CCB 4423

Polymer Process Engineering

LABORATORY MANUAL

Chemical Engineering Department,

Bandar Seri Iskandar, 31750 Tronoh,
Perak

Introduction
The experiments described in this booklet have been designed to introduce sine
fundamental aspect of polymer engineering.
Safety
At all time you must comply with safe working practices. You should refer to MSDS
provided for information on handling the chemicals used in this lab.

When you plan your experiment take care to avoid any unduly hazardous
procedure.

Safety glasses must be worn at all times in the laboratory.

Eating, drinking and smoking are not permitted in the laboratory.

Walkways between benches and machinery should be kept clear and free from
obstruction.

Glassware should be cleaned and put away as soon as possible after used.

Many of the chemicals to be used in the polymer chemistry laboratories are hazardous
and some are highly toxic. The procedures provided in MSDS should be adhered to when
handling hazardous substances. If in doubt consult the technician. Always wear gloves
and use a fume cupboard when handling with toxic materials.
Before storing samples (e.g. monomers, polymers, etc) you must label them with both
your name and the name of the substance.

EXPERIMENT 1: Gel time determination of reacting thermosetting resins.

1. Introduction
This experiment is designed to help student to understand the process of curing in
forming thermosetting resins. Gel time is one of the important parameters in this curing
process. Different ratio of epoxy and amine are used to see the effect on gel time. The
experiments are also conducted at two different temperatures to see the effect of
temperature on gel time.
2. Theory
Epoxy or epoxide resins are those resins or polymers which are produced by
condensation reactions using an epoxy compound as an ingredient in the monomeric
reactant mixture. The curing or cross-linkage agents commonly in use are diamines. With
amines, the reaction involves through opening of the epoxide rings giving -hydroxy
amino. Amines are fast curing agent even at room temperature, they can react with
epoxide groups and form a good chemical resistance material but they are toxic and skinsensitive.
Gel Point
Gel time is the time required for a liquid material to form gel under specified conditions
of temperature. The detail procedure to determine gel time should be referred to ASTM
D2471-94.
Activation Energy
The reaction kinetics of epoxy resins can be studied using differential scanning calorimeter
(DSC).. The basic assumption in the kinetic study using DSC is the heat flow relative to
the instrumental base line is proportional to the reaction rate. It is also assumed that the
temperature gradient through the sample and the temperature difference between the
sample and reference are small.
.

The degree of conversion, p at any time (t) during isothermal reaction is given by the
following equation:
p

H t
H c

(1)

Where Ht is the heat of reaction after time t, during each isothermal experiment and Hc
is the heat of complete reaction obtained from dynamic curing (temperature-scan mode).
By integrating equation (1) the rate of reaction, r is defined as:
r

dp
1 dH t

dt H c dt

(2)

Calculation of Activation Energy, Ea from the Isothermal Reaction Kinetics of epoxy

resin.
Without knowing the exact reaction mechanism, it is assumed that the reaction rate, dp/dt
at a given temperature is only dependent on the degree of conversion, (p).
The basic equation for the kinetic study can be written as:
dp
kf ( p )
dt

(3)

where k is the Arrhenius rate constant. In this approach the reaction mechanism does not
change during the reaction process and equation (3) has the same form, for the same
degree of conversion, regardless of temperature. By integrating equation (3) from a
reaction time of t = 0 where p = 0 to a reaction time t with a conversion p, then equation
(3) is reduced to:
p

kdt
0

dp
f ( p)

For a given p, dp / f(p) is a constant (C) at any given temperature.

Therefore,
kt = C

(4)

Equation (4) shows that the rate constant k is inversely proportional to time for a given p
regardless of the f(p) at a given temperature.
The dependency of the reaction constant on temperature follows the Arrhenius law:

k k0e

EA
RT

(5)

By substituting equation (5) in equation (4) and taking logarithms on both sides, yields
the following
ln t

Ea
A
RT

(6)

where Ea is the activation energy (kJ mol-1), A is a constant that is the sum of the
logarithm of the constant C of equation (4) and the logarithm of the frequency factor k0,
and R is the gas constant, 8.315 J K-1 mol-1. From equation (6), a plot of the logarithm of
the time needed to reach a conversion p versus the inverse of reaction temperature, 1/Tc
will be linear with a slope Ea/R. This equation was used to follow the activation energy
during the reaction of the unmodified and modified epoxy systems.
The above equation (6), can be used to calculate the activation energy, Ea for epoxy
polymer or any polymer system by measuring the time taken, t, for the sample to gel at a
particular temperature, T.
3. Procedure
a. Conduct two experiments to determine the gel time between epoxy with
molecular weight EPOLAM 50, Mw - 700 G/mol and diamine with MW 448
g/mol.
i.

The ratio of difunctional epoxy/diamine is 20/6.4 (wt/wt).

ii.

The ratio of difunctional epoxy/diamine is 20/8 (wt/wt).

b. Conduct two experiments to determine gel time at different temperatures for one
of the pair of epoxy-amine (20/6.4 (wt/wt) above to see the effect of temperature
on gel time.
i.

