You are on page 1of 78

Structure and Properties of

Polymers
Christopher Y. Li

Department of Materials Science and Engineering


Drexel University
http://soft.materials.drexel.edu/
MATE 501 Structure and Properties of Polymers

Instructor: Professor: Christopher Y. Li; Office: LeBOW 27-443


Laboratory: LeBOW 27-337; Phone: 215-895-2083
Email: chrisli@drexel.edu; Website: http://soft.materials.drexel.edu/
Office Hours: Thursdays 10:00 am – 12:00 pm, or by appointment

Course Description:
Structure and properties of polymers in solid states will be discussed in the class. Topics include polymer
chain structure, polymer morphology, polymer structure, amorphous state, crosslinked polymer and rubber
elasticity, and polymer surface and interfaces. The objectives of the course are:
 Understanding of the breadth and nature of a large range of structural characterizations for the
ordering in polymeric materials.
 Understanding the structure of condensed state polymeric materials.
 Understanding the basics of characterization techniques, including microscopy and scattering
techniques.
 Being able to design a research project that emphasizes the importance of structure and morphology
to the physical properties of polymeric materials.

MATE 501: Structure and Properties of Polymers-CYL


Project Design and Presentation:
 Two students will form a study group. Each
study group will present a polymer-related
project proposal. An oral presentation will be
given. Broad research areas can be chosen
and examples are: polymer nanocomposite,
polymer membranes, polymer electrolytes,
polymer nanofibers, polymer novel block
copolymers, biopolymers, conducting
polymers, etc.

MATE 501: Structure and Properties of Polymers-CYL


Schedule
 Form study group, decide topic (week 3)
 Decide topic (week 4)
 Written proposal due (week 6). The proposal should be 5-page, single
spaced, include: introduction (challenge and needs in the direction
you are working on), research rationale (why your approach will
work), proposed work (what are you going to do), and challenge
and perspectives, references.
 Comments due. (week 8) You proposal will be sent to another group,
who will provide their honest comments (at least one page) regarding
the strength and weaknesses of your proposal.
 Final proposal due/oral presentation, 12 min each. (week 11) The final
proposal should be an improved version of the first one, including the
rebuttal letter stating why you took/discard the previous comments.
 The final score on the project will be based on the final proposal, the
presentation, and the comments that you provide to other groups.

MATE 501: Structure and Properties of Polymers-CYL


Week Topic Reading Comments
Introduction, polymer Sperling Chapter 1 & 2
1, 1/ 9 chain structure, crystal
morphology
University Holiday
2, 1/16 Martin Luther King Day

Polymer crystal Sperling Chapter 6; Form study group


3, 1/ 23 morphology, crystal Wunderlich V1 Chapter 3
structure.
Sperling Chapter 6; Decide topic
Polymer crystal structure,
4, 1/30 Wunderlich V1 Chapter 2, 3
polymer crystallization
Wunderlich V2 Chapter 5, 6
Polymer liquid crystals, Sperling Chapter 7;
5, 2/6
Review
6, 2/13 Exam Written project due
7, 2/20 Polymer viscoelsticity Sperling, Chapter 10
Polymer viscoelasticity, Sperling, Chapter 10,11 Comments due
8, 2/27
Mechanical behavior
Mechanical behavior, Sperling, Chapter 11, 13
9, 3/6 Multicomponent
polymeric materials
Multicomponent Sperling, Chapter 13
10, 3/13 polymeric materials
/Projects
Final project due,
Multicomponent
presentation,
11, 3/20 polymeric materials
including comments,
/Projects
rebuttal
12 FINAL EXAM
MATE 501: Structure and Properties of Polymers-CYL
To catch up “background”

MATE 501: Structure and Properties of Polymers-CYL


Nobel Laureates in Polymer Science- Chemistry

1953 HERMANN STAUDINGER for his discoveries in the field of macromolecular


chemistry.

Staudinger

1963 KARL ZIEGLER and GIULIO NATTA for their discoveries in the field of the
chemistry and technology of high polymers.

Ziegler Natta

1974 PAUL J. FLORY for his fundamental achievements, both theoretical and
experimental, in the physical chemistry of the macromolecules.

