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ISRO-IISc Space Technology Cell

Indian Institute Science, Bangalore

31st Annual Symposium on


Space Science and Technology
8-9 January 2015
Abstracts

31st Annual Symposium on Space Science and Technology

Abstracts

1.

A setup for the study of thermal properties of nanoscale devices of ultrathin layered materials

2.

Low temperature giant magnetocaloric effect in magnetic ferroelectric GdMnO3 single crystals

3.
4.
5.
6.
7.
8.

9.

Suman Sarkar, Kazi Rafsanjani Amin and Aveek bid

Aditya A. Wagh, P. S. Anil Kumar and Suja Elizabeth

Anomalous piezoelectric response in BaTiO based lead-free piezoceramics


Ajay Kumar Kalyani, Kumar Brajesh and Rajeev Ranjan

Geospatial scenario based modelling of urban revolution in five major cities in India
T.V. Ramachandra, Bharath H. A, Vinay S., Venugopal Rao K and. N V Joshi

Quantum communication and security using entangled states


Ankur Raina, Shayan G. Srinivasa, Chithrabhanu P., Aadhi A., Shashi P. and R. P. Singh

Investigation of vegetation changes in the arid Trans-Himalayan ecosystem of northern India


Sumanta Bagchi, Ekta Gupta, and Karthik Murthy

Study on self-assembly of donor-acceptor-donor molecular materials and melamine


Nileshi Saraf, Joydeep Dhar and Satish Patil

High-resolution image restoration and enhancement using GPU


Nithish Divakar and R. Venkatesh Babu

Turbulence-transport-chemistry interaction in statistically planar premixed flames in near isotropic


turbulence
A. Harshavardhana U, Swetaprovo Chaudhuri and K. N. Lakshmisha

10.

Thermally activated unimolecular decomposition mechanisms of dimethylnitramine-aluminum


(DMNA-Al) and dimethylnitramine-Zinc (DMNA-Zn) complex
Anupam Bera and Atanu Bhattacharya

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31st Annual Symposium on Space Science and Technology

Abstracts

11.

Investigation of spatial and temporal dynamics of vegetation in semi-arid-ecosystems

12.

Development of semiconductor nanocrystals for photovoltaics

13.

Die level 3D packaging of hybrid systems

14.

A small volume droplet dispenser based on electrohydrodynamic pulling

15.

Synthesis optical and electrical characterization of II-VI colloidal quantum dots for IR applications

16.

Movement strategies for commensalism: coexistence of meso-carnivores in


human-dominated landscapes

Sumithra Sankaran, Sabiha Sachdeva, Ashwin Viswanathan and Vishwesha Guttal

Biswajit Bhattacharyya, Rekha Mahadevu and Anshu Pandey

N. P. Vamsi Krishna and Prosenjit Sen

K. R. Sreejith, and G. R. Jayanth

Atul Prakash Abhale , Abhijit Chatterjee, Naresh Babu, Arup Banerjee and K.S.R. Koteswara Rao

Maria Thaker and AbiTamimVanak

17.

Development and performance evaluation of a PCM coupled heat pipe

18.

Theoretical and computational study of frictional effects in viscoelastic and generalized


elastic contacts

G. M. Karthik, Girish Kini, A. Ambirajan and P. Kumar

D. Satish Kumar and Narayan K. Sundaram

19.

Combustion studies of composite propellants containing nano- burn rate catalysts

20.

Electromagnetic field enhancement in sub-nm gaps

21.

Modelling primary atomization of liquid jets

Charlie Oommen and R Arun Chandru

Debadrita Paria and Ambarish Ghosh

Santosh Hemchandra

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31st Annual Symposium on Space Science and Technology

22.

Abstracts

Development of an optimization based image processing software system for Indian forest resource
assessment using Radar Imaging Satellite (RISAT-1) Images
S N Omkar and G. Narayana Naik

23.
24.

25.

Numerical simulations of Darcy-Brinkman-Forccheimer equations for flow in porous media


Karthick M and Gaurav Tomar

Double diffusive convection in the earths core


Venkatesh Gopinath and Binod Sreenivasan

Utilizing ionic liquid and mixed solvent electrolytes to synthesize polymer electrolytes
for lithium-based batteries
Sudeshna Sen, Sneha Malunavar, C. Gouri and Aninda J. Bhattacharyya

26.

Sparsity-based cross-terms-suppressed time-frequency distribution of multi-component linear


frequency modulated signals
Shreyas Hampali, Subhankar Ghose, and Chandra Sekhar Seelamantula

27.

Investigating the origin of the Indian ocean Geoid low

28.

Evolution of mesoproterozoic suture zones western India: Implications on India-Madagascar correlations

Attreyee Ghosh

C. Ishwar-Kumar and K. Sajeev

29.

Estimation of soil hydraulic properties in a catchment using agro-hydrological models and microwave remote sensing
K. Sreelash, M. Sekhar, S. K. Tomer, S. Bandyopadhyay and M.S. Mohan Kumar

30.

Tribological properties of polytetrafluorethylene at cryogenic temperatures


D.S. Nadig, V.K. Pavan and Paul P. George

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31st Annual Symposium on Space Science and Technology

Abstracts

31.

Portable imaging flow analyzer for biological research applications in space

32.

Processing of metallic thermal interface materials using liquid phase sintering followed
by accumulative roll-bonding

Veerendra Kalyan Jagannadh and Sai Siva Gorthi

Deepak Sharma, Rajesh Kumar Tiwari, P. Ramesh Narayan and Praveen Kumar

33.

Development of nanoparticle based radiation detectors for space applications


B.H.M. Darukesha, V. Radhakrishna, M. Ravindra and K. Rajanna

34.

Spatial coherence of tropical rain

35.

Amorphous silicon carbide thinfilms by pulsed DC magnetron sputtering for micro


electro-mechanical systems (MEMS) applications

R. Ratan, V. Venugopal, J. Sukhatme and R. Murtugudde

Habibuddin Shaik, M.A. Sumesh and G. Mohan Rao

36.

Low temperature electrical transport studies on carbon nitride films prepared by


chemical vapour deposition
K. Ramesh, M. Prashantha, R.Venkatesh, N. Naresh and M.V.N. Prasad

37.

Generation of BPSK/QPSK modulated microwave signals using optical techniques

38.

Development and characterisation of nano-porous aluminium alloy surfaces

K R Yogesh Prasad, T Srinivas, Gopal Hegde and Abdul Hameed

Arti Yadav, Subrata Chakarbarti, A. Manimaran, M.S Bobji

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

A setup for the study of thermal properties of nanoscale devices of


ultrathin layered materials
Suman Sarkar, Kazi Rafsanjani Amin and Aveek bid
Department of Physics
Indian Institute of Science
Abstract: The aim of the proposed project
is to develop a research facility for
exploring thermal properties (Seebeck
effect, thermal conductivity etc.) of
nanoscale devices based on different forms
of layered semiconductor materials like
graphene and Bi2Se3/Bi2Te3. This will be
integrated to an electrical transport
characterization system to allow a
comprehensive study of transport and
thermodynamic
properties
in
nanostructured materials. In addition we
would like to measure fluctuations in
thermal conductivity to probe the effect of
defects on thermal conductivity of
technologically important materials. The
set up developed by us over the last few
months is capable of measuring voltage
fluctuations as low as 10-20 V2/Hz over a
wide band-width. We are currently in the
process of integrating the system with a low
temperature cryostat that will enable us to
carry out the measurements of thermal
conductivity over a temperature range 1.5300K. We have also done preliminary
measurements of single layer graphene
devices using this set-up.

of any metal. In addition to an exceptionally large


thermal conductivity, graphene is highly conductive
even in very low carrier density regimes2 and hence has
extremely low levels of Johnson-Nyquist thermal noise
as compared to semiconductor based sensors. It also
has fewer kinds of defects and hence has intrinsically
low levels of 1/f noise3 arising out of thermal switching
of defects. It is relatively easy to make four terminal
measurements on graphene strips making contact
resistances much easier to deal with than for example
in carbon nanotubes which share almost all other
advantages of graphene. On the mechanical side,
suspended graphene flakes have been shown to have a
very high Youngs modulus (~ 1TPa) and to have a
much higher elasticity than membrane materials like
silicon nitrate commonly used in NEMS4.

I. INTRODUCTION

The measured thermal conductivity of graphene on


SiO2 substrate, although very high, is still lower than
the theoretical predicted value. In order to understand
the factors that limit the thermal conductivity of
substrated graphene below the theoretical limit
extensive measurements of the fluctuations (or noise)
in thermal conductivity of graphene need to be carried
out. To the best of our knowledge no such studies have
been carried out till date either in pristine graphene
or in graphene based matrices.

In recent years layered semiconductor materials like


graphene and MoS2 have emerged as possible
candidates for post silicon technologies. Although
most present studies focus on their electrical properties,
their unique thermal properties make them very
interesting candidate for potential applications. It has
been proposed that the thermal conductivity of
graphene is highest ever measured in any material. For
graphene on silicon-dioxide substrate the thermal
conductivity is about 500W/mK, which is much
higher than that of bulk gold. For suspended graphene
devices the value of thermal conductivity can be as
high as 5000W/mK1, almost ten timed higher than that

Both graphene and single-walled carbon nanotubes


exhibit excellent electrical conductivities and large
specific surface areas. Calculations show that a
covalently bonded graphene/single-walled carbon
nanotube hybrid material would extend those
properties to three dimensions. There have been several
proposals for exploiting the unique properties of
graphene-CNT hybrid for making body of aircraft.
Such a hybrid would have a reasonably good electrical
conductivity an important criterion for spacecraft
safety. The large thermal conductivity of the matrix
could provide a strong, light weight and thermally
conducting outer shell for reentry vehicles. A study of
the thermoelectric figure of merit of the material would
give an indication of the applicability of these materials
as waste energy harvesters.

.
II. METHODS
We have taken two different approaches to measuring
the thermal conductivity of layered semiconducting

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materials. In the first approach, we have optimized a


technique to fabricate microheaters that have extremely
large intrinsic thermal time constants. This technique is
essential for devices where the thermal conductivity is
less than that of the substrate (for example
Bi2Se3/Bi2Te3 on SiO2).This will enable us to detect
small changes in the thermal signature of single or few
layered materials. The thermal conductivity of layered
semiconductors vary over several orders of magnitudefrom about 1W/mK in the case of BiSe to about 5000
W/mK for suspended graphene devices. The
microheaters have to be optimized to handle this entire
dynamic range of thermal properties. Figure 1 shows
the SEM image of one such device.

Figure 2: Electronic contribution to the thermal conductivity


of graphene

We are currently also studying the thermal


conductivity of MoS2 - a material which is interesting
for many practical applications. A typical image of the
device is shown in figure

Figure 1: Microheater for measuring thermal conductivity of


layered materials.

In the second approach we are measuring the thermal


conductivity of graphene and BiSe systems using the 3
Omega technique. This is useful for devices where the
conductivity of the sample is larger than that of the
substrate (for example - graphene on SiO2 substrate)
Data for a typical measurement on graphene single
layer is shown in Figure 2. The data is plotted as a
function of the number density of charge carriers
introduced in the system by a back gate. We note that
as the carrier density increases the electronic
contribution to thermal conductivity increases as is
expected from Wiedemann-Franz law.

A. Balandia et.al., Nano letts. 8, 902 (2008).


K. S. Novoselov et.al. Nature 438, 197 (2005).
3
P. Dutta et.al. Rev. Mod. Phys. 53, 497 (1981).
2

Figure 3: Optical microscope image of multi-layer MoS2


device.

III. CONCLUSION
We are in the process of developing the necessary
techniques for measuring thermal properties of single
layered and few layered semiconducting materials. The
measurements are extremely challenging because in
most cases the thermal signal from the substrates can
be orders of magnitude larger than that from the sample
under test. We have done preliminary tests and are now
in the process of measuring thermal properties of
graphene, MoS2 and BiSe single and few layered
devices.

I. W. Frank et.al. J. Vac. Sci. Technol. B 25 2558


(2007

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Low Temperature Giant Magnetocaloric Effect in Magnetic Ferroelectric


GdMnO3 Single Crystals
Aditya A. Wagh,P. S. Anil Kumar, and Suja Elizabeth
Department of Physics, Indian Institute of Science,
Bangalore 560012, India

In a typical magnetic material,


magnetic sublattice is sensitive to external
magnetic fields and, due to this coupling, the
magnetic part of the entropy changes with
variation of magnetic field. Magnetocaloric
effect (MCE) is generally demonstrated by
isothermal change in magnetic entropy or
adiabatic change in temperature with change
in magnetic field. At room temperature,
GdMnO3 is paramagnetic and paraelectric.It
exhibits complex magnetic phase diagram
(H-T phase diagram).1, 2 At 42 K (TN(Mn)),
paramagnetic
phase
transforms
to
sinusoidally-modulated
collinear
antiferromagnetic phase with modulation
vector directed along the b axis which is
incommensurate in nature where no
spontaneous
electric
polarization
is
1,
observed. . The competing AFM and
ferromagnetic exchanges in ab-plane cause
magnetic frustration, which in turn is
responsible for long wavelength modulated
AFM spin structures at low temperature.3, 4
Near 23 K (Tlock), the system transforms to a
CA-AFM phase with weak canting
component of Mn3+ spins lying along c
axis.2 GdMnO3 is known to display AFM
ordering of rare earth (Gd3+) sublattice when
the temperature is lowered further.2
Single crystals of GdMnO3 were
grown using optical float-zone method. A
four-mirror image furnace (argon ambience;
flow rate ~ 1 lit/min) was employed which
yields crystals of typical length 36 mm at
growth rate of ~ 5mm/h. A photograph of the
grown crystal is shown in Fig.1.

field protocol as shown in Fig.2.


Magnetization as a function of temperature
data were extracted from measured M-H
isotherms and used for the calculation of
SM.

Fig.1: Single crystal of GdMnO3


M-H isotherms were recorded along
the three crystallographic axes using zero-

The temperature evolution of


numerically calculated SMfor the three axes
is plotted in Fig.3. The magnitude of

Fig.2: (a) Typical set of zero field-cooled


magnetization field (M-H) isotherms
recorded at short temperature intervals
along (a) `c' axis, (b) `a' axis and (c) `b' axis.

Project Number:ISTC/PPH/SE/325

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SMincreases prominently below Tlock


transition and records the highest value in the
proximity of 7 K. This is likely to occur due
to enhanced polarized paramagnetic moment
of Gd3+ from weak ferromagnetic component
of the canted Mn3+ moment in this phase.
Further decrease in the temperature leads to a
sharp fall in SMresulting in an asymmetric
broad peak. An anomaly is observed in
SMin the form of a sharp peak at 5 K along
`c' axis, but it is feeble in other axes. This
feature becomes pronounced as the field is
increased and is perceived to be due to spin
reorientation of the rare earth sublattice.
Above a critical field, along `b' axis, the
ferroelectric phase (ab-cycloidal) stabilizes
which then transforms to paraelectric phase
with increase in temperature. This manifests
in step-like decrease in the SMvs T (shown
by arrow in Fig.3.c. The field-induced

transformation (FOPT) to ferroelectric phase


(i.e. from CA-AFM to ab-cycloidal phase)
along 'b' axis is clearly discernible as a steplike feature in the plot of field variation of
SMFig3.d. The distinct step-like feature,
observed along `b' axis, is absent along other
axes.The calculated value ofSM is very
large (~ 31.8 J/kg K) along 'c' axis for the
field variation 0-80 kOe at 7 K. The
anisotropy inSMVs T is not strong (At ~7
K, SM = 29.1 and 25.7 J/kg K for 'a' and 'b'
axes, respectively). From the phase diagram,
'c' and 'a' are 'easy' and 'hard' axes. However,
at higher fields along 'b' axis the system
exists in ferroelectric cycloid AFM phase. In
the respective ab-cycloid spin structure, the
'b' axis could be considered the 'hard' axis. It
is prudent to compare SMvalues in various
AFM phases.

Fig. 3:Temperature evolution of estimated SM for field variation up to 80 kOe along


different crystallographic axes: (a) `c'axis, (b) `a' axis and (c) `b' axis. (d) ) Field variation of
SM along `b' axis. The inset shows the magnified view of the low-field region.

References
[1] T. Kimura, et al.,Physical ReviewB 71, 224425 (2005).
[2] J. Hemberger, et al., Physical Review B 70, 024414 (2004).
[3] M. Mochizuki, N. Furukawa, Physical Review B 80, 134416 (2009).
[4] J. Ribeiro, Ferroelectrics 368, 114 (2008).

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Anomalous Piezoelectric Response in BaTiO3based Lead-free Piezoceramics


Ajay Kumar Kalyani, Kumar Brajesh, Rajeev Ranjan
Department of Materials Engineering, Indian Institute of Science, Bangalore-560012, Karnataka, India
Abstract
The effect of Zr, Hf and Sn substitutions in BaTiO3has
been investigated at close composition intervals in the
dilute concentration limit. Detailed structural analysis
by x-ray and neutron powder diffraction revealed that
merely 2 mol percent of Zr, Sn and Hf stabilizes a
coexistence of orthorhombic (Amm2) and tetragonal
(P4mm) phases at room temperature. As a consequence
all the three systems show substantial enhancement in
the longitudinal piezoelectric coefficient (d33), with
Snmodification exhibiting the highest value ~425 pC/N.

I.

INTRODUCTION

Research on lead free piezoelectric materials have


received considerable momentum in the recent past
because of serious environmental concerns with regard to
the toxicity of the commercial piezoelectric, lead zirconate
titanate (PZT), which contains ~60 weight percent of lead.
Lead free compounds such as Na1/2Bi1/2TiO3 (NBT).
(K,Na)NbO3 (KNN) and BaTiO3 (BT) have been
extensively investigated in pure and modified form with
renewed interest. Both BaTiO3 and KNbO3 exhibit the
same sequence of phase transformations, namely cubic(C)
tetragonal (T) orthorhombic (O) rhombohedral
(R) on cooling from high temperature [1]. Though the high
Curie point of KN (Tc ~410 C) as compared to BT (Tc
~120 C) is attractive, the difficulties associated with the
fabrication of dense ceramic bodies, among other issues,
have not yielded encouraging piezoelectric properties in
KN based systems. The best property has been reported for
a textured Li and Sb modified (K,Na)NbO3 [2]. Very high
electric field driven strain values have been reported for
certain compositions in the quaternary (K,Na)NbO3-NBTBT system [3]. BT based ceramics have received attention
only in the recent few years after discovery of anomalous
properties in the (Ba, Ca)(Ti, Zr)O3system [4]. The
essential idea used by Ren et al is to bring about a triple
point morphotropic phase boundary (TMPB) state, i.e a
coexistence of tetragonal, orthorhombic and cubic
phasesclose to room temperature. Though this approach
can drastically increase the piezoelectric property due to
the systems proximity to triple point criticality, the
piezoelectric properties would drastically deteriorate by
slight increase in temperature since one of the phase at the
triple point is cubic phase and therefore non-ferroelectric
in nature. From this standpoint, it is always desirable to
have piezoelectrics with Curie point well above room
temperature.

The dielectric and piezoelectric properties of


modified and pure BaTiO3 ceramics have been
documented by Jaffe and Jaffe [1]. Of particular interest
are the compositional modifications which can induce
inter-ferroelectric instability, and coexistence of
ferroelectric phases at room temperature. The two interferroelectric transitions, tetragonal-orthorhombic and
orthorhombic-rhombohedral occur at ~ 0 C and -90 C in
pure BaTiO3. A perusal of literature suggests thatZr [5],
Sn [6]and Hf [7]substitution in BaTiO3increase both the
inter-ferroelectric transition temperatures from below
room temperature. This offers interesting opportunity to
chemically tune the orthorhombic-tetragonal and
rhombohedral-orthorhombic phase transition near to room
temperature for enhanced piezoelectric properties
mimicking a morphotropic phase boundary scenario.We
have carried out detailed structural, ferroelectric and
piezoelectric measurements on a series of compositionally
modified (Zr, Sn and Hf) BaTiO3. It was found that 2 mole
percent of the other two substituents,SnZr and Hf
remarkably increase the piezoelectric property by
stabilizing coexistence of ferroelectric tetragonal and
orthorhombic phases at room temperature. A longitudinal
direct piezoelectric coefficient of 425 pC/N was obtained
for Sn modified BaTiO3.
II.

EXPERIMENTAL

Solid solution of Ba(Ti1-xZrx)O3(BZT), Ba(Ti1Ba(Ti1-xHfx)O3(BHT) were prepared by


solid state route using high purity BaCO3, TiO2, ZrO2,
SnO2, HfO2 compounds. Powders were milled in planetary
ball mill (P5, Fritch) using acetone medium for 10-12 hrs.
Milled powder were dried and calcined at temperature of
1100 C for 4hrs. Sintering was done by two step process
first heated to 1300 for 4 hrs and then heated to 1500 C for
6hrs. X-ray powder diffraction was done using Bruker
(D8, advance). Neutron powder-diffraction (NPD)
experiment was carried out at the SPODI diffractometer at
FRM II, Germany using a wavelength of 1.548 .
Dielectric measurement were done on Novocontrol (Alpha
AN) impedance analyzer. Measurement of longitudinal
piezoelectric coefficient (d33) was carried using Piezotest
PM 300 by poling the pellets at room temperature for ~ 1
hour at a field of ~ 2 kV/cm. Rietveld refinement was
carried out using FULLPROF software[8].
xSnx)O3(BST),

ProjectNo.ISTC/MET/RR/323

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RESULTS AND DISCUSSION

15000

Figure 1 shows thecomposition dependence of the


longitudinal piezoelectric coefficient (d33) ofBZT, BST
and BHTsystems. All the three systems exhibits
substantial enhancement of the piezoelectric coefficient. In
BST d33increases from 190 pC/N (for x=0) to ~270 pC/N
at x = 0.01, reaching a maximum ~425 pC/N at x = 0.02.
Then onwards the value exhibits saturation after a slight
decrease.For BZT, fig 1(b), a similar enhancement in d33 is
observed reaching a maximum of ~370 pC/N at x = 0.02.
After a slight drop at x=0.03, d33is nearly constant in the
range 0.03x0.06. For BHT (fig 1(c)) maximum d33
(~370 pC/N) was again obtained at x = 0.02.

9000
30

3000
0
15000

Sn = 0.04
Sn = 0.02

(b)

12000
9000

30

40

50

6000
3000

40

80

120

160

200

Temperature (C)

(a)

Figure 2 Temperature dependence of dielectric constant of


BaTi1-yXyO3 (X = Zr, Hf, Sn). The insets show the
magnified plot near room temperature

300
200
100
0

Mole % Sn

10

400

150

(b)

(a)

300

Tc

100

200
TT-O

50

100
0

Mole % Zr

10

400

(c)
300
200
100
0

Transition temperatures ( C)

d33 (pC/N)

60

6000

400

Zr = 0.02
Hf = 0.02

(a)

12000

Relative permittivity

III.

150

(b)

Tc
100
TT-O

50

TO-R
0 2 4 6 8 10 12 14 16
Mole % Zr

150

(c)

Mole % Hf

Tc

100

Figure 1. Composition dependence of longitudinal


piezoelectric coefficient (d33) in BaTi1-y XyO3. (a) X = Sn,
(b) X = Zr and (c) X =Hf.
Fig 2 shows the temperature variation of relative
permittivity of BZT, BHT and BST. For 2 mol %
substitution all the three systems exhibit sharp dielectric
anomaly corresponding to the tetragonal-cubic transition at
Tc ~120 C. Interestingly the tetragonal-orthorhombic
dielectric anomaly TT-O is shifted from 0 C to just above
room temperature ~35 C for BZT (x=0.02) and BHT
(x=0.02). This anomaly was not captured above room
temperature in BST (x=0.02), which exhibits the highest
d33 among the three systems but was clearly revealed for
higher Snconcentration (4 mol %).

8 10 12

Mole % Sn

TT-O

50

TO-R
0

8 10 12

Mole % Hf

Figure 3: Phase diagram of BaTi1-yXyO3 (X = Sn, Zr, Hf)


constructed from the anomaly temperatures in dielectric
studies.
Based on the dielectric anomaly temperatures
measured for different compositions of the three systems
under investigation, a phase diagram has been plotted in
Fig. 3. The three substitutions Zr, Hf and Sn raise the
orthorhombic-tetragonal (TO-T) and the rhombohedralorthorhombic (TR-O) transition temperatures and decrease
the tetragonal-cubic transition (Tc) temperature. The phase

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{200}C

{222}C

{220}C

Zr = 0.03

(g)

12

(a)Zr = 2 mole %

{400}C

8
46 65.6

(f)

66.4

46 65.6

66.4

83.5

45

65.6

46

66.4 83

84

(d) O

84.0

Hf = 0.03

(e)

100

84.0

Zr = 0.02

45

Intensity (arb. units)

83.5

Hf = 0.02

101

102

118 119 120


Yobs
Ycal
Y diff
peak position

Intensity (counts 104)

45

{204}C

P4mm
Amm2

20
6

40

60

(b)Sn = 4 mole %

80

100

120

140

{240}C

{400}C

4
100

102

118.5

120.0

2
45

46

65.6

66.4

84

(c)

83

Sn = 0.04

0
20

44.8

45.6

65.6

66.4

83.2

84.0

(b)

Sn = 0.02

45

46 65.6

66.4

83.5

45

84.0
BT

(a)

46 65.8

66.5

2 (degree)

83.5

84.0

Figure 4. X-ray powder Bragg profiles of pseudo cubic


{200}c, {220}c and {222}c reflections of BaTi1-xXyO3 The
arrows indicates the reflections from the respective phases
( O = orthorhombic reflection)
diagrams based on dielectric measurements suggest that
the minimum concentrations of the substituents which can
help stabilize the orthorhombic phase at room temperature
is x=0.02 for BZT and BHT and x=0.04 for BST. Both
BZT and BHT exhibits rhombohedral-orthorhombic
dielectric anomaly above room temperature in the
composition range 0.08<x0.011. This anomaly could not
be captured in the Sn modified BaTiO3. From the trend of
the three phase boundaries in the phase diagrams of BZT
and BHTthe possibility of the merging of the boundaries
can be anticipated somewhere in the composition range
0.11<x<0.15. Though this scenario may suggest the
possibility of coexistence of four phases-cubic, tetragonal,
orthorhombic and rhombohedral, as has been reported in a
recent work by Yaoet al [9],this is not feasible from
thermodynamic view point since for a (pseudo)binary
systemGibbs phase rule does not allow more than three
phases to coexist in equilibrium at any given pressure.

P4mm
Amm2

40

60

80

100

120

140

2 (degree)

Fig 5 Rietveld fitted neutron powder diffraction patterns of


(a) BaTi0.98Zr0.02O3 and (b) BaTi0.96Sn0.04O3 with tetragonal
(P4mm) + orthorhombic (Amm2) phase coexistence
model. The insets show magnified plot of two pseudocubic
reflections {400}c and {240}c
Sinceas per the dielectric study the highest d33 in
BST seems to occur in the tetragonal phase whereas in
BZT and BHT in the orthorhombic phase, a unified
structure-property correlation for all the three systems was
not possible to establish. A detailed structural
characterization was therefore carried out. Figure 4(a-g)
shows the x-ray powder Bragg profiles of three
pseudocubic reflections {200}C, {220}C and {222}C for
different compositions of the three systems.For sake of
direct comparison, the corresponding Bragg profiles of
are
also
given
(figure
unmodified
BaTiO3
4a).Interestingly, in contrast to the dielectric study which
suggests a tetragonal phase for BST x=0.02, the XRD
pattern of this composition revealed additional features
(pointed with arrow) apart from the tetragonal peaks.
Further, though the phase diagram suggests orthorhombic
phase for BST with x=0.04 at room temperature,
tetragonal peaks are also present along with the
orthorhombic peaks for this composition. The same phase
coexistence was found in both BZT and BHT with x=0.02.
Thus irrespective of whether the tetragonal-orthorhombic
criticality as revealed by the dielectric anomaly is above or
below room temperature, the structural analysis clearly
proves that all the three systems exhibit coexistence
orthorhombic and tetragonal phases at room temperature
for the composition (x=0.02). Fig. 5 shows Rietveld fitted
neutron diffraction patterns of BZT (x=0.02) and BST
(x=0.04) with tetragonal (P4mm) + orthorhombic (Amm2)
phase coexistence model.The insetsshow magnified plot of
fits of two high angle pseudocubic reflections {400}c and
{204}c. For both the cases, if the structure were single

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phase (either tetragonal or orthorhombic)the each of the


pseudocubic {400}Cand {204}c profiles wouldbe expected
to split into two peaks. The presence of the extra
reflectionsand their satisfactory modeling confirms the
chosen phase coexistence model. The refined structural
parametersare given in tables 1 and 2.
The observation of enhanced piezoelectric
response in a system comprising of two ferroelectric
phases is analogous to PZT which exhibits anomalous
piezoelectric response at the morphotropic phase boundary
(MPB) compositions exhibiting coexistence tetragonal +
rhombohedral/monoclinic ferroelectric phases. The
anisotropic lowering of the energy barrier separating two
different ferroelectric phases with different orientation of

the
polarization
vector
near
a
temperature/composition/pressuredriven critical point
provides low energy polarization rotation pathway [10].
Similar to BaTiO3, KNN also exhibits three polymorphic
phase transitions (Tc ~410 oC, TT-O ~200 oC, and TO-R ~ 123 oC). In this system also, the enhanced
electromechanical response is observed by tailoring the TTO, Li-substitution at the (K0.5Na0.5)site in KNN has been
reported to lower the TT-Otransition temperature close to
room temperature, and stabilizes the two ferroelectric
(P4mm+Amm2) phases [11]. Similarly Sb substitution at
the Nb-site in KNN raises the TO-Rtransition temperature.

Table1: Refined structural parameters and agreement factors for Ba(Ti0.98Zr0.02)O3 using Tetragonal(P4mm) +
orthorhombic(Amm2) phase coexistence models.
Space group: P4mm

Space group: Amm2

B( 2)

B(2)

Ba

0.000

0.000

0.000

0.46(5)

0.000

0.000

0.000

0.1(1)

Ti/Zr

0.500

0.5000

0.470(1)

0.3(1)

0.500

0.000

0.526(1)

0.31(9)

O1

0.500

0.5000

0.029(1)

0.31(6)

0.000

0.000

0.5114(9)

0.62(5)

O2

0.500

0.000

0.523(1)

0.37(1)

0.500

0.2491(4)

0.2464(5)

0.61(4)

Atoms

a=3.99782(7) , c=4.03493(9)

a= 3.99597(5) , b=5.69071(8) ,

v= 64.488(2) 3, %Phase = 33(1)

c=5.67698(8) v=129.094(3) 3, %Phase = 67(1)

Rp: 6.80,

Rwp: 5.06,

Rexp: 3.05, Chi2: 2.75

Table2: Refined structural parameters and agreement factors for Ba(Ti0.96Sn0.04)O3 using Tetragonal(P4mm) +
orthorhombic(Amm2) phase coexistence models.
Space group: P4mm

Space group: Amm2

B( 2)

B(2)

Ba

0.000

0.000

0.000

0.5 (1)

0.000

0.000

0.000

0.07(9)

Ti/Sn

0.500

0.5000

0.471(2)

0.2(2)

0.500

0.000

0.495(2)

1.3(1)

O1

0.500

0.5000

0.024(1)

0.1(1)

0.000

0.000

0.498(2)

0.6(1)

O2

0.500

0.000

0.510(2)

0.5(1)

0.500

0.2577(8)

0.2371(5)

0.83(6)

Atoms

a=4.00183(8) , c=4.02807(12)

a= 3.99980(8) , b=5.6857(1) ,

v= 64.508(3) 3, %Phase = 39(2)

c=5.6754(1) v=129.096(5) 3, %Phase = 61(2)

Rp: 8.90, Rwp: 5.94,

Rexp: 4.16, Chi2: 2.04

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Thus the mechanism associated with the enhanced piezoresponse in BaTiO3 and KNN based systems is primarily
based on the similarity of the topology of their respective
phase diagrams. While two different types of chemical
substitutions are required to stabilize two different
combinations of ferroelectric phasesat room temperature in
KNN,in BaTiO3 the same substituent (either Zr, or Hf or
Sn) does the job by varying the concentration. The first
order nature of the P4mm-Amm2 and R3m-Amm2
transitions in these systems ensures their coexistence
around the critical point. The temperature range of this
coexistence islikely to be increased due to random elastic
strain induced in the lattice by substitution of Zr/Hf/Sn at
the Ti site. This explains why BST still exhibits the same
phase coexistence as BZT and BHT for x=0.02 inspite of
the difference in their respective critical temperatures.
IV.

CONCLUSIONS

BaTiO3considerably enhances the piezoelectric response


of the system with Sn modification exhibiting the highest
piezoelectric response of 425 pC/N. A detailed structural
analysis by x-ray and neutron powder diffraction revealed
that these dilute modifications stabilize a coexistence of
ferroelectric phases, orthorhombic and tetragonal,at room
temperature. It is this phase coexistence that is responsible
for the anomalous piezoelectric response exhibited by
these systems. Our results suggests the possibilities that
there might be other elements as well which can enhance
the piezoelectric properties of BaTiO3. More work needs
to be carried out to explore this possibility.

Acknowledgement
RR thanks the ISRO-IISc Space Technology Cell for
financial assistance.

In conclusion, we have shown that merely 1-3


mole percent of Zr, Sn and Hf substitution in
References
[1] B. Jaffe, Piezoelectric Ceramics (Elsevier Science,
(2012).
[2] Y. Saito, H. Takao, T. Tani, T. Nonoyama, K.
Takatori, T. Homma, T. Nagaya, M. Nakamura, Nature,
432, 84 (2004).
[3] W. Jo, T. Granzow, E. Aulbach, J. Rdel, and D.
Damjanovic, J. Appl. Phys. 105, 094102 (2009).
[4] W. Liu and X. Ren, Phys. Rev. Lett. 103,
257602(2009)
[5]
G. H. Jonker, and W. Kwestroo, J. Am. Ceram.
Soc. 41, 390 (1958).
[6] G. A. Smolenskii, V. A. Isupov, Dokl. Akad. Nauk
USSR, 96, 53 (1954).

[8] J. R. Carvajal, FULLPROF, A Rietveld Refinement


and Pattern Matching Analysis Program,
Laboratoire Leon Brillouin (CEA-CNRS),
France.
[9] Y. Yao, C. Zhou, D. Lv, D. Wang, H. Wu, Y. Yang,
and X. Ren, Europhys. Lett, 98, 27008 (2012).
[10] D. Damjanovic, Appl. Phys. Lett. 97, 062906 (2010).
[11] Y. Dai, X. Zhang, G. Zhou, Appl. Phys. Lett, 90,
262903 (2007
[12]
R. Zuo, J. Fu, D. Lv, and Y. Liu, J. Am. Ceram.
Soc. 93, 2783 (2010).

[7] E. G. Fesenko, O. I. Prokopalo, Soviet Phys. Cryst. 6,


373 (1961)

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Geospatial scenario based modelling of urban revolution in five major cities in India
T.V. Ramachandra, Bharath H. A, Vinay S., Venugopal Rao K and. Joshi N V

Abstract - Urbanisation being irreversible and very


rapid with fast growth of population and
settlements during the last century, needs to be
monitored and visualised for evolving strategies
towards sustainable development approaches. This
study visualises the growth of major Tier I cities of
India such as Delhi, Mumbai, Pune, Chennai and
Coimbatore, India through AHP Fuzzy based
Cellular Automata Markov model. CA Markov
model is considered to be one of most effective
algorithm to visualise the growth of urban spatial
structures. The analysis performed in previous
studies such as spatial pattern of land use change in
the area was considered and the future growth was
modelled considering agents of growth applying
fuzzy AHP CA-Markov model. The projection as
predicted using the model was validated to obtain
better validation and was then used to predict
future projections. Modelling suggested a clear
trend of various land use classes transformation in
the area of urban built up expansions.
I.

INTRODUCTION

Rapid urbanization is one of the most important factor


affecting the local ecology and loss of biodiversity in
India during the last two decades (Shivaramakrishnan
et al., 2005; MOUD., India, 2011; Ramachandra et al.,
2012; Bharath H. A., 2012; Ramachandra et al.,
2014a). Urbanisation is a form of growth with
implications of economic, social, and political forces
and to the physical geography of an area (Sudhira et
al., 2007; Ramachandra et al., 2014a). The sprawl
takes place at the urban fringes resulted in radial
development of the urban areas or development along
the highways results in the elongated development of
urban forms (Sudhira et al., 2003).
Dr. T V Ramachandra, Coordinator of Energy and Wetlands
Research Group (EWRG), Centre for Ecological Sciences (CES),
Indian
Institute
of
Science
(IISc),
Bangalore.
cestvr@ces.iisc.ernet.in
Bharath H Aithal, is a Junior Research Fellow at Indian Institute
of Science (IISc). bharath@ces.iisc.ernet.in
Vinay S, is a research scholar at Energy and Wetlands Research
Group (EWRG), Centre for Ecological Sciences (CES), Indian
Institute of Science (IISc). vinay@ces.iisc.ernet.in
Joshi N V, Faculty at Centre for Ecological Sciences (CES), Indian
Institute of Science (IISc), Bangalore
Venugopal Rao K, is Group Head, Urban Studies &
Geoinformatics, National Remote Sensing Centre (NRSC), Indian
Space
Research
Organisation,
Hyderabad,
India.
venu_koppaka@nrsc.gov.in

It can also be defined as a finite cycle through which


nations evolve to form industrially dominant regions,
which further results in rural push and spreading of
city towards outskirts (Ramachandra et al., 2013) also
refers to urban sprawl.
This urban development in the fringes is called sprawl.
The study on urban sprawl was attempted by various
researchers across the globe (Batty et al., 1999;
Torrens, 2000; Sudhira et al., 2004; Huang et.al 2007;
Bhatta, 2009a, 2009b, 2010; Ramachandra et al.,
2012). These sprawl areas do not have a fixed plan or
process of development due to which the process of
preparing visionary documents such as developmental
plans, specific corridors of developments are being
ineffective considering the fact that spatial patterns
and dynamic behaviour of growth and also may be
attributed to lack of skills and tools to help in
informed, accurate decision making (Adhvaryu, 2011;
Bharath H.A., et al., 2014). This can be improved and
timely decisions may be enabled using technological
improvements such as remote sensing and tools such
as Geographic Information system (GIS).
Remote Sensing data acquired through space borne
remote sensors enables a bird eye view of the
landscape at low cost (Lillesand and Kiefer, 2005).
The advantage of remote sensing data is to acquire
repeated measurements of the same area on periodic
basis which helps in detection and monitoring of
LULCC and surveillance of problematic sites
(Campbell, 2002). The analysis of changes at local,
regional and global scales is possible through the
collection of remote sensed data covering the larger
spatial extent. Remote sensing aids in identification
and assessment of land use patterns which is important
for environmental management and decision making.
Further it is essential to visualise and provide better
planning strategies for future urban growth. This can
be planned and visualised using various modelling
techniques.
Traditional large-scale urban simulation approaches of
early 90s were based on theories, and suffered from
significant weaknesses such as poor handling of spacetime dynamics and too much generalisation of data.
The integration of space, time, and attributes in
modelling was further enhanced with the
implementation of Cellular automata (CA) models
(Allen 1997; Batty 1999; EPA 2000; Alberti and
Waddell 2000). CA modelling is capable of addressing
the spatial complexity with discrete time change. A

ISTC/BES/TVR/313

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number of CA-based models of urban growth have


produced satisfactory simulations of spatial urban
expansion over time (Clarke et al., 1997; Leao et al.
2004; Bharath and Ramachandra, 2013; Ramachandra
et al., 2013; Arsanjani et al., 2013).The main
advantages of CA are simplicity, easy integration with
raster GIS, and adaptability to various urban growth
situations. CA models can realistically generate and
represent complex patterns through the use of simple
rules and considering its neighbouring properties since
these models operate on basis of cell states, size,
neighbourhood and transition rules (White and
Engelen 2000). This communication presents the Land
use change modeller (Bharath H.A. et al., 2013) and
Fuzzy AHP based CA (Bharath H.A et al., 2014)
models implemented to visualise the urban growth in
five Tier I cities in India.
II.
DATA AND METHOD
Temporal remote sensing data of Landsat TM and
ETM+ downloaded from GLCF were preprocessed to
correct geometrical and radiometrical accuracy USGS
(http://www.usgs.gov). This was further used to
analyse and model LULC changes. Remote sensing
data were supplemented with the Survey of India
topographic maps (of 1:50000 and 1:250000 scale),
which were used to generate base layers of the
administrative boundary, drainage network, Road
network etc. Slope map was extracted using ASTER
data (30 m) downloaded from USGS (www.usgs.gov).
Ground control points (GCPs) and training data were
collected using pre calibrated Global Positioning
System (GPS) and virtual online spatial maps such as
Bhuvan and Google Earth. GCPs were useful in
geometric correction of remote sensing data. Census
data (1991, 2001 and 2011) was used to capture
population dynamics.
Modelling of urbanization and sprawl involved: i)
Remote Sensing data acquisition, geometric
correction, field data collection, ii) Classification of
remote sensing data and accuracy assessment using
GRASS, iii) Land use analysis, iv) Identification of
agents and development of attribute information, v)
Prediction: Designing scenarios of urban growth and
calibrating the model to find out the best weights based
on the influence on the neighborhood pixels vi)
Accuracy assessment and validation of the model, vii)
Prediction of future growth based on validated data.
Land use analysis was carried out using supervised
pattern classifier - Gaussian maximum likelihood
algorithm based on probability and cost functions
(Duda et al., 2000). Land use with gradient analysis
results were further used in Modelling. These results
can be accessed in previous working literatures

(Ramachandra et al., 2014a, 2014b, 2014c, 2014d,


Chandan et al., 2014). These data was used in
Modelling and visualizing the growth of these cities.
III.

MODELLING USING FUZZY AHP-CA

Using the combination of Fuzzy Logic, Analytical


Hierarchical Process (AHP), Multi Criteria Evaluation
(MCE), Markov chains and Cellular Automata (CA).
Agents of urbanisation such as roads, industries,
educational institutions, bus stands, railway stations,
metro, population, etc. were normalized. Conservation
regions as per city development plan (CDP) water
bodies were considered as constraints. The fuzzy
based analysis is used to normalize the contributing
factors between 0 and 255, where 255 showing the
maximum probability of change and 0 indicating no
change, for different land uses. The normalized agents
were taken as input to AHP to determine the weights
of driving factors using pair wise comparisons ith
weights as Eigen vectors. The weights analysed and
calibrated through AHP is verified using measured
consistency ratio (CR). CR below 0.1, the model is
consistent and used for subsequent processes.
These weights along with the factors of growth are
combined along with the constraints to obtain site
suitability maps for different land uses using equation
below
. (1)
LC =

Where LC is the linear combination of weights, n is


the number of factors, D decision factor, W is the
weight of the factor.
The Markov chains are used to determine the change
probability between two historical datasets to derive
the growth in the future scenarios based on different
criterias. The Markovian transition matrix indicates
the probability of the particular land use being
converted to other land uses on single time step.
Criteria
Without
CDP as a
constraint
With CDP

Factors and Constraints


Slope, Distance from roads, Distance to
industries, Distance to Bus stops and Railway
stations, Distance from metro, Distance from
educational institutions, Population Density
Slope, Distance from roads, Distance to
industries, Distance to Bus stops and Railway
stations, Distance from metro, Distance from
educational institutions, City Development
Plan, Population Density

Table 1: Criterias for simulating and predicting urban sprawl

The cellular automata based on the site suitability and


the transition matrix is used to spatially predict the
changes in land use based on current land use at every

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single time step, based on the neighbouring pixels.


Two scenarios were designed to predict the land use
changes as shown in table 1.
Validation of the simulated datasets of were performed
with classified datasets through kappa indices, as a
measure of agreement. Once these data and agents are
trained and validated, data is used to model and
simulate for the year 2030 (ten years) with definite
time steps.
IV.

Year

Built up

Vegetation

Water

Others

2017

45.80

17.98

1.25

34.97

2024

57.37

8.77

1.18

32.68

2031

70.86

3.76

1.19

24.18

All units as percentage area


Table 2: Predicted landscape dynamics of Delhi

Modelling growth of Mumbai

RESULTS

Geo-visualisation of urbanisation of five tier I cities


are depicted in fig.1 to fig.5 and results are provided
in tables 2 to 6 respectively. The cities on an average
would grow by 1.5 to over 2 times the current state in
next decade. By 2025, it is predicted that built up area
in these cities and surroundings, grows over 57%
(Delhi), 27% (Mumbai), 45.8% (Chennai), 50%
(Pune) and 37% (Coimbatore) respectively. The
various drivers of growth for different cities are as in
annexure 1. In all these cases, spatially it could be
understood that the CDP if implemented properly
would play a major role in curtailing the unsustainable
growth of the city in its limits, while some growth still
takes place at the outskirts. Prime factors of growth
include the transportation network, industrialisation,
and educational sector.

Predicted 2020

Predicted 2031

Fig.2: Predicted landscape dynamics of Mumbai

Year

Built up

Vegetation

Water

Others

2020

25.83

9.09

44.52

20.56

2031

31.27

6.33

44.52

17.88

All units as percentage area


Table 3: Predicted landscape dynamics of Mumbai

Modelling growth of Delhi


Modelling growth of Chennai

Predicted 2017

Predicted 2024

Predicted 2026
Fig.3: Predicted landscape dynamics of Chennai

Predicted 2031
Fig.1: Predicted landscape dynamics of Delhi

Built up

Year
2026

45.80

Vegetation
17.98

Water

Others

1.25

34.97

All units as percentage area


Table 4: Predicted landscape dynamics of Chennai

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Modelling growth of Pune

Predicted 2016

Predicted 2019

Predicted 2022

Predicted 2025

Fig.4: Predicted landscape dynamics of Pune

Year

Built up

Water

Vegetation

Others

2016

37.78

1.75

16.37

44.11

2019

41.64

1.75

20.16

36.45

2022

47.89

1.75

20.16

30.20

2025

50.02

1.75

20.16

28.06

V.
CONCLUSION
This study demonstrates the application of temporal
remote sensing data and Geoinformatics in mapping
and understanding of urban dynamics. Advance geovisualisation of urban growth would aid in decision
making towards sustainable cities with basic
infrastructure and amenities. Identification of regional
factors that are most likely to influence a land-use
changes has improved the accuracy of prediction. The
predictions of land use/cover changes through CAMarkov model suggest a continual increase in urban
settlements with a decline in local ecology and natural
vegetation covers. The prediction using CA help to
design sustainable urban transportation system.
VI.
ACKNOWLEDGEMENT
We are grateful to ISRO-IISc Space Technology Cell,
Indian Institute of Science and NRDMS division,
Ministry of Science and Technology, DST,
Government of India for the financial support. We
thank USGS Earth Resources Observation and
Science (EROS) Center for providing the
environmental layers and Global Land Cover Facility
(GLCF) for providing Landsat data.
VII.
1.

2.

All units as percentage area


Table 5: Predicted landscape dynamics of Pune

Modelling growth of Coimbatore

3.

4.

Predicted 2023

Predicted 2033

5.

Fig.5: Predicted landscape dynamics of Coimbatore

Year

Built up

Water

Vegetation

Others

2023

32.64

0.29

17.14

49.94

2033

42.92

0.29

17.58

39.21

All units as percentage area


Table 6: Predicted landscape dynamics of Coimbatore

6.

7.

Publications

Ramachandra, T. V., Bharath, H. A. and Sowmyashree,


M.V., 2014. Urban structure in Kolkata: metrics and
modelling through geo-informatics, Appl Geomat
6(22): DOI 10.1007/s12518-014-0135-y
Ramachandra, T. V., Bharath, H. A. and Sowmyashree,
M.V., 2014. Monitoring spatial dynamics of
urbanisation in Ahmed city, Textile hub of India,
SPATIUM International review, 31(2):85-91
Ramachandra, T. V., Bharath S., Bharath, H. A. 2014.
Spatio-temporal dynamics along the terrain gradient of
diverse landscape, Journal of Environmental
Engineering and Landscape Management, 22(1): 5063
doi:10.3846/16486897.2014.808639.
Ramachandra, T.V., Bharath H. Aithal and
Sowmyashree M V., 2014. Monitoring urbanization
and its implications in a mega city from space:
Spatiotemporal patterns and its indicators, Journal of
Environmental
Management
http://dx.doi.org/10.1016/j.jenvman.2014.02.015
Ramachandra, T. V., Bharath, H. A. and Barik, B.,
2014. Urbanisation Pattern of Incipient Mega Region in
India, TEMA - Journal of Land Use, Mobility and
Environment, 7(1): 83-100.
Ramachandra, T. V., Bharath, H. A. and Sowmyashree,
M.V., 2014. Urban footprint of Mumbai - the
commercial capital of India, Journal of Urban and
Regional Analysis, VI (1): p. 71 94
Ramachandra, T. V., Bharath, H. A., 2014. Geovisualisation of Urbanisation in Greater Bangalore,
India Geospatial Digest, September 2014, pp 12-18
http://www.geospatialworld.net/Paper/Application/Art
icleView.aspx?aid=31130#sthash.NZScwjHH.dpuf

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8.

9.

10.

11.

12.

13.

Ramachandra, T. V., Bharath, H. A. and Sowmyashree,


M.V., 2013. Analysis of spatial patterns of urbanisation
using geo-informatics and spatial metrics, Theoretical
and Empirical Research in Urban Management, 8(4):524
Ramachandra, T.V., Bharath, H. A., and Vinay S, Land
Use Land Cover Dynamics in a Rapidly Urbanising
Landscape, SCIT Journal, Volume XIII, August 2013,
XIII(1):1-13
Bharath, S., Rajan, K.S., Ramachandra, T.V., 2013.
Land Surface Temperature Responses to Land Use
Land Cover Dynamics. Journal of Geoinformatics and
Geostatistics:
An
Overview
1(4):1-10.
doi:10.4172/2327-4581.1000112.
Ramachandra, T.V., Meera, D.S., and Alakananda B.,
2013. Influence of Catchment Land Cover Dynamics
on the Physical, Chemical and Biological Integrity of
Wetlands, Environment & We -International Journal of
Science & Technology - (EWIJST), pp 8(1): 37-54
Ramachandra T. V., Sreejith K. and Bharath H. A.,
2014. Sector-Wise Assessment of Carbon Footprint
across Major Cities in India, Assessment of Carbon
Footprint in Different Industrial Sectors, Volume 2,
Muthu S. S. (ed.), Eco-Production, DOI: 10.1007/978981-4585-75-0_8, Springer Science Business Media
Singapore, 2014.
Ramachandra, T. V., Shwetmala, K., Dania, T.M.,
2014. Carbon footprint of solid waste sector in Greater
Bangalore, India, In: Assessment of Carbon Footprint
in Different Industrial Sectors (ed. S.S. Muthu),
Volume 1, Eco-Production, DOI: 10.1007/978-9814560-41-2_11, Springer Science, Singapore Pp 265292

VIII.
1.
2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

References

Campbell, J. B., 2002. Introduction to Remote


Sensing (3rd Edn). Taylor & Francis, London, UK,
605.
Lillesand, T. M., Kiefer, R. W., 2002. Remote Sensing
and Image Interpretation, 4th ed. John Wiley and
Sons, 215216.
Ramachandra, T.V., Bharath, H.A., Barik, B., 2014c.
Urbanisation Pattern of Incipient Mega Region in
India, Tema. Journal of Land Use, Mobility and
Environment, 7(1), 83-100.
Ramachandra, T.V., Bharath, H. A., Sowmyashree,
M. V., 2014d. Urban Footprint of Mumbai - The
Commercial Capital of India, Journal of Urban and
Regional Analysis, Vol. 6(1), 71-94.
Ramachandra, T.V., Bharath H. Aithal and Durgappa
D. Sanna, 2012. Insights to Urban Dynamics through
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Ramachandra, T.V., Bharath, H.A., Sowmyashree M.
V., 2014a. Monitoring urbanization and its
implications in a mega city from space:
Spatiotemporal patterns and its indicators, Journal of
Environmental Management, accepted, in press,
doi:10.1016/j.jenvman.2014.02.015
Ramachandra, T.V., Bharath, H.A., Sowmyashree M.
V., 2014b. Urban Structure in Kolkata: Metrics and

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Modeling through Geo-informatics, Applied


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and spatial metrics-a case study of madras, In
proceedings of Lake 2014: Conference on
Conservation and Sustainable Management of
Wetland Ecosystems in Western Ghats, 13th -15th
Nov., Uttara Kannada, India
Bharath, H. A., Vinay, S., Ramachandra, T.V., 2014.
Landscape dynamics modelling through integrated
Markov, Fuzzy-AHP and Cellular Automata, in the
proceeding of International Geoscience and Remote
Sensing Symposium (IEEE IGARSS 2014), July 13th
July 19th 2014, Quebec City convention centre,
Quebec,
Canada.
Available
at
http://www.igarss2014.org/Papers/ViewPapers_MS.a
sp?PaperNum=1010
Bharath, H.A., Bharath, S., Sannadurgappa, D.,
Ramachandra, T. V., 2012, Effectiveness of landscape
Spatial Metrics with reference to the Spatial
Resolutions of Remote Sensing Data, Proceedings of
India Conference on Geo-spatial Technologies &
Applications 2012, IIT Bombay, Mumbai, India, 1214 April, 2012.
Bharath, H.A., Vinay, S., Ramachandra, T.V., 2013.
Prediction of Land use dynamics in the rapidly
urbanising landscape using land change modeller In
proceedings of Fourth International Joint Conference
on Advances in Engineering and Technology, AET
2013, December 13-14, NCR Delhi, India.
MOUD. 2011.Urban development management for
the formulation of the twelfth five year plan (2012
2017): Report of the working group on capacity
building for the twelfth plan. New Delhi
Sivaramakrishnan, K.C., Kundu, A., Singh, B.N.
2005. Handbook of Urbanization in India, Oxford
University Press, New Delhi, India.
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N. V., Kumar, U., Venugopal, R. K., 2013. Modelling
Urban Revolution in Greater Bangalore, India , 30th
Annual In-House Symposium on Space Science and
Technology, ISRO-IISc Space Technology Cell,
Indian Institute of Science, Bangalore, 7-8 November
2013.
Sudhira H. S., Ramachandra T. V., Subrahmanya, M.
H., Bala, 2007. Urban Sprawl Management: Need for
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Jagadish, K.S., 2003. Urban Growth Analysis using
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systems work, Centre for Advanced Spatial Analysis,
University College London, Working Paper Series,
Paper 28.

ISTC/BES/TVR/313

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19. Bhatta, B., 2009a. Analysis of urban growth pattern


using remote sensing and GIS: a case study of
Kolkata, India. International Journal of Remote
Sensing, 30(18):47334746.
20. Bhatta, B., 2009b. Modeling of urban growth
boundary using geoinformatics. International Journal
of Digital Earth, 2(4):359381.
21. Bhatta, B., 2010. Analysis of urban growth and sprawl
from remote sensing data. Berlin, Heidelberg:
Springer-Verlag.
22. Sudhira, H.S., Ramachandra, T.V. and Jagadish, K.S.,
2004. Urban sprawl: metrics, dynamics and modelling
using GIS, International Journal of Applied Earth
Observation and Geoinformation, 5(1):29-39.
23. Allen, J., Lu, K., 2003. Modeling and prediction of
future urban growth in the Charleston region of South
Carolina: A GIS-based integrated approach. Ecology
and Society, 8(2), 2
24. EPA, 2000. Projecting land-use change: A summary
of models for assessing the effects of community
growth and change on land-use patterns. EPA/600/R00/098, Office of Research and Development,
Washington DC, USA.
25. Alberti, M., Waddell, P., 2000. An integrated urban
development and ecological simulation model. Integr.
Assess. 1(3), 213-227.

26. Arsanjani, J. J., Helbich, M., Kainz, W., Darvishi


Boloorani, A., 2013. Integration of logistic regression,
Markov chain and cellular automata models to
simulate urban expansion. Int. J. of Appl Earth
Observation and Geo., 21, 265275.
27. Clarke, K. C., Hoppen, S., Gaydos, L., 1997. A selfmodifying cellular automation model of historical
urbanization in the San Francisco Bay area.
Environment and Planning B: Planning and Design,
24(2), 247261
28. Leao, S., Bishop, I., and Evans, D., 2004. Simulating
urban growth in a developing nations region using a
cellular automata-based model. J. Urban Plann. Dev.,
3(145), 145158.
29. White, R., Engelen, G., 2000. High-resolution
integrated modelling of the spatial dynamics of urban
and regional systems. Comput. Environ. Urban Syst.,
24(5), 383400.
30. Adhvaryu, B., 2011. The Ahmedabad urban
development plan-making process: A critical review.
Planning Practice and Research, 26(2), 229250

Annexure

Road

DEM
Annexure 1: Factors and constraints of growth for Delhi

CPD

Road

DEM
Annexure 2: Factors and constraints of growth for Mumbai

CPD

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Road and railway
Annexure 3: Factors and constraints of growth for Chennai

Road

Road

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Annexure 4: Factors and constraints of growth for Pune

CPD

CPD

DEM
CPD
Annexure 5: Factors and constraints of growth for Coimbatore

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Quantum communication and security using


entangled states
Ankur Raina and Shayan G. Srinivasa

Chithrabhanu P., Aadhi A., Shashi P., R. P. Singh

Dept. of Electronics Systems Engineering


Indian Institute of Science, Bengaluru, India
Email correspondence: shayan.gs@dese.iisc.ernet.in

Division of Quantum Optics


Physical Research Labs, Ahmedabad, India
Email correspondence: rpsingh@prl.res.in

AbstractThis research report has two main parts related


to the theoretical and experimental investigations into quantum
communications and security. In the first part, we consider super
dense coding over the noisy bit flip channel with a shared Bell pair
and show that the encoding scheme is perfectly secure using the
information-theoretic criterion. We also extend the super dense
coding idea to the tripartite system. In the second part, using a
three particle hyper entangled state, we set up an experimental
platform for illustrating the idea of multiparty quantum key
distribution protocol using photons. Our results are useful for
realizing the fundamental limits of transmission and information
security over quantum channels with an eye towards experimental
realization of the same via photonics.

I.

I NTRODUCTION

Super dense coding [1], a well known quantum protocol


was one of the first few pioneering discoveries in quantum
information processing, that exploits the advantage of quantum
entanglement. Ever since the discovery, quantum entanglement
is considered as a resource in quantum information processing.
It lets users pre-sharing an entangled pair of qubits, communicate two classical bits. The protocol as given by Bennett
and Wiesner is as follows - An entangled pair of qubits, also
called the Bell pair, is prepared and distributed to two nodes.
One of the nodes performs unitary encoding and transfers
its qubit to the other node via noiseless quantum channel.
The receiving node performs measurement and decodes the
information conveyed. However, there is one caveat. The
quantum channel transferring the qubit from the source to the
destination is assumed to be noiseless. In practice, no channel,
classical or quantum is physically noiseless.
Quantum communication using entanglement is increasingly receiving attention and is an actively pursued topic of
current research. In this work, we consider the super dense
coding over the noisy bit flip channel. The quantum advantage
of using entanglement is brought out. We also extend the idea
of super dense coding to a tripartite system initially in the GHZ
state. We assume that the GHZ state is somehow prepared and
distributed to three parties namely A, B and C. We address the
question whether 3 classical bits can be communicated using
such a tripartite state.
With entanglement between two quantum bits, protocols
have been demonstrated for teleporting an unknown quantum state [2], super dense coding of information [1] and
This is an ongoing collaboration between IISc and PRL funded by
ISTC/EED/SGS/311. The first part of the work is from IISc and the second
part is from PRL.

secure communication [3]. We describe a hyper-entangled state


formed by orbital angular momentum (OAM) and polarization
degree of freedom and use it for multiparty quantum key distribution (QKD) protocol. The scheme is being experimentally
investigated via photonics.
The report is organized as follows. In sections 2 and 3,
we describe super dense coding over the bit flip channel for
bipartitite and tripartite states respectively. We also present
information security results over noisy quantum channels. In
section 4, we describe the construction of hyper entangled
states. We describe the experimental set up for state preparation
in section 5 followed by the description of the QKD protocol
in section 6 and conclusions.
II.

S UPER DENSE CODING OF B ELL STATES THROUGH A


BIT FLIP CHANNEL

We present the protocol for communication between nodes


A and B through a quantum bit flip channel [4]. The action of
the quantum bit flip channel with parameter p on any state
is given by [5]
N () = pX X + (1 p).

(1)

We assume that a fully entangled bipartite state namely the


Bell pair + is shared between nodes A and B.
To encode classical information, A encodes its qubit using
Pauli matrices i , i {0, 1, 2, 3} [5]. A chooses I, 1 , 2 , 3
to respectively communicate two bits 00, 01, 10, and 11.
Based on what A chooses, we get the following Bell pairs
shared between A and B.
00 11
01 10
=
, =
.
2
2
The encoding operation by A is described using density
matrices as follows:
i = (i I) (i I) ,

(2)

where = + + , the initially shared Bell pair.


A. Calculation of Holevo capacity for a bit flip channel
We know from [6], that capacity of a classical channel
is obtained by maximizing the mutual information between
communicating nodes, over all input distributions. When it
comes to the quantum scenario, the situation is very interesing.
There exist notions of classical capacity and quantum capacity.
Morever, there is an additional resource which can be used,
namely entanglement. In this way four types of capacities have

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been defined [7]. Holevo [8], Hausladen et al. [9], gave the
expression for classical capacity of a quantum channel using
quantum states. We are interested in the classical capacity of a
bit flip channel with entanglement shared between nodes. We
have what is known as the HSW theorem, which states the
classical capacity, also called the Holevo capacity of a quantum
channel N , using the ensemble {pi , i } at the encoder, is given
by,
!
X

({pi , i }) = S (N I)
pi i
i

X
i

pi S (N I)(i ) ,

(3)

where S denotes the Von Neumann entropy. It can be shown


that the uniform distribution also maximizes the Holevo capacity for the noisy quantum bit flip channel. The Holevo capacity
evaluates to the following expression:
= 2 h(p).

B. Connections to perfect security


Classically, Shannon [10] defined informationally secure
encryption for message M and encrypted message E as
I(M ; E) = H(E) H(E|M ) = 0.

