You are on page 1of 88

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)

ACTIVE CENTRE
H
C C H
H X

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 Structure Free-radical Cationic Anionic

Ethylene CH2 = CH2 √ √ x

1-Alkyl olefins + CH2 = CHR1 (x) (x) x

1,1-Dialkyl olefins CH2 = CR1R2 (x) √ x


CH2 = CH – CR =
1,3-Dienes √ √ √
CH2
Styrene, α-methyl
CH2 = CRPh √ √ √
styrene
Vinyl halides CH2 = CHX √ x (x)

Vinyl esters CH2 = CHOCOR1 √ x (x)

Vinyl ethers CH2 = CHOR1 (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. 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. 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

- +
CH3CH2CH2 CH2 Li = R Li
karbonion
@
O R-

4
b) monomer activation (formation of active centre)

-+ ki
R Li + CH2 CH RCH2 CH Li

RM Li

5
2. Propagation

kp
RM Li + M RM2 Li

R CH2 CH Li + CH2 CH

kp

R CH2CHCH2 CH Li

6
3. Termination → methanol often used

O
H
C Li + CH3OH

CH2 + LiOCH3

Kinetic scheme

ki
R Li + M RM Li ………………initiation

kp
RM Li + nM RM n Li ……………..propagation

kt
RM n Li + CH3OH RM n
+
LiOH3
…………….termination

7
Rate of polymerisation = Rp

-
R Li = I & RM n Li = P

1) 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


k i [ I][ M ]
[P − ] =
k t [CH 3 OH ]

R p = k p [ P − ][ M ]

k i k p [ I][ M ] 2
Rp =
k t [CH 3 OH ]

Degree of polymerisation = X n

rate of polymerisa tion


Xn =
initiation rate

rate of propagatio n
Xn =
rate of terminati on

k p [M ]
Xn =
k t [CH 3 OH ]

Factors affecting anionic polymerization

8
1. Temperature
−E RT
k = A exp

- Discussed in term of activation energy

2. counter-ion

Butyl lithium ≈
Bu M

M ⊕ → Li Na K Rb Ce

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 → Rp ↓

And vice-versa.

3. Solvent
- Solvent gives significant contribution in the Rp 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 Rp to be
depending on [M] @ [I]
- Whereby, solvent such as THF (tetrahydrofuran) allows the Rp 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
H
≈[ P −+]
C Li
d
X i
s
t
P a
n

9
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 P Li P
10
X
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. H2SO4 and HClO4 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. BF3, AlCl3 and SnCl4 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


BF3 + H2O → H+(BF3OH)–

ii. Activation of active centre


H+(BF3OH)- + CH2 CR1R2

+
CH3 CR1R2(BF3OH)-

In general,

R+A- + CH2 CR1R2 RCH2


+ -
CR1R2A

karbokation

Propagation

12
+
RCH2 CR1R2A- + CH2 CR1R2

+ -
RCH2 CR1R2 CH2 CR1R2A

Termination

i. Spontaneous decomposition

+ -
CH CR1R2A CH CR1R2 + H+A-

ii. Chain transfer

+
CH2 CR1R2A- CH CR1R2
+
+
CH3 CR1R2A-

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
+ - ki + -
R A + M RM1 A

+- ki +-
I + M I M

2) Propagation

kp
RM+n A- + M RM+n+1 A
-

kp
P+- + M P+-M

3) Termination

k 't + -
RM+ A- RMn + H A
n

+ - k "t
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

− d[ M ]
Rp = = rate of monomer used
dt

R p = K p [ RM + −
n A ][ M ]

− d[ M ]
R p = K p [ P ± ][ M ] =
dt

[ P ± ] = active centre concentrat ion (carbocati on)

14
Rate of termination = R t

' + −
i. Spontaneously = K t [ RM n A ]
' ±
= K t [P ]

" ±
ii. 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 = Rate of disappearance of active centre

Ri = Rt

Initiation rate = termination rate

∴K i [ I ± ][ M ] = K t [ P ± ]

Ki ±
[P ± ] = [ I ][ M ]
Kt

R p = K p [ P ± ][ M ]

Kp Ki
Rp = [ I ± ][ M ]
Kt

Degree of polymerisation = X n

Polymerisa tion rate


Xn =
Initiation rate

15
Propagatio n rate
=
Terminatio n rate

K p [ P ± ][ M ]
=
K t [P ± ]

