KIT 254 (POLYMER) 2008/2009

BY
DR. COSWALD STEPHEN SIPAUT @ MOHD NASRI
ROOM NO. 124, SCHOOL OF CHEMICAL SCIENCES, USM
TOPICS LECTURE
DATE
(TENTATIVE)
1. BASIC INTRODUCTION OF POLYMERISATION IONIC
POLYMERISATION
a. ANIONIC POLYMERISATION (INCLUDES:
MECHANISM, KINETICS AND FACTORS
AFFECTING ANIONIC POLYMERIZATION)
b. CATIONIC POLYMERIZATION
(INCLUDES: MECHANISM AND KINETICS)
2. CROSSLINKING OR NETWORK FORMATION IN
POLYMERS AND THEIR APPLICATIONS
3. POLYMER CHARACTERIZATIONS
a. MOLAR MASS
b. GEL PERMEATION CHROMATOGRAPHY
c. DILUTE SOLUTION VISCOSITY
4. BASIC INTRODUCTION ON PHYSICAL AND
MECHANICAL PROPERTIES
a. GLASS TRANSITION TEMPERATURE
b. CRYSTALLINE AND MELTING
TEMPERATURE
c. MECHANICAL PROPERTIES OF POLYMER
TEST
LECTURES:11 HOURS TUTORIAL: 1 HOURS
TEST: 1 HOUR
ONE ASSIGNMENT = 100 % ONE TEST = 100 %
CHE SU = 15 % and DR. COSWALD = 15 %
Total = 30 %
1
BASIC INTRODUCTION OF POLYMERIZATION
COMMON TECHNIQUES FOR POLYMERIZATION
1. Solution polymerization
2. Bulk polymerization
3. Suspension polymerization
4. Emulsion polymerization
All techniques can either used free radical or ionic polymerization method.
IONIC POLYMERIZATION
2 types : i) Cationic (active centre, +ve charge)
ii) Anionic (active centre, -ve charge)
Ionic polymerization is monomer selective compare to radical polymerization.Ionic
polymerization only can occur with a monomer having side group that stabilized the
active group.
Active centre for cationic monomer
(polymerization will occur if the side group (X) is electron donor or can delocalize +ve
charge)
C C
H
H
X
H
SIDE GROUP
ACTIVE CENTRE
Active centre for anionic monomer
(polymerization will occur if the side group (X) is electron acceptor or can delocalize -ve
charge)
C C
H
H
X
H
However, not all monomer can be polymerized using both types of this ionic
polymerization.
2
Table 1: Susceptibility of various types of monomers to free-radical, cationic and anionic
polymerization
Monomer Structure Free-radical Cationic Anionic
Ethylene CH
2
= CH
2
√ √ x
1-Alkyl olefins + CH
2
= CHR
1
(x) (x) x
1,1-Dialkyl olefins CH
2
= CR
1
R
2
(x) √ x
1,3-Dienes
CH
2
= CH – CR =
CH
2
√ √ √
Styrene, α-methyl
styrene
CH
2
= CRPh √ √ √
Vinyl halides CH
2
= CHX √ x (x)
Vinyl esters CH
2
= CHOCOR
1
√ x (x)
Vinyl ethers CH
2
= CHOR
1
(x) √ x
Acrylates,
methacrylates
CH
2
= CRCOOR
1
√ x √
√ means susceptible, x means not susceptible, and (x) indicates that whilst the monomer
might be expected to polymerize (e.g. on the basis of inductive and/or mesomeric effects)
it does not do so successfully because of side-reactions (e.g. chain transfer)
R
1
and R
2
= alkyl, R = H or CH
3
, Ph = phenyl, and X = halogen
+ Also called α-olefins
Note that: Styrene and Diene monomer can be polymerized using both anionic and
cationic as well as free radical polymerization:
i) the monomer side group have significantly lower inductive effects.
ii) side group can delocalized both charges.
Differences between free radical polymerization and ionic polymerization.
i. Rate of polymerization for ionic faster compare to radical.
ii. In the propagation step, ionic active centre must couple with different charge
counter-ion,
iii. Rate and stereochemistry for ionic : the propagation depends on counter-ion
and degree of active centre formation.
iv. For ionic polymerization, termination by 2 active chains could not occur
compared to free radical polymerization.
v. R
p
and X
n
(degree of polymerization) for ionic highly dependent on the solvent
used.
3
ANIONIC POLYMERIZATION
 Active centre –ve
 Monomer side group, x = e- acceptor and delocalized –ve charge
 Normally occur for monomer conmtaining strong electronegative side group.
(forming carbonion). e.g. side group : benzene
 E.g:
NH
2
-
CH
2
CH + NH
2
CH
2
CH
-
karbonion

solvent requirement
Mechanism
1. Initiation
a) Formation of ionic initiator
- butyl lithium + solvent (dioxane)
CH
3
CH
2
CH
2
CH
2
Li +
O
O
CH
3
CH
2
CH
2
CH
2
-
O
O
O
O
+
Li
=
R Li
karbonion
@
R
-
4
b) monomer activation (formation of active centre)
R
-+
Li
+ CH
2
CH
k
i
RCH
2
CH
Li
O
O
O
O
RM Li
5
2. Propagation
RM Li + M RM
2
Li
k
p
R CH
2
CH Li
O
O
O
O
+ CH
2
CH
R CH
2
CHCH
2
CH Li
O
O
O
O
k
p
6
3. Termination

methanol often used
C
H
Li
O
O
O
O
+ CH
3
OH
CH
2
+ LiOCH
3
Kinetic scheme
R Li M RM Li
k
i
+
………………initiation
RM Li
nM RM
n
Li
k
p
+
……………..propagation
RM
n
Li
RM
n
k
t
+ CH
3
OH
LiOH
3
+
…………….termination
7
Rate of polymerisation = R
p
R Li
=
& RM
n
Li = P
-
I
1) Initiation rate = Active centre formation rate
] I [ ] M [ k
dt
] M [ d
i
·


2) Propagation rate = R
p
] M [ ] P [ k
dt
] M [ d
p

·
3) Termination rate = rate of disappearance of active centre

] OH CH [ k
] M [ ] I [ k
] P [
3 t
i
·

] M [ ] P [ k R
p p

·
] OH CH [ k
] M [ ] I [ k k
R
3 t
2
p i
p
·
Degree of polymerisation =
n X
rate initiation
tion polymerisa of rate
Xn ·
on terminati of rate
n propagatio of rate
Xn ·
] OH CH [ k
] M [ k
X
3 t
p
n ·
Factors affecting anionic polymerization
8
1. Temperature
RT E
exp A k

·
- Discussed in term of activation energy
2. counter-ion
Butyl lithium ≈
Ce Rb K Na Li M →


Li : the smallest counter-ion
Ce : the biggest counter-ion
∴the smallest the counter-ion, therefore the smallest the separation between
monomer and counter-ion, so activation energy increases

R
p

And vice-versa.
3. Solvent
- Solvent gives significant contribution in the R
p
for ionic polymerization.
- ∴selection of solvent is a critical. Depends on particular system.
- Solvent e.g. dioxane normally used because it will not allowing the R
p
to be
depending on [M] @ [I]
- Whereby, solvent such as THF (tetrahydrofuran) allows the R
p
to be
dependent on [M] & [I]
If the THF were used, it will form both carbonion and free cation.
e.g.: styrene polymerisation, BuLi

] P [
+ −

d
i
s
t
a
n
9
Bu M
C
H
X
Li
P
P
c
e

b
e
t
w
e
e
n

c
o
u
n
t
e
r
-
i
o
n

a
n
d

m
o
n
o
m
e
r

s
m
a
l
l
e
r
10
C
H
X
Li
P
P
P
P
] P [


Distances between counter-ion and monomer bigger, therefore it will form free cation
and carbonion. This cation will take part in the reaction.
CATIONIC POLYMERSATION
 Chain polymerization: initiation, propagation and termination
 Active centre created by reaction;
Monomer (R) + electrophiles

R
+
(carbonium ions)
11
 Protonic acid e.g. H
2
SO
4
and HClO
4
often used as initiators.
 This involves addition of proton (H
+
) to monomer.
 However hydrogen halide – not suitable (because the halide counter-ion combines
to active centre to form stable covalent bond.
 Therefore lewis acids e.g. BF
3
, AlCl
3
and SnCl
4
most important for cationic
polymerisation.
 But must be used inconjunction with co-catalyst e.g. water or acid or organic
halide.
Initiation
i. Asid + Air

complex
BF
3
+ H
2
O

H
+
(BF
3
OH)

ii. Activation of active centre
H
+
(BF
3
OH)
-
CH
2
CR
1
R
2
+
CH
3
+
CR
1
R
2
(BF
3
OH)
-
In general,
R
+
A
-
CH
2
CR
1
R
2
+
RCH
2
+
CR
1
R
2
A
-
karbokation
Propagation
12
RCH
2
+
CR
1
R
2
A
-
CH
2
CR
1
R
2
RCH
2
CR
1
R
2
CH
2
+
CR
1
R
2
A
-
+
Termination
i. Spontaneous decomposition
CH
+
CR
1
R
2
A
-
CH CR
1
R
2
H
+
A
-
+
ii. Chain transfer
CH
2
+
CR
1
R
2
A
-
CH CR
1
R
2
CH
3
+
CR
1
R
2
A
-
+
Polymerisation kinetics
Polymerisation mechanism depends on:
1. types of initiator
2. monomer structure
3. solvent
Cationic polymerization; occur heterogeneously because initiator is only partially soluble
in the reaction medium. This feature makes the formulation of general kinetic scheme
somewhat difficult. Nevertheless, a kinetic scheme can be applied but BUT observation
on the specific reaction mechanism must be applied with discretion.
General kinetic scheme
1) initiation
13
R
+
A
-
+ M
RM
1
+
A
-
k
i
I
+-
M +
I
+-
M
k
i
2) Propagation
RM
+
n
A
-
+ M
RM
+
n+1
A
-
P
+-
+ M
P
+-
M
k
p
k
p
3) Termination
RM
+
n
A
-
RM
n
+
H
+
A
- k
t
'
RM
+
n
A
-
RM
n
+
HM
+
A
-
k
t
"
Rate of polymerisation
Rate of polymerisation = R
p
= ] M [ ] A R [ K
i
− +
= ] M [ ] I [ K
i
t
] I [
t
= Initiator concentration
[M] = Monomer concentration
rate of polymerisation = Propagation rate
used monomer of rate
dt
] M [ d
R
p
·

·
] M [ ] A RM [ K R
n p p
− +
·
dt
] M [ d
] M [ ] P [ K R
p p

· ·
t
on) (carbocati ion concentrat centre active ] P [ ·
t
14
Rate of termination = t
R
i. Spontaneously =
] A RM [ K
n
'
t
− +
=
] P [ K
'
t
t
ii. Transfer =
] P [ K
"
t
t
In general, rate of termination
] P [ K R
t t
t
·
If reaction occur in steady state
Rate of active centre formation = Rate of disappearance of active centre
i
R
= t
R
Initiation rate = termination rate
] P [ K ] M [ ] I [ K
t i
t t
· ∴
] M [ ] I [
K
K
] P [
t
i t t
·
] M [ ] P [ K R
p p
t
·
] M [ ] I [
K
K K
R
t
i p
p
t
·
Degree of polymerisation =
n X
rate Initiation
rate tion Polymerisa
Xn ·
15

rate n Terminatio
rate n Propagatio
·

] P [ K
] M [ ] P [ K
t
p
t
t
·
] M [
K
K
X
t
p
n ·
Additional knowledge on ionic polymerisation
Effect of p
R
and
n X on temperature
] M [ ] I [
K
K K
R
t
i p
p
t
·
K = constant
↓ → ↑ T R
p
* ARRHENIUS ] exp A K [
RT E −
·
] M [ ] I [
exp A
exp A exp A
R
RT E
t
RT E
i
RT E
p
p
t
i
p
t



×
·

·
`

(
| − +

·
RT
E E E
t
i p
p
t i p
exp
A
A A
R
Activation energy of propagation lower (very small) therefore:
t i p
E , E E <<<
Hence, overall E will be +ve
∴R
p
or overall rate increases when the temperature decreases.
Degree of polymerization
] M [
K
K
t
p
n · α
16
Arrhenius:
( )
] M [ exp
A
A
D
RT
E E
t
p
p
t p
− −
·
Normally, E
p
–ve for degree of polymerization. Therefore molecular weight increases
when temperature decreases.
NON-LINEAR POLYMERIZATION AND NETWORK FORMATION
All the polymerization studied before either condensation or chain polymerization
basically lead to the formation of linear polymer. The linear polymer can be either
homopolymer or co-polymer. However, non-linear polymerization to form network
is rather very useful in industry or for advance nano-technology study. So, why do
we need network formation in polymers?
Think! Think harder!
17
Simple answer; Linear polymer normally a long polymeric chain, it is flexible and
soft. There also linear polymers in the foam of liquid with high viscosity.
Furthermore, many polymers have lower thermal stability and mechanical strength;
therefore it may not withstand the requirements of heat during processing
(designing polymer packaging) or after shape of the polymer (commercial used). So,
crosslinks or networks are needed to satisfy the end product used.
Crosslink Features
1. At least one monomer have more than 2 functionality
2. Structure cannot be uniquely defined for a given number of monomer unit (many
isomers)
3. As molecular size increases the number of reactive group increase
4. For a given large number of reactive group, the molecule grow more quickly
5. Whole polymerization system give one molecule i.e. a network
6. Network formation first occurs at a gel point
7. After gel point the amount of network increase and reach up to 100% network
8. At gel points reached infinite viscosity, therefore no flow exceeds this gel points
9. Properties depend on the structure and the density of junction points (i.e. crosslink
density)
10. Short chain has stiffer and rigid material
11. Long chain has elastromer behaviour
The examples of non-linear polymerization or network formation will be divided into
TWO groups
i) condensation type (2 monomers of different functional group)
ii) polymeric chain (polymer chain with basic carbon-hydrogen bond)
Condensation type
1. Alkyd-Resins
18
CH
2
OH
CHOH
CH
2
OH
3 f.g.
+
C
C
O
O
O
+ H
2
O/trace
COOH
COOH
C CH
2
CH
2
O
O C C
CO CO
OH
H
O
O
junction point
To form a flexible network add glycol (diol)
OH CH CH HO
2 2
− − →
∴more dilute junction points
2. Phenoplasts (thermosetting resins)
Phenol formaldehyde resins (PFDR)
19
C O
H
H
H
2
O
+ CH
2
OH
OH
formalin aqeous
media
formaldehyde
PFDR formed by
Formaldehyde + phenol
Condensation

ortho and para position
20
HOCH
2
OH
OH
+
o o
p
m m
OH
CH
2
OH
CH
2
OH
HOCH
2
H
2
O +
or catalyst
3
CH
2
OH H
+ CH
2
and
methylene
bridge
CH
2
OH HOCH
2
+
CH
2
O CH
2
ethylene bridge
2 f.g.
gives 3 f.g.
CH
2
O CH
2
OH
CH
2
O
CH
2
CH
2
OH
Short chain between junction points gives rigid material
3. Aminoplast (Urea Formaldehyde Resin)
21
Carbamide + formaldehyde in alkaline solution
H
2
N CO NH
2
+ HO CH
2
OH
N CH
2
CO
H
OH H
2
N + H
2
O
+
n
(HOCH
2
OH)
and H
2
NCONH
2
CH
2
N N CO CO NH
2
CH
2
CH
2
N N CH
2
CO CO
Use as coating
4. Melamine Formaldehyde Resin
22
Melamine + formaldehyde
C
N
C
N
C
N
NH
2
NH
2
H
2
N
HOCH
2
OH
C N CH
2
OH
N
N
C
CH
2
OH
C N
N
N
C
CH
2
N C
N
N
H
H
O
n +
neutral or
alkaline
conditions
acid condition
H
2
O +
Short chain between junctions ∴rigid material
Used MF resin + PFDR

formica
5. Polyurethanes
23
Triol
Formation of triol

glycerol + epoxy alkane (epoxy ethylene)
or epoxy propylene
CH
2
OH
CHOH
CH
2
OH
CH
2
CH
2
O
+ NaOH
HO CH
2
CH
2
O
or
+
CH
2
CH
CH
3
O
via ring
opening
CH
2
O CH
2
CH
2
OH
CH O CH
2
CH
2
OH
CH
2
O CH
2
CH
2
OH
triol
(polyol)
3 f.g.
PPE (primary OH) ∴more reactive than PPO (secondary OH)
But PPO better adhesive
Diisocyanate:
1. TDI (toluene diisocyanate)
Mixture of 2/4 and 2/6 isomer
CH
3
NCO
NCO
NCO
CH
3
OCN
+
2,4
2,6
2. MDI (diphenyl methyl diisocyanate)
24
OCN CH
2
NCO
Polyurethane formation: diisocyanate + polyol (triol)
CH
2
N C O
O H
( ) CH
2

