PST351-POLYMER CHARACTERISATION

LABORATORY MANUAL

PST351
POLYMER CHARACTERISATION

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 PST351-POLYMER CHARACTERISATION

LABORATORY SAFETY

Preparing the laboratory work

Before starting the work in a laboratory, familiarize yourself with the following:

● The hazards of the materials in the lab, as well as appropriate safe handling, storage and
emergency protocol. Read labels and material safety data sheets (MSDS) before moving,
handling or opening chemicals. Never use a product from an unlabeled container, and report
missing labels to the laboratory technician.
● The agents, processes and equipments in the laboratory. If you are unsure of any aspect of a
procedure, check with your instructor before proceeding.
● The locations and operation of safety and emergency equipments such as fire extinguishers,
eye wash and shower, first aid and spill response kits, fire alarm pull stations, telephone and
emergency exits.
● Emergency spill response procedures for the materials you will handle
● Emergency reporting procedures and telephone numbers
● Designates and alternate escape route

General safety rules during laboratory work

● Restrict laboratory access to authorized persons only. Children are not permitted in labs
● Smoking, eating, drinking, storage food, beverages or tobacco, applying cosmetic or lip bam
and handling contact lenses are not permitted in laboratories.
● Wear lab coats (knee length) and safety glasses in laboratory employing chemicals,
biohazards, radioisotopes. Open shoes, such as sandals, should never be worn in the lab.
● Tie back or otherwise restrain long hair when working with chemicals, biohazards,
radioisotopes.
● Keep workplace clean and free of unwanted chemicals.
● Reports accidents and dangerous incidents promptly to your instructor
● Wash your hand thoroughly before leaving the laboratory

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REPORT WRITING

All written laboratory reports must be your own individual work/group. A complete laboratory
report should contain the following section:

i) LOGBOOK

It is very important that every scientist records all experimental data. Hence, students must
have a logbook to record the chemical used, weight, volume, concentration, and all
observations made during the laboratory experiments. Students must write the outline of the
lab experiment before coming to lab session and present it along with the answer to Pre Lab-
Questions to the instructor before each experiment.

ii) COVER PAGE

The cover page of your laboratory reports should include:

i) Experimental number and title

ii) Name and student number
iii) Lab Partner’s name and student number\
iv) Lab group
v) Date (lab work and report submission)
vi) Lecturer’s name

iii) SECTIONS OF THE LABORATORY REPORT

Your laboratory report should consist of all the following information:

i) Objective(s)
ii) Apparatus/chemical/procedure – must be written in PASSIVE FORM
iii)Results and Data
iv) Discussion – refer appendix 1
v) Conclusion – This section should be short, concise, and straight to the point. Your
conclusion should be related to the objective(s) of the experiment.
vi) References

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Experiment 1

Paper Chromatography

Objective:

1. To prepare the Paper Chromatography

2. To separate food dyes
3. To determine retention factor, Rf for each spot

Introduction:

Paper Chromatography is one of the most common types of chromatography. In paper

chromatography, a strip of paper and capillary action is used to pull the solvents up through the
paper to separate the solutes. In many respects, paper chromatography is similar to TLC. In paper
chromatography, a strip of paper is used instead of and adsorbent coated plate.

Generally, filter paper can be used for paper chromatography because it is almost pure
cellulose with few impurities. Under most atmospheric conditions, filter paper absorbs moisture
from the air. This absorbed water makes up about 20% by weight of the filter paper and is usually
sufficient for successfully paper chromatography.

In this experiment, we will try to separate and identify some components in food dyes by
using paper chromatography. The dyes use in this experiment is in concentrated from.

Materials:

a. Microcapillary (75mm x 0.5 mm ID)

b. Filter Paper (46 x 57 cm sheet of a Whatman No 1)
c. 4 colours of food dyes (blue, green, yellow. Red)
d. Developing solvent, 0.2% (2g/L aqueous solution of NaCl)
e. Plastic wrap
f. Stapler

Procedure:

1. Draw a line parallel to the long dimension about 2cm from the edge of the filter paper.
2. Draw 4 small “X” on the line beginning 5 cm from the edge of the paper and the spacing mark
about 3 cm apart. (The ‘X” marks is the point where you will later spot the dyes).
3. Put 70mL of the developing solvent in clean, dry 800 ml beaker and cover it with plastics wrap
held in place by rubber bend.
4. Lay the filter paper on clean table. By using microcapillary, place a tiny spot of each spot of
the food colours on the “X” mark., one colour per X.

