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Ravi (CNT Flow Sensors)
Ravi (CNT Flow Sensors)
Seminar Report
2004
Presented by
ACKNOWLEDGMENT
CONTENTS
Abstract 4
1. Introduction
5
2. CNT structures and General properties
6
3. CNT electronic properties
9
4. Fluid flow through CNTs
11
4.1 Effect of Liquid Flow through Carbon Nanotubes
11
4.1.1 Verifications of Theoretical Predictions
12
4.1.2 Specifications of the materials
17
4.3.1 Specifications of the materials
and Instruments used
18
4.3.2 Experimental setup, observations
and inferences
18
4.4 Applications
24
5. Conclusions
25
6. References
26
ABSTRACT
1. INTRODUCTION
As the state of art moves towards the atomic scales, sensing presents a major
hurdle. The discovery of carbon nanotubes by Sujio Iijima at NEC, Japan in 1991
has provided new channels towards this end.
A carbon nanotube (CNT) is a sheet of graphene which has been rolled up and
capped with fullerenes at the end. The nanotubes are exceptionally strong, have
excellent thermal conductivity, are chemically inert and have interesting electronic
properties which depend on its chirality.
The main reason for the popularity of the CNTs is their unique properties.
Nanotubes are very strong, mechanically robust, and have a high Young’s modulus
and aspect ratio. These properties have been studied experimentally as well as using
numerical tools. Bandgap of CNTs is in the range of 0~100 meV, and hence they
can behave as both metals and semiconductors. A lot of factors like the presence of
a chemical species, mechanical deformation and magnetic field can cause
significant changes in the band gap, which consequently affect the conductance of
the CNTs. Its unique electronic properties coupled with its strong mechanical
strength are exploited as various sensors. And now with the discovery of a new
property of flow induced voltage exhibited by nanotubes discovered by two Indian
scientists recently, has added another dimension to micro sensing devices.
There are two main types of nanotubes that can have high structural perfection.
Single walled nanotubes (SWNTs) consist of a single graphite sheet seamlessly
wrapped into a cylindrical tube (Fig. 1, A to D). Multiwalled nanotubes (MWNTs)
comprise an array of such nanotubes that are concentrically nested like rings of a
tree trunk (Fig. 1, E).
The structure of a nanotube can be defined using a roll-up vector r and/or a chiral
angle θ as shown in Fig. 2. The rollup vector can be defined as a linear combination
of base vectors a and b of the basic hexagon r = na + mb with m and n being
integers. The roll-up vector is perpendicular to the axis of the nanotube. In Fig. 2,
the shaded zone is the area which is rolled up along an axis perpendicular to the
roll-up vector. Different types of nanotubes are defined by the values of m and n
thus chosen. Three major categories of nanotube structures can be identified based
on the values of m and n:
m=n “Armchair”
m = 0 or
n=0 “Zigzag”
m≠n “Chiral”
C.
Fig 2: Relation between the hexagonal carbon lattice and the chirality of Carbon
Nanotubes.
(A) The construction of a carbon nanotube from a single graphene sheet. By rolling
up the sheet along the wrapping vector C, that is, such that the origin (0, 0)
coincides with point C, nanotube is formed. Wrapping vectors along the dotted
lines lead to tubes that are zigzag or armchair. All other wrapping angles lead to
chiral tubes whose wrapping angle is specified relative to either the zigzag direction
(q ) or to the armchair direction (F= 30 ْ - q ). Dashed lines are perpendicular to C
and run in the direction of the tube axis indicated by vector T. The solid vector H is
perpendicular to the armchair direction and specifies the direction of nearest-
neighbor hexagon rows indicated by the black dots. The angle between T and H is
the chiral angle F.
( B ) Schematic of a two-dimensional graphene sheet illustrating lattice vectors a1
and a2, and the roll-up vector Ch = na + mb. The limiting cases of (n, 0) zigzag and
(n, n) armchair tubes are indicated with dashed lines. As represented here, the angle
between the zigzag configuration and Ch is negative.