4
C N CH
2

O
O H
CH
2

4
( ) O

hydrogen bonding

hand segment
6. Epoxy Resin
Epichlorohydrin + bisphenol A
25
26
Diepoxy with a Diamine
27
28
29
Crosslinking of Polymer Chain
Alternative to form crosslinking is by vulcanization (Δ by sulphur)
1. Natural Rubber
Used poly isoprenes

2 isomers
CH
2
C CH CH
2
CH
3
CH
2
C CH CH
2
CH
3
NR poly (cis isoprenes)
C C
CH
3
CH
2
CH
2
H
H CH
3
CH
2
CH
2
C C
NR poly (trans isoprenes)
C C
CH
2
CH
2
CH
3
H H
CH
2
CH
3
CH
3
C C
• Open ring less elasticity
• 6000 – 30,000 bond per chain
• NR is linear chain not elastomer – needs to form network by crosslinking
• To form crosslinking – used heat and sulphur
30
CH
3
C CH CH
2
CH
2
+
sulphur (S
x
)
C CH
2
CH
2
CH
2
CH
3
S
x
H
+
C
CH
3
CH
2
CH
2
CH
2
C
CH
3
CH
2 CH
2
CH
2
S
x
C CH
2
CH
2
CH
2
CH
3

1% sulphur

soft material e.g. elastomer
30% sulphur

hard material with fillers
Few % sulphur

tyres
31
2. Butyl Rubber
Isobutylene + 2% isoprene the crosslinked
CH
2
C
CH
3
CH
3
CH
2
C CH
2
C CH
2
CH
3
CH
3
CH
3
CH
3
PIB
+ 2% isoprene
CH
2
C CH CH
2
CH
2
C CH
2
C
CH
3
CH
3
CH
3
CH
3
CH
3
32
3. Peroxide Crosslinking
t-butyl peroxide
(CH
3
)
3
C O O C(CH
3
)
3
(CH
3
)
3
CO OC (CH
3
)
3
In general
R O OR OR 2
For Natural rubber & butyl rubber can be crosslinked by this free radical
CH
2
C CH CH
2
CH
3
OR +
CH C CH CH
2
CH
3
ROH +
CH C CH CH
2
CH
3
crosslinked
150
o
C
33
4. Polyolefin crosslinking
i. using peroxide
The peroxy-radicals (free radical) then the radical abstracts a hydrogen atom from
the carbon-hydrogen bond in the polymer molecule (which is preferentially the weak
tertiary hydrogen atom from chain branching sites). This polymer radical may then
undergo either combination or cleavage.
where RO-OR is the peroxide, -CH
2
-CRH-CH
2
- represents a polyolefin chain and R is a
chain branch which is common in low density polyethylenes.
The resultant polymeric radicals, formed by the primary radical abstracting
preferentially tertiary hydrogen from polymer chain (reaction 1.2) [Kircher 1987], then
can combine with other polymeric radicals to form carbon-carbon crosslinks. This mutual
termination of the polymer radicals (normally alkyl radicals [Yamazaki and Seguchi
1997]) is the predominant reaction if net crosslinking is observed and is shown in
reaction 1.3.
34
RO OR RO 2
heat
RO
ROH
polymer radical
Tertiary hydrogen
CH
2
C CH
2
R
+
+
Reac. 1.1
Reac 1.2
R
CH
2
CH
2
CH
CH
2
CR CH
2
CH
2
CR CH
2
CH
2
CR CH
2
CH
2
CR CH
2
Crosslinking
Reac. 1.3
The mutual termination of polymer radicals represents the desired formation of a
crosslink and is the essential step. In order to achieve net crosslinking, the rate of
combination must exceed the rate of the alternative chain scission reaction. However in
the case of polypropylene (PP) it is much more highly prone to radical decomposition
(cleavage), making it difficult to achieve net crosslinking as the polymer “unzips”. This is
promoted at high temperatures and with increasing tertiary hydrogen concentration in the
main chain [Kircher 1987]. PP contains a tertiary hydrogen on alternate carbon atoms and
unzips (reaction 1.4) with chain scission dominating the chain scission/crosslinking
balance giving net molecular weight reduction and no network.
Also chain radicals can lose their activity by formation of an alternative radical (reaction
1.5)

Reaction 1.6 shows that polymer radicals may also be deactivated by reaction with a
primary radical.
35
CH
2
C
CH
3
CH
2
CH
CH
3
CH
2
CH
CH
3
CH
2
C
CH
3
CH
2
CHCH
2
CH
CH
3
CH
3
+
Reac. 1.4
CH
2
CR CH
2
OR + CH
2
CR
OR
CH
2
Reac. 1.6
CH
2
CR
H
+
CH
2
CR CH CH
2
CH CH
2
H
Reac. 1.5
Under certain conditions other radicals can recombine resulting in inefficient termination
of active radicals (reaction 1.7).
Finally it is also possible that radicals shift along the polymer chain (reaction1.8).
ii. Using Irradiation
β -radiation produced by large accelerators is therefore commonly used in
crosslinking polyethylene. The energetic electrons strike the molecules near to the C-H
bond. As the electron gives up energy when striking the C-H bond, the energy is enough
to break the C-H bond to produce a hydrogen radical and a polymer molecule in an
excited state (free radical). Therefore the excited carbon atoms can use their energy to
form covalent C-C bonds. A simplistic scheme is shown.
iii. Silane System
Vinyl silane is grafted on to the base polymer (e.g. polyethylene) using a small
quantity of peroxide compared with traditional crosslinking. Typically it is 20 times
smaller. The peroxide will break the double or unsaturated bond in vinyl silane e.g.
trivinylmethoxysilane, CH
2
=CH-Si(OCH
3
)
3
, and bind it to the polymer chain.
Then the subsequent steps to crosslink formation where the silanol condensation
reaction occurs very slowly at room temperature but proceeds relatively swiftly at
elevated temperatures in the presence of a specific silanol condensation catalyst such as
dibutyltindilaurate (DBTDL).
36
CH
2
CR CH
2
+
H CH
2
CH
R
CH
2
Reac. 1.7
CH
2
CH CH
2
CH
2
CH
2
CH CH
2
CH
2
Reac. 1.8
PH
PH
P
P
P P
P P
H
H
H
2
(crosslinking)
+
+
+
+
rad
The disadvantages of using silanes for crosslinking reported in the literature are [Kircher
1987, Gale 1984]:
(i) once grafted, the half-life of the material is short especially if exposed to
moisture which results in storage problems.
37
CH
2
CH Si(OMe)
3
CH
2
CH
2
Si(OMe)
3
Peroxide
+
Polyethylene Vinyltrimetoxysilane Grafted component
H
2
O
Hydrolisis
CH
2
CH
2
Si(OH)
3
+
MeOH 3
Reac. 1.12
Reac. 1.13
CH
2
CH
2
Si(OH)
3
CH
2
CH
2
Si(OH)
3
+
Heat
(Condensation)
Catalyst (DBDTL)
CH
2
CH
2
Si O Si CH
2
CH
2
OH
OH
OH
OH
H
2
O +
Reac. 1.14
Crosslinked polyethylene
(ii) curing is often performed in a temperature controlled water bath, which
can cause diffusion of moisture into the polyethylene.
POLYMER CHARACTERIZATION
Polymers may be
38
• Oily liquids
• Soft, deformable rubbers
• Hard, brittle glasses
• Tough, flexible semi-crystalline materials
The properties of a polymeric material may be related to its
• Molecular characteristics (nature of the repeat units; arrangement of the repeat
units; molecular size and its distribution) which depend on polymerization
chemistry
• Morphology (arrangement of molecules), which may vary according to processing
conditions (thermal history)
Most techniques for studying the molecular characteristics of a polymer require it to be in
dilute solution.
Question
What physical quantities may be used as measures of the size of a polymer molecule?
Molar Mass Distributions
Number-fraction distribution
n
i
= number-fraction of species i
=


·1 i
i
i
N
N
N
i
= number of molecules with molar mass Mi
Weight-fraction distribution
wi = weight-fraction of species i
=
∑ ∑

·

·
·
1 i
i i
i i
1 i
i
i
M N
M N
W
W
W
i
= mass of molecules with molar mass Mi
= N
i
M
i
Continuous representation of number-fraction distribution
39
N(M)dM = number-fraction of molecules with molar mass
between M and M+dM
N(M)dM is proportional to the area of the strip
Total area under the distribution is
( )


·
0
1 dM M n
Continuous representation of weight-fraction distribution
W(M)dM = weight-fraction of molecules with molar mass
between M and M+dM
W(M)dM =
( )
( )


0
MdM M n
MdM M n

Total area under the distribution is
( )


·
0
1 MdM M n
Average Molar Mass
Number-average molar mass:
( )
i i
i
i
i i
n
M W
W
N
M N
M
Σ
Σ
·
Σ
Σ
·
Weight-average molar mass:
i i
2
i i
i
i i
w
M N
M N
W
M W
M
Σ
Σ
·
Σ
Σ
·
z-average molar mass:
i i
2
i i
z
M W
M W
M
Σ
Σ
·
Relative values of average molar masses
Polydisperse polymers: z w n M M M < <
Uniform polymers: z w n M M M · ·
Most probable distribution:
3 : 2 : 1 M : M : M z w n ·
The ratio
n
w M M
is a measure of the width of the number distribution
The ratio
w
z M M
is a measure of the width of the weight distribution
40
Techniques For The Determination of Molar Mass
Technique Direct Calibration M range
End group analysis
Vapour pressure osmometry
Membrane osmometry
Light scattering
Sedimentation equilibrium
Sedimentation velocity
Diffusion
Dilute solution viscometry
Gel Permeation Chromatography
n M
< 2 x 10
4
< 2 x 10
4
10
4
– 10
6
10
4
– 10
7
10
4
– 10
7
> <
2
s
: mean square radius of gyration rh : hydrodynamic radius
S : sedimentation coefficient [η]: intrinsic viscosity
D : diffusion coefficient V : elution volume
MMD : molar mass distribution
GEL PERMEATION CHROMATOGRAPHY
41
n M
n M
z s , M
2
w > <
z w n M , M , M
h
r , s
h
r , D
[ ]
h
r , η
V

D M
MMD , r
h
V M
Gel permeation chromatography (size exclusion chromatography)
Polymer molecules are separated according to size, the largest molecules being eluted
first
With calibration, molar mass distributions may be determined
An excellent method for comparison of one sample with another, i.e. for process and
product control
Not so good for quantitative work: molar mass ratios are usually accurate, but average
molar masses are very uncertain
Question
Apparatus for gel permeation chromatography is illustrated schematically below. Label
each of the components
Dilute polymer solution is injected into solvent stream
Columns contain porous beads, e.g.
42
Crosslinked poly(styrene) for organic solvents
Crosslinked (polyvinyl alcohol) for aqueous solvents
Silica gel, often with its surface treated with trimethylchlorosilane to promote
compatibility with organic solvents
Eluent stream emerges into a detector (e.g. differential refractometer)
Detector signal is plotted against alution volume to obtain the GPC curve
Thermodynamics of the Separation Process
Total volume of liquid inside column i o total
V V V + ·
Where o
V
= void volume; volume of liquid outside porous beads
i
V
= internal volume; volume of liquid inside porous beads
Volume available to the solute is the elution volume e
V
Which is between o
V
and i o
V V +
Assume equilibrium between solute in the void and in the pores
Solute in void ⇔ solute in pores
Equilibrium constant (or distribution coefficient) o i e
c c K ·
Where o
c
= concentration of solute in void
i
c
= concentration of solute in pores
Standard state Gibbs energy change for permeation
e
o
K ln RT G − · ∆
If exclusion is the only separation process, 0 H
o
· ∆ and
o o
S T G ∆ − · ∆
i.e. ) R S exp( K
o
e
∆ ·
Entropy change on reducing the available pore volume from
i
V to o e
V V −
is
] V ) V V [( ln R S
i o e
− · ∆
Thus i o e e
V ) V V ( K − ·
i.e. the elution volume of the solute is i e o e
V K V V + ·
When the solute molecules are very large and do not penetrate the pores
0 K
e
·
and
o e
V V ·
When the solute molecules are very small and penetrate the pores to the same extent as
the solvent
1 K
e
·
and i o e
V V V + ·
Between these limits, e
K
is determined by the exclusion of solute within pores
43
Statistical-thermodynamical treatments of the exclusion problem show that:
size) (slolute log K
e

Consequently, e
V
is expected to vary with log (solute size)
The size involved is the hydrodynamic volume
) V (
h
i.e. the effective volume of the polymeric solute in the solvent
For a polymer in a given solvent at a given temperature,
M V
h

