CCB 4423

Polymer Process Engineering

LABORATORY MANUAL
Chemical Engineering Dear!men!"
Ban#ar $eri %s&an#ar" 3'()* Tronoh"
Pera&
%n!ro#+c!ion
The experiments described in this booklet are designed to introduce some fundamental
aspects of polymer engineering.
$a,e!y
During lab, all the time you must comply with safe working practices. You should refer to
MSDS provided for information on handling the chemicals used in this lab.
hen you plan your experiment take care to avoid any unduly ha!ardous
procedure.
Safety glasses must be worn at all times in the laboratory.
"ating, drinking and smoking are not allowed in the laboratory.
alkways between benches and machinery should be kept clear and free from
obstruction.
#lassware should be cleaned and put away as soon as possible after use.
Many of the chemicals used in the polymer chemistry laboratories are ha!ardous and
some are extremely toxic. The procedures provided in MSDS should be adhered to when
handling ha!ardous substances. $f in doubt, consult the technician. %lways wear gloves
and use a fume cupboard when handling with toxic materials.
&efore storing samples 'e.g. monomers, polymers, etc( you must label them properly with
both your name and the name of the substance.
E-PER%MENT '. /el !ime #e!ermina!ion o, reac!ing !hermose!!ing resins
'0 %n!ro#+c!ion
This experiment is designed to help student to understand the process of curing in
forming thermosetting resins. #el time is one of the important parameters in this curing
process. Different ratios 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.
20 Theory
"poxy 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. ith
amines, the reaction involves through opening of the epoxide rings giving *)hydroxy
amino. %mines 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 skin)
sensitive.
#el +oint
#el time is the time re,uired for a li,uid material to form gel under specified conditions
of temperature. The detail procedure to determine gel time should be referred to %STM
D-./0)1..
%ctivation "nergy
The reaction kinetics of epoxy resins can be studied using differential scanning calorimeter
'DS2(. The basic assumption in the kinetic study using DS2 is the heat flow relative to the
instrumental base line is proportional to the reaction rate. $t 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 e,uation3
c
t
H
H
p

=
'0(
here 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(.
&y integrating e,uation '0( the rate of reaction, r is defined as3

= =
dt
dH
H dt
dp
r
t
c
0
'-(
Calculation of Activation Energy, Ea from the Isothermal Reaction Kinetics of epoxy
resin.
ithout knowing the exact reaction mechanism, it is assumed that the reaction rate, dp4dt
at a given temperature is only dependent on the degree of conversion, 'p(.
The basic e,uation for the kinetic study can be written as3
( ' p kf
dt
dp
=
'5(
here k is the %rrhenius rate constant. $n this approach the reaction mechanism does not
change during the reaction process and e,uation '5( has the same form, for the same
degree of conversion, regardless of temperature. &y integrating e,uation '5( from a
reaction time of t 6 7 where p 6 7 to a reaction time t with a conversion p, then e,uation
'5( is reduced to3

t
kdt
7
6

p
p f
dp
7
( '

8or a given p, dp f!p" is a constant '2( at any given temperature.
Therefore,
kt 6 2 '.(
",uation '.( 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 %rrhenius law3
R#
E
A
e k k

=
7
'9(
&y substituting e,uation '9( in e,uation '.( and taking logarithms on both sides, yields
the following
A
R#
E
t
a
+ = ln ':(
here Ea is the activation energy 'k; mol
)0
(, A is a constant that is the sum of the
logarithm of the constant C of e,uation '.( and the logarithm of the fre,uency factor k7,
and R is the gas constant, <.509 ; =
)0
mol
)0
. 8rom e,uation ':(, a plot of the logarithm of
the time needed to reach a conversion p versus the inverse of reaction temperature, 04#c
will be linear with a slope Ea4R. This e,uation was used to follow the activation energy
during the reaction of the unmodified and modified epoxy systems.
The above e,uation ':(, 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, #.
30 Proce#+re
a. 2onduct two experiments to determine the gel time between epoxy "+>?%M 97
with molecular weight, Mw ) /77 #4mol and diamine with M ..< g4mol.
i. The ratio of difunctional epoxy4diamine is -74:.. 'wt4wt(.
ii. The ratio of difunctional epoxy4diamine is -74< 'wt4wt(.
b. 2onduct two experiments to determine gel time at different temperatures for one
of the pair of epoxy)amine '-74:.. 'wt4wt( above to see the effect of temperature
on gel time.
i. @eaction temperature is -9A2 'room temperature(
ii. @eaction temperature is 59A2
iii. @eaction temperature is 97A2
The detailed procedure to determine gel time should be referred to %STM D-./0)1.
40 Res+l! an# Disc+ssion
..0 @eport the relevant information as stated in %STM D-./0)1..
..- 'a( 2ompare the gel time for different ratio of epoxy4amine system. "xplain the
result obtained.
'b( 2ompare the gel time for the same pair of epoxy)amine at different
temperature. "xplain the results obtained.
..5 2alculate theoretical amount 'B mol( of epoxy that has reacted at gel point.
... The gel time)temperature profile follows an %rrhenius relationship.
..9 8rom ..- 'b(, calculate the activation energy using the e,uation 3
a. ln t gel 6 C C
R#
E
a
b. Dote 3 y 6 ax C b
i. y 6 ln t gel
ii. x 6 04T
iii. a 6 "a4@
c. hat is the importance of gel point 't gel( from processing point of viewE
..: rite the chemical reaction that take place between epoxy and amine.
../ #ive one compound beside amine that can be used as a crosslinker. "xplain how
this compound will react and form a network system.
..< #ive T> '-( examples of applications and discuss why epoxy resin is proffered
as compared to polyester or other polymers.
..1 "xplain the different between crosslink and network polymers
E-PER%MENT 2. $ol+1ili!y #e!ermina!ion o, !hermose!!ing an# !hermolas!ic
olymers0
'0 %n!ro#+c!ion
This experiment is designed to help student to understand the solubility of polymer in
solvent from thermodynamic point of view. Different types of polymers are mixed with
different types of solvents to see their solubility in each other.
20 Theory
The solubility parameter 'of a polymer(, F, is a thermodynamic parameter, which is a
characteristic of a polymer used in predicting the solubility of that polymer in a given
solvent.
F 6
$
% d

