ELECTROSPINNING POLYMER NANOFIBERS - ELECTRICAL AND OPTICAL

CHARACTERIZATION

A dissertation presented to
the faculty of
the College of Arts and Science of Ohio University

In partial fulfillment
of the requirements for the degree
Doctor of Philosophy

Saima N. Khan

November 2007
(Signature invalid, document altered) Signed by ETD Program <etd@ohio.edu> Time:
2007.08.14 09:15:49 -04'00'
This dissertation titled
ELECTROSPINNING POLYMER NANOFIBERS - ELECTRICAL AND OPTICAL

CHARACTERIZATION

by
SAIMA N. KHAN

has been approved for

the Department of Physics and Astronomy
and the College of Arts and Science by

Martin E. Kordesch
Professor of Physics and Astronomy

Benjamin M. Ogles
Dean, College of Arts and Science
Abstract
KHAN, SAIMA, Ph.D., November 2007, Physics and Astronomy
ELECTROSPINNING POLYMER NANOFIBERS - ELECTRICAL AND OPTICAL
CHARACTERIZATION (107 pp.)
Director of Thesis: Martin E. Kordesch
Electro spinning is a technique used for the production of thin continuous fiber
s
from a variety of materials including polymers, composites and ceramics [1-3]. T
he
extremely small diameters (~ nm) and high surface to volume and aspect ratios fo
und in
electrospun fibers can not be achieved through conventional spinning.
Electrically conducting polymers are materials which simultaneously possess the
physical and chemical properties of organic polymers and the electronic characte
ristics of
metals. In this work fibers were electrospun from polymer blends of polyaniline
doped
with Camphorsulfonic acid (PAn.HCSA) and polyethylene oxide (PEO) in chloroform.
Electrical conductivities of the fibers were measured using the four-point-probe
method.
The conductivities of the cast films were measured for comparison purposes. It w
as
noticed that the conductivity of both the fibers and films increase exponentiall
y with the
concentration of (PAn.HCSA), the conductivity of the film however is higher than
that of
the mat for any given concentration of PAn.HCSA in PEO. Electrical conductivitie
s of
single fibers containing different PAn: HCSA concentrations were measured for th
e first
time and were found to be the highest (3.2S/cm) among the mats and films. The ef
fect of
the non-conductive PEO on the conductivity of the polyaniline fibers was studied
.
Keeping the PAn.HCSA concentration constant films and fibers were obtained from
blends containing PEO (300,000 g/mol) and PEO (900,000 g/mol). Higher electrical
conductivities were recorded in fibers and mats containing PEO (900,000 g/mol) t
han
those containing PEO (300,000 g/mol).
Silicon Carbide (SiC) fibers were obtained by electrospinning a blend of SiC and
PEO in chloroform and sintering the as spun fibers at temperatures of 800ºC and 10
00ºC.
The compositional analysis of the annealed samples confirmed the presence of (30
-40)
µm long SiC fibers with diameters in the range (1-3) µm. Optical spectra of the fibe
rs
show red emission extending to the infrared.
For the first time complexes of ruthenium with picolinate and polypyridine
ligands were introduced into nanofibers. Fibers containing ruthenium picolinate
([Ru
(pic)2 (dmso)2]) turn orange from pale yellow on exposure to ultraviolet radiati
on
(350nm). Fibers containing ruthenium bi-pyridine ([Ru(bpy)2](PF6)2) exhibit
photoluminescence with steady state red emission upon 450 nm excitation.
Approved:
Martin E. Kordesch
Professor of Physics and Astronomy
Dedication
To my father Mumtaz Khan,
Who provided me a strong academic foundation and whose determination to provide
me
education serves as an inspirational example to a society and culture where wome
n have
always been underestimated and under-treated. He is not in this world any more b
ut I
hope he knows that I can t be proud enough of being his daughter and that I love h
im as
much as he loved me.
(Signer's identity unknown) Signed by TAD Services <etd@ohio.edu> Time: 2007.12.
14 10:27:31 -05'00'
Acknowledgements
First and foremost I would like to express my heartfelt gratitude towards my
supervisor Professor Martin E. Kordesch for his academic guidance, continuous su
pport
and encouragement throughout this project. He is a pleasant person, a remarkable
teacher
and a great human being. I appreciate his generosity in providing me the opportu
nity to
attend various conferences that gave me good academic exposure. He has been very
cooperative
all along and gave me his precious time and advice whenever I needed it.
I am very thankful to Dr. Saw Wai Hla, Dr. Alexander Neiman and Dr. P. G. Van
Patten for being members of my thesis committee. I am sincerely thankful to Dr.
Jeffery
Rack for his help and co-operation in this work.
My heartfelt gratitude extends to Dr. Aurangzeb Khan who makes me proud for bein
g my
loving husband, wonderful friend and a nice colleague. I can t thank him enough fo
r
believing in me and making me believe in myself.
I want to acknowledge the little sacrifices our lovely daughter Gulsanga Khan ha
s
been making every day, for three years now. I love her and I owe her every bit o
f the
pride I take in my degree today.
I want to offer a very special thanks to my mother and my brothers who always
took pride in my academic achievements and facilitated me in all the ways possib
le.
I offer my special thanks to my mother-in-law for her love and support. She is a
n
extraordinary woman and truly believes in the value of education. I also want to
thank my
friends and relatives for their support and co-operation.
Table of Contents
ABSTRACT........................................................................
............................................... 3
DEDICATION......................................................................
............................................. 5
ACKNOWLEDGEMENTS ...............................................................
.............................. 6
LIST OF FIGURES ................................................................
........................................ 11
CHAPTER 1.......................................................................
............................................. 15
BACKGROUND AND EXPERIMENTAL TOOLS ..............................................
..... 15

1.1 Introduction................................................................
........................................... 15

1.2 Electrospinning ............................................................

......................................... 16

1.3 Working principle ..........................................................

....................................... 21

1.4 Scanning electron microscope (SEM) .........................................

......................... 25

1.5 Transmission electron microscope (TEM)......................................

...................... 27

1.6 Energy dispersive x-ray spectrometry (EDX)..................................

..................... 29

1.7 Four-Point-Probe method of conductivity measurement.........................

............. 31

1.8 Cathodoluminescence ........................................................

................................... 34
8
1.9 Conclusion .................................................................
........................................... 34

CHAPTER2........................................................................
............................................. 36

ELECTROSPINNING POLYETHYLENE OXIDE NANOFIBERS........................ 36

2.1 Introduction................................................................
........................................... 36

2.2 Sample preparation and obtaining fibers ....................................

.......................... 37

2.3 Important process parameters ...............................................

................................ 39

2.3.1 Applied voltage...........................................................

.................................. 39

2.3.2 Distance between the nozzle and the collector ............................

................. 42

2.4 Conclusion .................................................................

........................................... 44

CHAPTER 3.......................................................................
............................................. 45

CONDUCTING POLYMER NANOFIBERS ..................................................

............ 45

3.1 Introduction................................................................
........................................... 45

3.2 Different types of doping...................................................

................................... 48

3.2.1 Redox doping..............................................................

.................................. 48

3.2.2 Photo doping .............................................................

.................................... 48
3.2.3 Charge-injection doping...................................................
............................. 48

3.2.4 Non-Redox doping or Protonic-acid doping..................................

............... 49
9
3.3 Polyaniline ................................................................
............................................ 50

3.3.1 Oxidation states of polyaniline ..........................................

........................... 51

3.3.2 Doping polyaniline........................................................

................................ 52

3.4 Sample preparation .........................................................

...................................... 55

3.5 Electrospinning fibers .....................................................

...................................... 56

3.6 Characterization of the nanofibers..........................................

.............................. 57

3.7 Electrical Conductivity measurement.........................................

.......................... 60

3.7.1 Using PEO (300,000 g/mol) as the matrix...................................

................. 61

3.7.2 Using PEO (900,000 g/mol) as the matrix...................................

................. 63

3.7.3 Effect of PEO on the conductivity of PAn..................................

.................. 67

3.8 Conclusion .................................................................

........................................... 70

CHAPTER 4.......................................................................
............................................. 71

FABRICATION AND OPTICAL CHARACTERIZATION OF SILICON

CARBIDE NANOFIBERS..............................................................
............................... 71
4.1 Introduction................................................................
........................................... 71

4.2 Silicon Carbide Nanostructures .............................................

............................... 73

4.3 Electrospinning silicon carbide nanofibers..................................

......................... 75
10
4.4 Structural and Compositional Analysis ......................................
.......................... 81

4.5 Cathodoluminescence ........................................................

................................... 83

4.6 Conclusion .................................................................

........................................... 84

CHAPTER 5.......................................................................
............................................. 85

POLYMER NANOFIBERS CONTAINING RUTHENIUM COMPOUNDS.......... 85

5.1 Introduction................................................................
........................................... 85

5.2 Experimental................................................................
......................................... 87

5.3 Results and Discussion .....................................................

.................................... 87

5.4 Fibers Containing [Ru (BPY) 3] (PF6)2 ......................................

........................... 92

5.4 Conclusion .................................................................

........................................... 94

CHAPTER 6.......................................................................
............................................. 96

CONCLUSION AND FUTURE PROSPECTS.................................................

........... 96

BIBLIOGRAPHY....................................................................
....................................... 99

List of Publications ...........................................................

.............................................. 106
Conferences Attended............................................................
......................................... 107
List of Figures
FIGURE 1.1:SCHEMATIC DIAGRAM OF THE ELECTROSPINNING PROCESS.....................
.................20
FIGURE 1.2: SEM IMAGES OF THE PATTERNS FORMED BY FIBERS DURING ELECTROSPINNING (
A) V
=5 KV, D=10 CM (V= 7 KV,D=10 CM)................................................
..............................22
FIGURE 1.3: DIGITAL PHOTOGRAPH OF THE EXPERIMENTAL SET UP USED FOR ELECTROSPINNI
NG.
................................................................................
..............................................................24
FIGURE 1.4: SCHEMATIC DIAGRAM OF SCANNING ELECTRON MICROSCOPE...................
...............26
FIGURE 1.5: SCHEMATIC DIAGRAM OF TRANSMISSION ELECTRON MICROSCOPE. .............
............28
FIGURE 1.6:X-RAYS SCATTERING FROM THE CRYSTAL PLANES OF THE SAMPLE..............
............30
FIGURE 1.7: SCHEMATIC DIAGRAM OF THE OF EDX SPECTROMETER........................
....................30
FIGURE 1.8:SCHEMATIC OF THE FOUR-POINT-PROBE SET UP.............................
...........................33
FIGURE 1.9: OPTICAL IMAGE OF THE COMMERCIAL FOUR PROBE CHIP.....................
.....................33
FIGURE 1.10: SCHEMATIC OF THE CL SET UP.........................................
........................................35
FIGURE 2.1: SEM IMAGES OF ELECTROSPUN FIBERS WITH BEAD DEFECTS (A) 1500X (B) 750
X (C)
200X (D) 750X. IMAGES WERE TAKEN USING 30 KV AND 80 .A..........................
...............38
FIGURE 2.2: EFFECT OF THE APPLIED VOLTAGE ON THE DIAMETER OF FIBERS ELECTROSPUN
FROM
PEO/CHLOROFORM AT A CONSTANT NOZZLE TO COLLECTOR DISTANCE OF 10 CM.............4
0
FIGURE 2.3: ELECTROSPINNING CURRENT MEASURED AS A FUNCTION OF APPLIED VOLTAGE. .
...41
FIGURE 2.4: EFFECT OF NOZZLE TO COLLECTOR DISTANCE ON THE DIAMETER OF FIBERS
ELECTROSPUN FROM PEO AT A CONSTANT VOLTAGE OF 7 KV..............................
...............43
FIGURE 2.5: SEM IMAGES OF ELECTROSPUN FIBERS WITH MINIMUM BEAD DEFECTS (A) 500X
(B)
1200X...........................................................................
........................................................44
FIGURE 3.1: BAND STRUCTURE IN ELECTRICALLY CONDUCTING POLYMERS. EACH BAND
CONSISTS OF CLOSELY PLACED DISCRETE STATES IN POLYMERS UNLIKE THE CONTINUOUS
ONES AS IN SEMI-CONDUCTORS......................................................
.......................................46
FIGURE 3.2: EXAMPLES OF CONDUCTING POLYMERS. ...................................
................................47
FIGURE 3.3: NON-REDOX DOPING PROCESS OF POLYANILINE [45]........................
........................49
FIGURE 3.4: MAIN POLYANILINE STRUCTURES N + M = 1, X = DEGREE OF POLYMERIZATION.
......51
FIGURE 3.5: MOLECULAR STRUCTURE OF CAMPHORSULFONIC ACID.........................
...................53
FIGURE 3.6: (A) INSULATING EMERALDINE BASE FORM OF POLYANILINE (B) CONDUCTING