(5)

That is, message should be statistically independent of the


encrypted message for the encryption to be perfectly secure. The necessary condition for perfect secrecy implies that
H(K) H(M ), where K represents the random variable for
the key. Boykin and Roychowdhury [11] provide conditions
for perfect secrecy of qubits. In that work, condition for secure
encryption of n qubits is formalized. The protocol is secure
if for every message state , the encrypted state, c is the
maximally mixed state, i.e.,
pk Uk Uk =

I2n
.
2n

(6)

Note that the encoding by A gives


3
X
i=0

pi (i I)(i I) =

S UPER DENSE CODING USING TRIPARTITE STATES

We now explore tripartite system with prior entanglement.


This is a natural extension from the bipartite case and helps
us take a peep into the world of higher dimensional Hilbert
spaces. Considerable amount of research has been done on
the GHZ state [12], [13] and its preparation [14], [15]. Going
forward, one can think of having a network N nodes with
prior entanglement [16] among more than two nodes. With this
insight in mind, various communication scenarios like point
to point communication, multicast communication, broadcast
communication gain prominence in the quantum world. The
links between various nodes in a physical setting would be
noisy and information carrying capacities of such links would
be of immediate interest. The GHZ state is defined as
ABC =

3
X
i=0

pi i =

I4
.
4

Thus, this scheme leads to a perfectly secure encryption [11].


It can be shown that the encrypted state does not lose its
mixedness even after it goes through a noisy bit flip channel.
Infact, it is the unitality of the quantum channels that keeps
the perfect secrecy intact.

000 + 111

.
2

A. Protocol for the noiseless case

(4)

Observing (4), we find it is very akin to the capacity of a classical binary symmetric channel with a cross over probability
of p. When the channel is most random (p = 0.5), we get a
capacity of zero for the classical channel but a capacity of 1 bit
for the quantum channel. There seems to be a clear advantage
in using entangled quantum states for communication!

III.

A
N1
B
Fig. 1.

N2

Super dense coding over tripartite state.

Referring to Figure 1, A and B together encode their


qubits and send them over noiseless quantum channels N1 and
N2 respectively. Upon receiving the two qubits, C performs
measurement in an appropriate basis. We show that it is
possible to send 3 classical bits by joint encoding by A and
B. A chooses one of the two unitary operations namely I, 1
and B chooses one of the four unitary operations namely
I, 1 , 2 , 3 to encode their respective qubits. Without loss
of generality, let A encode first followed by B. The encoding
can be represented mathematically by
(A)

i
i =

(B)
i

= (i I I) ABC (i I I) .

= (I i

(A)
I)i (I

i I) .

(7)
(8)

Note that (7) represents the joint state after encoding by


A and (8) represents the joint state after encoding by B.
Depending upon the pair of encodings by A and B, the
joint state ends up being one of the eight orthonormal states.
Hence, measurement in this basis gives one of the above
eight possible outcomes. This brings us to summarizing our
protocol as:
If A wants to communicate 1 bit and B wants to communicate
2 bits then,
1. A chooses either I or 1 to respectively transmit 0 or 1.
2. B chooses among I,1 , 2 , 3 to respectively transmit
00, 01, 10, 11.
3. Both A and B send their qubits to C, which performs
measurement in the appropriate basis.
4. Based on the measurement outcome, C unambiguously
recovers three bits of classical data.
5. The roles of A and B can be interchanged if A wants to
communicate 2 bits and B wants to communicate 1 bit.

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IV.

H YPER ENTANGLED Q UANTUM S TATES

We consider a hyper-entangled state formed by OAM


and polarization degree of freedom and use it for multiparty
QKD protocol. In this protocol, one person can distribute two
independent quantum keys with two different parties at the
same time.
Consider a system of particles in such a way that one
particle is entangled to all other particles in different degrees
of freedom (DOF). Let us consider a system consisting of three
photons as described in Fig. 2. Here, photon 2 is entangled with
photons 1 and 3 in different degrees of freedom namely OAM
and polarization respectively. The polarization state of photon
1 and the OAM state of photon 3 are arbitrary or unknown.

|i123 = |p i1 (|l, l0 i12 + |l0 , li12 ) (|HV i23 + |V Hi23 )|o i3 .


(10)
This state corresponds to a description given in Fig 2.
V.

E XPERIMENTAL SCHEME FOR STATE PREPARATION

We are proposing a method in which initially two photons


are entangled in OAM and another photon is in an independent
pure state of OAM and polarization. By polarization gate
operations in one of the entangled photons and the independent
photon, one can arrive at the described state. Experimental
scheme for generation of the state is given in Fig. 4.
SM

Entangled in OAM

Entangled in Polarization

BBO

V
Unknown Polarization

Fig. 2.

Unknown OAM

The physical description of the defined quantum state.

Since OAM of a photon can have infinite values, one can


have higher dimensional entangled states. We take an arbitrary
two dimensional subspace of the infinite dimensional OAM
basis as {|li, |l0 i}.
The described state can be prepared using a pair of
Hadamard and CN OT gates in different DOFs which correspond to polarization and OAM. The initial states of three

1
2

!% e

#$ o

"

&

123

Pol
HWP C Not

Fig. 4. Schematic experimental set up for the state preparation. SM- SimonMukunda gadget, HWP- half wave plate, BBO- second order nonlinear crystal
(Beta Barium Borate) .

To generate the described state, we start with a Type I


spontaneous parametric down conversion of light in a second
order nonlinear crystal that results a pair of photons entangled
in OAM [17]. A vertically polarized optical vortex beam of
azimuthal index 1 has been considered as pump. The state
corresponding to this pair of photons is given by

123

OAM

|i12 =

+
X
m=

cm |mi1 |1 mi2 |Hi1 |Hi2

(11)

3
For the ease of experimental realization, we reduce the
infinite dimensional entangled state to a simple two-qubit
entangled state by grouping all even and odd OAM states and
rewrite the expression for the OAM state in Eq. 11 as

Polarization

Fig. 3.

Schematic diagram for preparation of the initial state.

particles can be written as


|1i = |p i1 |li1 ; |2i = |Hi2 |li2 ; |3i = |Hi3 |o i3

+
X

(9)

|p i is the unknown state of polarization of photon 1, while


|o i is the unknown OAM state of photon 3. |Hi represents
horizontal and |V i represents vertical polarization states of a
photon. The schematic diagram is given in Fig. 3. To entangle
photons 1 and 2 in OAM, a Hadamard gate (Ho ) on photon
1 and subsequent CN OT gate on photon 1 and 2 are applied.
Both gates act in OAM degree of freedom. Similarly, another
Hadamard (Hp ) acting on photon 2 and a CN OT between
photons 2 and 3 entangle them in polarization. Here both
gates are acting on the polarization states of photons. After
performing the gate operations mentioned above, the final state
becomes,

m=

cm (|mi1 |1 mi2 )

+
X
k=
+
X
k=

c2k (|2ki1 |1 2ki2 ) +


c2k+1 (|2k + 1i1 | 2ki2 ).
(12)

We define a transformation from the general OAM space


to the even-odd OAM space as
g(|ui1 |vi2 ) = f (|ui1 )f (|vi2 ), where

|Ei, for even x;
f (|xi) =
|Oi, for odd x.

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Note that g is nonlinear, but f is linear. Applying g on the


left-hand-side of Eq. 12 yields 12 (|Ei1 |Oi2 + |Oi1 |Ei2 ).
P+
From the conservation of OAM, we have k= (c2k )2 =
P+
P
+
1
1
2
2
k= (c2k+1 ) = 2
m= (cm ) = 2 . Thus, we can
rewrite Eq. 11 as
1
|i12 = (|Ei1 |Oi2 + |Oi1 |Ei2 ) |Hi1 |Hi2 .
2

(13)

Note that the photons are entangled in even/odd OAM


states. Let photon 1 pass through a Simon-Mukunda polarizing
gadget which can convert its polarization to any arbitrary state
[18], [19]. Photon 2 pass through a half wave plate at 8 which
performs a Hadamard operation. Thus polarization state of
particle 1 is encoded as the unknown state a|Hi1 + b|V i1
and state of photon 2 is encoded as 12 (|Hi2 + |V i2 ). Action
of HWP on photon 2 is a Hadamard operation. Thus, the state
becomes
|i12

1
(|Ei1 |Oi2 + |Oi1 |Ei2 ) (a|Hi1 + b|V i1 )
2
1
(|Hi2 + |V i2 ).
(14)
2

Now, consider photon 3 with unknown superposition state in


OAM and with definite polarization. Its state can be expressed
as,
|i3 = (|qi3 + |1 qi3 ) |V i3
(15)
where q is an integer. A polarization CN OT gate [20] is applied
on photon 2 (control) and 3 (target). This operation leads to
polarization entanglement between photon 2 and 3. Thus, the
three particle state will become

Here we are proposing a multiparty QKD protocol using


the entangled system described in section IV. We take a similar
state as in Eq. 10 given by
|i123 = |p i1 (|00i12 + |1 1i12 + | 11i12 )
(|HHi23 + |V V i23 )|o i3 ,
where |0i, |1i and | 1i are OAM states of photons.
Here we take a three dimensional subspace of infinite
dimensional OAM entangled state produced by SPDC process
with Gaussian beam as pump instead of even/odd entangled
state. This state can be used for multiparty QKD. The advantage of this state is that it can generate two sets of independent
keys, one for Alice-Bob and another for Alice-Charlie. In
ordinary three particle QKD, all the three parties will share the
same key and one can not get the key without the help of other
[30]. So if Alice wants to pass some information to Bob, not
to Charlie, this protocol is no longer useful. We have resolved
this problem with the use of a quantum state mentioned in Eq.
17.

Charly
D1
D2
D3

+1

|i123

Bob

1
D10

-1

Alice
Polarizing
Beam splitter

+1

OAM sorter

-1

D9
0

D8
D7

Detector

HWP

-1 0

+1

D4 D5 D6

(16)

This is the proposed three particle entangled state given in Eq.


10
VI.

D11

Source

Hologram

1
= (a|Hi1 + b|V i1 ) (|Ei1 |Oi2 + |Oi1 |Ei2 )
2
(|HV i23 + |V Hi23 )(|qi3 + |1 qi3 )

(17)

Fig. 5. Schematic diagram for quantum key distribution between AliceBob and Alice-Charlie. Alice- Bob has Polarization entanglement and AliceCharlie has OAM entanglement. Di - detectors, HWP - half wave plate, PBS
- polarizing beam splitter.

Q UANTUM K EY DISTRIBUTION

Quantum key distribution is essential for secure communication to share a confidential message between two indented
parties, namely Alice and Bob. A QKD protocol can be
implemented by a single photon source or entangled photon
source [21], [22]. Entangled photons with one to one photon
correlations are better source for QKD than a single photon
source. This strong correlation helps to share the key and get
the information about eavesdropping [23]. QKD is perfectly
secure, subject to all kinds of attacking strategies [24]. There
are various protocols for QKD with the utilization of entangled
photons in different degrees of freedom such as polarization,
OAM, and time-bin [25], [26], [27], [28]. Entanglement based
protocols have been studied and implemented since long because of its interesting properties such as strong correlation and
non-locality. Multipartite entanglement increases the coding
capacity and security of the key. It also provides multiparty
communication through the same channel [29].

The experimental implementation of the protocol is shown


in Fig. 5. Bob, Alice and Charlie will receive the particles
1, 2 and 3 respectively. Alices photon is entangled with
Bobs photon in polarization and it is entangled with Charlies
photon in OAM. Bobs and Charlies photons do not have any
correlation between them. Alice will measure both OAM and
Polarization states, Bob will measure polarization and Charlie
will measure OAM of their received photons.
Alice and Bob share their keys by polarization measurements. They randomly measure polarization state of their
photons in the following set of basis (i = 0 , 22.5 , 45 ,
67.5 ), (i = 22.5 , 45 , 67.5 , 180 ) respectively. These
measurements can be done by a half wave plate and polarizing
beam splitter. The pairs of angles used by Alice and Bob for
which the sum is 0 and 180 will give perfect correlation
between them. The data corresponding to these correlated
photons have same bits and can be used for the key. Alice

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Alice
Bob
1
2
3
4

and Bob will compare their polarization measurement basis


for key distribution as well as for security of the key. After
sufficient number of measurements 4/16 of the data are useful
for key, two sets of 4/16 of the data are used to check CHSH
inequalities (S and S0 ) and the remaining 4/16 are discarded.
Alice and Charlie share their keys by OAM correlation
of entangled photons. Here we follow the key sharing scheme
used in Ref [31]. In this scheme Alice and Charlie measure the
OAM state of their photons in three different randomly chosen
bases A1 , A2 , A3 and C1 , C2 , C3 respectively. This is done
by a pair of shifted holograms and an OAM sorter. The set of
bases (A3 and C3 ) has perfect correlation and the coincidence
corresponding to it can be used to generate the key. Alice and
Charlie will compare their hologram settings for QKD and
security check. In total there are 9 possible measurements.
After enough number of measurements, 1/9 of the produced
data can be used for the key. For Bell-type inequality check,
4/9 of the data will be used which confirms the security of the
key and the remaining 4/9 of the data are useless.
If Ekert protocol [3] is used in a pairwise fashion, then
around 8n pairs of photons (in practice, little more than 8n) are
required to establish a pair of secret keys of length n between
Alice and Bob and between Alice and Charlie. In our approach,
around 6n pairs of photons would be required for the same
purpose. Hence, in terms of number of photons required, our
scheme is 33% more efficient than Ekert protocol.
On the other hand, if the same number of photons are used
in Ekert and our protocol and if the target key length is also
the same, then because of more entanglement resource, our
protocol would have more redundancy and hence can tolerate
more noise. It is easy to see that the security in each degree
of freedom is equivalent to that of the Ekert protocol.
The security of the protocol is mainly checked by the
violation of Bells inequality test. All the three parties should
check Bell like inequality with their data in order to check
eavesdropping. If there is violation of inequality the entanglement is preserved and there is no eavesdropping in the
channel. The CHSH parameters S and S0 for photons entangled
in polarization DOF are given by [32]
S = E(1 , 1 ) E(1 , 3 ) + E(3 , 1 ) + E(3 , 3 ) (18a)
S 0 = E(2 , 2 ) + E(2 , 4 ) + E(4 , 2 ) E(4 , 4 ) (18b)
with
E(, ) =

R12 (, ) + R10 20 (, ) R120 (, ) R10 2 (, )


R12 (, ) + R10 20 (, ) + R120 (, ) + R10 2 (, )
(19)

where R12 , R10 20 , R120 and R10 2 are the coincidences


P (D11, D9 + D8 + D7), P (D10, D4 + D5 +
D6), P (D11, D4 + D5 + D6) and P (D10, D9 + D8 + D7)
respectively.
For any local realistic theory, the CHSH parameters S, S 0
2. Non-local nature of the entanglement will violate any of
these inequalities and this violation can be used for checking
the security of the key shared by Alice and Bob. The combination of and for Bells inequality test and for the key
distribution is given in Table I.

S
Key

Key
S0

S0

S
Key
S

S0
Key
S0

TABLE I.
D ESCRIPTION OF DATA USAGE CORRESPONDING TO
A LICE S AND B OB S MEASUREMENT ANGLES . H ERE S AND S0 ARE USED
FOR SECURITY CHECK THROUGH CHSH INEQUALITY AND IS THE
DISCARDED DATA .

Particles of Alice and Charlie have OAM correlation, so it


will violate the following Bells inequality for 3 dimensional
case [31], [33]
S =P (A1 = C1 ) + P (A2 = C1 1) + P (A2 = C2 ) + P (A1 = C2 )
P (A1 = C1 1) P (A2 = C1 ) + P (A2 = C2 1)+
P (A1 = C2 + 1) 2, where
(20)
P (Aa = Cb +k) =

2
X

P (Aa = j, Cb = (j+k)M od 3). (21)

j=0

The shifts of holograms are chosen in such a way that


they maximally violate the Bell-type inequality. j=0,1,2 corresponds to the detection of OAM states 0, 1 and -1 respectively.
The coincidence measurements with the combinations of P(D1,
D6+D9), P(D1, D5+D8), P(D2, D4+D7), P(D2, D6+D9),
P(D2, D5+D8), P(D2, D4+D7), P(D3, D6+D9), P(D3, D5+D8)
and P(D3, D4+D7) are required for the key distribution and to
check the security of the key using Eq. 20 and 21.
VII.

C ONCLUSION AND FUTURE WORK

We evaluated the Holevo capacity of the bit flip channel


existing between two entanglement sharing nodes. We also
point out that the encoding scheme ensures perfect secrecy
unaffected by the noisy bit flip channel. We extended the
ideas of super dense coding to three nodes with a brief
practical motivation for the generalization. Theoretical understanding into the limits of transmission capacity and security
are important for quantum communication channels. From an
experimental angle, we looked into the possibility of a new
entangled state and its application in multiparty QKD. With
the new QKD protocol, a common sender can share different
and independent keys with many parties. Our eventual goal is
to unify the theoretical investigations within an experimental
framework via novel quantum coding schemes we are building
to demonstrate the feasibility of a quantum communication
system.
R EFERENCES
[1]

C. Bennett and S. J. Wiesner, Communication via one- and two-particle


operators on Einstein-Podolsky-Rosen states, Phys. Rev. Lett. vol. 69,
pp. 2881-2884, 1992.
[2] C. H. Bennett, G. Brassard, C. Crepeau, R. Jozsa, A. Peres, and W. K.
Wootters. Teleporting an unknown quantum state via dual classical and
einstein-podolsky-rosen channels. Phys. Rev. Lett., 70:1895, 1993.
[3] A. K. Ekert. Quantum cryptography based on bells theorem. Phys. Rev.
Lett., 67:661663, 1991.
[4] A. Raina and S. G. Srinivasa, Quantum communication over bit flip
channels using entangled bipartite and tripartite states, IEEE. Allerton.
Conf. Control. Computers and Comm. , Oct. 2014.

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[5]
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M. A. Nielsen and I. L. Chuang, Quantum computation and Quantum


Information, Cambridge University Press, 2010.
T. M. Cover and J. A. Thomas, Elements of Information Theory, Wiley,
New York, 2006
C. H. Bennett, P. W. Shor, J. A. Smolin and A. V. Thapliyal,
Entanglement-Assisted Capacity of a Quantum Channel and the Reverse
Shannon Theorem, IEEE Trans. Inf. Theory, vol. 48, pp. 2637-2655,
2002.
A. S. Holevo, The capacity of the quantum channel with general signal
states, IEEE Trans. Info. Theory., vol. 44, pp. 269-273, 1998.
P. Hausladen, R. Jozsa, B. Schumacher, M. D. Westmoreland and W. K.
Wooters, Classical information capacity of a quantum channel, Phys.
Rev. A, vol. 54, p. 1869, 1996.
C. E. Shannon, Communication theory of secrecy systems, Bell Syst.
Tech. J., vol. 28, pp. 656-715, 1949.
P. O. Boykin and V. Roychowdhury, Optimal encryption of quantum
bits, Physical Review A, vol. 67, p. 042317, 2003.
J. Pan and A. Zeilinger, Greenberger-Horne-Zeilinger-state analyzer,
Phys. Rev. A, vol. 57, pp. 2208-2211, 1998.
C. Eltschka and J. Siewert, Entanglement of Three-Qubit GreenbergerHorne-ZeilingerSymmetric States, Phys. Rev. Lett., vol. 108, p. 020502,
2012.
D. Bouwmeester, J. Pan, M. Daniell, H. Weinfurter and A. Zeilinger,
Observation of Three-Photon Greenberger-Horne-Zeilinger Entanglement, Phys. Rev. Lett., vol. 82, pp. 1345-1349, 1999.
L. Xin, L. Qing-Hong, F. Guang-Yu, W. Yue-Yuan and L. Shu-Tian,
Resonant interaction scheme for GHZ state preparation and quantum
phase gate with superconducting qubits in a cavity, Chinese Phys. B,
vol. 23, p. 020311, 2014.
Y. Xia, J. Song, H. Song, Remote preparation of the N-particle GHZ
state using quantum statistics, Optics Communications, vol. 277, pp.
219-222, 2007.
S. Walborn, A. de Oliveira, R. Thebaldi, and C. Monken. Entanglement
and conservation of orbital angular momentum in spontaneous parametric
down-conversion. Phys. Rev. A, 69:023811, 2004.
R. Simon and N. Mukunda. Minimal three-component su (2) gadget
for polarization optics. Phys. Lett. A, 143:165169, 1990.
Salla Gangi Reddy, Shashi Prabhakar, A. Aadhi, Ashok Kumar, Megh
Shah, R. P. Singh, and R. Simon. Measuring the mueller matrix of an
arbitrary optical element with a universal su(2) polarization gadget. J.
Opt. Soc. Am. A, 31(3):610615, Mar 2014.
X. H. Bao, T. Y. Chen, Q. Zhang, J. Yang, H. Zhang, T. Yang, and J. W.
Pan. Optical nondestructive controlled-not gate without using entangled
photons. Phys. Rev. Lett., 98:170502, 2007.
A. Beveratos, R. Brouri, T. Gacoin, A. Villing, J. P. Poizat, and
P. Grangier. Single photon quantum cryptography. Phys. Rev. Lett.,
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Quantum cryptography with entangled photons. Phys. Rev. Lett., 84:4729,
2000.
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information, volume 38. Springer Berlin, 2000.
E. Waks, A. Zeevi, and Y. Yamamoto. Security of quantum key
distribution with entangled photons against individual attacks. Phys. Rev.
A, 65:052310, 2002.
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M. Lindenthal, B. Blauensteiner, T. Jennewein, J. Perdigues, P. Trojek,

B. Omer,
M. Furst, M. Meyenburg, J. Rarity, Z. Sodnik, C. Barbieri,
H. Weinfurter, and A. Zeilinger. Entanglement-based quantum communication over 144km. Nat. Phys., 3:481486, 2007.
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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Investigation of vegetation changes in the arid Trans-Himalayan ecosystem of


northern India
Sumanta Bagchi, Ekta Gupta, Karthik Murthy
Abstract Understanding ecosystem
responses to current and projected
climate change is important for sustainable land-use policies. The cold
and arid Trans-Himalayan ecosystem
is experiencing changes in regional
climate (precipitation and temperature) amidst concerns over landdegradation. We are assessing vegetation growth and distribution using satellite imagery to investigate the nature
and severity of degradation. We analyzed changes in Normalized Difference Vegetation Index (NDVI), for
phenological and biomass indicators
in the watersheds of major wetlands in
Ladakh region of northern India. The
results will help resolve long-standing
concerns over climate-induced desertification in the Trans-Himalaya.
I. INTRODUCTION
Central Asian highlands are a vast expanse of mountainous terrain that includes of Trans-Himalaya in northern
India. These represent arid ecosystems
of high anthropological, biogeochemical,
ecological, and hydrological significance
(1-3). But they are also highly susceptible to ongoing and projected changes in
regional climate (4, 5). The TransHimalayan ecosystem covers large expanses of arid and semiarid rangelands
in Ladakh (India), Spiti (India), Tibet
(China) and Mustang (Nepal), and is ex-

Dr. Sumanta Bagchi is Assistant Professor at Centre


for Ecological Sciences, Indian Institute of Science
(CES-IISc), Bangalore 560012, India. sbagchi@ces.iisc.ernet.in
Ekta Gupta is a research fellow at CES-IISc.
Karthik Murthy is a Ph.D. student at CES-IISc

periencing the effects of changes in both


precipitation and temperature. There are
widespread
concerns
over
landdegradation and desertification that have
adverse effects on biodiversity as well as
on human livelihoods (5, 6).
The general climatic trend over
the last three decades in this region, and
more broadly across the western Himalayan alpine shrub and meadow biome
(5) is towards: (i) increasing mean annual temperature, (ii) decreasing winter
precipitation (November-February), and
(iii) increasing summer precipitation
(August-September). Although there
may be a net increase in total annual precipitation, counter-intuitively, there is
also evidence for desertification. It remains unclear whether and how climatic
changes may play a major role in land
degradation and desertification. The extent, intensity, and magnitude of land
degradation also remain poorly documented.
In this project, we are analyzing
temporal patterns of change in vegetation phenology and biomass in the
Trans-Himalayas using satellite-derived
indices (Normalized Difference Vegetation Index, NDVI). Initially we investigated changes in watersheds of major
wetlands in Ladakh region, as these support the highest densities of livestock
grazers, and are likely highly susceptible
to vegetation degradation.
II. METHODS

Project number: ISTC/BES/SB/332

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1.0

Fig. 1: Illustrative example for vegetation growth

0.6
0.4

rate of decrease

0.6
0.5
0.4
0.3

NDVI score

0.2
0.1
0

50

100

150

200

250

300

350

Julian day (Jan-Dec)

Table 1. Model parameters estimated by


nonlinear (double-sigmoidal) regression
for five parameters of vegetation growth.
Parameter
Peak growth

95% Confidence limits

Estimate
0.8

0.6-1.6

Rate of increase

0.01 day-1

0.009-0.013

Onset of growth

272nd day

215-355

Rate of decrease

0.03 day-1

0.02-0.04

289th day

281-301

End of growth

rate of increase

References

0.2

NDVI score

0.8

peak

Fig. 2: Tso-Kar watershed, 2003

0.0

We used available NDVI data from


MODIS for 500 m resolution. We extracted NDVI data from 16-day interval
MODIS images between 2004 and 2013.
From this we extracted pixels from different major watersheds in Ladakh,
namely: Tso-Kar, Tso-Moriri, and Pangong-Tso. We screened these pixels
based on additional information (pixel
quality and data reliability).
Vegetation growth, as indicated
by NDVI scores, follows a well-known
double-sigmoidal pattern over an annual
cycle (January to December, Fig. 1). We
used nonlinear regression models in R
3.0.3 software to estimate the following
parameters for each year: time of onset
of growth, rate of increase after onset,
peak vegetation biomass, rate of decline
after peak, and duration of growth season.

0.0

onset
0

50

100

150

end
200

250

300

350

Julian day (Jan-Dec)

III. RESULTS & DISCUSSION


Here we show results for the Tso-Kar
watershed (Fig. 2). Key results of
nonlinear regression models for 2003 are
summarized in Table 1. In general, the
statistical models perform well in estimating four of the parameters, but need
further improvements in estimates of
onset of growth season. In future work,
we will compare estimates across time.

1. G. Miehe et al., Palaeogeography,


Palaeoclimatology, Palaeoecology
276, 130 (2009).
2. S. Bagchi, M. E. Ritchie, Ecol.
Lett. 13, 959 (2010).
3. W. R. Boos, Z. Kuang, Nature 463,
218 (2010).
4. X. Liu, B. Chen, Int J Climatol 20,
1729 (2000).
5. U. B. Shreshta, S. Gautam, K. S.
Bawa, PLoS One 7(5), e36741
(2012).
6. W. Shaohong, Y. Yunhe, Z. Du, Y.
Qinye, J Geogr Sci 17, 141 (2007).

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Study on Self-assembly of Donor-Acceptor-Donor Molecular


Materials and Melamine
Nileshi Saraf, Joydeep Dhar and Satish Patil*

Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore, India 560012
Email: satish@sscu.iisc.ernet.in

Abstract

Introduction

In the present work, the interaction


between donor-acceptor-donor molecular
oligomers (TTB) and melamine is studied
with the help of various spectroscopic and
electron microscopy techniques. TTB is a conjugated molecule which has donoracceptor-donor (D-A-D) structure and can be
used as an active chromophore in solar cell
devices. However, we observed that the selfassembled ribbon like morphology of TTB
results in low PCE due to phase separation
within the active layer of bulk heterojunction
solar cells. Melamine is introduced to disrupt
the intermolecular hydrogen bonding within
the TTB molecules which results in change in
optical properties. The FTIR and NMR
analysis suggests the presence of hydrogen
bonding between the barbituric unit of TTB
and amine group of melamine. AFM studies
show the morphological variations in the
films after adding melamine in different
ratios.

The donor-acceptor-donor (D-A-D)


based small molecules and polymers have
been
extensively
investigated
for
applications in organic FETs and solar cell
devices.1-3 In this context, our group
explored
self-assembly
approach
of
barbituric acid TTB (D-A-D) molecules in
organic solar cells and field-effect
transistors.4 Barbituric acid based TTB
molecule is synthesized by Knoevenagel
condensation of terthiophenecarbaldehyde
and barbiturate appended pyran derivative
as discussed in our earlier studies.5 The
barbiturate and thiophene units act as donor
and acceptor group, respectively. This
molecule
undergoes
inter-molecular
hydrogen bonding due to the presence of
acidic proton (NH) and electronegative
oxygen (C=O) of barbiturate functional
group. The H-bond mediated self-assembled
morphology of TTB results in long ribbon
like structures which might be disrupted by
introducing melamine as shown in Fig. 1.

Figure 1: Plausible intermolecular H-bonding between TTB and Melamine

Page 1

ISTC/CSS/STP/0339

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Results and Discussions

B) FTIR analysis

The interaction between TTB and


melamine was examined with the help of
various
characterization
techniques.
Photophysical properties were investigated
by UV-vis spectroscopy and fluorescence
studies. Atomic force microscopy (AFM) was
used to observe morphological changes in the
film after adding melamine. FTIR and NMR
results demonstrate the presence of
hydrogen bonding between the molecules of
melamine and TTB.
A) NMR spectroscopy
The NMR study of TTB and TTBmelamine at different molar ratio (1:0.25,
1:0.5, 1:1, 1:2, 1:4) is shown in the Fig. 2. The
samples were prepared in CDCl3. It can be
seen that there is an apparent shift in the
peak (~7.54) of proton of the barbiturate
unit present in TTB with the addition of
melamine. The maximum downfield shift
(~7.57) with the broadening of the peakwidth is observed at 1:1 molar ratio of
TTB/melamine indicating strongest Hbonding interaction. Further, the peak
position slightly shifts upfield and broadens
with further increase in melamine
concentration. This suggests that with
further increase in melamine concentration
number of H-bond increases, but the strength
of the H-bond decreases.

Figure 2: NMR analysis of TTB and TTB-Melamine


with varying molar ratio of melamine.

Figure 3: FTIR spectra of TTB and TTB-Melamine

The FTIR analysis of TTB and TTBmelamine composite (Fig. 3) was performed
in KBr pellet method. It was observed that
the C-N stretching at 1357 cm-1 and 1295 cm-1
in TTB molecules diminished after adding
melamine. The peak due to C=O stretching
(1620 cm-1, 1640 cm-1) and NH bending
(amide II) (1496 cm-1) in TTB shifts at higher
frequency after addition of melamine due to
the formation of H-bond between TTB and
melamine.
C) Optical Properties
The thin film normalized absorption
spectra of TTB and TTB/melamine at
different molar ratio are shown in Fig. 4(a).
The band at 390 nm corresponds to the -*
transition and the band at 517 nm is due to
the intramolecular charge transfer from the
donor to the acceptor moiety in TTB. It can
be seen that there is no shift in the
absorption maxima of TTB with gradual
addition of melamine. The thin film emission
spectra (Fig. 4(b)) shows that the
fluorescence intensity varies with varying
melamine concentration. The intensity is
maximum at 1:1 molar ratio followed by 1:2
whereas 1:4, 1:2 and TTB shows similar
emission intensity. Therefore, the results of
Page 2

ISTC/CSS/STP/0339

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the fluorescence study indicate that at 1:1


molar ratio the favorable interaction between
TTB and melamine efficiently restricts the
self-quenching phenomenon of TTB.

were spin-coated onto pre-cleaned Si wafers


at 1000rpm for 60 sec. The AFM image of
TTB (1mg/ml) as shown in Fig. 5 shows
nanoribbon-like structure with width around
60nm and height ranging from 5-15 nm (Fig.
5(b)).

(a)

Figure 5(a): AFM analysis of TTB dissolved in


chlorobenzene (1mg/ml)

(b)
Figure 4: (a) Normalized Absorption and (b)
Emission Spectra of TTB and TTB-Melamine at
different molar ratio of melamine in thin film

D) AFM analysis
The p-type Si (100) wafers were precleaned by repeated sonication in acetone
followed by piranha treatment. The wafers
were then thoroughly rinsed with distilled
water and dried with nitrogen flow. Oxygen
plasma treatment was done for 15 min
before depositing films in order to make the
surface hydrophilic to ensure the uniformity
of the deposited films. Thin films of TTB and
TTB-melamine dissolved in chlorobenzene

Figure 5(b): Depth profile of AFM image of TTB


dissolved in chlorobenzene (1mg/ml)

Melamine in the molar ratio of 1:0.05,


1:0.1, 1:0.2, 1:0.4 was added in TTB and
changes in the morphology is studied as
shown in Fig. 6(a-d). It can be seen that as the
concentration of melamine is increased, the
TTB network is becoming denser. Melamine
assists the TTB molecule to form a better
interdigitated network enhancing the area of
coverage.
Page 3

ISTC/CSS/STP/0339

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the disruption of strong H-bonding between


the TTB molecules. The crystallization
behavior in cooling cycle was not observed.

Conclusion and Future Plan


(a)

(c)

(b)

(d)

Figure 6: AFM images of TTB-Melamine at (a) 1:0.05,


(b) 1:0.1, (c) 1:0.2 and (d) 1:0.4 molar ratios.

E) DSC measurements

In conclusion, we have investigated


the morphological, thermal and optical
properties of TTB and TTB-Melamine
composite. The results reported here clearly
states that melamine disrupts the selfassembly between the TTB molecules. The
TTB-Melamine in a ratio of 1:1 shows
promising behavior for further use in solar
cells with strongest hydrogen bond
interaction. Further studies on its electronic
properties are under progress in order to
investigate the utility of these materials for
solar cells.

Acknowledgement
We sincerely acknowledge funding
from ISRO-STC.

References

Figure 7: DSC thermogram of TTB and TTB-Melamine


with different molar ratio of melamine

The thermal properties of TTB and


TTB-Melamine were investigated by using
differential scanning calorimetry (DSC). It
was observed that TTB shows a higher
melting point of around 237C which is due
to the intermolecular hydrogen bonding. DSC
results as shown in Fig. 7 suggests that as
melamine concentration is increased, the
melting point shifts to lower value with
minimum of 174C in 1:1 molar ratio due to

1. Garnier F.; Hajlaoui R.; Yassa A.;


Srivastava P. Science 1994, 265, 1684
1688
2. Burroughes J.; Bradley C; Brown A.;
Marks R.; Mackay K.; Friend R.; Burns,
P.; Holmes A.; Nature 1990, 347, 539
540.
3. Liang, Y.; Feng, D.; Wu, Y.; Tsai, S. T.; Li,
G.; Ray, C.; Yu, L.; J. Am. Chem. Soc.
2009, 131, 77927799.
4. Bhaskar, R.; Tandy, K.; Horecha, M.;
Formanek, P.; Stamm, M.; Gevorgyan,
S.; Krebs, F.; Kiriy, A.; Meredith, P.;
Burn, P.; Namdas, E.; Patil, S.; J. Phys.
Chem. C 2011, 115, 1436914376.
5. Bhaskar, R.; Stephen, M.; Ali, F.; Patil,
S.; J. Phys. Chem. C 2013, 117,
91299136.

Page 4

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

High-resolution Image restoration


and enhancement using GPU
Nithish Divakar and R. Venkatesh Babu

AbstractThe Weighted Nuclear Norm Minimisation for


denoising is an effective denoising algorithm which has a very
good denoising performance at high noise levels. But it requires
a huge amount of computational time. Here we propose a
methodology by which the computationally intensive part of
WNNM is accelerated using GPUs. The acceleration requires
computation of singular value decomposition of large number of
average sized matrices. We also discuss a better way to place data
in GPU memory so that it results in high memory bandwidth.

I. I NTRODUCTION
A digital image can be considered as a discrete representation of continuous 2D signal. A generic noisy image model
can be expressed as follows.
y(p) = x(p) + (p)
where x is original image,y is the noisy image and is the
noise that gets mixed. Image denoising algorithms attempt to
obtain an approximation x
of the the signal x, when only the
signal y and some knowledge of noise is known.
Image denoising using weights nuclear norm minimisation
is a denoising algorithm which shows a very good recovery
rate even at high noise levels [1], but WNNM denoising requires huge computational time. Here we propose an approach
which can accelerate this algorithm using GPUs.
II. R ELATED W ORK
Many state of the art denoising algorithms exist for image
denoising, most, differing only in their model of what noise
is. From the assumptions that natural images constitutes piecewise smooth functions, image denoising algorithms like the
ones given by Lindenbaum et al. in [2] uses smoothening filter
to remove noise. But this approaches fails to preserve image
edges as their noise model includes all sudden variations in
the signal.
Non Local means algorithm suggested by Buades et al.
in [3] removes noise by taking contribution from only those
pixels which are similar to the key pixel.
BM3D algorithm proposed by Dabov et al. in [4] computes
neighbourhood of blocks in transform domain and collaborative filtering is used to estimate pixel intensities.
Although the non local neighbourhood model appears to
be concrete in estimating the noise model, it is intrinsically
depending on the fact that a major portion of original image
Nithish Divakar is masters student in the SERC Department,
Indian
Institute
of
Science,
Bangalore,
India
nithish.divakar@ssl.serc.iisc.ernet.in
R. Venkatesh Babu is an assistant professor in the SERC Department, Indian
Institute of Science, Bangalore, India venky@serc.iisc.ernet.in

details can still be extracted despite the corruption from noise.


This assumption fails at higher noise levels.
Low rank matrix approximation based image denoising
methods uphold there denoising efficiency even at higher noise
levels. Weighted nuclear norm minimisation based denoising
proposed by Gu et al. in [1] is such a strategy which uses
weighted reduction of data variability along different dimensions to reduce noise.
Although this method shows good denoising performance,
the algorithms heavy resource consumption in terms of computation time makes it unusable for application that require on
the line processing. This research effort is to improve WNNM
denoising algorithms execution time.
III. W EIGHTED N UCLEAR N ORM M INIMISATION FOR
IMAGE DENOISING

Weighted nuclear norm minimisation is a problem in low


rank matrix approximation theory [5], which uses a nuclear
norm as the objective function for low rank matrix completion.
The problem can be stated as follows
= arg min kY Xk2F + kXkw,
X
X

w is a weight vector and kXkw, , is defined to be dot


product of the singular values of X and the weight vector.
The algorithm is throughtly described in Gu et al. [1]
WNNM is used in image denoising by constructing a matrix
whose columns are vectorised patches which are obtained from
a local neighbourhood of a key patch. Local neighbourhood
of each patch is defined as the set of patches which are closer
to it in terms of some distance measure. Usually, `2 norm
distance is used.
Denoising is essentially constructing the low rank approximation of the original matrix. WNNM helps us in achieving
this.
IV. P ROPOSED APPROACH
The most computationally intense part of the WNNM
algorithm is to compute the singular value decomposition of
the neighbourhood matrix for evech key patch. But the computation corresponding to one key patch is totally independent
of another.
The key part of the proposed approach is a technique to
compute all the required SVDs on a GPU device. Since the
neighbourhood matrix is not very large, the usual algorithms
for computing singular value decomposition does not provide
an optimum performance as they have been designed to handle
large matrices.

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More over, the WNNM algorithm requires computation of


SVDs for a large number of matrices.
V. ACCELERATION USING GPU
An easy approach for computing all the required SVDs
would be to simply offload the computation to GPU such
that a single thread compute SVD per matrix. The execution
timings of this approach can be seen in Table I. This approach
has many possible improvement because it uses only a small
fraction of the thread pool available.
A better idea would be to use multiple threads to compute
the SVDs in parallel, leading to 2 levels of parallelism.
We have used the lowest number of threads which have
implicit synchronisation between them. This atomic set of
threads are called as warps. The hardware on which our
experiments were conducted restricts this number to be 32.
But the following methodology can be easily adapted to any
other hardware specification.
Our specific problem structure advocates us to use a different algorithm for SVD computations. Biorthogonalisation
algorithm [6] for svd computation offers a faster and more
unifrm memory access pattern when used in parallel than
standard bi-diagonalisation algorithm.
Biorthogonalisation procedure was first proposed by
Hestenes in [6]. A good discussion about better accuracy of
biorthogonalisation procedure and its implementation can be
found in [7]. The Complete algorithm is given in Figure 1.
1:
2:
3:
4:
5:
6:
7:
8:
9:
10:
11:
12:
13:
14:
15:
16:

procedure B IORTHOGONALISATION(A)
[a1 |a2 | . . . |an ] = A conv = f alse . Columns of A
V = In di = aTi ai i = {1, . . . , n}
.
while 30 or less iteration and conv = f alse do
for Each column pair
p (ai , aj ) : i < j do
.
if |aTi aj | > m di dj then
Compute the givens rotation angles
Rotate column vector through the angle
Update corresponding dot products
end if
end for
Set conv = true if no columns were updated
end while

if conv=true, then set ii = di and ui = ai ii .


U = [u1 |u2 | . . . |un ]
end procedure
Fig. 1.

SVD decomposition by Biorthogonalisation

A. Data distribution in GPU memory for optimum performance


The statements marked by in Figure 1 can be executed
in parallel by a a set of GPU threads. During the comutation,
because of the structure of the algorithm, adjacent threads in
the warp access elements of a olumn i matrix together. This
suggest us to use a stacked transpose storage of matrices in
the memory for faciliting non strided memory access. So we
will use a P N M order stacking where P is number of
matrices and M N is matrix dimensions.

VI. E XPERIMENTAL RESULTS


All experiments were carried out in a system with Intel
Xeon CPU E5-1650 v2 processor and Tesla K20 GPU card
with 5 GB of GDDR5 memory.
The patch size used by the algorithm is 9. So the dimension
of the vectorised patches is fixed at 81 components. Also, the
number of SVDs to be performed throughout the algorithm
also stays the same at 7056 for an image size of 256 256.
The running times are calculated for matrix size which the
algorithm encounters during a successful run.
TABLE I
E XECUTION TIME OF BOTH SINGLE AND 32 THREAD PARALLEL SVD
COMPUTATION

Problem size (m n p)
81 130 7056
81 120 7056
81 110 7056
81 100 7056
81 90 7056
81 80 7056
81 70 7056

One Thread
10.4893s
9.5463s
8.0076s
7.3253s
6.9263s
5.0035s
4.5902s

32 Threads
1201ms
954ms
800ms
653ms
490ms
383ms
271ms

A. Final speedup
The original algorithm spent about 575.739 seconds for all
required SVD computations. Our method is able to perform
same amount of comutation in 9.504 seconds. Thus we have
obtained about 60x acceleration in required decomposition
part.
VII. C ONCLUSION
The results from the experiments suggested that WNNM
method has lots of potential to become a fast and efficient
denoising algorithm. We were able to reduce the time taken for
the most computationally intensive part of the algorithm by 60
times. If other parts of the algorithm are equally accelerated,
WNNM can become a fast algorithm indeed.
R EFERENCES
[1] S. Gu, L. Zhang, W. Zuo, and X. Feng, Weighted nuclear norm
minimization with application to image denoising, in IEEE Conf. on
Computer Vision and Pattern Recognition, 2014.
[2] M. Lindenbaum, M. Fischer, and A. Bruckstein, On gabors contribution
to image enhancement, Pattern Recognition, vol. 27, no. 1, pp. 18, 1994.
[3] A. Buades, B. Coll, and J.-M. Morel, A non-local algorithm for image
denoising, in Computer Vision and Pattern Recognition, 2005. CVPR
2005. IEEE Computer Society Conference on, vol. 2. IEEE, 2005, pp.
6065.
[4] K. Dabov, A. Foi, V. Katkovnik, and K. Egiazarian, Image denoising by
sparse 3-d transform-domain collaborative filtering, Image Processing,
IEEE Transactions on, vol. 16, no. 8, pp. 20802095, 2007.
[5] I. Markovsky and K. USEVICH, Low rank approximation. Springer,
2012.
[6] M. R. Hestenes, Inversion of matrices by biorthogonalization and related
results, Journal of the Society for Industrial & Applied Mathematics,
vol. 6, no. 1, pp. 5190, 1958.
[7] Z. Drmac, Implementation of jacobi rotations for accurate singular value
computation in floating point arithmetic, SIAM Journal on Scientific
Computing, vol. 18, no. 4, pp. 12001222, 1997.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Turbulence-transport-chemistry interaction in statistically planar


premixed flames in near isotropic turbulence
Harshavardhana A. U, Swetaprovo Chaudhuri* and K. N. Lakshmisha
Department of Aerospace Engineering, Indian Institute of Science, Bangalore, INDIA
Abstract - Turbulence-transport-chemistry interaction plays a crucial role on the flame surface
geometry, local and global reaction rates, and therefore, on the propagation and extinction
characteristics of intensely turbulent flames encountered high speed combustors. The aim of the
present work is to understand these interaction effects on the flame surface. This will be useful
in developing an insight into the annihilation and extinction mechanism of lean premixed
flames, interacting with near isotropic turbulence. As an example case, lean premixed H2-air
mixture is considered with detailed chemistry effects in Direct Numerical Simulations (DNS).
The work is carried out in two cases where a statistically planar flame interacts with near
isotropic turbulence of different turbulence intensities (Case 1 ReT = 146 and Case 2 ReT = 351).
A recently proposed Flame Particle Tracking (FPT) technique was used for this purpose. Flame
particles are surface points residing and comoving with an iso-scalar surface within a premixed
flame. Tracking flame particles allows us to study the evolution of propagating surface locations
uniquely identified with time along with the evolution of various properties at those locations. In
this work, using DNS and FPT we study the flame speed, reaction rate and transport histories of
such flame particles residing on iso-scalar surfaces. An analytical expression for the local
displacement flame speed (Sd) is derived, and the contribution of transport and chemistry on the
displacement flame speed is identified. An examination of the results of both the cases leads to a
conclusion that the cause of variation in Sd may be attributed to the effects of turbulent
transport and curvature.

I.

INTRODUCTION

Turbulent combustion can be


understood to a greater extent in terms of
propagating iso-scalar surfaces particularly
for studying the phenomena such as
turbulent mixing and reactions on these
surfaces [1]. This approach is followed by
many researchers working on the turbulent
combustion by using detailed, reduced
and/or single step chemistry to model the
reactions.
The previous studies on the
statistically planar premixed flames
considered an iso-scalar surface of mass
fraction [2-3] and reaction progress
variable [4]. In the work of Echekki et al.
[2-3] the effects of strain rate, and
curvature are examined on the propagation
of an iso-scalar surface of mass fraction of
CH4. Further, in [4] the effects of non-

unity Lewis number were assessed on the


behaviour of the displacement flame
speed. These studies used either reduced or
single step chemistry to model the
reactions. In spite of important insights
gained from these studies, the focus was
on understanding the global effects of the
turbulence flame interaction and the local
effects are not studied.
The effects of turbulent mixing and
dispersion are understood to a great extent
with Lagrangian type of flow description.
However, a semi-Lagrangian approach is
an attractive way to study the interaction
of premixed flame with turbulence. A brief
of this approach is described below.
In the recent work of S. Chaudhuri [5], a
new technique is proposed to study the
local effects on the flame surface by

*Corresponding Author, Email: schaudhuri@aero.iisc.ernet.in.


IISC-ISRO STC Project Code Number: ISTC/MAE/SC/334
Part of this work appeared as Technical Publication Nos. ASME GTINDIA 2014-8340 in the 2014
ASME GT India Conference, New Delhi

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tracking the evolution of discrete locations


on an iso-scalar surface within a premixed
flame and is called as Flame Particle
Tracking (FPT). Further, the FPT
technique is used to study the kinematic
effects such as strain rate and curvature on
propagation characteristics of the premixed
flame.

turbulence-transport-chemistry is studied
by
considering
statistically
planar
premixed flames interacting with near
isotropic turbulence with two turbulence
intensity levels namely,
1. Low turbulence intensity level
(Case 1, ReT = 146)
2. High turbulence intensity level
(Case 2, ReT = 351)

In the present work utilizing the FPT


technique, the interaction between

Figure 1 Computational domain of statistically planar flame in near isotropic turbulence. a) 2D schematic and b)
3D domain showing flame surface with black dots representing the flame particles

II.
A.

COMPUTATIONS

Direct Numerical Simulations

In the present work, three dimensional


Direct Numerical Simulations of lean,
premixed, H2-air mixture are performed
using the open source PENCIL CODE [6].
The combustion chemistry part in the
pencil
code
is
implemented
by
Babkovskaia et al. [7], where the NavierStokes, energy and species equations are
solved in the compressible form for a
turbulent, reacting mixture. Further, for
both the cases the combustion chemistry is
modelled by using detailed H2-air
mechanism developed by Li et al. [8],
consisting of 19 elementary reactions and
9 species. The inlet conditions namely,
temperature (T) = 310 K, pressure (P) = 1
atm, equivalence ratio () = 0.81 and
Lewis number (Le) = 0.84 (diffusivity

calculated with that of the deficient species


H2), are maintained same for both cases.
Also, all the variables pertaining to both
the cases are listed in Tab. 1.
B.

Flame Particle Tracking


Algorithm
The DNS data obtained from the above
simulation serves as an input to the FPT
algorithm. On a given iso-scalar surface
various parameters are calculated for each
flame particle and for the iso-surface. The
FPT algorithm is described briefly in the
following paragraph and readers can refer
to [5] for further details.
The position of the flame particle at any
time instant (t) is governed by,

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(1)

where, ( [ ], ) is the flow velocity;


( [ ], ) is the local displacement
flame speed of the iso-surface and
( [ ], ) local unit normal. Each of
( ) at
these variables are dependent on
time t.
In the FPT technique, a constant property
surface which propagates into the flow is
chosen and the discrete locations on the
surface are marked and are called as
flame particles. This flame particles are
surface points [1] on a reacting
propagating surface. The evolution of
III.

RESULTS AND DISCUSSION

A. Statistically planar flames


In [5] two statistically planar flame
cases (Case 1 and Case2) experiencing
different turbulent intensity levels were
investigated using FPT. It was found that
the tangential strain rate and also,
curvature increased to large values towards
the end of the flame particle lifetime
(Here, the negative is used to indicate that
the flame surface is concave towards
reactants. A positive value indicates that
flame surface is convex towards reactants).
These observations were attributed to the
(a)

flame particles with time obeys the Eq. (1).


The particle locations are advanced with
the time and the co-ordinates of the flame
particles at time level t+t is obtained
from the previous time level t using the
triangle-ray intersection algorithm. The
noticeable distinction between the present
method and the previous works on particle
tracking is that, the flame particles are
reactive and they are confined to a specific
iso-scalar surface.

reorientation of local surface normal w.r.t.


the most extensive component of the
principal strain rate. This leads to
persistently increasing tangential strain
rate, cusp formation and further leading to
annihilation of the flame surface. It was
also shown that the local displacement
flame speed Sd sharply increased towards
the end of flame particles. In recent
computational
work
[9],
similar
phenomena was also observed, albeit with
single step chemistry.

(b)

Figure 2 Displacement flame speed variation with normalized time for Tiso = 1493K (a) Case 1 (b) Case 2

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(a)

(b)

(c)

Figure 3 (a) Heat flux (b) Diffusion flux and (c) Heat release rate variation with normalized time for Tiso =
1493K and Case 1

(a)

(b)

(c)

Figure 4 (a) Heat flux, (b) Diffusion flux and (c) Heat release rate variation with normalized time for Tiso =
1493K and Case 2

(b)

(a)

Figure 5 Magnitude of gradient of T variation with normalized time (a) Case 1 and (b) Case 2 for Tiso = 1493K

For an iso-temperature surface the analytical expression for Sd is as follows,


=

1
|

.(

)+

In the Figs. 2 to 5, the red lines represent


the variation in the property for individual
particles and the black line with circles is
the ensemble average of the property over
all the particles at that instant.
Figures 2a and 2b shows the
variation of Sd with
for Case 1 and
,
Case 2, respectively for the isotemperature surface of Tiso = 1493K. Here,
, is the life time of the flame particle. It
is total duration between the instant at

( )

which the particle is placed on the isosurface to the time instant at which it is
lost. It is observed from Fig. 2a that the Sd
remains constant up to
0.8 and
,
increases rapidly towards the end. To
assess this behavior, individual terms of Sd
equation (Ref. Eq.(2)) are analyzed.
The first term of the Sd equation is the heat
flux term and it shows an increase with the
normalized time, as shown in Fig. 3a. The
Figs. 3b and 3c shows the behavior of

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diffusion flux term and the heat release


rate term, respectively. These terms show a
decreasing trend with normalized time
signifying negative contribution to the Sd.
Further, the | | in the denominator of
the expression, as plotted in Fig. 5a, shows
a decreasing trend with normalized time.
The negative contribution of diffusion flux
and heat release rate to Sd is overcome by
the drop in | |, leading to an overall
increase in resultant. Since, the | | can
be related to the curvature, it can be argued
that for a constant temperature surface the
increase in Sd is due to curvature and heat
focusing effects.
Similar to the Case 1 of Tiso=1493K,
Fig. 2b shows the variation of Sd for the
Case 2 for the same iso-surface. Here
though the Sd value increases continuously
from the initial time itself, the variation
however, is more steep from
0.8
,
onwards. To understand this behavior of
Sd, again the individual terms of Eq. (2) are
analyzed. The behavior of individual terms
pertaining to Case 2 and Tiso = 1493K are
shown in Fig. 4 and Fig. 5b. The nature of
heat flux, diffusion flux and heat release
rate is shown in Fig. 4a, 4b and 4c
respectively. Further, Fig. 5b shows the
variation in magnitude of gradient of T
with normalized time. Similar to the Case
1, the analysis of the individual terms
shows that the increase in Sd towards the
end of particle life time can be attributed to
the heat focusing and curvature effects.

IV.

Thus, from the study presented in this


paper, it can be concluded that the increase
in Sd is universal for the constant
temperature iso-surfaces towards the end
of the flame particle lifetime. Further, the
increase in Sd is mainly attributed to pure
curvature and heat focusing effects.

Grid
Domain (cm)



(cm/s)
(cm)
( )
( )
( )
(K)
Flame
Thickness
(m)

( )
( )

Case 1
256x128x128
1x0.5x0.5
9

Case 2
256x128x128
1x0.5x0.5
9

300
192
146
0.119
627
28
52
310
0.81
361

500
503
351
0.109
217
13
12
310
0.81
361

4 of Parameters
Table 1 List
680

2.5
292

CONCLUSIONS AND FUTURE WORK

In the present work, by using flame


particle tracking algorithm, the flame
surface annihilation and propagation of
statistically planar premixed flames is
studied. The increase in the displacement
flame speed towards the end of the particle
lifetime is universal irrespective of the
turbulence intensity level and initial
condition of the flame surface. This

increase in Sd is attributed to decrease in


| | which influences the Sd through the
curvature increase to large negative values.
The FPT technique is an important
tool in understanding the local phenomena
of the flame surface. Further, FPT
technique will be employed to understand
the flames in the shear layers in high speed
flows. The stabilization of flames at high

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speeds is a challenging task as the flow


time scales are very small compared to
chemical time scales. The phenomenon
such as local to global extinction transition

is very crucial to understand the flame


stabilization. The FPT technique offers us
elegant way to study this extinction
transition.

REFERNCES
1. Pope, S., 1988. The evolution of
surfaces in turbulence. International
journal of engineering science,
26(5),pp. 445469.
2. Echekki, T., and Chen, J. H., 1996.
Unsteady strain rate and curvature
effects in turbulent premixed methaneair flames. Combustion and Flame,
106(1), pp. 184202.
3. Echekki, T., and Chen, J. H., 1999.
Analysis of the contribution of
curvature
to
premixed
flame
propagation. Combustion and Flame,
118(1), pp. 308311.
4. Chakraborty, N., and Cant, R. S.,
2005. Influence of lewis number on
curvature effects in turbulent premixed
flame propagation in the thin reaction
zones regime. Physics of Fluids
(1994-present), 17(10), p. 105105.
5. Chaudhuri, S., 2014. Life of flame
particles embedded in premixed
flames interacting with near isotropic
turbulence. Proc. Combust. Inst.
(2014),http://dx.doi.org/10.1016/j.proc
i.2014.08.007.
6. http://www.nordita.org/software/penci
l-code/.
7. Babkovskaia, N., Haugen, N., and
Brandenburg, A., 2011. A high-order
public domain code for direct
numerical simulations of turbulent
combustion. Journal of computational
physics, 230(1), pp. 112.
8. Li, J., Zhao, Z., Kazakov, A., and
Dryer, F. L., 2004. An updated
comprehensive kinetic model of
hydrogen combustion. International
Journal of Chemical Kinetics, 36(10),
pp. 566575.
9. Andrei N. Lipatnikov, Vladimir A.
Sabelnikov, S. N., and Hasegawa, T.,
2014. Unburned mixture fingers in
premixed turbulent flames. Proc.
Combust.
Inst.
(2014),

http://dx.doi.org/10.1016/j.proci.2014.
06.081.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Thermally Activated Unimolecular Decomposition Mechanisms of


Dimethylnitramine-Aluminum (DMNA-Al) and Dimethylnitramine-Zinc
(DMNA-Zn) Complex
Anupam Bera and Atanu Bhattacharya*
Department of Inorganic and Physical Chemistry, Indian Institute of Science,
Bangalore 560012, India *atanub@ipc.iisc.ernet.in

Abstract
In this report we discuss the effects of metal
atoms in the ground state decomposition
mechanisms of dimethylnitramine (DMNA),
which is the simplest nitramine molecule, by
means of quantum chemical calculations. For the
present study, we have considered two important
metal atoms, aluminum (Al) and zinc (Zn). The
decomposition pathways of isolated DMNA,
DMNA-Al and DMNA-Zn have been explored
at the MP2/6-31G(d) level of theory. The
reaction pathways of the isolated DMNA,
DMNA-Al, and DMNA-Zn are also compared
and contrasted in this report. MP2 level of
theory predicts that isolated DMNA can follow
N-NO2 dissociation as well as nitro-nitrite
isomerization pathways; however, N-NO2 bond
dissociation pathway is associated with the
lowest activation energy barrier. DMNA-Al
complex, on the other hand, shows significantly
different decomposition pathway: it involves
several steps, such as Al-O bond dissociation,
and then N-N bond dissociation followed by an
isomerization. DMNA-Zn complex exhibits,
first, N-N bond dissociation, and after
transforming to a very stable dimethyl ( 2-nitro)
amine zinc complex it undergoes a Zn-O bond
dissociation which leads to the similar nitrite
isomerization product and finally NO
elimination. In contrary to the DMNA results,
NO elimination is found to be the lowest energy
pathway for both DMNA-Al and DMNA-Zn
complexes.

Introduction
For a long time, molecular energetic
materials (EMs), produced by mixing oxidizer
and fuel constituents into one molecule, (e.g.,
nitroglycerine, RDX, HMX, etc.), have been the
centre of attraction for high energy propellant
applications.
However,
recently,
novel
composite metalized energetic materials
(mEMs),[1] containing metal particles (e.g., Fe,
Al, etc.) and traditional molecular EMs, have
drawn significant attention due to their superior
performance
in
advanced
propellant
applications.[2] They are found to release more
than twice as much energy as the best molecular
explosives do.[3] As compared to the
conventional molecular EMs, mEMs offer the
possibility of faster energy release, more
complete combustion and greater control over
performance. Burn rates of metalized energetic
propellants can be accelerated by controlling the
size of the constituent metal particles. Tuning
the surface-to-volume ratio of the metal
particles, the rate of chemical reactions of
composite mEMs can also be controlled.1
Enhanced performance of mEM is often
accounted for the exothermicity of oxide
formation reaction for constituent metal during
combustion. For an example, heat of formation
of alumina from aluminum (4Al+3O22Al2O3)
is -1676kJ/mol.[4] During burning of molecular
EMs in mEM, the Al particles are oxidized and
Project # ISTC/CIP/AB/333

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the exothermic heat is added to the total heat of


reaction. This thermodynamic explanation of
superior performance of mEM over molecular
EM is well accepted in energetic material
community. However, another part of this
problem has never been seriously considered:
the presence of metal (particle) surface can also
alter the decomposition mechanisms and
dynamics of molecular EMs. How does metal
surface alter decomposition mechanisms and
dynamics of molecular EMs? How does metal
surface transfer energy to the molecular EMs
during burning? These questions have mostly
remained unanswered, thus far. In the quest of
the answers to these questions, this article
presents theoretically predicted decomposition
pathways of a simple analogue nitramine
molecule and its complex with aluminum atom.

RDX(hexahydro-1,3,5-trinitro-1,3,5triazine), HMX (Octahydro-1,3,5,7-tetranitro1,3,5,7-tetrazocine, C4H8N8O8) and CL-20


(2,4,6,8,10,12-hexanitro-2,4,6,8,10,12hexaazaisowurtzitane) are well known nitramine
(N-NO2)-based energetic materials. Their
chemical structures are depicted in Figure 1.
These molecules possess a number of N-NO2
(nitramine energetic moieties. Due to the
complex structures of nitramine energetic
molecules, often a structurally simple analogue
molecule dimethylnitramine (DMNA, see Figure
1 for structure), containing only one N-NO2
energetic moiety, is subjected to the laboratory
experiment to explore intrinsic decomposition
mechanisms and dynamics of a single nitramine
moiety. [5]. To date, thermally activated
decomposition (which occurs on ground
electronic state surface) of isolated DMNA has
been investigated experimentally [6] and
theoretically
[7];
however,
thermal
decomposition of DMNA-Al and DMNA-Zn
complexes, which can be considered to be a
simple analogue molecule of metalized
nitramine energetic material, is hithertounexplored. Furthermore, a comparative study of
the decomposition mechanisms of isolated
DMNA, DMNA-Al, and DMNA-Zn complexes
at the ground electronic state will enable us to
predict how presence of metal atom can
change/alter the decomposition behavior of
single nitramine moiety.

Figure 1: Structure of RDX, HMX, CL20 and


DMNA
In the present work, ground electronic
state decomposition pathways of isolated
DMNA and DMNA-Al complex have been
explored utilizing second order Mller-Plesset
(MP2) perturbation theory with 6-31(d) basis
set. The decomposition pathways of these two
systems are compared and contrasted. Isolated
DMNA exhibits N-NO2 bond dissociation
(rendering NO2 product) as the lowest energy
pathway; however, both DMNA-Zn and
DMNA-Al complexes exhibit a novel lowest
energy decomposition pathway, which is similar
to nitro-nitrite isomerization; however, the
pathway finally yields NO as a final
decomposition product.

