Polymer Physics

Introduction &
Ideal Chain in Solution
A.Higuchi

NCU
Polymer Physics (2013)

1. History of Polymer Physics April 17,18
2. Ideal chains April 24,25
3. Real chains May 1,2
4. Polymer Solution May 8,9
5. Polymer Characterization (MW measurement) Part 1 May 15,16
6. Mid-term Exam May15,16
7. Polymer Characterization (MW measurement) Part 2 May 22,23
8. Polymer Solid May 22,23
9. Rheology May 29, 30
10. Crystalline and glassy polymer June 5,6
11. Final exam June 12
Histroy of Polymer Science (Physics)

Much of human history has been influenced by the availability of materials!
History is divided into eras named after the primary materials used:
The Stone Age, the Bronze Age, the Iron Age (& Ceramics, Semiconductor,
Polymer & Composite Age?).

Chemists started polymerizing synthetic macromolecules in the middle of the
nineteenth century, but they did not believe that they were creating very large
molecules! The beginning of the twentieth century was that these materials (natural
rubber) were believed as colloids-physically associated clusters of small molecules.
Why?
Many scientists actually measured high molar masses for these materials (of order
10
4
g/mol or even 10
5
g/mol), but rejected their own measurements because the
values changed systematically with concentration.

Loed Ernest Rutherford said:
Science is divided into two categories, physics and stamp-
collecting.

The wisdom of Werner Heisenberg:
Science progresses not only because it helps to explain newly discovered facts,
but also because it teaches us over and over again what the word understanding
may mean
In 1920, Staudinger (1953 Nobel prize winner) proposed the macromolecular
hypothesis: Polymers are molecules made of covalently bonded elementary units,
called monomers.
By 1929, Carothers had synthesized a variety of polymers with well-defined
structures, and the Polymer Age was born.
During the following 30 years (1930-1960), the main concepts of polymer science
were established.
The work of Kuhn on macromolecular sizes (Chp. 2), the work of swelling a single
chain in a good solvent (Chp.3), the work of Huggins and Flory (Nobel Prizer
(Chemistry), 1974) on thermodynamics (Chp. 4), the work of Flory and Stockmayer
on gelation (Chp. 6).

Textbook:

Flory, P.J. Principle of Polymer Chemistry (Cornell University Press, Ithaca, New
York 1953, Nobel Prizer (Chemistry))
De Gennes (Nobel Prizer (Physics), 1991), P.-G., Scaling Concepts in Polymer
Physics, Cornell University Press, Ithaca, New York 1979)
Michael Rubinstein, Ralph H. Colby, Polymer Physics, Oxford University
Press, 2003
1883gasoline1895tire
1905rubbercarbon blackrubber

tire
Wilhelm I I
1859-1941
rubber tire
1912
Polyethylene
Polyethylene or polythe (IUPAC name polyethene or poly(methylene)) is the
most widely used plastic, with an annual production of approximately 80 million
metric tons.
[1]
Its primary use is within packaging (plastic bag, plastic films,
geomembranes, etc.).
Bio-derived polyethylene
Braskem and Toyota Tsusho Corporation started Joint marketing activities for
producing polyethylene from sugar cane. Braskem will build a new facility at their
existing industrial unit in Triunfo, RS, Brazil with an annual production capacity of
200,000 short tons (180,000,000 kg), and will produce high-density polyethylene
(HDPE) and low-density polyethylene (LDPE) from bioethanol derived from
sugarcane.

Polyethylene can also be made from other feedstocks, including wheat
grain and sugar beet.
The Texture of Polyethylene
C.W. Bunn and T.C. Alcock
Trans. Farady Soc., 41, 317 (1945)
Thin Film of PE between corssed Nicols ; x 500
Electron Microscope of Thin Film of PE ; x 10,000
Mechanism of Cold-drawing
Fringed Micelle
Polyethylene Fine Strucutre
W.M.D. Bryant
J. Polym. Sci., 2, 547 (1947)
PE and Paraffin
PE Paraffin
A Note on Single Crystals in Polymers :
Evidence for a Folded Chain Configuration
A. Keller
Phil. Mag. Ser. 8, Vol-2, 1171 (1957)
Flat Single Crystals. The molecules must bend sharply back
on themselves forming a regular folded configuration.
1945 57
1. Electron Diffraction pattern of thin polymer films
2. Polymer single crystal
3. Lamellar morphology in spherulite
4. Small angle diffraction pattern (Long spacing)
5. Crystal facets and scetorization
6. No molecular weight change during crystallization
Lots of Evidences of chain folding
No other possibility but the chains fold up at regular intervals
If the contribution of Storks sets the birth data of chain folding,
Kellers major merit has been to popularize and, more importantly,
to transfer the concept of chain folding to bulk materials, thus
opening the way to the modern analysis of the polymer
crystalline state.
Polymer Single Crystals: What About the Impact of the Folds?
B.A. Lotz
Polym. Mater.Sci. & Eng. 97, 66 (2007)
50 Years after the Discovery of Polymer Single Crystals, ACS Meeting at Boston
52902003
Chain folding at Dupoint in the mid-50s.
P.H.Geil: J. Polym. Sci., Phys. 34, 1165 (1957)
Wallace Carothers (left), inventor of nylon--now used to
produce monofilament fishing line and other modern
conveniences-and Carl Marvel, another pioneer in the
field of polymer chemistry, fishing at Squaw
Lake,W7isconsin, ca. 1935. Photo from the Carl Marvel
Archives, CHE
Wallace Carothers
1939
Nylon

