Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.

P, India)

DIFFERENTIAL SCANNING CALORIMETER (DSC)

INTRODUCTION:
A solid material can be amorphous, crystalline, or a combination of the two. An amorphous
material is one with no discernable orientation for its atoms or molecules; they are arranged in a
random fashion. Crystals on the other hand are arranged in a specific pattern, which is repeatable
and predictable. A material may also be a combination of amorphous and crystal structure; this
material could be crystalline in one area, and amorphous in another, or islands of crystalline
arrangements which are randomly distributed in an amorphous system. The thermodynamic state
affects the structure of a material which in turn affects its properties. Variations in the
thermodynamic state of a material thus lead to variations in its properties. Using Differential
Scanning Calorimetry (DSC), one can better understand phase transitions and reactions in
materials, and how they contribute to the properties and characteristics of the material.
The differential scanning calorimeter (DSC) is a fundamental tool in thermal analysis. It can be
used in many industries from pharmaceuticals to polymers and from Nano-materials to 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.

DEFINATION: Differential Scanning Calorimetry, DSC, is a thermo analytical technique in

which the difference in the amount of heat required to increase the temperature of a sample and
reference are measured as a function of temperature. Both the sample and reference are
maintained at nearly the same temperature throughout the experiment. Generally, the
temperature program for a DSC analysis is designed such that the sample holder temperature
increases linearly as a function of time. Only a few milligrams of material are required to run the
analysis.

PRINCIPLE: The basic principle underlying this technique is that when the sample
undergoes a physical transformation such as phase transitions, more or less heat will need to flow
to it than the reference to maintain both at the same temperature. Whether less or more heat must
flow to the sample depends on whether the process is exothermic or endothermic. For example,
as a solid sample melts to a liquid it will require more heat flowing to the sample to increase its
temperature at the same rate as the reference. This is due to the absorption of heat by the sample
as it undergoes the endothermic phase transition from solid to liquid. Likewise, as the sample
undergoes exothermic processes (such as crystallization) less heat is required to raise the sample
temperature. By observing the difference in heat flow between the sample and reference,
differential scanning calorimeters are able to measure the amount of heat absorbed or released
during such transitions. DSC may also be used to observe more subtle physical changes, such

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

as glass transitions. It is widely used in industrial settings as a quality control instrument due to
its applicability in evaluating sample purity and for studying polymer curing.

THEORY: DSCisamethodofthermalanalysisthatiswidelyusedtostudythermaltransitions, i.e. .,

solid- solidtransitionsaswellassolid-liquidandvariousothertransitionsandreactions. A solid-solid
phase transition would be if the material had its structure altered, but not gain enough energy to
become a liquid. Using thermal analysis, it is possible to understand what is happening in a
material, even if there is no visual evidence that a change has occurred. For instance, it is easy to
see when an ice cube melts into water and when water boils into steam; these are visible changes.
There are however several different phase changes within water in a solid state. Ice at colder and
colder temperatures can have several different crystal structures and undergo many solid-solid
phase transitions, and in each of these phases, the ice has different properties ranging from
brittleness to conductivity. By understanding the technique and instrumentation of DSC, it is
possible to understand what the materials go through during energy gain or loss. Earlier versions
of the DSC were known as Differential Thermal Analyzers (DTA).
Differential scanning calorimetry is a technique we use to study what happens to polymers when
they're heated. We use it to study what we call the thermal transitions of a polymer. And what
are thermal transitions? They're the changes that take place in a polymer when you heat it. The
melting of a crystalline polymer is one example. The glass transition is also a thermal transition.
So how do we study what happens to a polymer when we heat it? The first step would be to heat
it, obviously. And that's what we do in differential scanning calorimetry or DSC for short.
We heat our polymer in a device that looks something like this:

It's pretty simple, really. There are two pans. In one pan, the sample pan, you put your polymer
sample. The other one is the reference pan. You leave it empty. Each pan sits on top of a heater.
Then you tell the nifty computer to turn on the heaters. So the computer turns on the heaters, and
tells it to heat the two pans at a specific rate, usually something like 10 oC per minute. The

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

computer makes absolutely sure that the heating the rate stays exactly the same throughout the
experiment.
But more importantly, it makes sure that the two separate pans, with their two separate heaters,
heat at the same rate as each other.
Huh? Why wouldn't they heat at the same rate? The simple reason is that the two pans are
different. One has polymer in it, and one doesn't. The polymer sample means there is extra
material in the sample pan. Having extra material means that it will take more heat to keeps the
temperature of the sample pan increasing at the same rate as the reference pan.
So the heater underneath the sample pan has to work harder than the heater underneath the
reference pan. It has to put out more heat. By measuring just how much more heat it has to put
out is what we measure in a DSC experiment.
Specifically what we do is this: We make a plot as the temperature increases. On the x-axis we
plot the temperature. On the y-axis we plot difference in heat output of the two heaters at a given
temperature.

Heat capacity:
We can learn a lot from this plot. Let's imagine we're heating a polymer. When we start heating
our two pans, the computer will plot the difference in heat output of the two heaters against
temperature. That is to say, we're plotting the heat absorbed by the polymer against temperature.
The plot will look something like this at first.

The heat flow at a given temperature can tell us something. The heat flow is going to be shown
in units of heat, q supplied per unit time, t. The heating rate is temperature increase T per unit
time, t. got it?

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

Let's say now that we divide the heat flow q/t by the heating rate T/t. We end up with heat
supplied, divided by the temperature increase.

Remember from the glass transition page that when you put a certain amount of heat into
something, its temperature will go up by a certain amount, and the amount of heat it takes to get
a certain temperature increase is called the heat capacity, or Cp. We get the heat capacity by
dividing the heat supplied by the resulting temperature increase. And that's just what we've done
in that equation up there. We've figured up the heat capacity from the DSC plot.

The Glass Transition Temperature

Of course, we can learn a lot more than just a polymer's heat capacity with DSC. Let's see what
happens when we heat the polymer a little more. After a certain temperature, our plot will shift
upward suddenly, like this:

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

This means we're now getting more heat flow. This means we've also got an increase in the heat
capacity of our polymer. This happens because the polymer has just gone through the glass
transition. And as you learned on the glass transition page, polymers have a higher heat capacity
above the glass transition temperature than they do below it. Because of this change in heat
capacity that occurs at the glass transition, we can use DSC to measure a polymer's glass
transition temperature. You may notice that the change doesn't occur suddenly, but takes place
over a temperature range. This makes picking one discreet Tg kind of tricky, but we usually just
take the middle of the incline to be the Tg.

Crystallization
But wait there is more, so much more. Above the glass transition, the polymers have a lot of
mobility. They wiggle and squirm, and never stay in one position for very long. They're kind of
like passengers trying to get comfortable in airline seats, and never quite succeeding, because
they can move around more. When they reach the right temperature, they will have gained
enough energy to move into very ordered arrangements, which we call crystals, of course.
When polymers fall into these crystalline arrangements, they give off heat. When this heat is
dumped out, it makes the little computer-controlled heater under the sample pan really happy. It's
happy because it doesn't have to put out much heat to keep the temperature of the sample pan
rising. You can see this drop in the heat flow as a big dip in the plot of heat flow versus
temperature:

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

This dip tells us a lot of things. The temperature at the lowest point of the dip is usually
considered to be the polymer's crystallization temperature, or Tc. Also, we can measure the area
of the dip, and that will tell us the latent energy of crystallization for the polymer. But most
importantly, this dip tells us that the polymer can in fact crystallize. If you analyzed a 100%
amorphous polymer, like atactic polystyrene, you wouldn't get one of these dips, because such
materials don't crystallize.
Also, because the polymer gives off heat when it crystallizes, we call crystallization an
exothermic transition.