M log V
e

Ideally separation should be only the basis of size. In practice the separation often
includes contributions from partition and adsorption. These processes can move the peak
towards (and beyond) the permeation limit (total volume, i o
V V +
). An additional
problem occurs with aqueous solvents and negatively charged solutes, when electrical
exclusion moves the peak towards the exclusion limit (void volume, o
V
). These
unwanted effects must be minimized in order to avoid misleading results.
Calibration
Standards samples, with different average molar masses and narrow molar mass
distributions, may be used for calibration. Each polymer/solvent pair has a different
calibration curve.
44
Ideally, calibration should be carried out with standard samples of the same polymer as
the sample under investigation. This is not always possible.
When appropriate standards are not available, one may
Quote ‘polystyrene equivalent’ or ‘poly(oxyethylene) equivalent’ molar masses
Assume that polymer molecules with the same extended chain length have the same
h
V

and so elute at the same e
V
; this is usually a reasonable approximation for vinyl
polymers
Use a ‘universal’ calibration plot of
M ] [ log η
against pk
V
, where
] [η
is intrinsic
viscosity; this is based on the relationship
h
V M ] [ ∝ η
Utilize on-line detectors (e.g. light scattering) which provide an absolute measure of
molar mass
45
Question
Analysis of gel permeation chromatography data for a polysaccharide gave the following
plots. Explain what each plot represents, and why they differ from each other in shape.
46
DILUTE SOLUTION VISCOMETRY
Capillary viscometer
Used to study dilute polymer solutions
Method consists of measuring, for both solvent and solution, either:
i. the time taken for a known volume to flow through a capillary at a given
hydrostatic pressure, or
ii. the hydrostatic pressure needed to force a known volume to flow through a
capillary in a given time
According to the Poiseuille formula, the viscosity of a liquid is proportional to the time it
takes to flow through a capillary
In practice, you may need to correct for density, kinetic energy or shear
Relative viscosity (viscosity ratio), η
r
o o
r
t
t

η
η
· η
η: viscosity of the solution
η
o
: viscosity of the solvent
t: time for a specified volume of solution to flow through a
capillary tube
t
o
: corresponding time for a pure solvent
Specific viscosity, η
sp
o
o
o
o
r sp
t
t t
1


η
η − η
· − η · η
A measure of the relative increase in viscosity
Both η
r
and η
sp
depend on polymer concentration, c.
Intrinsic viscosity (limiting viscosity number), [η]
A measure of viscosifying power
Plot
c
sp
η
and
c
ln
r
η
versus c
Intercept:
[ ] η ·
·
`

(
| η
·

·
`

(



0 c
r
0 c
sp
c
ln
c
Slopes: [ ] [ ] c k
c
2 sp
η + η ·
η
(Huggins)
[ ] [ ] c
c
ln
2
r
η β − η ·
η
(Kraemer)
Units of [η]: reciprocal concentration, e.g. cm
3
g
-3
or dl g
-1
Relationship Between [η] and M
47
Mark-Houwink relationship applies for a given
polymer in a given solvent at a given temperature
[ ] M log a K log log + · η
[ ]
a
KM · η
In a θ-solvent: a = 0.5
In a good solvent: a>0.5 (up to 0.8 for arandom coil,
greater for a rigid rod)
For a highly branched polymer: a<0.5
Viscosity-average molar mass,
v M
For a polydisperse polymer
a
1
i
a
i i
v
w
M w
M

·
`

(
|
Σ
Σ
· v M depends on the solvent and on the temperature
through the parameter a
w v M M <
For most probable distribution:
77 . 1 M M , 2 M M
n
v
n
w · ·
(for a = 0.5) 1.88 (for a =
0.7)
Question
Show that if the Mark-Houwink relationship [η] = KM
a
is applied to a polydisperse
polymer, the average molar mass obtained is
a
1
i
a
i i
v
w
M w
M

·
`

(
|
Σ
Σ
·
Where w
i
is the weight fraction of species of molar mass M
i
.
Hydrodynamic radius, r
h
The radius of a rigid spherical particle which behaves in the same way as the polymer
molecule in the same liquid.
A coiled polymer molecule may be modeled as an equivalent hard sphere, assuming that
the coil is not distorted by the shear stress and that solvent does not drain from the coil
(impermeable coil model).
Question
48
Einstein showed that for rigid spheres: η
sp
= 2.5
φ
, where
φ
is the volume fraction of
spheres. On the basis, show that
[ ]
M
r
3
∝ η
Where r is the radius of the sphere and M is its molar mass.
Universal calibration in gel permeation chromatography
Separation in GPC is determined by the hydrodynamic volume, V
h
, of the solute.
[ ]M r V
3
h h
η ∝ ∝
Plot log [η] M against elution volume, V
e
Or, since [η] = KM
a
, plot log KM
1+a
against V
e
.
BASIC INTRODUCTION ON PHYSICAL AND MECHANICAL PROPERTIES
49
TRANSITION IN POLYMERS
Introduction
An understanding of the physical properties of polymers and in particular the relationship
between these properties and molecular structure can only be achieved by an
understanding of the transition that occur in these materials.
These transitions include crystal melting, crystalline transitions, the glass transition and
secondary transitions. The first two are only observed in crystalline polymers; the others
are found in all polymers to a greater or lesser extent.
A transition is a point at which the properties of the material change due to a change in
the movement of the molecules, which is generally a consequence of a change in
temperature but in viscoelastic materials can also be brought about by a change in time
scale.
Consider a polymer at high temperature in the molten state; all kinds of molecular motion
are taking place: transition, rotation and vibration of the main backbone chain and of the
side groups. All these movements require different amounts of energy. Consider a
material which remains amorphous through the whole temperature range. As the
temperature is lowered, translation requires the most energy and therefore is the first to
stop and the polymer stops flowing. Further temperature reduction leads to segmental
rotation of the main chain stopping. This leaves only vibration of the main chain but
rotation of side-groups can continue until further lowering of the temperature causes all
movement to stop at absolute zero. If the polymer wishes to crystallize then
crystallization will be the first transition. However because a polymer consists of
crystalline and amorphous phases the molecular movements discussed above will still
take place in the amorphous region.
The Glass Transition Temperature (T
g
)
This is the most important transition to be found in amorphous polymers although it does
occur in crystalline polymers its effects are less significant as it is associated with main
chain movement in the amorphous region. It is the temperature at which the properties of
the polymer change from rubbery (low modulus and large elastic deformation) to glassy
(high modulus and brittle).
The changes in physical properties are completely reversible in that a glassy polymer can
be made rubbery or vice versa depending on whether it is above or below its transition
temperature.
The explanation for these changes is that above the glass transition point the molecules
are free to rotate about bonds and the forces between molecules are weak such that when
a force is applied segments of the molecule are capable of changing their conformation.
This gives rise to a soft material with large elastic deformation. As the temperature is
50
lowered the thermal energy of the chain segments progressively falls until a point is
reached at which the energy is no longer sufficient to overcome the energy barriers to
rotation and the forces between molecules. When this happens the chain segments
become frozen into fixed positions and the random rotation about are suppressed and
with it the capacity for undergoing large deformations.
The mechanical properties of all amorphous polymers in their glassy state are
approximately the same with a modulus of about 2GNm
-2
and a breaking strain of 2-3%.
In the rubbery region the modulus is usually about 2MNm
-2
and the breaking strain can
be up to several hundred percent. Whether a polymer is glassy or rubbery at room
temperature depends on the location of its glass transition temperature; if it is above then
it is glassy and if it is below then it is rubbery.
Other properties change significantly at the glass transition temperature: thermal
expansion coefficients, heat capacity, refractive index, specific volume, modulus,
damping behaviour, electrical properties, etc.
Factors Affecting Glass Transition (Chemical Structure)
1. chain flexibility
a) flexible chains – low energy barrier
– low T
g
Polydimethyl silozane
Polyethylene
Si
CH
3
CH
3
O Si
CH
3
CH
3
T
g
-123
o
C
C
H
H
C
H
H
-120
o
C
b) rigid chains – high energy barrier
– high T
g
O C
CH
3
CH
3
O C
O
Polycarbonate
T
g
+150
o
C
Energy barrier to rotate the molecule contain benzene ring is high
↑ ∴
g
T
51
2. bulkiness of side group
The bigger/bulkier of the side group the more the energy to rotate the molecule ∴
high T
g
C C
H
H
H
H
C C
H H
H CH
3
C C
H H
H
polyethylene
polypropylene
polystyrene
Tg
-120
O
C
-18
O
C
+100
O
C
3. increase length of flexible side group – lower the T
g
Although increasing the side group T
g
↑ but if the side group is flexible side group
∴lowering the energy to rotate the molecule
Because the flexible side group easier to rotate and contribute the mobility of rotation
∴lowering the T
g
C C
H
H
H
OR
2
CH
3
CH
2
CH
3
CH
2
CH
2
CH
3
CH
2
CH
2
CH
2
CH
3
R
2
T
g
-10
o
C
-17
o
C
-27
o
C
-32
o
C
4. steric hindrance, increases T
g
52
Where the CH
3
located will effect the T
g
C C
H H
H
C C
H H
H
CH
3
C C
H H
H CH
3
Polystyrene
Poly p-methyl styrene
Poly o-methyl styrene
T
g
+100
o
C
+110
o
C
+120
o
C
5. polarity of side group increases T
g
C C
H H
H H
C C
H H
H Cl
C C
H H
H CN
Polyethylene
Polyvinyl chloride
Polyacrylonitrile
T
g
-120
o
C
+87
o
C
+104
o
C
Cl is electronegative group therefore it will form a bonding will hydrogen with the
second molecule this will give strong molecular force ∴not easy to rotate
53
C C
Cl
H
C C
Cl
H
+
-
The more polar the side groups the more difficult to rotation g
T ↑ ∴
(CN more
polar than Cl)
6. symmetry of side group decreases T
g
equivalent mass on the both side of the side group will
∴ ↓E
easier to rotation
g
T ∴↓
C C
H H
H CH
3
C C
H
H
CH
3
CH
3
C C
H H
H Cl
C C
H
H
Cl
Cl
Polypropylene
Poly isobutylene
Poly vinyl chloride
Poly vinylidene
chloride
T
g
-18
o
C
-70
o
C
+87
o
C
-19
o
C
The Used Of Free Volume Concept To Determine T
g
54
T
V
o To demonstrate the glass transition and determine the T
g
value of a polymer is
specific volume (measuring) as a function of temperature
o As in the region above and below the T
g
→ is a linear variation in specific
volume with temperature
o But in the vicinity of T
g
there is a change in slope
o Tg determine by extrapolation of the 2 lines meet
o The exact temperature depend upon the cooling rate. Lower cooling rate ↓T
g
o Because of the semicrystalline polymer contain crystals and amorphous ∴
difficult to determine the T
g
accurately
o ∴free volume concept use to determine
Tg
o Free volume is the space in solid or liquid that not occupied by polymer
molecules

empty space between molecules
o In liquid – free volume is high ∴molecular motion can take place easier
because the unoccupied volume allows the molecule to move ∴change their
conformation
o Lower the temperature
 Reduce the thermal energy for molecular movement
 Lower the amount of free volume ∴the molecule cannot move
eventually

glassy polymer
o Lower temperature
 ↓ thermal energy to rotate
 ↓ free volume to move
*
f
V - free volume constant (below T
g
)
V
o
– volume occupied by molecule ( ↑ temperature)
V
f
– free volume
f o
V V V , volume sample Total + ·
55
Free volume (V
f
)
Occupied volume (V
o
)
V
f
*
V
f
High molecular weight
Few long chain
Few chain end
Low molecular weight
Lots of small chain
Lots chain end

·
`

(
|
·
total
free
V
V
f , volume free Fractional
f
Below T
g
V
V
f
*
f
g
·
Above T
g
( )
·
`

(
|
− + ·
dT
dV
T T V V
g
*
f f
( )

·
`

(
|
− + ·
dT
dV
V
1
T T
V
V
V
V
g
*
f f
Expansion coefficient of free volume

·
`

(
|
· α
dT
dV
V
1
f
( )
f g g
T T f f α − + · ∴
For many polymers f
g
is found to have same value
Molecular Weight
o For low molecular weight → low T
g
o Increase in molecular weight → increase T
g
o This can be explained by free volume concept. NOT in changing in molecular
structure of side group
o Free volume explanation
o ↑ molecular weight
56
 ↓chain end

↓ free volume
 ↓mobility volume

↑T
g

Dependence of T
g
on Molar Mass
T
g
increases on molar mass increases
M
K
T T
g g
− ·


g
T
is T
g
at infinite molar mass
K is constant
chain each of
volume
mass number
Density
×
· ρ
A
n
N
M
chain each of Mass ·
N
A
= Avogadro number
A
n
N
M
V
N
× · ρ
n
A
M
N
V
N ρ
· ∴
Number of chain ends per unit volume
n
A
M
N
2
ρ
·
θ = amount of fractional free volume at each chain end
Total fractional free volume f
c
n
A
c
M
N 2
f
θ ρ
·
f
c
represents increase in free volume above T
g
i.e. between T
g
and

g
T
( )
g g f c
T T f − α ·

( )
n
A
g g f
M
N 2
T T
θ ρ
· − α ∴

57
Or
n
f
A
g g
M
N 2
T T
α
θ ρ
− ·

M
K
T T
g g
− ·

Branching and T
g
Branching ↑free volume

↑mobility, ↓T
g
Crosslinking and T
g
o Crosslinking will pull the chain together
o ↑crosslinking
 ↓ free volume
 ↓ mobility
 ↑ T
g
Copolymer and T
g
o Copolymer is 2 polymers combine together by chemically made
 Random
 Alternate
 Block
o One T
g
between T
gA
and T
gB
(for compatible syatem)
o If not compatible (in compatible) → 2 T
g
’s
o For compatible system
2 g
2
1 g
1
g
T
W
T
W
T
1
+ ·
W = weight fraction of the 2 homopolymer
o With T
g1
and T
g2
the transition
Secondary Transition
o Most polymer show small secondary transition below the main T
g
o Which related to side chain movement
o Because side chain required less energy than the main chain to rotate the
temperature at which they occur is always less than T
g
o This is important in determining such properties as toughness and impact
strength
58
100
o
C
PMMA
PS
T
g
Secondary
transition
Energy loss
Temperature
20
o
C
A
B
C
D
R O O
C
o Secondary transition lower the T
g
due to:
1. A – limited main chain movement
2. B – whole side group movement
3. C – part side group movement
4. D – other interaction
o PMMA is higher than PS because of secondary transition
Crystal and melting of polymer
Crystalline Transitions
The most significant transition in crystalline polymers is the crystalline melting point,
Tm. It is the temperature at which the crystalline material is converted from a highly
ordered structure into an amorphous liquid. Tm is always higher than Tg.
59
Because T
m
involves an abrupt change in the primary thermodynamic function volume it
is usually referred to as a first-order transition whereas Tg is usually referred to as a
second order transition.
The structural features which give rise to high melting points are the same as those which
give rise to high glass transition temperatures i.e. strong inter-molecular forces, chain
stiffness, chain symmetry.
Other secondary transitions occur in the crystalline regions of crystalline polymers and
these are usually due to reordering of the crystalline structure leading to a greater
perfection of the crystalline units.
For example
o Eg. Polyethylene, polypropylene, nylon have T
g
and in addition have T
m
o Flexible, tough & hard than rubber but not brittle
o Phase separation
 amorphous
 crystalline
Specific
volume joint point

