1

Polypropylene Phase
Transitions Studied by DSC
John Doe
Chem ------Abstract:
Isotactic and Amorphous polypropylene were studied through Differential Scanning
Calorimeter (DSC). When analyzing amorphous polypropylene, both first order and
second order transition phases are observed with an enthalpy of crystallization of
13.22 J/g. This shows the sample was not 100% pure. The glass transition
temperature was found to be -12.68C. The degree of crystallinity for the
amorphous sample was calculated for a value of 6.83%. The isotactic sample had a
degree of crystallinity at 41.2% as well as an enthalpy of crystallization of 85.32 J/g.
The entropy of the glass transition phase was calculated through a series of
integrals ranging from 20C, this value was 1.58 J/mol-K. The entropy of
crystallization was 0.20 J/mol-K, this was calculated through utilization of the first
law of thermodynamics. This experiment demonstrated differences between
stereochemistry in molecules, which showed differences in thermodynamic
properties of two isomers of polypropylene.

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INTRODUCTION:
Differential Scanning Calorimetry (DSC) is used to determine and
compare the phase transitions of both amorphous and isotactic
polypropylene. 2Differential scanning calorimeters are a widely used
thermoanalyitcal instruments due to their ease of use, relatively fast
data collection times and ability to use small sample sizes. 3DSC is used
to measure thermal properties of nanocomposite thermal-plastics
widely used in the engineering of polymers. Polymer engineering is
important due to the demand on innovative ways to create plastic.
Using DSC can give thermodynamic properties, which help engineers
produce plastics that can resist high or low temperatures. DSC works
by measuring the heat flow to or from a sample when chemical or
physical changes occur during applied temperature increase. When
there is no chemical or physical change total heat is calculated by:
q p =C p T

(1)

Cp is independent of temperature and T is the temperature change. If

there is any excess heat transferred in the system equation 1 turns
into:
C p , ex=
2

qex
T

(2)

The excess heat can be viewed, as the change in heat capacity

therefore the DSC thermogram is essentially a chart of C p,ex vs. T. When

the system undergoes any chemical or physical changes a peak forms

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on the graph. These peaks can be integrated to find enthalpy of
transition. The integration is shown in Equation 3.
T2

H p= C p ,ex dT

(3)

T1

T1 and T2 represent the beginning and ending temperatures of

transition. There are two different types of transition being studied in
this lab. First order and second order transition. A steep peak in the
high

temperature

demonstrates

range

represents

crystallization.

Slow

first

order

rising

peaks

transition,
in

the

this
lower

temperature range represent second order. It is hypothesized before

lab that the amorphous polypropylene would only show second order
transition. This is due to its tacitcity, which is related to the
stereochemistry of a molecule. 1Tacticity is a term used to describe the
way pendent groups on a polymer chain are arranged on a polymer
backbone. 1The tacticity of a polymer is determined by what side of the
polymer chain the pendant groups are on. Amorphous Polypropylene is
a long carbon chain where each center carbon is connected to a
methyl group and hydrogen; these are situated in random order. This
random order of side groups forms an amorphous solid that does not
crystalize. Isotactic Polypropylene has all methyl groups in the same
position from the center carbon, which allows it to crystalize. These
phenomenas are studied through the graphs produced by DSC. 1 st
order transition occurs when the molecule crystallizes with an applied

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heat

flow,

thus

represent

Isotactic

Polypropylene.

Amorphous

Polypropylene was predicted to only form second order transition

because it does not crystallize. After observing the different peaks of
transition the entropy will be calculated through the integral shown in
Equation 4.
T2

S=
T1

Cp
dT
T

(4)

The first law of thermodynamics shown in equation 5 helps shape an

understanding of the system and is used for calculations of entropy
when the Gibbs free energy is zero.
G= HT S
EXPERIMENTAL:

(5)

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The pressure of the nitrogen (CAS 7727-37-9) feed was set to 20 psi,
exceeding this pressure would damage the instrument. Q200-1724 was
then opened on the computer monitor. The cell was set to room
temperature with a sample purge flow rate of 50mL/min. Amorphous
Polypropylene; Aldrich (CAS 9003-07-0) was then placed in DSC Q2000
differential scanning calorimeter. There are three Hermetic Tzero
aluminum sample pans in which the polymer samples sat on for the
experiment.

It was essential to use tweezers when handling the

samples; this prevented any skin oil interaction, which would affect

Figure 3: Diagram of Experiment

Attained from http://pslc.ws/macrog/dsc.htm
results. A simplistic diagram of the system is shown below.

The sample and reference pan are both placed on top of two
thermocouples inside the cell. The computer was set to 9.3 mg for
PPA_56, which was the sample being tested. After all experimental
constraints were confirmed the experiment started. DSC graphs were
made from the Q200-1724 program and integrated to find enthalpy of
transition. The Data for the PPC was attained from other sources after
completion.

RESULTS:

Figure 4: PPA_54 DSC thermogram

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Figure 4 represents the graph created from the DSC. It is observed that
both 1st order and 2nd order transitions take place in the supposed
amorphous polypropylene.

An average of the heating and cooling

peaks gave a glass transition temperature of -12.68C. The first order

crystallization peak had an enthalpy of 13.22 J/g with a melting
temperature of 137.69C. The degree of cystallinity was reported at

Figure 5: PPC_54 DSC Thermogram

6.83%. Figure 5 represents the thermogram for Isotactic Polypropylene.