Theoretical Procedure
All geometry optimizations at the
ground state of DMNA, DMNA-Al, and
DMNA-Zn are performed at the MP2/6-31(d)
level of theory using Gaussian 09.[8] MP2/631G(d) was previously found to be optimum
level of theory to estimate activation barriers for
DMNA system. [9] The transition state is
confirmed by performing frequency calculation.
The unstable normal mode of vibration at the
transition state shows an imaginary frequency
and an intrinsic reaction coordinate (IRC)
calculation starting from the relevant transition
state is indicative of the related pathway. The
basis set superposition error (BSSE) associated
with the NO and NO2 elimination pathways are
corrected by counterpoise method, as

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Results and Discussion


As previous experimental investigations
on the thermal decomposition of gas phase
isolated DMNA [6] shows that DMNA can
dissociate through two plausible mechanisms:
NO2 elimination and nitro-nitrite isomerization
followed by NO elimination, in the present work
we have explored these two reaction channels
for isolated DMNA, and DMNA-Al and
DMNA-Zn complexes. The results are presented
and contrasted below.
DMNA: The reaction pathways with relative
energies (in Kcal/mole) and structures of the
optimized geometries at different critical points
for DMNA are depicted in Figure 2. Relative
energies are given in Table 1. Previously,
decomposition pathways of DMNA in the
ground electronic state was explored by
Thomson and coworkers [7(a)] at MP2/6311G(d,p) level of they and NO2 elimination
was predicted to be the lowest energy
dissociation channel as compared to nitro-nitrite
isomerization, which is in concordance with the
present results. The nature of the transition state
(TS)
associated
with
the
nitro-nitrite
isomerization dissociation channel of DMNA
has been a subject of intense discussion for a
long time. [9] Both tight and loose TSs on the
ground electronic state surface of DMNA are
localized at MP2 level. The activation energy
barrier to the loose TS is calculated to be 69
kcal/mol, significantly lower in energy than that
of tight TS, as predicted at the MP2/6-31G(d)
level. NO2 elimination barrier, however, is
calculated to be 30 kcal/mol, which is
significantly lower in energy than that of both
isomerization TSs.

Ts2

100

94
80

Energy(Kcal/mole)

implemented in Gasssian09. Transition states for


both the NO and NO2 eliminations are also
performed through potential energy scanning. A
relaxed potential energy scan is performed using
Z-matrix by changing the scan variable
(respective bond distance).

Ts1

60

69
NO elimination

40

20

NO2 elimination

39
24 Opt3

30

0 Opt1

Figure 2: Decomposition pathway of DMNA in


the ground electronic state, as revealed at the
MP2/6-31G(d) level of theory. The relevant
energies are in Kcal/mole.
DMNA-Al: Figure 3 shows decomposition
pathway of DMAN-Al complex and the relative
energies are given in Table 1, as predicted at
MP2/6-31G(d) level of theory. Optimized
geometry of DMNA-Al complex at different
critical points are also depicted the figure.
Figure 3 shows that the Al atom is located below
the N-NO2 plane: this complexation finally
results in a non planar geometry of the N-NO2
moiety in DMNA-Al complex (Opt1), which is
in contrast to that of DMNA. The Al atom
shows bonding with both oxygen atoms (of NO2
moiety) and perhaps with the (N1) nitrogen atom
(of N-NO2 moiety). Furthermore, figure 3
clearly shows that decomposition of DMNA-Al
follows a number of steps, which can finally
render NO and NO2 eliminations. However, NO
elimination channel shows the lowest energy
pathway.
The first transition state (Ts1), in figure
3, suggests Al-O bond dissociation with an
activation energy of 23 kcal/mole. This
transition state is connected to an intermediate
(Opt2) in the forward direction, which is again
connected to a transition state (Ts2) for N-N
bond dissociation. Following this transition state
DMAN-Al complex can be converted to an
isomeric
form
(Opt3).
This
two-step

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isomerization pathway of DMNA-Al complex is


similar to a nitro-nitrite isomerization channel of
isolated DMNA. Interestingly, the overall
isomerization process is an exothermic process
in the case of DMNA-Al complex and is
endothermic process for isolated DMNA
molecule. The energy barriers associated with
NO elimination and the NO2 elimination with
respect to Opt3 are estimated to be 13 and 43
kcal/mol, respectively, which undoubtedly
indicates that the NO elimination following
isomerization is the lowest energy pathway.
Here note that NO2 elimination is predicted to be
the lowest energy dissociation channel for
isolated DMNA.

elimination is unlikely to occur on the ground


electronic state surface: this conclusion is,
however, reflected clearly in Figure 3, in which
NO elimination pathway is shown to be
energetically the most favorable process as
compared to the NO2 elimination.

Figure 4: Potential energy surface scan from


Opt3 along O1-Al1 bond elongation reaction
coordinate for DMNA-Al complex.

Figure 3: Decomposition pathway of DMNA-Al


complex in ground electronic state, as revealed
at the MP2/6-31G(d) level of theory. The
relative energies are given in Kcal/mole.

Potential energy surface scan is


performed along the O1-Al1 bond to explore
NO2 dissociation reaction coordinate starting
from the Opt3 (see Figure 3) of DMNA-Al
complex. Scan results are depicted in Figure 4.
This figure shows that the energy increases with
the increase of O1-Al1 bond length; however,
after certain O1-Al1 bond distance (~2.8 ),
energy starts decreasing due to shortening of the
other O2-Al2 bond distance. Thus, in attempt to
remove NO2 moiety, we have found that, due to
strong interaction of Al and O atoms, NO2

DMNA-Zn: The DMNA-Zn complex shows


geometry similar to that of DMNA-Al complex,
where the metal Zn is located below the N-NO2
plane, rendering non-planar N-NO2 moiety.
Figure 5 shows decomposition pathway of
DMAN-Zn complex and relevant relative
energies are given in Table I, as predicted at
MP2/6-31G(d) level of theory. As illustrated in
Figure 5, first, DMNA-Zn complex can follow a
transition state associated with N-N bond
dissociation from Opt1, which results in a very
stable geometry dimethyl ( 2-nitro) amine zinc
complex. This geometry is stabilized by 44
kcal/mole because of formation of two stable
Zn-O bonds. Thereafter, the complex undergoes
Zn-O bond dissociation which leads to the nitronitrite isomerization followed by NO
elimination. The isomerized product is
exothermic in nature compared to starting
geometry both for DMNA-Al and DMNA-Zn
complex. From the energy profile in Figure 5 it
is evident that the NO elimination is
endothermic for DMNA-Zn system.

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finally
NO
elimination
occurs.
The
isomerization is exothermic in nature for
DMNA-Al and DMNA-Zn complexes; however,
the subsequent NO elimination is exothermic for
DMNA-Al but endothermic for DMNA-Zn
system.

Figure 5: Decomposition pathway of DMNA-Zn


complex in ground electronic state, as revealed
at the MP2/6-31G(d) level of theory. The
relative energies are given in Kcal/mole.

Table1: All the energies (Kcal/mole) are


calculated with respect to the energy of Opt1, at
the MP2/6-31G (d) level of theory. Ts1 for
DMNA is N-N bond dissociation and for DMNAZn but for DMNA-Al is Al-O bond dissociation
Whereas Ts2 is N-N bond dissociation for
DMNA-Al and Zn-O for DMNA-Zn complex.

Critical
Points

Comparison: Energy profile diagrams for both


DMNA-Al and DMNA-Zn are illustrated
together in Figure 6 for comparison. Both
complexes exhibit non-planar N-NO2 moieties.
The starting geometries with different bond
angles and bond distances are given in the figure
6. The initial steps of decomposition of these
two complexes, however, are different. The first
transition state for DMNA-Al is associated with
Al-O bond dissociation, whereas, that same for
DMNA-Zn is N-N bond dissociation. In spite of
an exhaustive search of Zn-O bond dissociation
transition state, we have not found any Zn-O
transition state for DMNA-Zn, similar to
DMNA-Al. This difference leads to different
geometries at Opt2 state for these two
complexes. However, both complexes, in the
end, are showing nitro-nitrite isomerization and
NO elimination as the ultimate decomposition
product but their pathways to reach the ultimate
products are different. DMNA-Al exhibits Al-O
bond dissociation followed by N-N bond
dissociation which results in nitro-nitrite
isomerization product. On the other hand,
presence of transition metal like Zn, N-N bond
dissociation becomes the first step, yielding
dimethyl ( 2-nitro) amine zinc complex. Then it
undergoes Zn-O bond dissociation which leads
to the nitro- nitrite isomerized product and

DMNA

DMNA-

DMNA-

Al

Zn

Opt1

Ts1

94

23

12

Opt2

24

21

-44

Ts2

33

-26

Opt3

-20

-32

NO

39

-7

28

30

23

40

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elimination
NO2
elimination

FORWARD

Figure 6: Comparative study of the


decomposition mechanisms of DMNA-Al and
DMNA-Zn complexes in ground electronic state,
as revealed at the MP2/6-31G(d) level of theory.
The relative energies are given in Kcal/mole.

moiety is predicted to be altered completely in


presence of Al atom. Furthermore, overall
reaction of DMNA decomposition is found to be
endothermic; however, that of DMNA-Al
complex shows overall exothermic reaction.
Similar behavior can be anticipated for more
complex
metalized
nitramine
energetic
materials.
Now by changing the metal atom from a
non-transition metal aluminum to a transition
metal zinc what change can we anticipate in the
decomposition of DMNA? DMNA-Zn complex
also shows isomerization and finally NO
elimination in concordance with DMNA-Al;
however, on the contrary with DMNA-Al,
DMNA-Zn complex shows first N-N bond
dissociation and then metal-O bond dissociation.
Furthermore, the NO elimination process for
DMNA-Zn system is found to be endothermic in
nature as compared to DMNA-Al system. Thus
present results show that only metal atoms can
alter the decomposition of nitramine moieties,
but also nature of metal atoms can have
significant effect on the decomposition of
nitramines. Our next goal is to experimentally
investigate these changes using ultrafast
spectroscopy.

Conclusions
In the work presented in this article, the
ground state decomposition reaction pathways
are calculated for isolated DMNA, DMNA-Al,
and DMNA-Zn complexes at the MP2/6-31G(d)
level of theory. Theoretical results suggest that
DMNA can follow N-NO2 bond dissociation as
well as nitro-nitrite isomerization pathways;
however, N-NO2 bond dissociation pathway is
associated with the lowest activation energy
barrier. DMNA-Al complex, on the other hand,
shows
significantly
different
multi-step
decomposition pathway: first, Al-O bond
dissociation, then N-N bond dissociation
followed by an isomerization and finally NO
elimination. Our calculations also show that NO
elimination reaction pathway (followed by nitronitrite isomerization) of isolated DMNA is
energetic unfavorable at the ground electronic
state; but similar isomerization is favorable for
DMNA-Al
complex.
Therefore,
the
decomposition behavior of nitramine energetic

References
[1] (a) Fried, L.E.; Manaa, M.R.; Pagoria,
P.F.; Simpson, R. L. Annu. ReV. Mater.
Res., 31 (2001) 291-321. (b) Tilton,
T.M.; Gash, A.E.; Simpson, R.L.;
Hrubesh, L.W.; Satcher, J. H.; Poco, J.F.
J. Non Cryst. solids, 285 (2001) 338-345
[2] Ramaswamy, A. L. Combustion,
Expansion and Shock waves., 36(2000)
131-137.
[3] (a) Politzer, P.; Lane, P.; Grice, M. E. J.
Phys. Chem. A., 105(2001) 7473-7480.
(b) Swihart, M. T.; Catoire, L. Combust.
Flame, 121 (2000), 210-222.
[4] Snyder, E.P; Seltz, H. J. Am. Chem.
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Greenfield,
M;
[5] Guo,
Y.
Q;
Bhattacharya, A ; Bernstein, E. R. J.
Chem. Phys. 127 (2007) 154301-10.

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[6] (a) Stewart, P. H.; Jeffries, J. B.;


Zellweger, J. M.; McMillen, D. F.;
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3557. (b) Nigenda, S. E.; McMillen, D.
F.; Golden, D. M. J. Phys. Chem. , 93
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M. E.; Lin, M. C. J. Energ. Mater., 3
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Chem. Phys., 36 (1962) 1106. (e)
Lazarou, Y. G.; Papagiannakopoulos, P.
J. Phys. Chem. 94 (1990) 7114. (f)
Lazarou, Y. G.; Papagiannakopoulos, P.
Laser Chem. 13 (1993) 101.
[7] (a) Velardez, G. F.; Alavi, S.;
Thompson, D. L. J. Chem. Phys. 123
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3301. (c) Sumpter, B. G.;
Thompson, D. L. J. Chem. Phys.
88(1988) 6889.
[8] Frisch, M. J.; Trucks, G. W.; Schlegel,
H. B.; Scuseria, G. E.; Robb, M. A.;
Cheeseman, J. R.; Scalmani, G.; Barone,
V.; Mennucci, B.; Petersson, G. A.;
Nakatsuji, H.; Caricato, M.; Li, X.;
Hratchian, H. P.; Izmaylov, A. F.;
Bloino, J.; Zheng, G.; Sonnenberg, J. L.;
Hada, M.; Ehara, M.; Toyota, K.;
Fukuda, R.; Hasegawa, J.; Ishida, M.;
Nakajima, T.; Honda, Y.; Kitao, O.;
Nakai, H.; Vreven, T.; Montgomery, J.
A., Jr.; Peralta, J. E.; Ogliaro, F.;
Bearpark, M.; Heyd, J. J.; Brothers, E.;
Kudin, K. N.; Staroverov, V. N.;
Kobayashi,
R.;
Normand,
J.;
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J. C.; Iyengar, S. S.; Tomasi, J.; Cossi,
M.; Rega, N.; Millam, N. J.; Klene, M.;
Knox, J. E.; Cross, J. B.; Bakken, V.;
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Stratmann, R. E.; Yazyev, O.; Austin, A.
J.; Cammi, R.; Pomelli, C.; Ochterski, J.
W.; Martin, R. L.; Morokuma, K.;
Zakrzewski, V. G.; Voth, G. A.;
Salvador, P.; Dannenberg, J. J.;
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Foresman, J. B.; Ortiz, J. V.; Cioslowski,
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Bernstein, E. R. J. Phys. Chem. A 113
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Y. Q.; Bernstein, E. R. Acc. Chem. Res.
43 (2010) 1476-85.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Investigation of spatial and


temporal dynamics of vegetation
in semi-arid-ecosystems11

the scale of processes in a system based on


results from power spectrum analyses.

Sumithra Sankaran, Sabiha Sachdeva,


Ashwin Viswanathan and Vishwesha
Guttal (PI)

Semi-arid ecosystems support critical


flora, fauna together with large livestock
and human populations. Under threat
due to increasing anthropogenic
activities and climate change, they are
prone to regime shifts, i.e., abrupt
changes in their states and thus,
potentially leading to desertification [1].
Vegetation of these ecosystems may
exhibit striking self-organized patterns
ranging from regular periodic patterns
such as spots, labyrinths to irregular
scale-free patchiness. Recent studies
based on mathematical models and
computer simulation studies argue that
spatial patterns of vegetation in semiarid ecosystems may offer signatures of
resilience and its vulnerability to
perturbations [2, 3. 4, 5]. In this context,
understanding the local processes that
generate large scale self-organized
spatial patterns in semi-arid ecosystems
and how these patterns are affected by
stressors are questions of both basic and
applied ecological significance.

Centre for Ecological Sciences, Indian Institute


of Science, Bangalore, 560012

Abstract:Semi-arid ecosystems can exhibit


striking vegetation patterns, which may have
no characteristic size of patchiness.
Elucidating local scale processes that
generate these macroscopic patterns is of
fundamental ecological importance as well
as in being able to forecast the future
dynamics of these highly vulnerable
ecosystems. Recent studies have shown that,
these patterns can be explained by local
facilitative
interactions
with
global
competition for resources and have
suggested that these patterns can be
considered signatures of a systems
resilience. However, no alternative models
that could potentially explain similar
patterns have been investigated. In this
work, we compare and contrast the
predictions of a spatially explicit model of
vegetation in which both, facilitation and
competition, occur at local scales with that
of the previous models. We characterize
spatial patterns by using the distribution of
patch sizes and power spectrum analyses.
We show that power-law distribution of
patch sizes can result from local competitive
constraints combined with local facilitative
interactions, that a global scale of
competition is not necessary. Further we
also find that power law patch size
distributions are not necessarily indicative of
high resilience but can be even observed in
systems
approaching
regime
shifts,
depending on the scale of underlying
interactions. We find no means of discerning

Projectnumber:STC/P315.

I. INTRODUCTION

Many ecological interactions between


species of the same trophic level (such
as between different plants) can be
broadly classified into two fundamental
types competition and facilitation. The
relative scales over which interactions of
each type are operational could
potentially determine the nature of the
spatial patterns observed in the
landscape (Levin 1992).Some of the
early work in this area, in late 1990s
and early 2000s, developed various
mathematicalmodels to explain these
vegetation patterns. A key ecological
assumption of these models was that of
local positive feedback that helps

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increased germination of seeds in the


vicinity of other plants because of
reduced evaporation and/or increased
infiltration
of
water.
However,
competition sets in at local yet relatively
longer spatial scales since plants draw
water towards them from nearby regions.
Two key studies[3, 4] published in 2007
then showed, using computer simulation
models, that scale-free distribution of
patchiness in vegetation can be
explained by assuming local or nearneighbor
facilitative
interactions
amongst plants in combination with a
global scale of competition (motivated
by studies showing that rainfall
constrains global control of tree cover).
Although the competition in resource
limited regions such as semi-arid
ecosystems can indeed extend to long
distances, the assumption of a global
scale constraint seems unrealistic.
Moreover, analyzing a single metric of
spatial pattern suchas patch-size
distribution, could potentially be
misleading; for instance, we know from
the literature on percolation transitions
in physics that patch sizes can exhibit
scale-free features even in an entirely
non-interacting
system.Given
the
implications of such spatial patterns on
the stability of these systems, we ask:
(1) Can local processes (such as
competition for resources and
facilitation among nearby plants)
alone, in the absence of global
constraints, explain scale-free
patchiness of vegetation patterns
found in semi-arid ecosystems?
(2) Can we discern scale of interactions
by analyses of spatial patterns,
for example those available from
aerial imagery?

II. METHODS

We analyse two cellular automata based


spatially explicit stochastic models,
differing in their interaction rules;
specifically, the length scales over which
competitive interactions operate. We
compare various characterizations of
spatial patterns resulting from these two
models, henceforth called Kfis and
Lubecks models, along their respective
phase diagrams.Both models assume a
discrete space where each lattice cell
represents a small spatial scale that could
be occupied by an individual (plant).
Each cell has an associated probability
of switching from one state to another,
such as plant or no-plant state.
Competition and facilitation are captured
by
making
these
transition
rates/probabilities conditional on the
states of other cells in the lattice.
Note that the two models are
qualitatively similar in that the average
density/vegetation cover as a function of
birth ratecan show discontinuous or
continuous transitions (for high and low
death rates respectively) from vegetated
to barren state.
Kfis model: In this model, meant to
capture the biology of semi-arid
ecosystems, there are three possible
states for each cell: vegetated, empty and
degraded. Local facilitation interaction is
incorporated via a transition rate of
degraded to empty-inhabitable cells
which positively depends on the
proportion of vegetated cells in the
neighbourhood of the focal degraded
cell. Competition is assumed to occur on
a global scale and is incorporated by
making the transition rate (denoted by
b) of empty to vegetated cells depend
inversely on the mean global vegetation
density in the lattice. b is also

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constrained by other biological factors


such as aridity of the landscape.
Mortality rate (denoted by m) is the
rate at which vegetated cells transition to
occupied cells. It is the density
independent parameter and captures
biological factors such as extent of
grazing in the landscape. (See [3] for
detailed description of the model and its
parameters).

We simulate these models in two


dimensional discrete space of 1024 x
1024 grids. We use power spectrum
analyses and calculate patch size
distributions
(using
Maximum
Likelihood Estimate methods) to
characterize the resulting spatial
patterns.

Lubecks model: This model, also


known as tri-critical directed percolation
model and based on stochastic process
popularly known as contact process in
the
Mathematics
literature,
was
developed in the Physics literature to
investigate
nonequilibrium
phase
transitions. Here, we employ the model
with ecological interpretation of its rules.
Each lattice cell can occur in two
possible states corresponding to
occupied and unoccupied by a plant. At
each discrete time step, a randomly
chosen vegetation site becomes empty
with a probability (denoted by p), or an
empty cell in the vicinity of that
vegetated site undergoes a transition to a
vegetated state with another probability.
Positive local feedbacks are incorporated
in this model through the increased
probability (denoted by q) of
transitioning from unoccupied to
occupied cell as a consequence of the
neighbourhood of the parent cell.
Competition plays out through the
reduction in available (empty) cells
nearby the focal plant for propagation of
its seeds as the overall density increases.
In simple terms, this model assumes
local facilitation and local competition to
determine vegetation growth. (See [7]
for detailed description of the model and
its parameters).

The vegetation patterns realised from


Kefis model, across the parameter space
(all values of m), show a power law
distribution of patch sizes away from the
transition (high values of b), which
becomes increasingly truncated as the
system approaches the critical point (or
as b is decreased) [as already shown by
3,4]. Vegetation patterns realized from
Lubecks model also show power law
patch size distributions, however, only
when parameter values correspond to a
discontinuous regime shift (q=0.91) and
only when the system is very near the
critical point (b=0.2951) (Fig. 1; Table
1). This shows that only local processes
can also explain scale-free patch size
distributions. Additionally it also
challenges the reliability of patch size
distributions as an indicator of
approaching regime shifts.

III. RESULTS

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Fig.. 1: Inversee Cumulativve Distribuution


of patch
p
sizess realized from the two
moddels. All paarameters were
w
estimaated
usinng Maximuum Likelihoood Estimaation
metthod.

Fig. 2: Power spectruum results for the


two moddels for parameter values
correspondding to continuous regime
shifts. Thee (qualitativve) results of the
discontinuoous regime shifts were found
to be similaar.

USSION
IV. DISCU

Tabble 1: (MLE
E) Parameteer estimatess for
the best fit diistribution of patch sizes
s
reallized from thhe two moddels

Thee power sppectrum deecomposes the


spattial patternss into perioddic patterns and
quanntifies conntributions of diffeerent
spattial perioddicities (waavelengths) A
randdom patteern would have eqqual
conttributions from all frequenncies
wheereas a perioodic patchyy system woould
show
w a waveleength corressponding too the
patcch-size annd/or distaance betw
ween
patcches.
Speectral Analyses of sppatial patteerns
from
m both moddels (Fig. 2)) were founnd to
follo
ow an expponential distribution
d
(in
casee of parameeters correspponding to both
b
the continuous and disconntinuous reggime
shiffts).

Spatial chharacteristiccs of a system


depend on both, wheether the syystem is
p
(as
close to or far from thhe critical point
w as wheether the
shown by [3,4]), as well
system is undergoinng continuuous or
a
discontinuoous regime shift. Our analyses
of these two modeels with different
d
interaction scales, shoows that thee change
in patch sizze distributtions as thee system
moves tow
wards a transition is dependent
on the sccale of innteractions in the
system.Keffis model shows a sccale free
distributionn away from
m the criticcal point
while Lubeeks model shows a sccale free
distributionn near the crritical pointt and no
ubiquitous pattern of patch
h size
distributionns away frrom the traansition.
This challeenges the rreliability of
o patch
size distributions ass an indiccator of
approachinng regime shhifts.
It has beenn widely acccepted thaat scale
free patcch size distribution
ns, a
characteristtic of sseveral seemi-arid
landscapes, result speecifically frrom the
of
local
combinatioon
positive
interactionss with gllobal com
mpetition
constraints. Our workk, however, shows
nization
that this pattern of sppatial organ

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can also from only local scales of


competition coupled with local positive
feedbacks. Further, the scale of
interactions in the system can also not
discerned from power spectrum analyses
of the spatial organization of the
vegetation. We therefore conclude that it
may not be easy to distinguish the origin
or details of processes by analyzing
spatial vegetation patterns with these
metrics alone.

References

We speculate that temporal dynamics of


spatialpatterns may yet offer signatures
of interaction scales in the system as the
response to perturbations of a system
with global competitive constraints will,
in all likelihood, differ from that with
solely local constraints. It is also highly
probable that natural ecosystems, due to
continuous disturbances, are seldom
found in their steady states. We now
plan to study the non-steady state
behaviours of Kefi and Lubecks models
to investigate the effect of noise on the
spatial patterning of vegetation in
ecosystems with varying scales of
processes.

[3] Kefi et al, 2007, Spatial vegetation


patterns and imminent desertification in
Mediterranean aris sytems, Nature, Vol
449, 213-218.

[1]Scheffer et al, 2001, Catastrophic


regime shifts in ecosystems, Nature, Vol
413, 591-596.
[2] Rietkerk, et al, 2004, Self-organized
patchiness and Catastrophic Shifts in
Ecosystems, Science, Vol 305, 19261929.

[4] Scanlon et al, 2007, Positive


feedbacks promote power-law clustering
of Kalahari vegetation, Nature, Vol 449,
209-213.
[5] Guttal & Jayaprakash, 2009, Spatial
variance and spatial skewness: leading
indicators of regime shifts in spatial
ecological systems, Theoretical Ecology,
2: 1-11.
[6] Kefi, Guttal, et al, 2014, Early
warning signals of ecological transitions:
Methods for spatial patterns, Plos ONE.,
Vol 9: e92097.
[7] Lbeck
percolation,
Physics, Vol

2006, Tricritical directed


Journal of Statistical
123,193-224.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Development of Semiconductor Nanocrystals for Photovoltaics


Biswajit Bhattacharyya, Rekha Mahadevu and Anshu Pandey
Abstract: Photovoltaics require the
development of Semiconductors with
precisely tuned optical properties. Here
we report the development of materials
with very precise tuning of radiative
lifetimes and anomalous band gaps. The
synthesis of this novel class of materials
will motivate precise engineering of
material properties in order to optimize
device performance.

decay, luminescence efficiency, etc., the

INTRODUCTION

straightforward route to regulating the

deliberate use of structure to manipulate


radiative

decay

dynamics

of

single

excitons remains an untapped possibility.


In this article we demonstrate that dopants
may be used to regulate the density of
states

available

for

excitonic

recombination. This provides a very

radiative rates of carrier recombination in


Control over emission rates is of

QDs.

fundamental importance to a number of


areas of research and technology. Long

Copper is a known substitutional

spontaneous decay rates are extremely

impurity in II-VI QDs. When introduced

desirable in photovoltaics. A number of

into II-VI materials such as ZnSe and

strategies to regulating the rates of

CdSe, Copper is known to exclusively

spontaneous decay already exist. Most of

exist in a +2 oxidation state. The 3d9

these techniques plasmonics, photonic

configuration

crystals and cavities, high dielectric media,

impurities has been demonstrated to

etc. exclusively focus on tuning photon

exhibit exchange with semiconductor host,

density of states. Advances in colloidal

causing the emergence of diluted magnetic

chemistry have enabled the synthesis of

semiconducting character in doped QDs.

semiconductor quantum dots with a wide

Being Jahn-Teller ions, substitutional Cu+2

range of formulations, compositions and

species are EPR (electron paramagnetic

morphologies. This flexibility naturally

resonance)silent due to a combination of

provides several potential routes for

spin-orbit and electron-lattice coupling. In

manipulation and control over the physical

a II-VI lattice in particular, Cu+2 ions give

properties

While

rise to an emission band that arises from

considerable attention has been devoted

the radiative transition of a conduction

towards utilizing QD structure to control

band electron into the copper d9 level.

properties such as blinking, multiexciton

From this level, the electron is believed to

of

these

materials.

of

Cu+2

substitutional

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relax nonradiatively into the valence band


hole. This process is highlighted in Figure
1b. The CB-Cu radiative transition (thin
arrow) presents a significantly weaker
transition dipole than the band edge
excitonic

decay

(thick

arrow).

Both

processes are however emissive and lead


to the emission of a photon along with the
de-excitation of the quantum dot.
Despite its inherent weakness, the CB-Cu
transition is behaviorally very different
from other radiative

decay channels

available within a quantum dot (figure 1c).

Figure 1 a. Spontaneous emission involves


the relaxation of an excited electron to its
ground state. Material properties like
density of states do not play a role in the
process. b. A copper containing QD has
two alternate pathways for radiative
exciton recombination; either direct
recombination with a band edge hole or
else through the copper center. c.
Enhancing the number of copper atoms in
the QD increases the number of available
channels for radiative recombination,
speeding up radiative decay.

Regulation of the amount of copper doped


into a semiconductor lattice provides a

revealed that these QDs were composed of

direct handle on the available density of

a cadmium-copper-zinc selenide alloy. By

states for the radiative relaxation of the

varying the molar ratio of copper acetate to

conduction band electron. A typical copper

zinc

doped QD shows both band edge as well

synthesis, the copper inclusion may be

as dopant related emission(Fig 2a). While

tuned from 0% to 35%. Figure 3a shows

band edge emission typically occurs with a

the XRD patterns of a sample containing

lifetime of the order of 10 ns, the copper

copper, Zinc and Cadmium (ICP-OES

emission band is typically seen to decay in

analysis on cations basis). While the XRD

about 500 ns(Fig 2b). The doping levels

patterns are indeed consistent with a Zinc

for the Cu

+2

and

cadmium

acetates

during

impurity in II-VI QDs

Blende material, the positions of the peaks

typically correspond to the presence of

of signal do not correspond to either pure

one-two dopant ions in QDs.

ZnSe or to pure CdSe.

QDs were characterized through electron

Rather, the peak positions are intermediate

microscopy, X-ray diffraction (XRD) and

to ZnSe and CdSe, and correspond to a

Inductively

semiconductor

Emission

Coupled
spectroscopy

Plasma-Optical
(ICP-OES).

Studies of QD composition by ICP-OES,

alloy.

quantitative

statement may be made using Vegards


law.

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substitution of a large fraction of the Cd


and Zn ions by copper.
We studied the electronic structure
of these materials under a probabilistic
Figure 2 a. Absorption and emission
spectrum of a 1% doped Cu doped CdZnSe
QD. b. Emission decay kinetics of the host
and the copper band.

model. In particular, the probability of


cluster formation is expected to determine
the electronic and optical properties of the
materials. The probability of formation of
such clusters may be evaluated in the case

Copper and Zinc have similar ionic radii


and structure factors. This allows us to
write the lattice parameter of the alloy as a
weighted mean of Zinc Selenide and
Cadmium Selenide lattice parameters. This
leads us to expect a lattice parameter of
>0.5 nm for the alloy. Figure 3a also
presents a simulated pattern based on this
expectation.

The

excellent

of a completely random placement of


copper

ions.

In

this

situation,

the

probability of occurrence of two nearest


neighbor copper ions is proportional to x2,
where x is the mole fraction of copper. In a
similar

manner,

the

probability

of

occurrence of a cluster of size s is


proportional to xs.

agreement

between the simulated pattern of the alloy

Of significant importance for our

and the pattern that is observed in practice

discussion is the cluster connectivity or

as well as the absence of features

degeneracy. Consider for instance the

corresponding to potential impurity phases

simple

such as CdSe, ZnSe or CuSe in our

arrangement of copper ions. In such a

patterns prove that these QDs are indeed

situation, if V is the volume of such a

pure CdCuZnSe alloys. Figures 3b and 3c

cluster, then the radius of such a cluster is

show TEM images of QDs containing 1%

related to V1/3. Of course, the number of

and 10% Cu (measured relative to the total

atoms in the cluster is related to V. i.e.

cation content). Consistent with the XRD

. If we consider the addition of one

case

of

quasi-spherical

more atom into the cluster, the ways of

homogenous distribution of particles, with

doing so are linked to the surface area of

no evidence of extraneous phases. These

the cluster, viz. V2/3 or

analyses

dealing with mole fractions, one can

patterns,

TEM

thus

images

suggest

reveal

successful

. When

similarly relate N to x. This simple


argument illustrates two important points:
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firstly, the cluster formation probability is


dependent on the connectivity of a cluster
with one lesser atom. Secondly, this also
illustrates that for a spherical arrangement,
a cluster is expected to have a sublinear
dependence

of

available

cluster

dependence

on

the

mole

fraction. Here A and B are constants that


relate the variation of a particular property
to the probability of a cluster. This
expression is used to generate the fit to
experimental fluorescence data.

morphologies on the cluster size.


In most samples the decays are
In any practical situation the
occurrence of a spheroidal cluster is
extremely unlikely. Instead, a cluster with
much higher surface area is expected

adequately described by biexponentials. A


mean photon lifetime may be extracted by
considering the areas under various parts
of the PL decay curve. We therefore define

simply because of a high degeneracy and


more available conformations. In this

the photon lifetime by

. Here n

are the number of photons under a

, where s is the size of the cluster. The

particular component of the fit, while t is

probability expression for a cluster of size

the associated time constant. An increase

s is given by

. We are of course

in the number of copper centers causes a

interested in the total probability of

direct shortening of sample lifetimes. By

formation of any sized cluster. This is

changing the copper inclusion levels from

situation, one can write

given by

This expression leads to a series of the


form. =

For

contributes. It is further evaluated to be


(

ns.
In

most

systems

the

exciton

lifetime arises from the interplay of

sufficiently small x, only the first term

~ [

1% to 31% the lifetimes from 600 ns to 1

) 2 ]

radiative and nonradiative rates. Simply


increasing the nonradiative decay channels
in any system therefore also speeds up
exciton decay, although of course, this is

Therefore, for small x, the total probability


of the occurrence of a cluster of any size is
related to

. Any property that is affected

by the formation of clusters of copper may


therefore

be

expected

to

have

of little practical or scientific value. We


therefore turn to investigate the actual
causes of speeding up of the excitonic
decay rates in our systems.

the

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orders of magnitude lower than the


typically observed lifetimes in copper
containing QDs. We thus confirm that our
procedure represents the development of a
route

to

tune

spontaneous

emission

processes in QDs.
The procedure presented thus far
provides a straightforward recipe for
shortening spontaneous emission lifetimes
Figure 3. a. Observed and Simulated XRD
patterns of CdCuZnSe QDs along with
standard patterns of CdSe (top) and ZnSe
(bottom).

b. TEM micrograph of QDs

with 1% and c. 10 % Cu. Scale bars are 20

in QDs. We now turn to a method to


lengthen the same. While shortening
lifetimes relied on the propensity of
individual copper ions to offer alternate
decay channels, longer lifetimes may be
attained by regulating electron-copper

nm.

overlap. We start with ZnSe QDs where


For example, consider the PL

copper ions are doped into the QD core.

kinetics of a sample with a >30% inclusion

An electron extracting type-II CdS shell is

of copper. The sample exhibits a quantum

now grown over the core. This leads to

yield of 17 %, and an exciton lifetime of

reduced overlap between the conduction

1.4 ns. The sub-unity quantum yield could

band electron and the copper impurity,

possibly originate from the presence of

causing increase in the copper lifetimes.

non-emissive QDs in the ensemble or else

Figure 4a provides a schematic to describe

from the existence of a non-radiative decay

this effect. Aliquots were obtained during

mechanism in all the QDs. In the former

the process of shell growth.

event, the spontaneous lifetimes are simply


equal to the observed excitonic lifetimes.
Even in the latter case, with a 17%
quantum yield, the spontaneous emission
lifetime is estimated to be 8 ns. While the
actual spontaneous lifetime is expected to
lie

somewhere

between

these

two

estimates, even the upper bound is two

We analyzed sample composition


in each case and observed no variation in
Copper:Zinc ratio, indicating that no
copper escaped from the QDs during the
growth process. Figure 5b shows the
variation of the emission kinetics of these
materials as a function of energy of the
emission maximum. As anticipated from

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the straightforward arguments relating to

to a red shifting of the emission band as

electron-impurity overlap, we observe that

well as the reduced

the emission slows down substantially.

overlap. The methods suggested here

carrier-impurity

nevertheless allow us to develop materials


that show a remarkable tuning of excitonic
lifetimes, from 1 ns to over 1600 ns
(Figure 4c).
CONCLUSIONS
Figure 4a. Schematic of the change in
The

impurity-electron ovelap in a core/shell


structure. b. Variation of exciton lifetimes
as a function of emission maximum. c. A
combination of these approaches allow us
to tune the emission maxima of these

development

chromophores
paramount

and

of

custom

sensitizers

importance

for

is

the

of
next

generation of devices. Copper based


materials are of particular significance due
to the recent demonstration of feasibility of

materials from 1 ns to over 1 s.

these

substances

in

charge

transfer

Growth of CdS over the Zinc Selenide

processes. By employing dopants, we have

core allows for tuning of the emission

been able to significantly enhance the

lifetime from 650 ns to 1600 ns. We also

concepts

note that a shifting of the emission

chromophores that we have developed

maximum can by itself cause the slowing

during the course of this project. Future

down

estimated

studies will aim to apply these concepts in

magnitude of this effect is represented by a

practical devices containing ZnTe/CdS and

dashed line in Figure 4b. The variation in

doped materials.

of

emission.

The

of

idealized

photovoltaic

excitonic lifetimes clearly occurs both due

REFERENCES

(1) Bhattacharyya B. et. al. (Submitted)


(2) Mahadevu, R.; Yelameli, A. R.; Panigrahy, B.; Pandey, A., Controlling Light Absorption
in Charge-Separating Core/Shell Semiconductor Nanocrystals. ACS Nano 2013, 7, 1105511063.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Die Level 3D Packaging of Hybrid Systems


N. P. Vamsi Krishna and Prosenjit Sen
Centre for Nano Science and Engineering, Indian Institute of Science, Bangalore

Abstract The aim of this work1 is to develop


and optimize design rules and processing
technologies required for 3-D die level
packaging of hybrid systems including MEMS
components. In this paper we report the
development of the dielectric filler process
which works as the intermediate layer and
isolates the various chips. We also report the
initial results in using conductive printing to
obtain electrical interconnects between layers.

I. INTRODUCTION
Transistor scaling has led to ever smaller chips
with larger device density in integrated circuits.
The reduction in size is reaching a saturation
where further reduction of device dimensions is
limited by fundamental problems. Further
reduction in system weight and volume is
possible through realizing that the existing
technologies arrange dies in a horizontal
fashion on either a PCB or a multichip module
[1-2]. The semiconductor industry is seeking
solutions in 2.5D-3D systems using vertical
integration of devices using thru-silicon via
(TSV) technology. The technology being
developed is however expensive and available
only to the big fabrication facilities. The
technology that has been developed also does
not accommodate MEMS devices with moving
parts, which often have more severe
restrictions in packaging specifications. In order
to address the above issues we propose to
develop processing technologies which will
allow system developers to access 3D packaging
through post processing on individual dies. The
technology developed will also seek to address
issues related to integration of MEMS devices
1

Project#: ISTC0336 (2014-2017)

with moving parts. An example of such a 3D


packaged hybrid system is shown below.

Figure 1: A 3D integrated hybrid system

II. APPROACH AND RESULTS


The proposed technology for optimal vertical
stacking will require the thinning of dies from
standard 500-600 um thickness to less than 150
um thickness. This thinning process is expected
to have no effect on the performance of
electronic chips. For MEMS devices with
structural layer less than 100 m this thinning
process will not change its performance. The
die thinning can be carried out using back-grind
and chemical mechanical polishing process.
Wafer and die thinning process is a wellestablished process in industry and we will
bypass this step by fabricating our dummy dies
on thinned wafers.

Figure 2: Dielectric filler processing

The process starts with performing a die attach


to a handle substrate. The handle substrate can
be pre-patterned to provide interconnects as
shown in Figure 3. This layer also contains the
alignment marks for subsequent die attach
steps.

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After the bonding a spin coated dielectric is


used to fill and planarize the substrates. For this
project we are currently using SU-8 2150 [3].
The SU-8 is spin coated at 3000 rpm to coat and
planarize the 150 m. The SU-8 is soft baked at
65 C for 7 mins and at 95 C for 15 mins. The
temperature was ramped to reduce stress
issues. After the soft bake the wafers were
allowed relax at room temperature for 15 mins.
Figure 3: Layer 1 mask for handle substrate

A 150 m thick cover slip is used as a dummy


die in the current process. The dummy die is
also patterned using lift-off or etching to form
the metal contact pads, devices and
interconnects. The die is then aligned and
bonded to the handle layer using UV curable
epoxy EPO-TEK- UJ 1190. The aligned wafers are
exposed to an UV lamp to harden the epoxy.

Figure 6: Spin coated dielectric filler SU-8

The wafers were exposed using a mask aligner


to 450 mJ/cm2. This was followed by post
exposure bake at 65 C and 95 C for 7 and 15
mins respectively. The exposed wafers were
developed for 16 mins. The initial runs faced
issues with poor adhesion of SU-8 on the
substrate. This lead to SU-8 crack and peel of
due to stress in the SU-8 layer as seen in Figure
7. This issue was solved by improving the
adhesion of SU-8 to the glass surface using a 2
min RIE O2 plasma treatment.
Figure 4: Wafer temperature under the UV lamp

Figure 4 shows the rise in temperature of the


wafer during the epoxy exposure step. The
temperature remains low at less than 70 C.

Figure 7: Crack and peel off in the SU-8 layer.

Figure 5: Handle with bonded die.

Interconnections between the handle wafer and


the dummy die can be made in several ways.
Currently we are considering jet printing of a
silver paint and screen printing of conductive
paste. Figure 8 shows a SU-8 planarized sample
in which interconnects have been printed using

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the jetting of silver ink using a Diamatix [4]


printer. As is seen in the image the lines are
rough and at some places discontinuous. We
are in the process of improving the printing
process parameters such as number of drops,
number of runs and the surface condition of the
SU-8.

Figure 8: Interconnects fabricated using jest printing of


silver ink.

III. CONCLUSIONS AND FUTURE WORK


We have been able to optimize the dielectric
filler process that is essential in die level 3D
assembly. We are currently optimizing
interconnect printing technology. Following
optimization of the interconnect technology we
will work on demonstrating a 3 layer stack of
interconnected devices. We also intend to
explore several other dielectric filler materials.
Inspite of several attempts we were unable to
obtain photo-pattern-able polyimide due to
export control. We intend to try PDMS as
another option.

REFERENCES
[1].http://en.wikipedia.org/wiki/System_in_pack
age
[2]. http://www.amkor.com/go/SiP
[3].http://www.microchem.com/pdf/SU82000DataSheet2100and2150Ver5.pdf
[4].http://www.fujifilmusa.com/products/indus
trial_inkjet_printheads/

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1
31st Annual In-House Symposium on Space Science and Technology
ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

A Small Volume Droplet Dispenser based on


Electrohydrodynamic Pulling
K. R. Sreejith, and G. R. Jayanth

Abstract- This paper describes the design and development of a


small volume liquid dispenser that is capable of real-time
measurement of the mass of liquid dispensed. These features of
the dispenser are enabled by appropriate design of the three
subsystems of the dispenser, namely, the droplet generation
sub-system, the droplet mass measurement sub-system and the
droplet deposition sub-system. The droplet generation system
comprises a micro-pipette with a silvered surface along with a
syringe. The droplet mass measurement system enables
measurement of the volume of liquid dispensed by measuring
the resulting shift in resonant frequency of the micro-pipette.
The droplet deposition system employs electro-hydrodynamic
pulling and comprises a 330V voltage supply. All the three
systems are designed and fabricated. The developed overall
system is demonstrated to generate, measure and dispense
liquid droplets of volume down to about 260pL.

I INTRODUCTION
Microdispensing is the technique of producing liquid
dosages in volumes less than one microlitre.
Microdispensing finds applications in drug delivery, inkjet
printing, cell biology research, microelectromechanical
systems (MEMS), lubrication in automobiles, precision
deposition of soldering paste in electronic circuits industry,
among others. The continuing miniaturization in almost all
technical areas drives a constant need to improve the
microdispensing technologies. Such requirements include
the need to dispense smaller amounts of adhesive, liquid, oil,
grease and a multitude of other media reliably, accurately,
both in dosage and placement, and within small time.
The precise positioning and quantity of the dispensed fluids
such as glue and reagents have a great influence on the
overall quality of the final product.
Dispensing can be broadly considered to be of two types,
namely, contact type dispensing and the non-contact type
dispensing. In contact dispensing, the drop forms at the exit
of a nozzle, and is deposited by contact while the drop is still
on the nozzle. In non-contact dispensing, the drop formed at
K. R. Sreejith and G. R Jayanth are with the Department of
Instrumentation and Applied Physics. e-mail:sreejithkr12@yahoo.com,
jayanth@ isu.iisc.ernet.in, Phone: 22933197.

the end of a nozzle is deposited on a target area that is


situated relatively far away from the nozzle. Thus, the drop
separates from the nozzle before it hits the target area.
Compared to non-contact type dispensing, contact type
dispensing has a few important disadvantages. Since the
nozzle which forms the droplet has to touch the target area,
the target could be damaged. This is especially true with
micro-fabricated parts, such as MEMS structures. Further,
since viscous liquid forms threads, reproducibility in the
amount of liquid dispensed liquid amounts is poor. Thus,
owing to increasing requirements in regards to cycle time
and accuracy in almost all areas of production, non-contact
dispensing has steadily gained in importance. The different
technologies available for dispensing liquids in a
non-contact manner include piezoelectric [1], direct liquid
displacement [2], and pyroelectrodynamic shooting [3].
Here too, an important requirement to deposit droplets in a
controlled manner is to measure the volume of the liquid
precisely. The technologies that have been employed to
measure mass or volume of liquid dispensed include optical
techniques [4] capacitive type measurement [5][6], and flow
sensor based measurement[7].
This paper reports the design and development of a
non-contact
type
droplet
dispenser
based
on
electrohydrodynamic pulling. The dispenser is capable of
real time measurement of the mass of liquid dispensed and
thus, facilitates precise control of the mass of the liquid
deposited.
The rest of the paper is divided as follows: Section II
describes the principle and provides an overview of the
construction of the droplet dispenser. Section III describes
the development of each of the subsystems that constitute the
droplet dispenser. Section IV describes the results of liquid
dispensing.
II PRINCIPLE OF OPERATION
Fig. 1 is a schematic showing the construction of the
droplet dispenser. The experimental setup consists of a
syringe attached with a micropipette. The syringe can be
actuated to form a liquid drop at the tip of the micropipette.
An optical beam deflection system is employed to measure
the mass of the liquid droplet formed at the end of the syringe

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2
in real-time. Finally, a high voltage power supply is used to
deposit liquid droplet on to the target.

geometry, the performance of the system depends on the


ability to adequately control the taper and tip diameter of the
micro-pipette during its fabrication process. Accordingly, a
micro-pipette puller was designed and developed in order to
achieve control over these parameters. In order to facilitate
deposition of the droplet by means of electrohydrodynamic
pulling, the surface of the micropipette was rendered
conductive by coating it with silver using Brashears
process. The optimization and subsequent evaluation of the
pipette puller is described in Section III A(a). The process
employed to coat the pipette is described in Section III A(b).
(a) Development of a pipette puller for fabrication of glass
micro-pipettes
(a)

Fig. 1: Schematics showing the construction of the droplet dispenser.

To generate a droplet, the piston of the syringe is actuated


using a suitable actuator, such as a piezo- or a thermalactuator, to produce a liquid drop of volume in the range
nanoliters-picoliters. In order to measure the mass of the
droplet formed, the micro-pipette is excited and the resulting
motion is measured by means of optical beam deflection.
The change in resonant frequency of the micropipette upon
formation of a droplet is employed to determine the mass of
the droplet. After the formation of a droplet of the desired
volume, a potential difference is applied between the droplet
and the target. The liquid droplet is attracted towards the
conductive target due to coulomb force of attraction and gets
deposited on the target. By controlling the duration of
application of potential difference, the quantity of liquid
dispensed can be controlled. While the target is expected to
be electrically conductive, droplets can also be deposited on
insulating targets by mounting them on a conductive
substrate. The design and development of the entire system
is described in Section III.
III DESIGN AND DEVELOPMENT OF THE DROPLET DISPENSER
Section II reveals that the overall droplet dispenser can be
divided into three sub systems, namely, the droplet
generation system, droplet mass measurement system and
the droplet deposition system. This section describes the
design and development of each of these subsystems.
A. Design and development of the droplet generation system
The main objective of the droplet generation system is to
generate liquid droplet of volumes in the range of nanoliters
to picolitres and subsequently facilitate their deposition. In
order to generate liquid droplets of such low volume, a
conventional syringe attached with micropipette is
employed. Since the volume of the liquid and the dynamic
characteristics of the micro-pipette are decided by its

(b)

(c)

Pulley
Ball screw
Timer belt

(d)

Holder

Channel

Fig. 2: (a) Schematic showing the construction of the micro-pipette puller.


(b)-(d) Photographs showing the construction of the pipette puller.

Fig. 2(a) is a schematic showing the principle behind the


operation of the pipette puller [8]. The pipette puller heats a
glass tube to a temperature Th over a length h such that

Th exceeds the softening temperature Ts of glass. It is


subsequently pulled in opposite directions along the
longitudinal axis of the tube, viz., the X-axis, by means of
two motion stages. One stage is capable only of linear
motion along the X-axis and assists in pulling the pipette,
while the other is capable of three-axis in-plane motion, viz.,
linear motion along X- and Y-axes and angular motion about
Z-axis, and thereby assists also in bending the pipette. The
one-axis motion stage employs a guiding channel to restrict
the motion of the pipette holder along the axis of the channel,
viz., the X-axis. The three-axis stage and the one-axis stage
are connected by an inextensible wire such that, upon
actuation, the two stages can be retracted in opposite
directions at identical velocities. When the two motion
stages are pulled in opposite directions with velocity v, the
length p of the region that gets pulled is that whose
temperature exceeds Ts . If the time constant of cooling of
the micropipette after emerging from the heated region is c,
p is given by

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Th
(1)
Ts
To control the taper of the pipette, the pulling velocity v is
controlled to be sufficiently small so that p h , or
equivalently that the pulling velocity satisfies
T
v h 2c ln h . The resulting dependence of taper on
Ts
p

is obtained by assuming that the pipette possesses nearly

2vc ln

uniform cross-sectional area A within the region h .


Assuming that the cross section preserves its shape during
pulling, i.e., the ratio of the inner diameter to the outer
diameter din/d= remains constant, the profile d(x) of the
outer diameter of the pulled micropipette is given by
d(x) = d0 exp( x/ h)
(2)
If 'v' is the velocity with which the pipette is being pulled
andt is the time of pulling, x = vt. Thus, the taper of the
micropipette is controlled by controlling the length h
through which the glass capillary tube is heated. To achieve
active control over the length of capillary tube that is being
heated, the capillary tube is passed through a ceramic tube.
By adjusting the position of the ceramic tube relative to the
coils, the number of heater coil turns that are exposed to the
glass capillary tube can be controlled.
To control the tip diameter, the glass tube is pulled for a
duration t1 after which the heater is switched off. Continued
pulling fractures the glass tube in the middle, thereby
creating two micropipettes of identical diameters d1 given by
d1 d0 exp(vt1/ h). Thus, the time t1 at which the heater is to
be switched off in order to achieve a tip diameter d1 is given
by
(3)
t1 ( h / v) ln(d0 / d1 )
In the experiments, the glass capillary was heated for 135
seconds and then pulled. Experiments were carried out with
various values of h ranging from 4mm to 16 mm. The
profile of the pipettes obtained in each case is shown in Fig
3(a). Figure 3(b) plots ln [d(x)/d0] as a function of x, where x
is the distance from the base of the micro-pipette and d0 is the
original diameter of the glass capillary, and shows that the
dependence is linear in each case. Further, the slopes of the
four lines decrease monotonically with increased h , in
accordance with the theoretical result in Eq. (2). Figure 4(a)
is a micrograph showing tips of diameter d1 ranging from
500 m down to 20 m, obtained for values of t1 ranging
from 10s to 25s. The figure demonstrates that the tip
diameter reduces monotonically with increased t1. Figure
4(b) plots ln [d1/d0] as function of t1 and demonstrates a
linear relationship between the two in accordance with the
theoretical result obtained in Eq. (3).

Fig 3. (a) Micrograph showing the profiles of pipettes pulled with different
values of h and (b) plot of ln [d(x)/d0] as function of the distance x.

Fig 4. (a)Micrograph showing the tip diameters of pipettes obtained for


different values of t1. In all cases h was set to be 16 mm. (b) Plot of ln [d1/
d0] as function of the time t1.

(b) Silver coating of the fabricated micro-pipettes


After pulling a pipette of the required taper and tip
diameter, the pipette is coated with silver in order to render
its surface conductive. Silver coating is done by means of
Brashears process.
Brashears process facilitates
deposition of silver almost uniformly on any glass substrate.
It is a chemical process in which large surface area can be
coated in less than 15 minutes. The steps involved in
Brashear's process involve first dissolving equal amounts of
silver nitrate and sodium hydroxide in water. Next, the two
solutions are mixed so that a black precipitate of silver oxide
forms. Third, ammonia is added until the precipitate
re-dissolves. Fourth, sugar is added and stirred until it
dissolves in this solution. Finally, the article to be coated is
placed in this solution while the solution is gently heated.
This results in deposition of silver on the article. Fig. 5 is a
micrograph showing a micropipette coated with silver.

500m

Fig 5. Micrograph showing a micropipette coated with silver

Project #ISTC 0317

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4
B. Droplet mass measurement system
In order to measure mass of the liquid droplet, the shift in
resonance frequency caused by the droplet is measured. The
undamped resonant frequency of the micropipette is a
function of its stiffness k and effective mass m and is given
by 0 k m . Thus, for a small change in mass m , the
corresponding change in resonant frequency is given by
1 0 m
(4)

2 m
Thus, as m increases, the resonant frequency of the
micropipette gets reduced. If the density of the liquid is
known, it is possible to determine the volume of the droplet
formed at the tip of the micropipette. In the proposed system,
the resonant frequency is obtained by exciting the
micro-pipette and subsequently measuring its response by
means of optical beam deflection. The optical beam
deflection-based experimental setup for measurement of
droplet volume measurement consists of three components,
namely, a source of laser light, external actuator to vibrate
micropipette and an optical detector (Fig. 6).

20 kHz update rate. Within the real-time controller, the value


(VA+VB)-(VC+VD) was computed. The resulting signal is
proportional to the amplitude of angular oscillation of the
micropipette at the site of measurement. In order to excite the
micropipette, a piezo-buzzer was employed. In order to
obtain the resonant frequency of the micropipette, the
piezobuzzer was vibrated by providing a sinusoidal input
and the frequency of excitation was automatically swept
between two specified limits. Fig. 7(a) shows the photograph
of the measurement system. The normalized frequency
responses are plotted in Fig. 7(b) and clearly depict the
reduction in resonant frequency caused by generation of a
droplet.
(a)

Laser Source

I/V
Converter/
Amplifier

Laser Source

Silver Coated
Micropipette

Microscope

I/V Converter/
Amplifier

Quadrant
Photo
Detector

Syringe With
Silver Coated
Micropipette
Piezo Actuator

(b)
A

Quadrant
Photo
Detector

Syringe

Amplitude

Focusing Optics

Data Acquisition
and Processing

0.5
0

Without Droplet
With 260pL Droplet
With 1696pL Droplet

-0.5
1500 1750 2000 2250 2500 2750 3000

Droplet

Piezo Actuator

Fig 6. Schematic diagram of droplet volume measurement subsystem.

Light from a laser diode (wavelength 633 nm, power 3


mW) was focused using a converging lens on to the surface
of the micropipette. The micropipette attached with syringe
was arranged in such a way that the reflecting surface formed
an angle with the optical axis of the laser beam. The reflected
light from the surface of micropipette was collected on a
quadrant photo detector (QP100-6, First Sensor GmbH,
active diameter DD = 11 mm, responsivity 0.4 A / W )
kept at a distance of around 0.5mm from the reflecting
surface. It was ensured that the reflected spot was within the
active area of the detector. The photo-currents from the
quadrants of the detector were fed to the signal conditioning
circuitry, composed of I-V converters of gain 106 .The
voltages from each quadrant VA,VB, VC and VD were fed to
real-time controller (DS1103, dSPACE GmbH) operated at

Frequency (Hz)
Fig 7. (a) Photograph showing the measurement system (b) normalized
frequency responses of the micro-pipette carrying droplets of two different
volumes.

B. Droplet deposition system


After the formation of liquid droplet at the tip of the
syringe needle, the droplet is dispensed by applying a
voltage between the syringe needle and a target aluminium
plate. Upon application of the potential difference, the drop
becomes polarised and gets attracted to the plate owing to
coulomb force. If the force of attraction is larger than the
force due to surface tension of the liquid, it separates from
the pipette and gets deposited on the plate. This phenomenon
is known as electrohydrodynamic pulling. The shooting of
charged droplets depends on viscosity, the surface tension,
the density, the electrical permittivity and the electrical
conductivity of the fluid. In the experiments a 330 V, 100
mA dc power supply was constructed so that the distance

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5
between the micro-pipette and the target could be maintained
around 100-150m. The circuit diagram of the power supply
is shown in Fig 8(a). It employed a 230/230V transformer
followed by a bridge rectifier and a filter. The power supply
also comprised a short circuit protection circuit designed
using MOSFET (BUZ326). Fig 8(b) shows the photograph
of the power supply.
(a)

The silver-coated micro-pipette was attached at the end of


a 1ml insulin syringe. In order to produce a droplet, a
screw-driven stage was attached with the piston of the
syringe. The schematic diagram of the setup is shown in Fig
9(a) and the photograph of the system is shown in Fig 9(b).
The pitch of the screw used was 0.5 mm. The radius of the
syringe cavity was 0.36 cm. One full rotation of the bolt
displaced a liquid volume of around 20.3L. In this setup,
with careful manual actuation, it was possible to produce
liquid droplets of volume around 260 picolitres consistently.
The corresponding radius of the droplet was around 40 um.
The micrographs showing the formation and shooting of a
liquid droplet of volume about 260 pL on application of a
high voltage is shown in Fig. 15.

(b)
500um

Fig. 15. Electro hydrodynamic pulling of glue of volume about 260pL

Fig. 8: (a) Circuit diagram of the power supply (b) photograph of the
fabricated circuit.

IV EXPERIMENTAL RESULTS
(a)
Actuator
(Screw Driven
Stage)

(b)

Target
(Aluminium Plate)

Syringe

Silver Coated
Micropipette

Droplet

Power Supply

Fig 14. Photograph of droplet generation system

IV CONCLUSION
This paper reported the design and development of a small
volume droplet dispenser based on Electro Hydrodynamic
pulling. The dispenser is capable of real time measurement
of the mass of liquid dispensed. The developed liquid
dispenser consists of thee subsystems, namely, the droplet
generation subsystem, droplet mass measurement subsystem
and the non-contact type liquid droplet deposition
subsystem. The droplet deposition subsystem comprised a
silver coated micropipette attached to a syringe along with an
actuation system. The micropipette of desired characteristics
and dimensions was made using a pipette puller developed in
house. The silver coating on the micropipette was done by
Brashears process. The droplet mass measurement
subsystem works on the principle of shift in resonant
frequency of a micropipette due to formation of a liquid
droplet. The shift in resonant frequency was obtained by
employing an optical beam deflection measurement system.
The principle of the third subsystem, namely the non-contact
type liquid droplet deposition system is electro
hydrodynamic shooting, wherein an electric field is applied
between the droplet and the target to result in deposition of
the droplet. A 330 V power supply was designed and
developed to realize this subsystem. All of these developed
subsystems were experimentally evaluated. The droplet
generation subsystem was able to generate liquid droplets of
260pL consistently. The shift in resonant frequency of the
micropipette due to the formation of 260 pL and 1696 pL
liquid droplets were measured in real time with the liquid
droplet mass measurement subsystem. Finally, the droplets

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6
of different volumes were successfully deposited on a target
by means of electrohydrodynamic pulling.
REFERENCES
1. A. S.Yang, C. H. Cheng and F. S. Hsu, PZT actuator applied to a
femto-liter droplet ejector, Journal of Mechanical Science and
Technology 21, pp. 621, (2007) .
2. B.Heij, C. Steinert, H. Sandmaier, R.Zengerle, A tuneable and
highly-parallel picolitre-dispenser based on direct liquid displacement,
Sensors and Actuators A 103 (2003).
3. P. Ferraro, S. Coppola, S. Grilli, M. Paturzo and V. Vespini,
Dispensing nanopico droplets and liquid patterning by
pyroelectrodynamic shooting, Nature Nanotechnology 5(2010).
4. K.Thurow, T.Kruger , N. Stoll, An optical approach for determination
of droplet volumes in nano dispensing, Journal of automated methods
and management in Chemistry 2009(2009).
5. Ren, R.B Fair, M.G. Pollack, Automated onchip droplet dispensing
with volume control by electro wetting actuation and capacitance
metering, Sensors and Actuators B 98(2004).
6. Ernst, W. Streule, R. Zengerle, P Koltay, Quantitative Volume
Determination of Dispensed Nanoliter droplets on the fly, IEEETransducers 2009.
7. C. Haber, M. Boillat, B.V. D Schoot, Flow sensing driven nano
dispensing: The path to more reliable liquid handling operations,
Application Note: American Laboratory October 2004.
8. R. Tamizhanban, K. R. Sreejith, and G. R. Jayanth, An automated
pipette puller for fabrication of glass micropipettes, 85, 055105 (5pp),
2014.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Synthesis Optical and Electrical Characterization of IIVI colloidal quantum dots for IR applications
Atul Prakash Abhalea , Abhijit Chatterjeeb, Naresh Babub, Arup Banerjeeb and K.S.R. Koteswara
Raoa,*
a

Department of Physics, Indian Institute of Science, Bangalore- 560012


b
SAC (ISRO), Sensors Development Area, Ahmedabad -15

Abstract: colloidal quantum dots (CQDs) can


provide tuneable bandgap, cost effective and
relatively low processing temperature
materials for photo-detection. In this paper
we have discussed the synthesis of HgCdTe
and PbS colloidal quantum dots and their
application as IR photodetectors.

I.

Introduction

Colloidal quantum dots are potential


candidates for the light detection applications,1
due to its exceptional characteristics such as
tuneable bandgap, comparatively easy and cost
effective synthesis and tuneable properties by
post synthesis processes.1,2 In the CQD
materials bandgaps are tuneable with the values
greater than that of the bulk ones and hence
only low band gap compound semiconductors
can match the spectral range suitable for
Infrared photodetection applications. Among
several low band gap compound semiconductors HgCdTe (MCT), PbS are suitable
materials with higher exciton Bohr radius (~18
nm), which allows bandgap tuneablity and low
binding energy due to its high dielectric
constant (~17.2), which helps relatively easy
exciton dissociation and charge extraction.
Recent work on the PbS-CQD based schottky
barrier photodiodes highlights the importance of
the CQD based photodetection.3,4

II.