Melting
Heat may allow crystals to form in a polymer, but too much of it can be their undoing. If we keep
heating our polymer past its Tc, eventually we'll reach another thermal transition, one called
melting. When we reach the polymer's melting temperature, or Tm, those polymer crystals begin
to fall apart, that is they melt. The chains come out of their ordered arrangements, and begin to
move around freely. And in case you were wondering, we can spot this happening on a DSC
plot.
Remember that heat that the polymer gave off when it crystallized? Well when we reach the Tm,
it's payback time. There is a latent heat of melting as well as a latent heat of crystallization.
When the polymer crystals melt, they must absorb heat in order to do so. Remember melting is a
first order transition. This means that when you reach the melting temperature, the polymer's
temperature won't rise until all the crystals have melted. This means that the little heater under
the sample pan is going to have to put a lot of heat into the polymer in order to both melt the
crystals and keep the temperature rising at the same rate as that of the reference pan. This extra
heat flow during melting shows up as a big peak on our DSC plot, like this:

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

Putting It All Together

So let's review now: we saw a step in the plot when the polymer was heated past its glass
transition temperature. Then we saw a big dip when the polymer reached its crystallization
temperature. Then finally we saw a big peak when the polymer reached its melting temperature.
To put them all together, a whole plot will often look something like this:

Of course, not everything you see here will be on every DSC plot. The crystallization dip and the
melting peak will only show up for polymers that can form crystals. Completely amorphous
polymers won't show any crystallization, or any melting either. But polymers with both
crystalline and amorphous domains will show all the features you see above.

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

If you look at the DSC plot you can see a big difference between the glass transition and the
other two thermal transitions, crystallization and melting. For the glass transition, there is no dip,
and there's no peak, either. This is because there is no latent heat given off, or absorbed, by the
polymer during the glass transition. Both melting and crystallization involve giving off or
absorbing heat. The only thing we do see at the glass transition temperature is a change in the
heat capacity of the polymer.
Because there is a change in heat capacity, but there is no latent heat involved with the glass
transition, we call the glass transition a second order transition. Transitions like melting and
crystallization, which do have latent heats, are called first order transitions.

How much crystallinity?

DSC can also tell us how much of a polymer is crystalline and how much is amorphous. If you
read the page dealing with polymer crystallinity, you know that many polymers contain both
amorphous and crystalline material. But how much of each? DSC can tell us. If we know the
latent heat of melting, Hm, we can figure out the answer.
The first thing we have to do is measure the area of that big peak we have for the melting of the
polymer. Now our plot is a plot of heat flow per gram of material, versus temperature. Heat flow
is heat given off per second, so the area of the peak is given is units of heat x temperature x time 1
x mass-1. We usually would put this in units such as joules x kelvins x (seconds)-1 x (grams)-1:

Got that? Don't worry. It gets simpler. We usually divide the area by the heating rate of our DSC
experiment. The heating rate is in units of K/s. So the expression becomes simpler:

Now we have a number of joules per gram. But because we know the mass of the sample, we can
make it simpler. We just multiply this by the mass of the sample:

Now we just calculated the total heat given off when the polymer melted. Neat, huh? Now if we
do the same calculation for our dip that we got on the DSC plot for the crystallization of the
polymer, we can get the total heat absorbed during the crystallization. We'll call the heat total
heat given off during melting Hm, total, and we'll call the heat of the crystallization Hc, total.
Now we're going to subtract the two:

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

Why did we just do that? And what does that number H' mean? H' is the heat given off by that
part of the polymer sample which was already in the crystalline state before we heated the
polymer above the Tc. We want to know how much of the polymer was crystalline before we
induced more of it to become crystalline. That's why we subtract the heat given off at
crystallization. Is everyone following me?
Now with our magic number H' we can figure up the percent crystallinity. We're going to divide
it by the specific heat of melting, Hc*. The specific heat of melting? That's the amount of heat
given off by a certain amount, usually one gram, of a polymer. H' is in joules, and the specific
heat of melting is usually given in joules per gram, so we're going to get an answer in grams,
which we'll call mc.

