Introduction To The Physical Chemistry of Polymer
Introduction To The Physical Chemistry of Polymer
Introduction To The Physical Chemistry of Polymer
Chemistry Of Polymer
Lecture 1
Introduction to polymers
Poly = many, mer = unit, many units
Polymer science is relatively a new branch of science . It deals with chemistry
physics and mechanical properties of macromolecule .
Macromolecule are involved in all human aspect ; the human body itself is
made from proteins a polymer (made of poly amino acid ). Cellulose an
Important natural material essential for the existence of man since the down
of history, is the complicated polymer structure.
Beyond the many natural polymer , the man made polymers ore now for
human development . It is impossible to imagine modern life without all the
different types of synthetic textile materials (polyester , polyamide………..)
: In this course we will discuss the following
Types of polymer -1
Step polymerization -2
Addition free radical polymerization -3
Addition ionic polymerization -4
Copolymerization -5
Molecular weights of polymer -6
Elucidation of the structure of polymer -7
Definitions
Polymer –is a large molecule consisting of a number of repeating
units with molecular weight typically several thousand or
higher
Poly X
Homopolymer Copolymer
Homopolymer
Consist of only one type of constitutional repeating unit (A)
AAAAAAAAAAAAAAA
copolymer
Consists of two or more constitutional repeating units (A.B )
Several classes of copolymer are
possible
Statistical copolymer (Random)
ABAABABBBAABAABB
two or more different repeating unit
are distributed randomly
Alternating copolymer
ABABABABABABABAB
are made of alternating sequences
of the different monomers
Block copolymer
AAAAAAAAABBBBBBBBB
long sequences of a monomer are followed
by long sequences of another monomer
Graft copolymer
AAAAAAAAAAAAAAAAAA
B B B
B B B
Consist of a chain made from one type of
monomers with branches of another
type
)d(
Classification by Chain structure (molecular architecture)
Linear chains :a polymer consisting of a single continuous chain of
repeat units
Branched chains :a polymer that includes side chains of repeat
units connecting onto the main chain of repeat units
Hyper branched polymer consist of a constitutional repeating unit
including a branching groups
Cross linked polymer :a polymer that includes interconnections
between chains
Net work polymer :a cross linked polymer that includes numerous
interconnections between chains
CH2 CH CH CH2
Microstructure - Tacticity
CH3
n
CH3 CH3 CH3 CH3 CH3 CH3 CH3
Classification by Application
Plastics
Fibers
Elastomers
Coatings
Adhesives
where Mi represents the mean molecular weight of the size range i, and
Ni is the fraction of total number of chains within the corresponding size
range
A weight average molecular weight Mw is based on the weight .2
:fraction wi within the size ranges
Mw = ∑ M i W i / ∑ W i
(1)The number-average molecular weight for a
discrete distribution of molecular weights is
given as
PDI= Mw/Mn
Mw/Mn = 1 monodisperse
Polymer sample consisting of molecules all of which have the same
chain length
Amorphous Crystalline
7 – Crystalline melting temperature (Tm ) : temperature at which crystalline
Polymer converts to a liquid or crystalline domains of a semi crystalline
Polymer melt (increased molecular motion )
8- Glass transition temperature (Tg ) : temperature at which an amorphous
polymer converts to a liquid or amorphous domains of a semi crystalline
polymer melt
9 – Thermoplastics (plastics( :polymers that undergo thermally reversible
Interconversion between the solid state and the liquid state
10- Thermosets : polymers that continue reacted at elevated temperatures
generating increasing number of crosslinks such polymers do not exhibit
melting or glass transition
11- Liquid – crystalline polymers : polymers with a fluid phase that retains
some order
12- Elastomers : rubbery , stretchy polymers the effect is caused by light
crosslinking that pulls the chains back to their original state ا
Glass phase (hard plastic)
9
8 Leathery phase
Log (stiffness)7
Pa 6 Rubber phase (elastomer)
4
Liquid
3
Temperature
Polymerization mechanisms
- Step-growth polymerization
Stepwise (Condensation) polymerization Reaction
Stage 2
Combination
of small fragments
Stage 3
Reaction of
oligomers to give
high molecular
weight polymer
Example
formation of polyester
nHO-R-OH + nHOOC-Rˉ-COOH H-(O-R-OOC-Rˉ-CO-)nOH+(2n-1)H2O
) **( By substitution in
1 = k '[A]o t + 1
(1-p)
•Note that experimental data are usually linear only beyond ca. 80% conversion.
