NE 125 L

Title Page

Name: Rajesh Swaminathan

ID Number: 20194189

Partners’ Names: Sarvesh Varma – 20203153

Experiment Number: 3

Determination of Specific Heat Capacity

Experiment: (Cp) of Materials by Differential Scanning
Calorimetry (DSC)

Date Experiment was Started: 20-Feb-2006

Date Experiment was Finished: 20-Feb-2006

Date Report was Submitted: 13-Mar-2006

Days Late (-): 7

T.A.’s Initials:
Cp Determination by Differential Scanning Calorimetry NE 125L

1. Introduction
The main purpose of this experiment is to learn the basic concepts of the differential
scanning calorimeter and to illustrate its importance to materials science and engineering.
We do this by using the calorimeter to determine the specific heat capacity (Cp) of silicon
and low-density polyethylene at given temperatures.

The heat capacity of a material is defined as the amount of heat required to raise the
temperature of a given substance or material by 1 °C, or equivalently, 1 K. The specific
heat capacity is the heat capacity per unit mass. This relationship can be described
mathematically:

Q = mC p ΔT (1.1)

The subscript p in Cp is an indication that the specific heat capacity was obtained under
isobaric (constant volume) conditions. For isochoric (constant volume) conditions, we
would denote the specific heat capacity with Cv. For ideal gases, Cp and Cv are related by
the equation C p − Cv = R , where R is the universal gas constant.

Differential Scanning Calorimetry (DSC) is a thermal analysis technique used to measure

temperature and heat flow associated with important transitions in materials as a function
of time or temperature. Some measurements that can be made with the DSC are:

• Glass transition temperature

• Melting point
• Latent heat of melting
• Latent heat of crystallization
• Endothermic and exothermic natures of transitions
• Degree of Crystallinity
• Phase changes
• Specific heat capacity

In this lab, we will be using the Q10 differential scanning calorimeter to determine the
specific heat capacity of elemental silicon and low density polyethylene (LDPE). We will
also determine the melting point of LDPE and the enthalpy (latent heat) associated with
this change.

We subject the sample to some source heat and measure the heat flow between the
sample and a reference pan placed beside the sample pan. We then plot this data as a
function of temperature to obtain the thermal profile for our sample. We can then perform
many qualitative and quantitative observations from this graph. An example thermal
profile would look the following, although not all features will be observed on all DSC
plots:

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Cp Determination by Differential Scanning Calorimetry NE 125L

Figure 1 DSC Curve of Quenched PET

2. Materials and Equipment

1. Analytical balance
2. Q10 differential scanning calorimeter with mass flow control
3. Computer and data acquisition system
4. Data processing software
5. Sapphire (~25.0 mg)
6. Silicon (~10.0 mg)
7. Low density polyethylene – LDPE (~5.0 mg)

3. Procedure
The Q10 Differential Scanning Calorimeter used nitrogen as purge gas and the mass flow
control has been set to 50 ml/min for the sample purge.

Modified Heating Procedure

The heating procedure involved many steps for running different trials. The first step
involved the testing of empty pans to measure background heat flow. The second step
was to find the calibration constant k. The last and final step was to run each of the
samples of interest through the calorimeter to determine the heat flow at a specific
temperature and to calculate Cp at that temperature.

1. Empty Pan

a. Create thermal method as follows

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Cp Determination by Differential Scanning Calorimetry NE 125L

i. Equilibrate at 40.0 °C.

ii. Isothermal for 5.0 min
iii. Ramp 20.0 °C/min to 200.0 °C
iv. Isothermal for 5.00 min

b. Run empty pans to determine background heat flow to be subtracted from

following trials.

2. Determine the value of k (instrumental calibration constant) using sapphire standard

a. Heat sapphire disc (Cp standard) using above thermal procedure keeping in
mind that k is temperature dependent
b. Calculate k at the temperatures of interest using the following equation:

(1.2)

3. Measure Cp of silicon sample

a. Measure sample mass

b. Using same thermal procedure as above, measure heat flow at 87 °C
c. Calculate Cp by substituting k into the equation:

k × H × 60
Cp = (1.3)
Hr × M

4. Similarly, calculate Cp of LDPE at 67 °C

5. Analyze sources and magnitudes of error/uncertainty.
6. Return all samples and pans into their corresponding containers.

7. Results
We imported the raw data from the computer-aided data acquisition system into
Microsoft Excel for processing. The raw data provided us with the temperature of the
sample and the corresponding heat flow at that temperature. Our first task was to find the
value of k for any given temperature using the data from the sapphire run. We used
equation (1.2) for this purpose.