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5. Label in with pencil near each X with appropriated letter symbol (such as B, G, R, Y) to
identify the colour of the dye spotted there. Apply two more spots for each of the food dyes on
the same spot and allow the spots to dry.
6. After the spots have dried, staple the edge of the paper together (right end-to-left end) leaving
a gap so that the edge does not quite meet.
7. Put the paper cylinder in the beaker containing the development solvent. Make sure the paper
does not touch the wall of the beaker and the level of the solvents is below the spots.
8. Seal the beaker immediately with plastics wrap (if necessary) and allow the solvent to rise
within 1 cm from the top edge of the paper.
9. When development is finished, remove the paper from the beaker and immediately mark the
solvent front with a pencil before solvent evaporates.
10. Calculate and record the Rf values for every colored spot.

Pre-Laboratory Questions

1. Define chromatography.
2. State the stationary phase and mobile phase of liquid chromatography.
3. Discuss the mechanism involve in paper chromatography.

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Experiment 2

Ultra-Violet Visible Spectrophotometry

Objective:

1. To determine the wavelength of maximum absorbance for the above spectrum.

1. To produce a standard curve/calibration curve from a series of standard solutions by linear.
regression analysis and to calculate absorptivity from Beer’s law.
2. To determine the concentration of KMnO4 solution using the standard curve method.

Introduction:

Visible light is the name given to the narrow band of electromagnetic spectrum which the
pigment of our eyes can absorb and allow us to detect. Light itself can split into spectrum of colors
that we see in a rainbow; different color signify different wavelengths and therefore, different
energies. A beam of light consisting of only one color is called monochromatic. The energy of a
mole of photons of any one color is given by the relationship:

𝐸 = ℎ𝜐

Where E = energy, h = Plank’s constant and 𝜐 = frequency of light (remember that frequency and
wavelength of light are related by 𝑐 = 𝜐𝜆 where c = velocity of the light, 𝜐 = frequency and 𝜆 =
wavelength. Red light has a longer wavelength than blue light and therefore lower frequency and
lower energy.

Light will be absorbed by an atom, ion, or molecule when the energy of one quantum of
light matches the energy required to cause an electron in outer orbital to jump to a higher energy
level. Each absorption band is caused by the transition between a given pair of energy level;
because the energy level differences vary with the different electronic structures, absorption
spectra can be often used to identify the analyte atom, ion, or molecule.

The technique of spectrophotometry relies on the absorption of light by analyte; the

intensity of a beam of light is measured in the absence of analyte, followed by measurement in
the presence of analyte. The decrease in the transmitted intensity is used to determine the analyte

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concentration. The Beer’s Law expresses the relationship between absorption and concentration
such as:
𝐴 = 𝑎𝑏𝑐 or 𝐴 = 𝜖𝑏𝑐

Where A = absorbance, a = absorptivity in L/gcm, 𝜖 = molar absorptivity in L/molcm, c =

concentration in g/L or mol/L and b = optical length. This is the basic equation of spectrometery.
Note that the absorbance is zero when the transmittance is 100%, i.e. no light is absorbed by the
sample. Absorbance is a logarithmic function of transmittance, A = -log T.

Two types of analysis can be done with the visible absorption measurements.

