1

DSC:
Differential Scanning Calorimetry
A bulk analytical technique
What Does a DSC Measure?
A DSC measures the difference in heat flow rate
(mW = mJ/sec) between a sample and inert
reference as a function of time and
temperature
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Temperature (C)
Exo Up
Endothermic Heat Flow
Heat Flow
Endothermic: heat flows into the sample as
a result of either heat capacity (heating) or
some endothermic process (glass
transition, melting, evaporation, etc.)
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Temperature (C)
Exo Up
Exothermic Heat Flow
Heat Flow
Exothermic: heat flows out of the sample
as a result of either heat capacity
(cooling) or some exothermic process
(crystallization, cure, oxidation, etc.)
Temperature
What temperature is being measured and
displayed by the DSC?
Sensor Temp: used by most DSCs. It is
measured at the sample platform with a
thermocouple, thermopile or PRT.
Constantan Body
Chromel Wire
Chromel Area Detector
Constantan Wire
Chromel Wire
Base Surface
Thin Wall Tube
Sample Platform
Reference Platform
Temperature
What temperature is being measured and
displayed by the DSC?
Pan Temp: calculated by TA Q1000
based on pan material and shape
Uses weight of pan, resistance of pan, &
thermoconductivity of purge gas
What about sample temperature?
The actual temperature of the sample is
never measured by DSC
Temperature
What other temperatures are not typically
being displayed.
Program Temp: the set-point temperature
is usually not recorded. It is used to control
furnace temperature
Furnace Temp: usually not recorded. It
creates the temperature environment of
the sample and reference
Understanding DSC Signals
Heat Flow
Relative Heat Flow: measured by many
DSCs. The absolute value of the signal is
not relevant, only absolute changes are
used.
Absolute Heat Flow: used by TAs Q1000.
Dividing the signal by the measured heating
rate converts the heat flow signal into a heat
capacity signal
DSC Heat Flow
t) (T,
dt
dT
Cp
dt
dH
f + =
signal flow heat DSC
dt
dH
=
Weight Sample Heat x Specific Sample
Capacity Heat Sample Cp
=
=
Rate Heating
dt
dT
=
(kinetic) re temperatu absolute an at
time of function is that flow Heat t) (T, = f
Tzero Heat Flow Equation

R
s
R
r

q
s
q
r
C
s
C
r
T
r
T
0
T
s
Heat Flow
Sensor Model
( )
d
T d
C
d
dT
C C
R R
T
R
T
q
r
s
s r
r s r

=
1 1
0
How do we calculate these?
Besides the three
temperatures (T
s
, T
r
, T
0
);
what other values do we
need to calculate Heat
Flow?
Measuring the Cs & Rs
TzeroCalibration calculates the Cs & Rs
Calibration is a misnomer, THIS IS NOT A
CALIBRATION, but rather a measurement of
the Capacitance (C) and Resistance (R) of
each DSC cell
After determination of these values, they can be
used in the Four Term Heat Flow Equation
showed previously
Measuring the Cs & Rs
Preformed using TzeroCalibration Wizard
1. Run Empty Cell
2. Run Sapphire on both Sample & Reference
side
Measuring the Cs & Rs
Empty DSC constant heating rate
Assume:
0 =
r s
q q
Heat balance equations give sensor time constants

d
dT
T
R C
s
s s s
0

= =

d
T d
d
dT
T T
R C
s
r r r

= =
0
Measuring the Cs & Rs
Repeat first experiment with sapphire disks on sample
and reference (no pans)
Assume:
d
dT
c m q
s
sapph s s
=
d
dT
c m q
r
sapph r r
=
Use time constants to calculate heat capacities
1
0

=
s
s
sapph s
s
d
dT
T
c m
C

1
0

+
=
r
s
sapph r
r
d
T d
d
dT
T T
c m
C

Measuring the Cs & Rs
Use time constants and heat capacities to calculate
thermal resistances
s
s
s
C
R

=
r
r
r
C
R

=
A few words about the Cs and Rs
The curves should be smooth and continuous,
without evidence of noise or artifacts
Capacitance values should increase with
temperature (with a decreasing slope)
Resistance values should decrease with
temperature (also with a decreasing slope)
It is not unusual for there to be a difference
between the two sides, although often they are
very close to identical
Good TzeroCalibration Run
Can see that it is bad during
Tzerocal run
Bad TzeroCalibration Run
Before Running TzeroCalibration
System should be dry
Dry the cell and the cooler heat exchanger
using the cell/cooler conditioning template and
the default conditions (2 hrs at 75C) with the
cooler off
Preferably enable the secondary purge
Do not exceed 75C cell temperature with
the cooler off, although the time can be
extended indefinitely
Stabilization before Calibration
System must be stable before Tzero
Calibration
Stabilization is achieved by cycling the baseline
over the same temperature range and using the
same heating rate as will be used for the
subsequent calibration
Typical systems will stabilize after 3-4 cycles, 8
cycles recommended to ensure that the system
has stabilized
Example of Typical Results
40
50
60
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/
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a
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t
)
0.02
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0.04
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e
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c
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C
a
p
a
c
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/