This is the total amount of grams of polymer that were crystalline below the Tc. Now if we divide
this number by the weight of our sample, mtotal, we get the fraction of the sample that was
crystalline, and then of course, the percent crystallinity:

And that's how we use DSC to get percent crystallinity.

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

INSTRUMENTATION BASICS:
In a DSC, there are two pans isolated from the ambient environment in a chamber. One pan
contains the sample to be analyzed, and the other pan is empty and is used as a reference pan.
Both pans have heaters underneath them that are used to raise or lower the temperature. Each pan
also has a sensor that indicates what the temperatures of the pans are at any given moment. Using
computer controlled sensors and logic, the heaters are set to heat the pans at a constant rate
that is the rate of temperature change is the same, for example 5 degrees Celsius per
minute. The instrumentation is also designed to ensure that the pans heat at the same rate as each
other. Having the pans heat at a constant rate, but also the same rate as each other might seem
repetitious; however the heat flow, which is the rate at which thermal energy
is supplied
to the pans, does differ, due to the fact that there is material in one of the pans, and nothing in the
other pan. Consider, for example, two pots, one with water and one empty, and both pots start
out at the same initial temperature and are then placed on stoves. If each pot is heated at the same
rate ( both stove setting are placed on low , for example ) the pot with the water in it will heat up
slower ,that is the rate of temperature change will be smaller than the pot with nothing. This is
because heat capacity is different for water than it is for air. The same thing happens in the pans
of our instrument, the pan with the material/sample in it will heat up slower than the reference
pan which contains nothing. Going back to our example of the two pots, the computer would
control the stoves and set the pots to be heated at a constant 5 degrees per minute, and also
monitor the temperature of each pot and ensure that the two heat at the same rate. Since the pot
with the water in it will heat up slower than the empty pot, the computer will have to supply a
higher heat flow to the pot containing water in order to force the pots to heat at the same rate

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

DSC profile. In this profile, exothermic heat flow is measured versus temperature. Here the
endothermic heat flow is measured versus temperature.
The computer keeps track of the starting temperature, heating rate, and heat flow, and records the
difference in heat flow between the reference pan and the sample pan (water pot in our example),
which is the heat flow for the sample, and plots it against temperature
The heat flow may be measured as exothermic, or endothermic and plotted against temperature.
The slope of the curve is the rate of change of heat
heat flow may be
divided by the heating rate to obtain a value for heat
/(
= Cp. Knowing the mass (m) of the sample, the specific heat capacity (cp=Cp/m), as a function
of temperature may be obtained, thus yielding information on the variations in the physical
properties of the material.

Phase Transitions:
Every solid state material when continuously heated will come to a point where it changes phase.
For example ice, when heated, at standard atmospheric pressure, will undergo a phase change
from solid to liquid (melt) at a transition temperature (melting point) of 0 C, and when the

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

resulting water is heated, it will eventually undergo another phase transition from liquid to gas
(vaporize) at a transition temperature (boiling point) of 100 o C. We are also relatively familiar
with solid to gas transitions in solids such as dry ice. As a material is heated, the atoms and/or
molecules gain more energy. At the solid to liquid transition temperature, the atoms/ molecules
have enough energy to break away from their rigid structure to a less restricted state which is the
liquid state. The energy supplied simply goes into converting the solid to liquid, that is, the
energy is spent in breaking down the rigid solid structure into the much less rigid liquid state,
leading to gain in energy of the material (an endothermic transition).The energy per unit mass
used in bringing about such a phase change is known as the latent heat. Transitions that have
laten theats associated with them are said to be first order transitions. SSThe energy supplied
does not lead to a temperature change until the phase transformation is complete. A similar
process takes place during the phase transformation from liquid to gas.
As discussed earlier a DSC measures the heat absorbed or released by a material as a function of
temperature or time (isothermally). This then allows the determination of important thermal
characteristics such as transition temperatures, for example, melting and boiling points as well as
other transition temperatures such as glass transition temperature (TG), and crystallization
temperature (Tc), which are discussed earlier. It also allows for the determination of quantitative
measurements such as the specific heat capacity, heat of fusion, heat of vaporization, heat of
polymerization, heat of crystallization, and heat of reaction. Practically all DSC instruments
allow such measurements to be done under various atmospheres.