amorphous
rotation
vibration
T
g
T
m
Temp
o If amorphous is heated vibration occur, the F.V. and mobility increase
o At the joint point is these T
m
o By cooling

below T
g


the molecular movement stop, therefore, ∴stop
crystallizing
o At high T
g


high T
m
o T
m
≈ 2 T
g
(symmetric)

pack better, ∴molecule get together


polymer in main chain
o T
m
≈ 1.5 T
g
(unsymmetric)
T
m
K T
g
K T
m
/T
g
PE 410 153 2.68
Poly vinilidene chloride 470 254 1.85
PAN 590 377 1.57
PET 538 342 1.57
60
Nylon 6.6 538 323 1.67
PP 442 273 1.62
o As crystallinity increases:
1. density, modulus, hardness increases
2. thermal cond. increases
3. specific heat decreases
thermal expansion decreases
gas permeability decreases and creep decreases
Melting
Simply reverse of crystallization
But again melting is more complex with polymers than atomic solid
Main features
a) cannot define a simple value of melting points – melting takes place
over a range of temp
b) melting behavior depends on specimen history, e.g. crystallization
temp
61
o
m
T
T
c
T
m
y
x

c) melting depend upon heating rate, e.g. 10 oC/min
20 oC/min
∴need to establish as equilibrium melting temp.
o
m
T
e.g. crystallize at different T
c


give different crystal thickness ∴different T
m
Determination of
o
m
T
Some polymer crystallize at different T
c
, measure their T
m
value
Need to plot graph T
m
Vs T
c
Draw line at 45
o
that T
m
= T
c
The
o
m
T is the melting temp
∞ ⇒ L
Normally Tm > Tc for finite size crystal and Tm = Tc for ∞ size crystal
Why does Tm depends on crystal thickness?
1. due to molecular structure of the crystal
2. chain bonding
Thermodynamic of Crystal Melting
Surface free energy
Melting causes reduction in surface free energy (destroyed surface)
Decrease e s s
xy 2 y 2 x 2 γ + γ + γ ·  
Volume free energy ΔG
v
Increase
v
G xy ∆ · 
(due to molecules going from crystal to melt)
62
Not same T
m
value
T
m
= T
c
γ
e
γ
s
γ
e
= fold surface free
energy
γ
s
= side surface free
energy
T
m
o
m
T

1
Overall free energy change,
( )
e s v
xy 2 y x 2 G xy G γ − γ + − ∆ · ∆  
NB:
Crystal itself x, y >>> e ∴lose the side equation
Also
o
m
v v
T
T
H G

∆ · ∆
( )
m
o
m
T T T − · ∆
For melting ΔG = 0
e v
xy 2 G xy γ · ∆ ∴ 
e v
2 G γ · 
( )
o
m
m
o
m v e
v
T
T T H 2
G
− ∆
·
γ
· ∆

v
o
m e
o
m
m
H
T 2 T
T

γ −
· ∴

If known ΔH
v
for calorimetry, ∴can calculate γ
e
Factors Affecting T
m
1. Physical
2. Chemical
Physical factor
For a given chemical type of polymer then physical factor can control T
m
e.g.
molar mass (length of molecules)
branching (linear branched)
* this will introduced effects into crystal due to chain ends
63
extrapolation
Slope =
v
o
m e
H
T 2

γ −
1. molar mass – chain end effects
 If molar mass
∞ →
perfect crystal obtained
 If molar mass

finite – defractive crystal obtained
2. branching – branch points in crystal
 linear PE T
m
= 150
o
C
 branched PE T
m
= 110
o
C
Chain end (low molar mass & branches)

detect in crystal, this reduce Tm value
Can interpret in term of “chemical potential”
µ ⇒
Define
c
u
µ
= chemical potential per mole of repeat unit of polymer in crystalline state
o
u
µ
= chemical potential per mole of repeat unit of polymer in the liquid state
(standard state)
Free energy fussion = ΔGu
c
u
o
u u
G µ − µ · ∆
(1)
Pure polymer system
Change in chemical potential going from liquid to solid
( )

( )

( )
u u u
initial
o
u
final
c
u
S T H G ∆ − ∆ − · ∆ − · µ − µ
(2)
μ = per mole of repeat units
As before
o
m
u
u
T
H
S

· ∆
(3)

·
`

(
|
− ∆ − · µ − µ
o
m
u
o
u
c
u
T
T
1 H
(4)
Consider the effect of chain ends “impurities”
Introduce the concept of “activity”

a = activity of crystalline phase
For pure/perfect crystal a = 1
For defective crystal a < 1
∴chemical potential of crystalline phase related to activity
a ln RT
o
u
c
u
· µ − µ
(5)
64
Combining (4) & (5)
a ln RT
T
T
1 H
o
m
u
·

·
`

(
|
− ∆ −
At T = Tm
u
o
m m
H
a ln R
T
1
T
1


· −
(6)
Assume:
The polymer consist of mole fraction of crystalline material ⇒ X
A
The polymer consist of mole fraction of non crystalline material ⇒ X
B
So X
A
+ X
B
= 1
First approximation can relate activity of polymer crystal to mole fraction of
crystallisable material (i.e.
A
X a ≈
)
u
A
o
m m
H
X ln R
T
1
T
1


· − ∴
(7)
But X
A
= 1 – X
B
If X
A
is small, ln X
A
= ln (1 – X
B
) ~ X
B
u
B
o
m m
H
RX
T
1
T
1

· −
(8)
Consider chain end
Degree of polymerization X
n
(number of repeat unit)
Mole fraction of chain end
n
X
2
·
e.g. n = 100, 2 ends
50
1
100
2
X
B
· ·

·
`

(
|

· − ∴
n u
o
m m
X
2
H
R
T
1
T
1
(9)
∞ → →
n
o
m m
X as T T
Branches?
65
4 ends, 2 branches
From equation (9),
y 2 2 + →
y = number of branches

·
`

(
| +

· −
n u
o
m m
X
y 2
H
R
T
1
T
1
Chemical factor control T
m
Chemistry has a strong control over T
m
a) main chain stiffness
- flexible unit decrease T
m
- rigid unit increase T
m
Polymer repeat T
m
/K
CH
2
CH
2
410
CH
2
O CH
2
340
CH
2
CH
2
670
b) inter chain bonding
e.g. hydrogen bonding can stabilize the crystal
↑ →
T
m
nylon

have high T
m
value due to H bonding
Repeat T
m
/K
CH
2
CH
2
410
CH
2
CH
2
CONH
603
CH
2
CH
2
CH
2
CONH
533
c) odd and even effect
e.g.

NH(CH
2
)
n
NHCO(CH
2
)
4
CO
d) side group effect
side groups – affect chain rotation and increase T
m
e.g. vinyl polymer
X group Name T
m
/K
66
Specific
volume
Amorphous
Crystalline
T
g
T
m
Temperature
–H PE 410
CH
3
PP 460
CH
2
CH
3
Butane-1 398
CH
3
CH
7
Pentane-1 351
CH
2
CH
CH
3
CH
3
4-methyl-1-pentene 508
450
Bulky side group

restrict rotation ↑T
m
Long side group

separates chain make rotation easier reduce T
m
Method of Measurement T
g
and/ or T
m
1. Static

no stress

not apply dynamic or mechanical stress
a) dilatometer

is to generate specific volume and temperature




67
Ref. index
T
g Temperature
Polymer
θ
Capillary
tube
Sealed
Glass plug
Polymer (powder)
Containing liquid Hg
Water bath
T
m
= 1
st
order transition
T
g
= 2
nd
order transition
o Weight the polymer & measure the height of the capillary tube. ∴can calculate
the volume
o ∴can plot the graph
o Problems cannot go below -35
o
C
o Advantages:
1. Cheap: £ 50 – 60, 000
2. accurate – only control the temperature
– slow heating rate
3. very good for T
g
and T
m
o Disadvantages:
no secondary transition detected
b) refractometry
omeasure on reflective index
o usually measure critical angle

68
Polymer
Heat both of them in the same time
T
g T
m
Crystalline
Amorphous
Modulus/
Nm
-2
o heating & cooling also be found
o difficult

range of temperature
o not usually use
c) thermal capacity (specific heat)
i. DTA – differential thermal analysis
ii. DSC – differential scanning
these are commercial technique


o DTA – heat input same – measure temperature difference
o DSC – keep temp same – measure the heat energy difference
o Both measure in T
g
and T
m

o Advantages:
 good for T
m
, ok for T
g
 quick and fast
 automatic
o Disadvantages:
 no secondary T
g
 expensive
2. Static - Mechanical



69
Suspension
wire
counter balance
Inersia bar
Test specimen
Environmental
chamber
Dynamic shear
modulus
γ
α
θ
Temperature/K
o Modulus Vs temperature
o T
g
have narrow or broad graph value
o ∴difficult to predict where is the actual T
g
value
3. Dynamic - Mechanical


o this instrument produce osiloscope
o measure dynamic modulus – loss tangent
o dynamic mechanical

is effective because it measure energy loss


give secondary transition
4. Dynamic Electrical
70
Dielectric
constant
Dielectric loss
o ∴can measure dielectric loss
Mechanical Properties of Polymer
Introduction
Classification of polymers
71
Polymers
Thermoplastic Elastomers Thermoset
Crystalline Amorphous
Stretch
mechanically
relax
Molecules
random
Heat
stretch
* All the 3 categories have very different mechanical properties – due to molecular
structure
Molecular conformation
Molecules are prefer to form a random coil to give higher entrophy (s) (important in
rubber elasticity)
e.g.
e.g.: thermoplastic stretch
Crystallinity
Degree of crystallinity can affect the mechanical properties
e.g. 1
LDPE

soft/flexible material (20% crystallinity)
HDPE

more rigid (high crystallinity – 70%)
72
Undeformed
high S
Deformed (low S)
High S
Molecules are
random
High S
Molecules are
aligned
Low S
High S
molecules
fibre
ε
σ
· ·E Slope
σ σ
ε
σ
e.g. 2
Fibres – also can affect the mechanical properties
Glassy polymers (no crystallinity)
This materials is non-crystalline

amorphous solids. Below Tg, rigid/stiff

brittles
There are generally transparent e.g. contact lenses
This control by Tg

below Tg – glassy solids

above Tg – rubbery solids
Simple tensile deformation
length Original
length in Changing
Strain ,
Area
Force
Stress · ·
This behaviour

metal, ceramic, glass
Low strain behaviour

<0.1% strain
Behaviour of real polymer
e.g. 1
73
Crystal or molecules are
align parallel to the fibre
Good mech. properties
unload
load
σ
ε 2%
10% ε
σ
Yield point
PE
Rubber
No yield point
ε
σ
0
o
C
40
o
C
80
o
C
100
o
C
σ
glassy polymer. e.g. PS
Have slight historisis
Called non linear elastic behaviour
Also crosslinked elastomer
e.g.2
ductile thermoplastic e.g. polycarbonates
Plastic deformation (also some semi crystalline polymers e.g. PP)
High strain behaviour
Temperature dependent
With polymer we do get temperature dependent
Hard, brittle, rigid
74
Yield (plastic
deformation started)
500%
ε
constant
stress
time
strain
time
σ
glassy
V
T
T
g
Time dependent
e.g.: creep
Stress Relaxation
Transition and mechanical behaviour
2 main transition
1. melting at Tm
2. glass transition Tg
cause large changes in physical and mechanical properties
e.g.
mechanical

modulus, E
physical

specific volume
density
1
V ·
1. amorphous polymer – no T
m
75
E = function of
temperature and time E (t,
T)
rubbery
Brittle
glassy
solid
Soft rubbery
liquid
T T
g
E
Glassy
Crystal in
rubber
Rubbery
liquid
T
V
T
g
T
m
Tough
material
T T
m
T
g
E
Fibre
Glassy polymer
Semicrystalline polymer
σ
2. semicrystalline polymer
Theoretical Stiffness and Strength
Theoretical stiffness (modulus)
Stiffness varies with modulus
76
Elastomers
ε
1 GPa
100%
0%
1 MPa
f
f
α
α
L
a) elastomers, E ~ 1 MPa;
2 6 6
m N 10 Pa 10 MPa 1 ≈ ≈ (calculate using
thermodynamic)
b) semicrystalline,
2 9 9
m N 10 Pa 10 GPa 1 E · · ·
• modulus controlled by hard crystals is a glassy amorphous rubbery phase
• modulus depends upon degree of crystallinity Øc
c) glassy polymer, E ~ 3GPa (brittle)
d) fibre polymer, E ~ 100GPa++
• high orientated molecules
Calculation of E using L. Treloar
Bond angle = θ
Link length = 
Chain length = L
Angle wrt., force f = α
Number of links = n
Initially (undeformed) f = 0
α · cos n L 
Deformation – increasing length by dL
( ) α · cos n d dL 
n = constant,  & α = vary
77
θ
α
f
f cos α
x
f
α
pivot
2 
]
]
]
]
]

α α − α ·


  

c h a n g e
a n g l e b o n d
s t r e t c h i n g
b o n d
d s i n c o s d n
∴need to calculate d  and dα
Bond stretching,  d
From spectroscopy (infrared or Raman), force constant K
L
can be measured
Defined as
bond of extension
bond along force
K
L
·
 d
cos f
K
L
α
·
L
K
cos f
d
α
· 
From the diagram
( ) δα α − α · sin d cos n dL  


K
cos f α
· δ
δαis related to the bond angle change δθ
78
From geometry
o
90
2
·
θ
+ α
2
90
o
θ
− · α
( )
2
4
θ
δ − · δα −
Increasing the α angle will increase the θ in factor 2
Angular deformation force constant K
θ


defined from IR or Raman spectroscopy
angle bond in Change
bond a around acting Torgue
K ·
θ
pivot from distance lar perpendicu Force Torque × ·
x = distance from pivot
δθ
· ∴
θ
x f
K
α · → · α sin
2
x
2
x
sin


δθ
α
·
θ
sin ) 2 ( f
K

θ
α
· δθ
K 2
sin f 
Combine (4) = (5)
]
]
]

α −
· δα
θ
K 4
sin L f
Putting equation (6) and (3) into (2)
]
]
]

α
+
α
· δ
θ
K 4
sin
K
cos
nf L
2 2 2


79
Young modulus,
strain
stress
E ·
L dL
A f
E · ∴
]
]
]

α
+
α
α
·
θ
K 4
sin
K
cos
f n A
cos n f
E
2 2 2



]
]
]

α
+
α
α
·
θ
K 4
sin
K
cos
A
cos
E
2 2 2



2
90
o
θ
− · α
]
]
]