Nylon is a thermoplastic silky material, first used commercially in a nylon-
bristled toothbrush (1938), followed more famously by women's nylons
stockings (1940). It is made of repeating units linked by peptide bonds (another
name for amide bonds) and is frequently referred to as polyamide (PA). Nylon
was the first commercially successful polymer and the first synthetic fiber to be
made entirely from coal, water and air.

Nylon 6,6
Pleats and creases can be heat-set at higher temperatures
Difficult to dye
Nylon 6
Better dye Affinity
Softer Hand
Greater elasticity and elastic recovery
Better weathering properties; better sunlight resistance

Bill Pittendreigh, DuPont, and other individuals and corporations worked
diligently during the first few months of World War II to find a way to replace
Asian silk with nylon in parachutes. It was also used to make tires, tents, ropes,
ponchos, and other military supplies. It was even used in the production of a
high-grade paper for U.S. currency.
(----- History of Asahi Chemical Co. Toray Co. and Kuraray Co.---)
Polycarbonate (PC) -> ABS -> High molecular weight
polystyrene
The characteristics of polycarbonate are quite like those of polymethyl
methacrylate (PMMA, acrylic), but polycarbonate is stronger, usable in a wider
temperature range but more expensive. This polymer is highly transparent to
visible light and has better light transmission characteristics than many kinds of
glass.
IR transmittance of polycarbonate. Also,
polycarbonate is almost completely transparent
throughout the entire visible region until 400
nm, blocking UV light.
Polycarbonate (PC)
Kevlar (Aramid fiber)
[-CO-C
6
H
4
-CO-NH-C
6
H
4
-NH-]
n

high strength material was first commercially used in the early 1970s as a
replacement for steel in racing tires. Typically it is spun into ropes or fabric sheets
that can be used as such or as an ingredient in composite material components.
Currently, Kevlar has many applications, ranging from bicycle tires and racing
sails to body armor () because of its high tensile strength-to-weight ratio;
by this measure it is 5 times stronger than steel on an equal weight basis.
[2]

When used as a woven material, it is suitable for mooring lines and other
underwater applications.
Acrylonitrile butadiene styrene (ABS)
Monomer in ABS polymer
It is a copolymer made by polymerizing styrene and acrylonitrile in the presence of
polybutadiene. The proportions can vary from 15 to 35% acrylonitrile, 5 to 30%
butadiene and 40 to 60% styrene. The result is a long chain of polybutadiene criss-
crossed with shorter chains of poly(styrene-co-acrylonitrile). The nitrile groups from
neighboring chains, being polar, attract each other and bind the chains together,
making ABS stronger than pure polystyrene.
Biodegradable polymer
While aromatic polyesters are almost totally resistant to microbial attack, most
aliphatic polyesters are biodegradable due to their potentially hydrolysable
ester bonds:
Naturally Produced: Polyhydroxyalkanoates (PHAs) like the poly-3-
hydroxybutyrate (PHB), polyhydroxyvalerate (PHV) and
polyhydroxyhexanoate (PHH);
Renewable Resource: Polylactic acid (PLA);
Synthetic: Polybutylene succinate (PBS), polycaprolactone (PCL)...
Polyanhydrides
Polyvinyl alcohol
Most of the starch derivatives
Cellulose esters like cellulose acetate and nitrocellulose and their derivatives
(celluloid).
PLA
PLGA (poly(lactic-co-glycolic acid)
PLA PGA
Biodegradable polymer
Poly(-caprolactone)
Polyhydroxyalkanoates
ICI had developed the material to pilot plant stage in the 1980s, but interest
faded when it became clear that the cost of material was too high, and its
properties could not match those of polypropylene.
Poly-3-hydroxybutyrate (P3HB)
polyhydroxyvalerate (PHV)
In 1996 Monsanto (who sold PHB as a copolymer with PHV under the trade
name Biopol) bought all patents for making the polymer from ICI/Zeneca.
Monsanto's fermenters producing PHB from bacteria were closed down at the
start of 2004. Monsanto began to focus on producing PHB from plants instead
of bacteria.
Excise 1
1. Write chemical scheme of Nylon, polycarbonate,
and Kevlar. What are application usage of these
polymers?