Polyesterification Without Acidic Catalyst
The rate equation is given by
- d[A]
= k [A]2[B]
dt
Or
-d [A]
I f [A] = [B] = k [A]3
dt
By
integration 1 1 **
- = 2k t
[M]2 [M]o2
[M] = [M]o - [M]o P = [M]o (1- P )
) **( By substitution in
1 =2 k [A]2ot + 1
(1-p)2
Uncatalyzed Polyesterification
Note that experimental data for esterification reactions show that plots of 1/
(1-p)2 vs. time are linear only after ca. 80% conversion.
Polyesterification Without Acidic Catalyst (continued)
• For example, the kinetic plots for the polymerization of adipic acid and
1,10-decamethylene glycol show that at 202oC, the third-order rate
constant for the uncatalyzed polyesterification is k = 1.75 x 10-2
(kg/equiv)2 min-1.
The Number Average Molecular Weight in
Polycondensation
Xn = N o / N = [ M ] o / [ M ] [ M ] = [ M ]o ( 1 – P )
Xn = 1 / 1 - P
•This relationship is the Carother's Equation.
Example
If monomer conversion is 99% what is Xn ?
Xn = 1 / 1 – P = 1 / 1 - 0.99 = 100
If P =99.5 % Xn = 1 / 1 - 0.995 = 200
If P =99.6 % Xn = 1 / 1 - 0.996 = 250
H-(O-R-OOC-Rˉ-CO-)nOH
The number-average molecular weight Mn, defined as
Mn = Mo Xn + Meg = Mo / 1 – P + Meg
where Mo is the mean of the molecular weights of the structural
units, and Meg is the molecular weight of the end groups. The latter
becomes negligible at even moderate molecular weight
Mn = Mo Xn + Meg = Mo / 1 – P
1
= k '[A]ot + 1
(1-p)
Xn= k '[A]ot + 1
X2n=2 k [A]2ot + 1
Mn as a Function of Conversion
Molecular Weight Control in Linear Polymerization
In the synthesis of polymers one is usually interested in obtaining a
product
of very specific molecular weight since its properties are highly
dependent on its molecular weight.
2-By increasing one reactant over the other. In this way the monomer in
excess will block any further increase in the polymer chains.
Excess H2N-R-NH2 + HOOC-R'-COOH ---> H-(-NH-R-NHCO-R'-CO-)n-NH-R-NH2
The use of excess diacid accomplishes the same result; the polyamide
in this case has carboxyl end groups
ExcessHOOC-R'-COOH+H2N-R-NH2 --->HO-(-CO-R'-CONH-R-NH-)n-CO-R'-COOH
Another method of controlling the molecular weight is by adding -3
small amounts of monofunctional monomer. (Acetic acid )
Type (2)
For the polymerization of bifunctional monomers A-A and B-B where B-B
is present in excess, the numbers of A and B F.gs. are given by NA and NB
Notice that NA and NB are equal to twice the number of A-A and B-B .
molecules, respectively.
The stoichiometric imbalance r of the two f.gs. is given by
r = NA /NB. ≤ 1
The total number of monomer molecules is given by
(NA+NB)/2 or NA(1+1/r)/2.
, the total number of polymer molecules is one half the total number
of chain ends or
[NA(1-p)+NB(1-rp]/2.
The number-average DP( Xn )is the total number of A-A and B-B molecules
initially present divided by the total number of polymer molecules:
Xn = NA(1+1/r)/2.
[NA(1-p)+NB(1-rp]/2.