For example, k at 87 °C:

20 × 25.9
k = 0.885 × = 1.068
7.15 × 60

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The heat-flow vs. temperature profile for all three samples were plotted and the following
graph was obtained:

DSC Result Summary

2
0
-2 0 50 100 150 200 250
Heat Flow (mW)

-4 Sapphire
-6 Silicon
-8 LDPE
-10
-12
-14
Temperature (°C)

Figure 2 Comparison of DSC's of Silicon and LDPE against Sapphire standard

It is clear from the graph that only the LDPE curve has a dip in its thermal profile. In
other words, this is the only sample that underwent melting. This split in the melting
point dip is possible due to impurities in the sample, or more likely, due to the amount of
branching in the LDPE polymer chain.

We do not observe a melting point dip in silicon’s thermal profile because the melting
point of silicon is 1400 °C, well above the maximum temperature at which we examined
silicon (200 °C). Furthermore, we will never observe a glass transition for silicon as
silicon is 100% crystalline. Only materials with amorphous regions will exhibit a glass
transition.

8. Discussion
1. Calculate the specific heat capacities (Cp) of Si at 87 °C and 107 °C respectively.

Value of k at 87 °C = 1.068
Value of H for Si at 87 °C = 1.094 mW

k × H × 60 1.068 × 1.094 × 60
Using equation (1.3), C p = = = 0.565 J/g/ °C
Hr × M 20 × 6.2

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Similarly for 107 °C, k = 1.065 and H = 1.12 mW.

1.065 × 1.12 × 60
Using equation (1.3), C p = = 0.577 J/g/ °C
20 × 6.2

2. Calculate the specific heat capacities (Cp) of LDPE polymer at 67 °C, and
determine the glass transition point, melting and crystallization temperatures if
available.

We use the same method as that used for silicon:

For 67 °C, k = 1.085 and H = 4.919 mW.

1.085 × 4.919 × 60
Using equation (1.3), C p = = 3.20 J/g/ °C
20 × 5.0

No glass transition points were observed in the thermal profile for LDPE. The
temperature range at which the experiment was conducted was already well above
the glass transition temperature for LDPE.

On the same note, no crystallization temperatures were observed either as our

LDPE sample was subjected to a heating procedure only. We did not perform a
cooling procedure.

A melting temperature for LDPE was observed at around 112.40 °C. The latent
heat of melting (fusion) was estimated by the computer system (by integrating the
DSC curve within the boundaries specified by us) to be around 116.7 J/g.

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Cp Determination by Differential Scanning Calorimetry NE 125L

Figure 3 Thermal Profile for LDPE

We also note that the dip for LDPE is not a single distinctive peak because the
crystallization of the polymer was non-uniformly distributed which leads to some
parts melting faster than the others. Also, the existence of branching and sub-
branching contribute to different dips in the melting point. Another major fact is
that different arrangements and different molecular weights of the polymer can
change the way the dips appear in the DSC profile.

9. Questions
1. What were the sources and approximate magnitudes of uncertainties in your
various experiments?

We identified three different sources of uncertainty.

First, there is the natural uncertainty (both random as well as systematic)

associated with any equipment. There is going to be some amount of uncertainty
in the measured weight of the sample because of the analytical balance used.
There is also some uncertainty in the heat flow measurements and the temperature
measurements using the thermocouple.

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Second, the LDPE we were provided with was not industrial-scale LDPE and
therefore may not have been entirely LDPE. There could have been some
impurities in them that could induce a modicum of uncertainty in the accuracy of
our thermal profiles. These impurities could have also been present in the
silicon/sapphire samples.

Third, we assumed that the LDPE polymer was a pure material and not a
copolymer or a filled polymer of secondary variety. If this assumption is not
correct, we have a source of error in our results and conclusions.

None of these uncertainties are truly large to interfere significantly with the
conclusions drawn. The qualitative results drawn still hold true regardless.

2. What are some of the drawbacks to the DSC method and the samples used in it?

The biggest drawback to using the differential scanning calorimeter is the cost of
instrumentation. The DSC method is also a tedious method and does not allow us
to obtain the specific heat capacity of an unknown material quickly. We are
required to calibrate the instrument every time of its usage because of changes in
background heat flow. This could pose a problem when looking for quick and
speedy approximations. Lastly, the material used to find the calibration constant k,
sapphire, is expensive to purchase. This means that two labs with identical
equipment but using a different calibration material other than sapphire may
obtain unequal numerical results.