Fig.1The absorption spectrum of the PbS CQD


solid films.
Fig. 1 shows a typical absorption
spectrum of solid CQD films, where quantum
dots are grown at 120 C for different time
periods varying from 5 60 minutes. The
presence of clear first and second excitonic
peaks in all the spectra confirms the narrow size
distribution, which is also visible from the TEM
image in Fig. 2.

Experimental

Monodispersed colloidal quantum dots


of MCT and lead sulphide are synthesized with
the method reported by the MC Weidman et.
al.,5 with excitonic absorption peaks from
~1300-1600 nm. This method provides narrow
size distribution of the quantum dots, which are
essential for the better carrier transport in the

solid CQD films, which increases the hopping


probability 6.

EmailAddress:ksrkrao@physics.iisc.ernet.in

Fig. 2. Transmission electron micrograph of the


PbS quantum dots.
In the device point of view, schottky
barrier devices are fabricated with Aluminium
and Indium Tin Oxide (ITO) contacts, where
ITO works as Ohmic contact. Similarly PbS-

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CQD/Si heterojunctions are fabricated


f
onn a
<100> oriented
o
singlle crystal siliicon wafers. For
the schoottky devicess particular device
d
geometry
is utiliseed (Fig. 3) this
t
can be used as a pixel
p
array of size 300 300 m
m and posittion
dependaant photoressponse can be colleccted,
which is analogouus to the ROIC. In this
geometrry, patternedd transparennt ITO contacts
are depoosited on thhe glass subsstrate on whhich
~50 nm thick CQD film is spin coated and then
t
patterned Al is depposited as shhown in Figg. 3.
When potential
p
is applied to any two crross
contactss only one CQD
C
area, whhich appearss on
the crosss junction of
o the two linnear arrays will
have efffective conntribution. In
I this wayy a
complete 2N pixels can be haandled with 2N
number of contacts.

Fig
g. 4 I-V chaaracteristics of the PbS--CQD/Al
sch
hottky diode.

Fig
g. 5 Dark and
a
light I-V
V Characterristics of
Pb
bS-CQD/Si heterojunction
h
n under reveerse bias.

Fig. 3 Crossbar
C
conttact CQD pixxel array.
I-V characteeristics of thee schottky diiode
in the dark
d
and undder 40 W tuungsten lampp is
shown in
i Fig. 4. It
I is clear from
fr
the figure,
under thhe light phottocurrent dennsity dominates
in the reverse biass. Over a period
p
of time
t
degradattion is obseerved in thhe Al/PbS-C
CQD
schottkyy diodes, proobably due to
t the oxidation
of the Al,
A indicates a need for a protective laayer
to avoidd degradatioon.7 In the case of PbSP
is
CQD/p-Si heterojuunctions, photocurrent
p
observedd under thhe light illuumination. I-V
characteeristics of these heterrojunctions are
shown inn Fig. 5, wheere a contribbution from both
b
Si and PbS-CQD.
P
T observe the
To
t contribution
from thee CQD film
m, devices were
w
illuminaated
with thee Si filter whhere only wavvelengths abbove
~1100nm
m were passeed through.

IIII.

LBIC
C Imaging

PbS-CQD / p-Si devices aree imaged


wiith the remoote contact L
Light Beam
m Induced
Cu
urrent (RC-L
LBIC) technnique, the details
d
of
wh
hich are pressented else-w
where. Imag
ging with
thiis technique gives inform
mation about an active
areea on the deevice, wheree the built in
n electric
fileed is presentt. Fig. 6(a) shhows a 3-dim
mensional
RC
C-LBIC imaage of the P
PbS-CQD/p-S
Si square
shaaped devicee. Here, thee axes repreesent the
spaatial distancces parallel to the plan
ne of the
dev
vice and colour represents the mag
gnitude of
sig
gnal. In Figg. 6(b) the cross-sectio
on of the
sig
gnal is plotteed, which is bbipolar in naature. The
dettails will be discussed duuring the pressentation.

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IV.

Conclusion

We have synthesized monodispersed


colloidal MCT and PbS quantum dots with
chemical bath deposition technique with variable
excitonic absorption peaks. Schottky, as well as
heterojunction devices are fabricate with solid film
of CQD on Al and Silicon by spin coating
technique. In order to study the photodetection
capabilities of the devices I-V characteristics under
the dark and light conditions are studied, where a
good photoresponse is observed for both schottky
as well as heterojunction devices.

Fig. 6 a). 3D plot of RC-LBIC image. b) a


cross-section of 3D signal for PbS/Si
heterostructure.

References
1

G. Konstantatos and E.H. Sargent, Infrared


Phys. Technol. 54, 278 (2011).
2
E. Sargent, Nat. Nanotechnol. 7, 349 (2012).
3
J.P. Clifford, K.W. Johnston, L. Levina, and
E.H. Sargent, Appl. Phys. Lett. 91, 253117
(2007).
4
E. Heves, C. Ozturk, V. Ozguz, and Y.
Gurbuz, Electron Device Lett. 34, 662 (2013).

M. Weidman, M. Beck, and R. Hoffman,


ACS Nano (2014).
6
P. Guyot-Sionnest, J. Phys. Chem. Lett. 3,
1169 (2012).
7
H. Fu and S.-W. Tsang, Nanoscale 4, 2187
(2012).

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Movement strategies for commensalism:


coexistence of meso-carnivores in human-dominated landscapes
Maria Thaker1 and AbiTamimVanak2
1
1

Centre for Ecological Sciences, Indian Institute of Science


Ashoka Trust for Research in Ecology and the Environment

Abstract - In the increasingly humandominated landscapes of India, the


survival and long-term persistence of
mammalian carnivores is a key
conservation challenge. This is
especially the case for species that
survive in the semi-arid savanna
biomes of central India. The overall
aim of this study is to determine the
ecological parameters and behavioural
strategies that enable existence of the
golden jackal,Indian fox, and jungle
cat in human-dominated systems.
Here, we present the first part of the
study, which was to generate detailed
maps
of
the
study
areasin
Maharastrausing supervised and rulebased classification ofLISS IV
imagery. Comparison of these methods
indicates that object-based methods
have higher accuracy and is more
applicable
th 1 an
supervised
classification methods for delineating
habitat patches in grassland areas. Onground surveys of these areas confirm
the presence of focal species (Golden
Jackal, Indian fox and Jungle cat).
During the next phase of the project,
we will obtain fine-scaled movement
data of the focal species using
advanced GPS/UHF telemetry. These
data will be superimposed onto the
high-resolution maps generated thus
far to determine patterns of resource
use and movement ofmeso-carnivores
across the landscape mosaic.
I. INTRODUCTION
Tropical landscapes worldwide are
1

Project code: IST/BES/MT/329

being rapidly transformed into a


complex matrix of human-dominated
multiple use land cover types with
differing intensities of use (Gibbs et al.
2010). With the second largest human
population in only 2.4% of the worlds
land area, natural habitats in India have
undergone some of the greatest rates of
transformation
(FSI
2011).The
consequence for organisms that once
inhabited large, unbroken tracts of
native habitats has been either
population decline to local extinction
on the one hand, or tenuous survival on
the other (Karanth et al. 2010). The
majority of research has focused on
species in decline, with particular
attention given to the effects of habitat
fragmentation and general loss of
biodiversity, yet there are a range of
species that seem to be effective
commensals in human-dominated
landscapes.
An understanding of how willing
species are to traverse or even utilize
potentially inhospitable and risky
habitats is critical to understanding
coexistence (Russell et al. 2003).
Adaptations of animals to such risk in
the landscape can be measured in
terms of timing (whether at particular
times of day or night), residence (how
long they stay in landscape elements)
and speed of movement (Graham et al.
2009). Thus, understanding how
animals make decisions regarding
movement
and
incorporating
behavioral decisions into population
models is an important step for
predicting the consequences of
fragmentation
for
population

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persistence (Russell et al. 2003; Fahrig


2007; Vanak et al. 2010). Resource
selection by animals is a hierarchical
process of behavioral responses to
particular
environmental
characteristics (Horne et al. 2008).
Different environmental factors and
scales may influence the movement of
individuals within a landscape, and
therefore
animal-landscape
relationships should be examined
across a range of scales (Anderson et
al. 2005; Boyce 2006). This is
particularly important when examining
resource selection dynamics of species
inhabiting fragmented or humandominated landscapes (Anderson et al.
2005).
In India much wildlife exists in
human-dominated landscapes across a
variety of biomes. Yet, there are very
few detailed studies on the status,
ecology and behavioural strategies of
species living in these landscapes
(Akhtar et al. 2004; Athreya et al.
2007) or even of the semi-arid tropics
in particular (Vanak and Gompper
2010). The first step and a key
challenge in understanding how
animals utilize human-dominated areas
isin distinguishing human-modified
from natural habitats using remotely
sensed data. Here, we report the results
of our analyses of high-resolution
imageries using supervised and rulebased classification to effectively
delineate habitat patches at a fine
resolution.We focus on the dry
savanna grassland habitat, because the
spectral heterogeneity of these
landscapes are particularly difficult to
classify and because small carnivores
that utilize these areas are poorly
studied. These detailed maps of native
and human-modified habitat patches
have been surveyed on ground, and
will later be superimposed with the
movement information of Indian foxes
(Vulpesbengalensis), golden jackals
(Canisaureus)
and
jungle
cats

(Felischaus). In doing so, we will have


fine-scaled data on the habitat
requirements and levels of tolerances
for human modification for each of
these species.
II- METHODS
A. Study area
The dry savannah grasslands of
peninsular India are unique habitats
that support a vast proportion of
Indias agro-pastoralist community.
These ecosystems have also been
subject to land-use change (e.g.
irrigation or conversion to agriculture
or tree-plantations) resulting in major
decrease in extent. We focus our study
on the areas near the villages of TakaliDhokeshwar
and
KedagaonKurkumbhof
Maharashtra.
The
landscape there is typical of much of
the central Indian plateau, with a
matrix of savannah grasslands,
agriculture land, and settlements.
B. Classification of remote sensing
data
Landcover data were obtained
from high-resolution satellite imageries
(IRS LISS IV, dated 18 January 2013)
were acquired for the two study areas.
After atmospheric correction, we
conducted a supervised classification
using the Maximum Likelihood
Classifier in Erdas Imagine, using
ground truthed data from field survey
as training data for the classifier. We
mapped the following and cover
classes: grasslands, agriculture, fallow,
water and builtup/bare (Fig. 1a).
As a comparison, we also
conducted
an
object-based
classification of the same LISS IV
images in eCognition developer 8.7,
based on a rule-set (Fig. 1b). All
images
were
subjected
to
multiresolution segmentation in order
to cluster spectrally homogenous
entities into one object (Hofmann and

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Puzicha, 1998). We classified built-up


areas and bare rocky areas using
brightness and green band values to
avoid spectral mixing with barren
grasslands. To identify agricultural
fields with and without standing crops,
we incorporated two vegetation
indices,
Normalized
Differential
Vegetation
Index
(NDVI)
and
Normalized Differential Vegetation
Structural Index (NDVSI) within
eCognition as object features. NDVI
relates directly to vegetation health,
while NDVSI shows vegetation
structure (Yang, Willis and Mueller,
2008)
One of the biggest hindrances
in grassland mapping is the difficulty
in distinguishing between grasslands
and fallow agricultural fields. If a field
is left uncultivated for period of time,
we find little to no spectral difference
between these fallow fields and natural
grasslands. We thus utilized a
combination of rules to separate the
fallow land from grasslands; for
example, the mean value of the IR
band in summer images for grassland
objects was higher compared to
fallow fields objects. We set the
threshold for object classification
accordingly.
We further classified grasslands
into different classes using the GLCM
(Grey Level Co-occurrence Matrix)
texture
feature
within
eCognition(similar to Guo et al. 2004).
The GLCM is produced by putting
each pixel and its neighbour within an
object into a 256x 256 matrix, and the
number of pair occurrences is final
value of the GLCM feature. Since the
study area included a wide range of
spectral classes, GLCM dissimilarity
and homogeneity were used to extract
grasslands. Finally, patches that were
left unclassified because of the
heterogeneity of the landscape were
classified
using
relations
to

neighbouring objects properties. For


example, smaller patches of land
between agricultural fields were
assigned as agriculture and not
grassland. And grasslands with
undulating topography were included
in the grassland class if surrounded by
other grassland 'objects'.

(a) Pixel based classification

Legend
Grassland
Agriculture
Fallow land
Water
Vegetation

(b) Object based classification

Builtup area/Bare

Figure 1.(a) Pixel- and (b) Objectbased classification of the TakaliDhokeshwar (Maharastra) area.
C. Ground-truthing and animal
presence surveys
The land cover maps that we generated
were exported as shapefiles and largest
contiguous 'core' areas within our
study area were extracted using Patch
Analyst extension in ArcGIS. The core
areas were divided into 13km2 grids
and the grids above 60% grassland
cover were selected for survey (Fig. 2).
Extensive field-work, which included
transects and random sampling, was
conducted to survey presence of
grassland specific species, especially
golden jackals, Indian foxes, and

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Jungle cats. We searched grassland and


the surrounding areas along existing
trails and tracks for species-specific
signs, such as carnivore scat, track
impressions, herbivore pellets, and
opportunistic
sightings.
Local
information was used to confirm
presence of endangered and grassland
specialist species.

Figure
2.
Map
of
the
TakaliDhokeshwarstudy
area,
depicting the grids (white) and survey
tracksfor
animal
presence
(green).Image courtesy of Google
earth.
III- CONCLUSIONS AND FUTURE
WORK
Thus far, we have generated detailed
maps of our study area using both
maximum
likelihood
supervised
classification and object based
classification methods. As expected,
supervised classification of complex
heterogeneous landscapes, such as
grassland habitats, is limited. We find
that
this
classification
method
produces a salt and pepper effect
which greatly contributes to the
inaccuracy of the classification (see
also de Jong et al. 2001; Gao and Mas
2008; Van de Voorde et al. 2004). This
problem arises because supervised

classification assigns classes to pixels


ignoring their related spatial and
contextual information (Weih, Jr and
Riggan, Jr), which results in
incorrectly classifying a map as overly
fragmented. Instead, the object based
classification created a grassland map,
which incorporated the heterogeneity
of the class. For example, hilly
grasslands, ridges, scrub forest, and
grass covered plains were all classified
as a single class: grassland. This
method therefore the land cover class
as a habitat rather than a heterogeneous
milieu. Not surprisingly, comparison
between these methods shows that
object based classification had a higher
overall accuracy (81% accuracy) than
supervised classification (64%) for
detailed
mapping
of
semi-arid
grassland areas.
On ground surveys of both
study areas confirm the presence of the
target study species. During the next
phase of the project, we will capture
and collar the target animals (n = 10
per species) using GPS/UHF telemetry
devices. The detailed movement
information we then obtain from these
tracked animals will inform us of the
behavioural strategies that permit use
of the habitat matrix.
ACKNOWLEDGEMENTS
We thank AmeyaGode for help in the
analysis of remote sensing data, and
AbhijeetKulkarniand
HarshalBhosalefor help in the field
surveys.
REFERENCES
[1] Akhtar, N., H. Singh Bargali, & N.
Chauhan. (2004). Sloth bear habitat use
in disturbed and unprotected areas of
Madhya Pradesh, India. Ursus, 15,
203-211.
[2] Anderson, P., M. G. Turner, J. D.
Forester, J. Zhu, M. S. Boyce, H.
Beyer, & L. Stowell. (2005). Scale-

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dependent summer resource selection


by reintroduced elk in Wisconsin,
USA. Journal of Wildlife Management,
69, 298-310.
[3] Athreya, V. R., S. S. Thakur, S.
Chaudhuri, & A. V. Belsare. (2007).
Leopards in human-dominated areas: a
spillover from sustained translocations
into nearby forests? Journal of the
Bombay Natural History Society, 104,
45-50.
[4] Boyce, M. S. (2006). Scale for
resource selection functions. Diversity
and Distributions, 12, 269-276.
[5] de Jong, S. M., Hornstra, T., & Maas,
H.-G. (2001). An integrated spatial and
spectral approach to the classification
of Mediterranean land cover types: the
SSC method. International Journal of
Applied Earth Observation and
Geoinformation, 3(2), 176-183.
[6] Fahrig, L. (2003). Effects of habitat
fragmentation on biodiversity. Annual
review of ecology, evolution, and
systematics, 487-515.
[7] Gao, Y., & Mas, J. F. (2008). A
Comparison of the Performance of
Pixel Based and Object Based
Classifications over Images with
Various Spatial Resolutions. Online
journal of earth sciences, 2(1), 27-35.
[8] Gibbs, H., A. Ruesch, F. Achard, M.
Clayton, P. Holmgren, N. Ramankutty,
& J. Foley. (2010). Tropical forests
were the primary sources of new
agricultural land in the 1980s and
1990s. Proceedings of the National
Academy of Sciences, 107, 1673216737.
[9] Graham, M. D., I. Douglas Hamilton,
W. M. Adams, & P. C. Lee. (2009).
The movement of African elephants in
a human dominated land use mosaic.
Animal Conservation, 12, 445-455.
[10] Guo, X., et al. (2004). Measuring
spatial and vertical heterogeneity of
grasslands using remote sensing
techniques. Journal of Environmental
Informatics, 3(1), 24-32.
[11] Hofmann, T., & Puzicha, J. (1998).
Statistical models for co-occurrence
data.Technical
report,
Artifical
Intelligence Laboratory Memo 1625,
M.I.T., 1998.

[12] Horne, J. S., E. O. Garton, & J. L.


Rachlow. (2008). A synoptic model of
animal space use: Simultaneous
estimation of home range, habitat
selection,
and
inter/intra-specific
relationships. Ecological Modelling,
214, 338-348.
[13] Karanth, K. K., J. D. Nichols, K. U.
Karanth, J. E. Hines, & N. L.
Christensen. (2010). The shrinking ark:
patterns of large mammal extinctions in
India.Proceedings of the Royal Society
London-B. 277: 1971-1979.
[14] Russell, R. E., R. K. Swihart, & Z.
Feng. (2003). Population consequences
of movement decisions in a patchy
landscape. Oikos, 103, 142-152.
[15] Van de Voorde, T., De Genst, W.,
Canters, F., Stephenne, N., Wolff, E.,
& Binard, M. (2004). Extraction of
land use/land cover related information
from very high resolution data in urban
and suburban areas. Remote Sensing in
Transition, 237-244.
[16] Vanak, A. T., & M. E. Gompper.
(2010). Multi-scale resource selection
and spatial ecology of the Indian fox in
a human-dominated dry grassland
ecosystem. Journal of Zoology, 281,
140-148.
[17] Weih Jr, R. C., & Riggan Jr, N. D.
Object-Based Classification vs. PixelBased Classification: Comparative
Importance
of
Multi-Resolution
Imagery. The International Archives of
the Photogrammetry, Remote Sensing
and Spatial Information Sciences, 38,
4.
[18] Yang, Z., et al. (2008). Impact of
band-ratio enhanced AWIFS image to
crop classification accuracy. Proc.
Pecora
17
http://www.
asprs.org/a/publications/proceedings/p
ecora17/0041. pdf.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Development and Performance Evaluation of a PCM coupled Heat Pipe


G. M. Karthik, Girish Kini, A. Ambirajan and P. Kumar

Abstract - Designing a suitable thermal control system for


present day electronics is becoming more and more
complex with the invention of low mass(compact) high
dissipation electronic components. Heat pipe is an
innovative device used for removal of heat from a remote
source to far-away heat sink. Thermal control design of a
spacecraft requires transportation of heat from the
electronic packages which are housed inside, to a thermal
radiator which is located outside. Heat from thermal
radiator is eventually dissipated into the space by radiation.
Even if the spacecraft heat loads are cyclic in nature,
thermal radiators are being designed to meet peak load
requirements. To avoid oversizing of a thermal radiator, a
heat storage unit may be employed to store the peak load
and release it over a longer time. The present project
explores the possibility of integrating a Phase Change
Material (PCM) module to a conventional heat pipe to take
care of periodic heat load transience. The PCM acts as a
thermal capacitor storing heat during transient peaks in heat
loads and releasing it during the off peak load conditions to
the radiator.

NOMENCALTURE

In thermal management of electronics, Phase Change


Materials (PCMs) are extensively used to maintain
temperatures during transient heating. PCMs are highly
effective heat storage materials that undergo a phase
change at a particular temperature or a range of
temperatures. These materials generally have a high latent
heat of fusion allowing a small amount of PCM to meet the
heat storage needs of a majority of applications.

A
Dh
hfg
L

N
p
Q
rc
u
w
x

area (m2)
hydraulic diameter (m)
latent heat of vaporization (J/kg)
length (m)
mass flow rate (kg/s)
number of grooves
pressure (Pa)
heat rate (W)
capillary radius (m)
velocity (m/s)
groove width (m)
coordinate along the heat pipe (m)

Greek Symbols
surface tension coefficient (N/m)
density (kg/m3)

viscosity (kg/m/s)
Subscripts
a
adiabatic section
c
condenser
e
evaporator
in
input
l
liquid

vapor

I. INTRODUCTION
Axially grooved Aluminium Ammonia Heat pipes are used
in spacecraft applications to transport heat from electronic
packages (heat source) to heat radiator (heat sink). Heat
pipes are generally embedded in the honeycomb panels on
which electronic packages are mounted on the inside and
heat is radiated to space from the outside. A typical heat
pipe consists of a hermetically sealed envelope containing
wick structure filled with saturated working fluid in liquid
phase and remaining space (core) filled with vapour. Heat
transferred to the heat pipe (at evaporator) is removed by
evaporation of the working fluid in the wick, thereby
increasing the vapor pressure in the core causing flow of
vapor towards the cooler end, where it condenses (at
condenser) and heat is released. The condensate returns to
the evaporator due to pressure gradient along the length of
the wick caused by surface tension forces (capillary
pumping).

A key challenge in the design of a thermal control system


of a spacecraft, while ensuring its reliability and
effectiveness, lies in accommodating high heat dissipations
and varying orbital heat loads. When the thermal load is not
steady, as in the case of remote sensing satellites, the
thermal system adopted demands similar heat removal
capacity as that at constant thermal load. The reason for
this is that the number of heat pipes and radiator area
requirement are based on the peak thermal load and not the
orbital average thermal load. One method of optimally
managing the issue of varying heat load without
overdesigning the thermal system is by the use of a suitable
Phase Change Material in conjunction with heat pipe for
efficient and stable heat transfer. This concept would not
only optimize the thermal design, it would also result in
lesser number of heat pipes and reduced radiator area. This

ISTC0321

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in turn would result in a significant reduction of overall


mass of the spacecraft thermal control system.

Further substituting for the liquid and vapor velocities from


equations (5) and (6)

II. MATHEMATICAL MODEL OF HEAT PIPE

The radius of the meniscus which is formed at the liquidvapor interface is related to the pressure difference between
the liquid and vapor by the Young-Laplace equation [4],
which in differential form can be written as

( )

( )

(1)

Both liquid and vapor flow are modeled as laminar pipe


flow. The liquid pressure gradient in the grooves and vapor
pressure gradient in the core can be expressed as, [5],
=

32

32

(2)

The axial conduction of heat in the envelope is neglected.


Hence by conservation of energy, the mass flow rate can be
expressed as
=

( )

The liquid and vapor velocities are expressed as follows

(3)

( )

(4)

The heat load in the axial direction, [3], is

( )=

,
,

0<

<

<

<

<

<

(5)

32

( )

( )

32
,

( )

( )

( )

(7)

(8)

Maximum heat transport capability is obtained by


multiplying the maximum heat transported with effective
length of the heat pipe. For a given heat pipe geometry,
heat transport capability is a function of temperature. This
is due to the fact that working fluid properties like density,
viscosity, surface tension, latent heat, etc. varies with
temperature. Variation of computed maximum heat
transport capability over different operating temperatures is
plotted in the following figure.
350

300

250

200

150

-40

-30

-20

-10

10

20

30

40

50

60

Temperature(C)
Fig. 1. Variation of maximum Heat Transport Capability with
operating temperature

It can be seen from the plot that, maximum heat transport


capability reaches to its peak at a given temperature and
falls to minimum on either side.

III. HEAT PIPE EXPERIMENTAL SETUP

Combining equations (1) and (2) we obtain


32

( )

100

( )

The boundary condition having radius of meniscus at the


condenser end equal to the radius of the vapor groove [1] is
considered. The equation (9) is solved by the fourth-order
Runge-Kutta method and variation of curvature over the
length of the groove is obtained. The maximum heat that
can be transported by the heat pipe is obtained by equating
the radius of meniscus at the evaporator end to half of
groove width [2].

Heat Transport Capability(Wm)

The heat transport capability (measured in Watt-meter) is


one of the key factors in the thermal performance of heat
pipes. The mathematical model is developed to estimate
heat transport capability of a heat pipe based on capillary
limitation. Heat pipe with Aluminium alloy as envelope
material, extruded axial grooves as wick and ultrapure
anhydrous ammonia as working fluid is considered for this
study. The variation of the radius of curvature of the
meniscus at the liquid-vapor interface is used to calculate
the maximum heat transport capability of the heat pipe.

32

(6)

An experimental setup is built to measure maximum heat


transport capability of the given heat pipe. The
experimental setup consists of a horizontal working
platform, height adjustable fixture, instrumented heat pipe,
DC power supply, constant temperature bath and a data
acquisition unit, as shown in the following figure.

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Fig. 2. Schematic showing experimental setup

The heat pipe is divided into three zones, namely,


evaporator (where heat is added), adiabatic (where there is
no heat transfer across the heat pipe, to external
environment) and condenser (where heat is removed). The
given heat pipe is instrumented with resistance foil heaters
on the evaporator end and micro channel heat exchangers at
the condenser end. The zone between evaporator and
condenser (adiabatic) is covered with insulation material.
T-type thermocouples are mounted on external surface at
various locations along the length of the heat pipe. The
entire setup is connected to a data acquisition and control
unit (cRIO-9082 system). A Virtual Interface (VI) is
created using Lab-View program through which the
experiments are controlled.

Fig. 3. Complete Experimental Setup

The maximum heat transport capability values are


calculated for highest value of heat input before dry out
limit is reached, for different operating temperatures.
Figure 4 gives experimentally obtained values at -20oC,
0oC, 20oC and 40oC along with theoretical estimate.
It shall be noted that, at -20 oC experimental value is lower
than theoretical value and at higher temperatures,
experimental results are higher than theoretical estimates.
This is due to the fact that, mass of the working fluid is
estimated considering liquid volume equal to grooves
volume and vapour volume equal to core volume at 0 oC. At
temperatures below 0oC, specific volume of liquid
ammonia decreases causing shortage of liquid in the
grooves. While at higher temperatures, specific volume of
liquid ammonia increases causing availability of more
liquid in the grooves to absorb more heat in the evaporator.
This liquid puddle effect at higher temperatures will be
considered in the theoretical computation as a part of future
work.

Heat Transport Capability(Wm)

350

300

250

200

150

Theoretical
Experimental

100

-40

-30

-20

-10

10

20

30

40

50

60

Temperature( C)
Fig. 4. Experimental data of maximum Heat Transport Capability
compared with theoretical estimation

IV. DESIGN OF PCM MODULE


The Phase Change Material (PCM) module is designed so
as to store approximately 30 kJ of heat. Considering
paraffin wax or Eicosane as the candidate phase change
material, the size of the module was worked out to be
100mm x 100mm x 20mm based on the latent heat of the
chosen PCM material. Flanges are provided on all four
sides at the top to have Copper is chosen as the material of
the module. Two pressure relief valves are provided on the
top plate of the module to provide pressure relief in cases
of pressure build up inside the PCM module during its
operation. A silicone gasket of 1mm thickness is used
between the two parts of the PCM module to ensure
adequate sealing of the phase change material during
melting. The module also has a slot, at its base, through
which the heat pipe can be coupled thermally to the PCM
with minimum resistance.

Fig. 5. PCM module assembled with a top plate

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The thermo-physical properties of Paraffin Wax and


Eicosane are given in the following tables 1 and 2.

Density (kg/m )
Heat of Fusion (kJ/kg)
Thermal Conductivity
(W/m-K)

Paraffin Wax(MERCK make)


58-60
790 (liquid, 65 C)
916 (solid, 24 C)
173.6
0.167 (liquid, 63.5 C)
0.346 (solid, 33.6 C)

90
80

Temperature(C)

Material
Melting Point (C)

100

Heat of Fusion(kJ/kg)
Thermal Conductivity
(W/m-K)

Table 2: Properties of Eicosane

V. PCM MODULE CHARACTERIZATION STUDIES


PCM module is filled with 150g of Paraffin wax and is
instrumented with a resistance foil heater at its base.
Several thermocouples are mounted at various locations on
the external surfaces of PCM module. In addition, one
thermocouple is left floating inside the PCM module to
measure the temperature of the candidate PCM. The
thermocouples are connected to a NI 9213 DAQ card
which is connected to NI cRIO system. The heater is
powered through a programmable DC power supply unit.
The measured data are continuously stored on a dedicated
computer through Lab-View interface.
Few experiments are conducted to study phase change
behaviour of PCM inside the module, to verify heat storage
capacity and to measure temperature distribution within the
module. The experiments were repeated for various
configurations of the module, different heat inputs and
operating conditions.
It is found that for an input of 20 W of heater power for
4630 sec, 1.0 W was consumed by PCM module as sensible
heat, 3.5 W was expended as sensible heat within the PCM,
9.5 W of heat is lost through convection and remaining 6.0
W is utilised in melting the PCM. Approximately 28 kJ of
heat can be stored as latent heat using Paraffin wax as PCM
in this module. Since Copper is chosen as material for
building PCM module, temperature difference under stable
condition was found to be less than 5oC within the module.
Module temperatures and PCM melting characteristics are
shown in the following plot.

50
40
30

T_wall
T_heater
T_pcm

10
0

1200

2400

3600

4800

6000

7200

8400

Time(s)
Fig. 6. Experimental data showing temperature distribution on the
PCM module

VI. HEAT PIPE TRANSIENT EXPERIMENTS


Experiments were carried out to characterize the transient
behavior of the heat pipe. These experimental results serve
as a baseline reference to understand the characteristics of a
heat pipe when coupled with PCM module. To simulate 30
kJ of heat input, the heat pipe evaporator is powered to 50
W for 10 minutes in the two experiments described below.

1. In the first experiment, 50 W of heat applied for 10

minutes at the evaporator is removed from the


condenser, exposed to the surroundings, through natural
convection.
2. In the second experiment, heat exchanger is attached to
the heat pipe condenser which in turn is connected to
constant temperature bath. 50 W of heat is removed at a
constant temperature of 30oC through the continuous
flow of fluid inside the heat exchanger.
Heat pipe transient temperatures in the above experiments
are plotted in Figure 7.
60

Bath on
No Condenser

55

Temperature(C)

Density(kg/m3)

Eicosane (Sigma-Aldrich)
35-37
770 (liquid)
810 (solid)
241.0
0.157 (liquid)
0.390 (solid)

60

20

Table 1: Properties of Paraffin Wax

Material
Melting Point(C)

70

50
45
40
35
30
25

150

300

450

600

750

900

Time(s)
Fig. 7. Experimental data showing evaporator temperature during
heat pipe transient experiments

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removed at a constant temperature of 60oC through the


fluid circulation in the heat exchanger. Transient
temperatures of the heat pipe without PCM module and by
coupling PCM module are shown in the following plot.
66

VII. HEAT PIPE COUPLED WITH PCM MODULE


The PCM module is coupled to the heat pipe at the
evaporator with the help of thermal grease to ensure good
thermal contact. The other surface of the heat pipe is
instrumented with foil heater, as shown in the following
figure.

Fig. 8. Schematic showing Heat Pipe Coupled with PCM Module

The PCM module is filled with Paraffin wax (% fill). Two


experiments are carried out again. In the first experiment,
50 W of heat for 10 minutes is removed from the heat pipe
condenser through natural convection. Following plot
shows heat pipe transient temperatures without PCM
module and by coupling the PCM module.
HP+PCM
HP

Temperature(C)

55
50
45
40
35
30
25

150

63
62
61
60
59
58

150

300

450

600

750

900

Fig. 10. Heat Pipe evaporator temperature for Heat pipe coupled
with PCM Module having condenser section connected to a heat
exchanger

Heat Pipe

Heater

60

64

Time(s)

PCM module

EVA

PCM+HP
HP

65

Temperature(C)

It may be noticed from Figure 7 that, in the absence of heat


storage unit, 25C temperature raise is observed in the heat
pipe within 10 minutes of heat input. To maintain the heat
pipe at constant temperature during heat addition,
continuous removal of heat is required. This can be
achieved either through the use of complex active device
like constant temperature bath / heat exchanger or a simple
PCM module coupling.

300

450

600

750

An interesting phenomenon was observed during the


experiment on PCM coupled heat pipe. Though the
condenser was maintained at 60oC, the evaporator
temperature was less than 60oC initially due to the presence
of PCM module. Heat pipe was operating with flow of
ammonia vapour from condenser end to evaporator end and
flow of liquid ammonia in the grooves from evaporator end
to condenser end. When a heat load of 50 W was applied
on the evaporator, its temperature increased to condenser
temperature and heat pipe operation ceased. This resulted
in sudden rise of heat pipe temperature and PCM module
for next 90 seconds. When evaporator temperature
sufficiently rose above condenser temperature, heat pipe
started operating by reversing the direction of working fluid
in the vapour core and grooves. This flow reversal
phenomenon may be observed in the following plot which
shows evaporator and condenser temperatures of the heat
pipe.
66

900

Time(s)

It may be noticed that, by introducing PCM module on the


heat pipe evaporator, temperature raise falls by 7 to 8oC.
However, since heat source is coupled to the heat pipe, only
a small amount of heat flows towards PCM module.
Experiments by coupling the heat source directly to the
PCM module will be carried out as a part of future work.
In the second experiment, condenser end of the heat pipe is
connected to the heat exchanger, which in turn to the
constant temperature bath. 50 W of heat for 10 minutes is

Temperature(C)

Fig. 9. Heat Pipe evaporator temperature when coupled with PCM


Module (Paraffin Wax) having condenser section exposed to
ambient.

Evaporator
Condenser
PCM Module

65
64
63
62
61
60
59
58

150

300

450

600

750

900

Time(s)
Fig. 11. Temperature vs Time plot showing the flow reversal
process

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Heat of superheat equivalent to about 5oC temperature rise


for 90 seconds was required to cause the reversal of fluid
flow in the heat pipe. Such phenomenon is not reported in
any known literature of open source.

One more experiment is conducted by filling the PCM


module with n-Eicosane and coupling to heat pipe
evaporator. 50 W of heat for 10 minutes is removed from
the condenser through natural convection to the
surroundings. Following plot gives heat pipe transient
temperatures without PCM module and by coupling PCM
module.

55

HP
HP+PCM

Temperature(C)

50

All efforts will be made to develop a state-of-the-art PCM


coupled heat pipe for spacecraft thermal control
applications.
IX. REFERENCES
[1]Y. Chen, W. Zhu, C. Zhang and M. Shi, 'Thermal
Characteristics of Heat Pipe with Axially Swallow-tailed
Microgrooves', Chinese Journal of Chemical Engineering,
vol. 18, no. 2, pp. 185-193, 2010.

45
40
35
30
25

Coupling of PCM module in adiabatic zone and


condenser zone separately and analyse thermal
characteristics.
Shift the heat source from heat pipe side to PCM
module side and repeat all the above experiments.
Use thermal conductivity enhancers like finned top
plate, metal foam or honeycomb structure inside the
PCM module and repeat the experiments.

150

300

450

600

750

900

Time(s)
Fig. 12. Heat Pipe evaporator temperature when coupled with
PCM Module (Paraffin Wax) having condenser section exposed to
ambient.

Since n-Eicosane is a single compound pure substance


which melts at a temperature below 40 oC and has same
melting point and solidification point temperature, it is a
potential candidate for use in space applications.

VIII. CONCLUSIONS AND FUTURE WORK

[2]K. Do, S. Kim and S. Garimella, 'A mathematical model


for analyzing the thermal characteristics of a flat micro heat
pipe with a grooved wick', International Journal of Heat
and Mass Transfer, vol. 51, no. 19-20, pp. 4637-4650,
2008.
[3] Jeong-Se Suh and Young Sik Park, Analysis
of
Thermal Performance in a Micro Flat Heat Pipe with
Axially Trapezoidal Groove, Tamkang Journal of
Science and Engineering, Vol. 6, No. 4, pp. 201-206 (2003)
[4]A. Faghri, Heat pipe science and
Washington, DC: Taylor & Francis, 1995.

technology.

[5]D. Reay, P. Kew and P. Dunn, Heat pipes. Oxford:


Butterworth-Heinemann, 2000

Efforts have been put to develop 1-D mathematical model


to simulate steady state operation of an axially grooved
heat pipe and estimate maximum heat transport capability.
This model will be improved further to include puddle
effect of the working fluid at higher temperatures.
Operation of heat pipe under transient heat loads will be
studied by developing a transient mathematical model as a
part of future work.
Several experiments were conducted to characterise a given
heat pipe and calculate its maximum heat transport
capability at different temperatures. A PCM module is
designed and thermal characterisation tests were conducted.
This PCM module was thermally coupled to the evaporator
of the given heat pipe. Series of experiments were
conducted to study thermal behaviour of heat pipe in the
presence of PCM module. An interesting phenomenon of
flow reversal was noticed inside the heat pipe.
Following activities are planned as a part of future work:

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Theoretical and Computational Study of Frictional Effects in Viscoelastic and


Generalized Elastic Contacts
D. Satish Kumar, Narayan K. Sundaram

I. INTRODUCTION
The problem of contacts between nominally clamped
engineering components under the influence of
external cyclic loads is important because of their as
initiators of failure. Micro-slip, high edge-of-contact
stresses and stress gradients combine to produce the
phenomenon of fretting failure. The highly local
nature of fretting contact failure necessitates highfidelity contact stress modeling in such applications
as bearings, riveted joints, etc.
In this context, metal-metals contacts have
been studied extensively using elastic contact
mechanics. However, metal-polymer (elastic-visco
elastic) contacts have been studied only sparingly,
with far fewer solutions to problems of fundamental
interest. The list of such solutions dwindles to none
when frictional effects and geometrically conforming
bodies are considered. The present work is a progress
report on a computational and theoretical study to
remedy these deficiencies and better understand the
role of friction in viscoelastic contacts better. A
secondary objective is to explore more general
geometries for elastic frictional contacts.
II. PRELIMINARY COMPUTATIONAL STUDIES
A geometrically conforming pin-plate configuration
was chosen for the problem. As a first approximation,
the elastic pin was modeled as rigid, and the material
of the plate modeled as a delayed viscoelastic
element with two springs and one time-constant. A
material time constant =5 s was assumed for
PMMA. The ABAQUS STANDARD implicit Finite
Element analysis (FEA) solver was used to model the
contact. A custom structured contact mesh-maker,
FEMESH2D, developed by one of the authors1 was

Narayan K Sundaram is an Assistant Professor in the


Department of Civil Engineering, IISc

used to generate the mesh for the plate , as shown in


Fig. (1). A total of 324 contact elements were used to
mesh the hole, of which roughly 100 elements were
in contact at peak load. The indenter was modeled
using discrete rigid R2D2 elements. The ABAQUS
four-noded, plane strain CPE4R element with
reduced integration was chosen. At least 100 timestep increments were used per load step in the
analyses in order to capture the slip history and slip
reversals accurately.
The contact parameters are as follows: Hole
radius R=1 inch, pin-radius Rd=0.995 inch, E
(PMMA) =4.35x105 psi, Poissons ratio = 0.40. The
viscoelastic network parameters are =5 s, G1 = G2
= 2.14x105 psi. In the interest of simplicity, the
viscoelastic materials Poissons ratio was treated as
a constant. The coefficient of friction =0.35.
Multiple loading scenarios were tested: 1)
Monotonically increasing, uni-directional pin-load 2)
Monotonically increasing, oblique pin-load 3) Cyclic
pin-load. A peak load of P=10,000 lb/in was chosen,
giving an effective conforming contact parameter
Lp = 2G(R-Rd)/(P(+1)) of 0.21. The lower the value
of this parameter, the more geometrically conforming
the contact, and the less valid the half-plane approximation used in Hertz-type contact analyses.
In typical elastic contact analyses, a repeated
(fretting-type) load consists of the following: A
vertical load P applied in the first step with no
horizontal loading. In subsequent steps, P is held
constant, while horizontal load Q is cycled between
+Q0 and Q0. In an elastic contact, it is well known
that the pressure and shear tractions reach a state
called shakedown, in which the tractions achieved at

D. Satish Kumar is an MSc student in the Department


of Civil Engineering, IISc

ISTC/CCE/NKS/335

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he extremities of the load cycle do not change from


cycle to cycle.
In viscoelastic contacts, the expected lag in response
of the material makes the ratio of the time-period of
cycling to the time constant a critical parameter,

Figure 3: Normalized shear tractions T() R / P during


horizontal load cycling. The elastic tractions (cyan and
magenta lines) are shown for reference. The time steps
for these plots are t=2 (only P, black lines). The blue and
red lines are shear tractions after 7 and 7.5 cycles of
horizontal loading.
Figure 1 Close up view of the finite element mesh

which is absent in purely elastic fretting contacts. We


selected a Q amplitude of 0.5 P, and the cycling
time period Tp of the horizontal load as 0.5 . The
analysis was run for total time of T=10 to capture a
sufficient number of cycles of response.
The pressure and shear tractions in the two cases are
shown in Figures (2) and (3) respectively. The purely
elastic tractions are also shown for comparison. It is
seen that the viscoelastic tractions also shakedown,
just as in the elastic case. The steady-state pressure
tractions differ by very little between the elastic and
viscoelastic cases; however, the peak shear tractions
in the two cases differ by as much as 9 percent. In
future studies, it is planned to do a complete
convergence study of the tractions. Subsequently,
subsurface stresses will be examined. The latter
analyses requires ultra-fine meshes, and replacement
of the contact boundary conditions by traction
boundary conditions using T, N obtained from the
contact analysis, with quadratic elements used
subsurface.
REFERENCES

Figure 2: Normalized pressure tractions N() R / P during horizontal


load cycling. The elastic tractions (cyan and magenta lines) are shown Golden and Graham 1988; Boundary Value
for reference. The time steps for these plots are t=2 (only P, black Problems in Linear Viscoelasticity, Springer

lines). The blue and red lines are pressure tractions after 7 and Sundaram N., Farris T.N., 2010; J. Mech. Phys.
7.5 cycles of horizontal loading
Solids, 58(11) 1819-1833
ISTC/CCE/NKS/335

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Combustion studies of composite propellants


containing nano- burn rate catalysts
Charlie Oommen, R Arun Chandru
Department of Aerospace Engineering, Indian Institute of Science, Bangalore
and
R Rajeev
Vikram Sarabhai Space Center, Thiruvananthapuram

This paper presents our research initiative to


comprehensively
study
the
combustion
properties of composite propellants in the
presence of nano-burn rate catalysts, and their
relation to the thermal decomposition properties
of AP, and the properties of the nano-catalysts.
Our preliminary results indicate that a simple
and direct co-relation between the thermal
decomposition properties of AP and the burning
rate of composite propellant, as suggested in
recent literature, does not necessarily hold true
in the case of nano-catalysts. On-going studies
will provide further insights into the factors and
mechanisms affecting the ballistic properties of
composite propellants in the presence of nanoburning rate catalysts.

1. Introduction:
Ammonium Perchlorate (AP)-based solid rocket
propellants are extensively used in strategic
military vehicles and in launch vehicles for
space applications. The internal ballistic
properties of these composite propellants are
mainly governed by the thermal decomposition
characteristics of their major ingredient, AP (60
90% w/w). The decomposition properties of AP
are known to be particularly sensitive to the
presence of certain additives, even in small
amounts. These additives are used as ballistic
modifiers to tailor the propellants ballistic
properties. Transition metal oxides are effective
catalysts for the thermal sensitization of AP, and
are consequently incorporated as burning rate
enhancers in AP-based propellant formulations
(0.13% w/w). Some proven transition metal
oxide catalysts used for burning rate
enhancement include Fe2O3, CuO, CuCrO and
MnO2 [1,2].

Of late, numerous nano-catalytic systems are


being evaluated for the thermal sensitization of
AP. It is reported that nano-metal oxides exhibit
superior catalytic activity than their micronsized counterparts, by way of lowering the
decomposition temperature, increasing the
reaction rate and enhancing the specific heat
release of AP decomposition. The enhanced
activity of these nano-metal oxide systems
towards AP decomposition has generally been
attributed to the higher surface area in the case
of nanoparticles, the enhanced defects in nanostructures, and the synergistic effects of the
catalyst and support in nano-composites [3-5].
Although there are several reports on the
enhanced effect of nano-catalytic systems on AP
decomposition, reports regarding the ballistic
property modification of the composite
propellants with nano-catalysts are sketchy and
mostly contradictory. There are hardly any
studies that try to relate the properties of nanocatalysts to the decomposition properties of AP,
and subsequently to the combustion properties
(burning rate, pressure exponent etc.) of the
processed AP-based composite propellant.
Our research group has previously worked on
the syntheses, characterization and evaluation of
various nano-catalytic systems for AP
decomposition. Some of the nano-catalysts that
we have synthesized and evaluated include
nano-structured Cu-Cr-O, Fe2O3, mesoporous
MnO2, ZnO etc. (see Fig. 1). Particularly, the
mesoporous MnO2 catalyst prepared by our
group shows the best catalytic activity towards
AP decomposition reported till date in open
literature [5].

ISTC/MAE/CO/322

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This paper presents our research initiative to


comprehensively
study
the
combustion
properties of AP-based composite propellants
containing various nano-burn rate catalysts, and
some preliminary results regarding the same.
Efforts to relate the combustion properties of the
propellant to the decomposition properties of
nano-catalyzed AP, and in turn to the nanostructural properties of the catalysts are being
pursued. Various propellant processing aspects
involving the nano-catalysts like dispersion,
stability etc. are also being studied. During the
course of this research program, our objectives
mainly revolve around (a) creating a
comprehensive database of decomposition and
combustion characteristics
of
AP-based
composite propellants containing nano- burn rate
catalysts, (b) establishing co-relations between
the nano-catalyst properties, AP thermal
decomposition characteristics, and AP-based
composite propellant combustion characteristics,
and (c) investigating into the mechanism of
activity of nano- burn rate modifiers in APbased composite propellants.

Figure 1: Representative SEM images of some nanocatalysts prepared by our research group:
(a) nano-structured Cu-Cr-O, (b) nano-structured
Fe2O3, and (c) mesoporous MnO2

2. Experimental
2.1 Materials: Various transition metal salts and
other chemicals used in the preparation of
(nano)-catalysts were all of analytical grade and
used as received without further purification. AP
used in our experiments was kindly provided by
IIT, Madras. Hydroxyl-terminated polybutadiene
(HTPB), Dioctyl adipate (DOA), and Isophorone
diisocyanate (IPDI) used for making the
composite propellants were provided by VSSC,
Thiruvananthapuram.

2.2 Syntheses and characterization of nanocatalytic systems: Methods previously reported


in literature like homogeneous co-precipitation,
mesoporous templating, electrospinning etc.
were used to synthesize transition metal nanocatalysts. Also, synthesis methods developed inhouse by our research group like impinging
streams and submerged spray precipitation were
used. Some of the nano-catalysts that we have
synthesized and evaluated include nanostructured Cu-Cr-O, Fe2O3, mesoporous MnO2,
ZnO etc. The nano-catalysts were characterized
via techniques such as UV-Vis-IR Spectroscopy,
XRD, SEM, TEM, EDS and ICP-AES.
2.3 Evaluation of nano-catalytic systems: APHTPB (80:20% w/w) composite propellant
formulations containing nano-burn rate catalysts
were prepared by standard methodology.
Custom-designed micro-V-blender and planetary
micro-mixer with hot-water circulation jacket
were used to mix the propellant compositions.
Multiple blade configurations were designed and
tested experimentally. The mixing homogeneity
achieved using our custom-designed micromixers were comparable to that reported in
literature, as demonstrated using optical and
SEM imaging. Both micron-sized and nanostructured catalysts could be processed
efficiently, under slightly different conditions.
Cylindrical strands of 50mm length were cast
under vacuum using custom-made casting
apparatus, and cured in a PID controlled hot-air
oven. The mixing homogeneity in the presence
of nano-catalysts was verified by optical and
SEM images. The propellant strands were
ignited using a heated nichrome wire, and the
burning rate was acquired via fuse wires
connected to a data acquisition system. Burning
consistency was monitored via a long-range
high-speed optical camera. Experiments at high
pressures upto 120 bars are planned in our high
pressure propellant strand burner being
fabricated. Thermal analyses techniques like
DTA-TG, DSC and EGA with FTIR & GC-MS
are also being planned to investigate into the
mechanism of activity of nano- burn rate
modifiers in AP-based composite propellants.

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Table 1: Summary of catalyst surface area, decomposition temperature of catalyzed AP and burning rate
of AP-based composite propellant
Sample

Surface area of
catalyst
m 2 /g

Pure AP
AP+2% w/w micron-sized Fe 2O3
AP+2% w/w nano-structured Fe 2O3
AP+2% w/w mesoporous MnO2

3. Results and Discussion:


Fig. 1 shows representative SEM images of (a)
nano-structured Cu-Cr-O, (b) nano-structured
Fe2O3, and (c) mesoporous MnO2, prepared by
our research group. As shown in Fig. 2, the
addition of 2% w/w mesoporous MnO2 to AP
exhibits exceptional catalytic activity, as
compared to its micron-sized counterpart;
manifested
as
unprecedentedly
low
decomposition temperatures, fast reaction rates
and enhanced heat releases. Structural features
of the nano-catalyst like its high surface area and
the presence of a 3D mesoporous network,
which facilitate the adsorption and desorption of
reactive molecules during the secondary gasphase processes, account for its observed
excellent catalytic activity.

14.5
66.9
86.7

Decomposition
temperature
o

Burning rate
(atm)

mm/sec

426
361
310
273

2.1
3.0
3.8
3.2

its effect on the burning rate of AP-HTPB


composite propellants is modest compared to
Fe2O3. These preliminary results with
atmospheric pressure burning rates reveal that
there is no direct co-relation between the AP
thermal decomposition characteristics, and APbased
composite
propellant
combustion
characteristics in the presence of nano-catalysts.
Properties of the nano-catalysts such as its
phase, crystallanity, surface area and porosity
may be playing underlying roles in such
observation. Such a mechanism would be clear
after the on-going studies involving Fe2O3 nanocatalysts with varied morphologies and surface
areas. These Fe2O3 catalysts are being prepared
by our in-house developed continuous
submerged spray precipitation technique,
wherein the nano-catalyst properties can be
varied in a facile manner by varying the reactant
conc. and/ or the inlet air pressure. Further, the
combustion studies in a high-pressure strand
burner are being intended, and are expected to
provide insights on the burning rates of nanocatalyzed composite propellants at various
pressures and their corresponding pressure
exponents.

Figure 2: Non-Isothermal TG and DTA curves of (a)


pure AP, (b) AP + 2% w/w micron-sized -MnO2 and
(c) AP + 2% w/w mesoporous -MnO2

One of the main arguments reported in literature


is that nano-catalysts, which are effective for
thermal sensitization of AP, when incorporated
in AP-based composite propellants, lead to
significantly higher burning rates [3-5].
However, as seen from Fig.2 and 3, and Table 1,
this is not necessarily true. Though mesoporous
MnO2 exhibits the best catalytic activity towards
AP decomposition reported in literature till date,

Figure 3: Representative images of combustion of


AP-HTPB composite propellant strands (a) without
catalyst, (b) with 2% w/w mesoporous MnO2 and (c)
with 2% w/w nano-structured Fe2O3,

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Conclusion
This paper briefs about our research program
and progress regarding the combustion studies
of AP-based composite solid rocket propellants
containing nano- burn rate catalysts. Various
experimental set-ups have been/ are being
designed, fabricated and validated. Ongoing
studies indicate that the effectiveness of a nanocatalyst in the thermal decomposition of AP
does not always translate into higher burning
rates of the composite propellant.
References
1. P. W. M. Jacobs and H. M. Whitehead,
Decomposition
and
combustion
of
ammonium perchlorate; Chemical Reviews,
1969, 69 (4), 551590.
2. David L. Reid, Antonio E. Russo, Rodolphe
V. Carro, Matthew A. Stephens, Alexander
R. LePage, Thomas C. Spalding, Eric L.
Petersen, and Sudipta Seal, Nanoscale
Additives Tailor Energetic Materials; Nano
Letters, 2007, 7 (7), 21572161.
3. Wei Li and Hua Cheng, CuCrO
nanocomposites:
Synthesis
and
characterization as catalysts for solid state
propellants; Solid State Sciences, 2007,
9(8), 750755.
4. Satyawati S. Joshi, , Prajakta R. Patil and V.
N. Krishnamurthy, Thermal Decomposition
of ammmonium perchlorate in the presence
of nanosized ferric oxide; Defence Science
Journal, 2008, 58(6), 721-727.
5. R. Arun Chandru, Snehangshu Patra, Charlie
Oommen, N. Munichandraiah and B. N.
Raghunandan, Exceptional activity of
mesoporous -MnO2 in the catalytic thermal
sensitization of ammonium perchlorate;
Journal of Materials Chemistry, 2012, 22,
6536-6538.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Electromagnetic field enhancement in sub-nm gaps


Debadrita Paria and Ambarish Ghosh

Abstract- We describe computational results on the


calculation of electromagnetic field enhancement at the
junction of plasmonic nanoparticles. In particular, we
assume a pair of Silver nanoparticles at variable
distances from each other and calculate the wavelength
and gap size dependence of the electromagnetic field
enhancement.
I.

INTRODUCTION

The large concentration of electromagnetic fields near


metal nanoparticles upon illumination of light is one of the
defining concepts of light matter interactions at the
nanoscale [1,2]. The strength of this so called near field
can be very large at the junction of two metal nanoparticles,
which has facilitated promising technologies, such as the
detection of single molecules [3,4] through a large
enhancement of the Raman scattering signal. The degree of
enhancement of the near field increases rapidly as the
particles are brought closer, although at separations below a
few Angstorms, quantum tunneling of plasmons can limit
the enhancement. The purpose of this paper is to calculate
the degree of enhancement as a function of gap distance
down to few Angstorms, and investigate the wavelength
dependence of the field enhancement.

the particle at the wavelength of illumination. The


contributions to the net electric field for particle 1 come
from the incident field ( ), as well as the electric field due
to the dipole ( ) of particle2 at the location of particle 1,
, thus implying a
where the dominant term of
strong distance dependence of the dipolar coupling. This
approximation breaks down for
< , beyond which
higher order multipolar contributions needs to be taken into
account, where numerical calculations can provide an
accurate picture. Also important is the direction of
propagation and state of polarization of the incident beam,
and their relation to the interparticle axis.

III. RESULTS AND DISCUSSIONS

II. PLASMONIC COUPLING


In electrostatics, the electric field between two oppositely
charged plates varies inversely as the distance between
them, which arises due to Coulomb interactions between
the charges residing on the two plates. Similarly, the
dependence of the EM field enhancement9 on the size of the
gap (d) originates in the electromagnetic interactions
between the localized plasmon modes of two neighboring
nanoparticles (radius a). In the simplest approximation,
each particle can be approximated as an electric dipole ,
whose strength is proportional to the net electric field
( = ) at its location, where is the polarizabiltiy of

Figure 1: Light incident along the axis of a nanodimer. See


text for details.
As an example, depicted schematically in Fig. 1, we have
considered linearly polarized monochromatic light incident
along the axis of the interparticle separation for two silver
nanospheres of radius a = 70 nm separated by a distance d.
The calculated value (using Comsol) of the squared
enhancement (| || |) of the electric field, shows
concentration of the electric field at the junction of the
particles, which increases manifold as the distance d is
reduced. The maximum value of the enhancement within

Debadrita Paria is a PhD student in the Centre for Nano Science and Engineering at the Indian Institute of Science,
Bangalore, 560012, INDIA.
debadrita.paria@gmail.com
Ambarish Ghosh is an Assistant Professor at the Centre for Nano Science and Engineering, and an associate faculty in the
Departments of Physics and Electrical Communication Engineering, Indian Institute of Science, Bangalore, 560012, INDIA.
ambarish@ece.iisc.ernet.in

Project Ref No.: STC/P-337 dtd 25.3.2014

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the junction, given by (| || |)


, depended strongly on
the illumination wavelength and the interparticle separation,
as can be seen in Fig. 2a. The smallest d considered in
these simulations corresponded to the thickness of an atom,
which resulted in maximum value of(| || |) 10 in
the wavelength regime 405 nm to 530 nm (approx),
implying a system of plasmonic dimers with sub-nm
separation can achieve the strongest EM field
enhancements.
The
distance
dependence
of
(| || |)
for three illumination wavelengths is shown
in Fig. 2b.

Interestingly, at small gaps (d< 0.68 nm) the dipolar


plasmonic modes, which are typically in the UV, were seen
to shift in the visible regime. This is interesting, as one of
our major aims in this project is to develop radiation
detectors in the NIR and IR region of the electromagnetic
spectrum.
IV. SUMMARY AND FUTURE DIRECTIONS
Our efforts in last few months have been to develop a
computational model to calculate the electromagnetic field
enhancement at the junction of a nanosized plasmonic
dimer. These calculations although trivial at large values of
d, tend to become time consuming and difficult when d
becomes less than a nm. As expected, over six orders of
intensity enhancement could be observed. It is important to
note that the present calculation does not allow for quantum
tunneling of the plasmons [5], which can become a limiting
mechanism below a dimer gap of 0.3 nm. Accordingly, the
enhancements obtained here could be the largest possible,
as reducing the gap further will only result in a reduced
field magnitude.
Going forward, we wish to try experimental validation of
these calculations. Of particular interest would be to
investigate if the plasmonic enhancement can be moved
further to NIR and IR regimes of the EM spectrum, such as
to couple the system with a photodetector material.

REFERENCES

Figure 2:Light of certain wavelength, linearly polarized


along the x-axis, incident along the interparticle axis (zaxis) of two silver nanospheres separated by a distance d. a,
Spectral dependence of the maximum value of the enhanced
field(| || |) in the dimer junction for various d (labeled
in nm). b, Dependence of the maximum enhancement
(| || |)
at the dimer junction on the size of the gap d
= 0.34 nm, for three illumination wavelengths. The
particular choices of the wavelengths (red 620 nm, green
530 nm, blue 470 nm) are arbitrary, covering the visible
range of the electromagnetic spectrum.

[1] Maier, S. A. Plasmonics: Fundamentals and


Applications: Fundamentals and Applications. (Springer,
2007).
[2] Novotny, L. & Hecht, B. Principles of nano-optics.
(Cambridge university press, 2012).
[3] Kneipp, K. et al. Single molecule detection using
surface-enhanced Raman scattering (SERS). Physical
review letters 78, 1667 (1997).
[4] Nie, S. & Emory, S. R. Probing single molecules and
single nanoparticles by surface-enhanced Raman scattering.
science 275, 1102-1106 (1997).
[5] Savage, K. J. et al. Revealing the quantum regime in
tunnelling plasmonics. Nature491, 574-577 (2012).

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Modelling primary atomization of liquid jets


Santosh Hemchandra

1.

Introduction

The objective of this project is to develop a modelling technique using a fully compressible
approach for modelling the atomization of liquid jets. The approach comprises of three main
elements 1. Level-set method solver to track the location of the gas-liquid interface
2. Compressible flow solvers for the liquid and gaseous phases
3. A Ghost-fluid method module that captures jump conditions arising from mass, momentum and energy balance across the gas-liquid interface.
During the period 2013-2014, we analyzed several options for reinitialization scheme for item
1 above. These efforts were partially successful at the time of the previous interim report
submitted in April, 2014 due to the presence of bugs in the reinitialization scheme. We have
since fixed these bugs and are currently working on phase 2. All of these solvers are being
implemented within the custom MultiSolv framework developed within our group to realize
complex multi-physics flow simulations.The activities over the past six months have been divided
into phases as follows
1. Debug and fix the CR2 [1] level-set reinitialization scheme (current status: done).
2. Incorporate the level-set solver within the MultiSolv framework - (current status: done).
3. Implement a coupling framework within the MultiSolv kernel in and demonstrate coupling
between flow and level-set solver in order to learn how this can be achieved - (current
status: done).
4. Convert existing 2D flow solver to 3D - (current status: done)
5. Parallelize the 3D solver, using MPI, to use structured multi block meshes and support
input from commercial grid generation software - (current status: done).
The rest of this report is organized as follows. Section 2 provides details of the solver coupling
framework implemented within the kernel and presents results from test simulations with a 2D
compressible flow solver and the level-set method solver. Section 3 provides details about the
status of the 3D compressible solver development effort and presents some initial results from
ongoing simulations. Finally, this report closes with an outlook on next steps for the third year.

Assistant Professor, IISc, Bangalore


E-mail: hsantosh@aero.iisc.ernet.in, STC project # ISTC/MAE/SH/319

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Figure 1: Schematic of level-set and flow solver overset grids

2.