Kp
Xn = [M]
Kt

Additional knowledge on ionic polymerisation

Effect of R p and X n on temperature

Kp Ki
Rp = [ I ± ][ M ]
Kt

K = constant

Rp ↑ → T↓

−E RT
* ARRHENIUS [ K = A exp ]

− E p RT
A p exp × A i exp − E i RT

Rp = − E t RT
[ I ± ][ M ]
A t exp

 E p + Ei − E t 
A p Ai −
RT

Rp = exp  
At

Activation energy of propagation lower (very small) therefore:

Ep <
<< Ei , Et

Hence, overall E will be +ve


∴Rp or overall rate increases when the temperature decreases.
Degree of polymerization

Kp
αn = [M]
Kt

16
Arrhenius:

(
− Ep − Et )
Ap
Dp = exp RT
[M]
At

Normally, Ep –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
O

CH2OH
C

CHOH + O
C
CH2OH
3 f.g. O

+ H2O /trace

COOH

COOH

CO H CO

C O CH2 C CH2 O C

O OH 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
OH
H
C O + H2O CH2
H
OH
formalin aqeous
formaldehyde
media

PFDR formed by
Formaldehyde + phenol

Condensation → ortho and para position

20
OH

o o
HOCH2OH +
2 f.g. m m
p

OH
HOCH2 CH2OH
+ 3 H2O

CH2OH gives 3 f.g.

or catalyst

CH2OH + H CH2

methylene
and bridge

CH2OH + HOCH2 CH2 O CH2

ethylene bridge

OH
CH2 O CH2

CH2
CH2 O
CH2
OH

Short chain between junction points gives rigid material

3. Aminoplast (Urea Formaldehyde Resin)

21
Carbamide + formaldehyde in alkaline solution

H2N CO NH2 + HO CH2 OH

H2N CO N CH2 OH + H2O

+ n(HOCH2OH ) and H2NCONH2

NH2 CO N CH2 N CO

CH2 CH2

CO N CH2 N CO

Use as coating

4. Melamine Formaldehyde Resin

22
Melamine + formaldehyde

H2N N NH2
C C
+ n HOCH2OH
N N
C
NH2
neutral or
alkaline
conditions

N
C N CH2 OH + H2O
N CH2
C
OH

acid condition

H
N N
C N CH2 N C
N H N
O
C

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
CH2OH
CH2 CH2 + NaOH
CHOH + HO CH2CH2 O
O
CH2OH

or

CH2 CH via ring


opening
O CH3

CH2 O CH2CH2 OH triol


CH O CH2CH2 OH (polyol)
3 f.g.
CH2 O CH2CH2 OH

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 CH3
NCO OCN NCO

NCO
2,4 2,6

2. MDI (diphenyl methyl diisocyanate)

24
OCN CH2 NCO

Polyurethane formation: diisocyanate + polyol (triol)

CH2 N C O (CH2)4

H O
hydrogen bonding hand segment
O H

O(CH2)4 O C N CH2

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

CH2 C CH CH2 CH2 C CH CH2


CH3 CH3

NR poly (cis isoprenes)

CH2 CH2 CH3 H


C C C C
CH3 H CH2 CH2

NR poly (trans isoprenes)

CH3 H CH2 H
C C C C
CH3 CH2 CH3 CH2

• 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
CH3
+
CH2 C CH CH2 sulphur (Sx)

CH3 CH3

CH2 C CH2 CH2 + CH2 C CH2 CH2

SxH

CH3

CH2 C CH2 CH2

Sx

CH2 C CH2 CH2

CH3

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

CH3 CH3 CH3


CH2 C CH2 C CH2 C CH2
CH3 CH3 CH3

PIB

+ 2% isoprene

CH3 CH3
CH2 C CH CH2 CH2 C CH2 C
CH3 CH3 CH3

32
3. Peroxide Crosslinking

t-butyl peroxide

(CH3)3 C O O C(CH3)3

(CH3)3 CO OC (CH3)3

In general

R O OR 2 OR

For Natural rubber & butyl rubber can be crosslinked by this free radical

CH3
CH2 C CH CH2 + OR

150oC

CH C CH CH2 + ROH
CH3
crosslinked

CH C CH CH2
CH3

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.

heat
RO OR 2 RO Reac. 1.1

RO + CH2 CH CH2 ROH + CH2 C CH2 Reac 1.2


R R
Tertiary hydrogen polymer radical

where RO-OR is the peroxide, -CH2-CRH-CH2- 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.