1. Qualitative Analysis: To determine the wavelength of maximum absorbance (ëmax) from

the absorption spectra as well as characteristics value of the absorptivity of a specific
molecule
2. Quantitative Analysis: to determine the concentration of an unknown solution from the
standard calibration curve using Beer’s law

Materials:

Standard KMnO4 with concentration of 1000 ppm and an unknown concentration of KMnO4

Instruments:

SP8 – 400 UV – Visible Spectrometer

Procedure:

a. Sample preparation of KMnO4 (standard solutions)

1. Weight accurately 0.01g of potassium permanganate, KMnO4 on a weighing paper. Record
the reading. Transfer the solid into a small beaker.
2. Pour a small amount of distilled water to dissolve the KMnO4 and stir with a stirring rod
until a homogenized solution is obtained.
3. Using a filter funnel, transfer the KMnO4 solution to a 100 mL volumetric flask. Rinse the
beaker with the distilled water and transfer into the volumetric flask.
4. Add distilled water into the volumetric flask until just below the calibration mark. Use a
medicine dropper to add the last few drops of distilled water until the mark.
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5. Stopper and shake the volumetric flask several times to obtain a homogenized solution.
Label this as 1000ppm solution
6. From 1000 ppm solution, pipet 5mL and carefully transfer in 100mL volumetric flask.
Dilute the solution to the mark with distilled water. Stopper and shake the volumetric flask
several times to obtain a homogenized solution. Label this as 5ppm solution.
7. Repeat step number 6 to prepare 10 ppm, 15 ppm and 20 ppm solution. For 10 ppm
solution, pipet 10 mL of standard solution; for 15 ppm, pipet 15 mL of standard solution;
for 20 ppm, pipet 20 mL of standard solution.

b. Determination of absorption maxima ((ëmax))

1. Select Cary Win UV icon
2. Go to setup, click on the ‘CARY ON’, then key in the require start and stop scan
wavelength (nm)
a. Y-mode (min = 0 and max = 1)
b. X-mode = 800 – 200 nm
c. Beam mode = Dual Beam
d. Measurement mode (ABS = Absorbance) or % T (Transmission)
3. Select “Replicates”
4. Select cycle mode if more than one cycle is require
5. Select “Scan Control Speed” “Fast”
6. Click on ‘Baseline’ icon and check ‘Baseline Correction Function’
7. Click ‘Accessories 1’, check on the Use Cell Changer select cells
8. At the report icon, key in the operator name and the comment
9. At the peak table option, select maximum peak
10. In the Auto Store icon, set ‘storage on (Prompt At Start)’
11. To save the method, Go to the file and save the scan method
12. Fill the ‘BLANK’ cuvette solution with distilled water
13. Put the ‘BLANK’ cuvette solution and click ‘Zero’
14. Take out the ‘BLANK’ cuvette and put the ‘SAMPLE’ cuvette (high concentration –
20ppm)
15. Click ‘Start’ icon to start the measurement.

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c. Determination of the concentration

1. Go to Setup, click on Cary icon, then key in maximum wavelength, ëmax
2. Select Replicate = 3.
3. Click on ‘Standard’ icon, check the ‘Calibrate During Run’ function.
4. Set the calibration standard unit (mg/L) and the number of the standard samples together.
with the unknown concentration values.
5. Select the Fit Type (Linear Direct)
6. Go to the Sample icon, select the number of the samples and key in all the samples name.
7. Go to the Report icon, key in operator name and the comment.
8. In the Auto Store icon, set ‘Storage on (Prompt at Start)’
9. To save the method, click ‘File Save Method As Ok
10. Put the ‘BLANK’ cuvette and click ‘Zero’.
11. Take out the ‘BLANK’ cuvette and put the ‘SAMPLE’ cuvette (start with high
concentration)
12. Click ‘Start’ icon to start the concentration measurement.

Pre-Laboratory Questions

1. Define spectroscopy.
2. What type of electromagnetic radiation will be used in this experiment.
3. State Beer lambert Law mathematically and define each term.
4. Define ëmax

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Experiment 3

Fourier Transform Infra-Red Spectroscopy (FTIR)

Objectives:

1. To carry out a qualitative analysis of the IR spectra of solid sample, by identifying the
characteristics stretching and frequencies bonds of functional group
2. To identify the structure of unknown by comparison of its IR spectrum with that some known
compounds, and from the molecular formula given

Introduction:

The physical properties of polymeric systems depend, in the first instance, upon the
chemical constituents and the configuration of the macromolecules and on the relationships among
the chains (morphology) the parameters defining such as crystallinity and phase segregation. Many
spectroscopic techniques are available nowadays to access these features, and FTIR-spectroscopy
is perhaps the most widely used due to its versatility in determining composition, taticity,
conformation, crystallinity, among others.

