Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
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
1
BASIC INTRODUCTION OF 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
ACTIVE CENTRE
H
C C H
H X
SIDE GROUP
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
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.
3
ANIONIC POLYMERIZATION
- -
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
−d[ M − ]
= k i [ M ][ I]
dt
2) Propagation rate = Rp
d[ M ]
= k p [ P − ][ M ]
dt
→
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 propagatio n
Xn =
rate of terminati on
k p [M ]
Xn =
k t [CH 3 OH ]
8
1. Temperature
−E RT
k = A exp
2. counter-ion
Butyl lithium ≈
Bu M
M ⊕ → Li Na K Rb Ce
∴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.
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
11
Protonic acid e.g. H2SO4 and HClO4 often used as initiators.
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
+
CH3 CR1R2(BF3OH)-
In general,
karbokation
Propagation
12
+
RCH2 CR1R2A- + CH2 CR1R2
+ -
RCH2 CR1R2 CH2 CR1R2A
Termination
i. Spontaneous decomposition
+ -
CH CR1R2A CH CR1R2 + H+A-
+
CH2 CR1R2A- CH CR1R2
+
+
CH3 CR1R2A-
Polymerisation kinetics
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
− 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
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 ± ]
Ri = Rt
∴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
15
Propagatio n rate
=
Terminatio n rate
K p [ P ± ][ M ]
=
K t [P ± ]
Kp
Xn = [M]
Kt
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
Ep <
<< Ei , Et
Kp
αn = [M]
Kt
16
Arrhenius:
(
− Ep − Et )
Ap
Dp = exp RT
[M]
At
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
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
19
OH
H
C O + H2O CH2
H
OH
formalin aqeous
formaldehyde
media
PFDR formed by
Formaldehyde + phenol
20
OH
o o
HOCH2OH +
2 f.g. m m
p
OH
HOCH2 CH2OH
+ 3 H2O
or catalyst
CH2OH + H CH2
methylene
and bridge
ethylene bridge
OH
CH2 O CH2
CH2
CH2 O
CH2
OH
21
Carbamide + formaldehyde in alkaline solution
NH2 CO N CH2 N CO
CH2 CH2
CO N CH2 N CO
Use as coating
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
5. Polyurethanes
23
Triol
or
Diisocyanate:
CH3 CH3
NCO OCN NCO
NCO
2,4 2,6
24
OCN CH2 NCO
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
CH3 H CH2 H
C C C C
CH3 CH2 CH3 CH2
30
CH3
+
CH2 C CH CH2 sulphur (Sx)
CH3 CH3
SxH
CH3
Sx
CH3
31
2. Butyl Rubber
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
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.
35
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).
rad
PH P + H
H + PH P + H2
P + P P P (crosslinking)
36
Peroxide
+ CH2 CH Si(OMe)3 CH2 CH2 Si(OMe)3 Reac. 1.12
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
Question
What physical quantities may be used as measures of the size of a polymer molecule?
Number-fraction distribution
ni = number-fraction of species i
Ni
∞
=
∑Ni
i =1
Weight-fraction distribution
wi = weight-fraction of species i
Wi N M
∞
= ∞ i i
=
∑ Wi
i =1
∑ Ni Mi
i =1
39
N(M)dM = number-fraction of molecules with molar mass
between M and M+dM
n ( M ) MdM
∞
W(M)dM =
∫ n ( M ) MdM
0
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
40
Techniques For The Determination of Molar Mass
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
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
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
Detector signal is plotted against alution volume to obtain the GPC curve
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
43
Statistical-thermodynamical treatments of the exclusion problem show that:
K e ∝ log (slolute size)
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.
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
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
η − ηo t − to
ηsp = ηr − 1 = ≈ A measure of the relative increase in viscosity
ηo to
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
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
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
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.
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.
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
H H
C C
H OR2
R2 Tg
CH3 -10 oC
CH2CH3 -17 oC
CH2CH2CH3 -27 oC
CH2CH2CH2CH3 -32 oC
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
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)
Tg
H H
Polypropylene -18 oC
C C
H CH3
H Cl
H Cl
Poly vinylidene -19 oC
chloride C C
H Cl
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*
T
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
1 dV
αf =
V dT
∴f = f g + (T − Tg ) αf
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
o ↑ molecular weight
56
↓chainend → ↓ free volume
↓mobility volume → ↑Tg
K
Tg = Tg∞ −
M
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
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
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
20 oC
PMMA
PS
Tg Temperature
Secondary
transition
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
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
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
Normally Tm > Tc for finite size crystal and Tm = Tc for ∞ size crystal
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
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
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)
µ cu − µ ou = − ∆G u = − ( ∆H u − T∆S u )
(2)
( final ) ( initial )
∆H u
As before ∆S u = (3)
Tmo
T
µcu − µou = − ∆H u 1 − o (4)
Tm
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
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
1 1 R 2 + y
− o =
X
Tm Tm ∆H u n
Repeat Tm/K
CH2 CH2 410
66
–H PE 410
CH3 PP 460
CH3
CH2 CH 4-methyl-1-pentene 508
CH3
450
Specific
volume
Amorphous
Crystalline
Tg Tm Temperature
67
Tm = 1st order transition
Tg = 2nd order transition
Sealed
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
Polymer
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
Polymers
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
stretch
Heat Molecules
random
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
σ σ σ
Slope = E =
ε
73
glassy polymer. e.g. PS
σ
load
unload
2% ε
e.g.2
ductile thermoplastic e.g. polycarbonates
Yield (plastic
σ deformation started)
10% ε
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
Tg T
2. semicrystalline polymer
V
Rubbery
liquid
Glassy
Crystal in
rubber
Tg Tm T
E
Tough
material
Tg Tm T
Semicrystalline polymer
76
Elastomers
1 GPa
1 MPa
0% 100%
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
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
f cos α
KL =
d
f cos α
d =
KL
f cos α
δ =
K
α
f
x
2
pivot
78
From geometry
θ
α+ = 90 o
2
θ
α = 90 o −
2
( 4) − δ α= − δ θ
2
fx
∴K θ =
δθ
x
sin α = → x = sin α
2
2
f ( 2) sin α
Kθ =
δθ
f sin α
δθ=
2K θ
− f L sin α
δα=
4K θ
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
80
f
x-ray Ø
fibre Flim
detection
f
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
81
PE
Higher
modulus
rod
O O
C C N N
H H
n
O O
“PBO” zylon
N N
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 ↓
ey ε
Plastic deformation
Not reversible
Molecules move past each other
Shear
stress
σ
83
b
σ
h
x displacement
0 b
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
G ×0.125 G
σy = ≈
π×0.25 b
As temperature →0
G
σy ~ (theory only valid at 0oK)
b
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
u
h
x displacement
tension
compression
Equilibrium
separation
σ
σt
86
Work done
x separation
h x/2
x=0
2πx
σ = σt sin
λ
λ = wavelength
σt = theoretical strength
2πx
σ = σt
λ
Ex
σ = modulus strain =
h
2πx Ex
σt =
λ h
Eλ
∴σt =
2 πh
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