CH2 CR CH2
CH2 CR CH2
Reac. 1.3
CH2 CR CH2
CH2 CR CH2
Crosslinking

34
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.

CH2 C CH2
CH2 C CH2 CH CH2 CH CH3
+ Reac. 1.4
CH3 CH3 CH3
CH CH2 CH
CH3 CH3

Also chain radicals can lose their activity by formation of an alternative radical (reaction
1.5)

H
CH2 CR CH CH2 CH2 CR CH CH2
+ Reac. 1.5
H

Reaction 1.6 shows that polymer radicals may also be deactivated by reaction with a
primary radical.

CH2 CR CH2 + OR CH2 CR CH2 Reac. 1.6


OR

35
Under certain conditions other radicals can recombine resulting in inefficient termination
of active radicals (reaction 1.7).

CH2 CR CH2 + H CH2 CH CH2 Reac. 1.7


R

Finally it is also possible that radicals shift along the polymer chain (reaction1.8).

CH2 CH CH2 CH2 CH2 CH2 CH CH2 Reac. 1.8

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.

rad
PH P + H

H + PH P + H2

P + P P P (crosslinking)

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, CH2=CH-Si(OCH3)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
Peroxide
+ CH2 CH Si(OMe)3 CH2 CH2 Si(OMe)3 Reac. 1.12

Polyethylene Vinyltrimetoxysilane Grafted component


H2O
Hydrolisis

CH2 CH2 Si(OH)3 + 3 MeOH Reac. 1.13

CH2 CH2 Si(OH)3 + CH2 CH2 Si(OH)3

Heat Catalyst (DBDTL) Reac. 1.14


(Condensation)

OH OH
CH2 CH2 Si O Si CH2 CH2 + H2O
OH OH

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
i =1
∑ Ni Mi
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 ∫ n ( M )MdM


0
=1

Average Molar Mass

Σ NiMi Σ Wi
Number-average molar mass: Mn = =
Σ Ni Σ ( Wi M i )

Σ Wi M i Σ N i M i2
Weight-average molar mass: Mw = =
Σ Wi Σ NiMi

Σ Wi M i2
z-average molar mass: Mz =
Σ Wi M i

Relative values of average molar masses

Polydisperse polymers: M n <M w <M z


Uniform polymers: M n =M w =M z
Most probable distribution:
M n : M w : M z =1: 2 : 3
The ratio Mw Mn is a measure of the width of the number distribution
The ratio Mz Mw 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 Mn < 2 x 104
M pressure
Vapour n
osmometry < 2 x 104
M n osmometry
Membrane 104 – 106
2
M w , <s > z
Light scattering 104 – 107
M n , M w , M zequilibrium
Sedimentation 104 – 107
s,→
rh
Sedimentation velocity
DM
, rhD
Diffusion
[η]M, rVh
Dilute solution viscometry
rh , MMD
V
Gel Permeation Chromatography

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
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 Vtotal = Vo + Vi
Where Vo = void volume; volume of liquid outside porous beads
Vi = internal volume; 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


Where c o = concentration of solute in void
c i = concentration of solute in pores

Standard state Gibbs energy change for permeation ∆G = − RT ln K e


o

If exclusion is the only separation process, ∆H o = 0 and ∆G o = − T∆S o


i.e. K e = exp( ∆S o R )

Entropy change on reducing the available pore volume from Vi to Ve − Vo is


∆S = R ln [( Ve − Vo ) Vi ]
Thus 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
Statistical-thermodynamical treatments of the exclusion problem show that:
K e ∝ log (slolute size)

Consequently, Ve is expected to vary with log (solute size)


The size involved is the hydrodynamic volume ( Vh )
i.e. the effective volume of the polymeric solute in the solvent

For a polymer in a given solvent at a given temperature,


Vh ∝ M
Ve ∝ log M

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, Vo + Vi ). An additional
problem occurs with aqueous solvents and negatively charged solutes, when electrical
exclusion moves the peak towards the exclusion limit (void volume, Vo ). 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 Vh
and so elute at the same Ve ; this is usually a reasonable approximation for vinyl
polymers
Use a ‘universal’ calibration plot of log [η] M against Vpk , where [η] is intrinsic
viscosity; this is based on the relationship [η] M ∝ Vh
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), ηr

η t
ηr = ≈ η: viscosity of the solution
ηo to
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, ηsp

η − ηo t − to
ηsp = ηr − 1 = ≈ A measure of the relative increase in viscosity
ηo to

Both ηr and ηsp depend on polymer concentration, c.