(C) Chiral nanotube showing angle F.
heating. Phonons also propagate easily along the nanotube: The measured room
temperature thermal conductivity for an individual MWNT (3000 W/m K) is
greater than that of natural diamond and the basal plane of graphite (both 2000
W/m K). Superconductivity has also been observed, but only at low temperatures,
with transition temperatures of 0.55 K for 1.4-nm-diameter SWNTs and 5 K for
0.5-nm-diameter SWNTs grown in zeolites. Small-diameter SWNTs are quite stiff
and exceptionally strong, meaning that they have a high Young’s modulus and high
tensile strength. With the total area per nanotube in a nanotube bundle for
normalizing the applied force to obtain the applied stress, the calculated Young’s
modulus for an individual nanotube is 0.64 TPa, which is consistent with
measurements. Because small-diameter nanotube ropes have been extended
elastically by5.8% before breaking, the SWNT strength calculated from the product
of this strain and modulus is 37 GPa, which is close to the maximum strength of
silicon carbide nanorods (53 GPa) This modulus of 0.64 TPa is about the same as
that of silicon carbide nanofibers (0.66 TPa) but lower than that of highly oriented
pyrolytic graphite (1.06 TPa).
More impressive and important for applications needing light structural
materials, the density-normalized modulus and strength of this typical SWNT are,
respectively,19 and 56 times that of steel wire, respectively, and 1.7 times that of
silicon carbide nanorods. The challenge is to achieve these properties of individual
SWNTs in nanotube assemblies found in sheets and continuous fibers.
the Fermi level crosses i.e. the band gap energy merges. Otherwise it is expected
the properties of tube will be that of semiconductor. The table below (Table 1) is
the observations of experiments done on nanotubes by Scanning tunneling
microscope (STM) and Scanning tunneling spectroscopes (STS). The dependency
of energy gap or band gap energy on chiral angle and diameter is clear from the
observation below.
Table 1. Here d is the nanotube diameter; F is the chiral angle; E gap is the apparent
band gap in the STS I–V spectra and dE is the shift of the Fermi energy due to
doping of the tube by the substrate. Note that a chiral angle 0ْ denotes armchair
nanotube and an angle of 30ْ a zigzag tube. The flat Au surface allowed the
diameter d of the nanotubes to be determined with an accuracy of 0.1nm by
measuring the tube heights relative to the surface. A possible systematic uncertainty
in determining the diameter is due to a difference in barrier heights for the gold
substrate and the tubes. The wrapping angle F can be determined with an accuracy
of 1ْ. Accuracy in F is limited by the curvature of the tubes. A combination of high
accuracy in both F and d (0.05 nm) is required for an unambiguous identification of
the n, m indices. Accuracy in Egap and dE is 0.05–0.1 eV. For this sample a shift
in the Fermi energy towards the conduction band was observed, instead of a shift
towards the valence band as observed in the other samples.
From the table above, two categories can be distinguished: one with gap values
around 0.5–0.6 eV, the other with significantly larger gap values. The first category
of tubes is identified as the semi conducting type, the second as metallic tubes.
Another noted property of nanotube is that oscillation of Band Gap energy when
magnetic field is applied parallel to the tube axis. It has been showed theoretically
that the band gap energy would oscillate with increasing magnetic field, so a metallic
tube is converted to a semiconductor and then metallic again, with a period depending
on the magnetic field strength.
Recently there has been extensive study on the effect of fluid flow through
nanotubes,which is a part of an ongoing effort worldwide to have a representative
in the microscopic nano-world of all the sensing elements in our present
macroscopic world. Indian Institute of Science has a major contribution in this
regard. It was theorotically predicted that flow of liquid medium would lead to
generation of flow-induced voltage. This was experimetally established by two
Indian scientist at IISc. Only effect of liquid was theorotically investigated and
established experimentally, but effect of gas flow over nanotubes were not
investigated, until A.K Sood and Shankar Ghosh of IISc investigated it
experimentally and provided theorotical explanation for it. The same effect as in
case of liquid was observed, but for entirely different reason.
These results have interesting application in biotechnology and can be used in
sensing application. Micro devices can be powered by exploiting these properties.
molecules in the flowing liquid. They argued, however, that the latter mechanism
creates a current that is five orders of magnitude smaller than the current that results
from the phonon-induced electron drag.