Solver coupling framework

The solver coupling framework and the mechanism of communication between the flow and
level-set equation solvers is described in this section. The level-set solver advects gas-liquid
interface as per the velocity imposed by the flow field on either side. The objective of coupling
the level-set solver and flow solvers through an interface within the MultiSolv Kernel is to
ensure that the former can get the velocity information from flow solver and move the levelset/interface accordingly and the latter can get level-set field values from the former and apply
matching conditions via the Ghost Fluid Method (GFM).
The level-set solver uses uniformly spaced structured grids and uses the local level-set method
to solve the level-set equation in order to reduce computational cost. This allows for refinement of the the level-set grid in order to resolve small interface features without increasing
computational cost. The flow solvers on the other hand, use multi block structured grids with
non-uniform spacing that is necessary to correctly resolve flow features. Thus, coupling the two
solvers together requires mapping of the level-set solver grid on to flow solver grid and vice versa
so that level-set function values and flow velocities can be interpolated between the two grids as
needed. The level set grid is overlaid on the flow grid as shown in fig. 1. It is created such that
it encloses whole flow domain. The grid size chosen for the level-set grid is xLS = xF,min ,
where, xF,min is the smallest distance between any two given points on the flow grid and is
a parameter. Bilinear interpolation is used to interpolate velocities from neighboring flow grid
points to level-set grid points eg. see fig. 1 - the velocities at points marked a and b on the
level-set grid are determined from the flow grid points m-p using bilinear interpolation.
Figure 1 shows that the grid points on the two grids do not exactly overlap. Therefore
to interpolate the data (velocity) from flow solver, each level-set grid point needs to have
information about its neighboring flow grid points. This is achieved by mapping level-set grid
on the flow grid. Within the MultiSolv framework, each solver requests the other to map its
points onto the latters grid and return an index handle per point during computation setup.
Subsequent requests for function values at the the mapped points are obtained using these
handles to address points. Thus, neither solver needs to be aware of the others internal data
structures allowing for great flexibility in choosing the numerical method etc. for either solver.
We next show results from tracking the evolution of a closed material line in a two-dimensional
jet.

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(a)

(b)

Figure 2: (a) Schematic of flow configuration and boundary conditions (b) Initial level-set
location

2.1

Test flow problem

Figure 2a schematically shows a two dimensional planar jet flow that is chosen as the baseline
flow test case. Inflow forcing is applied such that the preferred varicose mode of the inflow
profile is excited in order to reduce the potential core breakdown length. The inflow velocity
profile is specified using the tanh function such that it varies smoothly from a value of 174.8
m/s along the jet centerline to a value of 88.0 m/s in the co-flow region (see fig. xx). The
slot width is chosen as 1.25 mm for this test case, yielding Re = 6795. The solution domain
is 50h long and is discretized with a uniform grid with x = 0.09h and y = 0.063h. Note,
this flow configuration was chosen in order to leverage a pre-existing computation available.
Both the shear layers are forced with and amplitude of 1% of the centerline velocity, in order to
excite the varicose mode. A time step of 0.001x is used and simulations are run for 0.5 flow
through times (approximately 2000 time steps). All boundary conditions are applied using the
Navier-Stokes characteristic boundary conditions (NSCBC) technique [2, 3].
Figure 2b shows the initial condition for the closed material curve as a red circle of diameter
1h located along the centerline at a distance of 15h from the jet inflow plane. This position corresponds to the start of the jet breakup location and would hence result in maximum distortion
of the material surface within the given simulation time. Figure 3a shows several snapshots of
the evolution of the the material curve at various times. The evolution of the curve is tracked
using the level-set solver which in turn, gets the velocity field from the flow solver. Note also
that the curve is deformed into very thin filaments over time. These filaments then break up
into smaller pockets as the curve evolves. This can be explained as follows. The thickness of
the filament reduces until such a point where it can no longer be locally resolved on the levelset mesh and hence breakup occurs. Physically, this would occur when the filament thickness
was of the order of molecular length scales - a length scale that cannot be resolved within the
framework of a continuum assumption based CFD solution. However, since the level-set mesh
can be refined in our method independently of the flow mesh, filament breakup can be caused to
occur arbitrarily close to the physical value without significant increase in computational cost.
This fact can be seen qualitatively in fig. 3 which shows the shape of the curve at t = 0.172
for various values of mesh refinement ratio, . Notice that finer mesh, i.e. progressively smaller
values of results in retention of longer unbroken filaments.
3

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Figure 3: Evolution of the material curve shown at various instants in time

Figure 4: Influence of level-set mesh refinement ratio, = xLS /xF low , on the material
line geometry (t = 0.172). The background field shows vorticity magnitude

This concludes the summary of the level-set - flow solver coupling framework implemented
within the overall framework of MultiSolv. We next summarize progress made on the development of a, 3D fully compressible, massively parallel, structured multi-block DNS/LES solver
since April 2014.

3.

Three dimensional flow solver

The 2D flow solver used for the above simulations has been extended to be able to compute
three dimensional flows. Together with the explicit filtering technique, this solver can in general
be used for LES of complex turbulent flows. The solver has also been parallelized using MPI
and has been implemented within the framework of MultiSolv. As such, the solver coupling
methodology described in the previous section extends to the present three dimensional case
as well. Our implementation solves the Navier-Stokes equations in strong conservation form in
generalized co-ordinates. As such, the present code can be used to compute flows in complex,
industrially relevant geometries as well. As such, an input interface for grids specified in the

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140
Speedup (1213)
Speedup(Linear)

Speedup [t(1)/t(k)]

120
100
80
60
40
20
0
0

20

40
60
80
100
Number of processes

(a)

120

140

(b)

Figure 5: (a) instantaneous slice plot of pressure (p-po ) showing evolution of gaussian
pressure pulse in a rectangular domain (b) a typical speedup plot up to 128 processors for
1213 grid points

CGNS format has been implemented in the solver. CGNS is a fairly widely used industry
standard format that is supported by many standard mesh generation packages including in
our case, ANSYS ICEM-CFD. Thus, the present 3D code has a significantly greater range of
problems, i.e. from academic geometries to industrially relevant geometries, to which it can be
potentially applied.
The two dimensional NSCBC procedure [2, 3] has been reformulated for NS equations in generalized co-ordinates. Currently, subsonic inlet, constant temperature no-slip wall and subsonic
non-reflecting outlet boundary conditions have been implemented as these will be necessary to
realize the spray simulations that are the final goal of this project. Currently, validation and
debugging of each of these boundary condition implementation is ongoing and is expected to be
finished by January 2014. We next present two test cases computed with this code and results
from scaling tests on our in-house compute cluster.

3.1

Spherical pressure pulse

This case computes the evolution of a spherical pressure pulse in a cube of dimension 0.1 m. The
domain is discretized using a uniform mesh with 121 121 121 points. No slip wall boundary
conditions are applied on all faces of the cube. The solution is initialized with a stationary flow
at a temperature of 300 K. The wall temperature is assumed to be the same at all times. The
initial pressure distribution is given by
(rro )2
p
(
)
= 1 + 0.0001 exp 2c2
po

(1)

where, po = 1.01325 105 and r is the radius vector referenced to the center of the cube.
Figure 5a shows a typical snapshot of the the solution at a time t = 3 105 s after the start of
the simulation. This test case was used to test scaling results. A result from preliminary scaling
tests with the inviscid version of the code, i.e. before transport terms were implemented, are
shown in fig. 5b. This shows a reasonable level of scaling upto 128 processors. We have not
been able to perform scaling tests with the current code at the moment as we are focusing on
debugging and implementing boundary conditions. We will perform scaling tests on the full
code during the next year.

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p
6
x 10

0.5

2.7
y/D

2.6
0

2.5
2.4

0.5
0

2.3
0.5

1.5

2.5

x/D

(a)

(b)

Figure 6: (a) schematic for the flow in a square duct showing boundary conditions and
inlet velocity profile. (b) pressure and velocity fields for the square duct case

3.2

Flow in a square duct

Figure 5a schematically shows the flow setup for a flow in a square duct. The profile of the
x-component of the velocity at the inflow is specified a top hat profile going from a centerline
velocity, UCL , of 4 m/s to 0 m/s using smooth profiles generated using hyperbolic tangent
functions. Likewize, the velocity profile at the inlet is extended into the domain along the
streamwise direction . The other velocity components are set to zero. The temperature at the
inlet is specified as 300K. The reference pressure at the outlet for the NSCBC procedure is
specified as 1.01325 105 Nm2 . Figure 6b shows the solution at time t = .04 s corresponding
to 0.32 flow through times (L/UCL ). The field shows the instantaneous pressure distribution.
Also shown are typical velocity vectors at selected locations close to the inlet. Note this solution
had not reached steady state as of the time of writing this report.

4.

Conclusion and next steps

The simple flows described in the previous section are being used at this time to debug and
validate the 3D solver. We will next generalize the thermodynamics model in the solver to be
able to use arbitrary equations of state, thereby, allowing the same code to be used for the
liquid phase as well. Finally, we envisage coupling the this solver with the level-set solver and
performing first multiphase flow simulations begining April 2015.

References
[1] D. Hartmann, M. Meinke, and W. Schroder. Differential equation based constrained reinitialization for level set methods. Journal of Computational Physics, 227(14):68216845,
2008.
[2] T. J. Poinsot and S. K. Lele. Boundary conditions for direct simulations of compressible
viscous flows. Journal of computational physics, 101(1):104129, 1992.
[3] K. W. Thompson. Time-dependent boundary conditions for hyperbolic systems, ii. Journal
of Computational Physics, 89(2):439461, 1990.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Development of an optimization based image


processing software system for Indian forest resource
assessment using Radar Imaging Satellite (RISAT-1)
Images
S N Omkar and G. Narayana Naik
Principal Investigator, Dept of Aerospace Engineering, Indian Institute of Science, Bangalore
Ashoka Vanjare andSourabh Rao A
Project Assistant, Dept of Aerospace Engineering, Indian Institute of Science, Bangalore
P G Diwakar
Co- Investigator, NRSC, Hyderabad, India
Prashant BK
Project Intern, Dept of Aerospace Engineering, Indian Institute of Science, Bangalore

Abstract- This paper examines the results of optimization based


Image processing software system developed at Research and
Development Center, Computational Intelligence Lab, Indian
Institute of Science, Bangalore. Currently we are developing data
processing system for processing forest land cover classification
problem by using RISAT-1 satellite images. In this paper, we are
exploring use of optimization techniques for improving the
results and advantage in image analysis.Developed imaging
system provides image enhancements, speckle reduction, and
image classification; substantially increase the functionality of
the software along with application of remote sensing data in
different fields. This leads to optimal usage of remote sensing
data.

I. INTRODUCTION
Basic essential of life is land, water and air. Land cover refers
to the physical and biological cover at the surface of the earth,
including water, vegetation, bare ground, man-made
structures, etc. Land cover information [1] acts as important
piece of information for assessment of land utilization and
resources optimally. Due to its advancement in digital
technology, robustness and cost-effectiveness, remote sensing
has been increasingly used to extract land cover information
through either manual interpretation or automated
classification. Further researchers are using optimization
techniques [2] in order to improve usage of available resource.
Pattern recognition techniques [3]are commonly conceived to
have the capability of improving automated classification
accuracy due to their distributed structure and strong
capability of handling complex data. Many researchers are
using neural networks techniques for land cover classification
and comparing with the traditional statistical methods. This
paper is divided into six sections, radar dataset, study area,
data processing methods, results and conclusion.

II. RADAR IMAGE DATASET

In this section, different space Agencies and their SAR


imaging products are given.
1) Indian Space Research Organization (ISRO) and National
Remote Sensing Centre (NRSC) Example:RISAT-1 and 2
2)National Aeronautics and Space Administration (NASA)
Example: radar Sensor SIR-A, SIR-B and SIR-C.
3) Japan Aerospace Exploration Agency (JAXA) Example:
Advanced Land Observing Satellite ALOS 1 and 2
4) European Space Agency (ESA) Example: ENVISAT
ASAR
Different space agencies have launched different earth
observation missions in order to collect earth land surface
features. Initially data is acquired, calibration and validation,
which involve sensor characterizations, image quality
measurements, and accuracy improvement. Processed data is
dissimilated to public use as standard products like L0, L1 and
L2 products for remote sensing applications. ISRO recently
launched a satellite mission with SAR sensor as payload called
RISAT-1 satellite. RISAT-1 radar satellite images have
information on land surface features. RISAT-1 dataset works
in ScanSAR, strip and spot modes to provide images with
coarse, fine and high spatial resolutions respectively. This is
very useful in different remote sensing applications and one
such application is forest resource assessment.
III. STUDY AREA

In this section, study is discussed. We have chosen Bangalore


region for studying urban vegetation features and Mandya and
Mysore region for studying forest vegetation. Forest region
consists of agricultural region, water region and hilly regions.
We have initially used unsupervised classified techniques for
forest region classification before collecting ground truth data.

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IV. DATA PROCESSING METHODS

In this section, we are discussing different data processing


methods. They are: 1) Preprocessing (Geometric correction
and Radiometric calibration), 2) Speckle reduction and3)
Image Classification.
1) Preprocessing: (Geometric correction and
Radiometric calibration)
Initially Polarimetric SAR satellite image are pre-processed.
Radio metrically [4] calibrate Calculate Sigma nought and
beta nought of the given image and after this step geometric
correction is performed. Antenna pattern correction is done to
calculate the variation and remove the variations caused in
transmission and receiving of signals.

2) Speckle reduction techniques:


As polarimetric SAR image is affected by noise [4] so filtering
techniques are applied in order to remove the noise.
a) Lee Filter: Lee filter is used to smoothen the image and
remove noise from data. Lee filtering is a standard deviation
based filter that filters data based on statistics computed. Lee
filters preserve image edges, sharpness and spatial information
compared to low-pass smoothing filter. The image pixel value
is replaced by a value calculated using the surrounding
connected pixels.
b) Enhanced Lee: Enhanced Lee filter is used to reduce
speckle in radar imagery which preserving texture and edge
information. The Enhanced Lee filter is an advanced version
of the Lee filter. Enhanced Lee filter uses local statisticscoefficient of variation for window information. Neighboring
image pixel value is put into one of three classes namely a)
Homogeneous: the neighboring image pixel value is replaced
by the average of the filter window, b) Heterogeneous: The
neighboring image pixel value is replaced by a weighted
average and c) Point target: The neighboring image pixel
value is not changed.
c) Frost filter: Frost filter is used to reduce speckle while
preserving edges and retaining texture information in radar
images. It is an exponentially damped circularly symmetric
filter that uses local statistics. The pixel being filtered is
replaced with a value calculated based on the distance from
the filter center, the damping factor, and the local variance.
d) Gamma filter:Gamma filter is used to reduce speckle
while preserving edges in radar images. Gamma filter assumes
that the data is gamma distributed and filtered image pixels are
replaced with a neighbor image pixel value calculated based
on the local statistics.

Fig: 1 a) RISAT-1 Polarimetric SAR (Combination hh-hv-hh)


is overlaid on the Landsat 8 multispectral optical satellite
image and b) RISAT-1 image is compared with Landsat 8
image for urban vegetation classification and c) MysoreForest
region is considered as region of interest for forest region
classification.
Given polarimetric SAR satellite image (HH and HV) is
geometrically registered [4-6] to optical satellite image in
order to geocoding the data. The geocoded image is shown in
figure -1.

e) Local Sigma filter:Local sigma filter is used to preserve


fine detail in low, medium and fine resolution image and low
contrast areas.It is to reduce speckle significantly by using the
local standard deviation computed for the filter box to
determine valid image pixels within the filter window.
f) Bit Error filter:Bit error filter is used to remove bit-error
noise, which is usually the result of speckles in the data caused
by isolated pixels that have extreme values unrelated to the
image scene. Bit-error removal method uses an adaptive based
technique to replace speckle or spike pixels with the average
of neighboring pixels. Local statistics like- mean and standard
deviation are computed within the filter box and it is used to
set a threshold for filtering the desired image quality.
g) Gray Level Co-occurrence Matrix filter: In statistical
texture analysis, texture features are computed from the

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statistical distribution of observed combinations of intensities


at specified positions relative to each other in the image.
According to the number of intensity points (pixels) in each
combination, statistics are classified into first-order, secondorder and higher-order statistics. Gray Level Co-occurrence
Matrix (GLCM) method [4-7] is a way of extracting second
order statistical texture features. GLCM is a matrix where the
number of rows and columns is equal to the number of gray
levels, in the image.
Suppose an image to be analyzed is rectangular and has Nx
resolution cells in the horizontal direction and Ny resolution
cells in the vertical direction.Let the gray tone appearing in
each resolution cellsis Ng quantized levels.
Let Lx = {1, 2 Nx} be the horizontal spatial domain,
Ly = {1, 2... Ny} be the vertical spatial domain and
G = {1, 2...Ng} be the set of Ng quantized gray tones.
The set LyxLx is the set of resolution cells of the image
ordered by their row- column designations.
The image I can be represented as a function which assigns
some gray tone in G to each resolution cell or pair of
coordinates in LyXLx, such that I: LyX Lx --> G.
GLCM is a matrix of relative frequencies Pij with which two
neighboring resolution cells separated by distance d occur on
the image, one with gray tone i and the other with gray tone j.
This matrix is a function of the angular relationship between
the neighboring resolution cells as well as a function of the
distance between them.
Texture measurement requires the choice of window size,
quantization levels, displacement value, and orientation
factors for each texture measure.
In this work, each texture measure/feature have been
calculated in all 4 orientation angles (0, 45, 90, 135) and
feature measures of the matrices of all the four orientations are
then averaged, to get a directionally invariant matrix.

3) Image Classification methods:


In this section, we are discussing different image classification
methods [3-4] used in this paper.
Unsupervised method:
In this section, two unsupervised classification methods are
discussed. K-means and ISO clustering method are applied to
SAR image in order to identify the vegetation regions.
a)K-means clustering: K-Means is an unsupervised
classification technique which calculates initial class means in
evenly distributed in the data space then iteratively clusters the
pixels into the nearest class using a minimum distance
technique.Each iteration recalculates class means and
reclassifies pixels with respect to the new means. All pixels
are classified to the nearest class. By setting a standard
deviation value or distance threshold value unclassified image
pixels are grouped till they meet threshold criteria. This
process is continued till thegive number of pixels in each class
are assigned till selected pixel change threshold value or the
maximum number of iterations is reached.K means parameters

Mean 1752.132369, Standard deviation 1360.323747, Classes8 and threshold-5 are used for all the filtered images.
b)ISO-Data Clustering: ISO-DATA is an unsupervised data
clustering technique which calculates class means considering
as evenly distributed in the data space then iteratively clusters
the remaining pixels using minimum distance techniques.In
each iteration,mean is recalculated and the same image
reclassified with respect to the new computed means. This
process is repeated until the number of pixels in each class
changes till selected threshold value is reached else the
maximum number of iterations is attained.
Supervised classification method:
In this section, the three ArtificialNeural Network methods
like Multi-Layer Perceptron (NN-MLP),Radial Basis Function
- Neural Network(NN-RBF) andCircular Complex valued
Extreme Learning Machine(CC-ELM) are discussed. These
methods are applied for classification of Multispectral and
Polarimetric SAR (Synthetic Aperture Radar) data.
Artificial neural network methods
c) Neural Networks-Multi Layer Perceptron: Neural
Network is a layered feed-forward neural network
classification technique. NN-MLP technique uses standard
back propagation as supervised learning technique. It can
select the number of hidden layers.It uses a logistic or
hyperbolic activation function for classification process.
NNMLP learns by adjusting the weights in the node to
minimize the difference between the output node activation
and the output. InNNMLP method, error is back propagated
through the network and weight adjustment is made using a
recursive process. NNMLP classification technique is used to
perform non-linear classification and this method is used as
optimized for pattern classification.
d) Neural networks-Radial Basis Function:Neural Network
- radial basis function (NN-RBF) also uses a feed forward
network. It is structurally similar to MLP-NN, but the
activation function in the hidden layer nodes is called radial
basis activation function and it also uses back propagation as
supervised technique. The output of the activation function
depends on the location of the center of the function and the
spread of the function. The output of a radial basis function
can be defined as:
(x) = exp(-|| x c ||2 / 2*2)
Eq 1
Where, c is the center of the RBF unit,x is the input and is
the spread of the RBF unit.
The inputs are first normalized using suitable normalization.
This activation function in the hidden layer produces a nonzero response when the input falls within kernel function.
Each hidden unit has its own receptive fields in input space.
The weights connecting the inputs to the hidden layer decide
the spread of the activation function and the weights

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connecting the hidden layer to the outputs is used as a scalar


multiplier to the hidden layer outputs.
The network output is the sum of weighted hidden layer
outputs. The training of the network involves the adjustment
of the two sets of weights and updating of centers of the
hidden nodes. The mean squared error is determined between
the network output and the target output values. The centers
and weights are initialized randomly. The weights and centers
are optimized using Gradient Descent Back Propagation
algorithm, by minimizing the instantaneous mean squared
error. The training algorithm aims at minimizing the error and
the optimization of the weights and the center location. The
training is carried out till the target performance is reached.
The network is then tested for performance and generalization
using the testing dataset.
e) Circular Complex Extreme Learning Machine (CCELM): Circular Complex-valued Extreme Learning Machine
(CC-ELM) [23] is designed for handling real-valued
classification problems. CC-ELM is a single hidden layer
network with non-linear input and hidden layers and a linear
output layer. A circular transformation with a translational or
rotational bias term that performs a one-to-one transformation
of real-valued features to the complex plane is used as an
activation function for the input neurons. The neurons in the
hidden layer employ a fully complex-valued Gaussian based
activation function. The input parameters of CC-ELM are
chosen randomly and the output weights are computed
analytically.
The input and output configurations of CC-ELM are similar to
that of MLP and RBF-NN. In CC-ELM the input layer
activation function is Circular Transformation, which maps
the real valued data to the complex domain. The
transformation function is give in equation 2.

zt = sin ( axt + ibxt + )

Eq 2

Where:xt is the input vector for the tth sample and


observation,such that each of xti is normalized in [0,1];
0 < a, b 1, and 0 << 2.
All the three NN-MLP, NN-RBF and NN-ELM methods are
used for urban vegetation because of similar techniques for
SAR image classification.

Training Set Size


300 Pixels per class
Testing Set Size
750 Pixels per class
Table 1: Comparison of different classification techniques
In table-1, three different image pixels-urban, vegetation and
water is given along with training and testing set size.

Fig 2: a) original Landsat image, b) MLP-NN classified SAR


image, c) NN-RBF classified SAR image and d) CC-ELM
classified SAR image.
Figure 2 gives details of classified images by using three
different methods-NN-MLP, NN-RBF and CC-ELM.Results
of classified image can be compared with original image.
Properties
Hidden
neurons

NN-MLP
10-30 (best 28)

NN-RBF
100 max
(accuracy
goal 0.007)
98.85%

CC-ELM
50

Train
97.30%
98.45%
accuracy
Testing
97.25%
98.63%
98.40%
accuracy
Table 2: Comparison of different classification techniques
From Table-2 we can see the classification accuracy. These
three algorithms are optimized so we are getting good results.
By quantitive analysis and value, we can understand by using
optimization techniques we can improve classification results.
For forest vegetation classification we have used RISAT-1
(HH and HV) images.
For forest region classification application we applied six
filters lee, enhanced lee, frost, gamma, local sigma, bit error.

V. RESULTS

In this section, two applications urban vegetation classification


and forest vegetation classification is discussed.For urban
vegetation classification, we have used Landsat 8
multispectral image and RISAT-1 SAR image. Initially the
SAR image are preprocessed using frost and GLCM filters and
enhanced images are classified using three different neural
networks-NNMLP, NNRBF and CC-ELM methods. Here we
have classified RISAT image and overlaid on multispectral
image.
Class
Number of Pixels
Urban
12405
Vegetation
3942
Water
5957

Figure 3: Results of lee filtered SAR classified image

Figure 4: Results of enhanced lee filtered SAR classified


image

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improves.Initially, we used filtering techniques for


preprocessing and enhanced images were classified. For urban
vegetation region as we use optimized neural network
techniques, results are good and in case of NN-RBF it has
classified the given image very well in comparisons to other
techniques. To classify forest regions, we initially used
unsupervised method to determine different unknown classes.
K-means clustering method performs well in comparisons
with ISO Data method. In urban vegetation applications, we
observed that optimization techniques are very useful in order
to improve classification results while in forest region
classification application K-means gives initial class
information.
Figure 5: Results of frost filtered SAR classified image

FUTURE WORKS

Develop different optimization techniques and compare for


different forest land classification problem and these
techniques are designed into asatellite image processing
application. Further these techniques have to be improved by
keeping time complexity.
ACKNOWLEDGMENT
Figure 6: Results of gamma filtered SAR classified image

Figure 7: Results of local sigma filtered SAR classified image

The authors thank the reviewers for their critical comments


which helped to improve the quality of the paper significantly.
This work is supported by IISc-STC cell and carried out by
research grant (Project no ISTC0340). Thanks to Aditi
Kanjolia, Student, Indian Institute of Technology, Indore,
Email: ee1200202@iiti.ac.in and Sandesh C, Student, Indian
Institute
of
Technology,
Kharagpur,
Email:
sandeshc@cse.iitkgp.ernet.in. We are grateful to Forest
department of India, Forest survey of India, survey of India,
NASA, JAXA and ESA for providing information and
support.
REFERENCES

Figure 8: Results of Bit error filtered SAR classified image


Figure 3-8 gives the different filtering techniques applied and
image quality is enhanced. Six filtered SAR images are
classified using K Means and ISO Data clustering techniques
into 8 different classes. As we dont have ground truth
data,hence we have usedK-means unsupervisedtechnique for
forest region classification.Enhanced lee and frost filtering
technique has improved image quality in comparison with
other filtering techniques. By visual inspection, we have to
determine the classified quality with the given image.
VI. CONCLUSION

Speckle reduction technique plays very important role in radar


image processing due to which pattern classification results

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[31] C.S. Arvind, Ashoka Vanjare, S.N. Omkar, J. Senthilnath, V. Mani and
P.G. Diwakar, Multi-temporal Satellite Image Analysis Using
Unsupervised Techniques, Advances in Computing and Information

Technology (Eds. Natarajan Meghanathan, DhinaharanNagamalai,


NabenduChaki), Advances in Intelligent Systems and Computing, 2013,
vol. 177, pp. 757-765, Springer Verlag, Berlin, Germany, ISBN 978-3642-31551-0.
[32] J. Senthilnath, S. N. Omkar, V. Mani, Ashoka Vanjare, P. G.
Diwakar"Multi-Temporal Satellite Image Analysis Using Gene
Expression Programming"Proceedings of the Second International
Conference on Soft Computing for Problem Solving (SocProS 2012),
December 28-30, 2012Advances in Intelligent Systems and Computing
Volume 236, 2014, pp 1039-1045.
[33] M. E. Shokr. Texture measures for sea-ice classification from radar
images. In Proceedings of the International Geoscience and Remote
Sensing Symposium (IGARSS), pages 763-768, Vancouver, Canada,
1989
[34] RISAT-1 Handbook, Indian Space Research Organization, India
[35]ALOS Data Users Handbook, JAXA, Japan
[36] Sentinel-1 User Handbook, European space agency
[37] SAR user marine manual
[38] CEO Users Guide book
[39]J.N Bruning, Radar Imagery: Radarsat-1
[40] PolSAR Tutorials for researchers, European space agency

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Numerical Simulations of Darcy-Brinkman-Forccheimer Equations


for Flow in Porous Media
Karthick M.and Gaurav Tomar

Abstract Implementation of Darcy-BrinkmanForccheimer equations in the open source code


Gerris. The adaptive mesh refinement and
variable time stepping in Gerris can be employed to perform high resolution simulations
of two phase flow in porous media.

Introduction

Multiphase flow in porous media has gained importance in the last decades due to demand for increased
efficiency in extracting oil and other fuel sources such
as shale gas. Porous wicks are employed in the evaporators of modern heat pipes such as capillary pumped
loop and loop heat pipes. Liquid refrigerant floods
the porous wick due to capillary suction and evaporates due to the heat flux from a heat load. The
vapour so formed is pushed out of the vents into the
vapour line and condenses away from the heat generation point. This provides great flexibility in designing heat exchangers for electronic cooling in satellites
where equipment located in the core of the satellite
need to dissipate heat in the outer space through radiation. Since the experimental investigation are limited by the lack of access to the flow regions in such
systems, numerical simulations can provide insights
into the complex phase change heat transfer and fluid
flow physics.

The flow through a porous medium is inherently


multiscale involving small length scale local resistance to flow due to tortuous paths and flow over
multiple order larger domains. Therefore mathematical models for flow in a porous media are derived
by generating volume averaged representations of the
flow at smaller micro length scales [1, 2, 3]. Flow in
porous media is generally governed by Darcys law
where the velocity, u, is directly proportional to the
pressure gradient:
u=

K
(p g)

(1)

The permeability, K, is a function of the porous


structure essentially pore diameter, porosity and tortuosity. However, the above equation is valid only for
moderate flow rates and at higher flow rates convective terms become important and should be included.
In the present study, we develop algorithms for
solving Darcy-Brinkman-Forccheimer equations for
flow in porous channels. An operator split algorithm has been employed in the open source code
Gerris which allows use of adaptive mesh refinement
and time stepping. We validate the above numerical implementation using an asymptotic Darcy flow
in a channel and Poisseuille flow through a high permeability channel. The developed algorithm can be
readily extended to simulate three dimensional flows
with complex geometries.

Project:

ISTC/0327
Assistant in the Department of Mechanical Engineering, IISc Bangalore
Assistant Professor in the Department of Mechanical Engineerin at Indian Institute of Science Bangalore - 560012.
Email: gtom@mecheng.iisc.ernet.in
Project

II

Governing Equations

The dimensionless form of the governing equations for


a non-homogeneous porous medium are given below.

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Figure 1: Linear variation in Darcy flow velocity with Figure 2: Parabolic velocity profile for permeabilpermeability. The theoretical stream wise velocity is ity K = 0.004 and = 0.05 in a channel with
no-slip boundary conditions at the top and bottom
U t and the numerical results are denoted by U n.
walls. The corresponding pressure decreases across
the channel linearly.
Continuity equation is given by:
u=0
The xdirection momentum equation is given

1
1
1
1 u
+
(u

)
u
=
(p)
 t
2




CF

+ 2 u u |u| u

K
k

(2) we solve for u/ instead of u. This scaling with porosity, results in modified momentum equations that are
by:
identical to Navier-Stokes, thus allowing us to employ
the standard Godunov schemes for advection terms
and Crank -Nicolson algorithm for viscous Brinkman
terms. The Darcy terms are modelled using an oper(3) ator split that results in:

u
= u
t
K

(5)
and the ydirection momentum equation is given by,

which essentially results in point updates for individ1 v
1
1
1
+
(u

)
v
=
(p)
2
ual grid cells. A similar scheme has been used for
 t




Forccheimer terms.

CF
+ 2 v v |u| v
(4)

k
k
The second term in the above equations are due to
Brinkman correction to porous media flow to include
the effect of viscous forces, third term is the linear
drag due to solid matrix resistance to the flow, and
the last term is the Forccheimer correction to include
the non-linear drag when inertial forces become important.

IV

Results and Discussions

We validate the above discussed operator split algorithm by solving the Darcy velocity by choosing
CF = 0 and not solving for the advection and the
Brinkman terms. Figure 1 shows the linear variation in the velocity for a specified pressure with permeability. The theoretical and numerical curves superimpose thus validating the implementation of the
Darcy flow. Figure 2 shows the parabolic profile with
III Numerical Formulation
no slip boundary conditions imposed at the top and
An operator split algorithm has been employed for bottom walls. The initial uniform velocity profile dethe implicit implementation of the Darcy and For- velops into the theoretical fully developed parabolic
cchiemer terms [4]. For constant permittivity flows, profile.

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Conclusions

The basic test cases validate the implementation


of the Darcy-Brinkman-Forcchiemer equations. The
present code needs to be validated against stricter
test cases such as natural convection in a porous media [5]. Subsequently, a two phase flow would be implemented by modelling the saturation equation as
an advection-diffusion equation [6, 7]. Further, heat
transfer and phase change models would enable us
to simulate evaporators of capillary pumped loops to
understand the conditions under which depriming of
the wick may occur.

References
[1] Bastian P., Numerical computation of multiphase
flows in porous media. Habilitation thesis, 1999.
[2] Bear J., Dynamics of Fluids in Porous Media.
Dover Publications, 1972.
[3] Bear A. and D. Nield, Convection in Porous Media. Springer, 2006.
[4] Versteeg H.K. and Malasekera W., An Introduction to Computational Fluid Dynamics. Longman
Scientific & Technical, 1995.
[5] Nithiarasu P. and Seetharamu K.N. and Sundarajan T. Natural convective heat transfer in a fluid
saturated variable porosity medium Int. J. Heat
Mass Transfer, 40, 1997.
[6] Chavent G and J. Jaffre., Mathematical Models and Finite Elements for Reservoir Simulations.
North Holland, 1978.
[7] Tomar G., Numerical Simulations of Two Phase
Flow in a Porous Medium using Volume of Fluid
Method STC Symposium, 2011.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Double diffusive convection in the Earths core


Venkatesh Gopinath and Binod Sreenivasan
AbstractThe present-day Earths dynamo is powered by the
release of light elements due to inner core freezing. Compositional
buoyancy dominates thermal buoyancy in the Earths core, but
before inner core nucleation, the geodynamo may have been
driven by purely thermal convection. A study is in progress to
understand the combined effects of thermal and compositional
convection in a rapidly rotating spherical system permeated by
a magnetic field. The onset of convection will be investigated as
an eigenvalue problem so that parameter regimes inaccessible
to direct numerical simulations can be reached. We shall then
investigate the full nonlinear problem with Earth-like boundary
conditions for heat and composition. This study constitutes an
important step in building Earth-like dynamo models.

I.

I NTRODUCTION

Evidence for the existence of a geomagnetic field goes back


to at least 3.5 Gyr. Estimates of the age of the inner core are
on the order of 1 Gyr. The geodynamo has therefore operated
in its early stages on purely thermal convection, and later on a
mixture of thermal and compositional convection. Recent large
estimates of the thermal conductivity of the Earths core have
reinforced the belief that present-day Earths core is largely
compositionally driven.
Double-diffusive phenomena have been studied in various contexts. However, in the context of the Earths core,
numerical studies of the dynamo process have used equal
thermal and compositional diffusivities. In this so-called codensity formulation [1], only one scalar transport equation
is solved for. A few recent studies [2], [3] deal with convective instabilities in thermal convection within a rapidly
rotating spherical shell. Where double diffusion is present, the
buoyancy profiles for heat and composition convection used
in these studies are not Earth-like. Moreover, no magnetic
field effects have been considered. It is accepted that the
Earths outer core convects more strongly at the bottom than
at the top. Whereas early studies have proposed that the top
10 20% of the core may be thermally stratified, recent
large estimates of thermal conductivity have pushed the stable
stratification to about 40%. In simple terms, the ratio of thermal
to compositional diffusivities in the core may vary significantly
across different regions of the Earths core. Although direct
numerical simulations of double diffusive convection applied
to planet Mercury are available [4], Earth-like regimes have not
been investigated. Three-dimensional dynamo simulations with
different thermal and compositional diffusivities and shown
that finger-like narrow plumes penetrate into the thermally
stable layer, causing an increase in magnetic field strength in
the stable layer [5] compared to dynamo models that used
Venkatesh Gopinath is a Senior Research Fellow at Centre of Earth
Sciences, IISc Bangalore, India. venkatesh.gopinath@ceas.iisc.ernet.in
Dr. Binod Sreenivasan is an Associate Professor at Centre for Earth
Sciences, IISc, Bangalore, India. bsreeni@ceas.iisc.ernet.in
Project number: ISTC/EES/BS/331

the codensity formulation. These studies provide the impetus


for a systematic investigation of dynamo action with doublediffusive convection.
Linear stability analysis offer significant advantages over
Direct Numerical Simulation (DNS) in Earth-like magnetohydrodynamic (MHD) systems. One can obtain meaningful
results at very low Ekman number E (ratio of viscous to
Coriolis forces, 1015 for the Earths core), which is
presently very difficult to obtain in fully non-linear simulations
because of computing constraints. In this study we perform a
linear stability analysis of combined thermal and compositional
convection in an applied magnetic field to obtain the critical
parameters at onset and the structure of convection.
II.

G OVERNING EQUATIONS

The governing equations for the velocity U , the magnetic


field B, the temperature T and the concentration C are solved
in the Boussinesq approximation. These equations are made
dimensionless [5] and written as follows:


U
E
+ U U + 2
z u + = E2 U
t
1
r
r
( B) B (1)
+RaT P rT T + RaC P rC C +
ro
ro
Pm
B
1
= (U B) +
2 B (2)
t
Pm
1
T
+ (U )T =
2 T (3)
t
P rT
1
C
+ (U )C =
2 C (4)
t
P rC
U = 0 (5)
B = 0, (6)
where E is the Ekman number, RaT is the thermal Rayleigh
number, RaC is the compositional Rayleigh number, P rT is
the thermal Prandtl number, P rC is the compositional Prandtl
number and P m is the magnetic Prandtl number. These are
our dimensionless control parameters. In order to study the
growth of instability in the system, the initial state of the
system is perturbed, and the perturbation variables u, b, ,
T 0 and C 0 are solved for at onset of convection. The velocity
and magnetic fields can be expressed as a sum of toroidal and
poloidal vectors:
u = r + r
b = r + r

(7)
(8)

and with the application of the operators () and ( )


to the NavierStokes equation and () to the induction
equation and taking r-components of the equations, the linearized equations governing the perturbations are obtained.

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The resulting perturbations quantities are expanded in normal


modes:

[2]

X(r, , , t) = X(r)Plm (cos ) exp(im + it),

(9)

[3]

where X = (, , , , T 0 , C 0 ) and Plm (cos ) is the associated Legendre function of degree l and order m.

[4]

III.

[5]

M ETHOD OF S OLUTION

In our eigenvalue problem, the eigenvalue is the frequency


. With temporal derivatives, onset of stationary convection
arises for Re() = 0 and oscillatory convection arises for
Re() > 0. For a range of given Rayleigh numbers Ra, a bisection algorithm is employed to find the eigenvalue . The Ra
corresponding to the eigenvalue obtained is the critical thermal
Rayleigh number RacT keeping the compositional Rayleigh
number fixed (or vice versa). The pseudospectral collocation
method is being employed in the radial (r) direction. The
resulting generalized complex eigenvalue problem is given by
AX = BX

[6]

Net, M., Garcia, F., Sanchez, J., On the onset of low-Prandtl-number


convection in rotating spherical shells: no-slip boundary conditions, J.
Fluid. Mech. 601, 317-337 (2008).
Net, M., Garcia, F., Sanchez, J., Numerical study of the onset of
thermosolutal convection, Phys. Fluids. 24, 064101 (2012).
Manglik, A., Wicht, J., Christensen, U.R., A dynamo model with double
diffusive convection for Mercurys core, Earth Planet. Sci. Lett. 289,
619628 (2010).
Christensen, U.R., Wicht, J., Models of magnetic field generation in
partly stable planetary cores: applications to Mercury and Saturn, Icarus
196, 1634 (2008).
Alboussiere, T., Deugen, R., Melzani, M., Melting-induced stratification
above the Earths inner core due to convective translation Nature 466,
744-747 (2010).

(10)

where = and X = (, , , , T 0 , C 0 ).
IV.

W ORK IN PROGRESS

The eigensolver is presently being benchmarked against


known thermal convection results. A systematic study will be
undertaken at low Ekman numbers where all dimensionless
control parameters are kept constant except for the ratio of
thermal to compositional diffusivities. The effect of this ratio
on the structure of the flow at onset is not well understood.
The role of a spatially varying azimuthal magnetic field with
equatorial antisymmetry (that mimics an axial dipole) will also
be examined. Finally, the onset will be studied at small radius
ratios that represent early-Earth regimes.
Apart from the linear stability calculations, a threedimensional nonlinear simulation study is also in progress, for
which a dynamo code is already available. Even as the linear
study gives insights into the low Ekman number regimes which
are otherwise difficult to simulate, the problem is not stepped
forward in time and the back reaction of the magnetic field
on the flow (via the magnetic Lorentz force) is not treated
adequately. Furthermore, the magnetic field is an applied one
rather than a self-generated one, which makes DNS more
realistic than linear onset analyses. The Lewis number (ratio
of thermal to concentration diffusivity) used in previous DNS
[4] was 10, which is much lower than the value expected in
planetary cores. In our study, we use Lewis numbers 1001000, and thermal buoyancy profiles that mimic stratification
in the upper regions of the core. As the dynamics of the inner
core is thought to affect outer core mixing [6], determining
the thermal and solutal conditions at the inner core boundary
poses an additional challenge in our study. It is hoped that our
analysis would eventually provide valuable data on the past
and present-day evolution of the Earths magnetic field.
R EFERENCES
[1]

Braginsky, S.I., Roberts, P.H., Equations governing convection in Earths


core and the geodynamo, Geophys. Astrophys. Fluid Dyn. 79, 197
(1995).

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Utilizing Ionic Liquid and Mixed Solvent Electrolytes to Synthesize Polymer


Electrolytes for Lithium-based Batteries
Sudeshna Sen,1 Sneha Malunavar,2 C. Gouri3 and Aninda J. Bhattacharyya4
Abstract: We have developed a polymer
electrolyte
prepared
from
room
temperature ionic liquid electrolytes. The
polymer electrolyte possesses ambient
temperature ionic conductivity 10-3 -1cm1
, mechanical strength with elastic modulus
1 MPa and electrochemical window 5 V.
Electrolyte films of (20-30)m thickness
were assembled in laboratory cells with
various nanostructured cathode and anode
materials for application in lithium-ion and
lithium-air batteries.
I INTRODUCTION
Over the last few decades, polymer
electrolytes have been demonstrated as an
important alternative to molecular liquid
electrolyte. Polymer electrolytes exhibit
compliable mechanical property compared to
crystalline compounds and may also exhibit
high ambient temperature ionic conductivity.
All these combined together make polymer
electrolytes very promising for prospective
electrochemical
devices.
In
polymer
electrolyte, the polymer plays the role of a
solid solvent. Polymers with different
chemical compositions, architectures are used
to completely or partially dissolve salts
containing ions such as Li+ /Na+ / H+ salts.
However, optimization and theoretical
comprehension of material's ion transport
mechanism is a non trivial issue. This is
primarily related to the extensive spatial and
temporal heterogeneity of the polymer host
which significantly influences ion transport
and in general the electrolytes mechanical and
electrochemical properties. The focus of the
present work is to synthesize cross-linked

polymer electrolytes from room temperature


ionic liquids (Scheme 1). The motivation here
is to employ them in lithium-ion batteries as an
electrolyte and separator. We also wish to
theoretically investigate the extent of influence
of the host complexities on the ion transport in
cross-linked polymer electrolytes. This will be
achieved via modeling of experimental data
using concepts based on statistical mechanics.
The motivation here is to obtain various
relaxation processes were analyzed using timetemperature
scaling
principles.
The
experimental investigations will include
infrared spectroscopy, Brillouin scattering, and
impedance spectroscopy. We summarize here
the work done under this project.

Scheme 1: Schematic representation of the


proposed gel polymer electrolyte

Sudeshna Sen is a JRF at SSCU, IISc, Bangalore,


India, sudeshnasen.01@gmail.com
2
Sneha Malunavar, PA at SSCU, IISc, India,
sneha.malunavar@gmail.com
3
C. Gouri is Scientist SG & Head, Lithium-ion
Electrodes Section, Lithium-ion and Fuel Cell Division
(LFCD) VSSC, Thiruvanthapuram 695022, India,
gouri_c@yahoo.com
4
Prof. Aninda J. Bhattacharyya is an Associate
Professor at SSCU, IISc. Bangalore 560012, India,
aninda_jb@sscu.iisc.ernet.in

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II PROPOSED WORK AND GOALS


A. Cross linked gel polymer electrolyte:
Gel polymer electrolytes are attractive
alternatives to liquid electrolytes in several
electrochemical devices including lithiumbased batteries. Gels display high ambient
temperature ionic conductivity and highly
compliable mechanical property. The main
motivation for the usage of gels is mainly
targeted towards the enhancement in energy
density of batteries. Conventional gel
polymers (polymer electrolyte + liquid
solvent) do not perform well as their
performance deteorates rapidly due to ageing
factors leading to very poor battery
performance. Thus, there is considerable need
to design gel polymers with superior
electrochemical and mechanical properties
using newer methods and materials. We
demonstrate
here
newer
forms
of
multifunctional gel polymer electrolytes using
low melting point solids such as room
temperature ionic liquids.
Room temperature ionic liquids (RTILs) have
been extensively demonstrated as a viable
alternative electrolyte in lithium-ion battery
applications due to their high thermal stability,
ionic conductivity and wide electrochemical
voltage window. RTILs have also been used as
a medium for synthesis of diverse compounds.
In our studies, RTIL was used as a medium to
synthesize gel polymer electrolytes. Earlier
acrylonitrile was polymerized inside ionic
liquid medium to obtain crosslinked gel
system [ref 3]. Although, the resulting polymer
electrolyte displayed high ionic conductivity,
its the mechanical properties were poor. In
this work we explore the possibility of
improving the mechanical property of the gel
polymer electrolyte by inclusion of more than
one monomer to synthesize cross linked blend
polymer-like
electrolyte.
Free
radical
polymerization
of
acrylonitrile
and
methacrylate (MPTMS) monomers was carried
out in pyrolidinium ionic liquid to synthesize

novel crosslinked gel polymer electrolytes.


Thermal stability, mechanical property and
ionic conductivity of the synthesized cross
linked blend-like polymer gel system were
studied.
From the thermogravimmetry
analysis (TGA) data it was observed that this
new system was thermally stabile up to 350 C
[figure 3]. At temperatures higher than 350 C,
significant weight loss 80 % (350-475 oC)
was observed. However, the weight retention
(> 475 oC) of the blend-like polymer was
higher than the pure ionic liquid suggesting
higher thermal stability.

Fig 1: Thermogravimetric analysis (above) and


differential scanning caloriemetry (bottom;
only relevant temperature regime shown) of
cross-linked gel samples vis a vis the pure
ionic liquid
The ionic conductivity is measured by acimpedance spectroscopy in the frequency
range from 1 Hz to 1 MHz (figure 2). The
2

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conductivity of this system was found to be of


the order of 10-3 -1cm-1 in the temperature
range -20 to 60 C, which is highly beneficial
for operation in battery applications.
The acrylate monomer was incorporated to
improve mechanical property of PAN/IL
system. The mechanical property of the blendlike gel polymer electrolytes were studied
using
static
and
dynamic
rheology
measurements (figure 3).

Fig 2: Temperature dependent ionic


conductivity of crosslinked polymer gel
electrolyte
The polymer network structure in the gel
polymer electrolyte was characterized by static
rheology measurement. In static rheology
measurement, the viscosity of the system was
monitored as a function of shear rate. The
decrease in viscosity with increasing shear rate
indicated presence of a connected network in
the gel. Along with the network formation, the
viscoelastic behavior was also studied by
dynamic rheology measurement.
Cyclic voltammetry were also carried out to
estimate the electrochemical voltage window
of the synthesized materials. It was observed
that the material is electrochemically stable in
the potential range from -0.5 to 5 V. This
makes it highly suitable for battery
applications with high voltage electrode
materials such as polyanions phosphates and
silicates.

Fig 3: Photographs of the polymer elecrolytes


at various monomer ratios (above). Dynamic
rheology measurement of cross-linked blendlike gel polymer electrolyte (bottom)
Additionally, the new cross-linked systems
were galvanostatically cycled with LiFePO4 as
a cathode material. Though the as-synthesized
polymer electrolyte showed electrochemical
performances, the applicability of the crosslinked systems in battery application is
presently restricted by the inability to cast thin
films ( 30-100 m). It is felt that further
improvement in the mechanical property of the
gel polymer is expected to improve overall
physical properties and device performance.

Fig 4: Electrochemical stability window of the


gel polymer electrolytes

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B: Mixed solvent based


electrolyte:

gel

polymer

Plastic crystals possess rotational disorder in


their crystalline lattice structure. The molecule
transformed to this rotator phase via solidsolid phase transition below their melting
point. Plastic phase is achieved via solid-solid
phase transition(s) below their melting point.
Depending on the plastic crystalline
compound, the role of rotators vary in their
influence on the ionic conductivity. In
insulating polar organic plastic crystalline
compounds such as succinonitrile, the
presence ofrotors significantly influence the
effective conductivity of the electrolyte (SN +
ionic salt, NaX, LiX). Succinonitrile consists
of three geometrical isomers, two gauche and
one trans above the normal to plastic transition
temperature (Tnp). These two isomers exist in
equilibrium in plastic phase and transform
from one to another form via 120o rotation
around C-C bond. The trans phase has been
proposed to act as impurity phase which
reduces activation energy barrier for ion
transport. Such fenomenon of solvent
dynamics, playing a important role in ion
transport has also been obsereved in various
ionic liquid, an important subclass of ionic
plastic crystalline materials. Among several
ionic liquid systems based on imidazolium,
piperidinium, alkyl ammonium based ionic
liquids,
N-methyl-N-butyl
pyrrolidinium
bis(trifluoromethane
sulfonyl)
imide
(PY14TFSI) has been well studied ionic liquid
for battery applications its owing to several
attractive physical properties. However the
intrinsic ionic conductivity is lower compared
to other ionic liquid.
We discuss here an electrolytic system
where a mixture of solvents comprising of a
plastic crystalline compound and RTIL has
been employed to synthesize the electrolyte.
Incorporation of small amount of ionic liquid
into succinonitrile matrix resulted in a highly
conducting electrolyte compared to both IL-

LiX or Succinonitrile-LiX systems. Similar


system has been earlier reported in dye
sensitized solar cell lead to an increase in
efficiency of dye DSSC. The ionic liquid
decreases melting point of the SN while
keeping normal-plastic transition temperature
unchanged. The room temperature ionic
conductivity and cyclic voltammetry have
been performed in order to investigate
applicability of the mixed solvent in lithium
battery application and a new type of gel
polymer electrolyte has also been synthesized
using this solvent matrix in this study.

Scheme 2: Schematic representation of the


synthesis of gel polymer electrolyte using SN
and IL as solvents
Prior to prepare the above mentioned mixed
plastic crystalline solvent, succinonitrile was
sublimed twice to reduce impurity. In order to
prepare mixed solvent based electrolytic
system, initially SN-LiTFSI system was
synthesized by dissolving required amount of
lithium salt, lithium bis(trifluoromethane
sulfonyl) imide (LiTFSI) in succinonitrile and
stirred at 60 0C. The salt concentration was
kept constant (0.5 M) for all the studies. The
ionic
liquid,
1-Butyl-1-Methyl
bis(trifluoromethane
sulfonyl)
imide
(PY14TFSI) was incorporated in the SNLiTFSI system in three different molar ratios
(with respect to SN) and stirred at room
temperature to get homogeneous liquid
electrolytic system. Three different molar
ratios of SN to IL studied are 20:1, 10:1 and
4

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5:1 keeping LiTFSI concentration


(0.5M). For the lower ionic liquid

same

The room temperature conductivities of mixed


solvents with various IL concentrations,
keeping salt concentration same, is presented
in the table 1.
Table 1: Room temperature conductivities of
SN-IL systems of different solvent ratio

Fig 5: Ionic conductivity of the gel polymer


electrolytes using SN+IL as solvents
concentration i.e. for the composition [SN:IL
20:1]-0.5M LiTFSI, an waxy appearance,
characteristic to SN was observed at room
temperature. But as we increase ionic liquid
concentration, i.e, for the compositions [SN:IL
10:1]-0.5M LiTFSI and [SN:IL 5:1]-0.5M
LiTFSI, a liquid appearance was observed at
room temperature. This shows a clear
indication of reduction of melting point of
succinonitrile upon addition of small amount
of ionic liquid.

Fig 6: Electrochemical stability window of the


gel polymer electrolytes using SN+IL as
solvents

Solvent composition

Conductivity ( -1cm-1)

SN-0.5M LiTFSI

2.4 x10-4

[SN:IL 20:1]-0.5M
LiTFSI
[SN:IL 10:1]-0.5M
LiTFSI
[SN:IL 5:1]-0.5M LiTFSI

2.3x10-3
5.9 x10-3

IL 0.5M LiTFSI

2.5 x10-3

4.5 x10-3

The
above
room
temperature
ionic
conductivity data clearly indicates that room
temeprature conductivity of the liquid
electrolyte strongly depends on molar ratio of
succinonitrile and ionic liquid. With increasing
ionic liquid concentration, conductivity
increases up to a maximum value (6.9 x10-3 1
cm-1 for the composition SN:IL 10:1). On
further increasing ionic liquid concentration,
i.e for the molar ratio 5:1, conductivity
decreases. As the lithium salt concentration
was kept constant, the effect of salt on the
ionic conductivity has not been taken into
account. Instead of the large variation in
conductivities, all of the compositions of the
plastic crystal mixed solvent (including the
composition [SN:IL 5:1]-0.5M LiTFSI) have
higher ionic conductivities compared to the
pristine SN-LiTFSI and IL-LiTFSI systems.
The composition, [SN:IL 10:1]-0.5M LiTFSI
exhibits highest conductivity (5.9 x10-3 -1cm1
), almost comparable to widely used liquid
EC/DMC based electrolyte. In order to
investigate the reason behind this significant
improvement in ionic conductivity using the
mixed solvent compared to both pristine IL an
succinonitrile, several factors like viscosity,
solvent dynamics and ion association effect
5

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should be taken into account carefully.


Reduction of viscosity and ion association in
SN-IL-LiTFSI systems compared to pristine
IL-LiTFSI and SN-LiTFSI systems may be
reason behind the improvement in ionic
conductivity in the proposed mixed solvent.
Besides, the decrease in ionic conductivity at
higher ionic liquid concentration (for the
composition [SN:IL 5:1]-0.5M LiTFSI)
compared to other compositions, indicates
possibility of increasing ion association in that
concentration compared to lower concentration
of ionic liquid. To explain the variation in
ionic conductivities with ionic liquid
concentration, the effect of ionic liquid
incorporation on succinonitrile dynamics and
nature of ion pairing in this solvent should be
studied in more details
The cyclic voltammetry was carried out for the
highest conducting composition to monitor
electrochemical window of the mixed plastic
crystal solvent and represented in figure 6. The
plot clearly indicates a wide electrochemical
voltage window for the solvent from 0.5V to
4.7V. In this plot a strong cathodic peak at
around 0.2 V and anodic peak at -0.5 V were
observed for characteristic lithium striping and
lithium plating processes. No further
electrochemical degradation of electrolyte is
observed up to the voltage 4.5V. The stability
of the solvent at upper voltage region is close
to ionic liquid PY14TFSI-0.5M LiTFSI system
(5V) and thus can be applied for high voltage
cathode materials.

electrolytes discussed here will also be


promising for other battery chemistries.
REFERENCES
[1] Das, S; Bhattacharyya, A. J. Phys. Chem.
Lett. 2012, 3, 35503554
[2] Patel, M; Bhattacharyya, A. J. Phys. Chem.
B 2010, 114, 52335240
[3] Patel, M; Gnanavel, M; Bhattacharyya, A.
J. J. Mater. Chem. 2011, 43, 17419-17424
[4] S. Sen, Bhattacharyya, A. J. 2014,
unpublished

III CONCLUSIONS
We have demonstrated here a novel class of
gel polymer electrolytes for possible
applications in lithium-based batteries. The ion
transport mechanism (not discussed here, c/f
proceeding paper 2013 and progress report
2014) is affected by both the dynamics of the
polymer and ion solvation. As other types of
salts viz. magnesium, sodium can be easily
incorporated in the synthesis, the gel polymer
6

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

SPARSITY-BASED CROSS-TERMS-SUPPRESSED TIME-FREQUENCY DISTRIBUTION OF


MULTI-COMPONENT LINEAR FREQUENCY MODULATED SIGNALS
Shreyas Hampali, Subhankar Ghose, and Chandra Sekhar Seelamantula

ABSTRACT
We address the problem of estimating the parameters of multiple
linear frequency-modulated (LFM) chirp signals. We consider signals corrupted by additive white noise and develop a new technique
based on the properties of the instantaneous autocorrelation (IA)
sequence of multiple LFM chirp signals. The IA matrix, whose
rows are the IA sequences obtained at different time instances of
the signal is introduced. We show that, by obtaining a sparse representation of the rows of IA matrix with a dictionary of sinusoids, the
inherent cross terms are eliminated. Further, by obtaining a sparse
representation of the columns of the IA matrix, the instantaneous
frequencies of the component chirps are estimated to obtain a high
resolution cross-term suppressed sparse WVD (CTSS-WVD).The
component chirps that manifest as straight lines in CTSS-WVD
are estimated using an iterative line parameter estimation method.
We show simulation results for four-component chirp signal with
varying SNR levels. We also validate the technique by suppressing
cross-terms in a bat echolation signal.
Index TermsInstantaneous autocorrelation sequence, Ambiguity function, sparsity, LASSO, Linear frequency modulated
chirps
I. INTRODUCTION
INEAR frequency modulated (LFM) signals are a class of
non-stationary signals widely used in applications such as
radar, sonar and wireless communication [1]. In all these cases
the transmitted signal undergoes a time-varying phase shift due
to relative motion between transmitter and the receiver. Further,
due to presence of multiple targets in the radar case and multiple
paths in the communication case, the received signal is a sum of
LFM signals and analysis of such multicomponent LFM signals
reveal properties of targets or communication paths. The multicomponent LFM signals also arise in applications such as electronic
counter measure systems for pulse-Doppler radars, where LFM
signals from various transmitters need to be analyzed. Due to its
wide applications the study of multiple LFM signals in noise has
received considerable interest during the past two to three decades
[2][5].

I-A. Contributions of this paper


In this paper, we propose a technique for obtaining crossterm suppressed WVD (CTS-WVD) by sparsifying the discrete
ambiguity function for multi-component LFM chirp signals in white
noise. Using CTS-WVD, we introduce high-resolution, noise and
cross-term suppressed sparse WVD (CTSS-WVD) that is suitable
for estimating multi-component chirp parameters in low SNRs (0
This work was supported by the Indian Space Research Organization
- Indian Institute of Science Space Technology Cell (Project:
ISTC/EEE/CSS/0293).
Authors email : shreyas.hampali@gmail.com, subhoghose@gmail.com,
chandra.sekhar@ieee.org
Phone : +91 80 2293 2695

dB). The estimation of the chirp parameters in the CTSS-WVD is


computationally far less complex than Hough transform. The CTSWVD is shown to have lower variance, better resolution in the timefrequency (TF) distribution and comparable cross-term suppression
ability than other cross-term suppression methods.
II. AMBIGUITY FUNCTION OF MULTICOMPONENT
LFM CHIRP SIGNAL
The instantaneous autocorrelation (IA) sequence of a signal s[n]
is defined as,
IA(n, k) = s [n k]s[n + k].

(1)

The ambiguity function (AF) of a signal is given in terms of IA


sequence as
X
M (, ) =
IA(n, /2)ejn
(2)
nZ

For a mono-component LFM chirp signal, the AF is given by,


X ja n jn
M (, ) = b20 eja0
e 1 e
(3)
n

Thus, for a given , the AF of an LFM chirp is the Fourier


transform of a sinusoid of frequency a1 . In case of multiple
chirps, equation (2) can be divided into two terms as cross-term
component, Mc (, ) and auto-term component, Ma (, ). For a
two component LFM chirp signal the AF is given by,
M (, )

2
X

b2i eja0i

eja1i n ejn

i=1

{z

Ma (,)

ej(C01 ( )+C11 ( )n+C21 n ) ejn

n
2

ej(C02 ( )+C12 ( )n+C22 n ) ejn ,

(4)

{z

Mc (,)

where,

1
+ a02 + (1)i (a11 a12 ) 2 ,
2
2
8

C1i ( ) = a11 + a12 + (1)i (a01 a02 ),


2
2
i1
C2i = (1) (a11 a12 )
2
It can be verified that in the scenario a11 6= a12 , the crossterms are Fourier transforms of LFM chirps. The auto-terms are
always sinusoids with frequency a1i . When the chirp rates a1i
of the component chirps are equal, the cross terms are sinusoids
of frequency a1i (a01 a02 ). In the presence of white noise,
the signal to noise cross-terms manifest as random signal. Thus,
the problem of cross-term suppression is that of extraction of low
frequency sinusoids in the ambiguity function domain.
C0i ( )

a01

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III. CROSS-TERM SUPPRESSION USING A SPARSE


REPRESENTATION FOR AMBIGUITY FUNCTION
We introduce the instantaneous autocorrelation (IA) matrix of
the signal s[n] and denote it by A. The size of A is N2 N and
the (i, j th ) element is given by,

Ai,j = s [j i] s[j + i].

(5)

The AF can be expressed in terms of IA matrix as,


M (2, ) = F B;

B = AT

, 0

(6)

where F is the discrete Fourier transform matrix.


The rows of the IA matrix contain signal auto-terms, signal-tosignal cross-terms and signal-to-noise cross-terms. The signal-tosignal cross-terms are LFM chirps when chirp rates are unequal
and the signal-to-noise cross-terms are random signals. The signal
auto-terms being the only sinusoids in this scenario, the cross-terms
are suppressed by identifying the sinusoids in the IA sequence.
The sinusoids can be identified by estimating its frequencies using
various parameter estimation techniques such as estimation of
signal parameters via rotational invariance techniques (ESPRIT)
[11] and multiple signal classification (MUSIC). However, such
techniques require the model parameter which is the number of
sinusoids present in the signal and is unknown a priori. Further, the
presence of signal dependent cross-terms deviates the IA sequence
from the signal model defined by sinusoidal parameter estimation
methods.
In our approach, we use sinusoidal dictionary based least absolute shrinkage and selection operator (LASSO) formulation defined
in [12].
III-A. Cross-term suppression problem formulation using
LASSO in ambiguity function domain
The cross-terms in the rows of IA matrix in (5) for unequal rate
chirp signals are separated by identifying the sinusoids, which are
the auto-terms in the IA sequence. A set of sinusoids in an IA
sequence along with their magnitudes are estimated using LASSO
formulation with dictionaries of sinusoids each of size P denoted
by X(i) and X(r) , respectively. The (i, j)th element of the Mn
P, P Mn dictionary matrices is given by,


2i(j P/2)
(i)
,
Xi,j = sin
P


2i(j P/2)
(r)
,
Xi,j = cos
P
j = 0, 1, 2, , P 1;
i = 0, 1, 2, , Mn 1.
(7)

coefficient vector wn denotes the auto-terms in the IA matrix, the


cross-term suppressed sparse AF (CTSS-AF) is obtained as,
CTSS-AF

[w1 , w2 , , wN ]

When the formulation in (8) is used for the case of a signal


constituted of equal rate LFM chirps, the cross-terms fail to get
suppressed and appear along with the auto-terms. This is because,
the cross-terms too appear as sinusoids when rates of component
chirps are equal.
The cross-terms in case of equal rate LFM chirps have frequencies higher than that of auto-terms. As explained in the Section
II when a11 a12 in (4), cross-terms appear along coordinates
, a11 (a01 a02 ) in the discrete AF domain, whereas the
auto-terms are present at coordinates (, a11 ). Thus, for small ,
the cross-terms appear on either side of the frequency origin as
seen from Figure 2.
The cost function (8) imposes equal penalty () on all the
coefficients in vector wi . Thus, we reformulate the auto-term
identification problem in (8) to encompass both the scenarios of
equal and unequal chirp rates and is given by,
2
minwn k X(r) wn real(AT
n ) k2 + k Dwn k1 , (9)

D Rpp ,
(
0
if i 6= j,

where
Di,j =

(ip/2)2
2

if i = j.

where is the penalty controlling factor. The diagonal penalty


matrix D satisfies the condition of imposing higher penalty for
frequency components that are away from zero. The penalty matrix
D is motivated by the Choi-Williams kernel, (, ) used for crossterm suppression and is given by,
2

(, ) = e( ) .
It should be noted that, in case of wide-band (large a11 ) equal
rate chirp signals, for large , (a11 (a01 a02 ))) is positive
if a11 > 0 and negative if a11 < 0. Hence, in this scenario the
cross-terms that appear on the same side of the frequency origin
are not suppressed by the cost function (9).
Figure 1 shows a normalized slice of the CTSS-AF obtained using the general formulation in (9). We observe that the cross-terms
which appear as sinusoids are suppressed by the new formulation.
Figure 3 shows the AF of a three chirp signal obtained using (6) and
Figure 4 shows the corresponding cross-term suppressed discrete
sparse AF.