FTIR spectroscopy is a measurement technique for collecting infrared spectra. Instead of

recording the amount of energy absorbed when the frequency of the infra-red light
(monochromator), the IR light is guided through an interferometer. The IR light is passing the
sample to produce interferogram (measured signal). To absorb infrared radiation, a molecule must
undergo a net change in dipole moment because of its vibrational or rotational motion. Nearly all
molecule containing covalent bonds will show some degree of IR absorption. The only exception
is the diatomic molecules, such as hydrogen, nitrogen, and oxygen in which there is no net change
in dipole moment when they vibrate or rotate. The IR spectra of polyatomic covalent compounds
are often exceedingly complex, consisting of numerous narrow absorption bonds. The relative
positions of atoms in a molecule are not exactly fixed. The relative positions of atoms in a molecule
are not exactly fixed. The positions fluctuate continuously because of different types of vibrations.
There are two fundamental types of vibration.

i. Stretching: Involves a continuous change in the interatomic distance along the axis of
the bond between the two atoms.
ii. Bending: Characterized by change in the angle between two bonds

IR spectroscopy has been employed for both qualitative and quantitative analysis, IR spectra
show the percent of certain groups of atoms in a molecule. A particular group of atoms gives rise
to characteristics stretching frequencies in the IR spectra. Thus, an IR spectrum of an organic
compound provides a unique fingerprint and is distinguished from spectra of other compounds.
Identification of an organic compound involves two steps:

i. Determine what functional groups are most likely present.

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ii. Detailed comparison of the spectrum of the unknown with the spectra of pure compounds
that contain all the functional groups found in the first step.

Polymer samples for IR analysis can have a variety of forms including thin film, solution, or
a pellet containing a mixture the granulated polymer and IR-transparent powder such as potassium
bromide.

Materials:

HDPE resin, PP resin and unknown film

Instrument:

IR spectrometer Perkin Elmer 1310

Procedure:

a. Sample Preparation:
1. Prepared using KBr disk.
a) Weught about 1gm solid sample (plastics resin/powder) and grind by using agate mortat
and pestle until it become powdered.
b) Mix the sample and powdered KBR in agate mortar for ratio 1:80 and grind the mixture
until homogeneous.
c) The mixture nust be finely ground. Or the mixture will scatter the infrared radiation
excessively.
d) Clean die set with ethanol.
e) Put the mixture of benzoic acid and KBR into the die set. Make sure the mixture fills
the surface of the die set. Tightly close the die set and put it into Hydraulic Press gauge.
Tighten the Hydraulic press gauge.
f) Press the hydraulic press gauge until the pressure goes to 7000 psi.
g) Release the air and let it rest for 2 minutes.
h) Press the hydraulic press gauge again until the pressure goes to 8500 psi and let it rest
for about 1 minute. Release the pressure.
i) Slowly remove the die set form the Hydraulic Press Gauge.
j) Put the KBR pellet into the pellet holder for further analysis.

b. Software setup
1. Select program ‘EZOMNIC’.
2. For solid or pellet sample, smart performer is used.
3. Select icon ‘COLLECT’ and chose ‘EXPERIMENT SETUP’
4. Check the data appear in the window.
a. No of scan : 32
b. Resolution : 4

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c. Final format: Transmittance, Absorbance

d. File handling: Save interferograms
e. Background handling: Collect background for every sample
5. Click ‘SAVE’ and ‘OK’
6. Select ‘COLLECT’ and click ‘COLLECT SAMPLE’
7. Type the title of the experiment then click ‘OK’
8. Click GE plat (sample holder)
9. Put the sample onto the smart performer and bring down the measurement pin onto the
sample at 10µm.
10. Click ‘OK’ and ‘YES’.
11. Automatically, the graph is plotted after several readings.
12. Save and print the data.
13. Analyze the results.