Intrinsic viscosity (limiting viscosity number), [η]


A measure of viscosifying power

ηsp ln ηr
Plot and versus c
c c
 ηsp   ln ηr 
Intercept:  
 =  = [ η]
 c c →0  c c→0
ηsp
= [ η] + k[ η] c (Huggins)
2
Slopes:
c
ln ηr
= [ η] − β[ η] c (Kraemer)
2

Units of [η]: reciprocal concentration, e.g. cm3 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
log [η] = log K + a log M
[η] = KM a

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, M v


For a polydisperse polymer
1
 Σ w i M ia  a
M v =   M v depends on the solvent and on the temperature
 Σwi 
through the parameter a
M v <M w

For most probable distribution: M w M n = 2, M v M n =1.77 (for a = 0.5) 1.88 (for a =


0.7)

Question
Show that if the Mark-Houwink relationship [η] = KMa is applied to a polydisperse
polymer, the average molar mass obtained is
1
 Σw i M ia  a
M v =  
 Σw i 
Where wi is the weight fraction of species of molar mass Mi.

Hydrodynamic radius, rh
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: ηsp = 2.5 φ, where φis the volume fraction of
spheres. On the basis, show that
3
[η] ∝ r
M

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, Vh, of the solute.


Vh ∝ rh3 ∝ [ η] M
Plot log [η] M against elution volume, Ve
Or, since [η] = KMa, plot log KM1+a against Ve.

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 (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. 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 Tg

Tg

CH3 CH3
Polydimethyl silozane -123 oC
Si O Si
CH3 CH3

H H
Polyethylene -120 oC
C C
H H
b) rigid chains – high energy barrier
– high Tg

Tg
Polycarbonate CH3 O
+150 oC
O C O C
CH3

Energy barrier to rotate the molecule contain benzene ring is high ∴Tg ↑

51
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
-120 OC
C C
H H

H H
polypropylene -18 OC
C C
H CH3

H H
polystyrene +100 OC
C C
H

3. 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 Tg
CH3 -10 oC
CH2CH3 -17 oC
CH2CH2CH3 -27 oC
CH2CH2CH2CH3 -32 oC

4. steric hindrance, increases Tg

52
Where the CH3 located will effect the Tg

Tg
Polystyrene H H
C C
+100 oC
H

H H
Poly p-methyl styrene
C C
+110 oC
H

CH3

H H
Poly o-methyl styrene +120 oC
C C
H CH3

5. polarity of side group increases Tg

Tg

Polyethylene H H
-120 oC
C C
H H

Polyvinyl chloride H H
+87 oC
C C
H Cl

Polyacrylonitrile H H
+104 oC
C C
H CN

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
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. symmetry of side group decreases Tg


equivalent mass on the both side of the side group will ↓E ∴easier to rotation

↓ Tg

Tg

H H
Polypropylene -18 oC
C C
H CH3

Poly isobutylene H CH3


-70 oC
C C
H CH3

Poly vinyl chloride H H


C C +87 oC

H Cl

H Cl
Poly vinylidene -19 oC
chloride C C
H Cl

The Used Of Free Volume Concept To Determine Tg

54
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. Lower cooling rate ↓Tg
o Because of the semicrystalline polymer contain crystals and amorphous ∴
difficult to determine the Tg 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

V
Free volume (Vf)

Vf Occupied volume (Vo)

Vf*
T

Vf* - free volume constant (below Tg)


Vo – volume occupied by molecule ( ↑ temperature)
Vf – free volume

Total sample volume , V = Vo + Vf

55
Vf  free 
Fractional free volume , f =  
V  total 

Below Tg

Vf*
fg =
V

Above Tg

Vf = Vf* + (T − Tg ) 
 dV 

 dT 

V*
= f + ( T − Tg )
Vf 1  dV 
 
V V V  dT 

Expansion coefficient of free volume

1  dV 
αf =  
V  dT 

∴f = f g + (T − Tg ) αf

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. NOT in changing in molecular
structure of side group
o Free volume explanation

