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Differential Scanning

Calorimetry
Stephen Collins

Technical Group Talk
Definitions
A calorimeter measures the heat into or out of a
sample.
A differential calorimete r measures the heat of a
sample relative to a reference.
A differential scanning calorimeter does all of the
above and heats the sample with a linear temperature
ramp.
Endothermic heat flows into the sample.
Exothermic heat flows out of the sample.

Technical Group Talk
Differential Scanning Calorimetry (DSC) measures the
temperatures and heat flows associated with transitions in
materials as a function of time and temperature in a
controlled atmosphere.
These measurements provide quantitative and qualitative
information about physical and chemical changes that
involve endothermic or exothermic processes , or changes
in heat capacity .
DSC: The Technique

Technical Group Talk
Conventional DSC
Metal
1
Metal
2
Metal
1
Metal
2
Sample Empty
Sample
Temperature
Reference
Temperature
Temperature
Difference =
Heat Flow

A linear heating profile even for isothermal methods

Technical Group Talk
What can DSC measure?
Glass transitions
Melting and boiling points
Crystallisation time and temperature
Percent crystallinity
Heats of fusion and reactions
Specific heat capacity
Oxidative/thermal stability
Rate and degree of cure
Reaction kinetics
Purity

Technical Group Talk
6
DSC Thermogram
Temperature
H
e
a
t

F
l
o
w

-
>

e
x
o
t
h
e
r
m
i
c

Glass
Transition
Crystallisation
Melting
Cross - Linking
(Cure)
Oxidation
79 . 70 C ( I )
75 . 41 C
81 . 80 C
144 . 72 C
137 . 58 C
20 . 30 J / g
245 . 24 C
228 . 80 C
22 . 48 J / g
Cycle 1
- 0 . 5
0 . 0
0 . 5
1 . 0
1 . 5
H
e
a
t

F
l
o
w


(
W
/
g
)

0 50 100 150 200 250 300
Temperature ( C )
Sample : PET 80 PC 20 _ MM 1 1 min
Size : 23 . 4300 mg
Method : standard dsc heat - cool - heat
Comment : 5 / 4 / 06
DSC
File : C :... \ DSC \ Melt Mixed 1 \ PET 80 PC 20 _ MM 1 . 001
Operator : SAC
Run Date : 05 - Apr - 2006 15 : 34
Instrument : DSC Q 1000 V 9 . 4 Build 287
Exo Down Universal V 4 . 2 E TA Instruments

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Example DSC - PET
T
g
T
c
T
m

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6 70
Influence of Sample Mass
Temperature (C)
150 152 154 156
0
-2
-4
-6
D
S
C

H
e
a
t

F
l
o
w

(
W
/
g
)

10mg
4.0mg
15mg
1.7mg
1.0mg
0.6mg
Indium at
10C/minute
Normalized Data
158 160 162 164 166
Onset not
influenced
by mass

Technical Group Talk
6
Effect of Heating Rate
on Indium Melting Temperature
154 156 158 160 162 164 166 168 170
- 5
- 4
- 3
- 2
- 1
0
1
Temperature ( C)
H
e
a
t

F
l
o
w

(
W
/
g
)

heating rates = 2, 5, 10, 20 C/min

Technical Group Talk
DSC: Main Sources of Errors
Calibration
Contamination
Sample preparation how sample is loaded into a pan
Residual solvents and moisture.
Thermal lag
Heating/Cooling rates
Sample mass
Processing errors



Technical Group Talk
99
Sample Preparation : Shape
Keep sample as thin as possible (to minimise thermal
gradients)
Cover as much of the pan bottom as possible
Samples should be cut rather than crushed to obtain a
thin sample (better and more uniform thermal contact
with pan)

Technical Group Talk
Other DSC Techniques
Hyper-DSC
Based on principle that high heating rates give large broad
transitions.
Heating rates typically 400-500
o
C/min
Need very small sample sizes (~nanograms)

Good for:
A quick overview of new sample
Picking out minute transition

Poor for:
Accuracy: transitions can be shifted by as much as 40
o
C
Repeatabiliy: Very sensitive to thermal lag.

Technical Group Talk
Other DSC Techniques
Modulated DSC

Composite heating profile:
Determines heat capacity and separates heat flow into that due
to reversible and non-reversible events.

Note that temperature is not decreasing during
Modulation i.e. no cooling
Modulate +/- 0.42 C every 40 seconds
Ramp 4.00 C/min to 290.00 C
52
54
56
58
60
62
M
o
d
u
l
a
t
e
d

T
e
m
p
e
r
a
t
u
r
e

(

C
)
52
54
56
58
60
62
T
e
m
p
e
r
a
t
u
r
e

(

C
)
13.0 13.5 14.0 14.5 15.0
Time (min)
Typicaly:
Heating rates: 0 - 5
0
C
Modulation:
Period: 60 second
Amplitude: +/-1
0
C



Benefits
Increased Sensitivity for Detecting Weak (Glass) Transitions
Eliminates baseline curvature and drift
Increased Resolution Without Loss of Sensitivity
Two heating rates (average and instantaneous)
Ability to Separate Complex Thermal Events and Transitions Into
Their Heat Capacity and Kinetic Components
Ability to Measure Heat Capacity (Structure) Changes During
Reactions and Under Isothermal Conditions

Downside
Slow data collection
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Modulated DSC

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Example MDSC

-0.12

-0.10

-0.08

-0.06

-0.04

-0.02

N
o
n
r
e
v

H
e
a
t

F
l
o
w

(
W
/
g
)

-0.14

-0.12

-0.10

-0.08

-0.06

-0.04

-0.02

0.00

R
e
v

H
e
a
t

F
l
o
w

(
W
/
g
)

-0.14

-0.12

-0.10

-0.08

-0.06

-0.04

-0.02

0.00

H
e
a
t

F
l
o
w

(
W
/
g
)

-50

0

50

100

150

200

250

Temperature (C)

Exo Up

Universal V4.2E TA Instruments

Technical Group Talk
Modulated DSC
Reversible Transitions
Glass Transition
Melting

Non-reversible
Crystallisation
Curing
Oxidation/degradation
Evaporation

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