θ
+
θ θ
· ∴
θ
K 4
2 cos
K
2 sin
A
2 sin
E
2 2 2
 

Young modulus of polymer chain
• θ
K , K
 can be determined from spectroscopy
• A comes from unit cell cleminsion
• They gives E
PE
~ 180GPa
• PE fibres can have E high ~ 200GPa
• The actual modulus can be higher due to inter molecular interaction
Determination of crystal modulus
80
Flim
detection
fibre
f
f
x-ray
Ø
f
f
Stretch the molecule
c – lattice parameter changes with stress by
c δ
Crystal/lattice strain
c
dc
A
f
Stress ·
modulus crystal
c c
A f
E ·
δ
· ∴
e.g.
For PE crystal modulus ~ 250GPa
More than steel modulus ~ 210GPa
Crystal more stiffness than steel
Even though PE less density than steel
Factor controlling crystal modulus
a) Chain stiffness
Bond angles affect stiffness
81
c
Higher
modulus
e.g. rigid rod molecules
C C N N
O O
H H
n
Crystal modulus ~ 220GPa (same as steel)
True rigid rod molecules
N
O O
N
Most higher modulus of fibre
Fibre modulus ~ 280GPa
Crystal modulus > 400GPa
(Diamond E > 1000 GPa)
Use – rigid rod fibre made by solution spinning
b) Side groups
Adding side groups reduce modulus
PE PP
82
PE
rod
“PBO” zylon
Yield
point
σ
σ
y
e
y
ε
Shear
stress
σ
σ
CH
2
CH
2
CH
2
CH
CH
2
CH
CH
3
CH
3
Since
A
1
E ∝
PP – increase A,
↓ ∴E
PP crystal modulus E ~ 50 GPa
PE crystal modulus E ~ 250 GPa
Theoretical yield strength
Molecule deformation process
Elastic
 Reversible
 Structure – deforms but spring back
Plastic deformation
 Not reversible
 Molecules move past each other
Model – sheet of molecules sliding past each other
Assume σ varies with displacement
83
Yield – outset of plastic deformation
σ
y
= yield stress
e
y
= yield strain
x displacement
σ
h
b
σ
y
0
8
b
Touching each other
σ
y
0 b b/2
x
σ
Assume the shear stress varies sinusoidally with displacement
Equation

·
`

(
| π
σ · σ
b
x
sin
y
0 0 x · σ → ·
y
2
1
x σ · σ → ·
0 b x · σ → ·
For lower value of displacement,
0 sin → θ
b
x
b
x
sin
y y
π
σ →
·
`

(
| π
σ · σ
strain shear
stress shear
G modulus, shear ·
for small x

γ
σ
·
h
x
separation phase
nt displaceme
· · γ
x
h
G
σ
·
Or
84
dislocation
10 nm
h
Gx
· σ
(2) = (3)
h
Gx
b
x
y
·
π
σ
]
]
]

π
· σ ∴
h
Gb
y
e.g.: PE
b = spacing of atom along the chain
nm 26 . 0 c , nm 125 . 0
2
c
b · · ·
h = 0.25 nm
b
G
25 . 0
125 . 0 G
y

× π
×
· σ
∴Yield stress is theoretical ½ shear modulus
Behaviour of real polymer
At room temperature
100
G
~
y
σ
for PE
As temperature
0 →
b
G
~
y
σ
(theory only valid at 0
o
K)
 Yield is thermally activated
 Yield may be controlled by the activation of dislocation
 Dislocation are thermally activated
85
x displacement
Equilibrium
separation
compression
h
σ
σ
t
tension
u
o Not breaking the covalent bond but the Van der Waals bond break
o Because it slide past each other
o Yield point → break Van der Waals bond
Theoretical Tensile Strength
Need to calculate the forces/stress required to break the covalent bond
e.g.: backbone chain
86
x separation
h
x=0
x/2
Work done
2 new surface
σ σ
Assume dependence of σ, σ upon displacement, x can be approximated by a sin curve

·
`

(
|
λ
π
σ · σ
x 2
sin
t
λ = wavelength
σ
t
= theoretical strength
Now strain or displacement
θ → θ →sin
λ
π
σ · σ
x 2
t
Now strain Hooke’s Law is obeyed
h
Ex
strain modulus · · σ
Combine (2) = (3)
h
Ex x 2
t
·
λ
π
σ
]
]
]

π
λ
· σ ∴
h 2
E
t
Consider fracture process – create new surface
Work done in creating the surface can be related to the surface energy of the surface
between surface energy = γ
Work done = area under σ vs λ curve
Surface energy ≡ work done
87
λ
·
`

(
|
λ
π
σ · γ

λ
d
x 2
sin 2
2
0
t
88

BASIC INTRODUCTION OF POLYMERIZATION COMMON TECHNIQUES FOR POLYMERIZATION 1. 2. 3. 4. Solution polymerization Bulk polymerization Suspension polymerization Emulsion polymerization

All techniques can either used free radical or ionic polymerization method. IONIC POLYMERIZATION 2 types : i) Cationic (active centre, +ve charge) ii) Anionic (active centre, -ve charge) Ionic polymerization is monomer selective compare to radical polymerization.Ionic polymerization only can occur with a monomer having side group that stabilized the active group. Active centre for cationic monomer (polymerization will occur if the side group (X) is electron donor or can delocalize +ve charge)

H C C H H X

ACTIVE CENTRE

SIDE GROUP
Active centre for anionic monomer (polymerization will occur if the side group (X) is electron acceptor or can delocalize -ve charge)

H C C H H X
However, not all monomer can be polymerized using both types of this ionic polymerization.

2

Table 1: Susceptibility of various types of monomers to free-radical, cationic and anionic polymerization Monomer Ethylene 1-Alkyl olefins + 1,1-Dialkyl olefins 1,3-Dienes Styrene, α-methyl styrene Vinyl halides Vinyl esters Vinyl ethers Structure CH2 = CH2 CH2 = CHR1 CH2 = CR1R2 CH2 = CH – CR = CH2 CH2 = CRPh CH2 = CHX CH2 = CHOCOR1 CH2 = CHOR1 Free-radical √ (x) (x) √ √ √ √ (x) Cationic √ (x) √ √ √ x x √ Anionic x x x √ √ (x) (x) x

Acrylates, CH2 = CRCOOR1 √ x √ methacrylates √ means susceptible, x means not susceptible, and (x) indicates that whilst the monomer might be expected to polymerize (e.g. on the basis of inductive and/or mesomeric effects) it does not do so successfully because of side-reactions (e.g. chain transfer) R1 and R2 = alkyl, R = H or CH3, Ph = phenyl, and X = halogen + Also called α-olefins Note that: Styrene and Diene monomer can be polymerized using both anionic and cationic as well as free radical polymerization: i) the monomer side group have significantly lower inductive effects. ii) side group can delocalized both charges. Differences between free radical polymerization and ionic polymerization. i. ii. iii. iv. v. Rate of polymerization for ionic faster compare to radical. In the propagation step, ionic active centre must couple with different charge counter-ion, Rate and stereochemistry for ionic : the propagation depends on counter-ion and degree of active centre formation. For ionic polymerization, termination by 2 active chains could not occur compared to free radical polymerization. Rp and Xn (degree of polymerization) for ionic highly dependent on the solvent used. 3

ANIONIC POLYMERIZATION  Active centre –ve  Monomer side group, x = e- acceptor and delocalized –ve charge  Normally occur for monomer conmtaining strong electronegative side group. (forming carbonion). e.g. side group : benzene  E.g:
NH2
-

+ CH2 CH

NH2 CH2 CH

-

karbonion

→ solvent requirement
Mechanism 1. Initiation a) Formation of ionic initiator - butyl lithium + solvent (dioxane)

O CH3CH2CH2CH2Li + O

O O
CH3CH2CH2 CH2 +

Li O O

=

R Li karbonion @ R-

4

b) monomer activation (formation of active centre) O O R Li -+ + CH2 CH ki RCH2 CH Li O O RM Li 5 .

2. Propagation RM Li + M kp O O R CH2 CH Li O O kp O O R CH2CHCH2 CH Li O O + CH2 CH RM2 Li 6 .

propagation kt RM n + LiOH3 + CH3OH …………….. Termination → methanol often used O O Li O O + CH3OH H C CH2 + LiOCH3 Kinetic scheme R Li RM Li RM n Li + + M nM ki kp RM Li ………………initiation RM n Li …………….termination 7 .3.

Rate of polymerisation = Rp R Li 1) = I & RM n Li = P Initiation rate = Active centre formation rate −d[ M − ] = k i [ M ][ I] dt 2) Propagation rate = Rp d[ M ] = k p [ P − ][ M ] dt 3) Termination rate = rate of disappearance of active centre [P − ] = k i [ I][ M ] k t [CH 3 OH ] R p = k p [ P − ][ M ] Rp = k i k p [ I][ M ] 2 k t [CH 3 OH ] Degree of polymerisation = X n Xn = rate of polymerisa tion initiation rate rate of propagatio n rate of terminati on Xn = Xn = k p [M ] k t [CH 3 OH ] Factors affecting anionic polymerization 8 .

Solvent e.g. solvent such as THF (tetrahydrofuran) allows the Rp to be dependent on [M] & [I] → Rp ↓ If the THF were used. so activation energy increases And vice-versa. Discussed in term of activation energy counter-ion Butyl lithium M ⊕ → Li ≈ K Rb Bu M Ce Na Li : the smallest counter-ion Ce : the biggest counter-ion ∴the smallest the counter-ion. BuLi P H C X P Li ≈[ P −+] d i s t a n 9 . e.g. Temperature k = A exp −E R T 2. ∴ selection of solvent is a critical.: styrene polymerisation. it will form both carbonion and free cation. therefore the smallest the separation between monomer and counter-ion. Depends on particular system. 3.1. Solvent Solvent gives significant contribution in the Rp for ionic polymerization. dioxane normally used because it will not allowing the Rp to be depending on [M] @ [I] Whereby.

c e b e t w e e n c o u n t e r i o n a n d m o n o m e r s m a l l e r P H C X P P Li P 10 .

This cation will take part in the reaction. propagation and termination Active centre created by reaction. electrophiles   Monomer (R) + → R+ (carbonium ions) 11 . CATIONIC POLYMERSATION Chain polymerization: initiation. therefore it will form free cation and carbonion.≈[P − ] Distances between counter-ion and monomer bigger.

 However hydrogen halide – not suitable (because the halide counter-ion combines to active centre to form stable covalent bond. H2SO4 and HClO4 often used as initiators. water or acid or organic halide. Asid BF3 + + Air H2O → → complex H+(BF3OH)– Activation of active centre H+(BF3OH)- + CH2 CR1R2 CH3 In general. BF3.g.  Therefore lewis acids e. This involves addition of proton (H+) to monomer.  Protonic acid e.g. + CR1R2(BF3OH)- R+A- + CH2 CR1R2 RCH2 + CR1R2A - karbokation Propagation 12 . AlCl3 and SnCl4 most important for cationic polymerisation. ii.g.  But must be used inconjunction with co-catalyst e. Initiation i.

Chain transfer CH2 + CR1R2A- CH CR1R2 + CH3 + CR1R2A- Polymerisation kinetics Polymerisation mechanism depends on: 1. monomer structure 3. occur heterogeneously because initiator is only partially soluble in the reaction medium.RCH2 + CR1R2A- + CH2 CR1R2 RCH2 CR1R2 CH2 Termination i. a kinetic scheme can be applied but BUT observation on the specific reaction mechanism must be applied with discretion. types of initiator 2. solvent Cationic polymerization. Nevertheless. General kinetic scheme 1) initiation 13 . Spontaneous decomposition + CH CR1R2A + CR1R2A - CH CR1R2 + H+A- ii. This feature makes the formulation of general kinetic scheme somewhat difficult.

R A I 2) +- + - + + M M ki ki RM1 A I M +- + - Propagation RM+ An P+3) Termination + + M M kp kp RM+ A n+1 P+-M - RM+ An + - k 't k" t RMn + H A + - RMn A RM n + HM+A- Rate of polymerisation Rate of polymerisation = Rp = K i [ R + A − ][ M ] = K i [ I ± ][ M ] [ I ±] = Initiator concentration [M] = Monomer concentration rate of polymerisation = Propagation rate Rp = − d[ M ] = rate of monomer used dt R p = K p [ RM +A − ][ M ] n R p = K p [ P ± ][ M ] = − d[ M ] dt [ P ± ] = active centre concentrat ion (carbocati on) 14 .

Rate of termination = R t i. Transfer = K [P ] " t ± In general. rate of termination R t = K t [P ± ] If reaction occur in steady state Rate of active centre formation Ri = = = Rate of disappearance of active centre Rt Initiation rate termination rate ∴ i [ I ± ][ M ] = K t [ P ± ] K [P ± ] = Ki ± [ I ][ M ] Kt R p = K p [ P ± ][ M ] Rp = Kp Ki Kt [ I ± ][ M ] Degree of polymerisation = X n Xn = Polymerisa tion rate Initiation rate 15 . ' + − Spontaneously = K t [ RM n A ] ' ± = K t [P ] ii.

= Propagatio n rate Terminatio n rate = K p [ P ± ][ M ] K t [P ± ] Kp Kt [M] Xn = Additional knowledge on ionic polymerisation Effect of R p and X n on temperature Rp = Kp Ki Kt [ I ± ][ M ] K = constant Rp ↑ → T↓ * ARRHENIUS [ K = A exp −E R T ] RT Rp = A p exp − E p RT × A i exp − E i − E t RT A t exp A p Ai At exp [ I ± ][ M ] Rp =  E p + Ei − E t −  RT      Activation energy of propagation lower (very small) therefore: E p << E i . overall E will be +ve 16 . Degree of polymerization αn = Kp Kt [M] Hence. E t < ∴Rp or overall rate increases when the temperature decreases.

However. Ep –ve for degree of polymerization. So. The linear polymer can be either homopolymer or co-polymer. why do we need network formation in polymers? Think! Think harder! 17 . non-linear polymerization to form network is rather very useful in industry or for advance nano-technology study.Arrhenius: Dp = Ap At − Ep − Et ( ) exp RT [M] Normally. NON-LINEAR POLYMERIZATION AND NETWORK FORMATION All the polymerization studied before either condensation or chain polymerization basically lead to the formation of linear polymer. Therefore molecular weight increases when temperature decreases.

crosslinks or networks are needed to satisfy the end product used. crosslink density) 10.e. Linear polymer normally a long polymeric chain. At gel points reached infinite viscosity. therefore it may not withstand the requirements of heat during processing (designing polymer packaging) or after shape of the polymer (commercial used). Alkyd-Resins 18 . So. Network formation first occurs at a gel point 7. After gel point the amount of network increase and reach up to 100% network 8.e. There also linear polymers in the foam of liquid with high viscosity. Long chain has elastromer behaviour The examples of non-linear polymerization or network formation will be divided into TWO groups i) condensation type (2 monomers of different functional group) ii) polymeric chain (polymer chain with basic carbon-hydrogen bond) Condensation type 1. a network 6. the molecule grow more quickly 5. As molecular size increases the number of reactive group increase 4. it is flexible and soft.Simple answer. For a given large number of reactive group. therefore no flow exceeds this gel points 9. At least one monomer have more than 2 functionality 2. Short chain has stiffer and rigid material 11. Whole polymerization system give one molecule i. Structure cannot be uniquely defined for a given number of monomer unit (many isomers) 3. Properties depend on the structure and the density of junction points (i. Crosslink Features 1. many polymers have lower thermal stability and mechanical strength. Furthermore.