If r = 1
Xn = 1 / 1-p
Xn = 1+r If p = 1
1 + r – 2rP Xn = 1 + r / 1 - r
Example
What is Xn when P = 1 but use 0. 9800 moles of A-A and 1. 0100
moles of B – B
r = NA / NB = 0.98 x 2 / 1.01 x 2 = 0.97
Xn = 1 + r / 1 – r = 1.97 / 0.03 = 66
Type (3)
the molecular weight can also be controlled by adding small
.amounts of monofunctional monomer
Moles of A-A = NA / 2
Moles of B-B = NB / 2
ˉMoles of mono functional B = NB
ˉr = ½ N A / ½ N B + N B ˉ = N A / NB + 2 N B
Example
Find Xn for 1 mole of A-A ,1mole of B-B and 0.01 mole of RBˉ when P = 1
r = 1/ 1 + 2x 0.01 = 0.99
Xn 1 + r / 1 – r = 1 + 0.99 / 1 – 0.99 = 199
Mn = Mo Xn + Meg = Mo / 1 – P
Xn= k '[A]ot + 1
X2n=2 k [A]2ot + 1
r = NA /NB. ≤ 1 ˉr = ½ N A / ½ N B + NB ˉ = N A / N B + 2 N B
Xn = 1 + r If r = 1 If p = 1
1 + r – 2rP Xn = 1 / 1-p Xn = 1 + r / 1 - r
The poly dispersity index
Xw / Xn = 1 + P
Xn = 1 /1-P Xw = 1 + p / 1 - P
Lecture 3
Polymerization mechanisms
Polymerization mechanisms
- Chain-growth polymerization
Chain polymerization
: The characteristic of chain polymerization are as follow
1- Growth is by the addition of the monomer at the end of the chain
2-Even at long reaction time some monomer are remain in the reaction
mixture
3-The molecular weight of the polymer are increase rapidly
4-Different mechanisms operates at different stages of the reaction
5-The polymerization rate initially increases and then become constant
6-An initiator is required to start the reaction
X X X
Monosubstituted
.Works fine
The only exceptions to the
unreactivity of tri- and tetra-
1,1-Disubstituted
substituted vinyl monomers are
Usually works.
those with fluorine, like
tetrafluoroethylene (CF2=CF2). The
main cause of this reactivity
Disubstituted-1,2 pattern is the steric size of the
.Seldom works substituents.
Trisubstituted
.Almost never works
Tetrasubstituted
.Almost never works
Free Radical Vinyl Chain Polymerization
Rate of Radical Chain Polymerization
Radical polymerization consists of three steps-initiation, propagation,
and termination.
The initiation step consists of two reactions.
1-The production of the free radical
kd
I ------> 2R˙
2- Addition of this radical to a monomer molecule to produce the
chain initiating species M1
ki
R˙ + M1 -----> M1˙
The propagation consists of the growth of M1
kp
Mn + M1˙ ------> Mn+1˙ (Rapid reaction )
Termination with the annihilation of the radical centers occurs by .
,,bimolecular reaction between radicals either by combination or
by disproportionation
ktc
M n˙ + M m ˙ -----> Mn+m
ktd
Mn˙ + Mm ˙ -----> M n+ Mm
The termination step can be represented by
kt
Mn ˙+ Mm ˙ ----> dead polymer
Kinetic Rate Expression
The rate of monomer disappearance, = the rate of polymerization,
is given by
d[M ]
Ri Rp
dt
Since for the production of high molar mass material Rp »
Ri this equation can be re-written as:
d[M]
R p k p [M ][M•] **
dt
Ri = 2kt[M.]2
[ M˙ ] = ( Ri /2kt ) ½
• Thermal initiators
• Photochemical
• Redox initiators
• Ionizing radiation
Thermal initiators:
•Unimolecular decomposition.
(I 2R•)
•First order kinetics.
Peroxides Ketones
Dilatometry
Dilatometry is the volume changes that occurs upon polymerization to
follow the conversion. It is the most accurate method for chain
polymerization because of the large difference in density between
monomer and polymer
Kinetic chain length
Kinetic chain length v is defined as the average number of monomer
molecules polymerized per each radical, which initiate a
polymer chain. In other words, v is the ratio between the
propagation
.rate to that of number
initiation,
of or termination
monomer units R p
initiating species Ri
By substitute
chemistry: H H H
CH2 C + C CH2 CH2 C C CH2
H
Polymerization
Monomer Polymer
Chain Transfer
Chain transfer is a chain breaking reaction; it is a premature termination
of polymer growing radical by the transfer of hydrogen or other atom
. or species to it from some compound present in the system
.This leads to a decrease in the molecular weight than expected
nM ˙ + XY ktr M -X +Y .
n
where XY may be monomer, solvent, initiator, or other molecule
.and X is the atom or species transferred
The rate of chain transfer reaction is given by
Cs
1/DP
1/DP0
[S]/[M]
k = A e – E / RT
or
lnk = lnA – E / RT
where A is the collision frequency factor, and E the Arrhenius
activation energy. A plot of ln k vs 1/T allows the determination
of both values.