Flory

MATE 501: Structure and Properties of Polymers-CYL


Nobel Laureates in Polymer Science- Physics

2000 ALAN J. HEEGER, ALAN G. MACDIARMID, and HIDEKI SHIRAKAWA


for the discovery and development of conductive polymers.

Heeger MacDiarmid Shirakawa

1991 PIERRE-GILLES DE GENNES for discovering that methods developed


for studying order phenomena in simple systems can be generalized to more
complex forms of matter, in particular to liquid crystals and polymers.

de Gennes

MATE 501: Structure and Properties of Polymers-CYL


The Nobel Prize in Chemistry 2005

"for the development of the metathesis method


in organic synthesis"

Yves Chauvin Robert H. Richard R.


Grubbs Schrock
Institut Français California Massachusetts
du Pétrole Institute of Institute of
Rueil-Malmaison, Technology Technology (MIT)
France (Caltech) Cambridge, MA,
Pasadena, CA, USA
USA
b. 1930 b. 1942 b. 1945
MATE 501: Structure and Properties of Polymers-CYL
Step Growth vs. Chain Polymerization

chain polymerization

chain polymerization

step growth

Which is step growth? Which is chain polymerization?

MATE 501: Structure and Properties of Polymers-CYL


Step growth

MATE 501: Structure and Properties of Polymers-CYL


MATE 501: Structure and Properties of Polymers-CYL
MATE 501: Structure and Properties of Polymers-CYL
Polyesters

Where can you find


polyesters? Or,
Where can’t you find
polyesters?
Made from recycled plastic water bottles
Fabric: Front: Dri-FIT 96% recycled
polyester/4% other fibers. Back: Dri-FIT
100% recycled polyester. Rib: 100%
recycled polyester.
Polyurethane
Spandex or elastane
It is a polyurethane-polyurea copolymerthat
was invented in 1959 by chemists C. L.
Sandquist and Joseph Shivers at DuPont's
Benger Laboratory in Waynesboro,
Virginia.
MATE 501: Structure and Properties of Polymers-CYL
The power of MW

See Sperling Table 1.4 and 1.6 for common polymers.

MATE 501: Structure and Properties of Polymers-CYL


Possible phase transitions in one component
system

Solid Intermediate Liquid

Increasing Crystal
order
Td Tm
Tg Ti
Mesophase Mesophase Melt
Glass

Tg
Disorder Glass

Immobile Increasingly more mobile

MATE 501: Structure and Properties of Polymers-CYL


Polymer Chain Structure

MATE 501: Structure and Properties of Polymers-CYL


Polymer Chain Structure
The molecular weight and molecular weight distribution of the
molecules.

The conformation of the chains in space. The term conformation refers


to the different arrangements of atoms and substituents of the polymer
chain brought about by rotations about single bonds. Examples of
different polymer conformations include the fully extended planar
zigzag, helical, folded chain, and random coils.

The configuration of the chain. The term “configuration” refers to the


organization of the atoms along the chain. Some authors prefer the
term “microstructure” rather than configuration. Configurational
isomerism involves the different arrangements of the atoms and
substituents in a chain, which can be interconverted only by the
breakage and reformation of primary chemical bonds.

MATE 501: Structure and Properties of Polymers-CYL


isomerism

Sequence Isomerism

Stereoisomerism

Optical Isomerism

Geometric Isomerism

Substitutional Isomerism

MATE 501: Structure and Properties of Polymers-CYL


Head-to-Head and Head-to-Tail Configurations

head-to-tail

head-to-head

MATE 501: Structure and Properties of Polymers-CYL


Stereochemistry of repeating units

Chiral Centers

Such carbon atoms are referred to as pseudochiral centers in long-chain


polymers because the polymers do not in fact exhibit optical activity
MATE 501: Structure and Properties of Polymers-CYL
Tacticity in Polymers

Three different configurations of a


monosubstituted polyethylene
MATE 501: Structure and Properties of Polymers-CYL
Meso- and Racemic Placements

The Fisher projection in equation


(2.10) shows that the placement
of the groups corresponds to a
meso- (same) or m placement of
a pair of consecutive
pseudochiral centers. The
syndiotactic structure in equation
(2.11) corresponds to a racemic
(opposite) or r placement of the
corresponding pair of
pseudochiral centers. It must be
emphasized that the m or r
notation refers to the
configuration of one
pseudochiral center relative to
its neighbor.