2. Iist up biodegradable polymers and their
chemical scheme.
What are application usage of these polymers?
Example of Polymers
Fibers
Clothes
Tent
Rope
Bulletproof vest
Plastics (paper, board, cup, plate, bottle)
Polarized Filter
Plastic glass
Contact lens
Adhesion agent
FRP (tennis racket)
Tissue culture flask
Catheter
Dialysis membranes
RO membranes
UF, MF membranes
Piezo unit
Conductive polymer
Example of Polymers (Chemical structure)
Synthetic polymer
Polyethylene, PE
Polypropylene
Polyvinylchloride, PVC
Polyvinyldenechloride
Polyvinyldenefluoride, PVDF
Nylon
Polyurethane
Polyethylenephtalate, PET
Polyvinylalcohol
Polystyrene
Polymethylmethacrylate, PMMA
Polyacrylic resin
Polyacrylonitrile
Polysulfone
Polyimide
Teflon
Polylactic acid
Polyhydroxyethylmethacrylate, HEMA
Silicone rubber
Natural rubber
Silk

M = NxM
monomer
Fig. 1.2 The two sequence isomers of polypropylene
Fig. 1.3 The three structual isomers of polybutadiene.
Fig. 1.4 Tacticities of vinyl polymers, illustrated with all backbone
carbons in the plane of the page and with H and R groups pointing
either into or out from the page.
Linear ring star H
Fig. 1.5 Examples of polymer architectures.
Comb ladder dendrimer randomly branched
Fig. 1.6 Schematic architecture of a polymer network, with the dots
indicating crosslinks
Excise 2
1. Write the chemical structure of Nylon 6 and PET (polyethylene
terephtalate)
2. Please explain the chemical structure of (a) isotactic polymer,
(b) syndiotactic polymer, and (c) atactic polymer
3. Please explain alternating copolymer, random copolymer,
fdiblock copolymer, triblock copolymer, graft copolymer, and
random copolymer.
A polymers conformation is dictated by its interactions, here illustrated using a chain
with 10
10
monomers (one of the largest DNA molecules) of size 1 cm (magnify by the
factor 10
8
(l = 1 cm).
Strong attraction between monomers
V=nl
3
=10
10
cm3=10
4
m
3
No interaction between
Monomer, random walk
R=n
1/2
l=1 km
Excluded volume repulsions
(short-range repulsion)
R=n
3/5
l=10 km
Long-range repulsions (such as electrostatic), R=nl=10
5
km
Most of polymer conformation are self-similar (fractal)
Fig. 1.14 Fractal structure of an ideal chain with fractal dimension D = 2
Obtained by computer simulation.
What is fractal?
~
V = (4/3) R
3
4.2R
3
~ mass (m) (1.2)

m ~ r
3
fractal dimension D =3
Two-dimensional object is a sheet of paper
with uniform thickness and density. The mass
m of the circle cut out of the piece of paper is
proportional to the square of the radius r of
this circle:

m ~ r
2
fractal dimension D = 2
m ~ r
D
fractal dimension D =3
What is fractal?
Fig. 1.11 Mass m of the part of the wire inside a sphere of radius r.
Both axes have logarithmic scales.
Excise 3 Explain this figure.
Fig. 1.12 Construction of a triadic Koch curve.
Divide a straight line into three equal subsections. On the top of the middle
subsection we draw an equlateral triangle and erase its bottom side. Repeat these
procedures.
In order to calculate the dependence of the mass of the triadic Koch curve on the
length scale, let us draw circles of diameter 2r equal to the lengths of the
segments of two consecutive generations.
The radius of the circles changes by the
factor of 3 (r1=3r2), while the mass m of
the section of the curve inside these circles
changes by the factor of 4 (m
1
=4m
2
)

m
1
=Ar
1
D
=A(3r
2
)
D

m
2
=4m
2
= 4Ar
2
D

Then,

(3r
2
)
D
= 4r
2
D
-> 3
D
=4


D = log4/log3 = 1.26






m ~ r
D
fractal dimension D =3
Excise 4 Consider Sierpinki gasket and find fractal number D
There are two types of polymer liquids; polymer melts and polymer solution
Polymer solutions can be obtained by dissolving a polymer in a solvent.

