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High throughput synthesis of ceramic

S. Sood
, G. Zheng
, P. Gouma
Department of materials science and engineering, State University of New York, Stony Brook, New
York 11794-2275
High yield nanomanufacturing is important to turning nanotechnology advances into industrial products.
Electrospinning is a nanomanufacturing process that has been used to process advanced ceramic
nanofibers suitable for functional applications in sensing and catalysis, yet it has been limited in its
scalability thus far. In this study a novel design of the electrospinning process and related equipment that
could produce large qualities of ceramic nanofibers is described. This scaled-up approach to traditional
needle electrospinning allows the formation of 24 jets operating under the same conditions as those set in
the single jet lab-based process. Due to a thin metallic disc design, with tiny (0.5mm) holes drilled at the
bottom corner of the disc, all jets experience a uniform impact of the electrostatic field. Continuous
replenishment of the source disk at higher flow rates allows for high yields of nanofibers.
Ceramic nanofibers are structures of high aspect ratio and there single crystallinity can be of use
to various applications like sensing [1], catalysis [2] etc. Earlier published work [3] has focused on using
PVP and CA as model systems to develop the workability of the set up and compare the morphology of
nanofibers synthesized with those synthesized by traditional needle set up. This has demonstrated a yield
increase of 10 to 12 folds while still keeping the morphology comparable. The mechanism of synthesis as
described [3], suggests having an optimum 24 number of holes and electric field analysis has shown a
uniform distribution of electric field on the source disk which is critical for a multi jet set up. Although
many attempts have been made [5-9] to increase the yield of polymer fibers, this is a first attempt at a
high throughput set up for high yield of electrospun ceramic nanofibers.
In this study we demonstrate an application of this set up for producing high yield of ceramic
nanofibers. A composite material of polymer and ceramic sol is electrospun to form high aspect ratio
nanofibers of single crystal MoO
similar to that accompalished by Gouma et al. earlier [4]. The source
disk of the set up was modified from the earlier set up [3], the holes diameter was reduced to mm as
shown in figure 1 (a-d), and the holes were placed at the bottom corners of the disk at an angle of 45
degrees. Figure 2 shows the schematic of the set up used. The source is constantly replenished using a
syringe pump (Kd scientific) at a constant flow rate. The working distance although variable, is kept
constant at 15cm for this study. High voltage is applied between the source disk and collector cylinder to
synthesize ceramic nanofibers.

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Figure 1: The source disk is a critical component of the set up;
(a) Schematic showing the side view of the source disk. (b)
Schemtic showing the bottom view of the source disk. (c) The
bottom view of the source disk. (d) The top view of the source
Figure 2: Schematic of the set up
used to synthesize ceramic

Process Parameters
Ascertaining the process parameter is essential to control the nanofiber morphology. To do so we
use the polymer Polyvinylpyrrolidone (PVP) with ethanol as the solvent. The ceramic nanofibers are
synthesized using a composite of PVP and MoO
sol-gel. Thus using PVP as a reference system to
develop these parameters can give a fair control over the nanofiber synthesis. Capillary action generated
by the needle in traditional needle electrospinning technique is an essential component to get
encapsulation of MoO
sol-gel inside the PVP polymer. The modification done to the disk [3] by having
the holes at an angle of 45 degrees and placing them at the inside edge of the disk in addition to the
reduction of the hole diameter to mm provides the capillary action that helps encapsulate the sol inside
the polymer.
Figure 3 shows the dependence of voltage
on the nanofiber diameter, there seems to be a
parabolic dependence, with fiber diameter smallest
at 22kv and 30kv, although at lower concentration
of 0.08mM there was bead formation and at higher
voltage of 30kv there was high distribution of
nanofiber diameter as can be seen by larger error
bars, thus 24kv was chosen for MoO
synthesis. Figure 3 also shows negligible
dependence of concentration as compared to
voltage towards nanofiber diameter. The
production rate has a similar parabolic dependence
to voltage and the error bars shown are due to the
concentration variation. On average the production
rate is 2.5gm/hr.
Figure 4 (a-d) shows SEM micrographs for
nanofibers for different concentration and voltage,

Figure 3: Nanofiber diameter and production rates
plotted as a function of voltage and concentration
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as can be seen the diameter is more uniform for lower voltages as compared to higher voltages.
(a) 0.08mM & 22kV

(b) 0.12mM & 22kV

(c) 0.1mM & 24kV (d) 0.1mM & 26kV

Figure 4: (a-d) SEM micrographs for different voltages and concentration for PVP fibers.

