DSC Beginners Guide
DSC Beginners Guide
DSC Beginners Guide
Calorimetry (DSC)
FREQUENTLY
ASKED
QUESTIONS
DSC 4000
DSC 8000
A Beginner's Guide
This booklet provides an introduction to the concepts of Differential Scanning
Calorimetry (DSC). It is written for the materials scientist unfamiliar with DSC.
The differential scanning calorimeter (DSC) is a fundamental tool in thermal
analysis. It can be used in many industries from pharmaceuticals and
polymers, to nanomaterials and food products. The information these
instruments generate is used to understand amorphous and crystalline
behavior, polymorph and eutectic transitions, curing and degree of cure,
and many other material properties used to design, manufacture, and test
products. While DSCs are manufactured in several variations, PerkinElmer is
the only company to make both single- and double-furnace styles. We have
manufactured thermal analysis instrumentation since 1960, and understand
applications better than anyone in the industry. In the following pages, we
answer common questions about how a DSC works, and what it tells you
about the thermal properties of materials you work with in your laboratory.
Table of Contents
20 Common Questions about DSC
What is DSC?.................................................................................................3
What is the difference between a heat flow and a heat flux DSC?....................3
How does the difference affect me?...............................................................3
Why do curves point in different directions?....................................................4
What is heat capacity?...................................................................................4
Why is measuring the glass transition important?............................................4
Why should I measure melting by DSC?..........................................................5
What else can I learn from DSC data?.............................................................5
How do I obtain good data?...........................................................................5
How can I improve my data?..........................................................................6
Why doesnt my data agree with other thermal techniques?............................6
What is the difference between controlled and ballistic cooling?......................6
Why should I care about isothermal performance?..........................................7
How do I study oxidative stability?..................................................................7
When do I need to use HP-DSC?.....................................................................7
When should I consider using UV-DSC?..........................................................7
How are kinetic studies done with a DSC?......................................................7
What is Modulated Temperature DSC?............................................................7
What is Fast Scan DSC or HyperDSC?............................................................8
What hyphenated techniques work with DSC?................................................8
Glossary............................................................................................................... 8-9
Additional Resources............................................................................................. 9
What is DSC?
Fast Heating (250 C/min plus)
Heat Flux
Yes
No
Modulated Techniques
Yes
Yes
Accuracy of Cp Values
High
Moderate
Delta H Accuracy
High
Moderate
Ease of cleaning
Heat Flow
Very
Moderate
OIT Testing
Moderate
Easy
Isotherm Performance
Excellent
Affected by sample
3
H
eat capacity (Cp) is the amount of energy a unit of
matter can hold. Think of a can of green pea soup: it is
a gelatinous mass at room temperature, but as it heats
up in a saucepan it becomes more fluid. Its heat capacity
also increases and the fluid soup at 100 C can hold more
energy than the solid at room temperature. All materials
show this increase in heat capacity with temperature. It is
reported as either J/g, J/Mol, or as calories/g in the
older literature.
As heat capacity increases with temperature, the run of
a real sample should show a slight upward slope toward
a higher temperature. There is also a step change in the
baseline across the melt as the heat capacity of a molten
material is higher than that of a solid. Lack of these
features suggests some form of data manipulation. Of
course, a strong peak will dwarf these features.
Heat capacity may seem academic, but it turns out to have
lots of practical implications, and engineers often need it.
For example, when running an extruder for polymeric or
food products, knowing the heat capacity of the material
can help you figure out how efficient your process is and
whether you are using too much energy. You can use it to
calculate the energy needed to run a distillation or recycle
column, or to estimate how much energy is needed to
keep something at a certain temperature.
Industry
Transitions Purpose
Pharmacueticals Tg
Cp
Processing conditions
Tm
Polymers
Tg
Tm
Exotherm
Cp
Tc
Food
Tg
Tm
Processing temperature
D
SC can detect any change that alters the heat flow in
and out of a sample. This includes more than just glass
transitions and melting. You can see solid state transitions
such as eutectic points, melting and conversions of different crystalline phases like polymorphic forms, dissolution and precipitation from solutions, crystallization and
re-crystallizations, curing exotherms, degradation, loss
of solvents, and chemical reactions.
Table 2 shows the type of transitions detected by DSC
sorted by industry and use in that industry.