Reaction temperature is 25C (room temperature)

ii.

Reaction temperature is 35C

iii.

Reaction temperature is 50C

The detail procedure to determine gel time should be referred to ASTM D2471-94
4. Result and Discussion
4.1 Report the relevant information as stated in ASTM D2471-94.
4.2 a. Compare the gel time for different ratio of epoxy/amine system. Explain the result
obtained.
b. Compare the gel time for the same pair of epoxy-amine at different temperature.
Explain the result obtained.
4.3 Calculate theoretical amount (% mol) of epoxy that has reacted at gel point.
4.4 The gel time-temperature profile follows an Arrhenius relationship.
From 4.2 (b), calculate the activation energy using the equation :
ln t gel = C +

Ea
RT

Note : y = ax + b
y = ln t gel
x = 1/T
a = Ea/R

4.5 What is the important of gel point (t gel) from processing point of view?
4.6 Write the chemical reaction that take place between epoxy and amine.
4.7 Give one compound beside amine that can be used as a crosslinker. Explain how this
compound will react and form a network system.

4.8 Give TWO (2) examples of applications and discuss why epoxy resin is proffered as
compared to polyester or other polymers.
4.9 Explain the different between crosslink and network polymers

EXPERIMENT 2: Solubility determination of thermosetting and thermoplastic

polymers.
1. Introduction
This experiment is designed to help student to understand the solubility of polymer in
solvent from thermodynamic point of view. Different types of polymer are mixed with
different types of solvent to see their solubility in each other.
2. Theory
The solubility parameter (of a polymer), , a thermodynamic parameter, which is a
characteristic of a polymer used in predicting the solubility of that polymer in a given
solvent.
=

d G
M

Notes : d

= specific density

= molecular weight

= molar attraction coefficient by Hoy or Small

3. Procedure
Mix the polymer with the solvent as shown in the table 1. Take 2-3 pellets and mix it
with 5 ml of solvent. Shake the mixture for a few minutes and observe whether the
polymer is partially soluble, completely soluble or not soluble. Change the solvent and
repeat the experiment. Each polymer should be tested with all the solvent given.

Table 1: List of polymers and solvent used

Polymer
Epoxy
Polycarbonate
Polystyrene
Polyethylene
Polypropylene
Polysulfone

Solvent
Cyclohexane
Toluene
Hexane
Acetone
Methanol
Ethanol
Dichloromethane
Chloroform

3. Result
3.1 Report the solubility of each pair of polymer and solvent
3.2 Calculate the solubility parameters of the above polymer using group contribution
technique; choose either by Hoy or Small methods.
3.3 Explain your observation/results from thermodynamic point of view.
3.4 What is the relationship between solubility parameter and phase separation.
3.5 Give ONE example of the application where the knowledge the solubility parameter
is required. Explain your answer

EXPERIMENT 3: Composite
1. Introduction

This experiment is designed to help student to understand the concept of composite

material and to acquire knowledge on the formation of composite material and to relate
the effect of curing temperatures on mechanical properties of composite.
Composite is defined as a material composed of two or more different materials, with the
properties of the resultant material being superior to the properties of the individual
materials that make up the composite. Composites are made from matrices of epoxy,
unsaturated polyester and some other thermosets, and a few thermoplastics. The
reinforcements are glass, graphite, metal, ceramic.
Hand lay-up is an open contact molding in one-sided molds are the lowest-cost and most
common processes for making fiberglass composite products and is the most common
method of producing composites materials.

Although epoxy resins are very attractive due to their high strength, stiffness, high
temperature resistance, low volatility and good adhesion to metal and ceramic, as organic
polymers, they are very vulnerable to the absorption of surrounding media of either liquid
or gasses which can diffuse into the polymer matrix causing a reduction of their
mechanical properties. Therefore, determination of water absorption will be carried out.
2. Procedure

2. Procedure
The mold (glass) is first waxed.
Cut the fiber glass mat and lay 2 pieces of fiber glass mat into the mold.
Mix epoxy with molecular weight EPOLAM 50, Mw - 700 g/mol and
diamine with MW 448 g/mol until gel time is reached.
o The ratio of difunctional epoxy/diamine is 20/6.4 (wt/wt).
Pour the epoxy resin onto the fibre glass and flat the composite using
roller and wait around 10 minutes.
Cut the composite into dimensions of 50 mm x 50 mm x 3 mm. (Prepare at
least 4 samples for two different curing temperatures).
Allow two sample to react (cure) at room temperature for 24 hour and
another two to react (cure) at 120C for 2 hours in the oven. These
samples will be used for water absorption

2.1 Water absorption

The percentage of water absorption is characterized using gravimetric method.
All samples must be polish to ensure a flat surface
Obtain their initial weights at room temperature.
Measure the dimension of each sample, average of thickness, length and
width at room temperature before immersion. Measure again after 1 week
immersion in water.
Immerse the samples in water at room temperature and 50C and then
periodically remove from the water bath, wipe with tissue paper, and
weigh before immersing the samples again. These steps to be repeated for
one week period
The amount of water absorbed by the sample is then calculated using the
following equation

Wt W0
x 100
W0
Mt is water content at any given time, Wt is sample weight at the time of

Mt (%) =

measurement, Wo is initial sample weight.