These predictions were experimentally verified by A K Sood and Shankar
Ghosh of IISc. In sharp contrast, Sood and coworkers have found that the behaviour
is highly sub linear where the induced voltage fits a logarithmic velocity
dependence over nearly six decades of velocity. Strong dependence of induced
voltage on polarity and ionic nature of the liquid and relatively weak dependence on
its viscosity was revealed from this experiment.
Experimental setup, observed results and hence the inference gathered from the
observations, dependencies of voltage induced on various factors that has been
observed are explained in following sections
The SWNT bundles used for the experiment were prepared by electric arc
method, followed by purification process. The dimensions and physical properties
of samples are listed below:
Sensor using this tube was prepared by densly packing nanotubes between two
metal electordes. The dimensions of Sensor:
The specimen was placed inside glass tube of innner dia 0.03 and length 0.9m ,
kept vertically. Voltage mesurment were used by using KEITHLEY 2000
multimeter.
Hydrocloric and Glycerine to increase polarity and viscocity of fluid media
respectively.
Fig 4 :
Experimental setup where R is the
reservoir, L is the valve controlling
the liquid flow, S is the cylindrical
glass flow chamber, and G is the
Voltmeter.
When the sample was immersed in water at rest, a voltage (~1 mV) developed
along the sample as an electrochemical potential difference at the interface of the
SWNT bundle with the metal electrodes. This offset voltage was subtracted from
the voltage measured at finite velocities of the liquid to obtain the flow-induced
voltage. The voltage developed only along the flow direction; no voltage was
generated in the direction perpendicular to the flow (i.e., along the width).
Figure 5 shows the observed dependence of the flow induced voltage on flow
velocity of water. Even at a
very low speed of 5x10-6 m/s, a
voltage of 0.65 mV was
generated. The solid line in
Fig5 is a fit to empirical
relation:
V= a log(ub+1)
velocity for a series of fluid mixtures. A notable effect is the strong dependence of
the flow-induced voltage on the ionic strength of the flowing liquid. It can be seen
that for u = 10-4 m/s, the voltage for 1.2 M HCl is about five times that for water.
A comparison of expected results as per Král and shapirov and experimental results
are compared in following paragraph,
They considered metallic nanotubes that were densely packed in two layers
separated by a layer of water of thickness d (~10 nm). In their mechanism, the
force exerted by the liquid with a flow velocity u on the surface of the nanotubes
is:
F = (hu/d) X interface periphery X interface length.
This force results in the steady-state quasi-momentum (p) transfer to the
phonon bath was calculated using p ~ Ft where h is the shear viscosity of the
liquid, t known as phonon umklapp time. Using this value of p, the resulting
current was calculated, the results showed that current depends on viscosity of
fluid and flow velocity Vs flow induced voltage would be linear in nature. Using
glycerol mixed with water at ratios 88:12 and 75:25 having h= 113 and h= 234
As ions and polar molecules have fluctuating Coulomb fields, Sood and
coworkers have assigned the observed behaviour to scattering of free carriers by
these fluctuating fields. The exact model is termed as ‘the pulsating asymmetrical
ratchet model’. The terms describe the phenomenon itself, whereby ions flowing
past a certain point in the nanotube produce Coulomb pulses while the asymmetry
is provided by the velocity gradient at the liquid–solid interface.
An important point must be made regarding the direction (polarity) of the
voltage and current in relation to the fluid flow direction. In the experiments, it
was observed that the electric current and the fluid were flowing in the same
direction. In a linear response theory based on the viscous drag (the phonon
wind), the particle current has the same direction as the fluid flow velocity, and,
therefore, the sign of the electric voltage and current is determined by the sign of
the charge carriers (electron or hole). Thus, for the hole like carriers, the induced
voltage and current have the same direction as the flow velocity. This, however, is
not the case for a pulsating ratchet model in general. For a given direction of the
asymmetry, the direction of the voltage is independent of the sign of the charge on
the carriers. It will, of course, depend on the sense of the bias (asymmetry) of the
ratchet potential. In a polar fluid of a given ionic strength, such as concentrations
of H+ and OH– ions (along with their hydration shells), it is expected to have
ratchet potentials of either sign (bias). The net effect is then determined by the
dominant ratchet. What is important here, however, is that there is no a priori
(symmetry) reason to expect the oppositely biased ratchets to give an exact
cancellation.
