Materials for Energy Conversion

8/6/2019 Materials for Energy Conversion

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Nanostructured Materials forNanostructured Materials for

Energy conversion devices (Solar &Energy conversion devices (Solar &Fuel cells)Fuel cells)

ByDr. Velumani Subramaniam

Coordinador de Relaciones Internationales yProfesor InvestigadorDepartment of Electrical EngineeringCinvestav-Zacatenco Campus, Mexico cityhttp://cori.cinvestav.mx/velumani

[email protected] or [email protected]
http://cori.cinvestav.mx/velumanimailto:[email protected]:[email protected]:[email protected]:[email protected]://cori.cinvestav.mx/velumani


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[email protected]

ResearchInterests

Fuel cells&

Hydrogen storage

Solar cells- usingnanostructures

Corrosion protection-Theft sensors

Coatings(nanoparticles)Nanoelectronics

Trimetallic nanoComposites

Pd-Co-Mo, Pd-Co.AuPd-Co-Ni

Identification oflow cost bipolar Platesand various protective

nano Coating(Ni-Cr & Polymers)

Dep and charof nanostructure

Materials- CISCIGS CdTe, CdSe,

PMeT, CdS

On the way toEstablish the

Technology

Main and the mostExpensive part

in any Oil Industry

Identification ofvarious coatingMaterials incl

polymer-metalNano composites

Photovoltaic cellson Micro-chips andnanointerconnects

Lab-on-Chip withoutexternal

Power connections


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Ongoing ProjectsOngoing Projects

[email protected]

1) Titanium dioxide (TiO-2) Nano tube Solar cells using CdX (S or Se) nanocrystals with P3HT

sensitizers, (Participant) CONACyT-INDIA project, (2006

2009)

2) Theoretical and experimental Analysis of Pd-Co-Mo, Pd-Co-Au and Pd-Co-Ni composites for its

catalytic activity in PEM fuel cells, (Principal Investigator) CONACyT, 2007-2008, Mexico

3) Fabrication of high efficiency solar cells using nanostructured materials, (Principal Investigator)

GOOGLE-TEC innovation cell, Tecnologico de Monterrey-

campus Monterrey, Mexico (April 2007

March

2009)

4) Nano-engineered 3-Dimensional impregnation of nano-catalysts [Pt, Pd(70)-Co(20)-Au(10) and

Pd(70)-Co(20)-Mo(10)) on CNT for PEM Fuel Cells BY S. Velumani (PI) -

ITESM & A. M. Kannan(PI),

ASU -

A joint project with Arizona state university & ITESM

Oct 2007 to Sept 2009.
mailto:[email protected]:[email protected]


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NEW Interdisciplinary

program

1.

Electrical Engr

2.

Physics

3.

Chemistry

4.

Biotechnology

5.

Cellular biology

6.

Materials Science

40 Professors3 unidades


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Fuel cells are electrochemical devices that can efficientlyFuel cells are electrochemical devices that can efficiently convertconvert

thethe

chemical energy (oxidation potential) of the fuel directly intochemical energy (oxidation potential) of the fuel directly into electricalelectrical

energy.energy.

They operate like batteries and are similar in components and chThey operate like batteries and are similar in components and ch

aracteristics,aracteristics,

but unlike batteries, they do not get exhausted and arebut unlike batteries, they do not get exhausted and are environmentallyenvironmentally

friendlyfriendly..

As long as fuelAs long as fuel

is supplied to the cell along with an oxidant (typically air),is supplied to the cell along with an oxidant (typically air), thethe

fuel cell continues to produce electrical energy and heat.fuel cell continues to produce electrical energy and heat.

Additional benefits includeAdditional benefits include low maintenance, excellent load performancelow maintenance, excellent load performance, etc., etc.

Consequently, this conversion is not limited by the CarnotConsequently, this conversion is not limited by the Carnots cycle ands cycle and

efficiencies as high as 90%efficiencies as high as 90%

can be obtained.can be obtained.