High molecular weight Low molecular weight


Few long chain Lots of small chain
Few chain end Lots chain end

o ↑ molecular weight

56
 ↓chainend → ↓ free volume
 ↓mobility volume → ↑Tg

Dependence of Tg on Molar Mass

Tg increases on molar mass increases

K
Tg = Tg∞ −
M

Tg∞ is Tg at infinite molar mass


K is constant

number × mass
Density ρ = of each chain
volume

Mn
Mass of each chain =
NA

NA = Avogadro number

N Mn
ρ= ×
V NA
N ρN A
∴ =
V Mn

ρN A
Number of chain ends per unit volume = 2
Mn

θ = amount of fractional free volume at each chain end

Total fractional free volume fc

2 ρN A θ
fc =
Mn

fc represents increase in free volume above Tg i.e. between Tg and Tg

f c = αf (Tg∞ − Tg )

2 ρN A θ
(
∴αf Tg∞ − Tg = )
Mn

57
2 ρN A θ
Or Tg = Tg∞ −
αf M n

K
Tg = Tg∞ −
M

Branching and Tg
Branching ↑free volume → ↑mobility, ↓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

1 W W
= 1 + 2 W = weight fraction of the 2 homopolymer
Tg Tg1 Tg 2

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
A
C
O O R
B D

o Secondary transition lower the Tg due to:


1. A – limited main chain movement
2. B – whole side group movement
3. C – part side group movement
4. D – other interaction

Energy loss 100 oC

20 oC
PMMA
PS

Tg Temperature

Secondary
transition

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 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.

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 Tg and in addition have Tm
o Flexible, tough & hard than rubber but not brittle
o Phase separation
 amorphous
 crystalline

Specific
volume joint point

amorphous
rotation
vibration

Tg Tm Temp

o If amorphous is heated vibration occur, the F.V. and mobility increase


o At the joint point is these Tm
o By cooling → below Tg → the molecular movement stop, therefore, ∴stop
crystallizing
o At high Tg → high Tm
o Tm ≈ 2 Tg (symmetric) → pack better, ∴molecule get together
→ polymer in main chain
o Tm ≈ 1.5 Tg (unsymmetric)

Tm K Tg K Tm/Tg
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
c) melting depend upon heating rate, e.g. 10 oC/min
Not same Tm value
20 oC/min

∴need to establish as equilibrium melting temp. Tmo


e.g. crystallize at different Tc → give different crystal thickness ∴different Tm

Determination of Tmo
Some polymer crystallize at different Tc, measure their Tm value
Need to plot graph Tm Vs Tc

Tm

Tmo

Tm = Tc
Tc

Draw line at 45o that Tm = Tc


The Tmo 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


γe γe = fold surface free

energy
γs = side surface free
x energy
γs y

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
Overall free energy change,
∆G = xy ∆G v − 2 ( x + y ) γs − 2 xy γ e

NB:
Crystal itself x, y >>> e ∴lose the side equation
∆T
Also ∆G v = ∆H v o
Tm

(
∆T = Tmo − Tm )
For melting ΔG = 0

∴xy ∆G v = 2 xy γe

G v = 2 γe

∆G v =
(
2 γ e ∆H v Tmo − Tm
=
)
 Tmo

Tmo − 2 γ e Tmo
∴Tm =
∆H v

Tm
extrapolation
o
Tm − 2 γ e Tmo
Slope =
∆H v

1

If known ΔHv for calorimetry, ∴can calculate γe

Factors Affecting Tm
1. Physical
2. Chemical

Physical factor
For a given chemical type of polymer then physical factor can control Tm
e.g.
molar mass (length of molecules)
branching (linear branched)
* this will introduced effects into crystal due to chain ends

63
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 Tm = 150 oC
 branched PE Tm = 110 oC

Chain end (low molar mass & branches) → detect in crystal, this reduce Tm value
Can interpret in term of “chemical potential” ⇒ µ

Define
µcu = chemical potential per mole of repeat unit of polymer in crystalline state
µou = chemical potential per mole of repeat unit of polymer in the liquid state
(standard state)

Free energy fussion = ΔGu

∆G u = µou − µcu (1)

Pure polymer system


Change in chemical potential going from liquid to solid

µ cu − µ ou = − ∆G u = − ( ∆H u − T∆S u )
  (2)
( final ) ( initial )