EMERALDINE SALT FORM OF POLYANILINE (POLARON STRUCTURE) (C) BIPOLARON

STRUCTURE IN DOPED POLYANILINE..................................................
...................................54
FIGURE 3.7: (A) PAN AND CAMPHORSULFONIC ACID RIGHT AFTER MIXING IN CHLOROFORM. (
B).
AFTER 6 HOURS OF STIRRING.......................................................
..........................................55
FIGURE 3.8: DIGITAL PHOTOGRAPH OF THE FIBROUS WEB ELECTROSPUN FROM PAN/PEO BLEND
.
(D = 10 CM AND V = 7 KV WERE USED DURING ELECTROSPINNING). .....................
..............57
FIGURE 3.9: SEM IMAGES OF THE FIBERS ELECTROSPUN FROM PAN.HCSA/PEO BLEND (A) 200
X
(B) 350X (C) 750X (D) 1000X. ...................................................
...........................................58
FIGURE 3.10: TEM IMAGES OF BEADED FIBERS. IMAGES WERE TAKEN USING 80 KV POTENTIA
L.59
FIGURE 3.11: TEM IMAGES (80 KV) OF BEADLESS FIBERS ELECTROSPUN FROM PAN: HCSA/PE
O
BLEND SCALE BAR IS (A) 1 UM (B) 500 NM..........................................
..................................60
FIGURE 3.12: FOUR PROBE IV S OF FIBROUS MATS ELECTROSPUN FROM (A) 50 WT. % (B) 58
WT.
% PAN.HCSA SOLUTION. THE CURRENT VALUES WERE AVERAGED 10 MEASUREMENTS... 61
FIGURE 3.13: ELECTRICAL CONDUCTIVITY OF THE FIBROUS MATS ELECTROSPUN FROM
PAN.HCSA/PEO (300,000 G/MOL) BLEND. CONDUCTIVITY VALUES WERE AVERAGED OVER
10 TRIALS, EACH TRIAL VALUE BEING THE AVERAGE OF 20 ITERATIONS. ................
............62
FIGURE 3.14: ELECTRICAL CONDUCTIVITY OF THE FIBROUS MATS ELECTROSPUN FROM
PAN.HCSA/PEO (900,000 G/MOL) BLEND. ............................................
..............................64
FIGURE 3.15: FOUR-PROBE I-V CHARACTERISTICS OF A SINGLE NANOFIBER ELECTROSPUN FR
OM
60 WT. % PAN.HCSA IN PEO (MW ~ 900,000 G/MOL). THE CURRENT VALUES SHOWN ARE
THE AVERAGE OF TEN MEASUREMENTS. ...............................................
................................65
FIGURE 3.16: (A) OPTICAL IMAGE OF THE 4-PROBE CHIP. (B) SEM IMAGE OF THE FIBER P
LACED
ON THE CHIP FOR CONDUCTIVITY MEASUREMENT. ......................................
.........................66
FIGURE 3.17: ELECTRICAL CONDUCTIVITIES OF SINGLE FIBERS, CAST FILMS AND FIBROUS
MATS
MEASURED AS FUNCTION OF PAN.HCSA CONCENTRATION IN THE POLYMERS SOLUTION..67
FIGURE3.18: ELECTRICAL CONDUCTIVITIES OF THE FIBERS AND FILMS ELECTROSPUN FROM
PAN.HCSA BLENDED WITH PEO (900,000 G/MOL) (UPPER THREE LAYERS) AND PEO
(300,000 G/MOL) (LOWER TWO LAYERS)..............................................
.................................68
FIGURE 4.1: TETRAHEDRAL ARRANGEMENT OF SI AND C ATOMS IN (A) 4H AND (B) 6H SIC
STRUCTURES [60]. ...............................................................
..................................................72
FIGURE 4.2: SCHEMATIC OF THE FACE CENTERED CUBIC (3C) CRYSTAL OF SIC (. PHASE)..
........73
FIGURE 4.3: SEM IMAGE OF SILICON CARBIDE PARTICLES. AVERAGE PARTICLE SIZE IS 800
NM.76
FIGURE 4.4: SEM IMAGES OF FIBERS ELECTROSPUN FROM A DISPERSION SOLUTION OF SIC I
N PEO
(A) LOW RESOLUTION (1000 X) AND (B) HIGH RESOLUTION (5000 X)....................
...............77
FIGURE 4.5: SEM IMAGE OF THE SIC/PEO FIBERS AFTER ANNEALING AT 800°C FOR 7 HOURS..
.78
FIGURE 4.6: SEM IMAGES OF SIC FIBERS OBTAINED AFTER ANNEALING THE SAMPLE AT 800°C
FOR 7 HOURS.....................................................................
.....................................................79