MATE 501: Structure and Properties of Polymers-CYL


Repeating unit isomerism
Optical Isomerism

Geometric Isomerism

Substitutional Isomerism

MATE 501: Structure and Properties of Polymers-CYL


Homopolymer vs. Copolymer

-A-A-A-A-B-B-B-B-B-B-A-A-A-A-

Poly-A-block-poly B -A-B-A-B-A-B-A-B-A-B-A-B-A-
Alternating copolymers

-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-
A-A-A-A-A-A-
A-A-A-A-A-A-A-A-

A-A-A-A-A-A-
-A-B-B-B-B-A-A-B-B-A-B-A-A-B-B-

Random copolymers

Poly-B-graft-poly A
MATE 501: Structure and Properties of Polymers-CYL
Six basic modes of linking two or more
polymers are identified . (a) A polymer
blend, constituted by a mixture or mutual
solution of two or more polymers, not
chemically bonded together. (b) A graft
copolymer, constituted by a backbone of
polymer I with covalently bonded side
chains of polymer II. (c) A block
copolymer, constituted by linking two
polymers end on end by covalent bonds.
(d ) A semi-interpenetrating polymer
network constituted by an entangled
combination of two polymers, one of which
is cross-linked, that are not bonded to
each other. (e) An interpenetrating
polymer network, abbreviated IPN, is an
entangled combination of two cross-linked
polymers that are not bonded to each
other. (f ) AB-cross-linked copolymer,
constituted by having the polymer II
species linked, at both ends, onto polymer
I. The ends may be grafted to different
chains or the same chain. The total
product is a network composed of two
different polymers.

MATE 501: Structure and Properties of Polymers-CYL


Important Concepts
Important Concepts
Polymer Architectures

MATE 501: Structure and Properties of Polymers-CYL


Contour length, Rmax

Quiz:
Polyethylene, with
a given MW (say
20,000 g/mol), what
is the contour
length

MATE 501: Structure and Properties of Polymers-CYL


Trans†–Gauche Conformations

MATE 501: Structure and Properties of Polymers-CYL


Butane CH3-CH2-CH2-CH3 potentials

kcal
( )
mole

MATE 501: Structure and Properties of Polymers-CYL


Polyethylene potentials

Quiz:
What is the most
stable conformation
for PE.

What about iPP?


Rotational isomeric state model

Random coil conformation


A number of different
conformations

320,000
Random conformation of a
macromolecular chain

Random flight

Free Joint Chain:

• There is not only totally free rotation around the bonds of the chain, but the chain
is freely joint (the valency bond angle is no longer fixed but can take any value)
• The chain can pass through regions of space that are already occupied by other
bits of itself.
Three-Dimensional Random Flight

N
R   li
i 1

<RN2>1/2 Root mean square end-to-end distance


Polymer conformation
 A polymer chain can take on an enormous range of
conformations as a result of bond rotations.
 These conformations can be described statistically, with the
end-to-end distance R being a useful parameter for doing this.
 The average value of R taken over all possible conformations
can be expressed in terms of its root mean square value
<R2>1/2, which is proportional to the square root of the number of
bonds, N1/2.
 The distribution function P(R) takes the form of a Gaussian
curve, to a first approximation.
From Free-Joint to Free Rotate
Free rotation:
1  cos 2 cos (1  cos N  )
<R2> = l2 N 
1  cos (1  cos ) 2

= Nl2
1  cos
1  cos
Considering restricted (hindered) rotation:
_______
1  cos 1  cos 
Quiz:
<R2> = Nl2 
1  cos 1  _______
cos 
Compare free-joint,
free rotation, and
restricted rotation
models. Differences
in assumptions,
and conclusions.
Real Chain

R 2
 C Nl 2
0

MATE 501: Structure and Properties of Polymers-CYL


Equivalent freely jointed chain

The equivalent chain has the same mean-square end-to-


end distance and the same maximum end-to-end
distance, but has N freely jointed effective bonds of length
b. b is called Kuhn length <R2> = C nl2 ∞

Nb = Rmax
<R2> = Nb2 =b Rmax =C ∞ nl2 Quiz:
Why using the
N = R2max/ C ∞ nl2 equivalent freely
b = <R2> /Rmax = C ∞ nl2/Rmax jointed chain
concept?