Rate of Polymerization
For a polymerization initiated by the thermal decomposition of an
initiator the polymerization rate depends on three rate constants
Kp ( kd / kt )1/2
A
1/ 2
ln RP ln AP d E
ln ( f [ I ])1/ 2 [ M ] - R (3 - 41)
At RT
2- The ionic polymerization proceeds with very high rates and is very
sensitive to the presence of small amounts of impurities
The initiator ion pair (the carbonium ion and its counter ion)
produced in the initiation step proceeds to grow by the
successive addition of monomer molecules
HMn+(IZ) - + M HMnM+(IZ)-
Termination
1-Chain Transfer to Monomer
. This involves transfer of a proton to a monomer molecule
with the formation of terminal unsaturation in the polymer
molecule
2-Spontaneous Termination
Spontaneous termination involves regeneration of the initiator-
coinitiator complex by expulsion from the propagating ion pair
with the polymer molecule left with terminal unsaturation.
HMnM+(IZ)- HMnMIZ
Kinetics
Under steady state conditions (Ri=Rt) follows in a manner similar
,to that for radical polymerization. The rates of initiation, propagation
and termination are given by
Then kP [M ]
Xn (4 - 17a)
kt ktr,M [ M ]
Or
1 k
t CM (4 -17b)
X n k P [M ]
the activation energies for the rate and degree of polymerization are
obtained as
ER = Ei+Ep-Et
Trommsdorff effect
ktr
Mi + T Mi + T
ki'
T + M M1
Kinetics of free-radical chain polymerization
considering chain transfer reactions
d[polymer]
k tc [M•]2 2k td [M•]2 k tr [M•][T ]
dt
The rate of polymerization as derived before:
d[ M ]
k p [M ][M•]
dt
From the definition of number average degree of polymerization it follows:
d[M ] d[ polymer]
Pn
dt dt
thus:
1 k tc [ M•]2 2k td [ M•]2 k tr [M•][T ]
Pn k p [M ][ M•] 1
Pn
k tc [ M•] 2k td [M•] k tr [T ] 1 [T ]
CT
k p [M] k p [M] k p [M] Pn , 0 [M]
Chain transfer to polymer
• Intermolecular chain transfer
• Intramolecular chain transfer
1
0 10 20 30 40 50
[BA]0 / %(w/w)
Summary
Chain-length L k p [ M ]t
1
Time of chain-growth t~
[ M ]
Rate of polymerization R p k p [ M ][ M ]
Initiator decomposition is the reaction step most strongly
influenced by temperature.
Thermodynamics of radical
polymerisation
Overall activation energy of polymerization: Ea = 1/2Ed+(Ep-1/2Et)
Ed 125 – 170 kJ mol-1 (Ep-1/2Et) 20 – 30 kJ mol-1 Thus, initiation is the rate determining step
Tc = H/(S + Rln[Me])
Copolymerization
k11
—M1• + M1 —M1•
k11
k12
} r1
k12
—M1• + M2 —M2•
k21
—M2• + M1 —M1• k 22
} r2
k 21
k22
—M2• + M2 —M2•
Copolymerization
fi : fraction of monomer i in reaction mixture
f1 = [M1] / ([M1] + [M2])
If f1 ≠ F1
0.6
F1 → f1 changes
0.4
→ F1 changes
0.2 What does composition
drift mean for the polymer
0 that is formed?