FIGURE 4.7: SEM IMAGES OF SIC FIBERS FORMED AFTER ANNEALING THE SIC/PEO FIBERS A
T
1000°C FOR 10 HOURS (A) 2000X (B) 2000X (C) 1500X (D) 1500X. IMAGES WERE TAKEN
USING 30 KV, 80 UA. ............................................................
.................................................80
FIGURE 4.8:EDX PATTERN OF SIC/PEO FIBERS AFTER ANNEALING........................
....................81
FIGURE 4.9:XRD PATTERNS OF SIC/PEO FIBERS AFTER ANNEALING.......................
....................82
FIGURE 4.10: CL SPECTRUM COLLECTED FROM SIC FIBERS AT 5 KEV.....................
.....................83
FIGURE 4.11: CL IMAGES OF SILICON CARBIDE FIBERS. SCALE BAR IS THE SAME ON THE
PICTURES.(5 KEV BEAM WAS USED)..................................................
...................................84
FIGURE 5.1: MOLECULAR STRUCTURE OF [RU (PIC)2 (DMSO)2] [84].....................
.........................86
FIGURE 5.2: OPTICAL IMAGES OF THE ELECTROSPUN MAT (A) BEFORE AND (B) AFTER EXPOS
URE
TO UV (.~350 NM) WITH A MASK ON IT. SCALE BAR IS THE SAME ON (A) AND (B)........
......88
FIGURE 5.3: SEM IMAGE OF THE FIBROUS MAT ELECTROSPUN FROM [RU (PIC)2 (DMSO)2]
BLENDED IN PEO (30 KV, 80 UA)...................................................
.......................................89
FIGURE 5.4: UV-VISIBLE ABSORPTION SPECTRUM OF [RU (PIC) 2 (DMSO) 2] / ETHANOL CH
ANGES
UPON IRRADIATION AT 344 NM.(SPECTRUM TAKEN BY RACHFORD ET AL.[84])..............
....91
FIGURE 5.5: SEM IMAGE OF FIBERS ELECTROSPUN FROM ([RU (BPY) 3] (PF6)2)/PEO IN
METHYLENE CHLORIDE. ............................................................
............................................93
FIGURE 5.6: FLUORESCENCE SPECTRA CORRESPONDING TO LOCATIONS A-G IN THE
FLUORESCENCE IMAGE OF A SINGLE FIBER AFTER EXCITATION WITH 532 NM...............
.......94
FIGURE 5.7: NSOM IMAGES OF (A) FIBER CROSS-SECTION WITH THE BRIGHT SPOTS SHOWING
[RU
(BPY) 3] (PF6)2 DISTRIBUTED IN THE FIBER AND (B) SINGLE LUMINESCENT FIBER,
ELECTROSPUN FROM [RU (BPY) 3] (PF6)2 /PEO IN CHLOROFORM ON EXCITATION WITH 532
NM. ............................................................................
...........................................................95
Chapter 1
Background and experimental tools
1.1 Introduction
According to the National Science Foundation (NSF) and in fiber science related
literature, nanofibers are defined as structures having at least one dimension o
f 100
nanometer (nm) or less, but generally nanofibers are considered as having a diam
eter of
less than one micron. The name derives from the nanometer, a scientific measurem
ent
unit representing a billionth of a meter, or three to four atoms wide.
Nanofibers due to their extremely high surface to volume ratio compared to
conventional fibers exhibit special properties such as low density, low specific
mass and
high pore volume which make them appropriate for a wide range of applications su
ch as
filtration and energy storage[4]. Nanofibrous mats with specific pore size can b
e used as
chemical and mechanical filters. These are ideally suited for filtering submicro
n particles
from air or water. Properly designed fibrous mat can actually trap and dissolve
certain
chemical and biological components through chemical reactions. These fibers comb
ined
with other nonwoven products have potential uses in a wide range of filtration
applications such as aerosol filters, facemasks, and protective clothing. Other
uses are
made in personal care products, wipes, garments and insulation. Fabrics made wit
h micro
fibers claim stain resistance and extremely soft hand. At present, military fabr
ics under
16
development designed for chemical and biological protection have been enhanced b
y
laminating a layer of nanofibers between the body side layer and the carbon fibe
rs [5].
Nanofibers are also used in medical applications, which include, drug and gene d
elivery,
artificial blood vessels, artificial organs, tissue engineering and medical face
masks [6].
For example, carbon fiber hollow nano tubes, smaller than blood cells, have pote
ntial to
carry drugs in to blood cells [7]. Other applications of nanofibers are made in
aerospace
capacitors, transistors, battery separators, energy storage, fuel cells, and inf
ormation
technology.
Nanofibers ob conducting polymers are predicted to possess unique electronic and
optical properties that can be tuned through doping. Theses fibers carry a whole
package
of applications in chemical and biological sensors, light emitting diodes, recha
rgeable
batteries nanoelectronic devices, electromagnetic shielding and wearable electro
nics.
Similarly nanofibers derived from ceramic materials such as zinc oxide and silic
on
carbide possess optical characteristics (luminescence) that can be made use of i
n light and
field emitters. The fibers are also used extensively as reinforcements in the de
velopment
of nano composites.
1.2 Electrospinning
Electro spinning is a simple technology known since 1930s for the production of
continuous fibers (as thin as 5 nm) from a variety of materials including polyme
rs,
composites and ceramics. The electrospun fibers possess properties not found in
conventional fibers e.g. they have a high surface to volume ratio, high aspect r
atio,
controlled pore size and superior mechanical performance. The superior mechanica
l
properties associated with the e-spun fibers arise from the decrease in diameter
that can
not be achieved through conventional spinning processes.
The process of electro spinning was first patented by Farmhals in 1934 [8].
Although the process of spinning artificial threads was experimented with even b
efore
Farmhals, it did not get much attention because of technical difficulties such a
s fiber
drying and collection. Farmhals process consisted of a movable thread-collecting
device
to collect the threads in a stretched condition. However drying the fiber was st
ill a
problem. In order to overcome this disadvantage, Farmhals repatented his work in
1940.
In the refined process, the distance between the feeding nozzle and the screen w
as altered
to give more drying time for the electrospun fibers.
In the 1960 s, Taylor initiated studies on the jet forming process [9]. Taylor stu
died the
shape of the polymer droplet produced at the tip of the needle in detail when an
electric
field is applied and showed that it is a cone and the jets are ejected from the
vertices of
the cone [9]. This cone shape is known as Taylor cone in the literature. The conic
al
shape of the jet defines the onset of the extension in the fiber forming process
. In
subsequent years, much attention was given to the structural morphology of the f
ibers.
Researchers took great interest in the structural characterization of the fibers
and
understanding the relationship between the structural features and the process p
arameters.
Wide angle x-ray diffraction (WAXD), scanning electron microscopy (SEM),
transmission electron microscopy (TEM) were used by researchers to characterize
the
electrospun nanofibers.
In 1971, Baumgarten reported the electrospinning of acrylic micro fibers whose
diameters ranged from 500 to 1100 nm [10] . He focused on how the diameter of th
e
fibers changed with the changing electric field. Larrondo and Mandley produced
polyethylene and polypropylene fibers from the melt, which were larger in diamet
er than
the solvent spun fibers [11, 12].
In 1987, work by Hayati et al. focused on the effects of electric field, experim
ental
conditions, and the factors affecting the fiber characteristics. They showed tha
t highly
conducting fluids with increasing applied voltage produced highly unstable strea
ms that
whipped around in different directions [13].
Doshi and Reneker [14] used electrospinning to make fibers from water soluble
poly(ethylene oxide) with diameters of 0.05 to 5 µm. They described the electro sp
inning
process, the processing conditions, fiber morphology and possible uses of electr
ospun
fibers. Jaeger (1998) et al. [15] observed chain packing in electrospun polyethy
lene oxide
(PEO) via the atomic force microscopy (AFM). They concluded that at the molecula
r
level the electrospun PEO fibers possess a highly ordered surface layer. That or
dered
surface layer could be the result of the electro spinning process, or it could b
e the residue
of the droplet formation.
Gibson and Rivin [16] studied the transport properties of electrospun fiber mats
.
They showed that the electro spun layers present minimal impedance to moisture v
apor
diffusional transport required for evaporative cooling.
Nanofibers of atomic heterocyclic polybenzimidazole PBI were electrospun by
Kim [17] with diameter of the fibers around 300 nm. The mechanical strength of t
hese
fibers was increased by treatment with sulfuric acid and heat. The effect of the
spinning
voltage and solution concentration, on the morphology of the electrospun fibers
was
systematically studied by Deitzel [18] et al. in 2001.
Demir et al. [19] successfully produced ultra fine elastic fibers with submicron
diameters by electro spinning of polyurethane urea solutions. Fiber diameters in
the range
7 nm to 1500 nm were obtained by varying the solution concentration. It was show
n that
fiber diameters increase as the third power of solution concentration. Besides a
ll these
efforts to understand the process of electro spinning and make fiber growth adap
table in
various technologies, new materials were adapted and their properties were studi
ed at
micro/nano scale.
The electronic properties of various types of nano fibers were studied by Wang e
t
al. [20]. Low temperature electronic transport properties of PAN-derived Carbon
nano
fibers were studied very recently [20]. The semi-conducting nature of the fiber
was
revealed by an increase in conductivity with temperature. A similar temperature
dependence of conductivity was found in Carbon micro fibers and was explained us
ing a
simple two-band model with temperature dependent mobility.
Figure 1.1: Schematic diagram of the electrospinning process.
1.3 Working principle
In the electrostatic technique, a high electric field is generated between the p
olymer
solution contained in a syringe and a grounded metallic collection plate by conn
ecting the
needle of the syringe to a high voltage power supply as shown in the Fig.1.1. At
a certain
threshold voltage, the polymer droplet is charged enough to overcome the surface
tension
of the solution. A fluid jet is thus ejected out of the droplet which is drawn d
own by
acceleration towards the grounded collector. The jet undergoes a series of elect
rically
induced bending instabilities and displays a whipping motion [21] that result in
the
stretching of the relatively thick jet in to fiber accompanied by the evaporatio
n of the
solvent. The diameter of electrospun fibers is at least one order of magnitude s
maller
than those made by conventional spinning techniques, and the fibers are typicall
y
deposited in the form of a nonwoven mats.
The concentration of the polymer solution is critical to the spinning process.
Electrospinning of very concentrated polymer solution results in fibers with
discontinuities. On the other hand solutions with insufficient viscosity lead to
electrospray the solution instead of electrospinning.
The fiber jet travels down in the electric field eventually hitting the collecti
on
plate making patterns shown in Fig. 1.2. These patterns can help visualize the w
hipping
motion of the jet in the electric field. The dry fibers are collected on the gro
unded
collector in the form of a non-woven mat. The distance between the nozzle and th
e
collector is generally varied between 15 and 30 cm. The process is carried out a
t room
temperature unless heat is required to keep the polymer in liquid state.
Figure 1.2: SEM images of the patterns formed by fibers during electrospinning (
a)
V =5 kV, D = 10 cm (V = 7 kV, D= 10 cm).
The morphology of the fibers depends on the type of polymer used and the
spinning conditions. Fiber fineness can be regulated from ten to a thousand nano
meters in
diameter. The actual set up devised for electrospinning is shown in Fig. 1.3
It consists of a variable high voltage low current Bertan power supply model
205B-20R. The polymer solution is contained in a BD 3ml syringe with a BD 25G1
needle. A positive potential is applied to the polymer blend by attaching the po
wer lead to
the tip of the vertically placed needle. Fibers are collected on 5x5 cm2 grounde
d
aluminum plate
The morphology, structure and chemical composition of the fibers was studied
using various characterization tools present in our lab. These include the scann
ing
electron microscope (SEM) with an inbuilt energy dispersive x-ray spectrometer (
EDX),
transmission electron microscope (TEM) and x-ray diffraction (XRD). The optical
characteristics of the (SiC) were studied using the Cathodoluminescence
(CL).spectroscopy. The electrical conductivity of the electrospun fibers was mea
sured
using the four point probe method. A short theoretical description of the Charac
terization
tools is given in the following section.
Figure 1.3: Digital photograph of the experimental set up used for electrospinni
ng.
1.4 Scanning electron microscope (SEM)
The scanning electron microscope (SEM) is an important tool capable of producing
high-
resolution images of a sample surface. A schematic diagram of a typical SEM is s
hown in
Fig. 1.4. Electrons are thermionically emitted from the tungsten cathode and are
accelerated towards an anode. Tungsten has the highest melting point and lowest
vapor
pressure of all metals and therefore can be heated enough for electron emission.
The
electron beam carries energy typically ranging from a few hundred to 100 keV. Th
e beam
is focused by one or two condenser lenses into al spot sized of 1 to 5 nm. The b
eam
passes through pairs of scanning coils in the objective lens, which deflect the
beam
horizontally and vertically so that it scans in a raster fashion over a rectangu
lar area of the
sample surface. When the primary electron beam interacts with the sample, the el
ectrons
lose energy by repeated scattering and absorption within a specimen volume known
as
the interaction volume that extends from less than 100 nm to around 5 µm into the
surface. The energy exchange between the electron beam and the sample results in
the
emission of secondary electrons and electromagnetic radiation from the sample wh
ich
can be detected and amplified by a photomultiplier tube and used to produce an
image[22]. The black and white image of the sample is obtained by correlating th
e
sample scan position with the resulting signal. Scanning electron microscope Joe
l JSM
5300 was used in this work. The SEM images in this document were taken using a
voltage and current of 30 kV and 80 µA respectively. Details about the constructio
n and
working principle of the SEM are available elsewhere [23].
Figure 1.4: Schematic diagram of scanning electron microscope.
1.5 Transmission electron microscope (TEM)
The working principle of a TEM is depicted in Fig. 1.5. The transmission electro
n
microscope (TEM) uses a highly energetic beam of electrons that passes through t
he
specimen. These electrons are scattered from the sample at different angles depe
nding on
the density of atoms encountered by the electron beam. The transmitted electron
signal is
magnified by a series of electromagnetic lenses and is observed through electron
diffraction or direct electron imaging. The enlarged version of the sample thus
appears
on a fluorescent screen or a layer of photographic film. The obtained electron d
iffraction
patterns are used to determine the crystallographic nature of the sample [24]. T
he
microstructures e.g. the grain size and lattice defects are investigated using T
EM in the
imaging mode. TEM in the diffraction mode is used to investigate the crystalline
structure of the specimen. A 100 keV TEM [Joel 1010] in was used in this work to

evaluate the dimensions of the electrospun fibers Other details about TEM can be
found
elsewhere [25].
Figure 1.5: Schematic diagram of transmission electron microscope.
1.6 Energy dispersive x-ray spectrometry (EDX)
Energy dispersive X-ray spectroscopy (EDS or EDX) is an important non-destructiv
e
analytical tool predominantly used for the chemical characterization of all kind
s of
matter. Each crystalline solid has a characteristic X-ray pattern associated wit
h it that is
used for its identification. In the EDX the sample is investigated through inter
actions with
x-rays.
Its characterization capabilities are due to the fundamental principle that each
element of
the periodic table has a unique electronic structure and, thus, a unique respons
e to
electromagnetic waves.There are four primary components of the EDS setup: the be
am
source; the X-ray detector; the pulse processor and the analyzer as shown in the
schematic diagram [26] in Fig. 1.7. The EDX set up used in this work is installe
d within
the scanning electron microscopes. Electron microscopes with in-built EDS set up
s are
equipped with a cathode and magnetic lenses to create and focus the electron bea
m and
thus carry the elemental analysis capabilities. X-rays are emitted from the samp
le atoms
after being hit by the energetic electrons. The x-ray energy is converted into a
voltage
signal by the detector. This information is sent in to a pulse processor, which
measures
the signals (count rate) and pass them onto an analyzer for data display and ana
lysis. The
X-rays are thus used to identify the elements present, quantify their relative o
r absolute
concentration, and map their distribution [27]. An X-ray set up Rigaka Geigerfle
x
DMAX-B with an X-ray source of wavelength Ka = 1.5405 A° was used in this work.
Figure 1.6: X-rays scattering from the crystal planes of the sample.

Figure 1.7: Schematic diagram of the of EDX spectrometer.

