ChE 393: Chemical Engineering Projects
To: Dr. David Drown
CC: Dr. Eric Aston
Ben Plaster
Lab Partner: Jack Williams
Chemical & Mechanical Effects of Fiber Networks on Wettability
Abstract
Through use of scanning confocal raman microscopy (CRM), local and area chemical surface
compositions of electrospun composite polyvinylpyrrolidone titanium dioxide (PVP-TiO2) fibers can be
determined and characterized. These fiber mats may exhibit signs of degradation into disordered
structures of graphene, manifested as the D (1350 cm-1) and G (1580 cm-1) bands, when subjected to
certain thermal and radiant conditions for extended periods of time. This occurs at temperatures well
below the expected degradation temperature, which has been documented as > 300 oC. Current
understanding of these fiber mats does not yield explanation why this may affect wicking and wetting
properties of samples. Through use of successive CRM area scans of PVP-TiO2, it was found that
photocatalytic activity alone was not able to cause degradation of pure PVP fiber mats; extended
curation under thermal conditions ranging from 100 oC – 200 oC yielded varied results. Fiber mats cured
at 150 oC showed no signs of degradation, while mats cured at or above 175 oC showed characteristic
broad D and G band raman signals.
Introduction possible. This becomes useful when preparing
solutions of polymers to be electrospun into
Electrospun polymer nanofibers have a wide
composite mats.
potential for real-world applications due to their
large surface area to volume ratio; for this
reason, it is important to be able to characterize
their surface properties; for this case, this is
specifically the wetting and wicking effects
exhibited by the electrospun composite mats
under certain dynamic conditions.
Figure 1: Polyvinylpyrrolidone monomer structure
Polyvinylpyrrolidone (PVP) is a common polymer
derived from N-vinylpyrrolidone with a variety of Titanium Dioxide, TiO2, is a naturally occurring
applications in the real world ranging from oxide of titanium. Generally, it is a combination
medical uses as a volume expander for trauma of both the rutile and anatase phases found in
victims to technical applications as a common nature. TiO2, particularly in the anatase form, is a
component of hot-melt adhesives. photocatalyst when subjected to UV light2.
PVP is uniquely soluble in both water and various For the purpose of this research, electrospun
organic solvents1. This can be attributed to the mats of PVP-TiO2 nanofibers of one micron
various functional groups, both hydrophobic and diameter and smaller are of concern. Current
hydrophilic, found in PVP; their presence makes understanding of the surface effects of the
molecular interactions with both solvent types randomly deposited bulk fiber mats has not
1
ChE 393: Chemical Engineering Projects
allowed for explanation of differences in wetting approximately 5-8 cm. Once the potential was
and wicking (i.e. hydrophobic and hydrophilic applied, droplets of the prepared solution were
behavior) between samples based on fabrication pushed out of a syringe attached to a standard
and drying treatments. syringe pump. 40 μL were ejected from the
syringe. The droplets entered the electric field
In addition, there is an unexplained presence of D
and accelerated towards a grounded receiver – in
(1350 cm1) and G (1580 cm-1) band signals,
this case a glass slide with one conductive side
indicating disordered structure of graphene,
and one non-conductive side. The spun fibers
when the spun fiber mats are cured at high
formed a disordered bulk structure on the face of
enough temperatures. The exact range is yet
the glass plate. The nanowire substrate was then
unknown, and the surface chemistry has not yet
subjected to heated treatment at temperatures
been properly explained and characterized.
ranging from 100-200 oC for 4 hours to remove
solvent.
Surface Chemistry Characterization
A WITec confocal raman microscopy unit was
utilized to characterize the surface chemistry and
functional groups present on the bulk fiber mats.
Scanning was taken both at precise points and
over 15 μm x 15 μm square areas. All scans were
run using a green 532 nm visible light laser at
varying intensities. All data obtained was at
ambient temperature inside the shaded
Figure 2: Raman spectra of graphene. container.
The characterization of the surface chemistry Results and Discussion
involved with curation temperature will yield
great insight into the chemical and mechanical The first sample was cured at 100 oC, and yielded
wetting and wicking effects previously discussed. no significant chemical difference between the
previously tested uncured samples. No D or G
Experimental bands were identified, leaving no evidence for
Nanofiber Preparation degradation due to thermal conditions.
The polymer used for the electrospun fibers was
polyvinylpyrrolidone, supplied from Sigma-
Aldrich. The polymer material was dissolved in
ethanol and sonicated for 30 minutes. TiO2 was
dissolved in acetic acid and stirred continuously
until ready to be mixed with the freshly sonicated
EtOH-PVP solution. These two solutions were
then combined, and allowed to mix for several
hours.
The nanofibers were spun using electrospinning.