For PE, b = C ∞ l2n/nl cos(/2) = C ∞ l/cos(/2)


Colby and Rubenstein MATE 501: Structure and Properties of Polymers-CYL
Chain characteristics of common polymers

Colby and Rubenstein

MATE 501: Structure and Properties of Polymers-CYL


Polymer Crystallization
Polyethylene potentials
Polytetrafluoroethylene rotational potentials

Rotation by +15° gives


a right-handed helix
Rotation by –15° yields
a left-handed helix

st a b le g a u c h e (+ ) g a u c h e (-) st a b le
p o sit io n p o sit io n p o sit io n p o sit io n

~+15° ~ -1 5 °

MATE 501: Structure and Properties of Polymers-CYL


Helical conformations of Class 1 Macromolecules

Polyethylene CH2-

21 helix

Polytetrafluoroethylene CF2-

137 helix

Wunderlich
MATE 501: Structure and Properties of Polymers-CYL
The three-fold helix of isotactic polypropylene in front of
Institut Charles Sadron Strasbourg
the Giulio Natta Research Center in Ferrara, Italy
Photo courtesy of Pr. Galli QuickTime™ et un
décompresseur Graphique
sont requis pour visionner cette image.

MATE 501: Structure and Properties of Polymers-CYL


Conformation helices

Wunderlich

21 31 32 31 41

Identify period 42= 21 51 52 61


c along z Projections
131 of various
62= 31 71 72 73
Perspective drawing and helices
projection along z
Aut: 81 83 91 92
Rotation necessary to go from lattice point t: turns to the next identical helix point
to lattice point:    2  t / u u: periodicity (# of helical lattice points
Translation necessary to go from lattice point per identical period)
to lattice point:  z  c / u c: distance to the next identical helix
point
MATE 501: Structure and Properties of Polymers-CYL
Secondary Structures of Proteins

pleated sheets
 helix
MATE 501: Structure and Properties of Polymers-CYL
Quiz:
What’s the conformation of the
chain, what’s the driving force?
MATE 501: Structure and Properties of Polymers-CYL
Kevlar

Quiz:
Why is Kevlar an excellent
candidate for a bullet proof vest?
MATE 501: Structure and Properties of Polymers-CYL
The three-fold helix of isotactic polypropylene in front of
Institut Charles Sadron Strasbourg
the Giulio Natta Research Center in Ferrara, Italy
Photo courtesy of Pr. Galli QuickTime™ et un
décompresseur Graphique
sont requis pour visionner cette image.

MATE 501: Structure and Properties of Polymers-CYL


Helical conformations of Class 2 Macromolecules

Polyoxymethylene

Wunderlich
CH2 O
2 95 helix
102° rotation for each angle from the
shown all-trans conformation

Quiz:
What’s a 95 helix?
Openness of helices

Wunderlich

Perspective Drawing of
Isotactic Vinyl Polymer Helices

The side group is marked 


and is taken
as the helix lattice point. The more
crowded the backbone chain becomes
due to a large side group close in, the
more does the helix open up. 1 and 2
decrease by about 20° in going from
231 272 241 2×31 to 2×41

MATE 501: Structure and Properties of Polymers-CYL


Dense packing of rods

Wunderlich

area of circles
K  0.907
total area
Packing fraction
Coordination Number CN = 6
Compare:
Close pack of sphere CN 12,
K = 0.741;
Packing of rods with CN 4,
K = 0.785

MATE 501: Structure and Properties of Polymers-CYL


Packing of Helices with Large Side groups

Wunderlich

CN = 4
K = 0.785 when touching
K = 0.92 with interpenetrating
RH screw intermeshing with LH screw helices of 59% thread depth

MATE 501: Structure and Properties of Polymers-CYL


Crystal Morphology

“Single crystals” have one lattice.


“Polycrystalline samples” are aggregates of many single crystals.