1.7 Four-Point-Probe method of conductivity measurement
The most common way of measuring the resistivity of a semiconductor material is
by using a four-point collinear probe. This technique involves bringing four equ
ally
spaced probes in contact with the material of unknown resistance
The two outer probes are used for sourcing current and inner two probes are used
for measuring the resulting voltage drop across the sample. Each probe has a res
istance
Rp, a probe contact resistance Rcp and a spreading resistance Rsp associated wit
h it.
However, these resistances can be neglected for the two voltage probes because t
he
voltage is measured with a high impedance voltmeter, which draws very little cur
rent.
Thus the voltage drops across these resistances are insignificantly small and th
e voltage
reading from the voltmeter is approximately equal to the voltage drop across the
semiconductor sheet resistance. A schematic of the process is shown in Fig. 1.8.

By using the four-point probe method, the semiconductor sheet resistance can be
calculated as;
V
Rs =
K
I
Where V is the voltage reading from the voltmeter, I is the current carried by t
he two
current carrying probes, and K is a correction factor. For collinear or in-line
probes with
equal probe spacing, the correction factor K can be written as a product of thre
e separate
correction factors, K= k1k2k3
Where k1 corrects for finite sample thickness, k2 corrects for finite lateral sa
mple
dimensions, and k3 corrects for placement of the probes with finite distances fr
om the
sample edges. For very thin samples with the probes being far from the sample ed
ge, k2
and k3 are approximately equal to one [28], and the expression of the semiconduc
tor sheet
resistance becomes:
p.V .
Rs =
..
ln 2 .
I .
The volume resistivity is calculated as follows:
p
V
.=
××
t ×
K
ln 2 I
Where: . is the volume resistivity in (O-cm)
V is the measured voltage in volts, I is the source current in amperes, t is the
sample
thickness in cm and k is a correction factor based on the ratio of the probe to
the sample
diameter and on the ratio of the sample thickness to probe separation.[28].
The electrical conductivity of the sample (fibrous mats and films with rectangul
ar
geometry) was calculated according to the equation [29];
(ln 2)L .
I .
s=
..
kpwt .V .

Where L and w are respectively the length and width of the mat (~mm).
The thickness t of the mat was measured carefully with a digital micrometer with
a 1µm
resolution. The actual set used in our lab consists of a Keithley 220 programmab
le
current source and a Keithley 2000-20 Multimeter. A commercially available four
probe
chip was used to make contact with the fibers/mats. An optical image of the chip
is
shown in Fig 1.9.
Fi
FiFib
bbr
rro
oou
uus m
s ms ma
aat
tt I
II
Keithley 220ProgrammableCurrent sourceKeithley 2000-20MultimeterKeithley 220
Programmable
Current source
Keithley 2000-20
Multimeter
Figure 1.8: Schematic of the four-point-probe set up.

Figure 1.9: Optical image of the commercial four probe chip.

1.8 Cathodoluminescence
Cathodoluminescence (CL) is a method used to analyze the crystal structure of a
specimen including lattice defects , lattice distortion and carrier dynamics [24
]. CL is an
optical and electrical phenomenon used for the characterization of luminescent m
aterials
especially semiconductors. The working principle of CL is depicted in Fig. 1.9.
The
electron beam generated by the electron gun hits the target material placed in t
he
gyrostat) at 45º angle. These electrons carry energy up to 5 keV and cause the tar
get to
emit visible light. Cathodoluminescence occurs because the impingement of a high
energy electron beam onto a semiconductor will result in the promotion of electr
ons from
the valence band into the conduction band, leaving behind a hole. When an electr
on and a
hole recombine, it is possible for a photon to be emitted. The energy (color) of
the
photon, and the probability that a photon and not a phonon will be emitted, depe
nds on
the material, its purity, and its defect state [30]. The emitted light passes th
rough a
converging lens and a monochromator and is detected by a camera.
1.9 Conclusion
A set up was devised for electrospinning polymer nanofibers. Background
knowledge of different tools was obtained that is required for characterization
of the
fibers. The four probe conductivity measurement of polymeric fibers and cast fil
ms was
practiced with convenience.
Figure 1.10: Schematic of the CL set up.
Chapter2
Electrospinning polyethylene oxide
nanofibers
2.1 Introduction
Various applications of nanofibers in medicine and surgery are known so far and
have been mentioned elsewhere [31]. These include scaffolds used in tissue engin
eering,
wound dressing, drug and medicine delivery, artificial organs and vascular graft
s. The
kind of fibers required for such purposes are obtained from polymers that are
biocompatible and biodegradable. One such polymer is polyethylene oxide (PEO) wh
ich
carries the additional advantages of processibility and low cost. PEO is also us
ed in
combination with other polymers in order to enhance their processibility and
biocompatibility.
Polyethylene oxide (PEO) is a commercially available polymer represented by the
chemical formula C2nH4n+2On+1. PEO is non-toxic and is used in a variety of prod
ucts
including clinical products such as laxatives and skin creams. The environmental
stability
of PEO and its ability to easily dissolve in a number of solvents such as water
and
chloroform were the reasons that encouraged our choice of the polymer for
electrospinning fibers.
2.2 Sample preparation and obtaining fibers
250 mg of PEO (Mw~ 300,000 g/mol) was added to 10 mL Chloroform at room
temperature. The mixture was magnetic stirred for 2 hours to make a homogeneous
solution. The obtained solution was viscous enough for electrospinning fibers. U
sing the
custom made set up fibers were electrospun from the solution at a voltage of 5kV
. A
threshold voltage of 4kV was established for electrospinning PEO fibers on trial
basis.
The nozzle to collector distance was varied between 8 and 15 cm to focus the spi
nning jet
on the collector. Fibers were electrospun for an hour and were collected on Alum
inum
plate in the form of a non-woven mat.
The fibers shown in Fig. 2.1 were electrospun at the threshold voltage and at a
nozzle to collector distance of 15 cm. The fibers exhibit high density of defect
s in the
form of bead like structures as has been described in literature [32] that intro
duce non-
uniformities into the fiber thickness. These defects arise from various factors
including
the viscosity, conductivity and flow rate of the polymer solution and the experi
mental
parameters such as the applied voltage and nozzle to collector distance. Some of
these
parameter were studied in detail to better understand the electrospinning proces
s and to
be able to obtain fibers free of defects.
38

Figure 2.1: SEM images of electrospun fibers with bead defects (a) 1500X (b) 750
X
(c) 200X (d) 750X. Images were taken using 30 kV and 80 µA.
2.3 Important process parameters
2.3.1 Applied voltage
The voltage applied during the electrospinning process plays important role in
determining the shape and diameter of the fibers. The formation of beaded fibers
during
the electrospinning depends on the applied voltage together with other parameter
s such as
viscosity of the solution and its flow rate. An increase in the applied voltage
reportedly
[33] favors the formation of fibers with high bead density. In this study howeve
r we
investigate the effect of the spinning voltage on the fiber diameter keeping oth
er
parameters constant.
A 5 wt. % solution of polyethylene oxide in chloroform was used for this purpose
.
Non woven mats of fibers were electrospun at spinning voltages of 7, 9, 10 and 1
2 kV.
The collector was maintained at a distance of 10 cm from the nozzle throughout t
he
experiment. Three samples were prepared for each particular voltage. These sampl
es
were observed in the scanning electron microscope (SEM). The average fiber diame
ter
was evaluated by randomly selecting up to 5 different portions of the fibrous ma
t and
averaging the diameter over the number of portion selected in each portion.
The data collected is shown in Fig. 2.2. The average diameter drops down from
950 to 500 nm as the voltage is increased from 7 to 9kV and gradually attains a
300 nm
value at 12kV. Keeping the nozzle to collector constant, an increase in the appl
ied
voltage increases the intensity of the electric field across the solution and th
e collector
that further accelerates the whipping motion of the jet resulting in the thinnin
g of the
fibers. These observations reported here are in qualitative agreement with liter
ature [34].
Figure 2.2: Effect of the applied voltage on the diameter of fibers electrospun
from
PEO/Chloroform at a constant nozzle to collector distance of 10 cm.
The effect of the spinning voltage on the current was also studied. As the charg
ed fiber
jet initiating from the nozzle hits the collector, the circuit is closed and cur
rent flow can
be monitored. In this part of the experiment the fibers were electrospun from a
5 % PEO
solution in Chloroform at a constant nozzle to collector distance of 8 cm. The v
oltage was
varied from 4 to 9kV in steps of one and the current was monitored through an in
built
ammeter in the power supply. The obtained I-V relation is shown in Fig. 2.3 indi
cating a
linear behavior of the spinning current with respect to the applied voltage.
Figure 2.3: Electrospinning current measured as a function of applied voltage.
This result is not in complete quantitative agreement with the previous studies
[33] but
pretty much explains various related effects such as the increase in bead format
ion with
the voltage. In fact the high spinning current (resulting from a high voltage) i
ncreases the
extraction rate of the solution from the nozzle that result in discontinuities (
beads) in the
fiber morphology.
 2.3.2 Distance between the nozzle and the collector
The distance between the nozzle and the collector (D) plays an equally important
role in
determining the ultimate diameter of the fibers during the electrospinning proce
ss. As
part of understanding the electrospinning process the effect of nozzle to collec
tor distance
was carefully investigated in this work.
Fibers were electrospun from a 2 wt. % PEO solution in chloroform. The nozzle
to collector distance (D) was adjusted between 8 and 24cm keeping a constant vol
tage of
7 kV. Four samples were prepared keeping D = 8, 14, 20 and 24 cm. The samples we
re
dried overnight. The average fiber diameter was evaluated in the SEM using a vol
tage of
30 kV and 80 µA current. The variation in diameter of the fibers with the distance
D is
shown in Fig. 2.4. The diameter decreases exponentially from 700 nm to 360 nm as
D is
increased from 8 cm to 20 cm and slowly goes down to 350 nm as D is increased to
23
cm. We understand that the fibers with smaller diameters are obtained by allowin
g the jet
to cover more distance in the electric field. This also allows more time for the
evaporation of solvent from the fibers that can result in a decrease in the diam
eter.
Other parameters affecting the diameter of the electrospun fibers include the
concentration, charge conduction and flow rate of the solution, nature of the so
lvent used
and the surrounding temperature etc. Some of these have been studied to some ext
ent
and are found in literature [33, 35, 36].
Figure 2.4: Effect of nozzle to collector distance on the diameter of fibers
electrospun from PEO at a constant voltage of 7 kV.
The study of the process parameters provided a useful insight into the electrosp
inning
process. The density of beads was successfully minimized by adjusting process
parameters and fibers with uniform thickness were electrospun in a repetitive ma
nner.
SEM images of the beadless electrospun fibrous mats are shown in Fig. 2.5.
Figure 2.5: SEM images of electrospun fibers with minimum bead defects (a) 500X
(b) 1200X.
2.4 Conclusion
Electrospinning of polymer fibers was demonstrated and fibers of PEO were
obtained. These fibers find important applications in medicine and surgery. The
effect of
some process parameters was studied that helped understand the electrospinning p
rocess
and obtain fibers with optimal dimensions.
Chapter 3
Conducting polymer nanofibers
3.1 Introduction
Electrically conducting polymers are organic semi-conductors comprising
conjugated molecules. Most commercially produced organic polymers are electrical
insulators. Conductive organic polymers have extended delocalized bonds composed
of
aromatic units. These bonds create a band structure similar to that of a semi-co
nductor,
but with localized states as has been depicted in Fig. 3.1. When charge carriers
are
introduced into the conduction or valence bands the electrical conductivity incr
eases
dramatically. Technically almost all known conductive polymers are semiconductor
s due
to the band structure and low electronic mobility. The most notable difference b
etween
conductive polymers and inorganic semiconductors is the carrier mobility, which
is
dramatically lower in conductive polymers.
Generally the conductivity mechanism in conducting polymers is based on the
motion of charged defects within the conjugated framework [37]. These defects ca
n be
positive (p-type) or negative (n-type) and result from the oxidation or reductio
n of the
polymer respectively. In contrast, typical "doping" in the polyacetylene-derived
conductive polymers involves actually oxidizing the compound. Oxidation of the
Figure 3.1: Band structure in electrically conducting polymers. Each band consis
ts
of closely placed discrete states in polymers unlike the continuous ones as in s
emiconductors.