4.2 Applications
used to make a voltage and current source in a flowing liquid environment, which
may have interesting biomedical applications.
In bio medical applications it is speculated that carbon nanotubes can be used
to power coronary heart pace makers using flowing blood as source of power this
would make the use of batteries in coronary heart pace makers obsolete. The
results using blood have shown encouraging results.
Another application would be as a chemical sensor which can be used to
check the polarity, acidity and detecting any impurities (that are polar in nature)
present in the liquid media.
If CNTs become cheaper and economically viable then it can be used in bulk
to produce electricity in small scale using flowing water as source of active media.
The effects of Gas flow over CNTs were not studied both theoretically and
experimentally, until A K Sood and his Co workers investigated on it. Papers
pertaining to these works were published in Physical Review letters on 20 Aug
2004. Research works on these findings and possible applications are being
investigated by Sood and coworkers.
The same effect of flow induced current/voltage observed with liquid media
was observed when gas medium was used. Although the effect is same, yet the
reason for it is completely different from that of liquid flow. Further this effect is
not confined to nanotubes, same effect is observed in wide range of solids
including semiconductors, metals for wide range of velocities.
The underlying principle is an interesting interplay of Bernoulli’s Principle
and Seebeck effect. Pressure differences along the streamlines give rise to
temperature difference along the tube which, in turn produce the measured
voltage. Unlike in case of liquid the flow induced voltage in gas, depends not only
on flow velocity but also on the orientation of specimen. The experimental setup,
observation, findings, inferences and theory behind this phenomenon is explained
in the following sections.
To establish the ubiquity of this phenomenon variety of solids were used, they
include nanotubes, semiconductors and metal which are described below:
kept at an angle α=π∕4 with respect to the horizontal axis to achieve the optimal
Fig 7 : (a) Schematic of the experimental setup. The flow rate at the exit point is
deduced from the measured flow rate at the side port using the rotameter. (b)
Sample: shaded portions mark the electrodes. The positive terminal of the
voltmeter is connected to the right ® of the sample of active length d kept at and
angle α=π∕4 with respect to the horizontal axis.
Figure 8 below shows the voltage across the n-Ge sample as a function of time
when the gas flow (u= 7 ms) over the sample is switched on and off. The gas used
here is argon. Data for the steady flow voltage V for a variety of samples and flow
velocities are shown in Figs. 9 and 10. It can be clearly seen that for nitrogen gas
over p-Si, n-Si, n-Ge, p-Ge, SWNT, MWNT and graphite, the voltage V
generated varies as u2 over a wide range of u ( as does the current, not shown).
Figure 9 shows the fit to V= Du2 with fit parameter D given in Table2. This is
even clearer in Fig 9 which shows the same data plotted versus M2, where M is the
Mach number given by M=u / c, c being the sound velocity (=333 m/s for
nitrogen and 323 m/s
for argon at 300K).
The solid lines fit to
curve V=AM2, where
A is a fitting parameter
also given in Table 2.
Experiments using
polycrystalline copper
sheet for which the
slope A is very small.
It can be seen that the
sign of P-type Si and SWNT is opposite to that for n-type Si, n-type Ge, graphite
and copper. SWNT samples are usually unintentionally p-doped, which can
explain the sign of the flow-induced voltage which was found to be the same for
SWNT and p-Si. The
inset in fig10 shows the
slope A versus the known
Seebeck coefficient S of
the samples of the same
d, as given in Table 2.
The coefficient depends
linearly on S, as shown
by fitted line in the inset,
with slope=60K.
Figure 10 shows the
generated voltage V over
a large range of values of
M2 for the flow of argon (solid squares) and nitrogen gases (open circles) over n-
Ge. A change in slope is clearly seen around M2≤.05 (Called regime 1) is higher
for argon than for nitrogen.
