Modulated DSC® Paper #1

Why Modulated DSC®? ; An Overview and Summary

of Advantages and Disadvantages Relative to Traditional DSC

Leonard C. Thomas
TA Instruments, 109 Lukens Drive, New Castle, DE 19720, USA

ABSTRACT
This paper outlines the basis for the Modulated DSC technique and shows its
value in solving analytical problems that cannot be readily tackled by traditional DSC.

INTRODUCTION
Differential Scanning Calorimetry (DSC) has been a highly successful analytical
technique for over 4 decades. Before then, material scientists used the similar, but non-
quantitative, Differential Thermal Analysis (DTA) technique to study changes
(transitions) in structure for a broad range of materials, including polymers, chemicals,
foods products, composites and drugs. The success of DSC in solving material problems
is attested to by the approximately forty-to-fifty thousand models in worldwide use today,
with some larger laboratories having five or more instruments. The reasons for the
commercial success of DSC are numerous and include:
• It is a relatively fast technique with most analyses taking less than thirty minutes.
• Sample preparation is easy. Solids, liquids, powders, films and fibers of
essentially any shape are encapsulated in metal pans and placed into a temperature
and atmosphere-controlled environment where the measurement occurs.
• The wide temperature operational range of -180 to 725 ºC permits the analysis of
transitions in a broad range of materials.
• Sophisticated, easy to use software permits a quantitative analysis of transitions as
a function of temperature and time.

Despite these positive features, standard DSC still has some well-known
limitations, which can complicate analysis of the results and also reduce measurement
accuracy and precision. The more serious limitations are discussed below and include:
• Interpretation of results is often difficult since most modern commercial materials
are made from blends of different components. The temperature range for
transitions in the different materials often overlap and experience is required to
create methods, which can assist with interpretation of results.
• DSC measures only the sum or average value of the heat flow rate from
overlapping processes. This makes quantitative analysis of the individual
processes impossible.
• For any DSC, the only way to improve sensitivity for detecting low energy
transitions is to increase sample size and / or heating rate. This however decreases
resolution (the ability to resolve transitions that occur close in temperature). DSC
thus cannot optimize both sensitivity and resolution in a single experiment.

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 • Flat, straight baselines are required for detection of small transitions, especially
glass transitions. Unfortunately, the absolute value of the DSC heat flow signal is
affected by instability in instrument electronics and cooling systems, and
environmental changes such as temperature and humidity in the laboratory. This
limits the real sensitivity even more than short-term noise in the heat flow signal.

The ideal calorimeter would have all of the advantages of traditional DSC and
none, or fewer, of its disadvantages. With the exception of the need to use lower heating
rates, and therefore use longer experimental times, Modulated DSC® is that ideal
calorimeter. Hence, the purpose of this paper is to provide a general introduction to the
technique of Modulated DSC® (MDSC®) and to illustrate its advantages over traditional
DSC. A detailed discussion of how MDSC® signals are calculated and calibrated is
provided in a following paper in this series (1).

OPERATING PRINCIPLES OF MDSC®

With traditional or standard DSC, the difference in heat flow rate between a
sample and an inert reference is measured as the sample is heated, cooled or held at an
isothermal temperature. The resulting differential heat flow rate signal is typically plotted
in milliwatts (mJ/sec) versus temperature or time. With standard DSC, temperature is
always changed linearly and the operator must specify the rate in degrees per minute
(ºC/min). With a single heating rate, a single heat flow rate signal is produced, which is
the sum of all heat flows occurring at any point in temperature or time. An example of
such a DSC experiment is shown in Figure 1 for a sample of Polyethylene Terephthalate
(PET) that had been quench-cooled from a temperature above its melting point.

Figure 1

The operating principle of MDSC® differs from standard DSC in that MDSC®
uses two simultaneous heating rates - a linear heating rate that provides information
similar to standard DSC, and a sinusoidal or modulated heating rate that permits the
simultaneous measurement of the sample's heat capacity. Creation of the sinusoidal

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temperature change requires the operator to select a modulation period (seconds) and
modulation temperature amplitude (± ºC). Figure 2 shows the temperature profile from
an MDSC® experiment.

Figure 2

The easiest way to understand the effect of these temperature changes on the heat
flow rate is to plot the time-based derivative of temperature, which is the heating rate in
units of ºC/min. Figure 3 shows the time-based derivatives for the temperature profiles
shown in Figure 2.

Figure 3

Before viewing the MDSC® heat flow signals, a common misunderstanding of the
technique needs clarification. From the appearance of the modulated heating rate in

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Figure 3, MDSC has been incorrectly viewed just as a heat-cool technique. In fact it only
requires that there be a periodic change in heating rate. The user is free to pick heat-only
or heat-cool conditions and as seen in Figure 2 the temperature never decreases during
the modulation. The sinusoidal heating rate causes a similar response in the measured
heat flow rate from the calorimeter (Figure 4), which is termed the Modulated Heat Flow
(MHF). Selection of optimum MDSC experimental conditions is covered in another in
this series of papers on MDSC (2).