polymer initially generates a radical cation with both spin and charge. This spe
cies is
referred to as a polaron and comprises both the hole site and the structural dis
tortion
which accompanies it. The cation and radical form a bound species, since any inc
rease in
the distance between them would necessitate the creation of additional higher en
ergy
quinoid units.
Polyphenylene Vinylene
Polypyrrole
Polythiophene
Polyphenylene Vinylene
Polypyrrole
Polythiophene
Polyacetylene
Polyaniline
Figure 3.2: Examples of conducting polymers.
The genesis of the conducting polymers can be traced back to the mid 1970s when
polyacetylene, the first polymer capable of conducting electricity was reportedl
y prepared
by accident by Shirakawa [38]. The subsequent discovery by Heeger and MacDiarmid

[39] that the polymer would undergo an increase in conductivity of 12 orders of

magnitude by oxidative doping lead to initiating an intensive search for other c
onducting
polymers.
48
The simplest possible form of conjugated polymers is the archetype polyacetylene
(CH)X
shown in Fig. 3.2. Polyacetylene itself is too unstable to be of any value but i
ts structure
constitutes the core of all conjugated polymers and is therefore well suited to
ab-initio
and empirical calculations required to elucidate other conducting polymers. Some
examples of conjugated polymer are given in Fig. 3.2.
3.2 Different types of doping
3.2.1 Redox doping
All conducting polymers and most of their derivatives e.g. polypyrrole,
polythiophene, polyfuran and polyaniline undergo either p- (partial oxidation) a
nd/or n-
(partial reduction) redox doping by chemical and/or electrochemical processes du
ring
which the number of electrons associated with the polymer backbone changes [40].

3.2.2 Photo doping

This type of doping does not involve dopants. The polymer is exposed to radiatio
n
of energy greater than its band-gap. The electrons are thus promoted across the
gap and
the polymer undergoes photo-doping [41].
3.2.3 Charge-injection doping
This type of doping is most conveniently carried out using a
metal/insulator/semiconductor (MIS) configuration involving a metal and a conduc
ting
polymer separated by a thin layer of a high dielectric strength insulator [42, 4
3].
3.2.4 Non-Redox doping or Protonic-acid doping
This type of doping differs from redox doping in that the number of electrons
associated with the polymer backbone does not change during the doping process.
The
energy levels are rearranged during doping. The emeraldine base form of polyanil
ine was
the first example of this process [44].
An example of non-redox doping process is depicted in Fig. 3.3. Conductive
polyaniline can be obtained by chemical oxidation (p-doping) of Leucoemeraldine
base.
It s the reaction of a solution of chlorine in carbon tetrachloride proceeds to gi
ve
emeraldine hydrochloride.

Figure 3.3: Non-redox doping process of Polyaniline [45].

3.3 Polyaniline
Polyaniline among the family of conductive polymers is unique in that it is a ty
pe
of semiconductor and can be configured to conduct across a wide range, from bein
g
utterly non-conductive for insulation to highly conductive for other electrical
purposes. It
was discovered in 1934 as aniline black . In the late 1990s it became evident that
polyaniline was a flexible and highly useful polymer, and could be used in appli
cations
ranging from intelligent windows to computer chips.
Polyaniline is used in a variety of applications, because it can be easily combi
ned
with other polymers to form desired shapes. It is frequently utilized in the com
puter
industry where it is incorporated into static free packaging, flexible electroni
c
components, and in testing to shield against electromagnetic radiation. New uses
of these
fibers are constantly being discovered, with more manufacturers adopting the ver
satile
material for a wide range of applications every day.
Depending on the desired conductivity of the polyaniline, the resulting polymer
will be exposed to other chemicals in a process called doping. Doping polyanilin
e leads
to a more stable polymer, and will also allow it to conduct current evenly.
Among conducting plastics polyaniline stands out due to its outstanding properti
es. It is
one of the so-called doped polymers, in which conductivity results from a proces
s of
partial oxidation or reduction. Polyaniline compounds can be designed to achieve
the
required conductivity for a given application. The resultant blends can be as co
nductive
as silicon and germanium or as insulating as glass. Another advantage is that it
is both
melt and solution processable. This means that the compound can be easily mixed
with
51
conventional polymers and that it is easy to fabricate polyaniline products into
required
shapes. Moreover products consisting of polyaniline compounds can be easily disp
osed
of without environmental risks.
The electrical conductivity of polyaniline based compositions can be closely
controlled over a wide range. For neat polyaniline compositions, conductivity le
vels as
high as 100 S/cm can be achieved. The full range of conductivity levels from les
s than
10-10 to 10-1 S/cm (melt processing) and 10 S/cm (solution processing), can be a
chieved
for polymer blends containing polyaniline compositions [46].
3.3.1 Oxidation states of polyaniline
The structural unit of Polyaniline is shown in Fig. 3.4. Polyaniline can be foun
d in
one of five distinct oxidation states [47]:
1. Leucoemeraldine, with n = 1, m = 0 is the fully reduced state.
2. Protoemeralsine (n = 0.7, m = 0.3)
3. Emeraldine (n = m = 0.5), is either neutral or only partially reduced or oxid
ized.
4. Nigraniline (n = 0.3, m = 0.7)
5. Pernigraniline is the fully oxidized state (n = 0, m = 1) with imine links on
ly.
Figure 3.4: Main polyaniline structures n + m = 1, x = degree of polymerization.
3.3.2 Doping polyaniline
The emeraldine (n = m = 0.5) form of polyaniline, often referred to as emeraldin
e
base (EB), is either neutral or only partially reduced or oxidized. Emeraldine b
ase is
regarded as the most useful form of polyaniline due to its high stability at roo
m
temperature, compared to the easily oxidized Leucoemeraldine and the easily degr
aded
Pernigraniline.
The emeraldine base is different from other conducting polymers in several
respects e.g. (1) Its energy gap arises from the electronic structure of the con
stituent C6
units instead of changes in bond lengths as in polyacetylene, polythiophene [48]
etc. (2)
EB can be converted from an insulating to metallic state (ES) if protons are add
ed to the
-N- sites and the number of electrons in the chain is held constant [49]. Additi
onally,
the emeraldine base polyaniline can function as a semiconductor when doped by a
protonic acid [46] such as HCl, HNO3 etc.
More recently, it was found that the emeraldine base form of polyaniline could b
e
made soluble in a number of organic solvents by choosing functionalized protonic
acids
as dopants [50]. One such dopant is an organic acid called the Camphorsulfonic a
cid,
HCSA. The molecular structure of HCSA (chemical formula: C10H16O4S) is shown in
Fig. 3.5 and the doping process of PAn with HCSA is shown in Fig.3.5. 2 moles of
HCSA is required to dope 1 mole of polyaniline. The process is carried out in a
compatible solvent such as chloroform. The imine sites in the PAn molecule in Fi
g.
3.6(a) are oxidized by the H+ ions of the HCSA in chloroform. A hole is thus cre
ated on
the site that restricts the CSA- ion to itself. due to coulombic forces. The eme
raldine salt
Figure 3.5: Molecular structure of Camphorsulfonic acid.
PAn is shown in Fig. 3.6 (b). The hole sites polarize the surrounding medium and
travel
across the molecular chain carrying along the polarization field associated with
them
when electrons from the adjacent amine sites jump to fill these sites. These hol
es together
with the phonons resulting from the medium distortion are called polarons and re
nder the
polymer its conductive nature.
Theoretical treatments [51, 52] have demonstrated that two nearby polarons combi
ne to
form the lower energy bipolaron as shown in Fig. 3.5 (c). One bipolaron is more
stable
than two polarons despite the coulombic repulsion of the two ions. This bipolaro
n with an
infinite conjugation chain on either side can migrate in either direction withou
t affecting
the energy of the backbone. It is this charge carrier mobility that leads to the
high
conductivity of these polymers. Experimental data [53] however supports the pola
ronic
band structure in polyamine.
Figure 3.6: (a) Insulating emeraldine base form of Polyaniline (b) Conducting
emeraldine salt form of polyaniline (Polaron structure) (c) Bipolaron structure
in
doped polyaniline.
Figure 3.7: (a) PAn and Camphorsulfonic acid right after mixing in Chloroform.
(b). after 6 hours of stirring.
3.4 Sample preparation
Polyethylene oxide (PEO) 10-Camphorsulfonic acid (HCSA) and Polyaniline (Mw~
300,000g/mol) in the emeraldine base (EB) form were purchased from Aldrich and w
ere
used as received to prepare solutions. Chloroform was used as solvent. A 100 mg
of
Polyaniline (EB) was doped with a129 mg of Camphorsulfonic acid (HCSA) in 10mL
Chloroform. The solution, originally in color blue was magnetic stirred for 4 h
and
filtered using a No. 40 Whatman filter paper in order to remove any undissolved
matter.
The solution gets a dark green appearance after stirring indicating the conducti
ng
emeraldine salt form (PAn: HCSA) of polyaniline as shown in Fig. 3.7. PEO (Mw~
56
300,000g/mol) was added to the filtrate and stirred for another 2 h to make a
homogeneous solution. The PEO enhances the viscosity of the emeraldine salt solu
tion so
that it can be used for electrospinning fibers. A number of polymer blends were
thus
prepared at room temperature with the concentration of doped Polyaniline i.e.
PAn.HCSA varying from 30 to 70 wt. %.
3.5 Electrospinning fibers
Nanofibers were electrospun from each of the polymer blends using the
electrospinning technique. Fibers were collected for an hour at room temperature
using a
high voltage of 7 kV. A 10 cm nozzle to collector distance was maintained during
the
spinning process. Due to the conductive nature of doped polyaniline it is hard t
o confine
the fiber jet to a particular position on the collector. Therefore instead of ma
king a fibrous
mat on the collection plate, the electrospun fibers form a web extending beyond
the
collector as shown in the digital photograph in Fig. 3.8. The fibers were dried
in air at
room temperature overnight in order to minimize the solvent (Chloroform) content
and
used for characterization and electrical conductivity measurements. To avoid any
damage
due to handling, fibers were directly electrospun onto 1 × 1 cm2 pieces of Silicon
and
TEM grids in order to be investigated in the SEM and TEM.
Figure 3.8: Digital photograph of the fibrous web electrospun from PAn/PEO blend
.
(D = 10 cm and V = 7 kV were used during electrospinning).
3.6 Characterization of the nanofibers
Fig. 3.9 represents the SEM images of the fibers electrospun from PAn:
HCSA/PEO blend. The fibers are randomly oriented in the non woven mat and the be
ad
density in the fibers is almost negligible. The thickness of the fibers is unifo
rm along the
length the distribution of diameter however varies across the mat. Overall fiber
s seem to
have circular cross-sections. It is worth mentioning that these fibers are very
fragile and
are deformed when exposed to intense electron beam (I> 82 µA) or regular electron
beam
for longer intervals.
58