The ratio of slopes [A (argon) / A (nitrogen) = 1.2]. That there are actually
two M2 regimes is clear from our theoretical analysis of the mechanism behind the
generation of electrical signal induced by the flow of gases over the solids, and is
discussed below. For the adiabatic steady inviscid flow of a gas, Bernoulli’s
equation gives the pressure difference along a streamline in terms of Mach
number M as:
CP (CV) being the specific heat at a constant pressure (volume). The values of
g for argon and nitrogen are 1.667 and 1.404, respectively. In eq1 P0 is the
maximum pressure at a point on the streamline where velocity is zero . Such a
point is the leading edge on the surface of the sample past which the gas is
moving and is called the stagnation point. For the sample geometry shown in Fig.
7 (b), the pressure difference between the two ends of the active sample exposed
to the gas flow (i.e., without the electrodes) is hence:
The subscripts L(R) denote the left (right) of the active sample when the gas
flows from left to right. From the ideal gas law, the fractional temperature
difference DT/T is related to the pressure difference DP/P and the density
difference Dr/r as
DT/T=DP/P-Dr/r. When M<<1, the change in density of the gas is
negligible, i.e., the fluid is essentially incompressible and hence DT/T=DP/P.
Therefore, the temperature difference along a streamline between two points
separated by distance d for M<<1 (called regime I) is:
Where, DT= TL - TR > 0. The gas flowing past the sample kept at an angle a
with respect to the horizontal axis corresponds to an accelerating flow and hence
MR>ML.The tangential component of the velocity u of the outer flow depends on
the streamline distance x measured along the flat boundary as:
For this geometry a= pi/4 and hence u(x) .The temperature difference along
the streamline in the gas flow will induce a temperature difference in the solid
along the flow direction. The temperature difference, in turn, will result in a
voltage difference V, defined as VL – VR, due to the Seebeck effect. Thus:
Where, S
is the Seebeck coefficient of the solids, positive for p-type and negative for n-type
materials. The factor k depends on the specific interactions between the gas and
the solid surface as well as on the boundary conditions of the temperature
difference between the gas and the solid. In nonrarefied gases, the boundary
conditions at the surface of a solid is that the temperatures of the gas and solid are
equal, in which case k=1. But this boundary condition applies only if the mean
free path of the gas molecules is vanishingly small. The factor k takes into account
all the differences from this ideal boundary condition. The present phenomenon of
voltage generation by flow of gases is not applicable to the flow of liquids where
the viscous drag dominates.
Beyond a certain value of M (~0.2), called regime II the density changes of the
gas should be taken into account, which gives:
And hence:
3. Another property can be deduced from the equations above that for
substance that has S=0 will have no induced voltage. Results with platinum
as specimen have showed no induced voltage (for Pt S~0).
Hence, the theoretical predictions deduced are consistent with the experiment.
4.4 Applications
The experiments clearly suggest that a sensor to measure the flow velocity of
the gases can be made based on the generated electrical signal. It is an active
sensor which gives direct electrical response to the gas flow. This should be
compared with the widely used gas flow sensor based on thermal anemometry,
wherein the fluid velocity is sensed by measuring changes in heat transfer from a
small, electrically heated sensor (wire or thin film) exposed to the fluid. Thermal
anemometry works on heat balance equations and hence any small changes in the
temperature, pressure, or composition of the gas can cause erroneous readings.
Such effects are minimum or can be easily taken into account in the sensors based
on the direct generation of flow-induced voltage or current in the sensor material.
The magnitude of generated voltage can be easily scaled up by using series and
parallel and connections of sensing elements. This suggests that flow energy can
be directly converted into electrical signal without any moving part, thus having a
potential for application in generating electricity.
Ajay Sood and his coworkers have shown that this property can be exploited
for construction of nanotube based vibrational sensor in liquids and as
accelerometer. The SWNT based accelerometer has so far measured the frequency
range 0.5 Hz to 1 kHz and the minimum detectable acceleration by the
accelerometer is 10-3 g.
5. CONCLUSION
6. REFERENCES