1
2

0.8

0
3

wn

min k X(r) wn real(Bn T ) k22 + k wn k1 .


wn

(8)

The two stages correspond to the imaginary and real parts of Bn .


The optimization problem in (8) identifies the auto-terms in the nth
column of the matrix B. The performance of this two stage process
is improved by retaining only those frequencies for the dictionary
in stage 2 whose amplitudes are non-zero in stage one. As the

0.8
0.6

0.4

0
0.4
Autoterm

0.2

min k X(i) wn imag(Bn T ) k22 + k wn k1 ,

1
Crossterms

0.6

The nth column vector of matrix B in (6) has Mn = N 2n


non-zero elements in it as can be verified from the construction of
IA matrix in (5). This Mn element vector is denoted by Bn . As
Bn is complex the auto-term identification problem is formulated
in the LASSO framework in two stages as,

1
0
1
FREQUENCY

Fig. 1: A slice of the sparseAF for two equal rate chirp


signals each at SNR = 0 dB.
The sparse-AF is obtained using cost function (9). The
cross-terms are suppressed.

0.2
50

100

150

200

250

Fig. 2: Ambiguity function of two


equal rate chirp signals with parameters a01 = 0.2513, a02 = 0.6283,
a11 = a12 = 7.33 104 .

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50

50

0.8

25

0.6

0.6
0

0.4
25
50

0.2
20

40

60

80

0.4
25
50

0.2
20

40

60

FREQUENCY

25

0.8
50

Fig. 4: CTSS-AF of a three component LFM chirp signal each at


high SNR

0.4

100

0.8
50

0.6
0.4

100

0.2

0.2
150

Fig. 3: Ambiguity function of


a three component LFM chirp
signal each at high SNR

0.6

FREQUENCY

1
0.8

150
100 200 300 400 500

100 200 300 400 500

TIME

(b) TF distribution using matching pursuit method [7]

(a) Wigner-Ville distribution

n = (X(r) + jX(i) )wn


B

(10)

is
The cross-term suppressed IA (CTS-IA) matrix denoted by A
i row-wise as,
obtained by arranging the vectors B
h
iT
= B
1, B
2, , B
N
A
(11)

0.8
50

0.6
0.4

100

0.2
150

FREQUENCY

The length of the AF sequence in n row of the IA matrix is


N 2n. The ability of the cost function (9) to provide an accurate
sparse representation of the signal is a function of the signal length
as shown in [12]. Thus, for large , when the IA sequence length
is small, the signal auto-terms are not consistently identified as
verified in Figure 4.
Denoting the minimizer of (9) by wn , the sparse approximation
i is given by,
of Bi denoted by B

FREQUENCY

1
th

TIME

0.8
50

0.4

100

0.2
150

100 200 300 400 500

0.6

100 200 300 400 500

TIME

TIME

(c) TF distribution using Choi- (d) TF distribution using proWilliams kernel method
posed method
Fig. 5: Comparison of the cross-term suppression methods for two
equal rate chirp signal in no noise scenario.

IV. SPARSE WVD AND MULTI-COMPONENT CHIRP


SIGNAL PARAMETERS ESTIMATION
In this section, we introduce cross-term suppressed sparse WVD
The CTSS-WVD is then used to esti(CTSS-WVD) using A.
mate chirp parameters using an iterative line parameter estimation

0.6
0.4

100

FREQUENCY

0.8
50

0.8
50

0.6
0.4

100

0.2

0.2
150

150
100 200 300 400 500

100 200 300 400 500

TIME

TIME

(b) TF distribution using matching pursuit method [7]

(a) Wigner-Ville distribution


1
20
0.8

40
60

0.6

80
0.4

100
120

0.2

140
100

200

300

400

500

FREQUENCY

By utilizing the cross-term suppressed IA matrix


 A, the cross-term
.
suppressed WVD is obtained as 2 real F A
Figure 5 shows cross-term suppressed WVD obtained from
different techniques in no noise scenario. The Choi-Williams
method which uses a low pass filter in the AF domain is known
to compromise on the TF resolution of the signal. The signal
decomposition based technique [7] which uses Gabor atoms is
free of cross-terms, however the TF resolution of the signal is
compromised as verified from Figure 5b. The proposed method
on the other hand has better TF resolution and also achieves cross
term suppression as observed in Figure 13, which shows a slice
of the TF distributions in Figure 5 along the dotted line. The
parameters considered in the simulation are a01 = 0.2513, a02 =
0.7504, a11 = a12 = 7.36 104 , p = 1024, N = 512.
Figure 6 compares the performance of the proposed method
when a signal is constituted of four LFM chirp signal in a noisy
scenario. The proposed method is seen to have better TF resolution
than Gabor atoms based signal decomposition method [7] and a better cross-term suppression ability than Choi-Williams method. The
parameters considered are a01 = 0.2513, a02 = 0.5027, a03 =
0.9425, a04 = 1.1310, a11 = 7.36 104 , a12 = 18 104 ,
a13 = 6.14 104 , a14 = 7.36 104 , p = 1024, N = 512
and SNR1 = SNR2 = SNR3 = SNR4 = 0 dB

FREQUENCY

FREQUENCY

Similar to AF, the Wigner-Ville distribution (WVD) of a signal


is directly obtained from its IA matrix A as,
  X

W V D n,
=
IA(n, k)ejk = 2 real F A
(12)
2

50

100

150

100

TIME

200

300

400

500

TIME

(c) TF distribution using Choi- (d) TF distribution using proWilliams kernel method
posed method
Fig. 6: Comparison of the proposed cross-term suppression method
for a four component chirp signal each with SNR = 0 dB

method. The CTSS-WVD is obtained by sparsifying CTS-WVD


introduced in Section III and has improved frequency resolution
aiding in accurate estimation of parameters of component chirp
signals.
The nth column of the CTS-IA matrix which we call as the IA
vector is denoted by zn . The auto-term component in the IA vector

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(i)

We observe that the frequency of each sinusoid is twice the


instantaneous frequency of the corresponding chirp at time instant
n. Thus, a sparse representation of the IA vector zn similar to
(8), with a dictionary of sinusoids as defined in (7), provides
information of the sinusoidal frequency content in the vector which
in turn is an estimate of the IFs of the component chirps. The
two cost functions for obtaining the sparse representation of zn is
provided below for clarity,
min k X(i) wn imag(zn ) k22 +
wn

p
X

kwn k1 ,

(14a)

kwn k1 ,

(14b)

i=1
p

min k X(r) wn real(zn ) k22 +


wn

X
i=1

where X(i) and X(r) are the sine and cosine dictionary matrix.
As discussed in Section III, (14b) is used for suppressing spurious
frequencies detected by optimizing (14a).
The sparse representation is obtained for each column of CTSIA matrix and the minimizer of (14) is denoted by wn for column
n. The CTSS-WVD matrix is obtained from wn as,
CTSS-WVD = [w1 , w2 , , wN ]

(15)

Figure 7 shows the WVD of a four chirp signal. The SNR of each
of the component chirps is 4 dB. The CTSS-WVD obtained using
the above described procedure is shown in Figure 8. A slice of the
TF distributions along the dotted line in Figure 7 and 8 is shown in
Figure 9. The resolution of CTSS-WVD is better than WVD due to
the the sparsity constraint used in the formulation. The cross-terms
are also suppressed thus providing better estimate of the IF of the
component chirps.
IV-A. Detection and estimation of line parameters in sparse
WVD
We develop a new technique termed as iterative line parameter
estimation method (ILPEM) that iteratively estimates the slope and
intercept parameters of intersecting lines in a sparse distribution.
ILPEM is an alternative to the conventional Hough transform and
has lower computational complexity.
Let the set of frequencies present at any time instant n, obtained
from CTSS-WVD be denoted by n . A single chirp scenario is first
considered and is later extended to multiple chirps at the end of
this section. The problem of line parameter estimation in sparse TF
plane with least squares cost function is written as,
N
X

min

a,b,
1 1 ,2 2 , ,N N n=1

(n (a n + b))2 ,

n n

1
50
0.8

100
150

0.6

200
0.4

250
300

0.2

350

n=1

100

0.8

100
150

0.6

200
0.4

250
300

0.2

200

300

100

TIME

200

300

TIME

Fig. 7: WVD of a four component LFM chirp signal each at


SNR = 4 dB.

0.7

Fig. 8: CTSS-WVD for a four


component LFM chirp signal
each at SNR = 4dB along with
frequency marginal used for initializing the line parameters. The
peak of the frequency marginal is
used to initialize the iterative line
parameter estimation method.
0.8
Autoterms

0.6
0.6

0.5
0.4

0.4
0.3
0.2

0.2

0.1
0
0

100

200

(a) WVD
(17b)

1
50

350

Frequency

a,b

(i)

(16)

where, at each time instant n, an optimal frequency is chosen form


the set n such that the frequencies at all time instants are co-linear
and is given by the line parameters (a, b). We propose a two step
suboptimal iterative solution to the (N + 2)-dimensional search
problem by assuming that the initial value of the line parameters
is close to the minimizer.

2
n(i) = arg min n (a(i1) n + b(i1) ) ;
(17a)
n = 0, 1, 2, , N 1
N
2
X  (i)
{a(i) , b(i) } = arg min
n (a n + b) ,

(i)

where a(i) , b(i) , 1 , 2 , N represent the optimization parameters at ith iteration.


The initial value of the line parameters in (17a) denoted by
(a(0) , b(0) ) is obtained using the frequency marginal which is
shown in Figure 8. The frequency corresponding to the maximum
value of the marginal is used as b(0) . In our simulation, the value
of a(0) is set to 0 as no information about the chirp rate is available
(i)
initially. For the case of multiple chirp lines, the frequencies n
of the set i corresponding to a line as obtained from (17a) are
removed from their corresponding sets and the two-step iterative
procedure is repeated.
We now evaluate the performance of the sparse WVD along
with ILPEM (sparse-WVD-ILPEM) by estimating the parameters
of a mono-component chirp signal.To facilitate comparison, the
chirp parameters are also estimated by applying Hough transform
to sparse-WVD (sparse-WVD-Hough). The case of a single chirp
signal in noise enables performance evaluation of sparse-WVD and
ILPEM in separation as the cross-term suppression described in
section III is not required.
For simulations we consider signal length N = 300 and the
number of sinusoids in the dictionary P = 750. Figure 10a and
10b shows the variance of the chirp parameter estimates using
various techniques. The resolution of the transformed variables
in the Hough transform (, ) is set to 0.1. The performance
of the ILPEM is comparable with the Hough transform based
technique (sparse-WVD-Hough) for SN R > 2 dB and is better
for SN R < 2 dB. A comparison with de-chirping based method
discussed by Peleg and Porat in [10] with 4096-point discrete
Fourier transform (DFT) shows that the threshold SNR of the
sparse-WVD-ILPEM technique is about 4 dB lesser than the de-

FREQUENCY

(13)

FREQUENCY

is a sum of complex sinusoids given by,


X 2 j2(a +a n)k
bi e 0,i 1,i .
zn [k] =

300

0
0

100

200
Frequency

300

(b) CTSS-WVD

Fig. 9: A slice of the WVD and CTSS-WVD along the dotted line
shown in Figure 7 and 8

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1 The authors wish to thank Curtis Condon, Ken White, and Al Feng of
the Beckman Institute of the University of Illinois for the bat data and for
permission to use it in this paper.

VARIANCE (dB)

VARIANCE (dB)

0
20
40
60

CRLB
DECHIRPING
METHOD [8]
SPARSEWVDILPEM
SPARSEWVDHOUGH

20
40
60
80
100

10

SNR (dB)

10

SNR (dB)

(a) Comparison of carrier fre- (b) Comparison of chirp rate esquency estimates.
timates.
Fig. 10: Chirp parameter estimates of a mono-component LFM
chirp in noise. The sparse WVD-Hough estimates are obtained by
applying Hough transform to the sparse WVD obtained using (14).
80

80

CTSSWVD
PHAF
WIGNERHOUGH

85

MSE (dB)

85

MSE (dB)

90
95
100
105
110
0

90
95
100
CTSSWVD
PHAF
WIGNERHOUGH

105
2

110
0

SNR (dB)

(a) Chirp 1
80

CTSSWVD
PHAF
WIGNERHOUGH

85
85
90

100
0

CTSSWVD
PHAF
WIGNERHOUGH
2

SNR (dB)

(c) Chirp 3

(b) Chirp 2
80

95

SNR (dB)

MSE (dB)

V. PERFORMANCE EVALUATION
We evaluate the robustness of the proposed algorithm by considering a four component chirp signal with varying SNR levels. The
performance is compared with two other methods namely WignerHough transform discussed by Barbarossa in [9] and product
higher order ambiguity function (PHAF) based method proposed by
Barbarossa et al. in [13]. We obtain CTSS-WVD of a bat echolation
signal and prove that the technique efficiently suppresses crossterms in real scenarios.
The multi-component signal considered is same as in Figure
6 whose parameters are given in Section III. The size P of the
sinusoidal dictionary defined in (7) is 750. For the PHAF method,
four different lags are considered as discussed in [13] with 2048point DFT. For Wigner-Hough based method, the size of the
transformed domain is 256 256. At low SNR, the probability
of detecting a chirp line in a sparse-TF distribution or in the
Wigner-Hough domain decreases. However, such false detections
can be identified by comparing the sum of squared errors as
obtained in cost function (17b) with a threshold. Deriving an
optimal detector for detecting such false alarms is beyond the scope
of this work and hence, in this paper we compare the estimated
parameters with the ground truth and declare as detected if the
deviation is within 10% of its original value (oracle). We consider
200 Monte-Carlo simulations to obtain variance of the estimated
chirp parameters. Figures 11 and 12 show the performance of the
proposed method for each of the detected component chirp signals
and compare it with other techniques for different SNR levels. The
chirp parameter estimates obtained using CTSS-WVD is observed
to have lower mean-squared-error (MSE) than Wigner-Hough or
PHAF estimates for three component chirps (chirps 1,2 and 4). The
error in estimation of chirp rate propagates in the PHAF method
and affects the carrier frequency estimates as discussed in [13]. The
carrier frequency estimates using CTSS-WVD does not suffer from
error propagation and hence has lower MSE than PHAF technique
as seen from Figure 12. The average probability of detection (PD )
of all the component chirps is shown in Figure 14. The WignerHough method is benefited from the coherent integration and has
PD = 1 for large SNRs. The PD of the proposed method is more
than 0.95 for all SNRs and decreases with SNR as the iterative line
parameter estimation method converges to local minimas.
Figure 15 shows the TF distributions of a bat echolation signal1 .
The bat echolation signal used here has deviations from the linear

CRLB
SPARSEWVDILPEM
DECHIRPING
METHOD [8]
SPARSEWVDHOUGH

20

MSE (dB)

chirping method. Further, the proposed method is consistent with


CRLB for SN R > 2 dB.
The advantages of the ILPEM over Hough transform are three
fold. 1)The estimates obtained using the ILPEM have lower variance than Hough transform based estimates. 2)For an N N sparse
matrix, the computational complexity of ILPEM is O(N 2 ) (linear
search in (17a) has a complexity of O(N )), whereas the complexity
of Hough transform is O(N 3 ), if the transformed space also has the
dimension N N . 3) ILPEM has the line-fitting property and can
detect lines in noisy scenarios. The Hough transform formulation
yields poor results when the observations are not co-linear.
The iterative line parameter estimation method converges to local
minimas of (16) when the distribution is noisy and less sparse. At
low SNRs, the sparse-WVD is noisy and the estimates of chirp
parameters are inaccurate as observed in Figures 10a and 10b.
Simulation results show that the iterative line parameter estimation
method converges to minima in less than 15 iterations for signal
length N = 300, dictionary size P = 375 and SNR >= 2 dB.

90
95
100
105

110
0

SNR (dB)

(d) Chirp 4

Fig. 11: Performance comparison of chirp rate estimator for a four


component LFM chirp signal with varying SNRs

chirp and the chirps do not occupy the full signal length. However,
we observe from Figure 15c that the cross-terms are suppressed
in CTSS-WVD without loss of TF frequency resolution. The low
amplitude second harmonic chirp at higher frequencies is not
completely captured by CTSS-WVD.
VI. CONCLUSION
We have proposed a novel technique for estimating the parameters of the multiple LFM chirp signals in noisy scenario. The
algorithm is based on the sparse representation of the instantaneous
autocorrelation sequence of the signal and is a three step process.
The cross-terms present in the IA sequence are suppressed in the
first step, followed by instantaneous frequency estimation in the
second step and an line parameter estimation method in the last
step. The sparse representation is obtained using LASSO with a
dictionary of sinusoids. A high-resolution cross-term suppressed
time frequency representation of the multiple chirp signals is also
obtained. Simulation results show the estimator performs efficiently
up to an SNR of -2dB for single chirp signals. We also evaluate the
performance using a four-component chirp signal in noise and show
that the resulting estimates are reliable. Finally, the effectiveness
of the technique is proved by applying it to a bat echolation signal
that has minor deviations from the signal model considered.

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[1] M. S. Wang, A. K. Chan, and C. K. Chui, Linear


frequency-modulated signal detection using Radon-ambiguity
tansform, IEEE Trans. Signal Process., vol. 46(3), pp. 571
586, Mar 1998.
[2] Y. Sun and P. Willett, Hough transform for long chirp
detection IEEE Trans. Aerosp. Electron. Syst., vol. 38(2),
pp. 553569, Apr. 2002
[3] X-G Xia, Discrete chirp-Fourier transform and its application
to chirp rate estimation, IEEE Trans. Signal Process., vol
48(11), pp. 31223133, Nov. 2000
[4] L. Qi, R. Tao, S. Y. Zhou and Y. Wang, Detection and
parameter estimation of multicomponent LFM signal based on
fractional Fourier transform, Sci. China (Ser F.),, vol 47(2),
pp. 184-198, 2004
[5] J. C. Wood and D. T. Barry, Radon transformation of
time-frequency distributions for analysis of multicomponent
signals, IEEE Trans. Signal Process., vol. 43, pp. 31663177,
Nov. 1994.
[6] H. I. Choi and W. J. Williams Improved time-frequency
representation of multicomponent signals using exponential

0
0.5

1.5

2.5
3

x 10

[7]
[8]
[9]
[10]
[11]

[12]
[13]

kernels, Proc. IEEE Int. Conf. Acoust., Speech, Signal Process., vol. 37, pp. 862871, Jun 1989.
S. Mallat and Z. Zhang,Matching pursuit with timefrequency dictionaries, IEEE Trans. on Signal Process.,
vol. 41, pp. 33973415, Dec. 1993.
R. A. Altes, Detection, estimation and classification with
spectrograms, J. Acoust. Soc. Am., vol. 67, pp. 12321246,
Apr. 1980
S. Barbarossa, Analysis of multicomponent LFM signals by
a combined Wigner-Hough transform, IEEE Trans. Signal
Process., vol. 43. pp. 15111515, Jun. 1995.
S. Peleg, B. Porat, Linear FM signal parameter estimation
from discrete-time observations, IEEE Trans. Aerosp. Electron. Syst., vol. 27, pp. 607-615, Jul. 1991.
R. Roy and T. Kailath, ESPRIT Estimation of signal
parameters via rotational invariance techniques, IEEE Trans.
Acoust., Speech, Signal Process.,vol. 37, pp. 984 995, Jul.
1989
Tibshirani, Regression shrinkage and selection via the lasso,
J. Roy. Statist. Soc., Series Bvol. 58, pp. 267288, 1996.
S. Barbarossa and A. Scaglione, Product high-order ambiguity function for multicomponent polynomial-phase signal
modeling, IEEE Trans. on Signal Process., vol. 46, pp. 691
708, Mar. 1998.

WVD
MATCHING PURSUIT [15]
CHOIWILLIAMS
SPARSEAF

0.95

0.7

0.9

0.6

PD

NORMALIZED AMPLITUDE

0.2

Fig. 15: TF distribution of bat echolation signal using different


techniques. The fundamental and the first harmonic are sharply
resolved in CTSS-WVD along with suppressing the cross-terms.

VII. REFERENCES

0.8

0.4
2

(c) CTSS-WVD

(d) Chirp 4

Fig. 12: Performance comparison of carrier frequency estimator for


a four component LFM chirp signal with varying SNRs

0.9

0.6

TIME (SECS)

SNR (dB)

(c) Chirp 3

0.8

0
0

0.5

0.85

0.4

0.8

0.3
0.2

CTSSWVD
PHAF
WIGNERHOUGH

0.75

0.1
0

50

100

150

FREQUENCY

Fig. 13: A slice of different


TF distributions along the dotted line shown in Figure 5. The
proposed method has the best
resolution.

0.7
0

SNR (dB)

Fig. 14: Comparison of average probability of detection of a


four component LFM chirp signal with varying SNRs

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Investigating the Origin of the Indian Ocean Geoid Low


Attreyee Ghosh
December 24, 2014

Abstract
This is an ongoing effort to interpret the geoid low in the Indian Ocean just south of the Indian peninsula. Several theories exist regarding the origin of the geoid low, which happens to be the lowest gravity
anomaly on Earth. However, none of them are wholly successful in explaining it. We wish to test different tomography models, both global and regional, as well as different viscosity models to investigate the
source of this gravity low.
Introduction
Very few methods exist that can provide us with information about the deep Earth. One way to learn about
the deep earth is through seismic tomography, which uses seismic waves to image the Earths interior.
Mapping gravity anomalies provides another way of understanding the Earths internal structure. It has
been shown by Hager [1984], Hager and Richards [1989] that the Earths long wavelength geoid is highly
correlated with density models of subducted slabs. Other studies have also shown how the observed geoid
anomalies can be explained by density anomalies in the Earths mantle. Recent satellite images from
GRACE and GOCE missions are yielding a more and more detailed map of the gravity anomalies and
hence a clearer image of the Earths mantle. Two of the most important parameters that control the dynamics of the deep Earth are density and rheology or viscosity of the rocks that make up the Earths mantle.
While we have some knowledge about the density structure from seismic tomography, the viscosity structure is largely unknown and the observed geoid anomalies can be crucial in constraining the viscosity
structure of the Earth.
The lowest geoid anomaly on Earth lies just south of the tip of the Indian peninsula in the Indian
Ocean. Origin of this geoid low is controversial. Several theories have been proposed to explain this geoid
low, most of which invoke past subduction [Chase and Sprowl, 1983; Hager and Richards, 1989; Richards
and Engebretson, 1992; Steinberger, 2000]. But, there is no general consensus regarding the source of this
geoid low. This project aims to investigate the source of this anomaly by using forward models of mantle
convection. The models aim to test various tomography models with different radial and lateral viscosity
variations. A proper reproduction of this gravity anomaly will not only provide a greater understanding
into the density and viscosity structure of the deep mantle, but may also provide insight regarding the role
of chemical composition in the mantle, which at present is poorly understood.
Numerical models of mantle convection
In the past few months, we have explored some preliminary models of mantle convection. These models
use different tomography (density) structures and different structures of radial viscosity variations.

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Figure 1: Predicted global geoid height from S20RTS tomography model


with radial viscosity structure.
All these models were run using the HC code
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[Hager and OConnell, 1981; Milner et al., 2009],


which is a semi-analytical code that solves the
equations of conservation of mass and momentum

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as well as the constitutive equation between stress

30

and strain rate. Of the models run so far, a few of


0

them yield a better fit to the global geoid (Figure

1) as well as to the Indian Ocean geoid low (Fig


2). The next step would be to run models of higher
30

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complexity, such as those with lateral strength variations, using the parallel finite element mantle con-

Tomography: s20rts,Viscosity:Visc_D
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vection code CitcomS, which we have just success-

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fully installed on one of the SERC supercomputers.

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Figure 2: Geoid anomaly zoomed over the Indian


Ocean region from the same model as in Figure 1.

Acknowledgement
The above work has been accomplished with the help of project assistant Ms. Shree Sumanas Badrinath.

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References
Chase, C. G., and D. R. Sprowl, The modern geoid and ancient plate boundaries, Earth Planet. Sci. Lett.,
62, 314320, 1983.
Hager, B. H., Subducted slabs and the geoid: Constraints on mantle rheology and flow, J. Geophys. Res.,
89, 60036015, 1984.
Hager, B. H., and R. J. OConnell, A simple global model of plate dynamics and mantle convection, J.
Geophys. Res., 86, 48434867, 1981.
Hager, B. H., and M. A. Richards, Long-wavelength variations in Earths geoidphysical models and
dynamic implications, Phil. Trans. R. Soc. Lond., 328, 309327, 1989.
Milner, K., T. W. Becker, L. Boschi, J. Sain, D. Schorlemmer, and H. Waterhouse, The solid earth research
and teaching environment: a new software framework to share research tools in the classroom and across
disciplines, EOS Trans. AGU, 90, 12, 2009.
Richards, M., and D. Engebretson, Large-scale mantle convection and the history of subduction, Nature,
355, 437440, 1992.
Steinberger, B., Slabs in the lower mantle - results of dynamic modelling compared with tomographic
images and the geoid, Phys. Earth Planet. Int., 118, 241257, 2000.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Evolution of Mesoproterozoic suture zones western India:


Implications on India-Madagascar correlations
C. Ishwar-Kumar and K. Sajeev

Abstract-The Kumta suture zone in western


India is in the point of paleogeographic
study of India and Madagascar. The ca.
1300 Ma Kumta suture separates the
Karwar and Dharwar blocks within the
western Dharwar craton of India (IshwarKumar et al., 2013a). Towards the east the
Sirsi shelf is unconformable on gneisses of
the Dharwar craton and towards the west
the Karwar block is mainly composed of
undeformed
tonalite-trondhjemitegranodiorite (TTG) with enclaves of
amphibolites. The TTGs from Karwar
block have U-Pb zircon magmatic ages of
ca. 3200 Ma (Ishwar-Kumar et al., 2013a).
The Coorg block mainly contains ca. 3200
Ma granulite grade rocks and separated
from Dharwar craton by ca. 1200 Ma Coorg
(Mercara) suture (Chetty et al., 2012;
Ishwar-Kumar et al., 2013b; Santosh et al.,
2014). Integration of the structural,
geological and geochronological results
suggests the presence of a 1300-1200 Ma
suture in western India, which is possibly an
eastern extension of the Betsimisaraka
suture zone in Madagascar.
I.

(1e.g., Yoshida et al., 1992; Mishra et al.,


2006; Grantham et al., 2008), and in particular
Eastern Gondwana (Yoshida, 1995; Meert,
2003a; Collins and Pisarevsky, 2005). For
example, much effort has been applied to
finding ways to convincingly re-unite
Madagascar and India (e.g., Katz and Premoli,
1979; Agarwal et al., 1992; Windley et al.,
1994; Yoshida et al., 1999; Torsvik et al.,
2000; Collins et al., 2007a).

INTRODUCTION

The amalgamation of Gondwana


supercontinent in the period 590-550 Ma and
its subsequent fragmentation into the
continental blocks of India, Madagascar,
Australia, Africa, Sri Lanka, South America
and Antarctica were key tectonic events in the
earth history (Fig. 1). Much multi-disciplinary
research in the last few decades has been
focused on finding tectonic criteria to
satisfactorily link, match and thus re-assemble
the separated blocks into their former parent

Fig. 1. Map showing the assembly of Eastern


Gondwana (after, Meert, 2003) consists of
India, Madagascar, Sri Lanka, Antarctica,
Australia, Congo craton and Kalahari craton.
The study area India and Madagascar lies in
the central part of Eastern Gondwana.
The position and morphological
relationship of India relative to Madagascar in

ISTC/CEAS/SJK/291

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the past is one of the most debated and current


problems in understanding the tectonics of
eastern Gondwana (e.g., Katz and Premoli,
1979; Collins and Windley, 2002; Braun and

Fig. 2. The regional geology map of southern


India (modified after, Geological Survey of
India, 2005), overlaid by reclassified shear
zones. The rectangles show the detailed study
area Karwar region and Coorg region.
Acronyms: KSZ- Kumta Shear Zone, ChSZChitradurga Shear Zone, MeSZ- Mettur Shear
Zone, KolSZ- Kolar Shear Zone; NSZNallamalai Shear Zone, MSZ- Moyar Shear
Zone, McSZ- Mercara Shear Zone, BSZBhavani Shear Zone, SASZ- Salem Attur
Shear Zone, CaSZ- Cauvery Shear Zone,
PCSZ-Palghat Cauvery Shear Zone, ASZAchankovil Shear Zone.
Kriegsman, 2003; Ghosh et al., 2004; Collins
and Pisarevsky, 2005; Collins, 2006; Ashwal
et al., 2013; Gibbons et al., 2013; IshwarKumar et al., 2013; Rekha et al., 2013). The
breakup of Gondwana started with the roughly
simultaneous
rifting
of
Madagascar,
Seychelles, India, Antarctica and Australia
from Africa at around ca. 150 Ma. Then,
Madagascar, Seychelles and India separated
together from Antarctica and Australia at
about 128-130 Ma (Biswas, 1999).

II.

GEOLOGICAL BACKGROUND

The period between the assembly of


Rodinia and its break-up to form the
Gondwana
supercontinent
in
the
Neoproterozoic marks an important stage in
the tectonic history of southern Peninsular
India. The position and morphological
relationship of India relative to Madagascar in
the past is one of the most debated and current
problems in understanding the tectonics of
eastern Gondwana (e.g., Katz and Premoli,
1979; Collins and Windley, 2002; Braun and
Kriegsman, 2003; Ghosh et al., 2004; Collins
and Pisarevsky, 2005; Collins, 2006; Ashwal
et al., 2013; Gibbons et al., 2013; IshwarKumar et al., 2013; Rekha et al., 2013, 2014;
Ratheesh-Kumar et al., 2014).
Katz and Premoli (1979) suggested
that crustal-scale tectonic lineaments/shear
zones/suture zones across the continental
fragments are one of the major tools that can
be used for paleo-geographic reconstruction,
based on which they proposed a correlation
between India andMadagascar.

Fig. 3. Sample locations and structural


lineaments overlayed on the geological map of
the Karwar block (modified after Geological
Survey of India, 1993, 1996 and 2005;
structural lineaments were extracted from
Landsat ETM+ satellite imagery and ASTER
digital elevation model).

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Following this study, several workers


attempted to place India and Madagascar into
the Gondwana reconstruction, based on
regional
lithological,
structural,
geochronological,
geochemical
and
geophysical evidence (e.g., Agarwal et al.,
1992; Windley et al., 1994; Windley and
Razakamanana, 1996; Collins and Windley,
2002; Raval and Veerasamy, 2003; Ghosh et
al., 2004; Raharimahefa and Kusky, 2006,
2009; Ishwar-Kumar et al., 2013b; Rekha et
al., 2013, 2014; Rekha and Bhattacharya,
2014; Ratheesh-Kumar et al., 2014). However,
the many and varied models have led to
considerable inconsistency, mismatch and
disagreements about specific correlations.
Some of the reasons for this inconsistency
arevariation in age and exact position/extent of
the shear/suture zones, problems with
bathymetry, and the variation or distortion in
scale, among other factors.
III.

(1998). Zircons from each sample were


mounted together with standards in an epoxy
resin disc that was polished to obtain crosssections through the grains. Prior to the U-Pb
analyses, the mount was cleaned and coated
with 40 thickness of gold. To determine the
internal structure of individual grains and to
identify suitable analytical sites, backscattered
electron (BSE) and cathodoluminescence (CL)
images were obtained using a scanning

ANALYTICAL TECHNIQUES

A. Electron Microprobe Analysis


Chemical analyses of all the minerals
were obtained using an electron microprobe
analyser (JEOL JXA-8900R microprobe)
housed at the Okayama University of Science,
Japan and by JXA-8530F at the University of
Tsukuba, Japan. The analyses were performed
under conditions of 15-20 kV accelerating
voltage, 10-12 nA sample current and a spot
size of 3 m. The data were regressed using
the oxide-ZAF correction method. Natural and
synthetic silicates and oxides were used for
calibration. All the major minerals were
analysed for SiO2, TiO2, Cr2O3, Al2O3, FeO,
MgO, MnO, CaO, Na2O, and K2O.
B. SHRIMP U-Pb zircon geochronology
and zircon Lu-Hf isotopic analysis
Zircon U-Pb dates were obtained
using a sensitive high-resolution ion
microprobe (SHRIMP II) at Curtin University,
Australia. Analytical procedures for the U-Pb
analysis followed those outlined by Williams

Fig. 4. P-T phase diagram modeled using the


calualted bulk composition of quartz-phengite
schist (IK-2302L) in the SiO2-TiO2-Al2O3FeO-MnO-MgO-CaO-Na2O-K2O-H2O
chemical system.
electron microscope (SEM; JEOL JSM-5900
LV) at Curtin University. To obtain the SEM
images a 0.2nA electron beam current and a
15kV acceleration voltage was used on the
gold coated mounts. For SHRIMP analyses, an
O2 primary ion beam of 2 nA intensity was
utilized to sputter the analytical spot of 2530m diameter. The zircon standard BR266
with a 206Pb/238U age of 599 Ma (Stern, 2001)
was used as external standard to correct
instrumental mass bias and isotopic
fractionation. A correction for common Pb
was made on the basis of the measured 204Pb
and the model for common Pb compositions
was that proposed by Stacey and Kramers
(1975). The U-Pb data were reduced using the
SQUID 2 and Isoplot 3 software (Ludwig,
2003, 2005). Uncertainties reported for

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individual analyses are at the 1 level, and for


pooled ages they are at the 95% confidence
level. In situ zircon hafnium isotopic analysis
was carried out at the Institute of Geology

Fig.5.a. Representative cathodolu-minescence


images of quartz-phengite schist (IK-2302L)
illustrating zircon structures. b. SHRIMP U-Pb
zircon
concordia
plot.
Inset
shows
representative CL images for zircons for each
sample, probability density graph for quartzphengite schist and bar chart.
and Geophysics, Chinese Academy of
Sciences, Beijing. Sites previously dated by
SHRIMP were selected for Lu-Hf analyses,
and the measurements were performed using a
Neptune MC-ICPMS, fitted with a 193 nm
ArF laser, with spot sizes 40-50m and laser
repetition rate of 8 Hz at a laser power of 100
mJ/pulse. Analytical and data correction
procedures were as described by Wu et al.
(2006). To calculate the 176Lu/ 177Hf ratio,
interference of 176Lu on 176Hf was corrected by
measuring the intensity of the interference free
175
Lu, by using the recommended 176Lu/175Lu
ratio of 0.02669 (DeBievre and Taylor, 1993).
To calculate the 176Hf/177Hf ratio isobaric
interference of 176Yb on 176Hf was corrected by
using the 176Yb/172Yb ratio of 0.5886 (Chu et

al., 2002). Each ten analysis were bracketed by


analyses of standards Mud Tank and GJ-1.
IV.

RESULTS

A. P-T evolution
A metamorphic pressure temperature
estimation has done for quartz-phengite schist
from the Kumta suture (Fig. 3). The mineral
pair phengite quartz is stable in all fields
(Fig. 10) and kyanite is stable on the highpressure/temperature side. Chlorite appears
when the pressure drops and chloritoid
disappears at an even lower pressure.
Lawsonite is stable only in the lowtemperature/high-pressure corner of the phase
diagram (Okamoto and Maruyama, 1999).
There are no significant variations in the
composition of phengite in Kumta suture
samples. Based on the assemblage (phengitequartz-rutile-chlorite-chloritoid-H2O) and the
XMg-XNa composition of phengite, the quartzphengite schist is calculated to have been
stable at c. 13 kbar at 525C (Fig. 4). The
presence of fine-grained alluminosillicates
(sillimanite/ kyanite) in the phengite matrix
(Fig. 4) (revealed by X-ray elemental mapping
using a field emission microprobe) extends the
P-T segment into the kyanite stability field.
Thus, based on the present composition, the
rock exhumed from a P-T condition of c. 18
kbar and 550C (Fig. 4) in the eclogite facies
and underwent re-equilibration in the
amphibolites facies (Liou et al., 1998; Oh and
Liou, 1998). Such a P-T evolution provides
confirmation that the Kumta suture is sited on
a subduction zone, which was capable of such
subduction and exhumation.
B. Timing of metamorphism
Zircons from quartz-phengite schist
(IK-110123-02L) sample have rounded to subrounded morphology (grain size <100 m) and
no metamorphic overgrowths (Fig. 5a). These
are detrital zircons with no metamorphic rims.
A total of 32 zircon grains were analyzed, 14
spots out of 32 spots in 14 zircon grains were

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used. The zircons from quartz-phengite schist


(IK-110123-02L) sample gave mainly four age
populations, ca. 2993 Ma, ca. 3101 Ma, ca.
3126 Ma, and ca. 3280 Ma (Fig. 5b). The
lower intercept ages ranges from 1000-1200
Ma and used to broadly constrain the timing of
metamorphism (Ishwar-Kumar et al., 2013).

Metasedimentary rocks from the Mercara


suture show prominent Paleoarchean to
Mesoproterozoic sources. The lower intercept
of zircons in all rocks suggest a metamorphic
event during the mid- to late

Fig. 7. A Hf (t) vs. U-Pb zircon age


(207Pb/206Pb age) plot for the metasedimentary
samples from the Kumta and Mercara suture
zones.
Mesoproterozoic (Fig. 6). Surprisingly, all the
zircons from samples KR23-20C, KR23-20K
and KR23-20F fall on a common discordia
line, suggesting source rocks of a similar age.
However the spread in Hf (t) values indicates
arrange from juvenile to ancient protolith
materials, suggesting either magma mixing or
a variety of rock-types with a similar age. The
hafnium isotopic compositions suggest that the
sediments were derived from mixed sources
including both juvenile and recycled
continental crust. The Hf (t) vs. U-Pb zircon
age (207Pb/206Pb age) plot defines a major
distribution along the 3.0 to 4.0 Ga Archean
crustal growth line (Fig. 7).
V.

Fig. 6. Concordia LA-ICPMS U-Pb plots of


zircons. a.. KR23-20C- Garnet-biotite-kyanitegedrite-cordierite gneiss. b. KR23-20KGarnet-biotite-kyanite gneiss. c. KR23-20FGarnet-biotite-hornblende gneiss.

DISCUSSION

Based on the present results from


western India and eastern Madagascar,
integrating with published results, we propose
a close-fit correlation between India and
Madagascar. The Betsimisaraka suture zone is
mainly composed of paragneisses (with
common augen, cataclastic and mylonitic
fabrics) associated with pelitic mica schists

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containing
garnet,
staurolite,
kyanite,
sillimanite and graphite) (Hottin, 1969; Collins
and Windley, 2002). The metasedimentary
rocks enclose abundant mafic-ultramafic
lenses. These rocks and relations can be
correlated with those of the Kumta and
Mercara suture zones that include quartzphengite schist, chlorite schist, garnet-biotite
schist, marble and amphibolite- to granulitefacies garnet-, kyanite-, sillimanite- and
quartz-, feldspar-bearing paragneisses with
metagabbro and calc-silicate granulites.
The Betsimisaraka suture zone of
northeastern Madagascar (Krner et al., 2000;
Collins and Windley, 2002; Collins et al.,
2006) correlates with the Kumta suture zone of
southern India (Ishwar-Kumar et al., 2013).
The southern end of the Betsimisaraka suture
of Madagascar extend into the Mercara suture
zone (Reported as Coorg suture zone in
Ishwar-Kumar et al., 2013 and same suture
mentioned as Mercara suture zone in Santosh
et al., 2014. But since the block is named as
Coorg block, suture is hereafter named as
Mercara suture zone (McSZ)) of southern
India (Ishwar-Kumar et al., 2013). The
Palghat-Cauvery shear zone of southern India
has been correlated with the Neoproterozoic
Angavo shear zone of Madagascar, and the
Tranomaro shear zone of the southern
Madagascar has been correlated with the
Achankovil shear zone of southern India.
VI.

CONCLUSIONS AND FUTURE


WORK
Structural and regional geological
evidence suggest the presence of shear zones
in western India. Textural evidence and
metamorphic P-T estimations for the
metasedimentary rocks suggest that the
sediments were subducted to depths of about
40-50 km depth, and were later exhumed.
The zircon SHRIMP and LA-ICPMS
U-Pb geochronology of metasedimentary
rocks from the Kumta and Mercara suture
zones suggest a common metamorphic event
in the Mesoproterozoic.

Integration of results with published


data indicates that the Archean blocks in
western Peninsular India were sutured during
the Mesoproterozoic. We therefore propose
that the Kumta and Mercara sutures are the
eastern extension of the northern and southern
parts of the Mesoproterozoic Betsimisaraka
suture of north-eastern Madagascar.
There are several challenges still exist in this
field and needs more detailed study in future.
A. Variation in metamorphic grade of
Karwar and Coorg region
The
Kumta
suture
contains
amphibolite- to greenschist-facies schistose
rocks and the Mercara suture contains
amphibolite- to granulite-facies rocks. The
Karwar block on the western side of the
Kumta suture contains ca. 3200 Ma TTG
gneisses with enclaves of amphibolite (IshwarKumar et al., 2013b). The Coorg block on the
western side of the Mercara suture consists of
ca. 3200 Ma gneisses and ca. 3200
charnockites with enclaves of amphibolite and
mafic granulite (Santosh et al., 2014). The
Coorg block can be considered as a high-grade
equivalent of the Karwar block, and the
Mercara suture as the high-grade equivalent of
the Kumta suture, with deeper crust exposed in
the Coorg area.
B. Extension of the BetsimisarakaKumta-Mercara suture zone
The northern and southern ends of
Betsimisaraka suture in eastern coast of
Madagascar are correlated with the Kumta and
Mercara suture respectively. However, the
further continuation of Mercara suture zone is
unclear. The N-S trending eastern end of
Mesoproterozoic Mercara suture zone is
structurally discordant with NNW-SSE
trending Moyar shear zone. The Moyar shear
zone is proposed as early Paleoproterozoic
suture by Plavsa et al. (2014). The detailed
study including structures and geochronology
are required to understand this problem.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Estimation of soil hydraulic properties in a catchment using agro-hydrological


models and microwave remote sensing
K. Sreelash, M. Sekhar, S. K. Tomer, S. Bandyopadhyayand M.S. Mohan Kumar
AbstractThis paper illustrates with results the
methodology of estimating multilayered soil
hydraulic properties by inversion of a crop model
using surface soil moisture and crop bio-physical
parameters from microwave remote sensing data.
Crop biophysical parameters such as leaf area index
(LAI) and above ground biomass are sensitive to the
properties of the root zone soil and hence these
observations can be useful for estimating the
properties of deeper soil layers. We used the radar
vegetation index (RVI) and a parametric growth
curve of LAI to estimate LAI from radar data. The
surface soil moisture (SSM) for vegetated areas is
estimated using the water cloud model (WCM). The
LAI and SSM estimated from RADARSAT-2 data
are then used to estimate multilayered soil hydraulic
properties by inversion of STICS crop model. The
methodology is tested with marigold crop at
AMBHAS field site (www.ambhas.com) for different
soil and climate combinations, theresults showthat
the proposed approach is a promising one in
estimating multilayered soil hydraulic properties.
I.

INTRODUCTION

Good estimates of soil hydraulic parameters and their


distribution in a catchment is essential for crop and
hydrological models. Measurements of soil properties
by experimental methods are expensive and often
time consuming, and in order to account for spatial
variability of these parameters in the catchment, it
becomes necessary to conduct large number of
measurements.
K. Sreelashis a CNES post-doctoral research fellow at INRA,
Avignon, France. ragasree02@gmail.com
M. Sekhar, Associate Professor in the Department of Civil
Engineering, IISc, Bangalore. sekar.muddu@gmail.com
S. K. Tomer is a post-doctoral research fellow at CESBIO,
Observatoire Midi-Pyrenees, Toulouse, France.
M.S. Mohan Kumar is a Professor in the Department of Civil
Engineering, IISc,Bangalore.
S. Bandyopadhyay is a scientist at EOS, ISRO headquarters at
Bangalore.

Estimation of soil parameters by inverse modelling


using observations on either surface soil moisture or
crop variables has been successfully attempted in
many studies, but difficulties to estimate root zone
properties arise for heterogeneous layered soils.
Inverse modeling has been extensively used at
column scale (Kumar et al., 2010) but the spatial
variability of the parameters and insufficient data sets
restricted its applicability at the catchment scale
(Vereeckenet al. 2008).
Montzkaet al. (2011)
demonstrated the possibility of estimating the soil
hydraulic parameters using remotely-sensed surface
soil moisture measurements by applying a sequential
filtering technique to the mechanistic soil-water
model HYDRUS 1-D.However, this approach is not
applicable for multilayered soils without soil
moisture measurements of the deeper horizons. Ines
and Mohanty (2008) used the assimilation of nearsurface soil moisture in a crop model and concluded
that additional soil moisture data from deeper depths
may be needed to better estimate the hydraulic
properties of layered soils. Vereeckenet al. (2008)
indicated that the use of surface soil moisture
measurements alone is not sufficient to provide
unique and physically reasonable estimates of
hydraulic properties at the field scale.
Crop variables such as LAI and biomass are sensitive
to the properties of the soil horizons belonging to the
root zone and hence these observations could be
useful for estimating soil properties of deeper
horizons. Recently, Jana and Mohanty (2011) showed
that using remote sensed crop variables (LAI) in
addition to classical soil texture data improved
estimation of soil hydraulic parameters (SHPs) by
pedo-transfer functions. Remotely sensed data of
crop variables have been used to estimate soil
parameters of crop models. Varellaet al. (2010)
performed the inversion of a crop model using LAI
and yield at harvest to estimate soil parameters in a
two-layer soil system and concluded that the
estimation of parameters related to soil water content
and soil depth could be significantly improved as

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compared to prior information especially when water


stress. Charoenhirunyingyos et al., (2011) and
Sreelash et al., (2012) showed that a combination of
crop and soil moisture variable can provide good
estimates of soil water content parameters.
Availability of remote sensed information of surface
soil moisture and leaf area index makes this approach
applicable at a larger scale.
Microwave methods have extensively been used to
characterize biophysical crop parameters. Many
studies have shown that there is a clear
interdependence between biomass, LAI and observed
backscattering coefficients from active microwave
systems. Leaf area index and biomass can be
estimated from microwave remote sensing data using
the radar vegetation index (RVI). RVI has been found
to one of the promising approaches in estimating the
crop biophysical parameters and our initial studies
showed good correlation between RVI and LAI.A
number of studies have been carried out to
investigate the relationship
between radar
backscattering and soil moisture for different study
areas. Various theoretical and empirical models have
been developed to retrieve the soil moisture from
active microwave data. The major challenge to the
theoretical and empirical models is the modeling of
backscatter behavior under the vegetation canopy. A
model which is frequently used in the modeling of
soil moisture in vegetated areas is the water-cloud
model (WCM) (Attema and Ulaby, 1978). The
variations in the canopy descriptors used in the
models that describe canopy backscattering are due to
the complexity of vegetation structure and relative
simplicity of the models. The parameters of the
WCM depend on the crop and soil type, and it is
necessary to calibrate the WCM for site specific
conditions using suitable vegetation descriptors.
In this study we illustrate and test the methodology of
estimating multilayered soil properties by inversion
of a crop model using the generalized likelihood
uncertainty estimation (GLUE) approach. The
approach of estimating LAI from RVI using the
parametric growth curve approach is also discussed.
Calibration of WCM is carried for site specific crops.
Estimability of multilayered soil properties is tested
for marigold crop in different soil and climate
combinations.

II. EXPERIMENTS, DATA AND MODEL


The experiments were carried out on several
agricultural plots of approximately one hectare in size
in the Berambadi watershed, 84 km2area (AMBHAS
Research Observatory, www.ambhas.com) located in
the Kabini river basin in South India, which is an
experimental watershed for carrying out agrohydrological, remote sensing and hydrological
investigations. The main crops are turmeric,
sunflower, maize, marigold, sugarcane, finger millet,
groundnut etc. Soil and crop related measurements
were performed during the cropping season from
May- 2011 to Dec-2013. Surface soil moisture,
profile soil moisture (PSM), leaf area index (LAI)
and above-ground biomass were measured at ten day
frequencyfrom the sowing to harvest and yield was
measured at harvest date.
Table 1.Activities in the experimental plots.
Duration of crop growth (in days): 100 (May to August)
No of plots monitored: 26
Measures Variables: SSM, PSM, LAI, biomass, yield.
Frequency of measurements: 10 day frequency
Satellite Data: RADARSAT-2, 4 images in 2011
3 images in 2012 and 3 images in 2013

STICS crop model (Brisson et al., 2008) is used in


this study. STICSis a dynamic, daily time-step model
which simulates the functioning of a soil-crop system
over a single or several successive crop cycles.
STICS simulates the daily carbon balance, the water
balance (evaporation and transpiration) and the
nitrogen balance in the system, which makes it
possible to calculate both agricultural and
environmental variables in a variety of agricultural
situations. STICS model has been calibrated for the
crops specific to the study area.
II. LAIFROM RADAR DATA
RVI (Kim and Van Zyl, (2009) has been proposed as
a method for monitoring the level of canopy growth
variables like LAI, biomass and VWC. RVI is near
zero for a smooth bare surface soil and increases as a
crop grows. In this study we used the parametric

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growth curve described in the previous section to


develop the RVI growth curve, since RVI represents
the LAI growth characteristics of the crop in some
form.
The RVI is given by
=

8
+ 2

(1)

whereHV is the cross-polarization backscattering


cross section and HH and VV are the co-polarization
backscattering cross sections represented in power
units. RVI generally ranges between 0 and 1 and is a
measure of the randomness of the scattering. RVI is
near zero for a smooth bare surface and increases as a
crop grows (up to a point in the growth cycle).
We used the standard Parametric Growth Curve
(Baret, 1986) which reproduces the time variations of
canopy variables like LAI, biomass and vegetation
water content (VWC). The growth curve for the
vegetation variable LAI is based on five parameters
(K, a, b, Ti and Tf) and is given by
1
() = [
1 + exp(() )

exp(() ))

(2)

Where K is related to the amplitude of the LAI


variations, a and b are responsible for the trend of the
crop growth and senescence and the time parameters
Ti and Tfcorresponds to the temporal characteristics
of the growth curve. The time related parameters Ti
and Tfto be constant for all plots in a particular year.
The LAI growth curve for each field plots are then
generated using the parametric growth curve by
estimating the values of a, b and K using the field
observed LAI values.

1 + exp( )

exp( ))

() = ()

(4)

Where defines the relation between K and .

The value of K, depends on the maximum LAI of the


crop and hence the can be expected to be a
function of the maximum value of RVI.
IV. SSM FROM RADAR DATA
In the general form the WCM (Attema and Ulaby
1978) for a given incidence angle ican be expressed
as a linear combination of backscattering by
vegetation and backscattering by soil and is given by
the following equation,

=
+ 2

(5)

= 1 (1 2 )

(6)

2 = exp(22 )

(7)

is the co-polarized total backscatter


Where

is the backscatter contribution of the


coefficient,

soil surface,
is the backscatter contribution of
the vegetation cover, expressed as,

and 2 is the two attenuation by the vegetation,


expressed as,

Where A and B are the vegetation parameters, 1 and


2 are the vegetation descriptors.

The RVI growth curve can be expressed as,


() = [

RVI growth curve corresponds to parameters a, b,


and of the LAI growth curve. These parameters
can be estimated using the time series of RVI
data.The shape of the RVI growth curve will be
similar to that of the LAI growth curve, since the
parametric growth curve is used in both cases. The
relation between the LAI and RVI growth curve now
depends on the amplifying factor K and , and the
relation can be established as

(3)

In this equation represents the amplitude of the


RVI variations similar to the parameter K in the LAI
growth curve. The parameters,, and of the

Following Lievens and Verhoest (2011), the


combination 1 = and 2 = is used in this
study primarily because of the interest to estimate
soil moisture and LAI for each vegetation and
experimental plots can be retrieved using RVI as
discussed in the previous section. The parameters A

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and B are obtained through nonlinear regression or


least square fitting approach.

The underlying soil contribution


can be
evaluated from a surface scattering model or, more
simply, from a linear function of its soil moisture .

= +

(8)

The parameters C and D are obtained with linear


model fitting.

of LAI and RVI values retrieved from RVI. It was


observed that the slope parameters and temporal
characteristics of LAI and RVI curves modeled by
Eq.(2) and (3) were close to each other, whereas the
amplification factor K and K varied with plot. The
kvalues for each field plots are estimated. The values
of k varied from 3.8 to 5.2 for field. The observed
LAI growth curve and the RVI growth curve
modeled using Eq. (2) is shown in Fig.1 along with
the corresponding observed values (median and
standard deviation of all plots.

V. SOIL PARAMETERS FROM RADAR DATA


Parameter estimation by inversion of a dynamic crop
model like STICS is a complex process, since such
models involve parameter interactions and hence
obtaining a single optimum soil parameter set is not
realistic. Generalized Likelihood Uncertainty
Estimation (GLUE) (Beven, 2008) an informal
Bayesian method using prior information about
parameter values for estimating model parametersis
used for the parameter estimation process. The sum
of absolute errors (SAE),is used in this study as the
likelihood measure.
The likelihood SAE is
calculated for each variable considered in the
inversion for each model run as,

= y
=1

= 1

Figure 1: RADARSAT-2 retrieved RVI and the RVI


growth curve, observed LAI and LAI growth curve
for Marigold crop (2011).

(9)

where,
is the sum of the absolute errors for any
parameter set k, k=1,N (N being the number of
ensembles, 20000 in this study), variable i, i = 1 to n
corresponding to each variable considered with n
being the total number of variables, and measurement
date j, j=1,,Mi (Mi being the total measurements for
the variable I) is the simulated value of the variable
for the (i,j)th parameter set and y is the measured
value of the variable. The parameters related to soil
water storage characteristics such as field capacity,
wilting point and thickness of soil layer are estimated
in this study.
V. RESULTS AND DISCUSSIONS
The parameters of Eq. (2), (3) and (4) are estimated
using the GLUE approach using the observed values

Figure 2: Scatter plot of observed LAI and LAI


estimated from RVI for different days after sowing
(DAS).

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Using Eq. (2) and Eq. (3) in combination will provide


a time series of LAI from a time series of RVI data.
Fig. 2 shows the scatter plot of observed LAI and the
LAI obtained using the RVI and growth curve
approach for 10, 20, 30, 40, 50, 60, 70, 80 and 90
days after sowing for a marigold crop.
The water cloud model was calibrated for the
marigold crop using LAI and the vegetation
descriptor. The parameters of the WCM A and B are
found to be 4.52 and 0.024 respectively. The
parameter C and D depends on soil type and are
estimated separately for each soil class. The
calibrated WCM was first used to estimate the HH
and then using inversion method the surface soil
moisture was estimated. The estimated HH and the
RADATSAT-2 retrieved HHagreed closely. The
scatter plots of the modelled HHand retrieved
HHshown in Fig. 5(a) and the scatter plots of surface
soil moisture is shown in Fig. 5(b).

The LAI and SSM estimated from RADARSAR-2


data were used to estimate the soil hydraulic
properties of two-layered vertically heterogeneous
soils in the experimental plots. The scatter plot of the
estimated field capacity of both horizons and the
observed values are shown in Fig.4 (a) and (b). The
SHPs obtained from model inversion agrees closely
with the SHPs obtained from field experiments.The
close agreement between the field experiments and
the estimates obtained from inversion of satellite data
shows that this approach has the potential to
estimates soil hydraulic properties at a catchment
scale, since remote sensing data of LAI and surface
soil moisture are available at that scale.

Figure 3 shows the scatter plot of the field capacity


and wilting points of different layers (2 layers in this
study) estimated from field based experiments and
estimates obtained using inversion of satellite LAI
and surface soil moisture.
Figure 3: Scatter plot of (a) HH and (b) surface soil
moisture.

VI. SUMMARY AND CONCLUSIONS

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The approach of estimating multilayered soil


hydraulic properties using remote sensing data is a
promising approach as demonstrated in this study. In
this paper we examined the applicability of the
approach usingmarigold crop. The suitability of the
method for different climatic conditions (low and
high rainfall) is examined using data from three
seasons with different rainfall and water stress
conditions. The approach of estimating LAI from
RVI using the growth curve approach is a promising
method for application in areas with data gaps. The
calibrated water cloud model was found to be
suitable for estimating the surface soil moisture under
vegetated areas.
Acknowledgement: We thank Dr. Laurent Ruiz
(INRA, Rennes), Dr Martine Guerif&DrSamuel Buis
(INRA, Avignon) andDrSamuel Corgne (University
of Rennes)for their technical support and advice at
various stages of the work.
REFERENCES
[1] Attema, E.P.W. and Ulaby, F.T. (1978).
Vegetation modeled as a water cloud. Radio
Science, 13 (2), 357364.
[2] Baret, F. (1986). Contribution au suive
radiomtrique de cultures de crales. Phd Thesis
Submitted to University of Paris South
(Universit Paris Sud).
[3] Beven, K. J., Smith, P., and Freer, J. 2008. So just
why would a modeller choose to be incoherent? J.
Hydrol., 354 (1-4), 1532.
[4] Brisson, N., Mary, B., Ripoche, D., Jeuffroy,
M.H., Ruget, F., Nicoullaud, B., Gate,
P.,Devienne-Baret, F., Antonioletti, R., Durr, C.,
Richard, G., Beaudoin, N., Recous, S.,Tayot,
X.P.D., Cellier, P., Machet, J.-M., Meynard, J.-M.
andDelecolle, R. 1998. STICS:a generic model
for simulating crops and their water and nitrogen
balances.I. Theory and parameterization applied
to wheat and corn. Agronomie 18,311-346.
[5] Charoenhirunyingyosa.,
S,
Hondaa.,
K.,
Kamthonkiatb., D. and Ines., A. V.M. (2011). Soil
moisture estimation from inverse modeling using
multiple criteria functions. Journal of Computers
and Electronics in Agriculture, 75(2), 278287.
[6] Ines, A. V. M. and Mohanty, B. P. 2008. NearSurface soil moisture assimilation for quantifying
effective soil hydraulic properties under different

hydroclimatic conditions. Vadose Zone Journal,


7(1), 39-52.
[7] Jana, R. B. and Mohanty, B. P. 2011. Enhancing
PTFs with remotely sensed data for multi-scale
soil water retention estimation. Journal of
Hydrology, 399, 201-211,
[8] Kim Y. J., and Van Zyl, J. (2009) A time-series
approach to estimate soil moisture using
polarimetric radar data, IEEE Trans. Geosci.
Remote Sens., vol. 47,no. 8, pp. 25192527, Aug.
2009.
[9] Kumar, S., Sekhar, M., Reddy, D. V. and
Mohan Kumar, M. S. 2010. Estimation of soil
hydraulic properties and their uncertainty:
comparison between laboratory and field
experiments. Hydrological Processes, 24, 34263435.
[10] Lievens, H. and Verhoest, N.E.C. (2011). On
the retrieval of soil moisture in wheat fields
from L-band SAR based on water cloud
modeling, the IEM, and effective roughness
parameters. IEEE Geoscience and Remote
Sensing Letters. 8(4): 740-744.
[11] Montzka, C., Moradkhani, H., Weihermuller,
L., Franssen, H.H., Canty, M., Vereecken, H.,
2011. Hydraulic parameter estimation by
remotely-sensed top soil moisture observations
with the particle filter. Journal of Hydrology
399, 410-421.
[12] Sreelash, K., Sekhar, M., Ruiz, L., Tomer, S.K.,
Guerif, M., Buis, S., Durand, P. and GascuelOdoux, C. 2012. Parameter estimation of a twohorizon soil profile by combining canopy and
surface soil observations using GLUE. Journal
of Hydrology. 456-457, 57-67.
[13] Varella, H., Guerif, M., Buis, S. and Beaudoin,
N. 2010b. Soil properties estimation by
inversion of a crop model and observations on
crops improves the prediction of agroenvironmental variables. Europ.J.Agronomy 33,
139-147.
[14] Vereecken, H., Huisman, J.A., Bogena, H.,
Vanderborght, J., Vrugt, J.A. and Hopmans,
J.W. 2008. On the value of soil moisture
measurements in vadose zone hydrology: a
review. Water Resources Research 44.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Tribologgical prop
perties of Polytetraafluoroeth
hylene at ccryogenicc
teemperaturres
D.S.Nadig, V.K.Pavan,
V
P
Paul P Georgge
Abstract
Many cryogenic applicattions like bearrings,
pumps, valves,
v
seals etc cannot be lubricated
d by
conventio
onal means wiith oils and grease
g
becausee the
cryogenicc temperaturee range is farr below the pour
points of these lubrican
nts. For these applications, solid
like
poolytetrafluoroethylene
TFE),
lubricants
(PT
num disulphid
de (MoS2), am
morphous carrbon,
molybden
polymers, etc. are used
d. In this studyy, experiments are
o plain and ccarbon filled PTFE
P
materiaals to
carried on
study th
heir tribologgical propertiies at cryoggenic
temperatu
ure. A cryotriibometer has been
b
designed
d and
developed
d which workss on the princciple of pin on
n disc
wear typ
pe tribometer according too ASTM stan
ndard
(ASTM G 99-95).Both
h plain and caarbon filled PTFE
P
pins
w
were
made to slide for 10 minutes oveer an
abrasive surface rotatin
ng at 400 rpm
m under the applied
1
Experimeents were carrried both at room
r
load of 10N.
and cryoogenic temperatures. The effect
e
of cryoggenic
temperatu
ure on the weaar, frictional foorce and coeffiicient
of friction
n are presented
d.