Pre-Laboratory Questions

1. What type of electromagnetic radiation will be used in this experiment.

2. Explain why a background of spectrum must be run before obtaining the sample spectrum.
3. For Polycarbonate
i) Draw the molecular structure.
ii) Using the IR correlation chart provided, predict the location of three peaks you might
expect from IR spectrum.
iii) Indicate what bonds were responsible for all the peaks you identified in (i).

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Experiment 4

Differential Scanning Calorimeter

Objective:

To determine glass transition temperature (Tg), melting temperature (Tm) and percent of
crystallinity of unknown sample

Introduction:

Differential Scanning Calorimetry (DSC) is a thermal analysis technique which has already
been used for several decades. It is applicable to a variety of materials including polymers,
pharmaceuticals, foods and inorganic. DSC measurement provides qualitative and quantitative
information as a function of time and temperature regarding transition in materials that involve
endothermic and exothermic processes, or changes in heat capacity. Some of the advantages
contributing to the widespread usage of DSC are the ease of sample preparation, the applicability
to solids and liquids, fast analysis time and wide temperature range.

In DSC, the difference in heat flow between a sample and inert reference is measured as a
function of time and temperature as both the sample and reference are subjected to a controlled
environment (pressure, purge gas). The degree of crystallinity, χ, is determined from the ratio of
the heat of fusion of a polymer sample, ΔHsc, and the enthalphy of fusion of a 100% crystalline
sample ΔHc.

𝛥𝐻𝑠𝑐
𝜒 =
𝛥𝐻𝑐

Material:

High density polyethylene (HDPE), unknown film

Instrument:

Perkin Elmer DSC7

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Procedure:

1. Weight about 5-10 mg sample into the aluminium pan using an analytical balance. Record the
exact mass of the sample.
2. Placed the sample in the DSC sample holder on the left side. Another pan on the right side is
leaving empty for references.
3. Open the software (Jade DSC)
4. Open METHOD EDITOR SAMPLE FILE NAME BROWSE SAVE
5. Open the INITIAL STATE INFO, setting the parameter:
● Temperature range : 20 – 300oC
● Heat flow : 20oC/min
● Flow of nitrogen : 30mL/min
6. Click INSTRUMENT VIEW APPLY START BUTTON
7. Graph analysis
● Rescale the graph using display function
● On calculate function, click peak area
● Tick onset and end peak height
● Click calculate

Pre-Laboratory Questions

1. Define thermal analysis.

2. State the properties measured by DSC during temperature scan process.
3. Discuss the two (2) types of DSC.

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DATASHEET EXPERIMENT 1

PAPER CHROMATOGRAPHY

Name: Date:

Student ID: Group:

Table 1.1: Tabulated data of color spot

Food Colour Blue Green Yellow Red

Number of
components

Colour of spot(s)

Distance traveled
by spot

Distance traveled
solvent front

Retention factor
(Rf)

Lecturer’s signature:

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DATASHEET EXPERIMENT 2

UV VISIBLE SPECTROSCOPY

Name: Date:

Student ID: Group:

Name and model of instrument:

Table 2.1: Table of concentration and absorbance

Solution Concentration (ppm) Absorbance

Standard 1

Standard 2

Standard 3

Standard 4

Unknown

Mass of KMnO4: λmax:

Unknown concentration:

Lecturer’s signature:

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DATASHEET EXPERIMENT 3

FTIR SPECTROSCOPY

Name: Date:

Student ID: Group:

Name and model of instrument:

Name of compound analysed:

Molecular formula of compound analysed:

FTIR SPECTRA :

Lecturer’s signature:

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DATASHEET EXPERIMENT 4

DIFFRENTIAL SCANNING CALORIMETRY

Name: Date:

Student ID: Group:

Name and model of instrument:

Table 4.1: Tabulation data of sample 1

Sample name

Weight

Heating Rate

Tg (Glass transition temperature)

Tm (Melting Temperature)

ΔHf (Heat of Fusion)

Tc (Crystallion temperature)

Lecturer’s signature:

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