APPLICATIONS:
Differential scanning calorimetry can be used to measure a number of characteristic properties of
a sample. Using this technique it is possible to observe fusion and crystallization events as well
as glass transition temperatures Tg. DSC can also be used to study oxidation, as well as other
chemical reactions.
Glass transitions may occur as the temperature of an amorphous solid is increased. These
transitions appear as a step in the baseline of the recorded DSC signal. This is due to the sample
undergoing a change in heat capacity; no formal phase change occurs.
As the temperature increases, an amorphous solid will become less viscous. At some point the
molecules may obtain enough freedom of motion to spontaneously arrange themselves into a
crystalline form. This is known as the crystallization temperature (Tc). This transition from
amorphous solid to crystalline solid is an exothermic process, and results in a peak in the DSC
signal. As the temperature increases the sample eventually reaches its melting temperature (Tm).
The melting process results in an endothermic peak in the DSC curve. The ability to determine
transition temperatures and enthalpies makes DSC a valuable tool in producing phase diagrams
for various chemical systems.

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

Top: A schematic DSC curve of amount of energy input (y) required to maintain each
temperature (x), scanned across a range of temperatures. Bottom: Normalized curves setting the
initial heat capacity as the reference. Buffer-buffer baseline (dashed) and protein-buffer variance
(solid).

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

Normalized DSC curves using the baseline as the reference (left), and fractions of each
conformational state (y) existing at each temperature (right), for two-state (top), and three-state
(bottom) proteins. Note the minuscule broadening in the peak of the three-state protein's DSC
curve, which may or may not appear statistically significant to the naked eye.

Examples:
The technique is widely used across a range of applications, both as a routine quality test and as
a research tool. The equipment is easy to calibrate, using low melting indium at 156.5985 C for
example, and is a rapid and reliable method of thermal analysis

Polymers:
DSC is used widely for examining polymeric materials to determine their thermal transitions.
The observed thermal transitions can be utilized to compare materials, however, the transitions
do not uniquely identify composition. Composition of unknown materials may be completed
using a technique such as IR. Melting points and glass transition temperatures for most polymers
are available from standard compilations, and the method can show polymer degradation by the
lowering of the expected melting point, Tm, for example. Tm depends on the molecular weight
of the polymer and thermal history, so lower grades may have lower melting points than
expected. The percent crystalline content of a polymer can be estimated from the
crystallization/melting peaks of the DSC graph as reference heats of fusion can be found in the
literature. [8] DSC can also be used to study thermal degradation of polymers using an approach

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

such as Oxidative Onset Temperature/Time (OOT), however, the user risks contamination of the
DSC cell, which can be problematic. Thermo gravimetric Analysis (TGA) may be more useful
for decomposition behavior determination. Impurities in polymers can be determined by
examining thermo grams for anomalous peaks, and plasticizers can be detected at their
characteristic boiling points. In addition, examination of minor events in first heat thermal
analysis data can be useful as these apparently "anomalous peaks" can in fact also be
representative of process or storage thermal history of the material or polymer physical aging.
Comparison of first and second heat data collected at consistent heating rates can allow the
analyst to learn about both polymer processing history and material properties.