C
)
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a
m
p
l
e

C
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p
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30
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50
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70
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a
m
p
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e

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s
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t
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e

(

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/
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a
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)
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Temperature (C)
Characteristics of the thermal resistances and heat capacities:
Both curves should be smooth, with no steps, spikes or inflection points.
Thermal resistances should always have negative slope that gradually decreases.
Heat capacities should always have positive slope that gradually decreases.
This cell is very well balanced. It is acceptable and usual
to have larger differences between sample and reference.
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Temperature (C)
Conventional Baseline
T zero Baseline
Tzerovs Conventional Baseline
Indium with Q Series Heat Flow Signals
Q1000
Q100
Q10
Keeping the DSC Cell Clean
One of the first steps to ensuring good data is
to keep the DSC cell clean
How do DSC cells get dirty?
Decomposing samples during DSC runs
Samples spilling out of the pan
Transfer from bottom of pan to sensor
How do we keep DSC cells clean?
DO NOT DECOMPOSE SAMPLES IN
THE DSC CELL!!!
Run TGA to determine the decomposition
temperature
Stay below that temperature!
Make sure bottom of pans stay clean
Use lids
Use hermetic pans if necessary
TGA Gives Decomposition Temperature
Cleaning Cell
If the cell gets dirty
Clean w/ brush
Brush gently both sensors and cell if
necessary
Be careful with the Tzerothermocouple
Blow out any remaining particles
Brushing the Sample Sensor
It Does Matter What Pan you use
Monohydrate
Pharmaceutical
sample
Sample Shape
Keep sample thin
Cover as much as the bottom of pan as
possible
Sample Shape
Cut sample to make thin, dont crush
If pellet, cut cross section
Sample Shape
Cut sample to make thin, dont crush
If pellet, cut cross section
If powder, spread evenly over the bottom of the
pan
Using Sample Press
When using crimped pans, dont over crimp
Bottom of pan should remain flat after crimping
When using Hermetic pans, a little more
pressure is needed
Hermetic pans are sealed by forming a cold
wield on the Aluminum pans
Crimped Pans
Hermetic Pans
Good Bad
Sealed
Not
Sealed
Sample Size
Larger samples will increase sensitivity
but.
Larger samples will decrease resolution
Goal is to have heat flow of 0.1-10mW going
through a transition
Sample Size
Sample size depends on what you are
measuring
If running an extremely reactive sample (like
an explosive) run very small samples (<1mg)
Pure organic materials, pharmaceuticals
(1-5mg)
Polymers - ~10mg
Composites 15-20mg
Effect of Sample Size on Indium Melt
Size: 0.4900 mg
Size: 1.2100 mg
Size: 5.7010 mg
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Temperature (C)
Weight Onset Peak Width
(mg) (C) (C) (C)
0.49 156.41 156.56 0.17
1.21 156.45 156.76 0.29
5.70 156.61 157.17 0.55
Purge Gas
Purge gas should always be used during DSC
experiments
Provides dry,inert atmosphere
Ensures even heating
Helps sweep away any off gases that might
be released
Nitrogen
Most common
Increases Sensitivity
Typical flow rate of 50ml/min
Purge Gas
Helium
Must be used with LNCS
High Thermo-conductivity
Increases Resolution
Upper temp limited to 350C
Typical flow rate of 25ml/min
Air or Oxygen
Used to view oxidative effects
Typical flow rate of 50ml/min
Sample Temperature Range
Rule of Thumb
Have 2-3 minutes of baseline before and
after transitions of interest - if possible
DO NOT DECOMPOSE SAMPLES
IN DSC CELL
Temperature range can affect choice of pans
Just because the instrument has a
temperature range of 90C to 550C (with
RCS) doesnt mean you need to heat every
sample to 550!
Start-up Hook
Do not attempt to interpret transitions
before Heating rate has stabilized
9.56mg PET @ 10C/min
0
2
4
6
8
10
12
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Temperature (C)
Exo Up
Heating Rate
Faster heating rates increase sensitivity
but.
Faster heating rates decrease resolution
Good starting point is 10C/min
Effect of Heating Rate
PMMA
10.04mg
Thermal History
The thermal history of a sample can and will
affect the results
The cooling rate that the sample undergoes can
affect :
Crystallinity of semi-crystalline materials
Enthalpic recovery at the glass transition
Run Heat-Cool Heat experiments to see effect
of & eliminate thermal history
Heat at 10C/min
Cool at 10C/min
Heat at 10C/min
Heat-Cool-Heat of PET
Second Heat
First Heat
Cool
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Temperature (C)