0 0.2 0.4 0.6 0.8 1
f1
Polymerization techniques
Sometimes for one monomer several techniques of
polymerizing are available. Choice of a specific
technique depends on a number of factors:
Heterogeneous systems
• Suspension polymerization
• Emulsion polymerization
• Precipitation polymerization
• Polymerization in solid state
• Polymerization in the gas phase
Bulk polymerization
Advantages: Disadvantages:
• Simple, only the monomer and initiator Exotherm of the reaction might be hard to
are present in the reaction mixture control- molecular weights very
• High molecular weight disperse
Rp
The polymer is soluble
in the monomer:
Viscosity of the reaction
increases markedly (gel
effect)
Disadvantages Advantages
* Product sometimes * Contamination with
directly usable solvent
* Controlled heat * Chain transfer to
release solvent
* Recycling solvent
Applications
Acrylic coating, fibrespinning, film casting
Suspension polymerization
• Water insoluble monomers are dispersed in water.
• Initiator dissolved in monomer.
• Stabilization of droplets/polymer particles with non-micelle forming
emulsifiers like polyvinylalcohol or Na-carboxymethylcellulose.
• Equivalent to bulk polymerization,
small droplets dispersed in water.
• Product can easily be separated,
particles 0.01-1mm.
• Pore sizes can be controlled by adding a combination of solvent
(swelling agent) and non-solvent.
• Viscosity does not change much.
Suspension Polymerization
Advantages Disadvantages
* Heat control simple * Contamination with
* Product directly stabilizing agent
usable * Coagulation possible
* Easy handling
Applications
Ion-exchange resins, polystyrene foam, PVC
Emulsion Polymerization
• A micelle forming emulsifier is used.
• Initiator is water soluble.
• The formed latex particles are much smaller
than suspension particles (0.05-2 µm).
• Kinetics differ considerable from other techniques.
• Polymer is formed within the micelles
and not in the monomer droplets.
Emulsion Polymerization
Advantages Disadvantages
* Low viscosity even * Contamination of
at high solid contents products with additives
* Independent control * More complicated
of rate and in case of water
molecular-weight soluble monomers
* Direct application of
complete reactor contents
:Overview of Ionic Polymerization
Selectivity
• Ionic polymerizations are more selective than radical processes due to strict
requirements for stabilization of ionic propagating species.
Cationic: limited to monomers with electrondonating groups
Most ionic polymerizations have equilibrium between ion pairs (II or III,
depending upon solvent) and free ion (IV).
:Overview of Ionic Chain Polymerization
Mechanistic Analysis
HA + (CH3)2C=CH2 → (CH3)3C+(A-)
H NOT H O
H O
O O S O
O S O
O S O OH
OH
OH
Electron donating groups are needed as the R groups because these can stabilize the
propagating species by resonance. Examples:
Propagation is usually very
fast. Therefore, cationic
vinyl polymerizations must
often be run at low
temperatures. Unfortunately,
cooling large reactors is
difficult and expensive.
Also, the reaction can be
inhibited by water if present
in more than trace amounts,
so careful drying of
ingredients is necessary
(another expense).
Lewis acids form active catalyst-co-catalyst
complexes with proton donors
Regiochemistry of propagation
H R H R H R
E NOT E
H H H H H H
R = Alkyl,
Aryl,
Halide,
OR
Common steps of cationic polymerization: (iii)
termination by unimolecular rearrangment of the ion pair
B
Common steps of cationic polymerization:
(iv) chain transfer to monomer
backbiting:
hydraide transfer:
H
H
+ +
General kinetic scheme for cationic polymerisation
•Initiation X
X
I+ A─ + M IM+ A─ I+ A + I A
i = kic[M] M
IM+A
•Propagation X X X X
IM1+ A─ + M IM2+ A─ I + I
M
IM1+A
… IM2+A
X X X X X
IMn A + M IM
+ ─
n+1
+
A
─
R + R
p = kp[M+][M] n-1
M
n
IMn+A IMn+1+A
•Termination X X X X
I A R + H+ A
IMn+ A─ IMn + H + A─ n-1 n
Steady-state approximation:
i = t
kic[M] = kt[M+]
[M+] = kic[M]/kt
p = kp[M+][M] = (kp ki /kt)c[M]2
Electron withdrawing groups (ester, cyano) or groups with double bonds (phenyl, vinyl)
are needed as the R groups because these can stabilize the propagating species by
resonance. Examples:
:Anionic initiators
For initiation to be successful, the free energy of the initiation step must be favorable.