O CH2OH CHOH CH2OH 3 f.g. + C O C O + H2O /trace COOH COOH CO C O O CH2 H C OH CH2 O CO C O junction point To form a flexible network add glycol (diol) → HO − CH 2 CH 2 − OH ∴more dilute junction points 2. Phenoplasts (thermosetting resins) Phenol formaldehyde resins (PFDR) 19 .

H H OH C O + H2O aqeous media CH2 OH formaldehyde formalin PFDR formed by Formaldehyde + phenol Condensation → ortho and para position 20 .

g. Aminoplast (Urea Formaldehyde Resin) 21 . 3 H2O CH2OH or catalyst CH2OH + and + H CH2 methylene bridge CH2OH HOCH2 CH2 O CH2 ethylene bridge OH CH2 O CH2 CH2 CH2 OH O CH2 Short chain between junction points gives rigid material 3.g. + o m p o m OH HOCH2 CH2OH + gives 3 f.OH HOCH2OH 2 f.

Melamine Formaldehyde Resin 22 .Carbamide + formaldehyde in alkaline solution H2N CO NH2 + HO CH2 OH H2N CO N H CH2 OH + H2O + n(HOCH2OH ) and H2NCONH2 NH2 CO N CH2 CO N CH2 CH2 N CH2 N CO CO Use as coating 4.

Polyurethanes 23 .Melamine + formaldehyde H2N C N N C C N NH2 + n HOCH2OH NH2 neutral or alkaline conditions N C C N N CH2 OH CH2 OH acid condition + H2O N C C N H H N CH2 N C N N O Short chain between junctions ∴ rigid material → formica Used MF resin + PFDR 5.

Triol Formation of triol CH2OH CHOH CH2OH + → glycerol + epoxy alkane (epoxy ethylene) or epoxy CH2 CH2 O or CH2 CH O CH3 via ring opening + NaOH propylene HO CH2CH2 O CH2 O CH O CH2 O CH2CH2 OH CH2CH2 OH CH2CH2 OH triol (polyol) 3 f.4 2.g. PPE (primary OH) ∴ more reactive than PPO (secondary OH) But PPO better adhesive Diisocyanate: 1. TDI (toluene diisocyanate) Mixture of 2/4 and 2/6 isomer CH3 NCO + OCN CH3 NCO NCO 2. MDI (diphenyl methyl diisocyanate) 24 .6 2.

Epoxy Resin Epichlorohydrin + bisphenol A 25 .OCN CH2 NCO Polyurethane formation: diisocyanate + polyol (triol) CH2 N H O O(CH2)4 O C C O hydrogen bonding H N CH2 hand segment O (CH2)4 6.

26 .

Diepoxy with a Diamine 27 .

28 .

29 .

Natural Rubber Used poly isoprenes CH2 C → 2 isomers CH2 C CH CH2 CH CH2 CH3 NR poly (cis isoprenes) CH2 CH3 CH2 H CH3 CH2 H C C CH3 C C CH2 NR poly (trans isoprenes) CH3 CH3 • • • • H C C CH2 CH2 CH3 H C C CH2 Open ring less elasticity 6000 – 30.Crosslinking of Polymer Chain Alternative to form crosslinking is by vulcanization (Δ by sulphur) 1.000 bond per chain NR is linear chain not elastomer – needs to form network by crosslinking To form crosslinking – used heat and sulphur 30 .

elastomer 30% sulphur → hard material with fillers Few % sulphur → tyres 31 .g.CH3 + CH2 C CH CH2 sulphur (Sx) CH3 CH2 C SxH CH2 CH2 + CH2 CH3 C CH2 CH2 CH3 CH2 C Sx CH2 C CH3 CH2 CH2 CH2 CH2 1% sulphur → soft material e.

Butyl Rubber Isobutylene + 2% isoprene the crosslinked CH3 CH2 C CH3 CH3 CH2 C CH3 PIB + 2% isoprene CH3 CH2 CH3 CH2 C CH3 CH2 C CH CH2 CH2 C CH3 CH3 CH3 CH3 CH2 C 32 .2.

3. Peroxide Crosslinking t-butyl peroxide (CH3)3 C O O C(CH3)3 (CH3)3 CO In general R O OR OC (CH3)3 2 OR For Natural rubber & butyl rubber can be crosslinked by this free radical CH3 CH2 C CH CH2 150oC CH C CH CH2 + ROH + OR CH3 crosslinked CH C CH CH2 CH3 33 .

1.represents a polyolefin chain and R is a chain branch which is common in low density polyethylenes. then can combine with other polymeric radicals to form carbon-carbon crosslinks. 1.1 Reac 1.4. RO OR CH2 CH CH2 R Tertiary hydrogen heat 2 RO ROH + CH2 C CH2 R polymer radical Reac.3. -CH2-CRH-CH2.3 CH2 CR CH2 34 . This mutual termination of the polymer radicals (normally alkyl radicals [Yamazaki and Seguchi 1997]) is the predominant reaction if net crosslinking is observed and is shown in reaction 1. CH2 CR CH2 CH2 CR CH2 CH2 CR CH2 Crosslinking Reac. using peroxide The peroxy-radicals (free radical) then the radical abstracts a hydrogen atom from the carbon-hydrogen bond in the polymer molecule (which is preferentially the weak tertiary hydrogen atom from chain branching sites). Polyolefin crosslinking i. The resultant polymeric radicals.2) [Kircher 1987]. formed by the primary radical abstracting preferentially tertiary hydrogen from polymer chain (reaction 1. This polymer radical may then undergo either combination or cleavage.2 RO + where RO-OR is the peroxide.

4 CH3 + CH CH2 CH CH3 CH3 Also chain radicals can lose their activity by formation of an alternative radical (reaction 1.5 Reaction 1. the rate of combination must exceed the rate of the alternative chain scission reaction. In order to achieve net crosslinking.6 35 . PP contains a tertiary hydrogen on alternate carbon atoms and unzips (reaction 1. CH2 CR CH2 + OR CH2 CR CH2 OR Reac.6 shows that polymer radicals may also be deactivated by reaction with a primary radical. However in the case of polypropylene (PP) it is much more highly prone to radical decomposition (cleavage). This is promoted at high temperatures and with increasing tertiary hydrogen concentration in the main chain [Kircher 1987]. making it difficult to achieve net crosslinking as the polymer “unzips”.4) with chain scission dominating the chain scission/crosslinking balance giving net molecular weight reduction and no network. 1. CH2 C CH2 C CH2 CH CH2 CH CH3 CH3 CH3 CH2 Reac. 1.The mutual termination of polymer radicals represents the desired formation of a crosslink and is the essential step. 1.5) H CH2 CR CH CH2 CH2 CR CH CH2 + H Reac.

Silane System + + P P P + + H H2 P (crosslinking) Vinyl silane is grafted on to the base polymer (e. 36 .g.7). As the electron gives up energy when striking the C-H bond. CH2 CR CH2 + H CH2 CH CH2 R Reac. A simplistic scheme is shown. Using Irradiation β -radiation produced by large accelerators is therefore commonly used in crosslinking polyethylene. CH2 CH CH2 CH2 ii. polyethylene) using a small quantity of peroxide compared with traditional crosslinking.Under certain conditions other radicals can recombine resulting in inefficient termination of active radicals (reaction 1. trivinylmethoxysilane. The peroxide will break the double or unsaturated bond in vinyl silane e.8 PH H P iii. 1.8). Then the subsequent steps to crosslink formation where the silanol condensation reaction occurs very slowly at room temperature but proceeds relatively swiftly at elevated temperatures in the presence of a specific silanol condensation catalyst such as dibutyltindilaurate (DBTDL). The energetic electrons strike the molecules near to the C-H bond. the energy is enough to break the C-H bond to produce a hydrogen radical and a polymer molecule in an excited state (free radical). Therefore the excited carbon atoms can use their energy to form covalent C-C bonds. 1. and bind it to the polymer chain. rad PH P CH2 CH2 CH CH2 Reac. CH2=CH-Si(OCH3)3.g. Typically it is 20 times smaller.7 Finally it is also possible that radicals shift along the polymer chain (reaction1.

+ CH2 CH Si(OMe)3

Peroxide

CH2 CH2 Si(OMe)3

Reac. 1.12

Polyethylene

Vinyltrimetoxysilane H2O Hydrolisis

Grafted component

CH2 CH2 Si(OH)3 + 3 MeOH

Reac. 1.13

CH2 CH2 Si(OH)3

+

CH2 CH2 Si(OH)3

Heat

Catalyst (DBDTL) (Condensation)

Reac. 1.14

OH OH

OH + H2O OH

CH2 CH2 Si O Si CH2 CH2

Crosslinked polyethylene

The disadvantages of using silanes for crosslinking reported in the literature are [Kircher 1987, Gale 1984]: (i) once grafted, the half-life of the material is short especially if exposed to moisture which results in storage problems.

37

(ii)

curing is often performed in a temperature controlled water bath, which can cause diffusion of moisture into the polyethylene.

POLYMER CHARACTERIZATION Polymers may be 38

• • • •

Oily liquids Soft, deformable rubbers Hard, brittle glasses Tough, flexible semi-crystalline materials

The properties of a polymeric material may be related to its • Molecular characteristics (nature of the repeat units; arrangement of the repeat units; molecular size and its distribution) which depend on polymerization chemistry • Morphology (arrangement of molecules), which may vary according to processing conditions (thermal history) Most techniques for studying the molecular characteristics of a polymer require it to be in dilute solution. Question What physical quantities may be used as measures of the size of a polymer molecule? Molar Mass Distributions Number-fraction distribution ni = number-fraction of species i Ni ∞ = ∑Ni
i =1

Ni = number of molecules with molar mass Mi

Weight-fraction distribution wi = weight-fraction of species i Wi N M = ∞ i i ∞ = ∑ Wi ∑ Ni Mi
i =1 i =1

Wi = mass of molecules with molar mass Mi = NiMi Continuous representation of number-fraction distribution

39

N(M)dM

= number-fraction of molecules with molar mass between M and M+dM N(M)dM is proportional to the area of the strip

Total area under the distribution is

∫n ( M )dM
0

=1

Continuous representation of weight-fraction distribution W(M)dM = weight-fraction of molecules with molar mass between M and M+dM
n ( M ) MdM

W(M)dM =

∫ n ( M ) MdM
0

Total area under the distribution is Average Molar Mass Number-average molar mass:

∫ n ( M )MdM
0

=1

Mn

=

Σ NiMi Σ Ni
Σ Wi M i Σ Wi Σ Wi M i2 Σ Wi M i

=

Σ Wi Σ ( Wi M i )
Σ N i M i2 Σ NiMi

Weight-average molar mass:

Mw

=

=

z-average molar mass:

Mz

=

Relative values of average molar masses Polydisperse polymers: Uniform polymers: Most probable distribution:
M n : M w : M z = : 2 :3 1 M n <M w <M z M n =M w =M z

The ratio The ratio

Mw Mn Mz Mw

is a measure of the width of the number distribution is a measure of the width of the weight distribution

40

rD M [η . rV ] h Dilute solution viscometry rh . M Sedimentation zequilibrium h Sedimentation velocity 2 Direct Mn Calibration M range < 2 x 104 < 2 x 104 104 – 106 104 – 107 104 – 107 s.Techniques For The Determination of Molar Mass Technique End group analysis Mn Vapour pressure osmometry Mn Membrane osmometry Mw .→ r Diffusion DMh . Mw . Light < s > z scattering Mn . M D M V Gel Permeation Chromatography S : sedimentation coefficient D : diffusion coefficient MMD : molar mass distribution <s > 2 : mean square radius of gyration rh : hydrodynamic radius [η]: intrinsic viscosity V : elution volume GEL PERMEATION CHROMATOGRAPHY 41 .

but average molar masses are very uncertain Question Apparatus for gel permeation chromatography is illustrated schematically below. 42 .Gel permeation chromatography (size exclusion chromatography) Polymer molecules are separated according to size. molar mass distributions may be determined An excellent method for comparison of one sample with another. e. i. Label each of the components Dilute polymer solution is injected into solvent stream Columns contain porous beads.g. the largest molecules being eluted first With calibration. for process and product control Not so good for quantitative work: molar mass ratios are usually accurate.e.

g.Crosslinked poly(styrene) for organic solvents Crosslinked (polyvinyl alcohol) for aqueous solvents Silica gel. volume of liquid outside porous beads Where Vi = internal volume. often with its surface treated with trimethylchlorosilane to promote compatibility with organic solvents Eluent stream emerges into a detector (e. differential refractometer) Detector signal is plotted against alution volume to obtain the GPC curve Thermodynamics of the Separation Process Total volume of liquid inside column Vtotal = Vo + Vi Vo = void volume. ∆ o = 0 and ∆G o = − T∆S o o K e = exp( ∆S R ) i. volume of liquid inside porous beads Volume available to the solute is the elution volume Ve Which is between Vo and Vo + Vi Assume equilibrium between solute in the void and in the pores Solute in void ⇔ solute in pores Equilibrium constant (or distribution coefficient) K e = c i c o c o = concentration of solute in void Where c i = concentration of solute in pores o Standard state Gibbs energy change for permeation ∆G = − RT ln K e H If exclusion is the only separation process. Entropy change on reducing the available pore volume from Vi to Ve − Vo is Thus ∆ = R ln [( Ve − Vo ) Vi ] S K e = ( Ve − Vo ) Vi i.e. the elution volume of the solute is Ve = Vo + K e Vi When the solute molecules are very large and do not penetrate the pores K e = 0 and Ve = Vo When the solute molecules are very small and penetrate the pores to the same extent as the solvent K e =1 and Ve = Vo + Vi Between these limits. K e is determined by the exclusion of solute within pores 43 .e.

Each polymer/solvent pair has a different calibration curve. In practice the separation often includes contributions from partition and adsorption. Calibration Standards samples. These unwanted effects must be minimized in order to avoid misleading results. with different average molar masses and narrow molar mass distributions. Ve is expected to vary with log (solute size) The size involved is the hydrodynamic volume ( Vh ) i. These processes can move the peak towards (and beyond) the permeation limit (total volume. An additional problem occurs with aqueous solvents and negatively charged solutes. 44 . Vh ∝ M Ve ∝ log M Ideally separation should be only the basis of size. Vo + Vi ). may be used for calibration. the effective volume of the polymeric solute in the solvent For a polymer in a given solvent at a given temperature.Statistical-thermodynamical treatments of the exclusion problem show that: K e ∝ log (slolute size) Consequently. when electrical exclusion moves the peak towards the exclusion limit (void volume. Vo ).e.

calibration should be carried out with standard samples of the same polymer as the sample under investigation. When appropriate standards are not available. where [η is intrinsic ] viscosity. light scattering) which provide an absolute measure of molar mass 45 . this is based on the relationship [η M ∝ Vh Utilize on-line detectors (e.g. this is usually a reasonable approximation for vinyl polymers ] ] Use a ‘universal’ calibration plot of log [η M against Vpk .Ideally. This is not always possible. one may Quote ‘polystyrene equivalent’ or ‘poly(oxyethylene) equivalent’ molar masses Assume that polymer molecules with the same extended chain length have the same Vh and so elute at the same Ve .