The enthalpy of crystallization of isotactic polypropylene is 85.32 J/g at

a temperature of 151.65C. The degree of crystallinity is 41.2%. The

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graph is symmetrical showing no glass transition. The entropy of
crystallization is calculated using the first law of thermodynamics and
has a value of 0.201J/g-K. Figure 6 represents Entropy vs. Temperature
of glass transition during the scanning of Amorphous Polypropylene.

Figure 6: Entropy vs. Temperature.

This

figure

represents

the

change

in

Entropy

dependent

on

temperature. Each point corresponds to its individual integrals with a

range of -20C to 20C. The max value gives the sum of all individual
integrals as a value 1.58 J/g-K, this is the entropy associated with glass
transition.

DISCUSSION:

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Figure 4 demonstrated the supposed pure amorphous polypropylene.
After witnessing the crystallization peak at 137.69C, it is proved that
the sample used was not 100% pure. The degree of crystallinity was
calculated using a reference enthalpy of crystallization as 207 J/g and a
value of 6.83% was reported. Since the sample was not 100% pure it
could not dissolve properly which caused a small portion crystallized.
In future if this sample was used, believing it was 100% pure, there
would be a significant amount of error when creating products. This is
can cause failure to future reactions and their products and would
lower the percent yield of a target chemical. 2The melting temperature
of amorphous polypropylene is reported to be 160-165C and a
transition temperature of -10C, these values were obtained from
Sigma Aldrich. Figure 4 gives values slightly off from literature values.
On a molecular level the bonds released at lower temperatures, a
melting temperature is observed at 152.57C. This could be caused by
inconsistency of pressure during the experiment. The pressure of the
cell could have fluctuated, since the melting temperature was reported
lower then ideal, it is assumed that the pressure decreased.

This

assumption is made due to the direct relationship between pressure

and temperature, when pressure is decreased so does the melting
point. Also the discrepancy could have been caused by too rapid of
increase in temperature. If temperature increases faster then the DSC
can read, the melting temperature will be recorded lower then ideal.

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Isotactic polypropylene reports a higher melting temperature of 189C,
this value is found in the chemical book website.2Since this melting
point is slightly higher then amorphous this proves that a consistent
stereochemistry within a molecule gives a stronger bond between
carbon and its corresponding R group. Using this phenomena when
comparing both Isotactic and Amorphous polypropylene, it shows the
bonds are either closer together or attracted to each other more when
stereochemistry

is

the

same

for

all

carbons,

the

isotactic

polypropylene.
The temperature range for the peak of crystallization varied when
comparing the amorphous to isotactic polypropylene. The wider the
temperature range and ultimately wider the peak corresponds to more
crystallization enthalpy of the molecule. In the amorphous sample, the
crystallization peak was much thinner than the isotactic sample. This
agrees with the values of enthalpy of each, the isotactic had a much
higher enthalpy compared to amorphous. This shows the isotactic
sample involved a greater temperature range during the crystallization
physical change.
The entropies of both amorphous and isotactic sample differed
significantly. Entropy is defined as the disorder or randomness of a
system. This is demonstrated in both Figure 4 and 5 and it corresponds
with their entropy values. When looking at the glass transition phase
the temperature changes at many different points of heat flow. This is

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the reason for the calculation of the integral ranging from -20 to 20C.
The sum of those gives a value of 1.58 J/g-K. As the temperature
changes so does the disorder of the system. The entropy of the
isotactic sample gave a value of 0.201 J/g-K, this is significantly lower
then the amorphous sample because temperature stays at a constant
value, the melting temperature. The first law of thermodynamics can
be applied and the total energy in the system is equal to the enthalpy
of crystallization, which gives lower disorder thus lower entropy.

CONCLUSION:
Differential scanning calorimeter was used to test both amorphous and
isotactic polypropylene. The DSC thermogram showed that the
amorphous polypropylene was not 100% pure; this was evaluated
through both its predicted glass transition phase as well as its 6.83%
crystallization 1st order peak with an enthalpy value of 13.22J/g. The
temperature of glass transition was an average of both hot and cold
temperatures and was a value of -12.68 C. Pure amorphous
polypropylene would not exhibit a 1st order peak. The entropy of the
glass transition was calculated through a series of integrals, which
gave a value of 1.58 J/g-K. The entropy of crystallization, observed in
the isotactic thermogram was a value of 0.20 J/g-K. The degree of
crystallization was 41.2 %. The variances between both the isotactic

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and amorphous sample are due to its stereochemistry and strength of
bonds. The more consistent a structure the stronger its bonds are.
Differences from ideal values could have occurred from rapid
temperature increase or decrease in cell pressure. DSC proves to be a
powerful tool when studying thermodynamic properties of isomers and
helps compare and contrast small differences within each compound.
ACKNOWLEDGMENTS:
I would like to thank Sean McCrea, Adam Bielski and Professor M for
their help with configuration and understanding of this experiment.
REFERENCES:
1) O'Lenick,
Anthony.
Comparatively
Speaking:
Isotactic
vs.
Syndiotactic vs. Atactic in Polymers. 2009.
2) Milosavljevic, Bratoljub. Lab Packet for Experimental Physical
Chemistry. 2013, 9(1)-9(6).
3) Polymer Engineering Science. Vol 54.,pp 2292-2300
4) Ewen, John. J. Am. Chem. Soc., 1984, 106 (21), pp 63556364