Therefore, it is necessary to match the monomer with the appropriate strength of
initiator so that the first addition is "downhill." If the propagating anion is not very
strongly stabilized, a powerful nucleophile is required as initiator. On the other hand,
if the propagating anion is strongly stabilized, a rather weak nucleophile will be
successful as initiator. (Of course, more powerful ones would work, too, in the latter
case.)
But two EWGs are so effective in stabilizing anions that even water can initiate
cyanoacrylate ("Super Glue"). Weak bases (such as those on the proteins in skin)
work even better.
:Anionic initiators (continuation)
There is one other category of initiator, known as electron transfer, that works best
with styrene and related monomers. The actual initiating species is derived from an
alkalai metal like sodium. An aromatic compound is required to catalyze the
process by accepting an electron from sodium to form a radical anion salt with Na+
counterion. A polar solvent is required to stabilize this complex salt. The electron is
subsequently transferred to the monomer to create a new radical anion which
quickly dimerizes by free radical combination (similar to the termination reaction in
free radical polymerization). The eventual result is a dianion, with reactive groups at
either end. Propagation then occurs from the middle outwards. This system is
especially useful for producing ABA block copolymers, which have important
technological uses as thermoplastic elastomers.
Common steps of anionic polymerization:
(iii) chain transfer
Acrylates have problems in anionic propagation because of chain transfer to
polymer. The hydrogen atoms adjacent to the ester groups are slightly acidic, and
can be pulled off by the propagating anion. The new anion thus created can
reinitiate, leading to branched polymers. This side reaction is difficult to suppress.
Common steps of anionic polymerization:
(iv) termination (continuation)
When carried out under the appropriate conditions, termination reactions do not
occur in anionic polymerization. One usually adds purposefully a compound such
as water or alcohol to terminate the process. The new anionic species is too weak
to reinitiate.
The "Dark Side:" Compounds such as water, alcohols, molecular oxygen, carbon dioxide,
etc. react very quickly with the carbanions at the chain ends, terminating the propagation.
Therefore, one must scrupulously dry and deaerate the polymerization ingredients to be able
to get a truly living system. This is not easy to do, and adds to the potential costs of the
process.
Functionalization of the chain ends in anionic polymerization
The beauty of anionic polymerization lies in the lack of termination reactions when
carried out under the appropriate conditions (living polymerization). This means that
the propagating species remains unchanged at the chain end when the monomer is
consumed, so subsequent chemical reactions can be carried out. (The chain end is a
carbanion, and the organic chemistry of carbanions is diverse.) Here are a few
examples among many possible:
Coupling agents:
Living anionic polymerization
M• + CH2=CHR → [CH2=/•CHR]-M+
monomer radical anion
2[CH2=/•CHR]-M+ → M+-RHCCH2CH2CHR-+M
dianion
M• + A: → A:• -M+
A:•-M+ + CH2=CHR → [CH2=/•CHR]-M+ + A:
Monomer radical anion
2[CH2=/•CHR]-Na+ → Na+-RHCCH2CH2CHR-+Na
Propagation from both ends! dianion
:Anionic Initiation
Transfer of an Electron to an Intermediate
• For Ri >> Rp, all chains start at almost the same time.
If there is no chain transfer and no termination, chains will have equal
lifetimes and grow to about the same size.
Termination
Benzene 2.2 2
Dioxane 2.2 5
Tetrahydrofuran 7.6 550
Dimethoxyethane 5.5 3,800-1,2
The separation between the counterion and the carbanion end group on
the polymer is the major factor determining the rate, equilibrium, and
stereochemistry.
Counterion kp, liter/mole sec
in tetrahydrofuran in dioxane
Cation
size
Li+ 160 0.94
Na+ 80 3.4
K+ 60-80 19.8
Rb+ 50-80 21.5
Cs+ 22 24.5
Free anion 65,000!
Reaction Set
Initiation:
GA → G+ + A-
G+ + A- + M → G+ + AM-
Note that the nature of the solvent will determine whether the propagating
anion behaves as a free ion, AM-, as a loose or tight ion pair, AM-G+, or
both. We will assume free ions for this treatment.
Propagation:
AM- + M → AMM-
AMM-+ M → AM2M-
AMn-1M- + M → AMnM-
Termination:
There is no termination step in the absence of impurities.