46 . and why they differ from each other in shape.Question Analysis of gel permeation chromatography data for a polysaccharide gave the following plots. Explain what each plot represents.

[η] A measure of viscosifying power Plot ηsp c and  ηsp  c ln ηr versus c c   ln ηr   = = [ η]   c →0  c c→0 2 Intercept:   Slopes: ηsp c ln ηr 2 = [ η] − β[ η] c (Kraemer) c = [ η] + k[ η] c (Huggins) Units of [η]: reciprocal concentration. the hydrostatic pressure needed to force a known volume to flow through a capillary in a given time According to the Poiseuille formula. cm3 g-3 or dl g-1 Relationship Between [η] and M 47 . ηr ηr = η t ≈ ηo to η: viscosity of the solution ηo: viscosity of the solvent t: time for a specified volume of solution to flow through a capillary tube to: corresponding time for a pure solvent Specific viscosity. for both solvent and solution.DILUTE SOLUTION VISCOMETRY Capillary viscometer Used to study dilute polymer solutions Method consists of measuring. the viscosity of a liquid is proportional to the time it takes to flow through a capillary In practice. e. Intrinsic viscosity (limiting viscosity number). or ii. kinetic energy or shear Relative viscosity (viscosity ratio). c. you may need to correct for density. the time taken for a known volume to flow through a capillary at a given hydrostatic pressure. either: i.g. ηsp ηsp = ηr − 1 = η − ηo t − to ≈ ηo to A measure of the relative increase in viscosity Both ηr and ηsp depend on polymer concentration.

A coiled polymer molecule may be modeled as an equivalent hard sphere.88 (for a = Question Show that if the Mark-Houwink relationship [η] = KMa is applied to a polydisperse polymer.5 (up to 0.5 Viscosity-average molar mass. greater for a rigid rod) For a highly branched polymer: a<0.5) 1.5 In a good solvent: a>0. M v For a polydisperse polymer  Σ w i M ia Mv =   Σw i      1 a M v depends on the solvent and on the temperature through the parameter a M v <M w For most probable distribution: 0.8 for arandom coil. the average molar mass obtained is  Σw i M ia  a Mv =   Σw   i   Where wi is the weight fraction of species of molar mass Mi. 1 Hydrodynamic radius. Question 48 . M v M n =1.77 (for a = 0.Mark-Houwink relationship applies for a given polymer in a given solvent at a given temperature [η] = KM a log [η = log K + a log M ] In a θ-solvent: a = 0. rh The radius of a rigid spherical particle which behaves in the same way as the polymer molecule in the same liquid. assuming that the coil is not distorted by the shear stress and that solvent does not drain from the coil (impermeable coil model).7) M w M n = 2.

of the solute.5 φ where φis the volume fraction of . 3 Vh ∝ rh ∝ [ η] M Plot log [η] M against elution volume. On the basis.Einstein showed that for rigid spheres: ηsp = 2. plot log KM1+a against Ve. show that [η] ∝ r 3 M Where r is the radius of the sphere and M is its molar mass. spheres. BASIC INTRODUCTION ON PHYSICAL AND MECHANICAL PROPERTIES 49 . Ve Or. Vh. since [η] = KMa. Universal calibration in gel permeation chromatography Separation in GPC is determined by the hydrodynamic volume.

However because a polymer consists of crystalline and amorphous phases the molecular movements discussed above will still take place in the amorphous region. the others are found in all polymers to a greater or lesser extent. Consider a polymer at high temperature in the molten state. The first two are only observed in crystalline polymers. This leaves only vibration of the main chain but rotation of side-groups can continue until further lowering of the temperature causes all movement to stop at absolute zero. As the temperature is 50 . A transition is a point at which the properties of the material change due to a change in the movement of the molecules. Consider a material which remains amorphous through the whole temperature range. These transitions include crystal melting. all kinds of molecular motion are taking place: transition. crystalline transitions. The Glass Transition Temperature (Tg) This is the most important transition to be found in amorphous polymers although it does occur in crystalline polymers its effects are less significant as it is associated with main chain movement in the amorphous region.TRANSITION IN POLYMERS Introduction An understanding of the physical properties of polymers and in particular the relationship between these properties and molecular structure can only be achieved by an understanding of the transition that occur in these materials. This gives rise to a soft material with large elastic deformation. The explanation for these changes is that above the glass transition point the molecules are free to rotate about bonds and the forces between molecules are weak such that when a force is applied segments of the molecule are capable of changing their conformation. As the temperature is lowered. the glass transition and secondary transitions. If the polymer wishes to crystallize then crystallization will be the first transition. It is the temperature at which the properties of the polymer change from rubbery (low modulus and large elastic deformation) to glassy (high modulus and brittle). All these movements require different amounts of energy. Further temperature reduction leads to segmental rotation of the main chain stopping. The changes in physical properties are completely reversible in that a glassy polymer can be made rubbery or vice versa depending on whether it is above or below its transition temperature. rotation and vibration of the main backbone chain and of the side groups. translation requires the most energy and therefore is the first to stop and the polymer stops flowing. which is generally a consequence of a change in temperature but in viscoelastic materials can also be brought about by a change in time scale.

Other properties change significantly at the glass transition temperature: thermal expansion coefficients. Factors Affecting Glass Transition (Chemical Structure) 1. electrical properties. heat capacity. etc. modulus. damping behaviour. refractive index. chain flexibility a) flexible chains – low energy barrier – low Tg Tg Polydimethyl silozane CH3 CH3 H H C C H H CH3 CH3 -123 oC Si O Si Polyethylene -120 oC b) rigid chains – high energy barrier – high Tg Tg Polycarbonate O CH3 C CH3 O O C +150 oC T Energy barrier to rotate the molecule contain benzene ring is high ∴ g ↑ 51 . When this happens the chain segments become frozen into fixed positions and the random rotation about are suppressed and with it the capacity for undergoing large deformations. In the rubbery region the modulus is usually about 2MNm-2 and the breaking strain can be up to several hundred percent.lowered the thermal energy of the chain segments progressively falls until a point is reached at which the energy is no longer sufficient to overcome the energy barriers to rotation and the forces between molecules. if it is above then it is glassy and if it is below then it is rubbery. The mechanical properties of all amorphous polymers in their glassy state are approximately the same with a modulus of about 2GNm-2 and a breaking strain of 2-3%. specific volume. Whether a polymer is glassy or rubbery at room temperature depends on the location of its glass transition temperature.

2. bulkiness of side group The bigger/bulkier of the side group the more the energy to rotate the molecule ∴ high Tg Tg polyethylene H H C C H H H H C C H CH3 polystyrene H H C C H -120 OC polypropylene -18 OC +100 OC 3. steric hindrance. increases Tg 52 . increase length of flexible side group – lower the Tg Although increasing the side group Tg ↑ but if the side group is flexible side group ∴ lowering the energy to rotate the molecule Because the flexible side group easier to rotate and contribute the mobility of rotation ∴ lowering the Tg H H C C H OR2 R2 CH3 CH2CH3 CH2CH2CH3 CH2CH2CH2CH3 Tg -10 oC -17 oC -27 oC -32 oC 4.

Where the CH3 located will effect the Tg Tg Polystyrene H H C C H +100 oC Poly p-methyl styrene H H C C H +110 oC CH3 Poly o-methyl styrene H H C C H CH3 +120 oC 5. polarity of side group increases Tg Tg Polyethylene H H C C H H Polyvinyl chloride H H C C H Cl Polyacrylonitrile H H C C H CN +87 oC -120 oC +104 oC Cl is electronegative group therefore it will form a bonding will hydrogen with the second molecule this will give strong molecular force ∴ easy to rotate not 53 .

symmetry of side group decreases Tg equivalent mass on the both side of the side group will ∴ Tg ↓ ↓ ∴ E easier to rotation Tg Polypropylene H H C C H CH3 Poly isobutylene H CH3 C C H CH3 Poly vinyl chloride H H C C H Cl Poly vinylidene chloride H Cl C C H Cl -19 oC +87 oC -70 oC -18 oC The Used Of Free Volume Concept To Determine Tg 54 .H C C Cl H+ C C Cl ↑ The more polar the side groups the more difficult to rotation ∴ Tg (CN more polar than Cl) 6.

V = Vo + Vf 55 .free volume constant (below Tg) Vo – volume occupied by molecule ( ↑ temperature) Vf – free volume Total sample volume . Lower cooling rate ↓Tg o Because of the semicrystalline polymer contain crystals and amorphous ∴ difficult to determine the Tg accurately o ∴ volume concept use to determine Tg free o Free volume is the space in solid or liquid that not occupied by polymer molecules → empty space between molecules o In liquid – free volume is high ∴ molecular motion can take place easier because the unoccupied volume allows the molecule to move ∴ change their conformation o Lower the temperature  Reduce the thermal energy for molecular movement  Lower the amount of free volume ∴ molecule cannot move the eventually → glassy polymer o Lower temperature  ↓ thermal energy to rotate  ↓ free volume to move V Free volume (Vf) Vf Vf* Occupied volume (Vo) T Vf* .o To demonstrate the glass transition and determine the Tg value of a polymer is specific volume (measuring) as a function of temperature o As in the region above and below the Tg → is a linear variation in specific volume with temperature o But in the vicinity of Tg there is a change in slope o Tg determine by extrapolation of the 2 lines meet o The exact temperature depend upon the cooling rate.

Fractional free volume . NOT in changing in molecular structure of side group o Free volume explanation High molecular weight Few long chain Few chain end o ↑ molecular Low molecular weight Lots of small chain Lots chain end weight 56 . f = Vf  free    V  total  Below Tg fg = Vf* V Above Tg  dV  Vf = Vf* + (T − Tg )    dT  Vf V* 1  dV  = f + ( T − Tg )   V V V  dT  Expansion coefficient of free volume αf = 1  dV    V  dT  ∴ = f g + (T − Tg ) α f f For many polymers fg is found to have same value Molecular Weight o For low molecular weight → low Tg o Increase in molecular weight → increase Tg o This can be explained by free volume concept.

between Tg and Tg f c = αf (Tg∞ − Tg ) ∴αf Tg∞ − Tg = ( ) 2 ρN A θ Mn 57 .   end → ↓ free volume ↓mobility volume → ↑Tg ↓chain Dependence of Tg on Molar Mass Tg increases on molar mass increases ∞ Tg = Tg − K M ∞ Tg is Tg at infinite molar mass K is constant Density ρ = number × mass of each chain volume Mass of each chain = Mn NA NA = Avogadro number ρ= N Mn × V NA ∴ ρN A N = V Mn ρN A Mn Number of chain ends per unit volume = 2 θ = amount of fractional free volume at each chain end Total fractional free volume fc fc = 2 ρN A θ Mn ∞ fc represents increase in free volume above Tg i.e.

↓Tg Crosslinking and Tg o Crosslinking will pull the chain together o ↑crosslinking  ↓ free volume  ↓ mobility  ↑ Tg Copolymer and Tg o Copolymer is 2 polymers combine together by chemically made  Random  Alternate  Block o One Tg between TgA and TgB (for compatible syatem) o If not compatible (in compatible) → 2 Tg’s o For compatible system W W 1 = 1 + 2 Tg Tg1 Tg 2 W = weight fraction of the 2 homopolymer o With Tg1 and Tg2 the transition Secondary Transition o Most polymer show small secondary transition below the main Tg o Which related to side chain movement o Because side chain required less energy than the main chain to rotate the temperature at which they occur is always less than Tg o This is important in determining such properties as toughness and impact strength 58 .Or ∞ Tg = Tg − 2 ρN A θ αf M n K M ∞ Tg = Tg − Branching and Tg Branching ↑free volume → ↑mobility.

B – whole side group movement 3. D – other interaction Energy loss 20 oC 100 oC PMMA PS Tg Secondary transition Temperature o PMMA is higher than PS because of secondary transition Crystal and melting of polymer Crystalline Transitions The most significant transition in crystalline polymers is the crystalline melting point. 59 .A O B C C O R D o Secondary transition lower the Tg due to: 1. Tm. Tm is always higher than Tg. It is the temperature at which the crystalline material is converted from a highly ordered structure into an amorphous liquid. C – part side group movement 4. A – limited main chain movement 2.

strong inter-molecular forces. ∴ molecule get together → polymer in main chain o Tm ≈ 1.57 1. polypropylene. For example o Eg. tough & hard than rubber but not brittle o Phase separation  amorphous  crystalline Specific volume amorphous rotation vibration Tg Tm Temp joint point o If amorphous is heated vibration occur.5 Tg (unsymmetric) Tm K 410 470 590 538 Tg K 153 254 377 342 ∴ stop PE Poly vinilidene chloride PAN PET Tm/Tg 2.68 1. Other secondary transitions occur in the crystalline regions of crystalline polymers and these are usually due to reordering of the crystalline structure leading to a greater perfection of the crystalline units. Polyethylene. chain symmetry. crystallizing o At high Tg → high Tm o Tm ≈ 2 Tg (symmetric) → pack better.85 1.57 60 .V.Because Tm involves an abrupt change in the primary thermodynamic function volume it is usually referred to as a first-order transition whereas Tg is usually referred to as a second order transition. chain stiffness. and mobility increase o At the joint point is these Tm o By cooling → below Tg → the molecular movement stop. The structural features which give rise to high melting points are the same as those which give rise to high glass transition temperatures i.e. the F. therefore. nylon have Tg and in addition have Tm o Flexible.

e. crystallization temp 61 . hardness increases 2.67 1. thermal cond. modulus. specific heat decreases thermal expansion decreases gas permeability decreases and creep decreases Melting Simply reverse of crystallization But again melting is more complex with polymers than atomic solid Main features a) cannot define a simple value of melting points – melting takes place over a range of temp b) melting behavior depends on specimen history. density.6 PP 538 442 323 273 1.62 o As crystallinity increases: 1.g. increases 3.Nylon 6.

e.c) melting depend upon heating rate. due to molecular structure of the crystal 2. 10 oC/min T value Not same m 20 oC/min ∴ to establish as equilibrium melting temp. chain bonding Thermodynamic of Crystal Melting γe  x γs y γe = fold surface free energy γs = side surface free energy Surface free energy Melting causes reduction in surface free energy (destroyed surface) Decrease = 2 xγs + 2 yγs + 2 xy γe Volume free energy ΔGv Increase = xy ∆G v (due to molecules going from crystal to melt) 62 .g. need e.g. crystallize at different Tc → o Tm give different crystal thickness ∴ different Tm o Determination of Tm Some polymer crystallize at different Tc. measure their Tm value Need to plot graph Tm Vs Tc Tm o Tm Tm = Tc Tc Draw line at 45o that Tm = Tc o The Tm is the melting temp L ⇒∞ Normally Tm > Tc for finite size crystal and Tm = Tc for ∞ size crystal Why does Tm depends on crystal thickness? 1.