Polymer solutions are classfied as dilute or semidilute depending on the polymer
mass concentration c.

(volume fraction) = c/ = c x v
monomer
N
AV
/M
monomer

The pervaded volume V is the volume of solution spanned by the polymer chain
V R
3


Fig. 1.15 Solution regimes of flexible polymers.
The fractal nature of polymers (N ~ R
D
) with typical fractal dimension D < 3, means
most of the pervaded volume is filled with solvent or other chains.

The volume fraction of a single molecule inside its pervaded volume is called the
overlap volume fraction * or the corresponding overlap concentration c*

* = N x v
monomer
/ V
c* = x N x v
monomer
/V = M / V x N
AV
Fig. 1.15 Solution regimes of flexible polymers.
Polymer Physics

Ideal Chain in Solution
A.Higuchi

NCU
What we learn & why we learn?
Ideal chains and real chains
-temperature & -solvent
End-to-end distance
Ideal chain models
Freely jointed chain model
Florys characteristic ratio, C
n
Kuhn length
Hindered rotation model (HR)
Rotational isomeric state model (RIS)


Ideal Chains and Real Chains
We consider the conformations of chains with no
interactions between monomers that are far apart along the
chain, even if they approach each other in space. Such
chains are called ideal chains. This situation is never
completely realized for real chains, but they are several
types of polymeric systems with nearly ideal chains. Real
chains interact with both their solvent and themselves. The
relative strength of these interactions determined whether
the monomers effectively attract or repel one another.
Real chains in a solvent at low temperatures can be
found in a collapsed conformation due to a
dominance of attractive over repulsive interactions
between monomers. At high temperatures, chains
swell due to dominance of repulsive interactions. At a
special intermediate temperature, called theta-
temperature, chains are in nearly ideal conformations
because the attractive and repulsive parts of
monomer-monomer interactions cancel each other.

The conformation of an ideal chain, with no
interactions between monomers, is the essential
starting point of most models in polymer physics.
Ideal Chains and Real Chains
-temperature is a special intermediate
temperature where chains are in nearly ideal
conformations because attractive and repulsive
parts of monomer-monomer interactions cancel
each other.

-solvent
Flexibility Mechanism
l=1.54A, =68 degree
The main source of polymer flexibility is the variation of torsion angles.
Consider a plane defined by three neighbouring carbon atoms C
i-2
, C
i-1
, C
i
.
Trans Gauche+ Gauche-
Any section of the chain with
consecutive trans states of torsion
angles is in a rod-like zig-zag
conformation. If all torsion angles of the
whole chain are in the trans state, the
chain has the largest possible value of
its end-to-end distance R
max
.
R
max
= n l cos (/2) (2.1)


Fig. 2.2 All-trans (zig-zag) conformation of a
short polymer with n=10 main-chain bonds.
Conformations of an ideal chain
Fig. 2.3 One conformation of a flexible polymer
The end-to-end vector is the sum of all n bond vectors in the chain:

The average end-to end vector of an isotropic collection of chains of n
backbone atoms is zero:
The simplest non-zero average is the mean-square end-to-end distance:
In a typical polymer chain, there are correlations between bond vectors
and <cos
ij
> is not zero.
Excise 5
Calculate the Kuhn length b of a polyethylene chain with
C

=7.4, main-chain length l = 1.54A, and bond angle

=68 degree.
The values of the Kuhn length b and
corresponding molar mass of a Kuhn monomer M
o

Hindered rotation model (HR)
The hindered rotation model assumes bond lengths and
bond angles are constant and torsion angles are taken to
be hindered by a potential U(). The probability of any
value of the torsion angle is taken to be proportional to
the Boltzmann factor exp[-U()/kT].
Hindered rotation model (HR)
Rotational Isomeric State Model (RIS)
Rotational Isomeric State Model (RIS)
Fig. One conformation of a randomly
branched polymer and its centre of
mass, denoted by cm.
Fig. One conformation of a randomly
branched polymer and its centre of
mass, denoted by cm.
Radius of gyration
Radius of gyration of an ideal linear chain
Classic Debye result!
Radius of gyration
Excise 6

Calculate the mean-square end-to-end distance of atactic
polystyrene with degree of polymerization 100 assuming
that it is an ideal chain with characteristic ratio C=9.5
(Note that the characteristic ratio is defined in terms of the
main-chain bonds length l=1.54 A rather than monomers.)