D EPARTMENT OF APPLIED CHEMISTRY

D ELHI TECHNOLOGICAL UNIVERSITY

D ELHI-110042

HIGH PERFORMANCE POLYMER

P T-361

PROJECT NAME: REVIEW PAPER ON CONDUCTING AND SEMI

CONDUCTING POLYMERS.
SUBMITTED BY: ADITYA PRATAP GUPTA (2K18.PS.005)

SUBMITTED TO: DR. POONAM

C ONTENTS
 INTRODUCTION

 HISTORY

 CONDUCTING POLYMER

 SEMI CONDUCTING POLYMER

 MECHANISM

 CLASSIFICATION

 APPLICATIONS

 REFERENCES

Introduction
Most organic polymers are insulators by nature. Most of the polymers are
used for electrical insulation, as they are bad conductor of electricity.
Since these polymers do not possess large number of free electrons,
they do not conduct electricity. Conductivity in polymers is observed
because of different reasons. Accordingly they can be categorized into
different types.

H istory
Conducting polymer research dates back to the 1960s, when Pohl,
Katon, and their coworkers, first synthesized and characterized
semiconducting polymers . The discovery of the high conductivity of
polysulfurnitride (SN), a polymeric material containing interesting
electrical properties, was a step forward for research in conducting
polymers.

The beginning of conducting polymer research started around 40 years

ago, when films of polyacetylene were found to exhibit profound
increases in electrical conductivity when exposed to halogen vapor. J.
Heeger, H.Shirakawa and G.MacDiarmid discovered conjugated
conducting polyacetylene when monomer of acetylene was doped with
bromine and iodine vapor; the resulting electrical conductivity was 10
times higher than the undoped monomers’. They were awarded Nobel
Prize in Chemistry, 2000, for their discovery.

After their discovery, research papers dealing with polyconjugated

systems were very extensive and systematic. The trend was to
understand the chemical and physical aspects, either in neutral
(undoped) state or charged (doped) states. According to Scifinder,
almost 40,000 scientific papers were published in this field of research
since 1977 [8]. This previously underestimated family of macromolecular
compounds turned out to be extremely interesting, from both the basic
research and application points of view. The polymer was produced by
the exposure of the polyacetylene to dopant compounds: oxidizing or
reducing agents; electrondonor or electron-receptor of electrons.

C ONDUCTING POLYMERS
Electrical conductivities are shown by few polymers because of it
fundamental characteristics. Such polymers are known as intrinsically
conducting polymers. However, intrinsically conducting polymers (ICPs)
have alternating single and double bonds along the polymer backbone
(conjugated bonds) or that are composed of aromatic rings such as
phenylene, naphthalene, anthracene, pyrrole, and thiophene which are
connected to one another through carbon-carbon single bonds.

These polymers can be easily oxidized or reduced as they have low

ionization potentials and high electron affinities. Their conductivities can
be increased by creating positive or negative charge on polymer
backbone by oxidation or reduction. The poor conductivity of polymers is
also explained by the band theory. This theory says that the energy
levels of electrons can occupy are grouped in allowed bands and may
have energy levels of electron that are forbidden, denominated band gap.
The lowest bands are called valence bands and are inert on an electrical
perspective. On the other hand, the highest bands, which participate in
the electric conduction, are called conduction bands.
Other conductors, such as divalent metals represented in b), can have an
overlap of the empty conductive band with a totally filled valence band.
For semiconductor and insulators, represented in d) and c) respectively,
the valence electrons must cross the band gap in order to result a
conduction. The difference is a semiconductor has a relatively smaller
band gap energy than insulators have .

S emiconducting polymers
Semiconducting polymers are described in terms of the energy bands
that originate from the bonding and anti-bonding energy levels
associated with the s-bonds between adjacent carbon atoms (formed
from the sp2 wavefunctions) and the orthogonal p-bonds that originate
from the pz wavefunctions. The s-bonds hold the structure together, but
the p-bonds are the origin of the properties that characterize conjugated
polymers as semiconductors
The thin film diode first described in 1987 provides a simple example of a
semiconductor device: the metal–semiconductor– metal (MSM) structure
comprised of a single layer of semiconducting polymer cast from solution
and sandwiched between metal contacts with different work functions
operates as a diode with relatively high rectification ratio.
 M echanism
Conducting polymers are responsible for flow of electricity because of
their conjugation in ∏ bond system. Due to delocalization of electrons in
molecule the conjugated double bands allow to flow of more number of
electron. Delocalization is the condition in which ∏ bonding electrons are
spread over a number of atoms rather than localized between 2 atoms.
This condition permits electrons to travel more easily making the
electrically conducting polymers.

