pan instead of Al40 ul pan
-> Al pans instead of alumina pans
Cs can be reduced by using smaller sample size
τSignal can be further decreased by using He as purge gas.
26
Cooling behavior
250
200 Air cooled
Intracooler
150
Liquid nitrogen
Temperature [°C]
100
50
-50
-100
-150
0 5 10 15 20 25
Time [min]
27
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