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CHL392: Polymer Science and Engineering

Topics covered

Lecture 1 (2!"#!1$%
Introduction to polymers as macromolecules and soft matter; Comparison to low molar mass substances
– conformational entropy in polymers; Importance of structure – property relationships; Dependence of
physical property of polymer product on polymer composition, morphology and processing, to be studied
in the course using polymer chemistry, polymer physics and polymer rheology.
Historical significance of polymers; five Nobel ri!e winners in the area of polymers – only one in polymer
physics – ierre "illes de "ennes #$%%$&; Definitions – monomer, oligomer, polymer, repeating unit,
degree of polymeri!ation; typical numbers and si!e of synthetic polymers and biopolymers.
'(e)t* Class notes+

Lecture 2 (31!"#!1$%
Chemical formulae for some synthetic polymers; olymer chain conformation – variation in potential
energy with torsion angle ¢ for C, molecule e.g. ethane, C- molecule e.g. butane; (hree .otational
Isomeric /tates #.I/& – trans, gauche+ and gauche- obtained by rotation about a single bond along polymer
chain; e)tended #planar !ig0!ag& chain for all0trans, random coil #non0planar& for g1 and g0; Importance of
energy difference between trans and gauche states Δe in chain fle)ibility; introduction of persistence
length of a polymeric chain; /tatic fle)ibility; .I/ model to generate replicas of chain conformations #using
random numbers& and calculating average property e.g. polymer si!e.
'(e)t* /trobl Ch. ,; 2umar 3 "upta $.$, $.4 3 $.5; 6dditional reading* de "ennes #/caling concepts&
Introduction+

Lecture 3 ("$!"!1$%
Importance of energy barrier ΔΕ for transition between states; (ransition time scale – referred to
persistence time; Dynamic fle)ibility; /pecial case of single chain glass when ΔΕ ≫ k
B
I.
Chain configuration – head0to0tail, head0to0head, tail0to0tail; /tereo0regularity isomerism – isotactic,
syndio0tactic, atactic polymers; Crystallinity, melting point and other properties dependence on tacticity;
"eometric isomerism – cis and trans molecules e.g. $,- poly0isoprene #natural rubber& in cis and trans
forms; Difference between conformation and configuration.
6morphous, crystalline and semi0crystalline polymers; relation between density and crystallinity of
polymers e.g. HD7, 8D7.
'(e)t* /perling ,.$, ,.9, ,.-; 2umar 3 "upta $.4+
Lecture $ ("#!"!1$%
(hermal behavior of polymers; solid0li:uid phase transition in low molar mass substances; /ymmetric
brea;ing; 8ong range order in crystalline solid; <irst and second order phase transitions; 6morphous
polymers – glass transition temperature I
g
between =glassy> and =rubbery> states; /pecific volume vs
temperature curve and ,
nd
order nature of glass transition; glass transition is no phase transition as long
range order is absent in both glassy and rubbery states and treating glass as sub0cooled li:uid; <low
temperature – rubbery #viscoelastic solid& state to li:uid #viscoelastic polymer melt& state; Notion of
segmental mobility and molecular mobility.
?elting temperature I
m
in perfectly crystalline polymers #melting of lamellae&; /pecific volume vs
temperature curve for semi0crystalline polymers – e)hibits both I
g
and I
m
; (ypical values of I
g
and I
m

for poly0ethylene and poly0styrene; glass transition temperature as single most important property
deciding the application of polymers; factors affecting glass transition temperature.
'(e)t* Class notes; /perling Ch. @; 2umar 3 "upta ,., #not detailed&+

Lecture & (11!"!1$%
"lass transition revisited; Importance of I
g
in polymer application; <actors affecting I
g
; AoungBs modulus
E as a function of temperature; Defining polymer crystallinity #volume crystallinity X
¡
and mass
crystallinity X
m
&; Cuiescent crystalli!ation – spherulitic growth of crystals; <low0induced crystalli!ation –
shish0;ebab crystals; olymer physics – ideal chain model; 7nd0to0end distance of an ideal chain.
'(e)t* Class notes; /perling @.,; 2umar 3 "upta $,., 3 $,.9+