The conductivity of non-doped,

conjugated polymers such as
polyacetylene is due to the
existence of a conducting band
similar to a metal. In a conjugated
polymer three or the four valence
electrons form strong σ bonds
through sp2 hybridization where
elctrons are strongly localized. The
remaining unpaired electron of each carbon atom remains in a pz orbital.
It overlaps with a neighboring pz orbital to form a π bond. The π electrons
of these conjugated pz orbitals overlap to form an extended pz orbital
system through which electrons can move freely (delocalization of π
electrons).
The process of doping of conductive polymers becomes easier due to
these conjugated bonds. In this process, defects and deformations in the
polymeric chain are formed. An electron-deformation pair, or also an
electron-photon cloud pair, is called polarons, which is responsible by the
conductivity in polymers. Bipolarons and solitons, other types of quasi-
particles, also participates in the conductivity mechanism. The type of
soliton, bipolaron, or polaron formed depends on the dopant used.
Only when an electron is removed from the valence band by oxidation (p-
doping) or is added to the conducting band by reduction (n-doping) does
the polymer become highly conductive. The four main methods of doping
are

 Redox p-doping: Some of the π-bonds are oxidized by treating the

polymer with an oxidizing agent such as iodine, chlorine, arsenic
pentafluoride etc.

 Redox n-doping: Some of the π-bonds are reduced by treating the

polymer with a reducing agents such as lithium, and sodium
naphthaline.
  Electrochemical p- and n-doping: Doping is achieved by cathodic
reduction (p) or by anodic oxidation (n).

 Photo-Induced Doping: The polymer is exposed to high energy

radiation that allows electrons to jump to the conducting band. In
this case, the positive and negative charges are localized over a few
bonds.

Doping increases. Values as high as 102 - 104 S/m have been reported.
Another method to increase conductivity is mechanical alignment of the
polymer chains. In the case of polyacetylene, conductivities as high as
105 S/m have been found which is still several magnitudes lower than the
conductivity of silver and copper (108 S/m) but more than sufficient for
electronic applications such as polymer-based transistors, light-emitting
diodes and lasers.

When the I2 oxidative dopants is added, it takes away an electron from

the ∏ backbone of the polyacetylene chain and creates a positive charge
(hole)on one of the carbon, now positively charged ,is termed as a radical
cation or polaron. The lone electrons of ∏ bond, from where an electron
was taken, can travel easily. As a moment the double bond moves along
the molecule. A bipolaron is formed on further oxidation.
If the polyacetylene chain is heavily oxidized, polarons condense pair-
wise into socalled solitons. Mobile charged solitons which enable
“spineless” conductivity are unique to polyacetylene. Here, conducting
polymers Poly (acetylene) & Polyaniline are taken as example to show
principle of conduction mechanism. By showing the uniqueness
property of unevenness of the poly (acetylene) in ground state, two
corresponding polyene chains R and L are interconverted through the
involvement of a mobile charge carrier, a soliton. The solitons are
mobile charged or neutral defect, or a “kink” in the poly(acetylene)
chain that spread down the chain and thus decrease the barrier for
inter conversion.
The conductivity of a conductive polymer is also temperature dependent,
because as the temperature increases the molecules becomes farther
from each other. Thus, the doping effect is more effective and,
consequently, the amount of charges, which is the doping level of the
polymer is greater, increasing the conductivity. Moreover, as the
temperature increases, the energy of an electron is related with the
temperature by the Boltzmann relationship. Because of that, the greater
the temperature, the greater is the energy of the electrons, and,
consequently, the easier is to excite the electron to the conduction band.
The table below lists typical conductivities of some common conjugated
polymers and their repeat units. The actual conductivity not only depends
on the structure and morphology of the polymer but also on the type of
dopant and its concentration.
Polymer - • * gap Conductivity*
(date conductivity
(eY) (S/cm)
discovered)
1. Polyacetylene
end analogues
Polyaceiylene H
» Polypyrrole j
(1977)
 1.5 I W — 1.7•105
(1979)
Polythiophene 3.1 1 — 7.5•10
(1981)
Il. Polyphenylene
and analogues 2.0 10 — 1o3
Poly(paraphenylene)
(1979)