The electrospinning was performed by applying 8 Figure 3: Multiple raman spectra of electrospun PVP-TiO2
baked at 100 oC for 6 hours.
kV electrostatic potential across a distance of
2
ChE 393: Chemical Engineering Projects
After 100 oC was ruled out for degradation however, the sharp peak observed at 166 cm-1
temperature, 150 oC was the next natural choice. cannot yet be explained. Early investigation into
This sample was cured for 6 hours, as per the the origins of this signal have thus far yielded the
experimental method previously mentioned. suggestion from Dr. Aston that this may be
evidence of an oxidative signal that’s being “cut
off” by the CRM unit’s light filter in place. This
will be further investigated in future works.
Finally, the sample cured at 200 oC again showed
the characteristic broad peaks of the D and G
band at 1375 cm-1 and 1589 cm-1. The
aforementioned peak at 166 cm-1 was again seen,
although with much lessened peak intensity.
Figure 4: Raman spectra of electrospun PVP-TiO2 baked at
150 oC for 6 hours.
The raman spectra for this sample shows no new
functional groups present at the surface. Once
again, no D or G band of carbon were seen,
indicating that 150 oC is not the temperature at
which PVP-TiO2 will degrade.
The sample cured at 175 oC showed signs of
Figure 6: Raman spectra of electrospun PVP-TiO2 baked at
significant deviation in raman signals compared
200 oC for 6 hours.
to the lower temperature samples. Both the D
and G band were observed, with broad peaks at In total, it is observed that curation of PVP-TiO2
1378 cm-1 and 1596 cm-1, respectively. samples at temperatures of at least 175 oC over 6
hours will cause some form of degradation within
the polymer structure, yielding disordered
graphene within the structure.
Once the general range of carbon degradation
had been determined, it became important to
characterize the impact of curing conditions on
the hydrophobic or hydrophilic behavior of the
cured mats. The mats cured to illustrate the
progression of static contact angle were cured at
165 oC, 175 oC, and 185 oC; this can be seen in the
following figure.
Figure 5: Raman spectra of electrospun PVP-TiO2 baked at
175 oC for 6 hours.
The presence of the D and G band signals indicate
disordered graphene structures in the fibers;
3
ChE 393: Chemical Engineering Projects
180
the presence of the associated D and G band
160 disordered carbon (or lack of aliphatic carbon
Static Contct Angle
140 signature) plays a very significant role in the
120
dynamic wetting and wicking properties of the
100
80 y = 4.8125x - 738.22
material.
60 R² = 0.669
40 Future work includes control (as an entire
20 research group) over curation time. That we
0 discovered late in the semester that the time of
160 170 180 190
curation was significant in the hydrophobic/philic
Curation Temperature (oC)
properties of the mats raises serious questions.
Figure 7: Static contact angle of electrospun nanofiber mats Perhaps a deeper look into the kinetics and
cured at 165, 175, and 185 degrees C. modeling of the transport phenomena related to
the PVP-TiO2 mats would prove useful in
Of note is the progression of the contact angle to
identifying and characterizing behavior going
~ 150o. This is first achieved at 175 oC, and is
forward.
replicated once more at 185 oC, within error. This
suggests that perhaps some reaction or surface It’s been a blast, Dr. Aston. I appreciate the
rearrangement occurs at 175 oC. From Simon’s opportunity to do research for you.
work, it is observed that super-hydrophobic
behavior is not seen until ~ 210 oC. Perhaps the
interval from 175 to 185 is not large enough to References:
properly observe this dynamic behavior change
with temperature. 1. Haaf, F.; Sanner, A.; Straub, A; Polymers of N-
vinylpyrrolidone: Synthesis, Characterization,
Conclusion & Future Work and Uses. Polymer Journal. 1985, Vol. 17,
Ultimately, Jack and I have had our fair share of 143-152.
both success and failure on this project. A year’s 2. Kazuhito, H.; Irie, H.; Fujishima, A.; Discovery
worth of technical difficulties have slowed our and applications of photocatalysis — Creating
progress. a comfortable future by making use of light
energy. Japanese Journal of Applied Physics.
However, we have shown that samples cured for 2005, Vol. 44, 8629-8285.
4 hours at 165 oC generally have a disordered
graphene structure, suggesting a reaction of PVP
to form said disordered carbon structures, as
there are no other available carbon sources to
react on the surface of the electrospun nanofiber
mats.
In addition, we were able to gain static contact
angles correlating the curation temperature to a
rough illustration of the hydrophilic/phobic
behavior of the mats cured under certain thermal
conditions. We were able to find a positive
correlation between curation temperature and
hydrophobic behavior, suggesting that perhaps
4
ChE 393: Chemical Engineering Projects