I. INTRODUCTION
N
N
In many
m
cryogeniic systems, there are interaccting
surfaces with relative motion like bearings, puumps,
valves, seals
s
etc. Thhey cannot be lubricatedd by
conventioonal means liike oils and grease
g
becausee the
cryogenicc temperaturee range is faar below the pour
points of these lubriicants. Thesee componentss are
critical in respect to
t wear andd frictional heat
generatioon. For thesee applicationss, solid lubriccants
like tefloon (PTFE), molybdenum diisulphide (MooS2),
amorphous carbon, polymers, etc. are used.
u
Tribologiical experim
mental data of materialss at
cryogenicc temperaturees are hardly available. Inn the
present experimental
e
sstudy, the focus is on plainn and
carbon fiilled PTFE maaterial. [1]
PTFE
E exhibits a very
v
low coeffficient of fricction
and rettains useful mechanical propertiess at
temperatuures from 133K upto 533K
K for continnuous
use. The crystalline melting point iss at 600K whiich is
much hiigher than m
most of thee semi-crystaalline
polymerss. PTFE is chemically
c
innert and doess not
absorb water and hence exhiibits very good
g
dimensioonal stability.
D.S. Naadig is a Principal Research Scienntist in the Centrre
for Cryogeenic Technology,, IISc., Bangaloree.

nadig@
@ccf.iisc.e
ernet.in
Dr. Pauul George is a Scieentist at Rotor dyynamics &
Tribology Division, LPSC,, ISRO, Valiyamaala

paulpgeorge@yaho
oo.com

The struucture of the polymer com


mposites is a
critical factoor at low temperaturess. The wearr
behaviour off the PTFE coomposite struccture dependss
on the percenntage compossition of carbo
on within. Ass
the temperatuure decreases,, the materiall properties off
the composittes change inndividually. Inn the presentt
study, experiiments are caarried on plaiin and carbonn
filled PTFE materials tto study thee tribologicall
properties botth at room andd cryogenic teemperatures.
II.CRYOTRIIBOMETER
The cryyotribometer has been designed
d
andd
developed baased on the prrinciple of pinn on disc wearr
type tribomeeters suitable for
room
m temperaturee
applications. The test speecimen in the form of a pinn
is made to sliide over the rrotating abrasiive disc underr
the load for the
t fixed timee duration. Du
uring this testt
period, the pin
p wears whiich is clearlyy indicated byy
reduction in length. The difference
d
in lengths
l
of thee
pin before annd after the tesst is a measurre of the wear.
Based on thiss concept, thee pin on disc tribometers iss
developed whhich is in accoordance with the
t guideliness
of ASTM sttandards (ASTM G99-95)).Wear of thee
material is a function of the applied load, rotatingg
speed of the disc,
d
track raddius of the pinn (with respectt
to centre of the disc) andd the friction
n between thee
contacting suurfaces. The schematic off the same iss
shown in the figure 1.

Figure 1. Schem
matic of the pin onn disc tribometer

This conncept is extennded to the deevelopment off


the cryotriboometer where the interfacee between thee
pin and thhe disc is maintained at cryogenicc
temperature using liquid nitrogen (LN2). Thee
schematic off the cryotribbometer is shown
s
in thee
figure 2.

ISTC/CC
CT/DSN/309

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Figure 2. Schematic of the cryotribometer

A motor drives a shaft through a V belt. This


shaft has an abrasive grinding wheel at the bottom.
The test specimen (pin) is made to slide against the
rotating wheel under the effect of applied load of
dead weights. The top end of the pin is connected to
an LVDT. As the pin wears, its length decreases
which is sensed by LVDT. The final displacement of
the LVDT is the actual wear of the test sample.
Frictional force between the pin and disc is measured
with the help of a load cell.
This system can be used to study the tribological
properties at low temperatures by creating a
cryogenic environment with liquid nitrogen. To
facilitate this, the interfacing pin and disc region is
housed within a double walled insulated chamber
produced out of stainless steel (SS304L). Liquid
nitrogen from a pressurised container is made to flow
over the interfacing zone to maintain the cryogenic
temperature. The motorised jack lifts up the insulated
cryochamber upwards so as to form a leak proof
assembly with the top cover of the tribometer.
III.DEVELOPMENT OF CRYOTRIBOMETER
The cryotribometer has been designed and
developed by extending the concept of conventional
pin on disc tribometer to suit cryogenic environment.
The entire system is housed in a metallic frame
of size 700X600X920mm. This tribometer assembly
is mounted to the top cover plate. The frame is
assembled with sufficient stiffness to absorb dynamic
forces developed during tests. The entire assembly is
supported on table top with pads.
A 0.4kW AC motor mounted below the top
cover drives a spindle assembly with a V belt. The
spindle made out of hylam is made to rotate at a
constant speed of 400rpm with the help of reduction

gear box. Hylam is specifically used since it is


compatible with cryogenic environment and exhibits
low value of thermal conductivity and good
mechanical strength properties. This shaft is mounted
on the cover plate with a labyrinth seal housing to
avoid cold leakages. The shaft has circular platform
at the bottom. Abrasive discs or papers of 100mm
diameter can be rigidly held on this platform.
Parallel to this spindle assembly, a plunger is
mounted on the cover plate at an axial distance of
30mm. This plunger made of hylam extends to both
top and bottom of the cover plate and it is housed
within a Teflon labyrinth seal which prevents cold
leaks. The plunger moves up/down freely inside two
stroke bearings enclosed within the bearing housing.
A circular platform is located on the top to hold dead
weights. These dead weights impart pressing force on
the pin against the rotating abrasive disc.
At the bottom of this plunger, test pins of 6mm
diameter and 15mm length can be vertically clamped
on to a holder which is connected with the plunger.
The pin is located at a constant track radius of 30mm
from the axis of the spindle. As the disc rotates at a
constant speed of 400 rpm for the selected time
duration, the pin continuously wears due to the
friction and its length reduces. This reduction is the
total wear.
Wear of the test pin is measured with the help of
an Linear Variable Differential Transducer (LVDT)
which has the maximum sensing limit of 4 mm.
LVDT is fixed vertically in inverted position on the
top cover plate with its spring loaded plunger
pressing against a horizontal reference plate which
is connected with the load carrying plunger. As the
pin wears, the reference plate moves downwards
pushing the LVDT plunger inwards. The continuous
inward movement of the plunger is a measure of
wear.
The frictional force between the pin and abrasive
disc is measured with the help of a button type load
cell which has the maximum sensing limit of 50N.
The frictional force sensor is firmly secured on a
stationary bracket mounted on the plunger. The
frictional force between the pin and disc is directly
transmitted to the sensor through the bracket. Since
the load cell pin is pressed against the sensor, the
frictional force is transmitted to the load cell. The
output readings of the calibrated load cell are the
readings of the frictional force.
This tribometer can be used to study the
tribological properties at cryogenic temperature using
liquid nitrogen and a cryogenic chamber. The
cryogenic chamber made of SS304 is a double walled
insulated cylindrical unit. The space between the
inner and outer vessel is filled with polyurethane

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foam (PUF) to minimise heat in leaks from the


ambient atmosphere.[4]This chamber encloses the
test area comprising of pin and disc. The chamber can
be raised with the help of a motorised jack so that its
top flange butts against the bottom surface of the
cover plate. An O ring is placed between them to
prevent leakage of LN2.The top cover consists of two
ports for inlet and exhaust of LN2, pressure relief
valve, coupling for electrical connections and a
pressure gauge. The motor of the jack is operated by
a portable remote switch.PT 100 sensor is used to
measure the temperature of the test region.
The tribometer is operated and monitored by an
electronic controller. The front panel displays the
wear, frictional force, temperature, speed and time.
Various experimental parameters like duration,
speed, applied load etc can be initialised before start
of the experiment. The graphical and digital output
readings of the tribometer like wear, frictional force,
speed, temperature and time can be continuously
observed on the monitor with a Data Acquisition
System (DAQ) connected with the controller. The
photographs of the cryotribometer assembly and the
pin on disc assembly are shown in figures 3 and 4.

Figure 3. Experimental system

Figure 4. Pin on disc assembly

IV.EXPERIMENTS
In this experimental work, tribological tests were
carried on two types of materials namely plain and
PTFE with 30% carbon composition. Trials were
conducted both at room and cryogenic temperature
using the developed cryotribometer. Large of test
specimens (test pins) with 7 mm diameter and 27mm
length were fabricated from plain and carbon filled
PTFE cylindrical rods. In order to obtain reliable test
results, it was planned to conduct many repeated
trials for various combinations of applied load and
various grades of abrasive emery paper for fixed
speed of 400 rpm, time duration of 10 minutes and
track diameter of 60mm respectively. Initial trials
were conducted with various combinations of 10N,
15N and 20N load and abrasive papers of grade 320,
600, 800, 1000 and 1200. Consistent results were
obtained with applied load of 10N and emery paper
of grade 1000.
The test pins were pre worn with the abrasive
paper with the same experimental parameters to
ensure parallelism between the mating surfaces of the
pin and the paper. This pre run ensures identical
rough surfaces for all the pins before the actual test
run.
Before start of the test run, the pin was securely
clamped on to the pin holder and the abrasive paper
was rigidly held on the top of the circular platform.
After placing the selected dead weight of 10N on the
weight platform, the pin surface was made to come in
surface contact with the abrasive paper. The initial
digital outputs of displacement (wear) and frictional
force were set to zero through the control panel.
Ensuring these set parameters, the tribometer was
switched on for the test duration of 10 minutes. As
the test progressed, continuous data of wear, fictional
force and coefficient of friction displayed on the
monitor were monitored. After the test run for 10
minutes, the output data was stored both in digital
and graphical form for further study and analysis.
The same tribometer was used to carry out the
wear tests in cryogenic environment with the help of
pressurised LN2. The wear takes place within the
space of a cryochamber. The cryochamber was
partially filled with LN2 and allowed to cool and
stabilise for some time. The chamber was raised up
with the motorised jack till its top flange seals with
the bottom surface of the cover plate with an O ring.
Pressurised LN2 was supplied into this chamber
allowing liquid to flow over the pin-disc interface. A
stabilised cryogenic temperature of 98K could be
obtained within the chamber. Wear tests were carried
out following the same procedure adopted for room
temperature tests. These results were compared with
the room temperature data and analyzed.

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V.RESULTS
The tribological behaviour of a material depends
on various factors like wear, coefficient of friction,
frictional force between contact surfaces, roughness
surface, applied load, rotational speed, duration, etc.
As the temperature changes, the material properties
also tend to change and in turn influence the
tribological behaviour. As mentioned earlier, the
emphasis was laid on the influence of cryogenic
temperature on the wear properties of PTFE.
Frictional force is a measure of the actual force
between the rubbing surfaces. This depends on the
applied load and is measured with the help of load
cell. Coefficient of friction is the ratio of the
frictional force to the applied load. This can range
between 0 to1 in the extreme cases. Higher values of
coefficient of friction indicate higher transmission of
applied load to the interfacing surfaces. The total
wear of the material in a wear test depends on the
frictional force and the coefficient of friction.
The wear test results at room and cryogenic
temperature are shown in the following figures 5, 6
and 7.

Wear property of a material depends on the


frictional force and the coefficient of friction in the
interface between the pin and disc assembly. The
results of both coefficient of friction and frictional
force at room and cryogenic temperature are shown
in the figures 6 and 7.

Figure 6. Frictional force at room and cryogenic temperature

Figure 7. Coefficient of friction at room and cryogenic


temperature

Figure 5. Wear at room and cryogenic temperature

PTFE is relatively a soft material. It exhibits low


coefficient of friction and high wear rate. This
limitation of high wear rate is overcome by
impregnating PTFE with carbon since carbon
particles exhibit low wear properties. As the
temperature is lowered to cryogenic zone, strength
and hardness of both PTFE and carbon filled PTFE
increase. [5, 6] Due to these combined effects, the
wear is expected to reduce at cryogenic temperature.
As per the test results, the fall in total wear was
significant for plain PTFE at cryogenic temperature.
Carbon filled PTFE exhibited lower wear at room
temperature as compared with plain material due to
the inherent wear resistance characteristics of carbon
particles. The reduction in wear at cryogenic
temperature was less as compared with the data of
plain PTFE.

Both frictional force and coefficient of friction


are temperature dependent. As compared with plain
material, carbon filled PTFE exhibits lower
coefficient of friction and frictional force at room and
cryogenic temperature. Since both these values are
comparatively lower at cryogenic temperature, wear
should be expected to reduce at cryogenic
temperatures. This effect has been observed by the
reduction in wear at low temperature zone.
VI.CONCLUSION
Experiments have been have been carried to
study the tribological properties of plain and carbon
filled PTFE material at room and cryogenic
temperatures. The results indicated reduction in wear
properties for both plain and carbon filled PTFE at
cryogenic temperature.
There is scope for further research to study the
tribological properties of PTFE at cryogenic
temperature with various percentage compositions of
carbon. It is also worth to extend studies on

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tribological properties of cryotreated PTFE and its


composites at cryogenic temperatures.
REFERENCES
[1]

[2]

[3]
[4]

[5]
[6]

G.Theiler, PTFE and PEEK Matrix composites for


tribological applications at cryogenic temperature and in
Hydrogen,Federal Institute for Materials Research and
Testing,Berlin (2005)
G. Theiler, Friction and wear of PTFE composites at
cryogenic temperature, Tribology International Vol 35,pp
449-458 (2002)
S.K.Biswas, Friction and wear of PTFE a review, Wear
Vol 158,pp 193-211(1992)
T.Gradt et al, Low temperature tribometers and the
behaviour of ADLC coatings in cryogenic environment,
Tribology International Vol 34,pp 225-230, (2001)
Properties Handbook-PTFE, Dupont
Randall F Barron Cryogenic systems, Oxford University
Press (1985)

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Portable Imaging Flow Analyzer for Biological Research Applications


in Space
Veerendra Kalyan Jagannadh and Sai Siva Gorthi
AbstractCell viability assays are performed to assess the
response of a population of biological cells to an external stimuli.
Conventional optical microscopy is one of the standard techniques
used to perform cell viability assay. Due to their bulky nature,
microscopes are not ideal candidates for studying the behaviour
of biological specimen in space. In this article, we report the
use of a portable imaging flow analyzer based on a mobile
phone to perform an automated cell viability assesment of a
given population of yeast cells. With the use of a cellphone
augmented with off-the-shelf optical components and custom
designed microfluidics, we demonstrate a portable optofluidic
digital microscope. We demonstrate an enhanced throughput of
about 450 cells/second, by implementing a multiple microfluidic
channel geometry.
KeywordsPortable Microscopy, Microfluidics, Flow Cytometry,
High-throughput Imaging, Cell viability assessment.

I.

I NTRODUCTION

In the recent past, there has been a significant growth of


interest in studying and understanding behaviour of biological cells in space. Researchers have attempted to perform
cell-culture and tissue engineering experiments in space to
understand the behaviour of biological cells in low-gravity
environments [1][3]. Cell viability assay is a fundamental
method used to study proliferation of cells in a given population subjected to any given external stimuli.
Morphological changes or changes in membrane permeability are used to asses the viability of cells [4][6]. Viability
assays can be loosely classified into two types: analysis of
whole population and analysis of individual cells in a given
population. Assessment of viability on a single cell level
provides a more detailed result, when compared to bulk
measurements carried out on the whole population [5]. The
membrane permeability and/or physiological state is inferred
by assessment of exclusion of certain types of dyes or uptake
and retention of other types of dyes. One of the widely
used viability assessment techniques is the trypan blue dye
exclusion test. It is based on the principle that live cells
with an intact plasma membrane exclude trypan blue; whereas
non-viable cells take up trypan blue as their cell membrane
is not intact and hence, unable to control the passage of
macromolecules through the cell membrane.
In general, optical detection techniques: flow cytometry
and microscopy are employed to asses the dye exclusion or
retention in cells and thereby infer their viability [7]. Both
Veerendra Kalyan Jagannadh is a graduate student at the Department of
Instrumentation and Applied Physics, Indian Institute of Science
Dr. Sai Siva Gorthi is an assistant professor at the Department of Instrumentation and Applied Physics, Indian Institute of Science. E-mailsaisiva.gorthi@gmail.com
STC Project Code - ISTC/IAP/SSG/299/2013

flow cytometry and microscopy are gold-standard techniques


employed in medical diagnostics as well as basic biological research. Flow cytometry enables automated high-speed
quantitative multi-parameter analysis of large population of
cells. In contrast to flow cytometry, microscopy has a simpler
architecture and enables viability assessment of cells via
examination of images of cells smeared on a slide. While
both flow cytometry and microscopy are widely used standard
techniques, their implementation in space / on flight is quite
difficult owing to their bulkyness.
While it is possible to perform cell viability assesment postflight, the availability of compact, low-weight and automated
imaging systems would enable on flight cellular studies and
further the progress of bio-medical / biological research in
space. Some of the recently reported portable microscopes [8]
[13] are relevant in this context. However, these portable microscopes inherit some limitations of conventional microscopy:
requirement of skilled personnel for sample handling and
preparation, need for focus adjustments and manual scanning
of the slide through multiple field of views to acquire images
of larger number of cells on the smear/slide etc.
On the other hand, there has been recent trend of enhancing
the throughput of conventional microscopy with the synergistic
use of optics and microfluidics. These imaging systems are in
general referred to as Imaging Flow Cytometry (IFC) systems
[14], [15]. Most of the reported IFC systems in literature
employed high-speed cameras, which tend to be bulky and
hence are not so ideal for realization of imaging flow analyzers,
which can be used on flight.
Following a similar approach, there have been a few
attempts to develop portable imaging flow analyzers [16],
which employ low weight consumer electronic devices (like
cellphones) for imaging and microfluidics for sample handling.
However, throughputs in these devices are limited by the low
frame rates of acquisition. The possibility of enhancing the
throughput of portable imaging systems with the use of custom
designed microfluidic devices has not been investigated upon
previously.
In this paper, while employing the principles of imaging
flow cytometry, we demonstrate a microfluidics based portable
bright-field imaging system with the use of a cell-phone
and low cost off-the shelf optical components. In this work,
with the use of a multiple microfluidic channel geometry, we
demonstrate the enhancement of throughput in the context
of imaging flow analyzer based on low-frame rate imaging
devices. With the frame rate of acquisition, being only 30
frames per second (fps), we demonstrate a throughput of about
450 cells per second. Further, we demonstrate an important
application of such a portable imaging system by performing
a cell viability assay on a given population of yeast cells.

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Fig. 2. Imaging system characterization using USAF 1951 negative resolution


target. (a)-(c) Images of 1st , 2nd and 3rd elements of the 9th group and their
corresponding line profiles. Length of scale bar is 5 m
Fig. 1.

Schematic of the cellphone based portable microscope.

II.

C ELL - PHONE BASED P ORTABLE D IGITAL


M ICROSCOPE

clogging of the channels/device. The representative schematic


of the microfluidic device is shown in figure 3.

As mentioned earlier, there have been several demonstrations of portable microscopy systems. Most of the previously
demonstrated systems predominantly fall into two distinct
categories, they are lens-based [8], [10][12], [17] and lensfree systems [9]. In this work, we have adopted a lens-based
system, wherein we have used an eye-piece (10X) and a
generic objective (40X, N.A = 0.65) to turn a cellphone into
a microscope. A 3W LED augmented with a ground glass
diffuser (Grit = 600, Diameter = 1 inch) and an aspheric
condenser lens (f = 20 mm, Diameter = 1 inch) have been
used to provide a uniform illumination on the sample plane.
The schematic of the imaging system is shown in figure 1.
A. Characterization of the Imaging System
A 1951 USAF Negative resolution target (Edmund Optics
55-622) has been used to characterize the imaging system. The
system field of view was estimated to be about 180 m
in diameter. The system is easily able to resolve the smallest
feature present on the target, which is a 0.78 m feature
(shown in figure 2). The line profiles across the images of
1st , 2nd , 3rd elements of the 9th group have been shown (figure
2 (c)).
III.

I NTEGRATED M ICROFLUIDIC P ORTABLE I MAGING


S YSTEM

Custom-fabricated microfluidic devices were integrated


into the portable microscope system so as to enable automated
imaging as in the case of a typical IFC system. Conventional
photo-lithography and soft-lithography [18] techniques were
used to fabricate microfluidic devices compatible with the
compact digital microscope. The microfluidic devices were
bonded to microscope cover slips (thickness = 0.13 mm) using
oxygen-plasma treatment, in order to seal the microfluidic
channels. Each device had parallel channels with a width =
20 m, depth = 6 m and an inter-channel spacing of about
60 m . At the inlet of the microfluidic device, a spatial
filter was incorporated so as to filter out particles bigger than
dimensions of the narrow portions of the channel to avoid

Fig. 3.
Design of the microfluidic device. Device consisted of straight
channels which were 20 m wide in the central portion of the device and
48 m at other locations.

An attachment to the cell-phone, for housing the optics


(LED, diffuser screen, condenser and objective lens) and the
replaceable microfluidic device (cartridge) was fabricated. The
attachment consists of a slot (opening), so that inserting the microfluidic cartridge into this slot positions it at the sample plane
of the imaging system. The positioning of the microfluidic
device in the sample plane, enables us to image the biological
specimen flowing through the microfluidic channels of the
device. The image of the fully integrated automated portable
microscope is shown in figure 4.
IV.

S YSTEM T HROUGHPUT C HARACTERIZATION IN F LOW

The achievable throughputs using the portable optofluidic


microscope were investigated by imaging a suspension of
Human Red Blood Cells (RBCs) in flow. The suspension
was flown through the microfluidic device at a flow rate of
about 40 lh1 and the videos of the flow stream were
recorded. Images of different cells were extracted from the
videos using background subtraction and morphological image
processing toolbox of MATLAB. Using the presented system,

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Fig. 4.

Image of the integrated opto-fluidic imaging flow analyzer.

Fig. 6. [Color Figure] Quantitative assessment of staining in the given yeast


cell population. Color and saturation level images of cells corresponding to
different gated regions of the histogram have been shown. Length of scale bar
is 8 m.

Fig. 5. [Color Figure] Imaging system field of view, while imaging the
microfluidic device with lesser inter-channel spacing. Field of View - 196
m 180 m. Length of scale bar is 20 m

we have been able to achieve imaging throughputs of upto


3000 cells per minute. Higher flow rates can be used to
ensure more particles in the field of view and thereby higher
possible imaging throughputs. However, it was observed that
further increase in flow rates resulted in loss of fidelity in
the acquired images due to motion-blur. In order to enhance
the throughput of the system, a multiple channel geometry
with inter-channel spacing about 9.8 m was employed. An
image of the field of view of the optofluidic microscope,
while imaging the device with closely spaced channels is
shown in figure 5. Multiple channels were used in order to
simultaneously image cells flowing across different channels
and thereby obtain an optimally high throughput. Using this
multiple channel geometry and optimizing the concentration
and pumping speeds for the given frame rate and exposure,
we have been able to enhance the throughput of the system to
about 27000 cells per minute.
V.

C ELL V IABILITY A SSESSMENT OF Y EAST C ELLS

In order to demonstrate the relevance of the presented


system to perform cellular studies in space / on flight settings,

we have performed an automated cell viability assay of a


given population of yeast cells. Yeast species Saccharomyces
cerevisiae was cultured in YPD (yeast extract, peptone and
dextrose) (Himedia G037) liquid medium overnight at 37 C
in orbital shaking incubator. The cells were harvested after
incubation by centrifuging at 500g for about 10 minutes.
Harvested cells were resuspended in distilled water. The yeast
suspension of appropriate dilution was divided into two parts
and one part of it was subjected to heating at 55 C for 5
minutes to prepare dead cells. The dead cells were stained
with 5% methylene blue for 10 minutes at room temperature
and were separated by centrifuging at 500g for 10 minutes
and supernatant was discarded. The stained dead cells and the
viable cells were mixed in distilled water. It is known fact that
only dead cells would take up and retain the methylene blue
stain [19].
The suspension of yeast cells was assessed using the
portable optofluidic imaging flow analyzer system. The suspension was flown through the microfluidic device at a flow
rate of about 40 lh1 and the videos of the flow stream were
recorded. A snapshot of the field of view (196 m 180 m),
while imaging the suspension of yeast cells is shown in figure
5. By computationally assessing the color content of the image
of a given cell, we determine its viability status. Since, both
the process of image acquisition and assessment of viability
are automated, errors / variations due to subjective perception
would be reduced to a minimum.
The frames of the video were extracted and processed
using the background subtraction to extract the images of cells
in MATLAB (R2013b, Mathworks Inc.). Images of the cells
extracted from videos were further processed to quantitatively
assess the relative amount of dye retention/exclusion in a given
cell. The saturation (color content) in a given image of cell
was quantitatively assessed by counting the total number of
pixels above the saturation level of the background (of the
image). To get an insight into the distribution of the staining
within the population, the histogram of total number of stained

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pixels for different images has been plotted (shown in figure


6). The histogram corresponds to images of about 4006 cells
corresponding to data recorded for about 9 seconds.

[8]

As it can be understood from the histogram, the cells


present in the gated region (a) are very feebly stained and
have their cell membranes intact, while the cells present in
the other regions allowed the dye to permeate through the cell
membrane and hence, their cell membranes were disrupted to
some extent. Automated assessment of dye exclusion or uptake
and retention provides a quantitative insight into the stage of
cell death over a large population of cells.

[9]

VI.

[10]

[11]

C ONCLUSION AND F UTURE S COPE

In this work, we have presented a cellphone based imaging


flow analyzer for applications in basic biological research
for on flight cellular studies in space. We have presented an
investigation into achievable throughputs with microfluidics
based system-level integrated portable imaging systems, which
employ inexpensive low frame-rate cameras (in our case 30
fps). In addition, we have demonstrated an enhanced throughput of about 450 cells/second with the use of closely spaced
multiple channel geometry. With the use of the presented system, we have performed an automated cell viability assessment
of a given population of yeast cells. Cell viability assessment
is an important technique for use in cytotoxicity and other
cell-based biological research.

[12]

Future work in this approach would involve improving


the design of our microfluidic catridge to perform on-chip
mixing of the stain / dye with the bio-sample [20] to enable
automatation of sample preparation needed for performing
variety of diagnostics and biological assays with the presented
optofluidic imaging analyzer.

[15]

ACKNOWLEDGMENT

[13]

[14]

[16]

[17]

This work was carried out under a project funded by Space


Technology Cell(ISRO-IISc).
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[2]

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[4]
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C. A. Nickerson, C. M. Ott, S. J. Mister, B. J. Morrow, L. BurnsKeliher, and D. L. Pierson, Microgravity as a novel environmental
signal affecting salmonella enterica serovar typhimurium virulence,
Infection and Immunity, vol. 68, no. 6, pp. 31473152, Jun. 2000.
[Online]. Available: http://iai.asm.org/content/68/6/3147
W. Strober, Trypan blue exclusion test of cell viability, Curr Protoc
Immunol, vol. Appendix 3, May 2001.
M. J. Stoddart, Cell viability assays: introduction, Methods Mol. Biol.,
vol. 740, pp. 16, 2011.
S. Johnson, V. Nguyen, and D. Coder, Assessment of cell viability,
Curr Protoc Cytom, vol. Chapter 9, p. Unit9.2, 2013.
A. Kummrow, M. Frankowski, N. Bock, C. Werner, T. Dziekan, and
J. Neukammer, Quantitative assessment of cell viability based on flow
cytometry and microscopy, Cytometry, vol. 83A, no. 2, pp. 197204,
Feb. 2013.

[18]

[19]

[20]

A. Skandarajah, C. D. Reber, N. A. Switz, and D. A. Fletcher,


Quantitative imaging with a mobile phone microscope, PLoS
ONE, vol. 9, no. 5, p. e96906, May 2014. [Online]. Available:
http://dx.doi.org/10.1371/journal.pone.0096906
M. Lee, O. Yaglidere, and A. Ozcan, Field-portable reflection and
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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

PROCESSING OF METALLIC THERMAL INTERFACE MATERIALS USING LIQUID


PHASE SINTERING FOLLOWED BY ACCUMULATIVE ROLL-BONDING
Deepak Sharma1, Rajesh Kumar Tiwari2, Ramesh Narayan P.3 and Praveen Kumar1
1

Department of Materials Engineering


Indian Institute of Science, Bangalore
2
Department of Manufacturing
National Institute of Foundry and Forge Technology, Ranchi
3
MCD / MMG,
VSSC, ISRO P.O., Trivandrum
praveenk@materials.iisc.ernet.in
Abstract This study reports on the processing and
characterization of composite solders, which comprise Cu, a
high-melting phase (HMP) embedded in In matrix, a lowmelting phase (LMP), produced by liquid phase sintering (LPS)
followed by accumulative roll-bonding (ARB). These solders
combine high electrical and thermal conductivities with high
mechanical compliance, and are suitable for a range of nextgeneration thermal interface material (TIM) and interconnect
applications. Following the previously published work, an In40%Cu was found to possess the requisite combination of
compliance and conductivity, we start with effect of different
short sintering periods (30 and 60 s at 160 C each) on
compressive strength and electrical conductivities for both assintered samples and samples processed through 0-10 passes of
ARB. Furthermore, rolling to a high compressive strain (50%)
increases the conductivity without significant increase in flow
stress; these findings prove to be promising for producing novel
TIM for new generation, advanced microelectronic packages.

I. INTRODUCTION
A continuous increase in computational power and the
miniaturization of the modern microelectronic devices, lead a
drastic increase in requirements for heat dissipation via TIMs
which cannot be met by the existing TIMs. Hence, the
packaging of advanced next generation microelectronic
devices demands development of new alloys with (1) high
thermal conductivity, (2) high shear compliance with
moderate compressive stiffness under creep conditions, and
(3) low melting temperature. To simultaneously attain the
above characteristics in a material, a novel composite
architecture, as shown in Fig. 1, composing of a highly
conductive HMP (e.g., Cu, Sn, etc.) uniformly distributed in
highly compliant LMP (e.g., In, Bi, etc.) matrix, has been
proposed and produced via LPS [1-5].

Fig. 1: Schematic of idealized microstructure with a uniform distribution of


HMP and LMP [1].

LPS of a HMP and a LMP above the melting temperature


of LMP has been suggested as a method to produce a
composite with the architecture shown in Fig. 1 [1,6]. A
composite system with Cu as the HMP and In as LMP was

chosen, one of the major advantages associated with In-Cu


system is that Cu is one of the materials with highest (thermal
as well as electrical) conductivity. As indicated in survey [1,
3, 6], current work involves an In-40vol.% Cu composition,
which possess the requisite combination of compliance and
conductivity. Preliminary experiments on Cu-In showed that
thermal conductivity of the composite solders were
significantly greater than that of In, although the flow stress
was high, most probably because of reactions between Cu and
In, and the formation of a solid skeleton structure of the HMP
and intermetallic compounds (IMCs) [6]. However, a critical
observation of the microstructures produced in the previous
works [1, 3, 6] reveals that: (i) the dispersion of Cu particles
was non-uniform in In matrix, resulting in agglomeration of
Cu particles in certain regions; this resulted in non-uniform
compliance (and equivalently, stiffness) and hence pre-mature
failure of the material, and (ii) the minimum thickness of the
Cu-In composites cannot be arbitrarily small, as the thickness
of such a composite is controlled by the diameter of Cu
particles and their agglomerates. These make these materials
unsuitable for the advanced microelectronic packages, which
have space only for few hundred microns thick TIM.
This work addresses the above two challenges by
suggesting implementation of a novel processing route
consisting of a combination of LPS and ARB, which is a
severe plastic deformation (SPD) technique. It is speculated
that ARB will not only flatten the Cu particulates but will also
increase the uniformity in mixing of Cu particles in Indium
matrix. Not only such an approach shows potential to resolve
the above two issues with Cu-In based TIMs, but it also
improve the thermal conductivity of such a composite, in
corroboration with the preliminary finite element analysis [7].
II. EXPERIMENTAL
Spherical Cu powders with average particle sizes of 10 m
and 99.9% purity, were etched using 10% HCl solution for 10
min to remove the native oxide layer. The etched powder was
thoroughly rinsed using deionized water and isopropyl
alcohol (IPA) and dried by storing in vacuum (10-4 torr) for
12 h. An appropriate amount of Cu powder (40% volume
fraction) was mixed with10-40 m diameter, 99.99% pure In
powder by vigorously shaking in a glass-vial inside a glovebox under N2 atmosphere. Subsequently, the mixed powder
was uniaxially compressed by using hydraulic press with a
load of 4 MPa for 45 seconds, in a lubricated hardened steel
die to produce green pellets of 10.1 mm diameter and 1.5
mm height with a relative density of 88 1%. The density
measurement for green pellets was conducted by using
ISTC/MET/PK/0305

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K
LT

(1)

where K and are the thermal and electrical conductivities,


respectively, L is Lorenz number, and T is the ambient
temperature, which was room temperature (i.e., ~303 K) in
the present study.
III. RESULTS AND DISCUSSION
Fig. 2 shows the effect of green density and sintering time
on sintered density of In-40%Cu composite; density values
are given in terms of relative density (calculated by taking
percentage of fully dense or theoretical density of composite
that is 7.962 g/cm3) and densification was calculated by
taking the increase in density relative to initial density. As
shown in Fig. 2, a densification of > 10% occurred when
green density was small (< 85%) and the densification

monotonically decreased with the green density. Higher


densification in these low aspect ratio samples can be
attributed to high heat transfer rate due to large surface area.
A decrease in densification with green density can be
attributed to the decrease in the volume fraction of open pores
which, unlike closed pores, are removed during sintering
process.
12

In - 40 Vol. % Cu
0

Sintered @160 C
Sintering time (s)

Densification (%)

10

60
45
30

8
6
4
2
0

84

85

86

87

88

Relative Green Density (%)

89

90

(b)
Fig. 2: Variation of densification over LPS with relative green density for
different LPS periods.

Fig. 3 shows the effect of ARB on the relative density of


Cu-In composite. Interestingly, ARB did not monotonically
affect the densification of the sintered samples: At first, the
density of the sample decreased; however, then it increased
monotonically approaching almost the as-sintered density. A
decrease in relative density of sample was not expected and
this might be attributed to collapse of apparent well bonded
microstructure of as-sintered sample.
94

In-40Vol%Cu
0

Sintered @160 for 60 s

92
Relative density (%)

geometry method, which was confirmed to be consistent with


that of Archimedes principle.
The green pellets were encapsulated in Al foil, and LPS
was done at 160 C by dipping them in a pre-heated, properly
agitated (using a magnetic stirrer for establishing a uniform
temperature distribution) 400 mL silicone-oil bath for
different lengths of time (30 and 60 s), followed by quenching
in water so as to inhibit the formation of IMCs. Sintered
relative density measurement was performed using
Archimedes principle so as to avoid the errors caused by
possible deviation in cylindrical shape of pellets during LPS.
ARB, ranging from 1 to 10 numbers of passes, and each
imposing a strain of ~50%, were conducted on the sintered
samples. A sintered sample was rolled, sectioned in two equal
halves along the original longitudinal direction, degreased
by generously applying acetone, stacked in such a way that
the surfaces that were originally perpendicular to the
cylindrical axis were lying adjacent to each other, and again
rolled for next cycle.
A few samples were prepared where reduced graphene
oxide (rGO) was placed in between the two surfaces of the
sample prior to the ARB processing. Electrical conductivity
and hence thermal conductivity of these samples were
measured.
Microstructures of the samples were characterized (both of
as-sintered and ARBed samples). The as-sintered pellet was
cross sectioned along transverse direction while the ARBed
samples were cross-sectioned along both transverse and
longitudinal directions. The cross-sections were observed
under a scanning electron microscope (SEM), using
backscattered and secondary electrons (BSE and SE,
respectively), as well as energy dispersive X-ray (EDX)
spectroscopy (FEI Quanta model 200).
The stress-strain behaviour of the LPS solder was
characterized by using an Instron Testing Machine (Instron
5967), which uses a 5 kN load cell to record the applied load.
Finally, the electrical resistivity of the sintered samples were
measured by using a custom designed 4-point Kelvin probe in
conjunction with a nano-voltmeter (Keithley Multi-meter,
Model 2010) to eliminate any contact resistance. Since in
metallic materials, electronic conduction is responsible for
current and heat flow, the electrical and thermal
conductivities are proportional to each other. Thus the
electrical resistivity measurements were used to calculate
thermal conductivity of the composite using WiedemannFranz Law, which is given as follows:

90

88

86

84

Number of ARB passes

Fig. 3: Effect of ARB processing on the relative density of sintered samples.

Fig. 4 shows representative SEM micrographs of assintered samples. As shown in Fig. 4a, a low magnification
micrograph of as sintered sample, the sample consisted of a
few agglomerated regions of cavities or pores (black regions)
and also the distribution of Cu and In was not uniform. The
latter is shown better in Fig. 4b, which is a high
magnification micrograph. A close inspection of Fig 4b also
shows that the bonding between Cu and In may not be very
strong following sintering for 60 s; this may explain the initial
drop in density following the first ARB pass (Fig 3).

(a)
(b)
Fig. 4: SEM micrographs of as-sintered samples produced after LPS for 60
seconds (a) low and (b) high magnification. Images were taken using backscattered electron where dark and bright regions are Cu and In, respectively,
whereas black regions denote pores.

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Fig. 5 shows the effect of ARB processing on the


microstructure of In-Cu samples. A comparison of Figs 4 and
5 readily reveals the following: (i) overall the pore density did
not change in the beginning of the ARB processing, (ii) the
distribution of Cu and In became more uniform with an
increase in ARB passes, (iii) In truly became continuous
matrix where Cu was spread following ARB processing, and
(iv) the interface between Cu and In appears to be free of
pores indicating better contact between Cu and In. While the
outcome (i) is not dersired but the other aforementioned
outcomes of ARB were intended effects.

Fig. 7 shows the effect of sintering time and strain rate on


YS of as-sintered samples. As shown in Fig. 7 that Eq. (2)
aptly captures the effect of strain rate on YS and the assintered In-Cu composites showed significant strain rate
sensitivity. Fig. 7 also reveals that m monotonically
increased with decreasing sintering period. K1 seemed to be
independent of sintering period, this implies that YS,
irrespective of sintering period, would be same if loading rate
was 1, and at very small strain rate, YS would be widely
different.
In - 40 Vol. % Cu
0

Sintered @160 C

30 sec
45 sec
60 sec

YS (Pa)

2 10

10
6
9 10
6

8 10

y = 1.47e+07 * x^(0.066638) R= 0.72987

y = 1.6489e+07 * x^(0.054552) R= 0.98435

7 10

(a)

y = 1.6872e+07 * x^(0.022814) R= 0.94306

6 10

(b)

-5

-4

10

10

-3

-2

10

-1

10

10

10

Strain Rate (s-1)

Fig. 7: Dependence of YS on applied strain rate.

0.2% YS K1m

(2)

where m is strain rate sensitivity and K1 is a constant.


2.5 10

True Stress (Pa)

1.5 10

1 10

5 10

True Stress (Pa)

2 10

1.5 10

45 sec

30 sec

In-40Vol% Cu

Sintering @ 160 C for 30s


ARB Pass: 1 (Strain : 50%)
0

1 10

5 10

-1

10
-3
10
0

0.05

0.1

0.15

0.2

True Strain

0.25

(a)
In-40 Vol.%Cu

3 107

Sintering @ 160 C, 1 pass, strain = 50 %


0

30 sec

(Pa)

45 sec
2 107

107
9 106
8 106

y = 2.3912e+07 * x^(0.10075) R= 0.93768

7 106
6 10

60 sec
2 10

2.5 10

YS

The impact of sintering time on stress-strain ()


behaviour at strain rates varying from 10-3 s-1 to 10-1 s-1 is
shown in Fig. 6. All samples were tested at room temperature
with relative green densities of ~85% and an aspect ratio of
~0.5. Fig. 6 reveals that flow stress of composite increased
with sintering time (this may be attributed to an increase in
volume fraction of IMCs) and also with applied strain rate.
We can speculate some strengthening due to Cu-In interface,
which may act as dislocation source [3]. With few exceptions,
all samples showed significant softening after limited strain
hardening. This indicates that dislocation generation rate was
significantly lower than dislocation recovery. This is due to In
as test temperature is close to 0.7Tm, where Tm is melting
temperature of In, and this enables fast recovery. To further
analyse the effect of strain rate on mechanical behaviour,
yield strength (YS) and strain rate sensitivity was calculated
as follows:

(c)
Fig. 5: High magnification SEM micrographs of samples processed through
ARB for (a) 1, (b) 2 and (c) 5 passes.

Study of stress-strain behaviour of ARBed samples was


done at room temperature, with varying strain rate of 10-4 to
10-1 s-1; Figs 8a and 8b show representative stress-strain and
effect of strain rate on YS for samples processed through 1
pass of ARB. Comparison of Fig. 8 with Figs 6 and 7 shows
that the general stress strain behaviour of samples following
ARB processing qualitatively remained the same, i.e., the
samples showed some strain hardening as well as the strain
rate sensitivity.

y = 2.3741e+07 * x^(0.080788) R= 0.97864

10-5

10-4

10-3

10-2

10-1

100

-1

Strain Rate (s )

(b)
Fig. 8: (a) True stress-strain behaviour and (b) YS versus strain rate plots of
single pass rolled In-40Cu composites.
-1

Strain Rate (s )
-1

10
-2
10
-3
10
0

0.25

0.5

0.75

True Strain

Fig. 6: True Stress-Strain Plot of as-sintered In-40%Cu having relative


sintered density of 87%. For plotting stress-strain data for 45s and 30s
sintered samples, strain axis was shifted by 0.25 & 0.5, respectively.

Fig. 9 shows the effect of ARB passes on the stress-strain


response of the In-Cu samples at the strain rate of 10-3 s-1.
Since, as shown in Fig. 3, the density of samples following
ARB processing did not show a monotonous variation in the
density of the sample and the density of a sample affects the
flow stress of a material, the stress endured by the samples

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0.006

significant reduction in the interfacial contact resistance, if


any, occurred only just after the first pass of ARB.
-7

6 10

In - 40 vol. % Cu
0

-7

4 10

-7

3 10
2 10

Sintered@160 C

-7

1 10

0.004

ARB strain per pass: 50%

0.003
0.002

0.1

0.15

True strain

0.2

40

45

50

55

60

Wiedemann-Franz Law
In - 40 vol. % Cu
-2

0.05

35

65

(a)

Strain rate: 10 s
0

30

500

0.001
0

25

Sintering time (s)

0 pass
1 pass
2 pass
5 pass

Thermal Conductivity (W-K)

True stress/(Density)

As-sintered
1 Pass
2 Passes

-7

In-40Vol%Cu
0.005

Sintered @160 C

-7

5 10

Resistivity (m)

were normalized by the square of the density of the sample.


Such normalization with respect to the density was conducted
following standard results on the cellular structure. Fig. 9
readily reveals that the flow stress of the material did not
change with the ARB passes. This can be attributed to the fact
that ARB proffered attainment of continuous channel of In,
which would then accommodate most of the applied strain, as
envisioned for such material system.

-1

0.25

Fig. 9: True stress-strain behaviour of sintered In-40Cu composites processed


through various ARB passes, each pass imposing a strain of 50 %.

Au

Sintered @160 C for 45 sec

Cu

300

Ag
Al

200

100

Sn

13 Pass

In

Ni

Pb
1

Electrical Conductivity (x 10 / -m)


7

(b)
Fig. 11: Variation of (a) electrical resistivity with sintering time, and (b)
thermal conductivity of as-sintered and ARBed samples of In-Vol.40% Cu
with electrical conductivity. The broken line in (b) represents Eq. (1).

Electrical conductivity(/m)

Electrical resistivity of composites was measured using a


custom design 4-wire Kelvin probe shown in Fig. 10.
Electrical conductivity and derived thermal conductivity
using Wiedemann-Franz Law (Eq. (1)) was calculated by
electrical resistivity for as-sintered and ARBed samples
(shown in Fig. 11b). Fig. 11a shows that electrical resistivity
decreased with increase in sintering time and number of ARB
passes. It appears to be against the observation of Cu-In IMC
for higher sintering period; however, it indicates the existence
of good contact or wetting between Cu and In; the latter may
be responsible for reducing the interface contact resistance
between the two phases of the composite. Fig. 11b shows that
thermal conductivity of as-sintered samples were actually still
considerably small compared to pure In and Cu, and this can
be attributed to poor relative density and existence of pores as
shown in Figs 4. However, the conductivity of the In-Cu
composites significantly increased with an increase of the
ARB passes. As shown in Fig. 11b, thermal (as well as
electrical) conductivity of In-Cu composites became greater
than that of pure In and Ni after 10 passes of ARB. Although
the maximum value attained in this study is smaller than that
of Al or Cu, it clearly shows that ARB can greatly improve
the thermal conductivities of samples.

400

1.5 10

1.4 10

1.3 10

1.2 10

1.1 10

1 10

9 10

8 10

7 10

In-40Vol. % Cu
0

Sintered@160 C
Sintering time (s)
30
60

84

86

88

90

92

94

Relative density after ARB

Fig. 12: Variation of electrical conductivity with density of the In-40 vol. %
Cu samples processed through ARB.

Fig. 13 shows the variation of electrical (and hence thermal)


conductivity of ARBed In-Cu composite as function of their
yield strength; the variation is monotonous. However, Fig. 13
reveals a striking result: an increase in the conductivity by
almost of factor of 2 was observed in In-Cu samples
following ARB processing while the yield strength increased
only by ~10% in between the same range. This actually
satisfies the most stringent criteria of the desired process of
attaining high conductivity without compromising
compliance.
1.6 10

1.4 10

1.2 10

1 10

8 10

In-40Vol%Cu

Fig. 10: Custom made stage for mechanically fixing the sample
(parallelepiped shape) and probes.

Fig. 12 establishes the effect of relative density on the


electrical (and hence thermal) conductivity of In-Cu
composites following ARB processing. The linear variation
between these two shows that density of the sample is an
important parameter determining the conductivity of the
sample. Also, the improvement of Cu-In interface or

Electrical conductivity(/m)

39

Sintering@160 C for 30 sec

40

41

42

43

44

45

Yeild stress (MPa)

Fig. 13: Variation of electrical conductivity with yield strength of the In-40
vol. % Cu samples processed through ARB.

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Further microstructural study was conducted to quantify


the homogenisation and breaking of agglomerates of the Cu
particles, as these are the probable changes that are affecting
the conductivity. Size distribution plots shown in Fig. 14
clearly reveal a narrowing of the range of Cu-particle size
with number of ARB passes as well as consistent with Fig. 5,
the distribution of Cu and In became homogenous with ARB
passes. This supports the proposed hypothesis of
homogenization with ARB.

a thin sheet of rGO was placed in between the mating


surfaces of the two In-Cu pieces. Fig. 16 clearly shows that
highly conductive materials, such as graphene, carbon
nanotubes, etc., can easily be embedded in In-Cu composites
through ARB processing of sintered sample.

50

40

Count

30

(a)
(b)
Fig. 16: Representative micrographs showing the incorporation of reduced
graphene oxide (rGO) in In-Cu composites. The black elongated region
shows rGo layer.

20

10

11

13

15

Diameter range (m)

17

19

(a)
100

80

Fig. 17 shows the effect of rGO on the thermal


conductivity of In-Cu composites. As expected, Fig. 17
clearly indicates a dramatic increase in the total thermal
conductivity of the In-Cu composites if rGO is placed
embedded into the In-Cu composites.
800

40

20

11

13

15

Diameter range (m)

17

19

(b)
120

Thermal Conductivity(W/mk)

Count

60

Sintering @ 160 C for 30 s


Without Graphene
With Graphene

600
500
400
300
200
100
0

100

In-40Vol%Cu + rGO

700

Number of ARB passes


80

Count

Fig. 17: Variation of Cu-particle size with number of ARB passes for In-Cu
samples sintered for 45sec.

60

40

20

11

13

15

Diameter range (m)

17

19

(c)
Fig. 14: SEM micrographs of sintered In-Cu samples processed through
ARB for (a) 1 pass, (b) 2 passes, (c) 5 passes. The right column histograms
show Cu-particle size in m. SEM micrographs were taken using backscattered electrons wherein dark and bright regions are Cu and In,
respectively, and black regions represent pores.

Fig. 15 shows the variation of the mean Cu particle size as


function of the ARB passes; Fig. 15 shows Cu particle size as
measured along the thickness (longitudinal) and rolling
direction (transverse) directions. In each direction, the Cu
particle size decreased with increase in the ARB pass.
10

In - 40 vol. % Cu
o

Sintered @ 160 C for 45 s

Cu-size (m)

9.5

8.5

Cross sectional view


Longitudinal

Transverse
0

Number of ARB passes

Fig. 15: Variation of Cu-particle size with number of ARB passes for In-Cu
samples sintered for 45sec.

Fig. 16 shows a representative microstructure of In-Cu


composites processed through 1 and 2 passes of ARB wherein

IV. CONCLUSIONS AND FUTURE WORKS


This study reports on the processing and characterization
of LPS In-Cu solders, starting with a green pellet, which
consists predominantly of particles of low melting In (60 %
by vol.) and smaller amount of particles of high melting Cu.
Short term LPS was conducted, which showed densification
dependence on sintering time. Once the metal compact
densified by LPS, it was processed through 1 to 10 passes of
ARB wherein each pass of rolling imposed a compressive
strain of 50%. Although the ARB did not cause a monotonous
increase in the density of the sample, the distribution of Cu
and In became uniform. ARB processing actually led to
uniform distribution of Cu (the HMP) into continuous matrix
of In (the LMP) which was never attained just after liquid
phase sintering. ARB also led to decrease in the Cu particle
size and hominization in the particle size distribution. The
electrical and thermal conductivities of composite were
observed to be increasing with number of passes of ARB and
with sintering period. Furthermore, the electrical and thermal
conductivities of In-Cu composite solders were increased by
more than an order of magnitude if a thin layer of rGO was
embedded into In-Cu composite through ARB processing.
Electrical Conductivity measurements confirm that
combining LPS with ARB is a promising route to meet the
requirements of a TIM.
Future work involves the mechanical characterization of
In-Cu/rGO samples. Also, mechanical response of all

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processed In-Cu composite solders (with or without rGO)


under shear loading and creep conditions will be evaluated.
ACKNOWLEDGMENT
Authors would like to thank IISc-ISRO STC for the
financial support.
REFERENCES
[1]

P. Kumar, I. Dutta, R. Raj, M. Renavikar, and V. Wakharkar, Proc.


Conf. on Thermal Issues in Emerging Technologies (ThETA 2), Cairo,
Egypt, IEEE, 17-20 Dec.(2008) pp. 339-346.

[2]
[3]
[4]

[5]
[6]
[7]

Solder Thermal Interphase Materials. Available online:


http://www.indium.com/TIM/solutions/index.php.
J. Liu, P. Kumar, I. Dutta, R. Raj, M. Renavikar and V. Wakharkar, J
Mater Sci 46 (2009) 7012.
J. Liu, P. Rottmann, S. Dutta, P. Kumar, R. Raj, M. Renavikar and I.
Dutta, Proceeding of the 12th Electronics Packaging Technology
Conference (EPTC) (IEEE, Singapore) (2009) pp. 506-511.
J. Liu, P. Kumar, I. Dutta, and M. Renavikar, Inter PACK, San
Francisco, USA (2009).
I. Dutta, R. Raj, P. Kumar, T. Chen, C. M. Nagaraj, J. Liu, M.
Renavikar and V. Wakharkar, J Electron Mater 38 (2009) 2735.
P. Kumar and S. Awasthi, J Comp Mater. 48 (2014) 1391

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Development of Nanoparticle Based Radiation Detectors for Space Applications


B.H.M. Darukesha1, V. Radhakrishna1, M. Ravindra1 and K. Rajanna2

Abstract: This paper contains the details of the


work carried out for the development of
nanoparticle based radiation detectors for space
applications. The design of experiments and
fabrication of detection medium are explained.
Detailed testing and characterization work
planned are indicated.

Key words: Radiation Detectors, Nanoparticles,


Scintillators
I.

INTRODUCTION

Main idea of this research is to use nanoparticles as


energy conversion sites for the detection of
ionising radiation. Nanoparticles embedded in a
plastic scintillating medium would convert
radiation energy into fast electron and the later
would scintillate the medium. Conventional
techniques using photomultiplier tubes and
photodiodes would be used to detect the light
output.
The Motivation of this work is to enhance the
efficiency, resolution and range of radiation
detection. Flexibility in form factor is a
significant advantage in Space Applications.
The design of experiments involves optimization
of species of nanoparticles, their size, and
percentage of loading and thickness of the
medium. Fabrication of 150 numbers of detection
medium covering these parameters is completed.
The First cut results are expected soon.

ISRO Satellite Centre, Bangalore-560017,


Department of Instrumentation and Applied Physics,
Indian Institute of Science, Bangalore-560012

Project Number: ISTC/PIN/KR/300

II.

THEORY

Upon interacting with the nanoparticle in the


medium, part of the energy of radiation is
converted as fast electrons. The resin chosen to
embed nanoparticles is such that these fast
electrons scintillate to release light in the suitable
wavelength of around 425 nm. This range is
suitable because most of the light counting
apparatus viz. photomultiplier tubes and
photodiodes have the sensitivity peak around it.
Efficiency of a nanoparticle in energy conversion
is proportional to Z4, where Z is the effective
atomic number. Since nanoparticles are smaller in
size than the wavelength of the light scintillated,
light would escape from the medium.
III.

EXPERIMENTS

Nanoparticles of Lead oxide, Tungsten oxide,


Silicon oxide and Gadolinium oxide are chosen in
this study. Commercial plastic scintillator which
has a peak emission around 425 nm has been used.
Plastic scintillator used has 3 parts. Catalyst and
the solvent are mixed first and then with the resin
in the specified ratios. Vacuum settling is carried
out at 10 mbar for about 20 minutes to get rid of
air-bubbles.
As control samples, without nanoparticles, the
compound is poured into moulds prepared by
machining the Teflon. Vacuum settling was again
performed at 10 mbar for 10 minutes. Whole of the
mould was kept in de-ionised water at 47 C for 14
days. Temperature was monitored twice a day
using a thermocouple and whenever required, deionised water pre-heated to 47 C was poured to
ensure that the cast is always immersed.
In order to form a thin film for the detection
medium, on a molded Teflon, the compound was
spun. Curing as mentioned above was performed
for this also.

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After 14 days of curing, the mold was taken out


and dried. The medium were baked at 80 C for 8
hours in inert Nitrogen atmosphere. A dedicated
oven was used for this purpose. Subsequently, the
detection medium was separated from the mould
using a surgical blade as shown in Fig. 1.

Fig. 2 (a) Mixing of nanoparticle and the resin

Fig. 1 Control samples, without any nanoparticles

It is found that separation becomes difficult when


Teflon mold is used. Surface of the mold showed
roughness complementing to the surface of the
Teflon. Cleaning the surface of the mold was tried
with alcohol and acetone. While neither of them
was able to clean the surface, acetone showed an
adverse effect to soften the mold. Slicing of top
surface with blade was found to leave the surface
clean. It was noted that there would be reduction of
the thickness of mold so as to form a curved top
surface. This reduction was considered for
calculating the percentage of loading of
nanoparticles during the fabrication of samples
with nanoparticles.
Fabrication of nanoparticle based medium
followed the similar sequence. After the first
vacuum settling, nanoparticles with the chosen
species & size, percentage of loading were mixed
with resin and were cast as shown in Fig. 2 (a) and
(b).

Fig. 2 (b) poring the compound into mold

Molds were prepared out of glass. Glass tubes of


10 mm diameter were cut in barrel shape. Size of
10 mm is chosen to suit the typical diameter of the
photomultiplier tube. Teflon tubes with 9 mm
diameter and 12.5 mm diameter were also used.
These molds are shown in Fig. 3.

Fig. 3 Different types of molds used

Percentage of loading was set to 0.5%, 1%, 1.5%,


5%, 10%, 20% and 40%. Last percentage was to
develop radiation shield for protecting the
electronic devices used in space applications.
Different thicknesses of medium were controlled
by pouring the compound to different heights of
these molds. One-quarter, on-half, three-fourth and
full heights were filled.

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Curing of the mold was performed in an oven as


shown in Fig. 4.

NP Radiation Detector

Optical grease

Si Photodiode/PMT

Front-end
Electronics

Processing
Electronics

Data
Acquisition

Fig. 6 Test set-up


V.

Fig. 4 Curing of mold at 47 C for 14 days in oven

The Glass tubes were broken easily and Teflon


tubes were cut vertically. The Surfaces were
smooth. The detection media thus obtained are
shown in Fig. 5.

CONCLUSIONS

Fabrication of nanoparticle based radiation


detectors is completed. Fabrication steps are
discussed in detail. Experiments for the evaluation
of uniform distribution of NPs in the medium are
being performed. Characterization of detection
medium is expected to be completed soon.

REFERENCE
[1] A multichannel nanoparticle scintillation
microdevice with integrated waveguides for Alpha,
Beta, Gamma, X-ray and Neutron Detection, Scott
M Pellegrin, Chad Whitney and Chester G. Wilson,
Journal of Microelectromechanical Systems,
Vol.19, No. 5, October 2010, p 1207 1214.

Fig. 5 Nanoparticle based radiation detection medium

IV.

TESTING & CHARACTERISATION

Nanoparticle based radiation detection medium are


being subjected to SEM study to ascertain the
uniformity of distribution. The test set-up as shown
in Fig. 6 is being arranged at ISITE, ISAC, ISRO.
Co-60 Gamma source is chosen for the initial
testing.

[2] Luminescence and Scintillation Properties at


the Nanoscale; Christophe Dujardin, David
Amans, Andrei Belsky, Chaput, Gilles Ledoux and
Anne Pilonnet, IEEE Transactions on Nuclear
Science, Vol., 57, No. 3, (June 2010), P 1348
1354.
[3] Synthesis of tungsten oxide nanoparticles by
acid precipitation method; Sitthisuntorn Supothina,
Ceramics International, Volume 33, Issue 6,
August 2007, Pages 931936

Further to testing, effect of various environmental


tests viz. high temperature storage, thermal
cycling, and vibration and thermo-vacuum tests
would be performed. The performance of samples
before and after the tests will be compared.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Spatial Coherence of Tropical Rain


R. Ratan1 , V. Venugopal1 , J. Sukhatme1 and R. Murtugudde2
1

Centre for Atmospheric and Oceanic Sciences, Indian Institute of Science, Bangalore, India.
2
Earth System Science Interdisciplinary Center, University of Maryland, Maryland,USA.

longer duration wet spells to the total number of rainy days


or seasonal accumulation separate reality from chance.

Abstract - We characterise the spatial coherence of tropical


rain from observations (TRMM) and assess if models (CMIP5)
are able to reproduce the observed features. Based on 15 years
(1998-2012) of TRMM 3B42 (V7) 1-degree, daily rainfall, we
estimate the spatial decorrelation scale (e-folding distance) of
rain at each location in the tropics. A ratio of zonal to meridional spatial scales clearly illustrates that while rain patterns
tend to be anisotropic (ratio of 3-4) over tropical ocean regions, over land regions, rain tends to be mostly isotropic (ratio of 1-1.5). This contrast between ocean and land appears to
be reasonably well captured by CMIP5 models, although the
anisotropy (ratio) over ocean is much higher than in observations.

As a follow-up, in this work, we have begun to explore


the role of organised convection in determining some of
these observed features. Specifically, the recent availability
of high-quality satellite observations of rain proxies or
derived observations of rain over the globe provided an
ideal opportunity to study the spatial scales associated
with convection and rainfall. Among previous studies of
rainfall proxies which focus on spatial scales of convection,
Roca and Ramanathan (2000) used infrared imagery (from
INSAT 1-B) to analyse the scale-dependence of convective
systems in the tropical Indian ocean. They found that
cloud systems span a wide range of spatial scales from
100 to 500 km2 . Nesbitt et al. (2000), using brightness
temperature measurements from the TRMM satellite, analysed mesoscale convective systems (MCSs) and identified
differences in the size of the systems over land and ocean
regions. Ricciardulli and Sardeshmukh (2002) have perhaps
provided one of the more comprehensive analyses on local
time and space scales of organized convection over the
global tropics. They analysed cloud imagery data and found
that typical spatial autocorrelation of deep convection is
of the order of 130km and mean duration of convective
events lasted approximately 5 to 6 hours over the global
tropics. More recently, Wood and Field (2011) approached
the cloud size distribution problem from a scaling point
of view, and find that the horizontal size distributions of
clouds are shown to be well captured by a unique power-law
relationship over a range of spatial scales from 0.1 to 1500
km. They also find geographic and seasonal variations, in
that the largest clouds are predominant over west Pacific
and Indian Oceans, as well as land regions influenced by
monsoons, while the smallest clouds are found over arid
regions and the trade wind zones of the tropics.