Poly(p-phenylene
vinylene) ( 1979) 3.0
Polyaniline
(1980) 2.5 3 - 5 103

30 — 200
 Classification

One can distinguish between three types of conducting polymers:

 Electron conducting polymers
 Proton conducting olymers
 Ion conducting polymers

Poly(acetylene)s
The first conducting polymer synthesised was poly(acetylene). The
first reports on acetylene polymers date back to the last century.
Cuprene, a highly crosslinked and extremely irregular product of
acetylene polymerisation in the presence of copper- containing
catalysts being a typical example for the initial efforts.
Poly(acetylene) is the simplest conjugated polymer. In its linear
form it precipitates as a black, air sensitive, infusible and intractable
powder out of solution and can not be processed. Ant et al. were
the first to polymerise acetylene in hexane using a mixed catalyst of
alkyl aluminium and titanium tetraalkoxides:

The inherent insolubility and infusibility of poly(acetylene) coupled

with its sensitivity to air imposes a barrier to the processability of
the polymer. As a result considerable research efforts have been
directed towards obtaining processable poly(acetylene) by means
of polymer analogous transformation. Two syntheses are of
particular importance.

Property advantages of poly(acetylene) prepared by precursor routes:

 Continous solid films with densities of 1.05-1.10
 Controlled morphology ranfe, amorphous ,semi
crystalline,crystalline.
 Films can be stretched during or prior to conversion.
The conductivity of all substituted poly(acetylene) analogues reported to
date is significantly lower than that for poly(acetylene) itself. The
reduction in conjugation length is attributed to steric repulsions between
adjacent side groups which causes the polymer chains to twist (rotation
barrier single bond: 6 kcal/mol). Grubbs showed that monosubstituted
cyclooctatetraenes can be “ROMPed” to give partially substituted
poly(acetylene)s) that are both soluble and highly conjugated.

Poly(diacetylene)s

Poly(diacetylene)s are prepared by the topochemical polymerisation of

diacetylenes.
 Poly(phenylene)s
Four synthetic routes have been employed for the preparation of
poly(phenylene)s. Oxidative coupling, organometallic coupling,
dehydrogenation of poly(cyclohexylene)s and cycloaddition
reactions.

Oxidative coupling

The structural features (meta or ortho linkages) and physical

properties of the polymer prepared by oxidative coupling depend to
a large extend on the nature of the oxidising reagent. Ortho linkages
can be introduced by using more substituted benzenes rather than
the parent compound. Polymers substituted in the para position are
in general more difficult to process, i.e. they are more ordered and
thus π stacking is more efficient.

Organometallic coupling

Ullmann and Wurtz-Fittig reactions have been utilised for the

synthesis of phenylene oligomers but these methods can not be
applied to the synthesis of poly(phenylene)s since yields are low.
Dehydrogenation of poly(cycohexylene)s

Diester derivatives of 5,6-dihydroxy-1,3-cyclohexadiene have been

polymerised radically after which the resulting poly(cyclohexylene)s
were converted to poly(phenylene)s by pyrolysis. Best results were
obtained with methyl carbonate derivatives. The dihydroxy
monomer precursor is accessible through enzymatic oxidation of
benzene. An environmentally friendly route to
conjugated/conducting polymers.

Cycloaddition reactions

1,4-cycloadditions of bis-cyclopentadienones with bisacetylenes

can yield high molecular weight polymers which contain
approximately equal amounts of meta and para substituted
phenylene units.

Suzuki coupling of p-bromophenyl boronic acid offers another

convenient route to poly(phenylene) although substituted
analogues require elaborate syntheses of monomer units. An
interesting extension of this methodology is the synthesis of
hyperbranched poly(phenylene)s from an AB2 monomer. In general
branching improves solubility and processibility compared to the
linear parent polymer, which is also true in the case of highly
conjugated polymers such as poly(phenylene)s.

