LECTURE – PRESENTATION
DECEMBER, 2009
CHEMISTRY DEPARTMENT
FACULTY OF SCIENCE
M.S.UNIVERSITY OF BARODA
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APPLIED CHEMISTRY DEPARTMENT
FACULTY OF TECHNOLY & ENGG
M.S.UNIVERSITY OF BARODA
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CHEMISTRY DEPARTMENT
SARDAR PATEL UNIVERSITY
ELECTRICAL BEHAVIOUR
OF POLYMERS
SUPER-CONDUCTOR
CONDUCTOR
SEMI-CONDUCTOR
INSULATOR
RESISTENCE
ORDER
INTRA-MOLECULAR BEHAVIOUR
INTER-MOLECULAR BEHAVIOUR
WIRES-LINEAR CHAIN
ORDER-CLOSE-PACKING
UNSATURATION
CONJUGATION
POLYMERISATION
DOPING
Conducting polymers have backbones of contiguous sp2
hybridized carbon centers. One valence electron on each
center resides in a pz orbital, which is orthogonal to the
other three sigma-bonds. The electrons in these delocalized
orbitals have high mobility, when the material is "doped"
by oxidation, which removes some of these delocalized
electrons. Thus the p-orbitals form a band, and the
electrons within this band become mobile when it is
partially emptied. In principle, these same materials can be
doped by reduction, which adds electrons to an otherwise
unfilled band. In practice, most organic conductors are
doped oxidatively to give p-type materials. The redox
doping of organic conductors is analogous to the doping of
silicon semiconductors
Calculations can be made of
highest occupied molecular
orbital energy, lowest
unoccupied molecular orbital
energy, ionization energy,
electron affinity, and
reorganization energy of a
molecular system.
Designing Polymers
The first step in designing a polymer is to ask what kind of
properties one wants:
What kind of solubility do you want?
What kind of solvents are you working with?
Do you want it solid? Crystalline?
Conductive? Semi-conductive? An insulator? Super-
conductive?
What kind of flexibility?
What kind of length? Do you need to control the
length?
Do you need anisotropic properties?
Should it be thermally conductive as well as
electrically?
What about mechanical properties ?
Structures of various conductive organic polymers.
Polyphenylenevinylene, polyacetylene, polythiophene (X =
S) and polypyrrole (X = NH), polyaniline (X = N, NH) and
polyphenylene sulfide (X=S).
POLY-ACETYLENES
The year was 1977. Hideki Shirakawa, Alan MacDiarmid,
and Alan Heeger (winners of the 2000 Nobel Prize in
Chemistry) published their discovery that upon reaction with
iodine, polyacetylene exhibited electrical conductivity many
orders of magnitude higher than the neutral unreacted film.
Here, it seemed, was a polymer chain on which electrons
could move—a molecular conductor. Chemists and
physicists who dreamed of lightweight batteries and a
replacement for copper power lines, and the billion-dollar
market for these products, got their hopes up; their goal
seemed just over the horizon
Three different types of thermoplastic elastomers,
styrenebutadiene-styrene, styrene-isoprene-styrene, and
styreneethylenebutylene-styrene triblock copolymers have
been blended with polyacetylene utilizing various blending
techniques. In one method, acetylene gas was polymerized
with the Ziegler-Natta catalyst in the presence of either the
thermoplastic elastomer film or a hydrocarbon solution of
the thermoplastic elastomer. The resulting
polyacetylene/thermoplastic elastomer blend has been
characterized. Upon doping with either iodine or ferric
chloride, the ultimate conductivities of the blends were
found to be 60–100 Ω−1 cm−1.
Polyacetylene shows catalytic activity in an aqueous
solution for electroless deposition of amorphous alloys.
The catalytic activity of polyacetylene is comparable to
the activity of some highly catalytic metals, i.e., Cu,
steel, and Pt. Modifications of the Shirakawa technique
led to the formation of a foam-like polyacetylene, which
is highly porous and has a low degree of crystallinity.
This material can be used as a catalytic substrate for
the preparation of amorphous metals in bulk form.
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porphyrin
ferrocene