Figure 3.9: SEM images of the fibers electrospun from PAn.HCSA/PEO blend (a)
200X (b) 350X (c) 750X (d) 1000X.
The irregular surfaces of the fibers shown in Fig. 3.8 (d) resulted from a 3 min
ute
exposure to the electron beam in the SEM using a high current of 82 µA. Transmissi
on
electron microscope (TEM) was used to accurately evaluate the dimensions of the
electrospun fibers. Few fibers with beads that were not visible in the SEM were
seen in
Figure 3.10: TEM images of beaded fibers. Images were taken using 80 kV
potential.
the TEM as shown in Fig. 3.11. Some of these fibers seem to wind around each oth
er
which indicate that they are thinner than they seem to be in the TEM images. Oth
ers just
cross over each other giving a bulky expression at the junctions. The average fi
ber
diameter was evaluated using the TEM. Fiber diameters were recorded in different
potions of the sample and averaged over the number of fibers in that portion. Th
e
diameter was further averaged over the number of portions selected on a given sa
mple.
This procedure was repeated for three different samples prepared under identical
spinning
conditions. An average fiber diameter of 300 nm was estimated in this manner alt
hough
the minimum fiber diameter observed was only 50 nm.
Figure 3.11: TEM images (80 kV) of beadless fibers electrospun from PAn:
HCSA/PEO blend Scale bar is (a) 1 um (b) 500 nm.
3.7 Electrical Conductivity measurement
The electrical conductivity of the electrospun fibers was measured at room
temperature using the four-point-probe method. In four-point-probe method the re
sistance
introduced into the circuit by the contacts between the mat and the four probe c
hip is
effectively omitted. The current voltage behavior (IV) of the electrospun fibrou
s mats
obtained from polymer blends with different PAn: HCSA compositions are shown in
Fig.3.12. These mats could conduct current on the micro meter scale with resista
nce ~
(2.8-2) MO. The ohmic nature of the IVs confirms that the four-probe resistance
measured is intrinsic to the fibers.
Figure 3.12: Four probe IV s of Fibrous mats electrospun from (a) 50 wt. % (b) 58
wt. % PAn.HCSA solution. The current values were averaged 10 measurements.
3.7.1 Using PEO (300,000 g/mol) as the matrix
Fig. 3.13 represents the electrical conductivity values of the electrospun fibro
us
mats and cast films for different weight % PAn: HCSA in the PEO. The conductivit
y of
the mat increases as the amount of doped PAn in the blend is increased from 30 t
o 50 wt.
% and tends to saturate beyond. The highest electrical conductivity value record
ed for 70
wt. % PAn.HCSA/PEO fibers is 0.001 S/cm. The conductivity for fibers with PAn.HC
SA
concentration higher than 70 wt. % however was not measured since fibers can not
be
electrospun from the blends due to their inadequate viscosity. For comparison pu
rposes
the electrical conductivities of the cast films were also measured using the fou
r probes set
Figure 3.13: Electrical conductivity of the fibrous mats electrospun from
PAn.HCSA/PEO (300,000 g/mol) blend. Conductivity values were averaged over 10
trials, each trial value being the average of 20 iterations.
up. The films were directly cast on to the four-probe-chip using a syringe and w
ere kept
in air at room temperature for 24 hours to dry out.
The electrical conductivity of the cast films is increased from 8.4 x 10-6 S/cm
to
0.019 S/cm as PAn: HCSA concentration is varied from 30 to 70 wt. %, a behavior
identical to the fibrous mats as shown in Fig. 3.13. The conductivity of the cas
t films
however is higher than that of the fibrous mat for any given concentration of th
e doped
63
PAn in the PEO matrix. This has been previously attributed to the presence of vo
ids in
the electrospun mats by Norris et al [54] who measured the conductivity of polya
niline
fibers in which the concentration of PAn: HCSA was varied only up to 50 wt.% in
PEO
(Mw~ 900,000 g/mol).
3.7.2 Using PEO (900,000 g/mol) as the matrix
Another set of experiments was performed using a higher molecular weight PEO
(molecular weight ~900,000 g/mol) as the matrix polymer. The concentration of th
e
PAn.HCSA was varied between 30 and 70 weight % in the polymer blends and the
blends were used to prepare cast films and fibers as described earlier.
The four-probe conductivity values of the fibrous mats and cast films were
measured for different wt % concentration of PAn: HCSA in PEO (900,000 g/mol). T
he
conductivity values shown in Fig. 3.14 represent the average over 10 trials, eac
h trial
value being the average of 20 iterations. The electrical conductivity of the fib
rous mats
was found to increase sharply up to a 50 wt. % concentration of the PAn: HCSA in
the
blend and started to slow down afterwards assuming a value of 0.192 S/cm for 70
%
PAn: HCSA in PEO [55]. The electrical conductivity of the cast films increased i
n an
identical manner with the concentration of doped PAn i.e. PAn.HCSA in the polyme
r
blend.
The conductivity values of the fibrous mats are consistently lower than their ca
st
film counter parts for any given concentration of the PAn.HCSA in the blend. Giv
en that
the four probe method measures the volume conductivity of a system, the anticipa
ted
increase in the conductivity of the fibrous mats compared to the films was not o
bserved
Figure 3.14: Electrical conductivity of the fibrous mats electrospun from
PAn.HCSA/PEO (900,000 g/mol) blend.
probably because of the presence of voids in these mats. It is therefore importa
nt to
measure the electrical conductivities in single fibers.
The four-probe IV s of single fibers electrospun from PAn.HCSA/PEO (Mw
~900,000 Da) blends were measured using the same set up. These fibers were (2-3)
cm
long. SEM was used to measure the thickness of the fibers. Fig. 3.15 shows the I
V
characteristics of a 760 nm thick single nanofiber electrospun from 60 wt. % PAn
.HCSA
Figure 3.15: Four-probe I-V characteristics of a single nanofiber electrospun fr
om
60 wt. % PAn.HCSA in PEO (Mw ~ 900,000 g/mol). The current values shown are
the average of ten measurements.
in PEO (900,000 g/mol). The resistance of the fiber is 10 MO that corresponds to
a
conductivity value of 3.29 S/cm [55]. Electrical conductivity values of (3.29 ±0.1
9) S/cm
were recorded in fibers in the diameter range (750 ± 30) nm. The conductivity valu
e
reported here is higher than that reported earlier by Zhou et al. [56] for a sin
gle fiber of
70 nm diameter. The SEM image of a single fiber placed on a four probe chip is s
hown in
Fig. 3.16.
Figure 3.16: (a) Optical image of the 4-probe chip. (b) SEM image of the fiber
placed on the chip for conductivity measurement.
The conductivity of the single fiber increases with respect to the amount of PAn
:
HCSA in the blend in a fashion similar to mats and films as shown in Fig. 3.16 b
ut is
higher than that of both the cast film and the fibrous mat for a given concentra
tion of
PAn.HCSA in PEO. A highest conductivity value of 3.29 S/cm was measured in fiber
s
with 70 wt. % PAn: HCSA in PEO (900,000 g/mol).The higher electrical conductivit
y of
single fibers compared to fibrous mats is obvious from the fact that unlike the
mats they
do not contain any voids. The poor contact among the fibers in the electrospun m
ats can
also account for the lower electrical conduction in these mats. This is not the
case in the
fibers. The higher conductivity in single fibers as compared to the cast films i
s not
unexpected in that the
Figure 3.17: Electrical conductivities of single fibers, cast films and fibrous
mats
measured as function of PAn.HCSA concentration in the polymers solution.
polymer chains in the fibers are more aligned as a result of the electrospinning
process.
The carrier mobility and hence the conductivity is higher in single fibers.
3.7.3 Effect of PEO on the conductivity of PAn
The electrical conductivities of fibers and cast films obtained from polymeric
blends for doped PAn using (1) PEO (Mw ~ 300,000 g/mol) and (2) PEO (Mw ~ 900,00
0
g/mol) as the matrix were shown in the previous section.
Figure3.18: Electrical conductivities of the fibers and films electrospun from
PAn.HCSA blended with PEO (900,000 g/mol) (upper three layers) and PEO
(300,000 g/mol) (lower two layers).
Qualitatively the variation in conductivity with respect to the amount of doped
PAn is identical in both cases. The conductivity values however are far higher i
n the case
of fibers and films obtained with PEO (900,000 g/mol).A comparison of the two ca
ses is
made in Fig. 3.18. The conductivity measurements were performed over 10 times an
d the
conductivity value was average over 20 iterations each time in order to establis
h a high
degree of experimental accuracy.
The different electrical conductivities associated with films and fibers derived
from blends using different molecular weight PEO matrices can be explained in te
rms of
the relative miscibility of the polymers in the blends and the molecular chain
conformations associated with them. It has been reported earlier that longer mol
ecular
chain polymers have poor dissolution in a miscible polymer as compared to a shor
ter
chain polymer [23]. The PEO (Mw~900,000 g/mol) in this case have longer molecula
r
chains and hence does not diffuse appreciably in Polyaniline as compared to the
PEO
(Mw~300,000 g/mol). This results in a lower density of twisting defects among th
e
polymer molecules in the blends allowing the PAn chains to maintain a stable pol
aronic
structure, and hence an enhanced electrical conductivity.
Secondly the higher molecular weight PEO is more crystalline with straight
chains as compared to the branched chains present in the comparatively less crys
talline
PEO (Mw~300,000 g/mol). The fibers and films prepared with PEO (Mw~900,000 g/mol
)
there possess higher electrical conductivity as compare to those obtained from s
olutions
using PEO (Mw~300,000 g/mol) as the matrix polymer in which the twisting defects
shield the adjacent isolated polarons resulting in the localization of the polar
on band. The
carrier mobility and hence the intrachain conductivity decreases.
This leaves us with the conclusion that the molecular weight of the polymer
matrix used does have an effect on the conductivity of the doped polymer in the
blend
and that a higher molecular weight matrix i.e. PEO in this case enhances the ele
ctrical
conductivity of the fibers. The two cases have been summarized in the Fig. 3.16.
3.8 Conclusion
Electrically conducting fibers of PAn.HCSA/PEO were prepared using the
electrospinning technique. The fiber diameter varied between 0.3-2µm in the fibrou
s mat.
Electrical conductivities (0.192 S/cm) comparable to the bulk value (2.04 S/cm)
were
obtained in the fibrous mats by varying the amount of doped Polyaniline in the p
olymer
blend. Electrical conductivities greater than the bulk value were recorded in si
ngle fibers
(3.2 S/cm). A linear current voltage behavior was observed in the fibrous mats a
s well as
in a single fiber. The convenience of producing electrically conducting polymer
fibers
was demonstrated that promise new functional opportunities in the field of nanoe
lectronic
devices together with the advantage of low cost.
Chapter 4
Fabrication and optical characterization
of silicon carbide nanofibers
4.1 Introduction
Silicon carbide (SiC) holds an important position among the semi conducting
ceramic materials because of its high (higher than silicon) breakdown electric f
ield (35MV/
cm), high thermal conductivity (350-490 W m-1 K-1) and low mass density [57-59].
Silicon carbide exists in at least 70 crystalline forms. The most commonly encou
ntered
polymorph has a hexagonal crystal structure similar to Wurtzite and is called th
e alpha
silicon carbide (a-SiC) [60]. Alpha SiC is formed at temperatures greater than 2
000 °C.
Pure a-SiC is an intrinsic semiconductor with band gaps of 3.28 eV (4H) and 3.03
eV
(6H) respectively [61]. The 4H and 6H SiC crystals are shown in Fig. 4.1. The fa
ce-
centered cubic crystal structure similar to diamond and zincblend is formed at