1 Introduction
In a recent study (Ratan and Venugopal, 2013), we statistically analysed and documented the wet and dry spell
characteristics of tropical rainfall, using Tropical Rainfall
Measurement Mission (TRMM) satellite-based (3B42
V6) daily 1-degree rainfall. Using an Intensity-DurationFrequency (IDF)-like approach (common in hydrology, but
seldom used in meteorology), they found that while both
ocean and land regions with high seasonal rainfall accumulation (humid regions; e.g., India, Amazon, Pacific Ocean)
show a predominance of 2-4 day wet spells, those regions
with low seasonal rainfall accumulation (arid regions; e.g.,
South Atlantic, South Australia) exhibit a wet spell duration
distribution that is essentially exponential in nature, with
a peak at 1 day. The behavior that is observed for wet
spells is reversed for the dry spell characteristics. In other
words, the main contribution to the non-rainy part of the
season comes from 3-4 day dry spells in the arid regions, as
opposed to 1-day dry spells in the humid regions. The total
rainfall accumulated in each wet spell was also analyzed,
and we find that the major contribution to seasonal rainfall
for arid regions comes from 1-5 day wet spells; however,
for humid regions, this contribution comes from wet spells
of duration as long as 30 days. We also explored the role
of chance as well as the influence of organized convection
in determining some of the observed features. Specifically,
we showed that while the 2-4 day mode might be present
in random realizations of rainfall in a humid region as well
as rainfall observations, the differences in contribution of
venucaos.iisc.ernet.in;

Moving on to studies which analysed rainfall observations,


Smith et al. (2005) reported that the mean spatial scale of
precipitation for land and ocean is around 90 and 122 km,
respectively. Dai et al. (1997) found that spatial correlation
scale of precipitation is higher over southern tropics then
over the northern tropics (200 km and 550 km for norther
and southern tropics, respectively). Baigorria et al. (2007)
showed that the spatial correlation is higher in winter than
summer in mid latitudes regions, with the type of precipita-

STC 320

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(a)

100
(10N,129W)
(10N,130W)
(10N,131W)

80
Rainfall (mm/d)

tion (frontal in winter versus convective in summer), cited


as the main reason for the observed differences. In this
work, we systematically analyse 15-years of TRMM 3B42
(V7) daily gridded (1-degree) rainfall observations (e.g., see
Kummerow et al., 1998; Adler et al., 2000; Huffman et al.,
2007) to estimate the spatial scale of rainfall and assess if the
coherence has any anisotropy associated with it. The paper
is structured as follows: Section 2 describes the methodology used in estimating the spatial scale, followed by a discussion of the main results in Section 3, and a summary in
Section 4.

60

40

20

2 Methodology

3 Results and Discussion


To begin with, we consider four locations - two over ocean
(Pacific and Atlantic) and two over land (India and Amazon). Figure 2 shows the climatological cross-correlation
curves for these four locations It is quite evident from
the decay rates of these curves and the e-folding lengths,
that rain over ocean regions is likely to be more spatially
coherent, at least zonally, than that over land regions.
Specifically, comparing Figures 2 a, b and Figures 2c,
d, we note that zonal scale of rain over oceans is larger
than that over land. This is perhaps not surprising given
the spatial structure of annual mean rainfall over tropical
convergence zones. The meridional spatial scales over land
appear to be more than over ocean. A comparison of the
two scales suggests that perhaps rain over land tends to be
more small-scale (at least zonally) and more isotropic (i.e.,

0
J

F M

(b)

1
0.8
Cross Correlation

We use the decorrelation or e-folding length as a measure


of the spatial scale of precipitation. Specifically, the crosscorrelation between the daily rainfall time series at a reference grid and its neighbouring grids is estimated, and the
distance at which the cross correlation becomes less than 1e
is considered to be the decorrelation length. To illustrate the
procedure, Figure 1a shows the daily rainfall (for 2005) at
a reference point over the Pacific Ocean (10N, 130W; red)
and its neighbouring grids in the x-direction, one to the east
(blue) and one to the west (grey) of the reference grid. Figure 1b shows the cross correlation between the daily rainfall
at the reference grid (10N, 130W) with its neighbours, 20
lags (degrees) to the east and west. The decorrelation or efolding length from Figure 1b is 5 degrees in the east as
well as west direction. This is repeated for each year, and
a climatological correlation curve is estimated for +x and
x directions for the reference grid. Noting that the decorrelation in the positive (east) and negative (west) directions
are mostly similar in magnitude (or decay; e.g., see Figure
1b), a climatological decorrelation length is estimated based
on the average of these two climatological curves (for +x
and x). The spatial scale estimated in this manner yields a
zonal (x) spatial scale at the reference grid. A similar procedure is followed to estimate a meridional (y) spatial scale
by considering lags in the north and south directions.

0.6
0.4

1
e

0.2
0
20

15

10

5
0
5
Lag (in degrees)

10

15

20

Figure 1: (a) TRMM-based daily rainfall in 2005 at a reference grid (10N, 130W) and at neighbouring locations. (b)
Cross-correlation curve as a function of spatial lag (in degrees). The solid black line represents 1/e, and the two filled
red circles show the e-folding lengths in east (+ve lag) and
west (-ve lag) directions.

comparable zonal and meridional spatial scales) compared


to that over ocean.
As mentioned earlier, repeating this procedure for each
1-degree grid for 15 years, we estimate the zonal and meridional climatological decorrelation (e-folding) lengths for
rain over the tropics. Figure 3a, b show the climatological
zonal and meridional decorrelation lengths (also called spatial scale), respectively, for tropical rain. The higher zonal
spatial scale over ocean regions compared to land, which
was partially evident from Figure 2, is now quite clear in
Figure 3a. Specifically, rainfall over most of the ocean
basins, especially over the core of the tropical convergence
zones near the equator, has a spatial scale of 6 degrees. On
the other hand, over many of the monsoon hotspots (India,
northern Australia, South America), the zonal spatial scale
is of the order of 3-4 degrees. Interestingly, the equatorial

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Cross Correlation

(a)

(b)

0.8

0.8

0.6

0.6

0.4

0.4

0.2

0.2

0.2
0

10

0.2
0

Cross Correlation

(c)
1

0.8

0.8

0.6

0.6

0.4

0.4

0.2

0.2

0
2
4
6
8
Spatial Lag (in degrees)

10

(d)

0.2
0

10

0.2
0

Zonal
Meridional

2
4
6
8
Spatial Lag (in degrees)

10

Figure 2: Climatological zonal (red) and meridional (blue) cross-correlation curves based on 15 years (1998-2012) of
daily, 1-degree TRMM 3B42 (V7) rainfall for two ocean and two land locations: (a) Pacific (10N, 130W) (b) Atlantic (5N,
30W) (c) Amazon (10S, 60W) and (d) India (20N, 76E). and represent the +ve (x and y) and -ve (x and y) directions,
respectively. The dashed line corresponds to 1/e, based on which decorrelation lengths are estimated.

Africa and South America show a substantially smaller


zonal spatial scale (< 1-degree) suggesting that rain over
those regions is highly localised, even though they receive
rain throughout the year much like the equatorial oceans.
The maritime-continent region also has a very low zonal
spatial scale, despite the fact that it receives high amount of
precipitation throughout the year. One possible reason can
be that this region gets mostly convective type of rain, which
lasts typically for a few hours, suggesting that moisture
transport is not from afar. The high zonal spatial scale over
southern Africa (6 8 degrees) could be attributed to the
presence of the intertropical convergence zone (ITCZ) in
southern hemisphere during the boreal winter. Moving
on to the meridional (y) spatial scale of rain (Figure 3b),
over most land regions it (2 3 degrees) is lesser than or
comparable to the zonal counterpart. Remarkably, over the
tropical convergence zones (except over equatorial Indian
Ocean) it ( 1-degree) is much lesser than the zonal spatial
scale ( 6 degrees).
The dominance of zonal or meridional scale over each
region can be assessed by their ratio, which can be seen to
be a measure of isotropy (or lack thereof) of rain, shown in
Figure 3c. The most striking aspect seen here is that, over
most land regions, rain tends to be small-scale (lower zonal
and meridional scales) and mostly isotropic (ratio of 1 to
1.5 in Figure 3c). Interestingly, the southern part of Africa,
which showed high zonal scale, also has a ratio between 1
and 2, suggesting that moisture transport is likely to be from

afar in both zonal and meridional directions. On the other


hand, oceanic rain, especially over the Pacific and Atlantic
convergence zones, is highly anisotropic (a ratio of 3 and
higher). This is generally consistent with the climatological
view of the (east-west elongated) spatial structure of rain
over the tropical convergence zones.
Following this, we analysed a set of 4 climate models to see
if they reproduce the feature reported above from observations. The models selected were from the suite of models
used in the Coupled Model Intercomparison Project (CMIP)
Phase 5. The four CMIP5 models used are CSIRO (Australia), MPI (Germany), NCAR-CCSM (USA) and NOAAGFDL (USA) with spatial resolutions of 1.87 1.86 ,
1.87 1.86 , 1.25 .9 and 2.5 2 . At the outset,
it is worth mentioning that the spatial resolution of 3 out
of the 4 models is around 2-degrees and thus a comparison between the zonal and meridional scales with observed
(at 1-degree) would not be fair or appropriate. However,
a meaningful assessment, at least qualitatively, can possibly be gleaned from the ratio, i.e., the measure of isotropy.
For completeness sake, Figure 4 shows the estimates of the
zonal (first column) and meridional (second column) spatial scales from model precipitation, using the procedure described in Section 2. The over-estimation of zonal spatial
scale is more pronounced than the meridional counterpart,
when compared to observations. Their ratio (shown in the
third column), on the other hand, suggests that the isotropy
of rain over land and anisotropy over ocean (especially, the

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Figure 3: Climatology (1998-2010) of the (a) zonal and (b) meridional spatial scales, based on daily, 1-degree rainfall.
Their ratio is shown in panel (c). The white area in the panels corresponds to regions which receive an annual mean rain
less than 2 mm/d.
Pacific and Atlantic convergence zones) are captured partic- References
ularly well in 3 of the four models, even though the magnitude is 2 to 3 times higher than in the models. Apart from the Adler, R. F., G. J. Huffman, D. T. Bolvin, S. Curtis, and
E. J. Nelkin (2000), Tropical rainfall distributions deterfact that models have a coarser resolution, the well-known
mined using TRMM combined with other satellite and
issue of the models not knowing when to stop raining (i.e.,
rain gauge information, J. Appl. Meteorol., 39, 2007
persistent drizzle) could also be a contributing factor to the
2023.
discrepancies shown here.

4 Summary

Baigorria, G. A., J. W. Jones, and J. J. OBrien (2007), Understanding rainfall spatial variability in southeast USA
at different timescales, International Journal of Climatology, 27(6), 749760, doi:10.1002/joc.1435.

Dai, A., I. Y. Fung, and A. D. Del Genio (1997), Surface Observed Global Land Precipitation Variations durIn this study we document the spatial scale characteristics
ing 190088, Journal of Climate, 10, 29432962, doi:
of tropical rainfall using 15 years (1998-2010) of daily, 110.1175/1520-0442(1997)0102943:SOGLPV2.0.CO;2.
degree TRMM-based rainfall. Using decorrelation or efolding lengths in zonal and meridional directions as a measure of the spatial coherence of rain, we find that (i) the zonal Huffman, G. J., R. F. Adler, D. T. Bolvin, G. Gu, E. J.
Nelkin, K. P. Bowman, Y. Hong, E. F. Stocker, and D. B.
spatial scale of ocean rain is much higher than land rain; (ii)
Wolff (2007), The TRMM multi-satellite precipitation
the meridional counterparts are comparable between ocean
analysis: Quasi-global, multi-year, combined-sensor preand land; surprisingly, the meridional spatial scale of rain in
cipitation estimates at fine scale, Journal of Hydrometeothe Pacific and Atlantic convergence zones, is much smaller.
rology, 8, 3855.
The dominance of zonal or meridional scales is captured by
their ratio; it clearly shows that while most land rain tends to Kummerow, C., W. Barnes, T. Kozu, J. Shiue, and J. Simpbe small-scale and isotropic (a ratio between 1 and 1.5), rain
son (1998), The tropical rainfall measuring mission
over ocean tends to be mostly anisotropic, with the ratio of
(TRMM) sensor package, J. Atmos. Oceanic Technol.,
4 in the Pacific and Atlantic oceans. Preliminary investiga15(3), 809817.
tion into the ability of climate models (albeit at coarser resolution) to reproduce some of these observed features sug- Nesbitt, S. W., E. J. Zipser, and D. J. Cecil (2000), A census of precipitation features in the tropics using TRMM:
gests that even though the two scales are significantly overRadar, ice scattering, and lightning observations, Journal
estimated, they are able to capture the qualitative feature of
of Climate, 13, 40874106.
anisotropy over ocean and isotropy over land.

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Figure 4: Same as Figure 3, but for rainfall from 4 CMIP-5 models (a) CSIRO (b) MPI (c) NCAR-CCM (d) NOAA GFDL. The first two columns show the zonal and meridional spatial scales, respectively, and their ratio is shown in the
third column.

Ratan, R., and V. Venugopal (2013), Wet and dry spell characteristics of global tropical rainfall, Water Resources Research, 49(6), 38303841, doi:10.1002/wrcr.20275.
Ricciardulli, L., and P. D. Sardeshmukh (2002), Local timeand space scales of organized deep convection, J. Clim.,
15, 27752790.
Roca, R., and V. Ramanathan (2000), Scale dependence of
monsoonal convective systems over the Indian Ocean, J.
Clim., 13, 12861298.
Smith, D., A. Gasiewski, D. Jackson, and G. Wick (2005),
Spatial scales of tropical precipitation inferred from
TRMM microwave imager data, Geoscience and Remote
Sensing, IEEE Transactions, (7), 15421551.
Wood, R., and P. R. Field (2011), The distribution of cloud
horizontal sizes, J. Clim., 24, 48004816.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Amorphous Silicon Carbide thinfilms by Pulsed DC Magnetron Sputtering


for Micro Electro-Mecanical Systems (MEMS) applications
Habibuddin Shaik, Sumesh M.A*, Mohan Rao G
Department of Instrumentation and Applied Physics
Indian Institute of Science, Bangalore
*LEOS, ISRO, Bangalore
Abstract- We are presenting here the synthesis and
feasibility studies of a-SiC thin films for
fabrication of a micro machined structure which
will be used for development of a Micro-bolometer
structure. In relation to this the micro machined
structures are demonstrated in different designs
on crystalline silicon substrate. Amorphous silicon
carbide (a-Si1xCx) films were deposited on silicon
(1 0 0) and quartz substrates by pulsed DC
reactive magnetron sputtering of Silicon in
methane (CH4)Argon (Ar) atmosphere. Optical,
compositional and mechanical properties were
investigated. We were able to synthesize a-Si1xCx
with x=0.5, and 100% Si-C bonding. We used Xray photoelectron spectroscopy (XPS) to confirm
this. These films, with 100% Si-C bonding, are
used for the fabrication of micro structures. We
studied the influence of substrate temperature and
target power on the composition, carbon bonding
configuration, band gap and hardness of a-SiC
thin films. Increase in substrate temperature
favors siliconcarbon (Si-C) bonding with
increased hardness. The deposited films are
chemically inert.
I. INTRODUCTION
The demand for sensors that can operate at high
temperatures and often in severe environments such
as aerospace, automotive, combustion processes or
gas turbine control and oil industry is always
increasing. Amorphous silicon carbide (a-SiC) is an
attractive material from a technological point of view
due to its excellent bandgap tunability, ability to
withstand at high temperatures, good thermal
conductivity, good mechanical strength and its
inertness to wear and corrosive environments. Each
or the combination of above properties have found

applications in different areas like MEMS,


photovoltaics and protective coatings etc [1-5].
In the present investigation, the material aspect of
a-SiC will be studied giving emphasis on its
applications as structural material for the fabrication
of MEMS systems, in particular for micro bolometer.
We present here the study of the effect of the process
parameters on stoichiometry and Si-C bonding
configurations of the films and which in turn
influence their optical and mechanical properties of
the films.
II. EXPERIMENTAL DETAILS
Vacuum chamber with a base pressure of 2106
mbar (with the combination of diffusion pump, cryosorption pump and rotary pump) was used to deposit
a-SiC films. Single crystal silicon target of 10 cm
diameter was sputtered in methane (CH4)argon (Ar)
ambient with a fixed CH4 partial pressure of 1.0
104 mbar and with working pressure of 2.0103
mbar. Target to substrate distance was maintained as
7 cm. Substrate heater with k-type thermocouple was
used. Pulsed (100 kHz) DC voltage (HUTTINGER
Electronics, GmBH) was applied to the target.
The deposited films were characterized with
DEKTAK profilometer for thickness measurement.
Elemental composition and binding energy was
analyzed using X-ray photoelectron spectroscopy
(SPECS GmbH spectrometer (Phobios 100MCD
Energy analyzer)). FTIR spectroscopy (Bruker
Tensor 27) was used for identifying the fundamental
vibrational modes and UVVIS spectroscopy
(HITACHI 3000) for bandgap calculations (using
Taucs plot). Mechanical properties of the films were
investigated using a nanoindenter (Triboindenter of
Hysitron, Minneapolis, USA).
Two sets of films were deposited. The first
set contains the films deposited at three different

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substrate temperatures (473, 673, and 873 K) with a


constant target power of 1200 mW cm2 and the
second set contains the films deposited with four
different target powers (360 (110 mA), 540 (150
mA), 740 (200 mA), and 1200 (300 mA) mW cm2)
at a constant substrate temperature of 473 K.
Hard a-SiC films were used for the
fabrication of microstructures. Microstructures in
different designs,
defined by mask and are
transferred to the a-SiC coated substrate by using
optical lithography. Microstructures were realized by
micromachining of the deposited a-SiC films on Si
by reactive ion etching (RIE from OXFORD
Instruments).

increase in Si-C bonds. This may be due to the fact


that at high substrate temperatures the weak C-H and
SiH bonds break and the dangling bonds of Si and C
combine to form strong Si-C bonds. Basa and Smit
[6] had also suggested that the breaking of the Si-H
and C-H bonds and the increased tendency towards
Si-C bonding.

III. RESULTS AND DISCUSSION


In order to check the composition and of Si-C
bonding configuration in the films X-ray photo
electron spectroscopy (XPS) was carried out. Al K
(1486.6 eV) was used as X-ray source. It was
observed that, as the substrate temperature is
increased from 473 to 873 K, the C concentration in
a-Si1xCx films decreased from 0.3 to 0.2.This is
because at higher substrate temperature, the adatoms
of C and H reaching the substrate having less kinetic
energy will get desorbed from the substrate and
hence the percentage of C and H decreases. This
reduction in C and H concentration has also been
confirmed by the decrease in the bandgap (Fig. 1a).
Similarly the C content in the films reduces from
0.54 to 0.3 with increase in the target power density
from 360 to 1200 mW cm2. This is due to the
obvious reason that, at higher target powers more Si
atoms sputter-out from the target and hence the
intake of Si atoms into the film is more and
dominates the intake of C. This decrease/increase in
C/Si concentration can also be confirmed by (i) the
decrease in the bandgap (Fig. 1b).
Fig. 2 shows the deconvoluted fine spectra of C 1s
core level into C-Si, C-C/C-H peaks for the first set
of samples and it indicates that, though the C content
is decreasing with increase in the substrate
temperature (for a fixed target power), the percentage
of C-Si bonding is increasing and C-C/C-H bonding
is decreasing. The observed decrease in the bandgap,
though the Si-C bonding is increasing with the
substrate temperature is due to the fact that, the
decrease in the C concentration is dominant than the

Fig 1. Variation of bandgap with (a) substrate temperature (b)


target power.

Similarly Fig. 3 shows the deconvoluted fine spectra


of C 1s core level into C-Si, C-C/C-H peaks for the
second set of samples and it indicates that, as the
target power is decreased (for a fixed substrate
temperature) the percentage of C-Si bonding is
increasing and C-C/C-H bonding is decreasing. This
is due to the fact that, as the target power is increased
(for fixed CH4 partial pressure) more Si atoms
sputter-out from the target so along with C-Si
bonding there is a more tendency towards Si-Si, OSi-C, SiOx and Si-Hn bonding. Therefore the Si-C
bond density is less at high target powers.

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Mechanical properties such as hardness and


modules were calculated using the representative
loaddisplacement curves (P-h curves) of both the
sets of films. The maximum penetration depth of the
indenter (hmax) at the peak load of 600 N is less than
10% of the films thickness, which ensures that the
substrate influence is negligible on the observed
mechanical response. The mechanical properties such
as hardness (H) and modulus (E) were calculated by
fitting the unloading curve of the P-h curve using
Oliver-Pharr method [7]. Fig. 4 and 5 show the
variation of hardness and modulus with the substrate
temperature and target power. Fig. 4 shows
increasing hardness with increase in the substrate
temperature for the first set of films. This can be
confirmed by XPS analysis (Fig. 2) which indicates
that, the Si-C bond density is increasing with
substrate temperature leading to an increase in
hardness and modulus. Increase in Si-C bond density
will lead to enhancement of cross-linkage of Si and C
atoms, resulting in a strengthened a-SiC material
frame and ultimately improved amorphous network
stiffness [8,9]. The same trend was observed for
second set of films which were deposited at constant
temperature and different target power densities as
shown in Fig. 5.
Fig. 2 Deconvoluted fine spectra of C 1s peak for the a-SiC thin
film deposited with the target power of 1200 mW cm2 at substrate
temperature of (a) 473 K (b) 673 K and (c) 873 K.

Fig. 4. Variation of hardness and modulus with substrate


temperature at constant target power of 1200 mW cm2.

Fig. 3 Deconvoluted fine spectra of C 1s peak for the a-SiC thin


film deposited at a substrate temperature of 473 K with a target
power of (a) 1200 mW cm2 (b) 740 mW cm2 and (c) 540 mW
cm2 (d) 360 mW cm2.

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Fig. 5. Varriation of hardness and modulus with


w target poweer at a
constant suubstrate temperatuure of 473 K.

We seleccted a film whhich is deposited with a poower


of 360 mW
m cm2 at a substrate tem
mperature of 473K
4
for the faabrication of micromachined
m
d structures.

The micrro patterns deefined on the negative


n
maskk
are shown in Fig.66. We transsferred thesee
micropattterns on to thhe a-SiC coated substrate byy
using opptical lithogrraphy. The details
d
of thee
optimizeed lithographyy parameters are shown inn
table 1.
Lithography
Piraanha Clean
10 mins
m
Phot-ressist (PR) usedd
AZ 4562
De--hydration
15minss@250C
Spiin coating
4000rpm
m for 40sec
Sooft Bake
2mins @110C
Exxposure
110m
mj cm-2
Post Exxposure Bake
N
N/A
Deeveloper
AZ 351
1 B (1:3)
Post Development
D
4mins @110C
Bake
Table 1. Lithhography parametters

mical inertnesss of the a-SiC


C is confirmedd
The chem
by leavinng the samplee in the piranh
ha solution forr
long tiime. We ddid not ob
bserved anyy
morpholoogical or thiickness changges of a-SiC.
After deeveloping thee PR, the samples
s
weree
transfereed to RIE chhamber to perform a PR
R
ashing sttep to removee the PR resid
duals from thee
developeed region. Thhe details of the
t PR ashingg
parameteers are shown in table 2.
PR Ashing
A
O2
50scccm
Prressure
10 mTorr
m
Table Temperature
T
15
5C
ICP
P Power
15000W
RF
F Power
1500W
Table 2. Recipeee for photoresist ashing
a

After PR
R ashing, we started a-SiC
C etching. Thee
details of
o the optimizzed recipee used for a-SiC
C
etching is
i detailed in ttable 3.
RIE a-S
SiC Etch
SF
F6/O2
18/9 scccm
Preessure
Valve position: 750
Table Temperature
15C
C
ICP
P Power
1000W
W
RF Power
400W
W
Fig.6. Opptical microscopee images of microostructures defineed on
the mask.

Table 3. Reccipee for a-SiC ettch

mplete etchingg of a-SiC, we performed a


After com
crystallinne silicon etcching step to
o release thee

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micrrostructures. T
The details of the optim
mized
recip
pee used for Si
S etch is show
wn in table 4.
IV. CONCLUSION
NS AND FUTUR
RE WORK
R
RIE Si Etch
SF6
Pressure
Table Temperaturre
ICP Power
RF Power

10
00 sccm
Valve position:
p
750
15C
9
900W
30W

Table 4. Recipee for C--Si etch

d-free
The SEM image of fixed-fideed and fixed
s
in fig 7 and
micrro machined sttructures are shown
Fig 8 respectivvely. The brroken beamss or
d-fixed patterrn (Fig 7) aree due
strucctures in fixed
to leess defined beam
b
width, which is geetting
etcheed out durin
ng Si etching
g. For the given
g
optim
mized recipe of
o Si etching,, we observed
d that
the beams
b
having
g a width leess than 5m
m are
getting etched-outt.

d-free
The bent or currled beams in the fixed
conffiguration (Fig 8) are duee to the resiidual
stressses developeed in the films
f
during the
depo
osition.

a-SiC miccromachined structures with


w
differentt
designs an
nd dimensionns were reaalized on Sii
substrate. The
T
synthesizzed a-SiC th
hinfilms weree
having 100
0% Si-C bonnding with good
g
hardnesss
which is very
v
crucial foor high temp
perature micro
o
bolometer application
a
ass it should be stable at high
h
temperaturee and also it should be
b wear and
d
corrosion reesistant. The a-SiC films are found to bee
chemically inert. We studied
s
the effect of thee
mperature and
d
process parrameters like substrate tem
target pow
wer on stoichiometry and
a
bonding
g
structure off the films whhich in turn in
nfluence theirr
mechanicall and optical pproperties. XP
PS data showss
that, the caarbon concen
ntration is geetting reduced
d
with increaasing the substtrate temperatture, however,
the percentage of C-Si bonding
b
is inccreasing whilee
the C-C/C--H bonding iss decreasing. Similarly thee
decrease in
n target power causing a rise in totall
carbon con
ncentration, annd the percen
ntage of C-Sii
bonding iss increasing and C-C/C-H
H bonding iss
decreasing. So we selecteed the optimizzed conditionss
p
m
mW.cm2 and (ii) substratee
(i) target power=360
temperaturee= 473K for 100% Si-C bonding, and
d
demonstrateed
the
ffeasibility of
o
differentt
micromachined structurres towards fabricating a
meter.
micro-bolom

RENCES
REFER
[1] I. AfdiYunazz, H. Nagashimaa, D. Hamashita, S. Miyajima, M.
M
Konagai, Sol. Ennergy Mater. Sol. Cells. 95 (2011) 107.
[2] D. Pysch, M.
M Bivour, M. H
Hermle, W.G. Sttefan, Thin Solidd
Films 519 (2011) 2550.
[3] C.Y. Chang, Y.K. Fang, C.F. Huang, B.S. Wuu, J. Electrochem.
Soc. 132 (1985) 418.
[4] L.S. Chang, P.L. Gendler, J.H. Jou, J. Mateer. Sci. 26 (1991))
1882.
X
J.M
M.
[5] N. Ledermannn, J. Baborowskii, P. Muralt, N. Xantopoulos,
Tellenbach, Surff. Coat. Technol. 125 (2000) 246.
[6] D.K. Basa, F.W. Smith, M
Mater. Res. Soc. Symp. Proc. 1622
(1990) 439.
Mater. Res. 7 (19992) 1564.
[7] W.C. Oliver, G.M. Pharr, J. M
[8] M.A. El Khaakani, M. Chakeer, A. Jean, S. Booily, J.C. Kiefferr,
M.E. OHern, M.F.
M Ravet, F. Roousseaux, J. Matter. Res. 9 (1994))
96.
A. El Khakani, M
M. Chaker, S. Booily, E. Gat, J.C
C.
[9] A. Jean, M.A
Kieffer, H. Pepin, M.F. Ravet, F
F. Rousseaux, Apppl. Phys. Lett. 622
(1993) 2200.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Low temperature electrical


transport studies on carbon
nitride films prepared by
chemical vapour deposition
K. Ramesh1, M. Prashantha1,
R.Venkatesh1, N. Naresh1, M.V.N. Prasad2
1

Department of Physics, Indian Institute of Science,


Bangalore 560 012.
2
LPSC, ISRO, Bangalore 560 008.
E-mail: kramesh@physics.iisc.ernet.in

Abstract - The carbon nitride films have


been prepared by chemical vapour
deposition (CVD) at pyrolysis temperatures
of 725, 750, 775, 800 and 825 oC. Electrical
transport studies at low temperature (RT to
4.5K) show that the carbon nitride films
exhibit Metal-Insulator (MI) transition. It is
observed that the increase in pyrolysis
temperature shifts the MI transition
temperature to lower values. The transition
temperatures for the samples prepared at 725
o
C, 750 oC and 775 oC are 84.7 K, 67.7 K and
9.5 K respectively. The reduced activation
energy indicates that the metallic regime of
the samples prepared
at
pyrolysis
temperatures > 800 oC lies at low
temperatures. It is also observed that the
activation energy decreases with the increase
in pyrolysis temperature.

1. INTRODUCTION

The search for new materials for advanced application


leads to the discovery of new materials with
interesting electrical, physical, chemical and
mechanical properties. The advancement of society
and quality of human life also depends on these
advanced materials. Carbon nitrides possess
outstanding properties like high hardness [1-3], wide
1

band gap, excellent thermal conductivity, wear


resistance, oxidation resistance, chemical inertness,
high velocity of sound (~104 m/s), low dielectric
constant (k~2), etc. These properties make them as a
promising material for various applications such as
organic semiconductors, fuel cells and photocatalysis,
mechanical cutting tools, protective coatings,
biomedical applications, electroluminescence devices,
optical materials etc [4-6]. Medical devices such as
bone joints, dental roots, heart valve etc which will be
implanted into human body can be coated with carbon
nitride films. The coating can reduce the wear and
corrosion, which occurs due to the reaction of the
device with body fluid. So coating the devices using
carbon nitride can result in increase of life time. Apart
from that, the coating is biocompatible [7].
In this article, the electrical transport properties of
carbon nitride films have been reported. The films
show the effect of disorderness and effect of
incorporation of nitrogen on electrical transport
properties. From earlier studies by Mott [8], some of
the disordered materials show a transition from
metallic to insulating behaviour at a particular
condition of temperature, pressure, doping level etc.
In view of this, the transition from metallic to
insulator behaviour has also been observed in the
prepared carbon nitride films.

2. EXPERIMENTAL
The samples were prepared by pyrolysis assisted
chemical vapor deposition (CVD) method with the
help of a home-built two zone furnace. 4Azabenzimidazole (C6H5N3) of purity 99% was used
as a precursor. About 0.1g of precursor was taken in a
quartz tube of 85 cm length and 10mm diameter. The
precursor was heated in the Zone I of a two zone
furnace at 400 oC. The dense vapours of the precursor
enter the zone II which was kept at a desired
temperature where the pyrolysis occurs and the
vapours get deposited on the quartz substrates and
inner walls of the quartz tube. The samples were
prepared at different pyrolysis temperatures of 725,
750, 775, 800 and 825 oC. As the C-N bond is
significantly strong, even at high temperatures a
considerable amount of the C-N bonding is retained.
This method is simple and enables one to have control
over the amount of nitrogen in the system by
controlling the pyrolysis temperature, volume of the
liquid and the process time.

Project Code: ISTC/PPH/KR/266.

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3. RESULTS AND DISCUSSION


The Raman spectrum of the prepared samples, shown
in FIG.1, exhibits the D and G bands characteristic of
amorphous carbon. The D (disorder) and G (graphite)

is incorporated into this ring structure, the carbonnitrogen bond breaks the symmetry in sp2 domains. As
a result, Raman spectra exhibits a D band. Similarly,
Sample

ID/IG

CN725
CN750
CN775
CN800
CN825

3.21
3.71
3.93
4.38
4.48

Table 1. Disorderness in the samples


and crystallite size.

FIG.1. Raman spectra of the prepared


Carbon nitride samples

bands are observed in disordered polycrystalline and


amorphous graphitic carbons. The G band is observed
in the region 1530-1600 cm-1 and D band
approximately at 1360 cm-1 respectively [9-11]. For
single crystalline graphite only G band is observed.
The G band arises due to the bond stretching of all

graphitic materials with nanometric-size crystallites,


impurities, doping, CN, imperfections, edges, exhibit
a Raman D band. The relative intensity ratio of
disorder band to graphite band (ID/IG) is a measure of
the degree of order in the carbon nitride sample.
Higher the value of ID/IG, higher the disorder in the
sample. In the present work, Raman studies on the
CNx film coated on the surface of quartz substrates
show the D band at 1365 cm-1 and G band around
1575 cm-1. From FIG 2 it is seen that the ratio ID/IG
increases with increase in preparation (pyrolysis)
temperature and the result indicates that structural
disorder increases in the samples with increase in
pyrolysis temperature.
CHN elemental analysis (Table 2) shows that the at%
of nitrogen is about 26% in the samples from CN725
to CN775 and gradually decreases for the samples
prepared at 800 and 825 oC.

3.1. Electrical transport study

FIG.2. Variation
temperature

of

ID/IG

with

pyrolysis

pairs of sp2 atoms in the ring structure. When nitrogen


Sample

at% of C

at% of N

at% of H

CN 725
CN 750
CN 775
CN 800
CN 825

70.70
70.89
70.54
75.36
77.81

25.98
26.03
26.30
22.52
20.85

3.31
3.08
3.16
2.12
1.34

Table 2. CHN data for samples prepared at different


pyrolysis temperatures.

Electrical transport study was done from room


temperature to 4.5 K. It is observed that the electrical
resistivities of prepared carbon nitride film decreases
with increase in preparation (pyrolysis) temperature.
The samples CN725, CN750 and CN775 clearly show
the metal-insulator transition at temperatures of
84.7K, 67.7K and 9.5K respectively. The results
indicate that the disorderness and the preparation
temperature of the films have a major role deciding
the transition temperature. The plot of normalized
resistivity versus temperature in FIG.3 shows a MetalInsulator transition. In the figure, it can be observed
that the transition temperature shifts to a lower value
with increase in preparation (pyrolysis) temperature.
Prasad et.al [12] reported that the electrical transport
properties of amorphous carbon films prepared at 900
o
C and above show Metal-Insulator transition. But our

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study shows the Metal-Insulator transition for the CNx


films prepared well below 900 oC. Moreover, the
metallic regimes of CN800 and CN825 at low
temperature are confirmed by the positive slope of the
plot of reduced activation energy versus temperature.
The reduced activation energy is calculated using the
equation,
w(T) = -(ln/lnT)
(1)
From the plot of reduced activation energy (w) versus

also has an important role deciding the transition


temperature. Some of the amorphous systems also
show the metal-insulator transition because of the
possible reason that the dopants can make the system
more ordered at low temperatures [13,14] and so
reducing the resistivity with decrease in temperature.
Similar kind of metal to insulator transition at low
temperature was observed in some disordered systems
also [15,16]. A reason for the metal-insulator
Sample

CN725
CN750
CN775
CN800
CN825

Activation
Energy
(meV)
94.36
60.22
24.22
18.61
8.58

Resistivity at
RT (.cm)
4.8910-1
1.2210-1
3.6510-3
3.1310-3
1.1910-3

Table. 3. Variation of activation energy and


resistivity of samples with pyrolysis temperature.

FIG.4. Reduced activation energy vs temperature.


The positive slope shows that the samples are in
metallic regime at low temperature

FIG.5. Calculation
CN825.

of

activation

energy

for

temperature as shown in FIG 4 we can conclude that


both CN800 and CN825 show metallic regime at low
temperatures, the positive slope is the indication of
metallic regime.

transition at low temperature may be due to the


formation of impurity band conduction, which occurs
because of overlapping of electron wavefunctions and
as a result a finite conductivity can be observed at 0K
[13]. Decrease in resistance may also be due to weak
phonon scattering of charge carriers. So, the samples
show a decrease in resistivity with decreasing
temperature below the transition temperature. Apart
from that, the electrical conductivity depends on the
density of states close to Fermi energy and the
radius of localization of the charge carriers bound
to the impurity states.

Apart from the effect of preparation temperature, the


impurity present in the amorphous network of carbon

From the results, it is observed that even though the


amount of nitrogen is almost same for first three

FIG.3. Normalized resistivity vs Temperature in log


scale for samples prepared at different pyrolysis
temperatures showing the Metal-Insulator transition.

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samples, the metal-insulator transition temperature


gradually shifted to lower values with increase in
preparation temperature.

[5].

At higher temperatures, resistivity follows Arrhenius


equation.

[6].

Ea

KT

0 exp

(2)

where, 0 is the pre-exponential factor, Ea is activation


energy and K is the Boltzmann constant. From the
values of activation energies (Table 3) it is observed
that the activation energy decreases with increase in
preparation temperature. Consequently, the resistivity
of the carbon nitride samples at room temperature
decreases with increase in pyrolysis temperature. The
room temperature resistivity decreases gradually from
4.8910-1 .cm for the films prepared at 725 oC to
1.1910-3 .cm for the films prepared at 825 oC.
FIG.5 shows the plot of resistivity versus temperature
for the sample CN825 for the calculation of activation
energy at high temperature (200-300K).

[7].

[8].
[9].

[10].

4. CONCLUSIONS
In conclusion, CNx films have been prepared using
chemical vapour deposition at different pyrolysis
temperatures
using
an
organic
precursor
Azabenzimidazole. Disorderness of films increases
with increase in pyrolysis temperature. Electrical
transport studies show that these films exhibit metal to
insulator transition at low temperatures.

[11].

[12].

[13].
REFERENCES

[1]. A.Y. Liu and M.H. Cohen, Prediction of New


[2].
[3].
[4].

Compressibility Solids, Science, 245, 841-842,


1989.
D.M. Teter, and R.J. Hemley, LowCompressibility Carbon Nitrides, Science, 271,
53-55, 1996.
A.Y. Liu and R.M. Wentzcovitch, Stability of
carbon nitride solids, Phy Rev B 50 (14),
10362-10365, 1994.
X. Wang, K. Maeda, X. Chen, K. Takanabe, K.
Domen, Y. Hou, X. Fu and M. Antonietti,
Polymer Semiconductors for Artificial
Photosynthesis: Hydrogen Evolution by
Mesoporous Graphitic Carbon Nitride with
Visible Light, JACS, 131, 16801681, 2009.

[14].
[15].
[16].

M. Zang, Y. Nakayama and M. Kume, Room


temperature
electroluminescence
from
hydrogenated amorphous carbon nitride film,
Solid State Commun. 110, 679-683, 1999.
Y. Zheng, J. Liu, J. Liang, M. Jaroniec,
S.Z.Qiao, Graphitic carbon nitride materials:
controllable synthesis and applications in fuel
cells and photocatalysis, Energy Environ. Sci,
5, 6717-6731, 2012.
F.Z. Cui and D.J. Li, A review of
investigations on biocompatibility of diamondlike carbon and carbon nitride films, Surf and
Coat Tech 131, 481-487, 2000.
N.F. Mott, Metal-Insulator Transition, Rev of
Mod Phys, 40, 677-683, 1968.
R.O. Dillon, J.A. Woollam, and V. Katkanant,
Use of Raman scattering to investigate disorder
and crystallite formation in as-deposited and
annealed carbon films, Phy Rev B, 29, 34823489, 1984.
A.K.M.S. Chowdhury, D.C. Cameron and
M.S.J. Hashmi, Vibrational properties of
carbon nitride films by Raman spectroscopy,
Thin Solid Films. 332, 62-68, 1998.
D. Das, K.H. Chen, S. Chattopadhyay, L.C.
Chen, Spectroscopic studies of nitrogenated
amorphous carbon films prepared by ion beam
sputtering, J. Appl. Phys, 91, 4944-4955, 2002.
V.
Prasad
and
S.V.
Subramanyam,
Magnetotransport in the amorphous carbon
films prepared from succinic anhydride,
Physica B: Cond Mat, 369, 168-176, 2005.
B.I. Shklovskii, A.L. Efros, Electronic
properties of doped semiconductors, Springer,
1984.
N.F. Mott, Electrons in disordered structures,
Advances in Physics, 16:61, 49-144, 1967.
C. Uher and L.M. Sander, Unusual temperature
dependence of the resistivity of exfoliated
graphites, Phy Rev B, 27, 1326-1332, 1983.
I.L. Spain, K.J. Volin, H.A. Goldberg and I.L.
Kalnin, Unusual electrical resistivity behaviour
of carbon fibers, Solid State Commun, 45, 817819, 1983.

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1
31st Annual In-House Symposium on Space Science and Technology
ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Generation of BPSK/QPSK Modulated


Microwave Signals Using Optical Techniques
K R Yogesh Prasad, T Srinivas, Gopal Hegde, Abdul Hameed

Abstract Generation of unmodulated microwave signals by


heterodyning optical signals is well established in literature. In
this paper it is shown that by modulating one of the optical
signals before heterodyning, a modulated microwave signal can
be synthesized. However, when the optical sources are freerunning, the resulting microwave signal lacks frequency stability
and exhibits poor phase noise. A novel approach for
implementing OPLL is proposed wherein angle modulated
microwave signals exhibiting high frequency stability can be
generated. Generation of BPSK and QPSK modulated microwave
signals by optical heterodyning is discussed in this paper. The
same principle can be extended to higher order modulation
schemes as well. Since optical modulators support very high bitrates as compared to microwave modulators, the proposed scheme
supports generation of high bit rate modulated microwave
signals.
Index TermsIntegrated optics, Microwave generation,
Microwave photonics, Optical modulation, BPSK, QPSK

I. INTRODUCTION

ENERATION of microwave signals using optical


techniques has been an active area of research. Several
heterodyne methods have been studied and proposed for the
optical generation of microwave signals. The optical signals
for heterodyning can be derived from two independent lasers
[1-2] or from one laser using the modulation-sideband
technique [3] or from a dual mode laser [4]. Optical
heterodyning using harmonic up-conversion in nonlinear lasers
[5], mode-locked lasers and pulsed lasers [6] have also been
reported. Techniques for improving the phase noise
characteristics have also been proposed [7]. These techniques
offer great flexibility in choosing the microwave frequency as
it is determined by the frequency spacing of the two lasers.
Generation of signals with frequencies ranging from few
megahertz up to terahertz is possible by optical heterodyning.
Most of the techniques based on optical heterodyning are
aimed at generating an unmodulated signal in microwave or
mm-wave region. Generation of angle modulated microwave
signals are discussed in this paper.
Section II of this paper discusses generation of unmodulated
microwaves signals by optical heterodyning. Optical PhaseLocked-Loop (OPLL) for achieving frequency stability of
heterodyned output is discussed in Section III. Optical
synthesis of BPSK/QPSK modulated microwave signals is
discussed in Section IV. Limitations imposed by OPLL in
generation of angle modulated microwave signals are brought

out in Section V. A novel scheme for generation of BPSK and


QPSK modulated microwave signals that overcomes these
limitations is proposed in Section VI. Conclusions are
presented in Section VII.
II. GENERATION OF UNMODULATED MICROWAVE SIGNALS BY
OPTICAL HETERODYNING

A. Heterodyning Principle
Consider two monochromatic optical sources at frequencies
f1 and f2, where | f1 - f2| << f1, f2. Their electric fields can be
represented by:

where f1 and f2 are the optical frequencies of the two sources


and 1 and 2 are the phase variations of the two sources. If
the two sources are combined and given to a photodetector
(PD), which is a square-law device, the resultant signal can be
expressed as:
where R is the responsivity of the PD.
We then get:
From the above equation it can be seen that heterodyned
output contains a term that corresponds to the frequency
difference between the two sources. By choosing the optical
frequencies such that their difference lies in the microwave
region, a microwave signal can be generated by optical
heterodyning.

Fig. 1. Block schematic of an optical heterodyning system

The block diagram for generation of microwave signals


based on optical heterodyning is shown in Fig. 1. The optical
outputs of the laser modules LD1 and LD2 are combined using
an optical power combiner and fed to a photodetector (PD) to
obtain microwave signal at frequency determined by the
frequency difference between the lasers.

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2
III. REALIZATION OF AN OPTICAL PHASE-LOCKED-LOOP FOR
ACHIEVING FREQUENCY STABILITY

When free-running lasers are used for optical heterodyning,


the resulting microwave signal, though centered at the
difference frequency, lacks frequency stability and hence
cannot be used directly for practical purposes. Figs. 2 and 3
show the heterodyned output of free-running lasers, captured
at two different instances. The figures clearly depict the
frequency variations of the generated microwave signal.
Frequency stability can be achieved by phase-locking one of
the lasers to a highly stable reference signal.

Fig. 4 Block diagram of OPLL

Phase noise values as low as -105 dBc/Hz at an offset of 10


KHz from the carrier frequency have been achieved.

Fig. 2 Snapshot # 1 of spectrum of unlocked signal

Fig. 5 Spectrum of locked signal at 5 GHz exhibiting phase noise of


-105 dBc/Hz at an offset of 10 KHz

IV. OPTICAL SYNTHESIS OF ANGLE MODULATED MICROWAVE


SIGNAL

Fig. 3 Snapshot # 2 of spectrum of unlocked signal

An Optical PLL, block schematic of which is shown in Fig.


4, can be implemented to achieve frequency stability.
Frequency-scaled heterodyned output and a reference signal
derived from a signal generator are compared using a phase
detector. The output of phase detector is passed through a loop
filter, which determines the dynamic performance of the
OPLL. The feedback voltage, which is proportional to the
phase difference between the heterodyned output and the
reference signal, is applied to the tune the laser output. Once
the optical PLL is locked, the frequency of the heterodyned
output is not allowed to deviate from that of the reference
signal. Also, the phase noise of the heterodyned output is
determined by that of the reference signal within the loop
bandwidth of the OPLL.

By extending the approach of generating unmodulated


microwave signal based on optical heterodyning, it is shown
that if one of the lasers is angle modulated then the output of
the photodetector contains a term corresponding to angle
modulated difference frequency. When an optical signal is
subjected to BPSK modulation, its phase is shifted by 0 or
radians depending on the modulating binary data being 0 or
1 respectively. Such a signal can be expressed as:

where is 0 or depending on binary data being 0 or 1


respectively.
If vbpsk is combined with an unmodulated laser output, v2, we
get:

where is 0 or depending on binary data being 0 or 1


respectively.

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3
If vc is passed through a square law device such as a
photodetector, we get current proportional to the square of
input voltage given by the expression:

where R is the responsivity of the photodetector.


The difference frequency term in the above expressions
suggests that the phase difference of radians introduced by
the modulation is preserved in the process of downconversion. Thus we can obtain a BPSK modulated microwave
signal by choosing the laser wavelengths appropriately.
Similarly it can be shown that QPSK modulation introduced in
optical domain is preserved in the microwave domain.
Fig. 7 OPLL scheme for generation of BPSK modulated microwave signal

V. LIMITATIONS IMPOSED BY OPTICAL PHASE-LOCKED-LOOP


IN GENERATION OF ANGLE MODULATED SIGNALS
In principle, angle modulation introduced in optical domain
will be preserved in the microwave domain by the
heterodyning process. However, when angle modulated
microwave signals are to be generated by optical heterodyning,
the presence of OPLL can prove to be a hindrance. As the
reference signal is unmodulated, angle modulation introduced
by the modulating signal will be tracked out by the OPLL if
the modulating frequency lies within the loop bandwidth.
Generation of BPSK/QPSK modulated microwave signals by
down-converting a modulated optical signal becomes
complicated with OPLL as BPSK/QPSK are suppressed
carrier modulation schemes with main lobe centered on the
carrier frequency. The heterodyned output within the OPLL
loop bandwidth is determined by the reference signal and will
not retain the modulation information as shown in Fig. 6.

Fig. 8 OPLL scheme for generation of QPSK modulated microwave signal

In the case of BPSK, the heterodyned signal containing


modulation information is self-heterodyned to extract the
carrier at the difference frequency of the lasers. The recovered
carrier is phase-locked to the reference signal by OPLL. Thus,
the OPLL tracks the carrier alone and the phase modulation
introduced in the optical domain is preserved in the microwave
domain.
In the case of QPSK, two levels of self-heterodyning are
required to extract the unmodulated carrier. The carrier thus
recovered is locked to the reference frequency as in the case of
BPSK. Optical heterodyne output, centered on difference
frequency of lasers, retains QPSK modulation.
Fig. 9 shows the QPSK modulated microwave signal in
which modulation remains unaffected by OPLL action by the
proposed approach.

Fig. 6 Effect of OPLL on QPSK modulated signal.


Full scale spectrum showing modulation being tracked out by OPLL.

VI. SCHEME FOR GENERATION OF BPSK/QPSK MODULATED


MICROWAVE SIGNAL

In this section, a simple scheme for generation of BPSK and


QPSK modulated microwave signals by heterodyning is
proposed wherein the problems due to phase-locking discussed
in the previous section are overcome. Figs. 7 and 8 show the
block schematics for generation of BPSK and QPSK
modulated signals respectively while still retaining the OPLL.
Fig. 9 QPSK spectrum achieved by proposed approach.
Spectrum zoomed in as compared to Fig. 6 to clearly show the modulation.

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4
VII. CONCLUSION
Generation of BPSK, QPSK modulated microwave signals
by optical heterodyning has been discussed. Since
BPSK/QPSK modulator design is based on electro-optic phase
modulators capable of being operated at frequencies of several
tens of GHz, it is possible to generate extremely high bit-rate
BPSK/QPSK modulated microwave signals by this approach.

REFERENCES
[1]

[2]

[3]

[4]

[5]

[6]

[7]

R.P. Braun, G. Grosskopf, D. Rohde, and F. Schmidt, Fiber optic mmwave generation and bandwidth efficient data transmission for 18-20
and 60 GHz-band communications, in Proc. Int. Top. Meet.
Microwave Photonics, MWP97, Germany, Sep. 1997, pp. 235-238,
paper FR2-5.
J. B. Georges, J. Park, Transmission of 300 Mbps BPSK at 39 GHz
using feedforward optical modulation, Electron. Lett., vol. 30, no. 2,
pp. 160-161, Jan. 1994.
H. Schmuck and R. Heidemann, Hybrid fiber-radio field experiment at
60 GHz, in Tech. Dig. 22nd Eur. Conf. Optical Communication,
Norway, Sept. 1996, vol. 4, pp. 59-62, paper ThC.1.2.
D. Wake et al, Optical generation of mm-wave signals for fiber-radio
systems using a dual-mode DFB semiconductor laser, IEEE Trans.
MTT, vol.43, pp. 2270-2276, Sept. 1995.
R.P. Braun et al, Fiberoptic microwave generation for bidirectional
broadband mobile communications, in Proc. IEEE MTT-S Int.
Microwave Symp., Denver, June 8-13, 1997, pp. 225-228, paper TU3E3.
C.H.V. Helmholt et al, A mobile broadband communication system,
based on mode locked lasers, IEEE Trans. MTT, vol. 45, pp. 14241430, Aug. 1997.
R.P. Braun et al, Low phase noise mm-wave generation at 64 GHz and
data transmission using optical sideband injection locking, IEEE
Photonics Tech. Letters, vol. 10, No. 5, pp. 728-730, May 1998.

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31st Annual In-House Symposium on Space Science and Technology


ISRO-IISc Space Technology Cell, Indian Institute of Science, Bangalore, 8-9 January 2015

Development and characterisation of nano-porous aluminium


alloy surfaces
Arti Yadav, Subrata Chakarbarti, A. Manimaran, M.S Bobji
Abstract- We have obtained ordered porous
alumina nanostructures on aluminium alloy
surfaces of ISROs interest. After obtaining the
nanostructures hot sealing and heat
treatment experiments were conducted to test
the samples for any cracks that are observed
in the anodized samples generated according
to anodisation process carried out by ISRO.
We have observed that production of ordered
porous alumina structures reduced the
cracking of the Al 6061 sample after
anodisation, hot water sealing and heat
treatment. Al 7075 samples didnt show crack
after anodisation and heat treatment but
cracked after hot water sealing.
I.

Anodic nano-porous aluminium oxides are most


commonly formed in the solution of sulphuric
acid, oxalic acid and phosphoric acid by
anodisation of aluminium [2]. By changing the
anodisation parameters like pH of the solution,
anodizing voltage and temperature of
electrolyte, the diameter and pitch of the pores
in anodic aluminium oxide layer can be
controlled [1,2,3,4]. The pore diameter is
observed to be linearly proportional to the
anodising potential.

Introduction:

Pure aluminium is a highly reactive metal and


develops a very thin oxide layer, of about 2-8 nm,
on the surface, whenever it is exposed to air. This
oxide layer acts as a protective layer on the
surface and prevents further oxidation of the
aluminium. In industry an anodic oxidation
process is used to produce a abrasive and
corrosion resistant protective oxide coating on
the surface. However, in the anodisation process
two different types of oxide layer forms, one type
is a porous oxide lm and the other is a barriertype anodic oxide film [1]. However, under
certain controlled conditions anodic process can
form highly ordered nano-porous alumina
(figure 1) coatings on the aluminium surface.
Arti yadav is a graduate student in the Mechanical Engineering
Department, Indian Institute of Science, Bangalore, India
Subratha chakrabarti is Scientist F, LPSC, ISRO, Trivandrum, India.
A. Manimaran is Group Head, Components Production Group,
LPSC, ISRO, Trivandrum, India.
M.S.Bobji is an Associate professor at Mechanical Engineering
Department, Indian Institute of Science, Bangalore, India

Figure 1: Schematic of nano-porous alumina


structure
Surface pretreatment processes like annealing
and electropolishing of the aluminium prior to
anodisation; help to improve the pore regularity.
Annealing helps relieve mechanical stress and
produces a coarse grained structure which
facilitates self-organization of the pores. Electro
polishing helps to produce a smooth surface
finish which plays an important role in regularity
of pore structure. Prior treatment of aluminium
is important because the roughness and other
parameters like voltage, type and concentration
of electrolyte, temperature, and impurities
present in aluminium including agitation of

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electrolytic bath influences the formation of selfordering porous alumina.


Fig. 2 shows a schematic diagram of pore
formation during the anodisation process. During
the process there is a balance between oxide
dissolution at electrolyte/oxide interface and
oxide formation at oxide/metal interface. This
balance is necessary for porous alumina
formation because it results in the formation of a
constant thickness barrier layer and hence allows
the steady state pore propagation into the
aluminium foil.
With regards to orderliness and pore uniformity,
the response of pure Aluminum to the above
mentioned condition is found to be extremely
good. However, the same cannot be said with

compare it with our observations made on AA 3


6061 T652 alloy to uniform anodisation
parameters involving Sulphuric acid electrolyte.
The comparison is based on our observations
made on both these alloys after completion of
anodisation, dyeing and hot water sealing. The
chemical composition and physical properties of
AA 7075 T 7352 alloy are as follows [5].
This study was necessitated due to the high
rate of incidence of delayed leakage of high
pressure helium gases through O-Ring and plastic
seals involving anodized Aluminium alloys as was
observed in the Liquid Propulsion Systems Centre
of Indian Space Research Organisation. In order
to compare the anodisation response of this alloy
with other Aluminium alloys, an AA 6061 alloy in
its T652 temper condition was also taken and a
study was conducted on both these alloys
simultaneously in an attempt to understand the
differences and similarities.

II.

Experimental Details:

We have obtained disc type specimens with AA


6061 T 652 alloy and AA 7075 T 7352 alloy
materials (20 mm and 4 mm thick respectively)
from ISRO and anodised by two step anodisation
process at a constant voltage of 40 V at 18 0C in
0.3M oxalic acid solution in IISc.

Fig.2. Schematic of porous alumina formation on


aluminum. 1. Formation of uniform barrier oxide.
2. Electric field distribution due to surface
fluctuation 3. Initiation of pores due to field
enhanced diffusion. (4) Stable pore growth.
certainty for structural alloys of aluminum which,
due to their high strength to weight ratio, finds
wide and extensive usage in the aerospace
industry. In this study we focus our attention on
the response of AA 7075 T7352 alloy and

Nano-porous alumina was formed by two step


anodisation process [6]. The pre-treatment of the
samples were performed before anodising.
Initially, to remove the impurity from the sample
after etching foil was rinsed with distilled water
for several times. Subsequently electropolishing
was performed in perchloric acid and Ethanol (in
the ratio of 1:4) solution at 10oC.
After pre-treatments the two step anodisation
begins, in the first anodisation process 0.3 M
oxalic acid solution was used to obtain porous
alumina layer. The applied constant voltage in
the anodisation process was 40V at temperature
of 180 C. The oxide layer created during the first

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anodisation is chemically etched by using


phosphoric-chromic acid solution. Second
anodisation process and parameters were same
as used in first anodisation.
III.

Controlled anodisation of Aluminium alloys.


Anodisation on alloy Al 6061

Results and Discussion

Characterisation of Standard anodisation


samples
To understand the existing industrial anodizing
process, we obtained samples from ISRO and
anodized as per their standard practices. SEM
images of the anodized samples show that for AA
7075 T 7352 has cracks on the surface. It is also
apparent that even after dying surface showed
cracks. However, for sealed and dyed AA 6061 T
652 alloy, there are no cracks present on the
sample.

Fig 4 Time variation of current during first


anodisation of aluminium ally Al6061
A typical currenttime relation (figure 4)
recorded during anodisation of aluminium in
oxalic acid at constant anodising voltage shows
that initially during the process current density
decreases rapidly with time and a minimum value
of current is achieved within first few seconds.
Current then slightly increases to give a local
maximum. After that it gradually reduced and
achieves a steady state current at around 3-4 min
of anodisation time. The SEM image (figure 5) of
the anodized sample showed non-uniform pores
formed on the surface

Fig 3 (a) SEM image of sealed Al7075 alloy (b)


magnified image of fig (a), (c) SEM image of dying and
sealing Al7075 alloy (d) magnified image of fig (c), (e)
SEM image of dying and sealing Al6061 alloy (f)
magnified image of fig (e)

Fig 5 SEM image of Al6061 alloy after first


anodisation

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Fig 6 Time variation of current during second


anodisation of aluminium ally Al6061

For Al 7075, current-time relation (figure 8) for


first anodisation is slightly different from that
observed for Al 6061 specially in the initial stages
of anodisation. Though current decreases rapidly
within first few seconds, it showed slight
oscillations in current not observed for Al 6061
alloy. However, after around 3-4 min a steadystate current of the porous oxide is achieved
similar to that for Al 6061 alloy. SEM image of
Al7075 alloy after first anodisation shows that
the pores were formed on the surface, but it is
not uniform and pore growth is random
compared to Al 6061.
Anodisation on alloy Al 7075

Fig 8 Time variation of current during first


anodisation of aluminium ally Al7075
Fig 7 (a) SEM image of Al6061 alloy, anodised at
ISRO (b) SEM image of Al6061 alloy after second
anodisation (anodised at IISc)
Currenttime relation during second anodisation
of aluminium alloy 6061 (figure 6) looked similar
to that observed for first anodisation. Fig 6 (a)
shows the SEM image of Al6061 alloy, anodised
at ISRO and Fig 6 (b) SEM image of Al 6061 alloy,
anodised at IISc by two step anodisation process.
From the images it is clear that the experimental
sample which was carried out at IISc has more
uniform porous structure compared to the
experimental sample from ISRO.

Fig 9: SEM image of Al7075 after first anodisation


From the graph it can be seen that, at the initial
period of the process current decreases quickly

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with time similar to alloy 6061. A linear increase


then leads to a local maximum current. After
reaching the second maximum, the current start
decreasing slightly and a steady-state current is
achieved.

Hot water treatment for 15 min on alloy Al 6061


& alloy Al 7075
After the two step anodisation process of both
the Al6061 and Al7075 aluminium alloys samples,
hot water treatment was performed on both the
surfaces for 15 min in boiling water. Figure 12 (a)
shows the SEM image of Al6061 alloy after
heating with boiling water and Fig 12 (b) SEM
image of Al7075 alloy after hot water treatment
using boiling water. It is found that there are no
cracks formed in the alloy Al6061 (figure 12(a)).

Fig 10 Time variation of current during second


anodisation of aluminium alloy Al7075

Fig 12 SEM images after hot water treatment


using boiling water for 15 min of (a) Al6061 alloy,
(b) Al7075 alloy
Hot water treatment for 1 hr on alloy Al 6061 &
alloy Al 7075

Fig 11 SEM image of Al7075 alloy, anodised at


ISRO and Fig13 (b) SEM image of Al7075 alloy
after second anodisation
From the Fig 11 (b), it is observed that Al 7075
alloy also have the uniform porous structure
compared to the process carried out at ISRO (Fig
10(b)).

The hot water treatment on both the surfaces


Al6061 and Al7075 aluminium alloys samples
have been carried out for 1hr in boiled water.
Figure 13 (a) shows the SEM image of Al6061
alloy after hot water treatment using boiling
water and Fig 13 (b) SEM image of Al7075 alloy
after hot water treatment using boiling water.
We have found there are cracks formed in alloy
Al6061 but some cracks are observed in Al 7075
sample.

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signs of cracks after anodisation and sealing in


hot water. It is also found that surfaces of the Al
7075 alloy are not forming cracks after
anodisation but form cracks after hot water
sealing. It is also found that there are no cracks
formed on both alloys Al 6061 and Al 7075
anodized and heat treated at 300oC for 3 hr.

Fig 13 SEM images after hot water treatment


using boiling water for 1 hr of (a) Al6061 alloy,
(b) Al7075 alloy
Heat treatment for 3 hr on alloy Al 6061 & alloy
Al 7075 at 300oC
We carried out heat treatment experiments to
check whether the cracking is resulting from
formation of hydroxide during sealing or due to
exposure to high temperature. For this we have
heated the sample in absence of water to 300oC
in a furnace preventing hydroxide formation.
Figure 14a, b show that both aluminium alloy
samples did not develop any crack even after a
soaking time of 3 hr at 300oC. This probably
confirms that cracks in aluminium alloy 7075 are
formed due to hydroxide formation. Further
confirmation could come from low temperature
methods of sealing

I.

Conclusion:

Standard anodisation procedures in ISRO


produce micro cracks on the surfaces of the Al
7075 alloy. Uniform and ordered nanostructures
in aluminium alloys of both Al 6061 & Al 7075 are
achieved using a lab scale procedure. It is found
that surfaces of the Al 6061 alloy showed no

Fig 14 SEM images after heat treatment at 300oC


for 3 hr (a) A l6061 alloy, (b) Al 7075 alloy

References
1) Masuda H, Hasegwa F and Ono S 1997 SelfOrdering of
Cell Arrangement of Anodic Porous Alumina Formed in
Sulfuric Acid Solution J. Electrochem. Soc. 144 L12730
2) OSullivan J P and Wood G C 1970 The Morphology and
Mechanism of Formation of Porous Anodic Films on
Aluminium Proc. R. Soc. Lond. Ser. Math. Phys. Sci. 317
51143
3) Masuda H and Satoh M 1996 Fabrication of Gold Nanodot
Array Using Anodic Porous Alumina as an Evaporation
Mask Jpn. J. Appl. Phys. 35 L126
4) Lei Y, Cai W and Wilde G 2007 Highly ordered
nanostructures with tunable size, shape and properties:
a new way to surface nano-patterning using ultra-thin
alumina masks Prog. Mater. Sci. 52 465539
5) Rocca E, Vantelon D, Gehin A, Augros M and Viola A 2011
Chemical reactivity of self-organized alumina nanopores
in aqueous medium Acta Mater. 59 96270
6) Masuda H and Fukuda K 1995 Ordered metal nanohole
arrays made by a two-step replication of honeycomb
structures of anodic alumina Science 268 14668

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