3. Result
1. Write down your observation. Explain how the curing temperature my affect the water
absorption of epoxy resin.
2. Explain how the arrangement of fiber can affect the modulus and strength of composite
materials.
3. Explain how the curing temperature may affect the water absorption and other
mechanical properties.
4. Using the literature values, obtain the density and modulus for DGEBA epoxy resin
and fiber glass (E-Glass). Calculate the theoretical modulus of your composite
sample.(using the known volume, and known density of epoxy, calculate the
theoretical weight of epoxy without fibers.)
5. What are the advantages of using thermoset as matrix as compared to thermoplastic?
6.

Which one is more suitable for making aircraft body, epoxy/glass or epoxy/carbon
fibers? Explain your answer.

7. Give ONE application of composite material based on glass, carbon and aramide
fibers. Explain your answer.

EXPERIMENT 4: Injection Molding Machine

1. Introduction

This experiment is designed to help student to be familiar with injection molding

machine.
Injection molding is one of the most common methods of shaping plastic resins.

Injection Molding Machine

2. Procedure
1. Ensure all the safety devices are operational and aware the EMERGENCY STOP
button
2. Switch On the Chiller Unit. Make sure cooling and water pump indicator is in ON
position
3. Release RESET button and switch on menu screen.
4. Set the require temperature and press ON heater key
5. Wait until required temperature raised as displayed on menu screen
6. Fill polymer ( polyethylene and polypropylene) into the hopper
7. Close the safety gate
8. Press the MOULD CLOSE key until the mould is locked up
9. Press the NOZZLE ADVANCE key until the nozzle presses tight against the
mould
10. Move the sensing ring until it is sensed by the nozzle forward proximity switch
11. Press the CHARGE key to fill polymer in the screw position. The screw will turn
and retract until the
required position.

12. Press the INJECT key to fill the mould cavity and wait for cooling process
12. Press the MOULD OPEN key until the mould is completely open.
13. Press the EJECTOR ADVANCE key twice to eject the injection product
14. Examine the injection product. According to the surface defects, etc. adjust
pressure,
stroke, time and temperature as needed.
15. Repeat the above procedure until the part is satisfactory
16. Press SEMI AUTO or AUTO OPERATION key for continuous injection.
17. Press RESET button to SHUT DOWN the system.
18. Switch off the isolator and DO the CLEANING PROCESS
3. Result
3.1 Explain the principle of injection molding machine.
3.2 Can we mix polymer A and Polymer B to produce a polymer Blend AB. Explain your
answer.

EXPERIMENT 5: Universal Testing Machine

1. Introduction

This experiment is designed to help student to be familiar with universal testing machine.
Universal testing machine is used to test the tensile and compressive properties of
materials.

Schematic diagram of a tensile test

2. Procedure
1. Switch ON power system
2. Press safe line yellow button until light off
3. Machine will starting up and at machine controller keyboard press A button to
establish open access
4. Select B for remote control program
5. Start up the computer system and select NEXYGEN software, after that select Lr
Lrx Console
6. Display monitor at machine controller keyboard must display Under control of
remote computer. From now the gripper frame can control from computer
(console).
7. From Nexygen program, go to EDIT, select Insert New Test and select sample
type (plastics, rubber, metals or etc.)
8. Select either Compression Setup or Tensile Setup

9. Fill in the dimension or specification of the sample.

10. Insert the specimen ( PE, PP, composite) to gripper frame.
11. Select zero 0 for zeroing the Load and Stroke. Start the test by select the Start
Test
12. The machine now under running condition and will stop automatically after
fracture detected.
13. Switch off POWER and DO the CLEANING PROCESS
3. Result
3.1. Plot the curve of Stress vs Strain
3.2 Calculate the tensile at yield, tensile strength and modulus of the polymer samples.
Compare the results and explain the difference.
3.2. Explain the phenomenon of necking from molecular point of view during the
experiment.
3.3 Explain the significance of tensile strength, tensile at yield, modulus and elongation
at break from engineering point of view.
3.4 How do you relate the tensile test or area under the curve with the energy required to
break the sample.

EXPERIMENT 6: Differential Scanning Calorimeter (DSC)

Polypropylene (PP) was analyzed for thermal transitions using differential scanning
calorimeter (DSC) in the temperature range from -50C to 200C. The DSC thermogram
is shown below.

Figure 1. Thermal transition of polypropylene (PP) with heating rate 20C/min

1). From Figure 1, what kind of thermal transitions will you observe if the sample is PP
polymer. Please indicate on the curve these transitions.
2) Explain why the thermal transition in Figure 1 (range temperature from -50C-0C) is
not clear?
3) Can we get clear thermal transition (range temperature from -50C-0C) by using
dynamic mechanical analysis (DMA) instead of differential scanning calorimeter (DSC)?
Explain your answer.
4) Explain the concept of DSC and DMA
4) Explain the process of exothermic and endothermic in DSC thermogram.