temperatures below 2000°C [61] and is called ß-SiC shown in Fig. 4.2.
Figure 4.1: Tetrahedral arrangement of Si and C atoms in (a) 4H and (b) 6H SiC
structures [60].
Figure 4.2: Schematic of the face centered cubic (3C) crystal of SiC (ß phase).
4.2 Silicon Carbide Nanostructures
Nanostructures of SiC are attracting a great deal of attention for their tremend
ous
potential in applications such as reinforcements in the development of nanocompo
sites
[62, 63]. Silicon carbide (SiC) nanofibers possess high mechanical strength and
oxidation
resistance at elevated temperature [62] and provide a perfect alternative for ca
rbon
nanotubes in the development of metal matrix composites. Carbon nanotubes carry
the
disadvantage of degradation and can not be used in such composites [63]. These
composite materials are used to prepare equipment parts capable of operating in
high
temperature environments. In addition, electronic devices based on SiC nanostruc
tures
are capable of operating at high powers, high temperatures and high frequencies
[64, 65].
Nanostructures of SiC are of great interest because of their broad range of pote
ntial
applications such as field electron emitters and light emitters[66]. In particul
ar, the
nanofibers of SiC possess high aspect ratios, which make them more suitable for
applications as field emitters [67-70].
Attempts have been made to synthesize SiC fibers using various methods such as
chemical vapor deposition (CVD) [69, 71], high power microwave plasma chemical
vapor deposition [72], heat treating carbon nanotubes covered with Si [73] and f
rom a
precursor of two types of polycarbosilanes (type-A and type-L) [74]. The procedu
res
mentioned above however, either require sophisticated equipment or expensive car
bon
nanotubes or involve several preparation steps. Moreover, the SiC fibers thus ob
tained
are only less than a 100 nm long. The synthesis of these fibers therefore remain
s a
challenge and needs a great deal of attention.
In this chapter we report for the first time (to the best of our knowledge) the
synthesis of SiC nanofibers from a dispersion of SiC powder in polymer solution
using
the electrospinning technique. The as spun SiC/polymer fibers were sintered at a
temperature of 1000°C at a low pressure of 10mTorr for 8 hours. The fibers obtaine
d are
(40-50) µm long and have uniform thickness. The optical properties of the SiC fibe
rs
75
were studied using PL and CL systems. The Cathodoluminescence (CL) spectrum
collected from the fibers lie in the red region of the spectrum.
4.3 Electrospinning silicon carbide nanofibers
SiC powder in the alpha-phase was purchased from Advanced Materials
Technology Company and polyethylene oxide was purchased from Aldrich. An 800 nm
grain size of SiC powder was estimated from SEM images shown in Fig. 4.3.
The dispersion solution was prepared by mixing 500 mg of SiC powder in 5mL
Chloroform (99.8 %). The solution was stirred for 3 hours to ensure a uniform
distribution of the powder in chloroform. 250mg of Polyethylene oxide was added
to the
solution. The mixture was stirred for another 3 hours in order to ensure a unifo
rm
dispersion of SiC particles in the polymer. The solution was used to obtain fibe
rs using
the electrospinning technique.
The spinning process was carried out at a high voltage of 10kV and a nozzle to
collector distance of 12cm. Fibers were electrospun for 1h at room temperature.
The
fibrous mats of the SiC/PEO fibers were collected on Silicon and quartz substrat
es and
kept in air for 15 h to dry out. Several samples were obtained in this manner an
d annealed
at 800°C and 1000°C temperature at a lower air pressure of 10mTorr for 8 hours. The
samples were cooled down in steps at the rate of 200°C/30 minutes. The morphology
and
dimensions of the electrospun fibers as well as the quantitative elemental analy
sis of the
fibers were investigated by scanning electron microscope (SEM) model Joel JSM 53
00
Figure 4.3: SEM image of silicon carbide particles. Average particle size is 800
nm.
with an energy dispersion X-ray (EDX) spectrometer. The XRD was carried in order
to
investigate any crystalline phases formed during the annealing process of the fi
bers.
Cathodoluminescence (CL) was done with 20kV. accelerating electron and ocean opt
ics
setup, described in detail elsewhere [75].
Fig. 4.4 represents the SEM images of the as-spun fibrous mats electrospun from
SiC/PEO dispersion solution. The fibers appear to have non uniform surfaces and
exhibit
a dual complexion. The comparatively brighter regions of the fibers are believed
to arise
from the clustering of the SiC particle.
Figure 4.4: SEM images of fibers electrospun from a dispersion solution of SiC i
n
PEO (a) Low resolution (1000 x) and (b) high resolution (5000 x).
These clusters render the fibers a non-uniform thickness as can be seen in the
SEM image shown in Fig. 4.4(b). The distribution of fiber diameter highly varied
across
the mats. Fiber diameters in the range (200-800) nm were observed in the SEM. Th
e
density of beads in the fibrous mats was almost negligible due to the apparently
high
viscosity of the solution and an appropriate combination of the spinning paramet
ers such
as voltage (10 kV) and nozzle to collector distance D (12 cm).
Fig. 4.5 shows the SEM images of the electrospun fibers after annealing at 800°C.
Large
portions of the sample appear like piles of dust in the SEM and mainly contain the
PEO
residual. Within these piles are present (20-40) µm long aggregates of particles w
hich
unlike the polymer fibers remain structurally stable under the electron beam for
any
length of exposure time.
Figure 4.5: SEM image of the SiC/PEO fibers after annealing at 800°C for 7 hours.
As shown in the high resolution SEM images in Fig. 4.6 the particles in the fibe
rs are not
closely packed rendering the fibers their rough appearance. Fig.4.7 represents S
EM
images of the electrospun fibers after annealing at 1000°C. These fibers possess r
elatively
smaller diameters and uniform surfaces.
Figure 4.6: SEM images of SiC fibers obtained after annealing the sample at 800°C
for 7 hours.
Figure 4.7: SEM images of SiC fibers formed after annealing the SiC/PEO fibers a
t
1000°C for 10 hours (a) 2000X (b) 2000X (c) 1500X (d) 1500X. Images were taken
using 30 kV, 80 uA.
Figure 4.8: EDX pattern of SiC/PEO fibers after annealing.
4.4 Structural and Compositional Analysis
The SiC nature of the obtained fibers was established by carrying out the compos
itional
analysis of the fibers using the energy dispersive X-ray (EDX) spectrometer atta
ched to
the SEM. The peaks at 280 and 1740 (keV) indicate respectively the presence of C
arbon
and Silicon in the sample. The intensity peak at 535 keV indicates the presence
of oxygen
in the fibers. It is anticipated that teat treatment of the sample at higher tem
perature will
completely eliminate the oxygen and enhance the crystallinity of the fibers. The
intensity
Figure 4.9:XRD patterns of SiC/PEO fibers after annealing.
peak at 1515 keV represents aluminum that is coming from the SEM grid. No other
significant peaks were seen in the EDX pattern as shown in Fig. 4.8.
The XRD study of the sample was also carried out in order to see any possible
phase changes in the SiC. Fig. 4.9 represents the x-ray diffraction pattern of t
he sample
annealed at 1000 deg ºC. All the intensity peaks were indexed to a-SiC [ICDD, card
# 00002-
1042], hence no phase change occurred during the heating process.
Figure 4.10: CL spectrum collected from SiC fibers at 5 keV.
4.5 Cathodoluminescence (CL)
The CL set up used in this work uses an electron beam with up to 5keV energy. Fi
g. 4.9
shows the Cathoduluminescence spectrum collected from the silicon carbide fibers
.
These fibers emit two peaks in the red regions upon excitation with 20kV electro
n gun in
the CL setup. The main peak is centered at 774 nm while the shoulder on the left
is at
740nm. The optical microscope image taken during the CL is shown as inset in Fig
. 4.10.
Figure 4.11: CL images of silicon carbide fibers. Scale bar is the same on the
pictures. (5 keV beam was used).
4.6 Conclusion
Silicon Carbide nanofibers were synthesized by sintering the as-spun fibers
obtained from SiC powder dispersed in polyethylene oxide (PEO) solution in Chlor
oform
using the electrospinning technique. Fibers as long as 40 µm were obtained.
Cathodoluminescence spectrum of the annealed fibers shows emission in the red re
gion
of the spectrum. Apart from their importance as reinforcements in the developmen
t of
nanocomposites, SiC fibers also show potential for applications in light emittin
g diodes
and in field emitters.
Chapter 5
Polymer Nanofibers containing
Ruthenium Compounds
5.1 Introduction
One of the many important applications of electrospun fibers is made in nanosens
ors
[63], [76] that utilize the electronic properties associated with these fibers.
The
sensor applications of nanofibers known so far however involve measurement of so
me
physical property associated with them, electrical conductivity for instance, be
fore and
after the fibers are exposed to the particular agents/environments [77].
Complexes of ruthenium with polypyridine ligands have been deeply studied from
an experimental point of view [78, 79] because of their tremendous potential ind
ustrial
applications such as photovoltaics (as components in solar batteries) [80], ligh
t switches
[81]and biochemistry , DNA binding for instance[82]. The peculiar photochemical
properties of these complexes were discovered 30 years ago [83] but effort is st
ill going
on to enhance these properties.
In this chapter we report for the first time, the electrospinning of nanofibers
from
polymer solutions containing the ruthenium compounds [Ru (pic)2 (dmso)2]and [Ru
(bpy)
3] (PF6)2 .
Figure 5.1: Molecular structure of [Ru (pic)2 (dmso)2] [84].
The fibers containing [Ru (pic)2 (dmso)2] are excellent sensors for ultraviolet
light
(wavelength ~ 350 nm). These fibers originally colorless or pale yellow turn ora
nge when
exposed to the UV radiation. The UV sensing is thus apparent from the change of
color
of these fibers and does not involve any complicated measurements. The molecular
structure of [Ru (pic)2 (dmso)2 ] is shown in Fig. 5.1.The picolinate ligands ar
e in a cis-
arrangement so that the carboxylate oxygen of one pic ligand (O1) is trans-to th
e pyridine
87
of the second picolinate 20 (N2). One dmso ligand (S1) is trans to a pyridine ni
trogen (N1)
while the second dmso (S2) is trans to a carboxylate oxygen (O3) [84].
5.2 Experimental
The ruthenium complexes [Ru (pic)2 (dmso)2], (pic is 2-pyridinecarboxylate;
dmso is dimethylsulfoxide) (chemical formula; C16H24N2O8RuS2) and [Ru (bpy) 3] (
PF6)2
used in this work were obtained from Department of Chemistry and Biochemistry Oh
io
University Athens Ohio. PEO (Mw~ 300,000 g/mol) was purchased from Aldrich and w
as
used as received to prepare solutions. Chloroform was used as a solvent.
165 mg PEO was mixed with 5 g Chloroform and stirred for 2 hours to prepare a
3 wt. % polymer solution. 0.5 g of [Ru (pic)2 (dmso)2] was added to the solution
and
stirred for another 2 hours in order to ensure a homogeneous mixture. Another so
lution
containing 0.5 g of [Ru (bpy) 3] (PF6)2 was prepared in a similar manner. Fibers
were
electrospun from both the solutions using the electrospinning technique.
5.3 Results and Discussion
Laser Flash Photolysis Spectroscopy (LFPS) was performed on the as-spun
nanofibrous mat using light wavelength of 350 nm. The mat changed color from pal
e
yellow to orange as soon as it was exposed to UV. This change in color is not pe
rmanent
and the fibers return to their original color in 2-3 days. The nanofibrous mat p
repared
from a solution of PEO in Chloroform does not change color when exposed to UV. T
hus
it is fair to say that the color changing ability of the fibers comes from the i
ntroduction of
the photo chromic compound [Ru (pic)2 (dmso)2]. Fig. 5.2(a) shows the digital
photograph of the non-woven nanofibrous mat before exposure to UV. It appears pa
le