Chemical Physical factor For a given chemical type of polymer then physical factor can control Tm e.g. ∆G = xy ∆G v − 2 ( x + y ) γs − 2 xy γ e NB: Crystal itself x. Physical 2. molar mass (length of molecules) branching (linear branched) * this will introduced effects into crystal due to chain ends 63 . y >>> e ∴ the side equation lose ∆T Also ∆G v = ∆H v o Tm o ∆T = Tm − Tm ( ) For melting ΔG = 0 ∴xy ∆ v = 2 xy γe G G v = 2 γe o 2 γ e ∆H v Tm − Tm ∆G v = = o  Tm o o Tm − 2 γ e Tm ∴Tm = ∆H v ( ) Tm T o m extrapolation o − 2 γ e Tm Slope = ∆H v 1  If known ΔHv for calorimetry. ∴ calculate γe can Factors Affecting Tm 1.Overall free energy change.

1. branching – branch points in crystal  linear PE Tm = 150 oC  branched PE Tm = 110 oC Chain end (low molar mass & branches) → detect in crystal. molar mass – chain end effects  If molar mass → ∞ perfect crystal obtained  If molar mass → finite – defractive crystal obtained 2. this reduce Tm value Can interpret in term of “chemical potential” ⇒ µ Define µc = chemical potential per mole of repeat unit of polymer in crystalline state u o µu = chemical potential per mole of repeat unit of polymer in the liquid state (standard state) Free energy fussion = ΔGu ∆G u = µo − µc u u (1) Pure polymer system Change in chemical potential going from liquid to solid ( final ) µ c − µ o = − ∆ G u = − ( ∆ H u − T ∆S u ) u u ( initial ) (2) μ = per mole of repeat units As before ∆S u = ∆H u o Tm     (3)  T µc − µo = − ∆H u 1 − o u u  Tm  (4) Consider the effect of chain ends “impurities” Introduce the concept of “activity” → a = activity of crystalline phase For pure/perfect crystal a = 1 For defective crystal a < 1 ∴ chemical potential of crystalline phase related to activity µc − µo = RT ln a u u (5) 64 .

n = 100. ln XA = ln (1 – XB) ~ XB RX B 1 1 − o = Tm Tm ∆H u Consider chain end Degree of polymerization Xn (number of repeat unit) Mole fraction of chain end = e.Combining (4) & (5)  T − ∆H u 1 − o  Tm    = RT ln a   At T = Tm 1 1 − R ln a − o = Tm ∆H u Tm (6) Assume: The polymer consist of mole fraction of crystalline material ⇒ XA The polymer consist of mole fraction of non crystalline material ⇒ XB So XA + XB = 1 First approximation can relate activity of polymer crystal to mole fraction of crystallisable material (i. 2 ends XB = 2 1 = 100 50  2  X  n     (8) 2 Xn 1 1 R ∴ − o = Tm ∆H u Tm (9) o Tm → Tm as X n → ∞ Branches? 65 .e.g. a ≈ X A ) ∴ − R ln X A 1 1 − o = Tm ∆H u Tm (7) But XA = 1 – XB If XA is small.

flexible unit decrease Tm .rigid unit increase Tm Polymer repeat CH2 CH2 CH2 O CH2 CH2 CH2 Tm/K 410 340 670 b) inter chain bonding e.g. 2 →2 + y 1 1 R − o = Tm ∆H u Tm 2 + y    X   n   y = number of branches Chemical factor control Tm Chemistry has a strong control over Tm a) main chain stiffness .4 ends. vinyl polymer X group Name Tm/K 66 Tm/K 410 603 533 .g. hydrogen bonding can stabilize the crystal → ↑Tm nylon → have high Tm value due to H bonding Repeat CH2 CH2 CH2 CH2 CONH CH2CH2CH2 CONH c) odd and even effect e.g. 2 branches From equation (9). NH(CH2)nNHCO(CH2)4CO d) side group effect side groups – affect chain rotation and increase Tm e.

–H CH3 CH2CH3 CH3CH7 CH2 CH CH3 CH3 PE PP Butane-1 Pentane-1 4-methyl-1-pentene 410 460 398 351 508 450 Bulky side group → restrict rotation ↑Tm Long side group → separates chain make rotation easier reduce Tm Method of Measurement Tg and/ or Tm 1. Static → no stress → not apply dynamic or mechanical stress a) dilatometer → is to generate specific volume and temperature Specific volume Amorphous Crystalline Tg Tm Temperature 67 .

accurate – only control the temperature – slow heating rate 3. index ∴ calculate can Tg o Temperature usually measure critical angle Polymer θ 68 . 000 2.Tm = 1st order transition Tg = 2nd order transition Sealed Capillary tube Glass plug Polymer (powder) Containing liquid Hg Water bath o Weight the polymer & measure the height of the capillary tube. the volume o ∴ plot the graph can o Problems cannot go below -35 oC o Advantages: 1. Cheap: £ 50 – 60. very good for Tg and Tm o Disadvantages: no secondary transition detected b) refractometry o measure on reflective index Ref.

ok for Tg  quick and fast  automatic o Disadvantages:  no secondary Tg  expensive 2. DSC – differential scanning these are commercial technique Polymer Heat both of them in the same time o DTA – heat input same – measure temperature difference o DSC – keep temp same – measure the heat energy difference o Both measure in Tg and Tm o Advantages:Tg  good for Tm.o o o heating & cooling also be found difficult → range of temperature not usually use c) thermal capacity (specific heat) i.Mechanical Tm 69 . DTA – differential thermal analysis ii. Modulus/ Nm-2 Crystalline Amorphous Static .

Dynamic Electrical 70 . Dynamic .Mechanical Suspension wire counter balance Inersia bar Test specimen Environmental chamber Dynamic shear modulus α γ θ Temperature/K o this instrument produce osiloscope o measure dynamic modulus – loss tangent o dynamic mechanical → is effective because it measure energy loss → give secondary transition 4.o Modulus Vs temperature o Tg have narrow or broad graph value o ∴difficult to predict where is the actual Tg value 3.

Dielectric constant Dielectric loss o ∴can measure dielectric loss Mechanical Properties of Polymer Introduction Classification of polymers Polymers Thermoplastic Elastomers Thermoset Crystalline Amorphous 71 .

* All the 3 categories have very different mechanical properties – due to molecular structure Molecular conformation Molecules are prefer to form a random coil to give higher entrophy (s) (important in rubber elasticity) e.g.g. 1 LDPE → soft/flexible material (20% crystallinity) HDPE → more rigid (high crystallinity – 70%) 72 .g.: thermoplastic stretch stretch Heat Molecules random High S Molecules are random High S Molecules are aligned Low S Crystallinity Degree of crystallinity can affect the mechanical properties e. Stretch mechanically Deformed (low S) relax High S Undeformed high S e.

g. ceramic. 1 73 . rigid/stiff There are generally transparent e.1% strain Behaviour of real polymer e. Area Strain = Changing in length Original length σ σ σ Slope = E = σ ε ε This behaviour → metal. glass Low strain behaviour → <0. 2 Fibres – also can affect the mechanical properties fibre Crystal or molecules are align parallel to the fibre Good mech.g.e. Below Tg. properties molecules Glassy polymers (no crystallinity) This materials is non-crystalline → amorphous solids.g. contact lenses This control by Tg → below Tg – glassy solids → above Tg – rubbery solids → brittles Simple tensile deformation Stress = Force .

PS σ load unload 2% ε Have slight historisis Called non linear elastic behaviour Also crosslinked elastomer e.2 ductile thermoplastic e. polycarbonates Yield (plastic deformation started) σ 10% ε Plastic deformation (also some semi crystalline polymers e.g. PP) High strain behaviour σ Yield point PE Rubber No yield point 500% ε Temperature dependent With polymer we do get temperature dependent Hard.g.glassy polymer. brittle. e.g. rigid σ 0oC 40oC 80oC 100oC 74 .g.

amorphous polymer – no Tm V glassy rubbery Tg T 75 .g. mechanical → modulus. glass transition Tg cause large changes in physical and mechanical properties e. melting at Tm 2. T) time Transition and mechanical behaviour 2 main transition 1.: creep strain constant stress time Stress Relaxation σ E = function of temperature and time E (t. E physical → specific volume V= 1 density 1.ε Time dependent e.g.

E Brittle glassy solid Tg Soft rubbery liquid T 2. semicrystalline polymer V Rubbery liquid Glassy Crystal in rubber Tg Tm T E Tough material Tg Tm T Theoretical Stiffness and Strength Theoretical stiffness (modulus) Stiffness varies with modulus σ Fibre Glassy polymer Semicrystalline polymer 76 .

1 M ≈10 6 Pa ≈10 6 N m 2 (calculate using thermodynamic) b) semicrystalline. Treloar f θ L Bond angle = θ Link length =  Chain length = L Angle wrt..  & α = vary 77 . E ~ 3GPa (brittle) d) fibre polymer. E ~ 100GPa++ • high orientated molecules Calculation of E using L. force f = α Number of links = n Initially (undeformed) f = 0 L = n cos α α α f Deformation – increasing length by dL dL = d ( n cos α) n = constant. E =1GPa =10 9 Pa =10 9 N m 2 • modulus controlled by hard crystals is a glassy amorphous rubbery phase • modulus depends upon degree of crystallinity Øc 1 GPa 1 MPa 0% 100% c) glassy polymer. E ~ 1 MPa.Elastomers ε Pa a) elastomers.

force constant KL can be measured Defined as K L = KL = d = f cos α d force along bond extension of bond f cos α KL From the diagram f cos α K dL = n ( cos αd − sin αδα ) δ =  δ α is related to the bond angle change δθ α x  2 f pivot 78 . d f cos α α f From spectroscopy (infrared or Raman).    = n  d c o sα − s inα dα          bond b o n d n g le  a s tre tc h in g change   ∴ to calculate d  and dα need Bond stretching.

From geometry α+ θ = 90 o 2 α = 90 o − θ 2 ( 4) − δ α= − δ θ 2 Increasing the α angle will increase the θ in factor 2 Angular deformation force constant Kθ Kθ = Torque → defined from IR or Raman spectroscopy Torgue acting around a bond Change in bond angle = Force × perpendicu lar distance from pivot x = distance from pivot ∴ θ= K fx δθ sin α = x  → x = sin α  2 2 Kθ = δθ= f ( 2) sin α δθ f sin α 2K θ Combine (4) = (5)  − f L sin α δα=  4K θ   Putting equation (6) and (3) into (2)  cos 2 α 2 sin 2 α  δL = nf  +  4K θ   K 79 .

Young modulus. E = ∴ = E f A d L L stress strain E= f n cos α  cos 2 α 2 sin 2 α  Anf +  4K θ   K cos α  cos 2 α 2 sin 2 α  A +  4K θ   K θ 2 E= α = 90 o − ∴E = sin θ 2 sin 2 θ 2 2 cos 2 θ 2  +   A 4K θ  K  Young modulus of polymer chain • • • • • K  . K θ can be determined from spectroscopy A comes from unit cell cleminsion They gives EPE ~ 180GPa PE fibres can have E high ~ 200GPa The actual modulus can be higher due to inter molecular interaction Determination of crystal modulus 80 .

f x-ray fibre f Ø Flim detection Stretch the molecule f c f c c – lattice parameter changes with stress by δ Crystal/lattice strain Stress = ∴ = E dc c f A m odulus f A = crystal δ c c e. For PE crystal modulus ~ 250GPa More than steel modulus ~ 210GPa Crystal more stiffness than steel Even though PE less density than steel Factor controlling crystal modulus a) Chain stiffness Bond angles affect stiffness 81 .g.

PE Higher modulus rod e.g. rigid rod molecules O C O C N H N H n Crystal modulus ~ 220GPa (same as steel) True rigid rod molecules O N O N “PBO” zylon Most higher modulus of fibre Fibre modulus ~ 280GPa Crystal modulus > 400GPa (Diamond E > 1000 GPa) Use – rigid rod fibre made by solution spinning b) Side groups Adding side groups reduce modulus PE PP 82 .

∴ ↓ PP crystal modulus E ~ 50 GPa PE crystal modulus E ~ 250 GPa Theoretical yield strength σ σy Yield point Yield – outset of plastic deformation σy = yield stress ey = yield strain ey ε Molecule deformation process Elastic  Reversible  Structure – deforms but spring back Plastic deformation  Not reversible  Molecules move past each other Model – sheet of molecules sliding past each other σ Shear stress σ Assume σ varies with displacement 83 .CH2 CH2 CH2 CH CH3 CH2 CH CH3 Since E ∝ 1 A E PP – increase A.

G = shear stress for small x shear strain σ γ = x h = displaceme nt phase separation γ= G= σh x Or 84 .σ b h 8 σy 0 b x displacement Touching each other Assume the shear stress varies sinusoidally with displacement Equation  πx  σ = σy sin    b  x =0 →σ = 0 σ σy x= 1 2 → σ = σy →σ = 0 0 b/2 b x x =b For lower value of displacement. sin θ →0 πx  πx  σ = σ y sin   → σy b  b  shear modulus.

g.25 b h = 0.σ= Gx h (2) = (3) σy πx Gx = b h Gb   ∴  σy = πh    e.26 nm 2 G ×0.25 nm σy = ∴Yield stress is theoretical ½ shear modulus Behaviour of real polymer At room temperature σy ~ G for PE 100 As temperature →0 σy ~ G (theory only valid at 0oK) b    Yield is thermally activated Yield may be controlled by the activation of dislocation Dislocation are thermally activated dislocation 10 nm 85 .: PE b = spacing of atom along the chain b= c = 0.125 nm .125 G ≈ π×0. c = 0.

: backbone chain u h x displacement compression tension Equilibrium separation σ σt 86 .g.o Not breaking the covalent bond but the Van der Waals bond break o Because it slide past each other o Yield point → break Van der Waals bond Theoretical Tensile Strength Need to calculate the forces/stress required to break the covalent bond e.

σ upon displacement.Work done x separation h x=0 x/2 Assume dependence of σ. x can be approximated by a sin curve  2πx  σ = σt sin    λ  λ = wavelength σt = theoretical strength Now strain or displacement →sin θ →θ σ = σt 2πx λ Now strain Hooke’s Law is obeyed σ = modulus strain = Ex h Combine (2) = (3) σt 2πx Ex = λ h  Eλ  ∴  σt =  2π  h  Consider fracture process – create new surface σ σ 2 new surface Work done in creating the surface can be related to the surface energy of the surface between surface energy = γ Work done = area under σ vs λ curve Surface energy ≡ work done 87 .

2γ = ∫ λ2 0  2πx  σt sin   dλ  λ  88 .

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