Nanofiber Synthesis
nanofiber synthesis is one of the applications that such a set up can be used for. To
synthesize the nanofibers of MoO
we electrospin a composite material with composition similar to ref. 4.
This resulted in MoO
sol gel encapsulated (in PVP) nanofibers similar to ref. 4. The analysis uptil now
suggests the process parameters need to be modified for this set up as compared to that used in ref 4. The
voltage used was 24kv, with working distance being fixed at 15cm and flow rate of 0.34ml/hour. The
polymer fibers were burned off by heat treating the electrospun material at 500 degree Celsius in a tube
furnace for 8 hours.
Figure 5 shows comparison between the post heat treated nanofibers formed by the traditional
needle set up similar to earlier study [4] and those formed by the set up in this study. The figures 5 (a) and
(b) are the SEM micrographs of the nanofiber formed. As can be seen the yield as a percent of total was
less but as a quantitative comparison to the whole was 6 to 8-fold higher. This calculation was achieved
by using the SEM analysis and weight of nanofibers produced. The weight of material synthesized after
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heat treatment was 12-fold higher. The growth of the single crystal of MoO3 nanofibers seems to be as a
concentric cylindrical layers of fibers forming on top of each other and growing as layered structures as is
evident from figure 5 (d), seen at the top of the nanofiber.
(a) MoO
nanofibers produced using
traditional needle electrospinning
(b) MoO
nanofibers produced using
High- throughput electrospinning

(c) TEM of MoO
nanofibers synthesized
using TNE, (Inset) shows the selected area
diffraction, with the planes labeled for
<010> zone axis.
(d) TEM of MoO
nanofibers synthesized
using high throughput set up, (Inset)
shows the selected area diffraction, with
the planes labeled for <001> zone axis.

Figure 5: Electron microscopy comparison between the nanofibers synthesized by traditional needle
setup (a & c) and those synthesized by high througput set up (b & d).

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Figure 6(a) Crystal structure of orthorhombic MoO3 along with zone axis as marked. (b) X-Ray
diffraction of MoO3 orthorhombic nanowires synthesized by both traditional and high throughput
nanowires, the planes marked are from JCPDS #05-0508.

Figure 5 (c) and (d) show the TEM micrographs of a single nanofiber of MoO3 synthesized using
traditional needle electrospinning and the high thoughput set up in this study. In the inset is the SAD
patterns of each of the nanofibers which show there single crystal morphology. Figure 5(c Inset) can be
indexed to the orthorhombic phase of MoO3 (JCPDS #05-0508) which is the stable phase of MoO3. The
indexed planes have been labeled for zone axis <010> as shown in figure 6(a). Figure 5(d Inset) is also
indexed to the orthorhombic phase of MoO3 (JCPDS #05-0508), the indexed planes are labeled for zone
axis <001> as shown in figure 6(a) which is also the growth axis and the long axis of the nanofiber.
Figure 6 (b) gives the XRD of the sample for both traditional needle and high throughput set up.
As is evident from the sharp peaks, both the XRD are of the single orthorhombic phase of MoO3. The
planes are labeled for JCPDS #05-0508.
We have demonstrated in this study that this high thoughput set up can produce high yield high
quality nanofibers with controllable morphology. An application for producing ceramic nanofibers of
has been elaborated. We successfully produced single crystal MoO
nanofibers similar to earlier
study [4]. The yield was much higher at 6 to 8 folds and the morphology and crystallinity of the
nanofibers was not compromised. This could have important implication for example for producing
nanosensors for ammonia detection [10]. With higher yield of controllable nanofibers of orthorhombic
phase of MoO
, the hindrance to slow processing of nanosensors could be overcome.
The process development research was funded by the NSF-DMR grant # 1106168 and the
materials development research was funded by the NSF-IIS grant # 1231761. Research carried out (in
part) at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by
the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-
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