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Using DSC

Krystyna R. Brzezinska
Materials Research Laboratory
kbrzez@mrl.ucsb.edu

Summary
1. Introduction to DSC.
2. Amorphous Structure (Tg).
3. Crystalline Structure (Tm)

DSC
DSC measures the difference in heat
absorbed or released by a sample, as
compared to an inert reference
(empty pan), as both are heated,
cooled or held at constant
temperature.

DSC Cell

DSC

Measure Transitions:
- Glass Transition Temperature
(Tg)
- Melting Temperature (Tm)
- Crystallization Temperature
(Tc)

Think FirstHeat Later


1. Does the sample contain volatile
components?

- 2 to 3% water/solvent can lower the


glass
transition temperature (Tg) by up to
100oC.
- Evaporation creates endothermic
peaks in standard (non-hermetic)
DSC pans and can be suppressed
with use of hermetic DSC pans.

2. At what temperature does the


sample decompose?
- Set the upper limit of the DSC
experiment based on decomposition
temperature (TGA). No meaningful DSC
data can be obtained once
decomposition results in a 5% weight
loss.
- Decomposition affect: the quality of the
baseline due to both endothermic and
exothermic heat flow, the quality of the
baseline for future experiments and can
affect the useful lifetime of the DSC cell
due to corrosion.

3. How does thermal history


(temperature and time) affect DSC
results on my sample?
4. Identical materials can look totally
different based on:
- Storage temperature and time.
- Cooling rate from a temperature above Tg or
above the melting point.
- Heating rate.
- Different kinds of experiments may need to be
performed in order to measure the current
structure vs. comparing samples to see if the
materials are the same.

Amorphous Structure
Glass Transition (Tg)
- Detectable by DSC due to a step

increase in heat capacity as the


sample is heated to a temperature
above the glass transition
temperature (Tg).
- Important transition because
significant changes in physical
properties, reactivity and storage
stability occur at Tg.

Glass Transition (Tg)


Reporting Tg as a single temp., it is
necessary to state:
- What point in the step change
(onset, midpoint or end) is being
measured.
- The experimental conditions used to
measure Tg: heating rate, sample
weight.

Glass Transition (Tg)

To increase sensitivity:
- Use >10mg samples.
- Quench cool sample from a
temperature above the melt to
maximize amorphous structure.

Tg sensitivity

Use >10oC/min heating rates.

Glass Transition (Tg)


As a little as 2-3% water can lower Tg
by up to 100oC.
- To measure an accurate Tg in a
sample with a volatile component by
running sample in a hermetic
(sealed) pan.
- Use a dry-box or dry-bag to prepare
samples in hermetic pans. This
eliminates water absorption during
preparation and loss water during
the measurement.

Crystalline Structure
Crystalline structure in a sample is

determined from the presence of an


endothermic melting peak.
Important complimentary techniques
to DSC include:
Hot Stage Microscopy
X-Ray Diffraction (XRD)
Nuclear Magnetic Resonance (NMR)
Infrared Spectroscopy

Crystalline Structure
Factors which complicate DSC analysis:
- Endotermic peaks can be created by evaporation
-

and decomposition as well as melting.


TGA should be done on all new samples prior to
DSC to determine volatile content and
decomposition temperature.
Dehydyration/Desolvation usually results in loss
of crystalline structure.
Melting is a thermodynamic transition and
therefore, the onset of melting does not change
significantly with heating rate.
Decomposition is a kinetic (time-dependent)
transition and therefore, the onset temperature of
the peak shifts to a significantly higher
temperature at higher heating rate.

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