What is a Fuel cellWhat is a Fuel cell

[email protected]

Fuel CellHydrogen

Oxygen

Electricity

Heat

Water


7/64H2O

- +

ANODE CATHODE

AIRGAS

ELECTRONS

HYDROGEN

IONS

DC VOLTAGE

Functional DiagramFunctional DiagramFunctional Diagram


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On going work at fuel cell lab

Simulation of Pd-Co-Au, Pd-Co-Mo nanocatalysts for the

PEM fuel cells

Nano-engineered 3-Dimensional impregnation of nano-

catalysts [Pt, Pd(70)-Co(20)-Au(10) and Pd(70)-Co(20)-Mo(10))on CNT for PEM Fuel Cells

Fabrication of stainless steel, alum inium, Teflon bipolar

plates at TEC

Exploring the possibilities of nanocoatings for thesebipolar plates to increase the conductivity (reduce ohmic losses)

Fabrication of fuel cell motor cycle

Design of fuel cell stack using the PLM (product life cyclemanagement)

[email protected]


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Different types of fuel cellsDifferent types of fuel cells

Fuel cells types Electrolyte

electrode

Working

temperatures

Fuel Oxidant Electrical

efficiency

PEMFC

Polymer electrolyte

membrane FC

Nafion

Electrodes with Pt

30 - 80C pure H2

Air or pure O2

~ 35%

DMFC

Direct Metanol FC

Nafion 30 - 80C Metanol

Airo r pure O2

~ 25%

AFCAlkaline FC

KOH concentratecarbon Electrodes with Pt, Ag

catalyst

60 - 100C pure H2Air or pure O2 ~ 35%

PAFC

Phosphoric acid FC

H3PO4 concentrate

Electrodes with Pt

~ 200C H2, CH4, CH3OH

Air

~ 40%

MCFC

Molten carbonate FC

Molten carbonate, Li2CO3/

Na2CO3

nickel Electrodes

~ 650C H2, CH4

Air

~ 50%

SOFC

Solid oxide FC

Ceramic solid oxide and

nickel Electrodes

~ 1000C H2, CH4, CH3OH,

Air

~ 55%

[email protected]


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FUEL CELL - Where to make an entry for nano?

[email protected]

Forces Driving Fuel cells


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TEM micrograph of a Pt-Ru/herringbone graphitic carbon nanofiber nanocompositeprepared by the Lukehart group

When tested as an anode catalyst in a working DMFC, this nanocomposite

exhibits a DMFC performance 50% greater than that recorded for a

commercial

Pt-Ru catalyst.

[email protected]

PtRu/carbon fiber attachment


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Assembly of PEM

Teflon sealing

Screws with

non-conductivesealing

[email protected]


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Stainless Steel Bipolar Plate

[email protected]


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Characterization Efficiency

[email protected]

(4)

In the case of the aluminum bipolar plates, the OCV was:

Efficiency calculations:

(3)

(5)

(6)

In the case of the stainless steel bipolar plates, the OCVwas:

,

,

.

.

VVBPALc

90846.0=

%04.69%10025.1==

FCAL

BPAL

c

f

V

VVBPSSc

903365.0=

%66.68%10025.1==

BPSS

BPSS

c

f

V


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A SEM image of theNitrided NiCr coating

on the stainless steel

coupon

CHARACTERISTICS OF NiCr COATINGS for BP

NiCr

Mapping of the Ni and Cr particles on the surface of thecoupons showing a uniform distribution of distribution of both

elements


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Nanosys500 sputter deposition system


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Molecular Simulation of Pd-Co-Au, Pd-Co-

Mo and Pd-Co-Ni (nanocomposites) for fuelcell catalytic applications Theory Behind the Software

CASTEP is based on Density FunctionalTheory (DFT).

CASTEP is based on a supercell approach.

All studies must be performed on a [email protected]


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The Chosen Structure: A5

B1

C1

[email protected]

A5

B3

C1An other version of

A5

B3

C1


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Collaborative project with ASU

Nano-engineered 3-Dimensional impregnation of nano-catalysts [Pt,

Pd(70)-Co(20)-Au(10) and Pd(70)-Co(20)-Mo(10)) on CNT for PEM FuelCells

Goals

Reduction of Pt loading in Proton Exchange Membrane fuel

cells (PEMFCs) with 3 dimensional distribution of catalysts over multi-walled carbon nanotubes (MWCNTs)

Introduction of novel loading technique in 3 dimensional

forms for the 100 % utilization of catalysts

Replacement of Pt catalysts with novel Pd-Co-Mo and Pd-Co-

Au nanocatalysts.

Fabrication and performance analysis of single cell using

novel catalysts and three dimensional impregnation of catalysts and

To promote Student and Faculty exchange programs between

ASU and ITESM in the masters and doctoral programs

To establish a platform for establishing an Energy Center

(Nanotechnology and Fuel cells) through NSF- CONACYT forproducing work ready graduates in [email protected]


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[email protected]

Supercell for the adsorbed CO specie on the Pd-Co-Mo (1 1 0) plane, Simulation of Pd-Co-Au

species and 3-dimensional distribution of nanocatalysts over CNT

electrolyte


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[email protected]


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[email protected]

Led

indicador

Fuel Cell

FuelCell

Stack

Vlvula

reguladora

Tanque de

hidrgeno


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Nanostructured Semiconductors

Nano structured semiconductors have attracted researchers interest for

their potential applications in optoelectronic devices like solar cells and

sensors.