Rate of Polymerization
Integrate to obtain:
Solid-State Properties
POLYMERS IN THE SOLID STATE
Amorphous
Semi-crystalline
Glassy Rubbery
Free Volume
Backbone Stiffness
Steric effects (side groups)
Network structure (thermosets)
Anything which makes movement more difficult will increase Tg
Crystallinity
Crystallization in linear polymers involves the folding back and forth
of the long chains upon themselves to achieve a very regular arrangement
of the mers
Crystalline polymers
stereoregular/ linear/ strong dipole-dipole interaction
Crystallites
Crystalline and ordered microdomains; fringed micelle
Induction of crystallinity
● cooling of molten polymer
● evaporation of polymer solution
● annealing heating of polymer at a specific temperature
● drawing stretching at a temperature above Tg
Crystalline regions
● a plateletlike
structure (~ 100 Å thick)
● folded-chain
lamella model
Extended-chain crystals
● less common; and often take a needle form
● usually formed with low MW polymer by slow crystallization or
under pressure
Nucleation onset of crystallinity
• homogeneous nucleation occur randomly throughout the
matrix
• heterogeneous nucleation occur at the interface of a foreign
impurity (e.g. a finely divided silica)
Crystalline morphologies
Spherulite aggregates of small fibrils in a radial pattern
(crystallization under no stress)
Drawn fibrillar obtained by drawing the spherulitic fibrils
Epitaxial one crystallite grown on another; lamella growth on
long fibrils; the so-called shish-kebab morphology
(crystallization under stirring)
Crystalline polymers (vs amorphous polymers)
● tougher, stiffer (due to stronger interactions)
● higher density, higher solvent resistance (due to closely packing
morphology)
● more opaque (due to light scattering by crystallites)
V
First-order Transition
Cp
=>
Detect the occurrence of glass transition
dilatometry measure volume increase
calorimetry measure the enthalpy change
mechanical measurements modulus and stiffness
Semi-crystalline Amorphous
V or V
H
Tm Tg
Modulus & Temperature
Rheology
Rheology the science of deformation and flow
To cause a polymer to deform or flow
● need a force
(a) if the force is withdrawn quickly)
polymer will rebound (a relaxation process)
(b) if the force is applied consistently
polymer will flow irreversibly
● the flowing polymer liquid will be very viscous
due to chain entanglement and frictional effects
● amorphous polymers are viscoelastic materials
combination of elasticity and viscous flow
Shear (tangential stress) the most concerned force type
Shear stress
F (dyne/cm 2
; newton/m 2
)
F: force (dynes; newtons) A: surface area (cm2;
A m2 )
Shear strain (amount of deformation of one plane with respect to
X another)
Y
Shear modulus
(Resistance to shear)
G
(: shear strain) ( = G )
Ae Ea / RT
A: related to molecular motion
Ea: activation energy for forming viscous flow
Ea
● determined mainly by local chain segmental motion
● relatively insensitive to MW
● highly depending on chain structure and branching
● bulkier chain branch or substituent higher Ea
● bulkier group makes viscosity more sensitive to
temperature
Bingham Newtonian
fluid (Eugene Cook Bingham)
τ τ c η γ c : critical shear stress; threshold stress
thixotropic liquid
● has gel-like properties or a high viscosity under low stress, but
thin out on stirring
● depending on shear time, but not shear rate (different from shear
thinning)
● commercial paints are typical examples
B
General expression A log log A B log
• for a Newtonian fluid B = 1 and A = ( = )
• plot log vs logγ slope = B; intercept = log A
B
General expression A log log A B log
• for a Newtonian fluid B = 1 and A = ( = )
• plot log vs logγ slope = B; intercept = log A
MW effect
M c critical molecular weight for entanglement to begin
● typical range 4,000 to 15,000
● typical chain length DP about 600
MW distribution effect
M
M: torque; dynes/cm (CGS) or newtons/m (SI) 3
R
R: cone radius; cm or m
shear rate
: angular velocity; degrees/s (CGS) or radians/s (SI)
: cone angle; degrees or radians
viscosity 3M kM 3
k
2 R 3
2R 3