Liquid crystals:
DSC is used in the study of liquid crystals. As some forms of matter go from solid to liquid they
go through a third state, which displays properties of both phases. This anisotropic liquid is
known as a liquid crystalline or mesomorphs state. Using DSC, it is possible to observe the
small energy changes that occur as matter transitions from a solid to a liquid crystal and from a
liquid crystal to an isotropic liquid.

Oxidative stability:
Using differential scanning calorimetry to study the stability to oxidation of samples generally
requires an airtight sample chamber. Usually, such tests are done isothermally (at constant
temperature) by changing the atmosphere of the sample. First, the sample is brought to the
desired test temperature under an inert atmosphere, usually nitrogen. Then, oxygen is added to
the system. Any oxidation that occurs is observed as a deviation in the baseline. Such analysis
can be used to determine the stability and optimum storage conditions for a material or
compound.

Safety screening:
DSC makes a reasonable initial safety screening tool. In this mode the sample will be housed in a
non-reactive crucible (often gold, or gold plated steel), and which will be able to withstand
pressure (typically up to 100 bar). The presence of an exothermic event can then be used to
assess the stability of a substance to heat. However, due to a combination of relatively poor
sensitivity, slower than normal scan rates (typically 2-3 /min - due to much heavier crucible)
and unknown activation energy, it is necessary to deduct about 75-100 C from the initial start of
the observed exothermic to suggest a maximum temperature for the material. A much more
accurate data set can be obtained from an adiabatic calorimeter, but such a test may take 23
days from ambient at a rate of a 3 C increment per half hour.

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

Drug analysis:
DSC is widely used in the pharmaceutical and polymer industries. For the polymer chemist, DSC
is a handy tool for studying curing processes, which allows the fine tuning of polymer properties.
The cross-linking of polymer molecules that occurs in the curing process is exothermic, resulting
in a positive peak in the DSC curve that usually appears soon after the glass transition.
In the pharmaceutical industry it is necessary to have well-characterized drug compounds in
order to define processing parameters. For instance, if it is necessary to deliver a drug in the
amorphous form, it is desirable to process the drug at temperatures below those at which
crystallization can occur.

General chemical analysis:

Freezing-point depression can be used as a purity analysis tool when analyzed by differential
scanning calorimetry. This is possible because the temperature range over which a mixture of
compounds melts is dependent on their relative amounts. Consequently, less pure compounds
will exhibit a broadened melting peak that begins at lower temperature than a pure compound.

Yamini (1st M.Pharm, Pharmaceutical analysis, NRI College of pharmacy, A.P, India)

REFERENCES
Methods of pharmaceutical analysis: Roger E Schirmer.
Instrumental methods of chemical analysis H.Kaur.

Instrumental methods of analysis: Willard Merritt dean settle.

Instrumental methods of chemical analysis: Gurdeep R. Chatwal, Sham K. Anand.
Introduction to instrumental analysis: Robert D Braun.
Text book of qualitative chemical analysis Vogels.
Dean, John A. (1995). The Analytical Chemistry Handbook. New York: McGraw Hill,
Inc. pp. 15.115.5. ISBN 0-07-016197-6.
Pungor, Erno (1995). A Practical Guide to Instrumental Analysis. Florida: Boca Raton.
pp. 181191.
Skoog, Douglas A., F. James Holler and Timothy Nieman (1998). Principles of
Instrumental Analysis (5 ed.). New York. pp. 805808. ISBN 0-03-002078-6.
M. J. O'Neill (1964). "The Analysis of a Temperature-Controlled Scanning Calorimeter".
Anal. Chem. 36 (7): 12381245. doi:10.1021/ac60213a020.
Differential scanning calorimetry calorimetry as a tool for as a tool for analysis of defects
in materials analysis of defects in materials : Daria Setman
http://radchem.nevada.edu/classes/chem455/lecture_22__thermal_methods.htm.
http://www.ami.ac.uk/courses/topics/0140_pl/index.html.
Wikipedia, the free encyclopedia.