Poly(phenylene vinylene)s
Poly(phenylene vinylene) (PPV) possess a chemical structure
which is intermediate between that of poly(acetylene) and
poly(phenylene). Oriented PPV is highly crystalline, mechanically
strong and environmentally stable. Early attempts utilised
dehydrohalogenation or Wittig condensation reactions which
resulted in the formation of intractable oligomeric powders. The
Wessling-Zimmermann precursor is a water-soluble PPV
prepolymer (cf. Durham route) which allows the reproducible
formation of high molecular weight free standing films.

PPVs were originally synthesised via the popular Gilch route which
uses the bis(chloromethyl)benzene precursor monomer in THF in
the presence of t-butoxide as non-nucleophilic base. The reaction
leads to a rather il-defined product with limited conjugation length
and defects along the polymer backbone. The precursor sulfonium
electrolyte is prepared in aqueous solution (Wessling route to PPV,
less defects, longer conjugation, milder) by the base induced
polymerisation of the appropriate bis-sulfonium monomer. The
polymerisation is quenched by addition of dilute acid and the
reaction mixture is then dialysed against water to separate the high
molecular weight fraction as well as the sodium and chloride ions. A
study of the polymerisation mechanism revealed the existence of a
quinoid intermediate during the early stages of the polymerisation.
An alternative radical mechanism has been considered but ruled
out by the experimental evidence.
 Oligomers
Drawn PPV films were analysed by X-ray diffraction and NMR. The
results demonstrated that the average tilt of the phenylene ring
relative to the chain axis was 7.7o, close but not exactly equal to the
9.2o predicted for a trans-stilbene-like structure. Highly oriented PPV
shows high electrical conductivity upon vapour-phase doping with
AsF5 but iodine doped films show only modest conductivities.

PPV oligomers have been synthesised by the Wittig reaction in

order to obtain model compounds for physical characterisation
studies aimed at a more detailed understanding of the conduction
mechanism present in doped conjugated polymers.
 L adderpolymers
Poly(thiophene)s
Heteroaromatic polyarylenes can be prepared employing similar
synthetic strategies as those described for poly(phenylene)s and
poly(phenylene vinylene)s. Not only has the heteroatom an
influence on the chemical and physical properties of the polymeric
product, it also has to be taken into account when preparing the
required monomer (cf. aromatic heterocycles lectures).

Polythiophene like many other linear polyaromatic compounds is

insoluble in organic solvents (rigid backbone) and substitution in the
3 and/or 4 position is necessary to render the polymer soluble.

With the introduction of 3-substituents, a number of different

regioisomers are possible. These are head-to-head, tail-to-tail and
head-to-tail. and random configurations. The issue of
regioregularity pervades all of polymer chemistry and is present
even in simple linear polymers such as polystyrene and poly(methyl
methacrylate). Potentially any -olefin is prone to polymerise to
yield all of these regiochemical variations. Thus it is a significant
challenge to find polymerisation reactions and/or reaction
conditions to allow to control the sequence of regioisomers at will.

Studies on regioregular poly(thiophene)s, that have become

accessible recently via a number of elegant routs, have shown that
crystallinity increases with stereoregularity and that the possibility of
sidechain crystallinity is essential for the development of optimal
properties. For regiorandom polymers the optimal chain length for
properties like conductivity and optical non- linearities has been
determined to be in the range of 7-9. In contrast doped regioregular
3-substituted poly(thiophene) reaches
its optimal conductivity (1000 S/cm) with an dodecyl sidechain
(octyl for the regiorandom polymer (20 S/cm)). 3,4- disubstitution
reduces conductivity in the case of methylene groups (loss of
coplanarity) because of steric hindrance. This can be overcome by
substituting the methylene group with an oxygen.

Oxidative coupling to poly(thiophene)s using FeCl 3 has also been

shown to produce regioregular polymers with up to 94% HT.