O
ne common question is why DSC data does not always
agree with other methods of analysis. This is most
commonly raised with the difference in values for the
glass transition for DSC and the mechanical methods
of Thermomechanical Analysis (TMA) and Dynamic
Mechanical Analysis (DMA). There are several reasons
for this, but the most important one involves the nature
of the glass transition. The glass transition is really a
C
ooling is often an under-appreciated property of both
DSC and material science in general. How a material is
cooled from its melt defines its heat history, and
the heat history can make a great deal of difference
in a materials properties. The classical example is
polyethylene terephthalate (PET), which becomes nearly
all amorphous when cooled rapidly from the melt, but
is mostly crystalline when cooled slowly. Since the heat
history is so important in how a material behaves, the
standard operating procedure in plastics is to run a
heat-cool-heat cycle. The first heat shows the material
as received, the cooling step if done with controlled
cooling imposes a standard heat history on the material,
while the second heat allows you to compare materials
directly to each other.
O
xidative Stability, or the Oxidative Induction Time (OIT),
test is often studied in both DSC and TGA. This is
normally done by heating a material to a set temperature
under an inert gas and switching to air or oxygen once
it has equilibrated. The time needed for the material to
begin to burn is then recorded. Normally, in a powercompensated DSC, a flow-thru cover is used to remove
the smoke from the DSC as quickly as possible. (It can
also be used to remove reactive gases generated by the
sample.) Often, it is best to run these tests in a TGA, as
this experiment is very dirty and these instruments are
designed to accommodate such samples.
H
igh Pressure (HP) DSC is used for several reasons:
first, an oxidative stability test may take too long at
atmospheric pressures to be convenient. An example
would be looking at an antioxidant package in motor oil.
Secondly, some reactions form water or methanol as a
byproduct, leading to foaming in the sample. Higher
pressure suppresses this. Thirdly, some reaction kinetics are affected by pressure and running the reaction
under controlled pressure is needed to study this effect.
Finally, transitions, like the Tg and boiling point, are
responsive to pressure and running DSC under pressure
U
V-DSC or Photo-DSC is a DSC that has been adapted
to allow the sample to be exposed to UV light
during the run. This can be done with several types
of light sources, including mercury vapor lamps or LEDs,
over a range of frequencies and intensities. UV-DSC
also allows the study of UV-initiated curing systems in
the DSC, such as those used for dental resins, orthopedic
bone cements, hydrogels, paints or coatings, and adhesives.
It complements the technique of UV-DMA, which allows
you to gain mechanical information on these systems.
UV-DSC also allows you to study the efficiency of curing
and to develop kinetic models for curing systems.
UV-DSC is additionally used to study the decomposition
of materials under UV radiation. This can be for understanding the effects on the storage of pharmaceuticals, on
antioxidant packages in polymers and rubbers, on food
properties, or on dyes in sunlight. It is possible to use
kinetics to model the degradation by UV light. Because
of the high intensities of UV available, accelerated testing
is possible.
K
inetic studies on the DSC can be done using scanning
methods, where the sample is either heated through a
temperature ramp, or isothermally, where the sample is
held at a set temperature. In the latter case, the ramp
rate to that temperature should be as fast as possible
to minimize the effect of the ramp. Data from these
methods can be exported to TIBCO Spotfire, Excel
or another program for analysis or run through several
commercially available programs. The advantage of
using DSC for kinetic studies is it tends to be faster and
more straightforward than other methods.
M
odulated Temperature DSC (MT-DSC) is the general
term for DSC techniques, where a non-linear heating
or cooling rate is applied to the sample to separate the
kinetic from the thermodynamic data. In StepScan
DSC, this is done by applying a series of heating (or
cooling) micro-steps followed by an isothermal hold.
This allows you to separate the data into an Equilibrium
Cp curve that shows the thermodynamic response of
the sample and an isokinetics baseline that shows the
kinetic response. Unlike some other techniques, these
are calculated independently. This technique removes
kinetic noises from transitions, such as enthalpic overshoot
or the curing exotherm, from an overlapping Tg.
F ast Scan DSC is the generic term for DSC techniques that
apply very high heating rates to a sample to increase
the sensitivity of a DSC or to trap kinetic behavior. Fast
scan heating rates range from 100 C/min - 300 C/min.,
where HyperDSC heating rates range from 300 C/min 750 C/min. Heating at high rates was originally
developed in power controlled DSC thanks to the small
furnace mass and the best results are still obtained in
these instruments. When heating rates of 100 C/min
- 750 C/min are applied, the response of the DSC to
weak transitions is enhanced. It is then possible to see
very low levels of amorphous materials in pharmaceuticals; measure small amounts of natural products; freeze
the curin of thermosetting compounds; inhibit the cool
crystallization of polymers; as well as the thermal
degradation of organic materials.