Figure 5.2: Optical images of the electrospun mat (a) before and (b) after expos
ure
to UV (.~350 nm) with a mask on it. Scale bar is the same on (a) and (b).
yellow in the beginning and turns orange when exposed to UV [85] as shown in Fig
. 5.2
(b). The intensity of the color increases with the exposure time and the mat tur
ns dark
orange in 2-3 minutes.Fig. 5.3 shows the SEM image of the electrospun fibers. Th
e
diameter of the fibers is pretty much uniform along their length. Overall the di
ameter
ranges from 0.1-1 µm. The SEM studies of the electrospun fibrous mat show that the
morphology of the fibers remains unchanged after they have been exposed to ultra
violet
radiation.
The fibrous mat electrospun from [Ru (pic)2 (dmso)2]/PEO blend responds to UV
in a fashion similar to [Ru (pic) 2(dmso) 2] solution in ethanol. The color of t
he fibers
after exposure to UV is apparently the same as that of [Ru (pic) 2(dmso) 2]/etha
nol

Figure 5.3: SEM image of the fibrous mat electrospun from [Ru (pic)2 (dmso)2]
blended in PEO (30 kV, 80 uA).
solution. The absorption spectrum of the electrospun mat was not taken for techn
ical
reasons. The UV sensing behavior of the fibers however was explained using the U
V-
visible absorption spectrum of [Ru (pic)2(dmso)2]/ethanol solution reported by R
ack et.
al., [84] as shown in Fig. 5.4. The spectrum features an intense p*.p absorption
at 250
nm (18940 M-1cm-1) and a broad (..fwhm = 11000 cm-1) less intense absorption cen
tered
at 327 nm (6400 M-1cm-1), with a low energy tail of significant intensity extend
ing past
450 nm. Upon excitation in ethanolic solution, the 327 nm absorption shifts 3700
cm-1
lower in energy (372 nm), consistent with formation of O-bonded dmso. Similar
observations following UV irradiation or exposure to sunlight are made in benzyl
alcohol
and propylene carbonate as well as in the microcrystalline solid and polymer fil
m. The
high energy MLCT (metal-to-ligand charge transfer) is a consequence of the relat
ively
Figure 5.4: UV-visible absorption spectrum of [Ru (pic) 2 (dmso) 2] / ethanol ch
anges
upon irradiation at 344 nm.(spectrum taken by Rachford et al. [84]).
high energy p* orbital of pic compared to that of bpy. The one-electron reductio
n
potential of picolinate occurs at -1.75 V in this complex. In contrast, the one-
electron
reduction potential for tpy occurs at ~ -1.1 V and ~ -1.5 V for bpy in related c
omplexes
[84]. The energy difference between the Ru3+/2+ E°' (1.28 V) and pic-/pic2-E°' (-1.7
5 V)
suggests that the lowest energy Ru dp. pic p* metal-to-ligand charge-transfer (M
LCT)
is estimated to be ~25000 cm-1. Thus, the absorption at 327 nm (30580 cm-1) is a
ssigned
92
as an MLCT transition. Evidence for isomerization is best observed in the UV-vis
ible
absorption spectrum. In alcoholic solutions, irradiation of [Ru (pic)2 (dmso) 2]
at 344nm
results in a new absorption at 372 nm and extends past 500nm. This new band is
attributable to O, O-[Ru (pic) 2 (dmso) 2].
5.4 Fibers Containing [Ru (BPY) 3] (PF6)2
Following the experimental procedures described in section 5.2, polymeric fibers
containing ruthenium bi-pyridine i.e. ([Ru (bpy) 3] (PF6)2) were prepared using
the
electrospinning process. Methylene Chloride was usedas solvent since the complex
is not
appreciably soluble in Chloroform. The electrospun fibers represent an identical
morphology to those containing [Ru (pic)2 (dmso)2] as shown in Fig.5.5. The opti
cal
characteristics of these fibers however are different.
Figure 5.5: SEM image of fibers electrospun from ([Ru (bpy) 3] (PF6)2)/PEO in
methylene chloride.
Optical spectra were collected from the fibers using the near field scanning opt
ical
microscopy (NSOM) for improved resolution. One such spectrum is shown in Fig. 5.
6
that shows fluorescence recorded from different locations (A-G) in the electrosp
un fiber.
The intensity of the light collected from different positions varies depending o
n the
concentration of [Ru (bpy) 3] (PF6)2) present at the particular position. An NSO
M image
of the fiber representing the specified locations with letters A-G is shown in F
ig. 5.7(a).
Figure 5.6: Fluorescence Spectra corresponding to locations A-G in the fluoresce
nce
image of a single fiber after excitation with 532 nm.
5.4 Conclusion
Photo chromic compounds of ruthenium with picolinate and bi-pyridine ligands wer
e
introduced into polymeric solutions and successfully electrospun into nanofibers
. The
nanofibers possess nice luminescent properties and are suitable for applications
as
photosensors.
Figure 5.7: NSOM images of (a) fiber cross-section with the bright spots showing
[Ru (bpy) 3] (PF6)2 distributed in the fiber and (b) single luminescent fiber,
electrospun from [Ru (bpy) 3] (PF6)2 /PEO in Chloroform on excitation with 532
nm.
Chapter 6
Conclusion and future prospects
Nanotechnology has got tremendous attention over the last two decades. One
important field of this nanotechnology is producing fibers with the nanoscale di
mensions.
Electrostatic generation of ultra fine fibers electrospinning has been known since
1930s. Fiber mechanical properties are improved with the decrease in the dimensi
ons and
electrospinning is the best technique known so far to achieve minimum diameter i
n the
fibers. The high surface to volume ratio of the electrospun fibers make them att
ractive for
various applications such as high performance filters and scaffolds in tissue en
gineering.
Other uses are made as reinforcements in the development of nanocomposites, in s
tain
resistant textiles, sensors, electromagnetic shielding, biomedical grafts and dr
ug delivery.
In this dissertation, we started by devising a custom made set up for
electrospinning. Electrospinning of fibers was successfully practiced using vari
ous
polymer solutions. The effect of some important process parameters on the size a
nd shape
of the fibers was investigated. The problem of bead defects in the electrospun f
ibers was
successfully eliminated by adjusting the experimental parameters such as the app
lied
voltage and the distance between the nozzle and the collector. SEM and TEM were
used
to characterize the fibers in detail.
Our work also focused on minimizing the thickness of the electrospun fibers and
fibers with diameters as small as 50 nm were successfully achieved. Next we focu
sed on
making our fibers functional. This was done in three steps.
(1) Electrospinning of conducting polyaniline fibers was demonstrated and the
conductivity values were optimized by changing the amount of doped polymer in
the polymer blends used for this purpose. The electrical conductivities of these
fibers were measured using the four probe method. Compared to the cast films
and fibrous mats, the electrical conductivity was improved by an order of
magnitude in single fibers.
(2)
SiC was introduced into the polymer solutions and used for spinning fibers. The
as spun fibers were heat treated at 1000°C. Crystallization of SiC particles was
achieved in this manner. XRD and EDX were used for the structural and
compositional analysis of these fibers. The obtained fibers were optically
characterized using CL and PL. Optical spectra of the fibers were recorded
showing emission in the red spectral region.
SiC is an important structural material and is speculated as an important candid
ate to
replace the Si technology. Nanofibers of SiC are oxidation resistant and can sta
nd
temperatures as high as 2700 oC which makes them superior to Carbon nanotubes in
applications such as metal matrix composites. The optical properties of the fibe
rs such as
those reported in this work further add to their value. Our work on conveniently
synthesizing these fibers will therefore continue in future.
(3)
Metal to ligand charge transfer (MLCT) complex of ruthenium
[Ru(pic)2(dmso)2] was utilized for the first time in order to obtain fibers with
the
ability to sense ultra-violet radiation. These complexes were used in solution
form together with the polymer. The polymer fibers alone do not show any UV
sensing characteristics. It was therefore concluded that the UV sensing ability
comes from the ruthenium complex alone.
(4)
Another ruthenium complex [Ru (bpy)2](PF6)2 was introduced into the
nanofibers and the photoluminescence properties were studied.
The introduction of these ruthenium complexes into nano fibers is an important
addition to optically active nano materials. These materials possess potential f
or
various applications such as sensors and light emitting diodes. The work present
ed
here however is only the beginning and a lot more remains to be done in order to
exploit these fibers in a useful manner.
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APPENDIX A
List of Publications

Saima N. Khan, Aurangzeb Khan and M. E. Kordesch, Electrical Conductivity

Measurements of Nanofibers Electrospun from Polyaniline/Polyethylene
Oxide Blend and Its Dependence on the Matrix Material Material Research
Society Symposium Proceedings 948 (2007).
Saima N.Khan, Jeffrey J. Rack, Aaron A. Rachford, M. E. Kordesch,
Electrospinning Polyethylene Oxide nanofibers and their application as
ultraviolet sensors Material Research Society Symposium Proceedings 948
(2007).
Aurangzeb Khan, Wojciech M. Jadwisienczak, Saima N. Khan, and Martin E.
Kordesch, ZnO Nanofibers Doped with Ga, In and Er Fabricated with
Electrospinning Technique , Material Research Society Symposium
Proceedings 957 (2007).
Saima N. Khan, Aurangzeb Khan and M. E. Kordesch, "Fabrication and Optical
Characterization of SiC Nanofibers"- (Accepted) Material Research Society
Symposium Proceedings (2007).).
APPENDIX B
Conferences Attended

APS March Meeting 2006, Baltimore, MD, March 13-17 2006, Poster
contributed.
2006 International Institute for Nanotechnology Symposium, Northwestern
University, Evanston, IL.
MRS 2006 Fall Meeting, Boston, MA, Nov-Dec 2006, Poster and Oral
Presentation contributed.
APS March Meeting 2007, Denver, Colorado, March 5-9 2006, Oral
Presentation contributed.
MRS 2007 Spring Meeting, San Francisco, CA, April (9-13) 2007, Oral
Presentation contributed.