Figure 4

Applying simultaneous heating rates (linear and modulated) provides further

information on sample heat capacity or structure. The equation that describes the heat
flow signal from a DSC or MDSC® experiment shows the benefit of this technique.

dH dT
= Cp + f (T, t)
dt dt
Where:
dH
is the Total Heat Flow due to the underlying or linear heating rate. It is
dt equivalent to standard DSC at the same average heating rate

Cp is the Heat Capacity Component of the Total heat flow and is calculated
from just the heat flow that responds to the modulated heating rate

dT is the measured heating rate, which has both a linear and sinusoidal
dt (modulated) component

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 f (T,t) is the Kinetic Component of the Total heat flow and is calculated from the
difference between the Total signal and Heat Capacity Component.

dT
Cp is the Reversing Heat Flow Component of the Total Heat Flow
dt

Figure 5 shows the three most often used MDSC signals and the benefits of the
dual heating rates. The Total signal (green) is equivalent to standard DSC; the Reversing
signal (blue) provides information on heat capacity and melting, while the Nonreversing
signal (brown) shows just the kinetic processes of enthalpic recovery at Tg, cold
crystallization and crystal perfection.

Figure 5

Before viewing examples of MDSC benefits, a second misunderstanding must be

addressed. MDSC measures neither reversibility nor non-reversibility of transitions. The
term "Reversing" was chosen because true heat capacity (heat associated with increasing
or decreasing a materials temperature) is reversible. However, a heat capacity change
during a transition is almost never reversible. While a transition in the Reversing signal is
associated with a heat capacity change, it may or may not be reversible.

EXAMPLES OF THE BENEFITS OF MDSC

Traditional DSC provides a single signal (dH/dt) that is the sum of all thermal
events occurring at a specific temperature or time during the experiment. This often
causes difficulty in detection of small transitions or in data interpretation. MDSC
improves upon traditional DSC since it measures the Total heat flow plus its Heat
Capacity Component and obtains the Kinetic Component from their difference. Its ability
to resolve complex transitions into specific components improves data interpretation.
The previous examples discussed all used a single, unblended, polymer (PET).
Another sample with slightly different physical properties was analyzed by DSC and the

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data (Figure 6) might incorrectly lead to the conclusion that the material was only PET.
However, this sample was a known mixture of PET and Polycarbonate (PC). PC is
amorphous with a Tg near 140 ºC. In this sample, however, the Tg is undetected by
traditional DSC since the heat flow due to cold crystallization in the PET occurs at the
same temperature. This interpretation error would also cause an incorrect calculation of
PET crystallinity (12.2 J/g from Figure 6). In fact it should be zero J/g for a quench-
cooled sample.

Figure 6

MDSC is superior to DSC since it can separate kinetic events (e.g., a cold
crystallization) from changes in heat capacity (e.g., a Tg). Figure 7 shows MDSC data for
the above sample. It clearly reveals the Tg for PC in the Reversing Heat Flow signal and
allows the correct calculation of crystallinity for quench-cooled PET from the sum of
crystallization and melting (sum of Nonreversing and Reversing signals).

Figure 7

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 Similar, or more complex analyses can occur with pharmaceutical materials. Drug
delivery systems are usually mixtures of the drug and other excipient materials. The drug
can be amorphous or exist in multiple crystal forms called polymorphs. It can also be
anhydrous or a hydrate, solvate or salt. As with polymers, the ability of MDSC to
enhance resolution of overlapping events while maintaining high sensitivity can greatly
simplify interpretation or eliminate errors in analyses. Figure 8 shows the analysis of a
drug delivery system based on amorphous, biodegradable polymer microspheres. Here,
the Total signal, which is the analog of standard DSC, makes it very hard to find the
polymer Tg. The MDSC Reversing signal has the kinetic processes (enthalpic recovery
and water evaporation) removed and permits an easy analysis of the polymer's Tg.

Figure 8
.

SUMMARY
Modulated DSC is an option with most TA Instruments DSC products. As seen
above and in additional papers to follow, it has significant advantages over traditional
DSC. Because the capability can be turned ON or OFF during an experiment, MDSC
provides all of the benefits of DSC but is not limited by its natural limitations. In general,
MDSC provides the following advantages:
• Separation of overlapping transitions
• Improved sensitivity for detecting weak transitions
• Improved sensitivity and resolution in a single experiment
• More accurate measurement of polymer initial crystallinity
• Direct measurement of heat capacity
• Quasi-isothermal measurement of heat capacity changes during reactions or
kinetic processes

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REFERENCES
1. MDSC Paper #2, Modulated DSC® Basics: Calculation and Calibration of MDSC
Signals; TA Instruments Technical Paper TP 007.
2. MDSC Paper #3, Modulated DSC®, Optimization of MDSC Experimental
Conditions; TA Instruments Technical Paper TP 008

KEY WORDS
modulated differential scanning calorimetry, mdsc, differential scanning calorimetry, dsc,
total heat flow, reversing heat flow, non reversing heat flow, heat capacity

© COPYRIGHT 2005 TA INSTRUMENTS

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