D
SC is not normally hyphenated as frequently as is TGA,
but hyphenation has been used. DSC-IR has been used
to look at the evolved solvents from pharmaceuticals
while DSC-MS has been used to look at the composition
of meteorites and lunar rocks. DSC has also been coupled
to FT-IR microscopy to look at changes in a sample during
a DSC run.
The most promising hyphenated technique is DSCRaman, where a sample is irradiated by a Raman laser
as the sample is run in DSC profile. Because of the nature
of the Raman spectrometer, it is ideally suited for this, as
it does not require any processing of reflectance spectra
nor the use of a special transmission path cell.
DSC-Raman shows great potential for the study of
polymorphic materials, polymeric recrystallization,
chain movements at the glass transition, and for
hydrogen bonding polymers.
Glossary
Annealing
is the slow controlled cooling of a material from its melt
temperature to room temperature. This employs controlled
cooling rates below 5 C/min. This is used to further study
the effects of structural ordering within the material.
Calorie
is the amount of heat required to raise one gram of H2O
by 1 C.
Crystallization Temperature
is an exothermic event where a liquid changes to a solid.
This is depicted as a peak. The extrapolated onset and
peak temperature characterize this event.
DMA Dynamic Mechanical Analysis
is the measurement of stiffness and modulus using forced
oscillations as a function of time, temperature, stress,
strain, or frequency.
DSC - Differential Scanning Calorimetry
is an analytical technique that measures the heat flow
rate to or from a sample specimen as it is subjected
to a controlled temperature program in a controlled
atmosphere.
DTA Differential Thermal Analysis
is a simpler form of DSC often called heat flux or single
furnace DSC.
Endothermic Event
is a thermal event of a material where energy is absorbed by
the material, i.e. melting.
Exothermic Event
is a thermal event of a material where energy is expelled
by the material, i.e. crystallization.
Fast Scanning DSC
is a DSC technique that employs controlled heating
rates above 100 C/minute. It is used to observe subtle
thermal events.
Glass Transition (Tg)
is an endothermic event, a change in heat capacity that
is depicted by a shift in the baseline. It is considered the
softening point of the material or the melting of the
amorphous regions of a semi-crystalline material.
Heat
is a form of energy. Heat is not temperature.
Heat Capacity (Cp)
is the amount of heat required to raise a unit mass of a
material one degree in temperature. Cp = Q/m T, where:
Cp = specific heat, Q = heat added, m = mass of material,
T = change in temperature.
Heat History
is the last thermal excursion the material has experienced.
In polymers, heat history is erasable by heating the
material slightly above the melt temperature and then
quenching or annealing a material to below its glass
transition temperature.
Heat of Fusion (hf)
is the amount of heat per unit mass needed to change
a substance from a solid to a liquid at its melting point.
hf = Q/M, where: hf = heat of fusion, Q = heat added,
m = mass of material.
Isothermal
holding at a certain temperature and observing material
changes in respect to time. An application of an isothermal
experiment is the examining the curing time of an epoxy.
Isothermal Kinetics
kinetics calculated using isothermal temperatures instead
of ramping rates.
Joule
is the SI unit of energy and is approximately equal to 4.18
calories.
Melting Point (Tm)
the temperature at which a materials melts. It is
measured as the peak temperature of an endothermic
event. For metals and pure organics, it is not the peak
temperature, but the extrapolated onset temperature
(To) of the endothermic event.
Morphology
refers to the crystalline properties and non-crystalline
(amorphous) properties of materials.
Quench Cooling
is a DSC technique that employs rapid cooling rates above
100 C/minute. This is used to further study the effects of
rapid crystallization of a material.
Scanning
heating or cooling at a controlled rate.
Specific Heat
see heat capacity. For engineering purposes, specific heat
and heat capacity can be assumed to be equal.
Start-up Transient
is the initial change in the baseline at the very beginning
of a scanning run before the instrument is in complete
scanning rate control.
Temperature
is the degree of heat measured on a definite scale.
TGA Thermogravimetric Analysis
tracking the change in the mass of a sample as a function
of time and/or temperature.
TMA Thermal Mechanical Analysis
measurement of changes in sample size or volume as a
function of temperature.
Watt
is the power expended when one joule of work is done
in one second of time.
Additional References
ASTM E 2161-08 Standard Terminology Relating to
Performance Validation in Thermal Analysis.
ASTM E 473-08 Standard Terminology Relating to
Thermal Analysis and Rheology.
P. Gabbott, The Principles and Applications of Thermal
Analysis, Wiley-Blackwell: London, 2007.
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