Lab 4: DSC

1. Purpose

Examine thermal transitions in a semi crystalline polymer Poly (ethylene terephthalate)

sample using DSC.

2. Theory

Differential scanning calorimeters (DSCs) are used to measure the temperatures and heat

flow during thermal transitions of materials in a wide range of applications such as polymer

characterization, food science, and pharmaceuticals.

Fig 1: Schematic representation of DSC sample cell.

The sample to be characterized is sealed in an aluminum pan and placed alongside an

empty aluminum reference pan in the DSC furnace. The sample and the reference pan are heated

at the same rate by a heating element in the furnace. Thermal transitions such as melting or

crystallization involve release or absorption of heat which leads to a difference in temperature

between the sample and reference. The DSC measures the difference in heat flow required to

maintain the sample and the reference at the same temperature. A purge gas such as helium or

nitrogen may be used to ensure thermal efficiency and to remove left over volatiles.

DSC is the most commonly used instrument for characterization of thermal transitions in

polymeric materials. Completely amorphous polymers such as polystyrene can be characterized

using their glass transition temperature (Tg) which represents a transition from a rigid glassy state

to a rubbery liquid like state. In DSC measurements the glass transition is captured by a step

change in the heat flow curve. Since amorphous polymers soften considerably beyond their Tg, it

often determines the end use temperature range for these materials. Semi crystalline polymers

such as poly (ethylene terephthalate) which is often referred as PET consist of amorphous and

crystalline domains and exhibit a glass transition and a melting transition. Furthermore,

depending on processing conditions semi crystalline materials may also exhibit a crystallization

peak on heating, as shown in Figure 2a.

a) b)

Fig 2: Thermal transitions in a semi crystalline polymer a) crystallization on heating b) No

crystallization on heating ( T. D' Amico, C.J. Donahue, E.A. Rais, J. Chem. Ed. (2008) 85, 404).

The degree of crystallinity is an important parameter for semi crystalline polymers. The

degree of crystallinity can be determined from the crystallization exotherm when crystallization

occurs on heating (see Fig 2a) using the Equation 1 below:

H f  H c
Degree of crystallinity = 100% (1)
H f 100%
where H f is the enthalpy of melting, H c is the enthalpy of crystallization, and H f 100% is the

enthalpy of melting for a fully crystalline polymer. When no crystallization is observed on

heating (See Fig 2b), the degree of crystallinity may be estimated from the melting peak as

shown in Equation 2:

H f
Degree of crystallinity = 100% (2)
H f 100%

The degree of crystallinity is influenced by processing conditions and thermal history of the

polymer. For example, when a semi-crystalline polymer is cooled from the melt, the degree of

crystallinity increases with decreasing cooling rates. In this lab, the impact of two different

cooling procedures on the thermal properties of a semi crystalline polymer is examined.

3. Procedure

3.1 Thermal Treatments

1) Cut three round pieces from a PET beverage bottle using punch tool and measure their

masses using the weighing balance.

2) Place one piece on a standard aluminum pan and cover with lid. To close the sample

using the sample press, place the pan on the green die and position it under the press.

Gently pull the handle forward to close the pan. Repeat the sample preparation procedure

for one more PET sample. Place the remaining PET piece in an aluminum pan and do

not cover with this lid (This sample will be used to observe the extent of melting during

thermal treatments). NOTE: Remember to keep track of sample mass in each pan!

3) Place the uncovered sample pan and the two covered sample pans on the top on the hot

plate. Set the hot plate temperature to 300 oC. Observe the extent of melting of the PET
 sample in the uncovered pan. This can be used as a reference to track the extent of

melting in the two covered pans.

4) Transfer some liquid nitrogen from the dewar to the green holding container.

4) When the PET sample in the uncovered pan is in a liquid-like melt, switch off the hot

plate and using tweezers quickly transfer one of the covered sample pans to the liquid

nitrogen container. Let the other covered sample pan remain on the hot plate to cool

slowly.

5) After the sample pan is allowed to remain in the liquid nitrogen contained for a few

minutes, proceed to perform DSC measurement. Finally, perform a DSC measurement

for the covered sample pan that was allowed to cool slowly on the hot top.

3.2 DSC measurements

Sample Preparation

Sample loading: use tweezers to place sample pan onto DSC cell closest to table edge (see

photo) and reference pan (empty, covered aluminum pan) on DSC cell farthest from table

edge. Replace both inner lids using the curved backside of the tweezers, and replace

outmost lid by hand.

Pre-test System Checks:

1. Purging gas cylinder (Nitrogen, shared with TGA Q50): gas level and open valve to DSC
2. Open TA Instrument Explorer and double-click Q20 icon. Check Purge gas flow rate
(50 ml/min)

Software Inputs:

1. Summary tab

Mode: Standard

Test: Custom

Sample Name: <give descriptive sample name>

Pan Type: Aluminum

Sample Size: <sample mass>

Comments: <give additional sample information> i.e. slow cooled, quenched etc.

Data File Name: \\GI3113-01\TA\Data\DSC\Users\yourfolder\your_file_name

NOTE: file name should first include initials, then descriptive information. (Ex:
John Andrew Smith’s 1:1 DCPD:dilulin sample: jasDilulinDCPD50% ).

2. Procedure tab

Test: Custom

Editor: Segment description: Ramp 20 K/min to 275 oC. (The same condition must be
maintained for every experiment)

3 Notes tab

Operator: <your name>

 Extended Text: <any additional information you would like to record>

Sample: #1 Nitrogen

Flow Rate: 50 mL/min

4. Click Apply to save changes to save changes.

5. When sample is loaded, start the experiment by pressing Start the Run button in the upper
left corner of the screen.

Post-test:

1. To cool the DSC down after a test, replace the DSC cell cover with the quench cool

accessory. Pour liquid nitrogen from the dewar carefully in the quench cool accessory until

the desired temperature is attained.

2. When run is complete and DSC is cooled, close the nitrogen gas valve and dispose of the

sample.

3. The experimental results such as glass transition temperature, melting temperature, cold

crystallization temperature, and enthalpy of melting may be obtained by opening the data

file in universal analysis software. After opening the data file use the analyze tab to obtain

the necessary values.

4. Assignment

1. Do both specimens exhibit a cold crystallization peak? Explain the reasons for differences, if

any.

2. Calculate the degree of crystallinity for the samples tested using the appropriate equations.

Are the degrees of crystallinity for the two specimens different? If so explain the origins of

the difference? The value of H f 100% is 140.1 J/g.

3. Compare the glass transition temperatures of the two specimens. Is there a relationship

between the glass transition temperature and degree of crystallinity?

4. Determine the melting point of each specimen? Does melting point depend on degree of

crystallinity?

5. Does the observed enthalpy of melting depend on the degree of crystallinity of the specimen?