μ = per mole of repeat units

∆H u
As before ∆S u = (3)
Tmo

 T 
µcu − µou = − ∆H u 1 − o  (4)
 Tm 

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
µcu − µou = RT ln a (5)

64
Combining (4) & (5)

 T 
− ∆H u 
1 − T o 
 = RT ln a
 m 

At T = Tm

1 1 − R ln a
− o = (6)
Tm Tm ∆H u

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.e. a ≈ X A )

1 1 − R ln X A
∴ − o = (7)
Tm Tm ∆H u

But XA = 1 – XB
If XA is small, ln XA = ln (1 – XB) ~ XB

1 1 RX B
− o = (8)
Tm Tm ∆H u

Consider chain end


Degree of polymerization Xn (number of repeat unit)
2
Mole fraction of chain end =
Xn

e.g. n = 100, 2 ends

2 1
XB = =
100 50

1 1 R  2 
∴ − o = 
X 
 (9)
Tm Tm ∆H u  n 

Tm → Tmo as X n → ∞

Branches?

65
4 ends, 2 branches

From equation (9), 2 →2 + y y = number of branches

1 1 R 2 + y 
− o = 
 X  
Tm Tm ∆H u  n 

Chemical factor control Tm


Chemistry has a strong control over Tm
a) main chain stiffness
- flexible unit decrease Tm
- rigid unit increase Tm

Polymer repeat Tm/K


CH2 CH2 410

CH2 O CH2 340

CH2 CH2 670

b) inter chain bonding


e.g. hydrogen bonding can stabilize the crystal → ↑Tm
nylon → have high Tm value due to H bonding

Repeat Tm/K
CH2 CH2 410

CH2 CH2 CONH 603

CH2CH2CH2 CONH 533

c) odd and even effect


e.g.
NH(CH2)nNHCO(CH2)4CO

d) side group effect


side groups – affect chain rotation and increase Tm
e.g. vinyl polymer

X group Name Tm/K

66
–H PE 410
CH3 PP 460

CH2CH3 Butane-1 398

CH3CH7 Pentane-1 351

CH3
CH2 CH 4-methyl-1-pentene 508
CH3
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
Tm = 1st order transition
Tg = 2nd order transition

Sealed

Capillary Glass plug


tube
Polymer (powder)

Containing liquid Hg

Water bath

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 oC
o Advantages:
1. Cheap: £ 50 – 60, 000
2. accurate – only control the temperature
– slow heating rate
3. very good for Tg and Tm
o Disadvantages:
no secondary transition detected
b) refractometry
o measure on reflective index

Ref. index

Tg Temperature
o usually measure critical angle

Polymer

68
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

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 Tm
 good for Tm, ok for Tg
 quick and fast
 automatic
o Disadvantages:
 no secondary Tg
 expensive

2. Static - Mechanical

Modulus/
Nm-2
Crystalline

Amorphous

69
o Modulus Vs temperature
o Tg have narrow or broad graph value
o ∴difficult to predict where is the actual Tg value

3. 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. Dynamic Electrical

70
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.

Stretch
mechanically Deformed (low S)
Undeformed relax
high S

High S

e.g.: thermoplastic stretch

stretch

Heat Molecules
random

Molecules are High S


Molecules are aligned
random Low S
High S

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
e.g. 2
Fibres – also can affect the mechanical properties

fibre
Crystal or molecules are
align parallel to the fibre
Good mech. properties

molecules

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

Force Changing in length


Stress = , Strain =
Area Original length

σ σ σ
Slope = E =
ε

This behaviour → metal, ceramic, glass


Low strain behaviour → <0.1% strain

Behaviour of real polymer


e.g. 1

73
glassy polymer. e.g. PS

σ
load
unload

2% ε

Have slight historisis


Called non linear elastic behaviour
Also crosslinked elastomer

e.g.2
ductile thermoplastic e.g. polycarbonates

Yield (plastic
σ deformation started)

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, brittle, rigid

σ 0oC 40oC
80oC
100oC

74
ε

Time dependent
e.g.: creep

strain

constant
stress

time

Stress Relaxation
σ
E = function of
temperature and time E (t,
T)

time
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
1
physical → specific volume V=
density