Dotes3 d 6 specific density

M 6 molecular weight
# 6 molar attraction coefficient by Goy or Small
30 Proce#+re
Mix the polymer with the solvent as shown in the table 0. Take -)5 pellets and mix it
with 9 ml of solvent. Shake the mixture for a few minutes and observe whether the
polymer is partially soluble, completely soluble or not soluble. 2hange the solvent and
repeat the experiment. "ach polymer should be tested with all the solvents given.
Table 03 ?ist of polymers and solvent used
Polymer $ol2en!
"poxy 2yclohexane
+olycarbonate Toluene
+olystyrene Gexane
+olyethylene %cetone
+olypropylene Methanol
+olysulfone "thanol
Dichloromethane
2hloroform
30 Res+l!s
5.0 @eport the solubility of each pair of polymer and solvent
5.- 2alculate the solubility parameters of the above polymer using group contribution
techni,ueH choose either Goy or Small methods.
5.5 "xplain your observations4results from thermodynamic point of view.
5.. hat is the relationship between solubility parameter and phase separationE
5.9 #ive >D" example of the application where the knowledge the solubility parameter
is re,uired. "xplain your answer.
E-PER%MENT 3. Comosi!e
'0 %n!ro#+c!ion
This experiment is designed to help students to understand the concept of composite
material and to ac,uire knowledge on the formation of composite material and to relate
the effect of curing temperatures on mechanical properties of composite.
2omposite 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. 2omposites are made from matrices of epoxy,
unsaturated polyester and some other thermosets, and a few thermoplastics. The
reinforcements are glass, graphite, metal and ceramic.
Gand lay)up is an open contact molding in one)sided moldsH the lowest)cost and most
common processes for making fiberglass composite products and is the most common
method of producing composites materials.
%lthough epoxy resins are very attractive due to their high strength, stiffness, high
temperature resistance, low volatility and good adhesion to metal and ceramic, however
as organic polymers, they are very vulnerable to the absorption of surrounding media of
either li,uid 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.
20 Proce#+re
The mold 'glass( is first waxed.
2ut the fiber glass mat and lay - pieces of fiber glass mat into the mold.
Mix epoxy with molecular weight "+>?%M 97, Mw ) /77 g4mol and
diamine with M ..< g4mol until gel time is reached.
o The ratio of difunctional epoxy4diamine is -74:.. 'wt4wt(.
+our the epoxy resin onto the fiber glass and flat the composite using
roller and wait around 07 minutes.
2ut the composite into dimensions of 97 mm x 97 mm x 5 mm. '+repare at
least . samples for two different curing temperatures(.
%llow two sample to react 'cure( at room temperature for -. hour and
another two to react 'cure( at 0-7A2 for - hours in the oven. These
samples will be used for water absorption.
20' 3a!er a1sor!ion
The percentage of water absorption is characteri!ed using gravimetric method.
%ll samples must be polished to ensure a flat surface.
>btain their initial weights at room temperature.
Measure the dimensions of each sample, average of thickness, length and
width at room temperature before immersion. Measure again after 0 week
of immersion in water.
$mmerse the samples in water at room temperature and 97A2 and then
periodically remove from the water bath, wipe with tissue paper, and
weigh before immersing the samples again. These steps are to be repeated
for one week period
The amount of water absorbed by the sample is then calculated using the
following e,uation
Mt 'B( 6
7
7
&
& &
t