Size Tailoring Band Gap Tuning

Wide Band gap Semiconductor Good Window material

A wide band gap semiconductor allows transmission of shorterwavelengths

[email protected]


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Low Material use and less energy intensive processing leads to lower

cost

Easier to fabricate large area devices required for PV applications

Performance comparable to single crystal materials

Manufacturing Technology is well established

Less stringent requirement on material properties

Easier Integration of device structure

THIN FILM SOLAR CELLSTHIN FILM SOLAR CELLS

[email protected]


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CdTe, CIS (CuInSe2), CIGS & TiO2

Thin film CdTe, CIGS and CIS - based solar cells have shown high

efficiencies in both small area devices and large area modules.

The direct band gap of these materials results in a large optical

absorption coefficient, which in turn require only 1-2 m of activelayer. Thickness of silicon wafer is generally 150 to 300 m.

Dye-sensitized TiO2 solar cells are environmentally friendly, low

cost and of large area

[email protected]


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Various Solar Cells structures

Window materials: ZnO:Al, TCO, SWCNT

CdZnTe or CIGS- Photon absorbing layer under the window, usuallydoped p-type, energy gap suited to solar spectrum

[email protected]


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Probable physical preparationtechniques

Physical Evaporation

Nanolithography

Laser Ablation

Mechanical grinding

Using templates

Sputtering

[email protected]


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Probable chemical preparationtechniques

Bio-reduction

Sol-gel

Electrochemical deposition

Phase transition

Passivating agents

[email protected]

Studies on synthesis of CuInGaSe nano


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Studies on synthesis of CuInGaSe2 nano-particles, ZnO:Al, CuIn(x)Ga(1-x)Se2, MW-

CBD CdZnS

Ingeniera Elctrica (SEES), CINVESTAV, Mxico.

PhD students working on the theme

B.Vidhya Bhojan

Ing. Rodrigo Cue Sampedro

Ing. Jagadeesh Babu

Masters Students

Ing. Rajesh Roshan Biswal

Ing. Ivn No Prez Ramrez

Ing. Pablo Itzam Reyes Figueroa

Ing. Arturo Lopez VillalpandoVillalpando


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Experimental details

In the preparation of CIGS nano powders, coppergranules (>99.9% pure), selenium and indium powders(>99.9% pure) and fine chips/granules of gallium wereweighed to correspond to the stoichiometry ofCuIn0.5Ga0.5Se2.

Five different mixtures dry, semi-dry and wet wereused.

This blended elemental mixture and Stainless balls wereloaded in a stainless container inside an argon-filledglove box.

The ball-to-powder weight ratio (BPR) was maintainedat 5 : 1. Milling was conducted using a SPEX-8000mixer/mill at 1200 rpm. [email protected]


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Experimental

Constituents Millingtime(hrs) Totalgrams(milled)

A Elemental

and

metal

powders(Cu,In,Ga

and

Se)powder11.5 12

B Powder1(dry) 1.5 2C Powder1+5mlethanol(wet) 1.5 2D Powder1+5mltetraethyleneglycol (wet) 1.5 2E Powder1+5dropsof ethylenediamine(semi

dry)1.5 2

All the chemicals are from Sigma Aldrich , tetraethylene glycol is from Merck [email protected]


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Reaction

The reactants (Cu,In,Ga and Se) is initiated by mechanical energysuch as collision and friction with the SS balls.

The explosive reaction ends in a short time. The reaction may be atype of chain reaction.

After the reaction is completed, the synthesized CIS powder ispulverized by the planetary ball milling.

T. Wada, H. Kinoshita / Journal of Physics and Chemistry of Solids 66 (2005) 19871989

Reaction mechanism for the preparation of CuInSe2

by MCP

[email protected]

Results and discussions


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10 20 30 40 50 60 70 80

Intensit

y(arbunits)

2 Theta

(112)

InSe

(220)/

(204) (312)/

(116)

(400) (332)

A

B

C

D

E

SeSe

The broadening of the peaks ,due to the small size particles. Ethyl alcohol doesnt affect the already formed CIGS structure . Trace of second phase InSe and Se is observed with Ethylene diamine andTetra ethylene glycol respectively.

Structural

(211)

(dry)

(wet)

(semi dry)

XRD pattern of chalcopyriteCIGS.