3. State another technique that could be used to determine the degree of crystallinity
of a polymer.

A proposed technique that can be used to determine the degree of crystallinity of

polymers is to exploit the characteristics of their mechanical properties versus
changes in temperature. This analysis can be done by comparing the modulus of
elasticity of an unknown sample to a known reference sample at certain
temperatures.

Polymers can have different proportions of amorphous regions. In this analysis, a

sample polymer of a known crystallinity can be selected to obtain the modulus of
elasticity at different temperatures. Then the modulus of elasticity of an unknown
sample can also be tested at these same temperatures and be compared to the
known sample. Depending on the difference, another known sample can be used
to generate a profile resembling the unknown sample. By successive trials, the
range of crystallinity can be narrowed down and a certain value of crystallinity
can be approximated for the sample.

If the experimentalist already has a pre-conceived idea about the range of

crystallinity in the unknown sample, the number of temperatures at which the

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comparisons are made can be reduced to two or three temperatures to make the
process faster. However, for this test to be successful, one major assumption that
is made is that the amount of cross-linking in the reference samples is the same
because an increased amount of cross-linking can significantly change the profile
of a sample with a given amount of crystallinity.

Figure 4 Relationship between Polymeric Crystallinity, Young's Modulus and Temperature

(Shackelford, Fig. 6.45)

4. Using what you understand about the way polymer chains behave above and
below Tg, why do you think glasses tend to be brittle whereas rubbers are not?

Above their glass transition temperatures (Tg), polymers have molecular chains
that are disorganized. These polymers have an appreciable relative mobility above
their Tg. At this stage, the polymers become more elastic. Above their glass
transition, the secondary, non-covalent bonds between the polymer chains become
even weaker, causing the polymer to become highly elastic and rubbery. This is
the case of elastomers [4] and rubbers. At room temperature, these materials are
found to be much above their glass transition temperatures and hence display high
elasticity.

In contrast, ceramics and glasses (that also have also amorphous portions)
demonstrate glass transition temperatures much higher than polymers. Below the
glass transition temperature, the glass gains a crystal structure and loses its
relative mobility. As a consequence, the crystal structure becomes brittle. Since

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the crystal groups become strong and form grains, the chances of a fracture
propagating though the material become much higher as opposed to when it is in a
semi-liquid state. Heating glasses up to high temperatures provides them with
elasticity and this phenomenon is used by glass blowers to shape glasses. Also,
super cooling to temperatures close to absolute zero brings rubbers around or
below their Tg and therefore makes them brittle.

10. Conclusion
From the above results and following discussion, we have seen how one could use a
differential scanning calorimeter (DSC) to obtain the specific heat capacity of silicon and
sapphire at two different temperatures. We were also able to obtain the melting point of
low density polyethylene (LDPE) and the latent heat associated with this transition. We
discussed why there was a split in the melting dip for LDPE (Figure 3); why no glass
transitions were observed for either silicon or LDPE; why no peaks of crystallization
were observed; and why no melting transition dip was observed for silicon.

More results were apparent upon further examination. We found that the specific heat
capacity is a function of temperature. This specific heat capacity was found to change
significantly after certain critical points in the material’s phase cycle. We calculated the
melting temperature for LDPE to be around 112.40 °C. The latent heat of melting was
estimated to be around 116.7 J/g.

Further analysis revealed sources of error and uncertainty in our various experiments. We
also analyzed specific drawbacks to the DSC method and the samples used in it. We
discussed an alternative method to determine the degree of crystallinity in a polymer.
Finally, we concluded the analysis on our understanding of polymer chains, brittle-to-
ductile temperatures and glass transitions to explain why glasses tended to be brittle
whereas rubbers were not.

Overall, the experiment was a success. We understood the basic working of a differential
scanning calorimeter and discovered new relationships between heating rates and
mechanisms of decomposition. This helped reinforce our knowledge on high temperature
material decomposition and also provided insight into how scientific experimentation and
testing was to be carried out.

11. References
[1] J. F. Shackelford, Introduction to Materials Science for Engineers, 6th edition,
Prentice-Hall Inc., New Jersey (2005).

[2] L. Simon, Nanotechnology Engineering NE 125 Lecture Notes, University of

Waterloo, Waterloo (2006).

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[3] Q. Xie, L. C. Simon, F. McCourt, Nanotechnology Engineering NE 125 Lab

Manual, University of Waterloo, Waterloo, pp 25-33 (2006).

[4] Wikipedia contributors, “Elastomer”, Wikipedia. Retrieved March 4, 2006 from

[Link]

[5] Wikipedia contributors, “Glass Transition Temperature”, Wikipedia. Retrieved

March 13, 2006 from [Link]

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