x 077
Mt is water content at any given time, t is sample weight at the time of
measurement, o is initial sample weight.
30 Res+l!
0. rite down your observations. "xplain how the curing temperature my affect the
water absorption of epoxy resin.
-. "xplain how the arrangement of fibers can affect the modulus and strength of
composite materials.
5. "xplain how the curing temperature may affect the water absorption and other
mechanical properties.
.. Ising the literature values, obtain the density and modulus for D#"&% epoxy
resin and fiber glass '")#lass(. 2alculate the theoretical modulus of your
composite sample 'using the known volume, and known density of epoxy,
calculate the theoretical weight of epoxy without fibers.(
9. hat are the advantages of using thermoset as matrix as compared to
thermoplasticE
:. hich one is more suitable for making aircraft body, epoxy4glass or epoxy4carbon
fibersE "xplain your answer.
/. #ive >D" application of composite material based on glass, carbon and aramide
fibers. "xplain your answer.
E-PER%MENT 4. %n4ec!ion Mol#ing Machine
'0 %n!ro#+c!ion
This experiment is designed to help student to be familiar with inJection molding
machine.
$nJection molding is one of the most common methods of shaping plastic resins.
$nJection Molding Machine
20 Proce#+re
0. "nsure all the safety devices are operational and aware the EMERGENCY STOP
button.
-. Switch >n the 2hiller Init. Make sure that cooling and water pump indicator is in
>D position.
5. @elease @"S"T button and switch on menu screen.
.. Set the re,uired temperature and press >D heater key.
9. ait until re,uired temperature raised as displayed on menu screen.
:. 8ill polymer 'polyethylene and polypropylene( into the hopper.
/. 2lose the safety gate.
<. +ress the M>I?D 2?>S" key until the mould is locked up.
1. +ress the D>KK?" %DL%D2" key until the no!!le presses tight against the
mould.
07. Move the sensing ring until it is sensed by the no!!le forward proximity switch.
00. +ress the 2G%@#" key to fill polymer in the screw position. The screw will turn
and retract until the re,uired position.
0-. +ress the $D;"2T key to fill the mould cavity and wait for cooling process.
0-. +ress the M>I?D >+"D key until the mould is completely open.
05. +ress the ";"2T>@ %DL%D2" key twice to eJect the inJection product.
0.. "xamine the inJection product. %ccording to the surface defects etc. adJust the
pressure, stroke, time and temperature as needed.
09. @epeat the above procedure until the part is satisfactory.
0:. +ress S"M$ %IT> or %IT> >+"@%T$>D key for continuous inJection.
0/. +ress @"S"T button to SGIT D>D the system.
0<. Switch off the isolator and D> the 2?"%D$D# +@>2"SS.
30 Res+l!
5.0 "xplain the principle of inJection molding machine.
5.- 2an we mix polymer % and +olymer & to produce a polymer &lend %&E "xplain your
answer.
E-PER%MENT ). Uni2ersal Tes!ing Machine
'0 %n!ro#+c!ion
This experiment is designed to help student to be familiar with universal testing machine.
Iniversal testing machine is used to test the tensile and compressive properties of
materials.
Schematic diagram of a tensile test
20 Proce#+re
0. Switch >D power system.
-. +ress safe line yellow button until light is off.
5. Machine will start up and at machine controller keyboard press M%N button to
establish open access.
.. Select M&N for remote control program.
9. Start up the computer system and select D"OY#"D software, after that select M?r
?rx 2onsoleN.
:. Display monitor at machine controller keyboard must display MInder control of
remote computerN. 8rom now the gripper frame can control from computer
'console(.
/. 8rom Dexygen program, go to "D$T, select $nsert Dew Test and select sample
type 'plastics, rubber, metals or etc.(.
<. Select either 2ompression Setup or Tensile Setup.
1. 8ill in the dimension or specification of the sample.
07. $nsert the specimen '+", ++, composite( to gripper frame.
00. Select !ero M7N for !eroing the ?oad and Stroke. Start the test by selecting the
MStart TestN.
0-. The machine is now under running condition and will stop automatically after
fracture detected.
05. Switch off +>"@ and D> the 2?"%D$D# +@>2"SS.
30 Res+l!
5.0. +lot the curve of Stress vs Strain.
5.- 2alculate the tensile at yield, tensile strength and modulus of the polymer samples.
2ompare the results and explain the difference.
5.- "xplain the phenomenon of necking from molecular point of view during the
experiment.
5.5 "xplain the significance of tensile strength, tensile at yield, modulus and elongation at
break from engineering point of view.
5.. Gow do you relate the tensile test or area under the curve with the energy re,uired to
break the sampleE
E-PER%MENT 5. Di,,eren!ial $canning Calorime!er 6D$C7
+olypropylene '++( was analy!ed for thermal transitions using differential scanning
calorimeter 'DS2( in the temperature range from )97A2 to -77A2. The DS2 thermogram
is shown below.
8igure 0. Thermal transition of polypropylene '++( with heating rate -7A24min
0( 8rom 8igure 0, what kind of thermal transitions will you observe if the sample is
++ polymerE +lease indicate on the curve these transitions.
-( "xplain why the thermal transition in 8igure 0 'range temperature from )97A2)
7A2( is not clearE
5( 2an we get clear thermal transition 'range temperature from )97A2)7A2( by using
dynamic mechanical analysis 'DM%( instead of differential scanning calorimeter
'DS2(E "xplain your answer.
.( "xplain the concept of DS2 and DM%
9( "xplain the process of exothermic and endothermic in DS2 thermogram.