Grainsize

D=(0.94)/(Cos)

Where =1.54 ,

FWHM

The

average

grain

sizeA

8.93nm

B

8.143nm

C

7.918nmD7.922nmE

7.55nm

Results and discussions


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SEM-Morphology (dry)

A) 1.5 hrs milled B) 3 hrs milled

The surface area of particles will increase and nanoparticles will be in intimate contact witheach other. The nano particles have a strong cohesive force and they tend to

join very easily

forming clusters [1]

[email protected]


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Morphology Wet milled

C) 1.5 hrs dry followed by addition

of 5ml ethyl alcohol and milled for1.5 hrs more

D) 1.5 hrs dry followed by addition

of 5ml tetra ethylene glycol and milledfor 1.5 hrs more

Some flake like structuresXRD results show the presence of Se apartfrom CIGS, may be this prevents theformation of clusters and so more uniform

distribution is observed.

[email protected]


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Morphology semi dry

Different granular shapes

E) 1.5 hrs dry followed by additionOf 5 drops of ethylenediamine and milled

for 1.5 hrs more

CIGS milled for 1.5 hrs

Supports the SEM image-Individual nano

particles have tendency to form nanoparticle

agglomerates during milling process.Some separate nano particles of 11 to 30nm

is observed.

FESEM

[email protected]


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Semi dry

(112)

(220)/(204)

(312)/(116)(400)

(332)

TEM micrograph of an

Agglomerate of nano-Particles in which darkparticles are Surroundedby non-dense materials.

* fine bright spots in the

pattern are related to the

Nanocrystalline phase of

CIGS .[Powder Technology

191 (2009) 235239]

E-with ethylene diamine [email protected]


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OPTICAL STUDIES

The band gap was determinedBy drawing the straight lineThrough the absorption edge

At 1068nm

h(eV)=1240/

Eg

=1.16eV400 600 800 1000 1200

0.5

1.0

1.5

2.0

2.5

3.0

Absorbance

Wavelength(nm)

3 hrs

with ehthanol(3 hrs)

45 mins

This value of Eg

is in good agreement with the reported band gap values CuIn0.56

Ga0.44

Se2

(1.14 eV)[Synthesis of CuInS2, CuInSe2, and Cu(InxGa1-x)Se2 (CIGS) Nano crystal Inks

for Printable Photovoltaics,

J. Am. Chem. Soc., 2008, 130 (49), 16770-16777].

The bandgap value of nanocrystal dispersions were also consistent with energy of thecorresponding bulk compound( 1.23eV).

The prepared powder is dispersed in methanol and the absorbance spectra ismeasured by UV-Vis spectrophotometer Schimadzu Japan. The band gap energiesof the Cu(In0.5

Ga0.5

)Se2

nano crystals is determined from room temperature

absorbance spectra.

Absorbance spectra of CIGS nano particle dispersions

[email protected]


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MW-CB Deposition of CdZnS

CdSO4 , ZnSO4 , NH3SO4, Ammonium hydroxide.

Well cleaned glass substrates.-(Ultrasonic cleaning with soapsolution,acetone,ethanol and degreasing with isopropyl alcohol).

100 ml solution , kept in microwave for radiation time of 60s ,90s

and 150s seconds. Cleaned glass substrates kept vertically in thesolution.

Deposited for different values of Y=[ZnSO4]/{[CdSO4]+[ZnSO4]}(0.1,0.3,0.5,0.7 and 0.9)

Cleaned with deionised water , after deposition.

Deposition turned whitish yellow with the increase in Zn content.

[email protected]


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Microwave heating

Schematic of microwave heatingThe transfer of microwave energy is rapid

and direct with any absorbing material.

This rapid energy transfer creates non

equilibrium conditions resulting In high

instaneous temperatures(Ti)

These high Ti activate a higher percentage

of molecules above the Required activation

energy.

With energy transmitted directly to thereactants, the more energizedMolecules will form products more

rapidly.