An interesting and intriguing property of substituted

poly(thiophene)s is the temperature dependence of the UV
absorption. An increase in temperature causes the max to shift to
shorter wavelengths. This thermochromism arises from the
conformational change in the aromatic backbone as a result of an
increased disorder of the alkyl sidechains. Two distinct structures
are possible depending on solvent and temperature; a
predominantly coplanar structure in an aggregated form in a poor
solvent (or low temperatures) and a conformationally disordered
non-planar structure in a good solvent (high temperature).

The synthesis of poly(pyrrole)s is very much related to that of

poly(thiophene)s. However there is one distinct difference and that
is the reactive nitrogen-hydrogen bond. Thus protection of the
amine is required to prevent sidereactions such as crosslinking to
occur. As in so many cases in polymer chemistry the t-Boc group
serves well as stable protecting group which subsequently can be
removed easily through acidic or thermal deprotection.

Poly(pyrrole)s
Poly(pyrrole) prepared by the Stille coupling/thermolysis sequence.
 Poly(aniline)s
Oxidation of aniline is the most widely employed synthetic
route to polyaniline and can be performed either
electrochemically or chemically. The reaction is usually
carried out in acidic medium with a chemical oxidising
agents such as ammoniumpersulfate. Branching or even
crosslinking during polymerisation occurs through the
formation of radicals at the 2 and 6 position.

Polyaniline can occur in a number of well-defined oxidation

states. The different states range from the fully reduced
leucoemeraldine via protoemeraldine, emeraldine and
nigraniline to the fully oxidised pernigraniline. Unlike most
other polyaromatics, the fully oxidised state in polyaniline is
not conducting as are all the others too!. Polyaniline
becomes conducting when the moderately oxidised states,
in particular the emeraldine base, are protonated and
charge carriers are generated. It is this process, generally
called protonic acid doping, which makes polyaniline so
unique. No electrons have to be added or removed from the
insulating material to make it conducting.

The different oxidation states of polyaniline can also be

generated by doping with oxidants such as iodine but the
resulting conductivity is lower than that obtained via protonic
acid doping. The conduction mechanism is believed to
involve polarons. In the case of the protonated emeraldine a
delocalised poly(semiquinone radical cation) is the polaronic
carrier.

The conductivity is affected by the water content.

Completely dry samples are five times less conductive than
samples containing some water.

Self-doped polyaniline, containing sulphonic acid substituents

has been synthesised by sulphonation of the emeraldine base.

A different approach to the production of polyaniline (instead

of long alkyl sidechain e.g.) is the use of n-alkyl sulphonic
acids as proton donor (and ionically anchored aliphatic
sidechains).

Stable thin films of polyaniline that can be processed out of

solution are prepared from the emeraldine base with
camphorsulphonic acid as dopant. m-Cresol as cosolvent is
essential to obtain a chiral crystalline structure.

Each polymer type has already found widespread use in

many, mainly optical and electronic applications such as
batteries, displays, plastic wires, optical signal processing,
information storage, solar energy conversion, etc..
 A PLLICATIONS

Conducting polymers have an immense advantage of

being simple to synthesis, with their chemical structure
tailored to alter their physical properties, such as their
band gap. They exhibit an extensive rangeof electrical
conductivity and can exhibit metallic to insulator
property(105 - 10-9 S/cm). The properties that make these
conductors attractive include a wide range of electrical
conductivity, which can be achieved with various doping
levels, while maintaining mechanical flexibility and high
thermal stability. Further to theirease of synthesis and with
lower cost, they are known to have low poisoning effects.
So that they have many application Even for rugged
applications including LED lighting and electrical
supercapacitors, conducting polymers have advantages
over other materials candidates such as conductive metal
oxides. In this special issue of Interface, conducting
polymers and their applications are featured.
Some common applications are:
Storage Batteries • Biosensors • Displays • Mechanical Actuators
• EMI Shielding • Conductive Textiles • Antistatic Films/Fibers •
Neutron Detection • Non-linear optics • Electroluminescence ●
Biosensors and medical devices ● Biocompatible electrodes

Field-Effect Transistors
Field-effect transistors (FETs) were among the first semiconductor-
based devices fabricated with a conducting polymer. A FET is a simple
device composed of three contacts (source, drain, and gate), a
dielectric layer, and a semiconducting layer (Fig. 1a). FETs act
essentially as electronic valves, by modulating the semiconductor
channel conductance via the gate field. In this device structure the
current flow between the source and the drain electrodes is controlled
by the application of two independent biases, one between the source
and the drain (Vd) and one between the source and the gate (Vg).