1. amorphous polymer – no Tm

V
glassy
rubbery

Tg T

75
E

Brittle Soft rubbery


glassy liquid
solid

Tg 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
Fibre
σ Glassy polymer

Semicrystalline polymer

76
Elastomers

a) elastomers, E ~ 1 MPa; 1 MPa ≈10 6 Pa ≈10 6 N m 2 (calculate using


thermodynamic)
b) semicrystalline, 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 ~ 3GPa (brittle)


d) fibre polymer, E ~ 100GPa++
• high orientated molecules
Calculation of E using L. Treloar

f θ f
α α

Bond angle = θ
Link length = 
Chain length = L
Angle wrt., force f = α
Number of links = n

Initially (undeformed) f = 0
L = n cos α

Deformation – increasing length by dL


dL = d ( n cos α) n = constant,  & α = vary

77
 
 
= n  d c o sα − s inα dα 
    
 bond b o n da n g le 
 s tre tc h in g c h a n g e 
∴need to calculate d  and dα
Bond stretching, d

f cos α α
f

From spectroscopy (infrared or Raman), force constant KL can be measured


force along bond
Defined as K L =
extension of bond

f cos α
KL =
d

f cos α
d =
KL

From the diagram


dL = n ( cos αd − sin αδα)

f cos α
δ =
K

δ α is related to the bond angle change δθ

α
f
x
 2

pivot

78
From geometry
θ
α+ = 90 o
2

θ
α = 90 o −
2

( 4) − δ α= − δ θ
2

Increasing the α angle will increase the θ in factor 2

Angular deformation force constant Kθ → defined from IR or Raman spectroscopy


Torgue acting around a bond
Kθ =
Change in bond angle

Torque = Force × perpendicu lar distance from pivot

x = distance from pivot

fx
∴K θ =
δθ

x 
sin α = → x = sin α
 2
2

f ( 2) sin α
Kθ =
δθ

f sin α
δθ=
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  + 
 K 4K θ 

79
stress
Young modulus, E =
strain

f A
∴E =
dL L

f n cos α
E=
 cos 2 α 2 sin 2 α 
Anf + 
 K 4K θ 

cos α
E=
 cos 2 α 2 sin 2 α 
A + 
 K 4K θ 

θ
α = 90 o −
2

sin θ 2 sin 2 θ 2 2 cos 2 θ 2 


∴E =  + 
A  K 4K θ 

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 Ø

fibre Flim
detection
f

Stretch the molecule

c – lattice parameter changes with stress by δc


dc
Crystal/lattice strain
c
f
Stress =
A

f A
∴E = = crystal modulus
δc c

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
PE
Higher
modulus

rod

e.g. rigid rod molecules

O O
C C N N
H H
n

Crystal modulus ~ 220GPa (same as steel)


True rigid rod molecules

O O
“PBO” zylon

N 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
CH2
CH CH
CH2 CH2
CH2 CH3 CH3

1
Since E ∝
A

PP – increase A, ∴E ↓

PP crystal modulus E ~ 50 GPa


PE crystal modulus E ~ 250 GPa

Theoretical yield strength

σ Yield Yield – outset of plastic deformation


point
σy
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
b
σ
h

8 Touching each other


σy

x displacement
0 b

Assume the shear stress varies sinusoidally with displacement

Equation

 πx  σ
σ = σy sin  
 b  σy

x =0 →σ = 0

1 x
x= → σ = σy 0 b/2 b
2

x =b →σ = 0
For lower value of displacement, sin θ →0

 πx  πx
σ = σ y sin   → σy
 b  b

shear stress
shear modulus, G = for small x
shear strain

σ
=
γ

displaceme nt x
γ= =
phase separation h

σh
G=
x

Or

84
Gx
σ=
h

(2) = (3)

πx Gx
σy =
b h

 Gb 
∴σy =
 πh 

e.g.: PE

b = spacing of atom along the chain


c
b= = 0.125 nm , c = 0.26 nm
2
h = 0.25 nm

G ×0.125 G
σy = ≈
π×0.25 b

∴Yield stress is theoretical ½ shear modulus

Behaviour of real polymer


At room temperature
G
σy ~ for PE
100

As temperature →0
G
σy ~ (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
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

u
h

x displacement
tension
compression

Equilibrium
separation
σ

σt

86
Work done

x separation
h x/2
x=0

Assume dependence of σ, σ upon displacement, 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

2πx
σ = σt
λ

Now strain Hooke’s Law is obeyed

Ex
σ = modulus strain =
h

Combine (2) = (3)

2πx Ex
σt =
λ h

 Eλ 
∴σt = 
 2 πh 

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

88