[email protected]


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Microwave set-up

To find the hot spot

[email protected]

Electrical connections

STRUCTURAL


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20 30 40 50 60 70

arbunits

2 Theta

Zn=0.5

Zn=0.3

Zn=0.1

Radiation time 60s

(002)

(110)

20 30 40 50

Intensity(arbunits)

2 Theta

Y=0.9

Y=0.7

Y=0.3

Y=0.1

Y=0

Radiation time 90s

(002)

2

shiftto

SlightlyhigherValue,withZnIncorporation.

diffraction peaks associated with the Hexagonal Wurtzite structure of CdZnS

Increase in

crystallinity

0.1 & 0.3

20 30 40 50 60 70

arbunits

2 theta

Zn=0.9

Zn=0.7Zn=0.5

Zn=0.3

Zn=0.1

(002)

Radiation time 150s

[email protected]


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Morphology

Scanning electron micrographs for a)Y=0.1,b)Y=0.3,c)Y=0.5,d)Y=0.7 and e)Y=0.9 for CdZnS thin films

deposited at 90s radiation time

There are more voids on the

film surface with the increase

in Zn concentration. This is inagreement with the structural

inferiority observed in the Xrd

result for Zn concentrations

above 0.5

[email protected]


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Morphology

Localized heating of thin films with Y=0.7 and 0.9 deposited for 150s radiation time

The clusters observed in the SEM images are actually composed

of numerous self assembled nano particles of 10 to 20 .

growing crystallites contacted each other at their bases, the

sidewalls zipped together until a balance was reached between

the energy associated with eliminating surface area, creating a

grain boundary

FESEM image of CdZnS of Y=0.3, 60s radiation

[email protected]


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EDX-composition

Y Cd At% Zn at% S at% Zn/Cd Cd/S

0.1 57.32 6.34 36.34 0.11 1.57

0.3 55.03 7.95 37.01 0.144 1.48

0.5 51.90 10.20 37.90 0.196 1.370.7 50.65 14.37 34.98 0.284 1.44

Y Cd At% Zn at% S at% Cd/Zn Cd/S

0.1 59.16 5.14 35.71 0.086 1.66

0.3 54.26 7.67 38.06 0.141 1.43

0.5 50.23 19.23 30.54 0.383 1.64

0.7 44.98 25.56 29.46 0.571 1.53

0.9 33.89 41.12 25.00 1.219 1.36

60s

90s

Cd surplus in CdS results in a considerable concentration of traps

and recombination states below the gap .

There is a steady increase in the Zn/Cd composition, with very

little change in the Cd/S composition , which ensures the

replacement of Cd by Zn ions.

[email protected]


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[email protected]

General schematic ofa residential PV

system with batterystorage

What to do here?


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AFM images of the ZnSe nanorods synthesized by electrodeposition

Electrochemical synthesis and characterization of zinc selenide thin filmsJ MATER SCI 41 (2006) 35533559 by T. MAHALINGAM, A. KATHALINGAM, S. VELUMANI et al


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Guest Editor, Special issue from the journal Vacuum, an Elsevier publication forthe IMRC 2008, To be published in 2009

Guest Editor, Special issue from the journal Advanced Materials Research (ATransTech Publication, Switzerland) for IMRC-2007, To be published in 2009.

Guest Editor, Special issue from the journal NanoResearch (A TransTechPublication) for 3rd Mexican Workshop on Nanostructured Materials, Vol 5, 2008

Editorial board member, NanoTrends, A journal of Nanotechnology and itsApplications, An International Online BiMonthly Publication, ISSN 0971-418X

Guest Editor, Special issue from the journal Materials Characterization (An ElsevierPublication) for IMRC-2005, Vol 58, Issue 8-9, 2007

Guest Editor, Special issue from the journal NanoTrends, A journal ofNanotechnology and its Applications (An International Journal from Nano Science andTechnology Consortium, C-56, A/ 28, Sector-62, Noida, U.P., India) for anInternational conference - Nanotech-2006 held at Coimbatore Institute of Technology,

Coimbatore India from 25

th

to 28

th

June 2006.


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Chairman for Symposium 13 on, Advances in Semiconducting materialsIMRC2008, Aug 16 to 20, 2009, Cancun, Mexico.

Chairman Workshop on Nanostructured Materials, June 11 to 13, 2008, atCinvestav, Mexico.

Chairman for Symposium 19 on, Advances in Semiconducting materialsIMRC2008, Aug 17 to 21, 2008, Cancun, Mexico.

Chairman for Symposium 19 on, Advances in Semiconducting materialsIMRC2007, Oct 26 to 1st Nov 2007, Cancun, Mexico.

Co-Chair, Symposium 6 Materials Characterization, IMRC-2007, at Cancun,Mexico

Academic coordinator for a course (CADI) on Nanostructured materials and

fuel cellsfrom 5th to 8th June 2007, at ITESM- Campus Monterrey

Co-Chair, Symposium 6Materials Characterization, IMRC-2006, at Cancun,Mexico.

Joint Organizing Secretary (International), Nanotec 2006, Coimbatore Instituteof Technology, Coimbatore, India, June 23 & 24, 2006.


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Materials for Energy Conversion

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