Crystal Habits
a: lamellar
b: platy
c: tabular
d: isometric
e: prismatic
f: acicular
g: needle-like
h: fibrous
Macromolecular crystals are often lamellar or fibrous.
MATE 501: Structure and Properties of Polymers-CYL
Morphology and Conformations

“Fringed Micelle” Extended chain (above


Herman, Gerngross 2000 Å in length along
and Abitz, 1928- C the chain axis)
1930 Staudinger and Sauter
1927-1932

Folded chain (best


from dilute solution) Amorphous glass
Storks, 1938

B A
Modern morphology-conformation study started with
the work of Keller, Fischer and Till in 1957.
MATE 501: Structure and Properties of Polymers-CYL
“Fringed Micelle”
Stems form roughly isometric crystallites
whose surfaces consist entirely of
amorphous material (disordered chains
span micelles)

Later work (by microscopy and x-ray


scattering) showed that this model is
invalid for most polymers, but may have
some validity for polymers containing
very short crystallizable sequences and
very low crystallinity (<5%; e.g., PVC,
metallocene PE of very high comonomer
content)

MATE 501: Structure and Properties of Polymers-CYL


How Widespread is Chain Folding?

Solution grown lamellar


crystals of polyethylene

Grown from dilute solution


in tetrachloroethylene at
70-75 C

Grown from 0.1% dilute solution in


o-xylene at 80 C
MATE 501: Structure and Properties of Polymers-CYL
Chain sliding upon deposition

Wunderlich, V1, P252.

MATE 501: Structure and Properties of Polymers-CYL


Chain Folding in PE Single Lamellar Crystal

Schematic view of chain folding +b

-a

-b
MATE 501: Structure and Properties of Polymers-CYL
Chain Folding in PE Single Lamellar Crystal

Schematic view of a polyethylene single


crystal exhibiting adjacent reentry

MATE 501: Structure and Properties of Polymers-CYL


How Rough Lamellar Surface Is?
Adjacent reentry

Gel permeation
analysis of Surface models
solution grown n is
polyethylene after proportional n
etching for the to Adjacent Reentry
different times concentration
listed
(etchant: fuming
HNO3)
Switchboard Model
high M.W. low M.W.
Elution volume
The elution volume is approximately proportional to –log(molecular weight).
Nitric acid attacks preferentially the disordered regions. The low molecular
weight peaks after etching represent single, double, and triple traverses of the
chain. Their sharpness does not permit large amount of non-adjacent reentry
of the molecules.
MATE 501: Structure and Properties of Polymers-CYL
What Affect Chain Folding?

1. Crystallization temperature

2. Crystallization pressure

3. Molecular weigh

4. Crystallization time
MATE 501: Structure and Properties of Polymers-CYL
PE Crystallized at Elevated Pressure

Extended Chain Crystals


of Polyethylene

Extended chain crystals


of polyethylene grown
at 220 °C at 4800
atmosphere pressures

Wunderlich, V1, P224.

MATE 501: Structure and Properties of Polymers-CYL


Shish single crystals

Fibrillar component of polyethylene grown on


stirring (bare backbone obtained by washing with
xylene at 109.2 °C in excess)
MATE 501: Structure and Properties of Polymers-CYL
Fibers of Polyethylene Grown from Sheared
Solution (shish-kebabs)
Turbulent or extensive
flow is needed for growth
of the fibers. From 5%
solution in o-xylene, no
crystallization above 96
°C in quiet solution, but
up to 112 °C
crystallization in
turbulent flow. (shish-
kebabs with decreasing
amount of overgrowth)
Quiz:
What’s the conformation
of the chain, what’s the
driving force?
MATE 501: Structure and Properties of Polymers-CYL
MATE 501: Structure and Properties of Polymers-CYL
Quiz:
Other methods to produce shish kebabs?
Why studying shish kebabs?

MATE 501: Structure and Properties of Polymers-CYL


From single crystals to macroscopic
aggregates

MATE 501: Structure and Properties of Polymers-CYL


Polyethylene spherulites

Typical for
spherulites are the
Maltese crosses
which indicate the
orientation of
polarizer and
analyzer and the
ring patterns

Crystallized on cooling from the melt, optical micrograph, crossed


polarizers.
MATE 501: Structure and Properties of Polymers-CYL