Light-Emitting Diodes
In 1990 the Cambridge group led by Richard Friend reported the
emission of light from a semiconducting polymer sandwiched between
two contacts and connected to a battery.54 426 B. de Boer and A.
Facchetti Downloaded by ["University at Buffalo Libraries"] at 17:12 05
October 2014 The discovery of electroluminescence (EL) in conjugated
polymers, i.e., the emission of light upon electron-hole recombination
as the result of an electric current flown, has provided a new impetus
for the development of polymer light-emitting diodes (PLEDs). These
elements are fundamental for display and other applications.55 In
PLEDs and in OLEDs (organic LEDs), the latter being their small
molecule-based equivalents, the holes and electrons injected from the
device contacts recombine and produce luminescence with a
wavelength (color) dictated by the energy difference between the
molecular excited and ground states.

Photovoltaic Cells
Two years after the PLED breakthrough at Cambridge, the Santa
Barbara group reported the first results on polymer-based photovoltaic
cells,56,57 of which the principles can be regarded as the inverse of the
EL process. In photovoltaic (PV) devices, bound electron – hole pairs
(excitons) are created upon illumination. To convert the absorbed light
into electricity, the excitons must first dissociate into the separate
charges which then have to be collected at the device contacts (holes at
the anode and electrons at the cathode). This process is possible thanks
to the use of contacts with different work functions enabling the
formation of a built-in potential field within the device.

Polymer solar cell

Polymer solar cells have attracted broad research interest
because of their advantageous solution processing capability and
formation of low-cost, flexible, and large area electronic devices.
(Williams, 2005); Vignesh et al, 2006, Schiff, 2002). However, the
efficiency of polymer solar cells is still low compared to that of
inorganic solar cells. Therefore, it is a challenge to find a polymer
that has all the required properties for high efficiency devices,
such as strong and broad absorption, high carrier mobility, and
appropriate energy levels. One possible solution to avoid the strict
material requirements is to stack two or more devices with
different spectral responses, which enables more efficient
utilization of solar energy. A typical example of the usability of
organic semiconductors is the dye-sensitised solar cell which
owes its first demonstration Gratzel and his co-workers (McEvoy
et al., (1994); Michael, 2003).
Conducting polymers (CP’s) could be utilized as discriminating
layer in a sensor or to be the transducer itself. Therefore, for
instance, change in conductivity of a Conducting Polymer as it is
exposed to a gas is the mechanism of sensing in a chemiresistor
or field effect transistor characteristic.

CHEMISTOR
a Chemiresistor is simply formed by two electrodes as contact
points with the conducting polymer (CP) put onto an insulate
substrate. When applying a constant current, the probable
difference occurs on the electrodes represents the response
output signal.
 Field-Effect Transistor (FET)
The interaction among the neutral gases and organic semi-
conductors has been utilized as the principle of transduction in
Field-Effect Transistor (FET) sensors from the late 1980s
(Josowicz & Janata, 1986), while it has been almost uncared for
within non-sensing applications.
For the TFT the current flows throughout a conducting polymer
(CP) that its conductivity produced from the reaction with the
analytes and/or by the electric fields. So, it can be said that the
response signal depends on two things; the work function and the
conductivity of the Conducting Polymer.

Corrosion
Conducting polymers of various forms will be electrodeposited
onto oxidisable metals and electrochemical and environmental
means will be used to access their applicably for corrosion
protection.
Polyaniline (Pani) and its derivatives (Bernard etal 2006) are
among the most frequently studied CPs used for corrosion
protection. In addition, the use of PANI for corrosion protection of
metals has been of wide interest since the works by (DeBerry
1988; Mengoli et al. 1981) reporting that electro active coatings of
the Pani could provide adequate protection against corrosion of
stainless steels and iron sheets, respectively. Ever since,
numerous studies have been published in which various CPs in
different configurations were evaluated for corrosion protection of
different metals and alloys: mild steel.
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