Lecture ' (1$!"!1$%
olymer hysics* Ideal polymer chain – No long range interaction between monomers #or segments& along
the chain; <reely Dointed chain model – free bond angle and torsion angle; 7:uilibrium chain si!e as given
by s:uare of end0to0end distance and its scaling with number of monomers; <reely rotating chain – fi)ed
valency #bond& angle, free torsion angle; 7nd0to0end distance follows same scaling with n as freely Dointed
chain, e)cept for a pre0factor containing bond angle; <loryBs characteristic ratio c
«
; 2uhn chain – any
fle)ible chain e)pressed as e:uivalent freely Dointed chain; 2uhn length b
K
and number of 2uhn monomers
N
K
; $0D random wal; on lattice.
'(e)t* .ubinstein 3 Colby ,.$, ,.,, ,.9.$; 6dditional reading* /trobl* ,.9; de "ennes #scaling concepts& $.$;
Doi 3 7dwards ,.$+

Lecture # (21!"!1$%
Ideal chain models revisited – freely Dointed and freely rotating chain models; 2uhnBs chain – e:uivalent
freely Dointed chain model; ersistent length of a polymer chain – defined as e)ponential decay of tangent0
tangent correlations #orientational correlations& along a continuous chain contour; .elationship between
c
«
, b
K
, and l
p
; $0D random wal; on a lattice; robability distribution for $0D random wal; in continuous
space; Definition of diffusivity based on ?/D #mean0s:uare distance travelled&; robability distribution in
90D space; Ey analogy with diffusion #90D Erownian motion&, the probability distribution for end0to0end
distance vector R in N steps – "aussian distribution, "aussian chain.
'(e)t* .ubinstein 3 Colby ,.9.$, ,.4; 6dditional reading* Doi 3 7dwards ,.,+

Lecture (2&!"!1$%
Conformational entropy of an ideal chain; <ree energy of an ideal chain; <orce0e)tension relation #Hoo;eBs
law& for an ideal chain; spring constant and notion of entropic spring; 7ntropic origin of polymer elasticity;
.eal chain in good solvent – e)cluded volume effect; .eal chain as self0avoiding random wal;; ?eaning of
e)cluded volume parameter #virial coefficient of monomer0monomer interactions&; <loryBs mean0field
approach for e:uilibrium coil si!e R
P
; /caling R
P
~N
v
, where v = S¡S for real chain; Definition of e)cluded
volume in terms of ?ayerBs f0function.
'(e)t* .ubinstein 3 Colby #.C& ,.5, 9.$; 6dditional reading* de "ennes #/caling concepts& $.$ 0 $.9; Doi 3
7dwards ,.4+


Tutorial 1 ($!"!1$ or "#!"!1$%
Classification of polymers – by origin, by chain, by monomer composition, by configuration, by thermal
behavior, by applications.
'(e)t* 2umar 3 "upta $.,, $.9+

Tutorial 2 (11!"!1$ or 1$!"!1$%
?olar mass distributions; Discrete and continuous distribution of molecular weight; Number0average
molecular weight; Feight0average molecular weight; Degree of poly0dispersity #DI&; (g measurement –
dilatometry and differential scanning calorimetry #D/C&.
'(e)t* /perling* @.9 0 @.9.$ 3 @.9.,; .ubinstein 3 Colby $.5, $.5.$; 6dditional reading* 2umar 3 "upta $,.,+

Tutorial 3 (21!"!1$ or 2&!"!1$%
(g measurement by D/C #continued&; .ate of crystalli!ation dependence on degree of sub0cooling; .adius
of gyration .g for ideal polymer chain; .g of a star0polymer.
'(e)t* .ubinstein 3 Colby ,.-+