MATERIALS RESEARCH MATERIALS RESEARCH IN

BHABHA ATOMIC RESEARCH CENTREBHABHA ATOMIC RESEARCH CENTRE

S. BanerjeeBhabha Atomic Research Centre

Mumbai, India

World Material Research Institute Forum - 2009

1

Physics Group Chemical Engineering Group

Chemistry Group Reactor Design and Development Group

BBRadiochemistry & Isotope

GroupReactor Group

BBAA Nuclear Fuels Group Reactor Projects Group

RRCC

Materials Group Beam Technology Development Group

CCNuclear Recycle Group Electronics &

Instrumentation Group

Bio-Medical Group Health, Safety & Environment Group

Engineering Services Group

Knowledge Management Group

Areas of Materials Research1. Nuclear Fuels 2 l M i l f N l R2. Structural Materials for Nuclear Reactors3. Neutron Scattering for Materials 3. Neutron Scattering for Materials

Characterization 4 Gl & C i4. Glass & Ceramics5. Magnetic & Spintronic Materialsg p6. Electronic Materials 7 E C i M i l 7. Energy Conversion Materials 8. Superconducting Materials8. Superconducting Materials

Three Stage Indian Nuclear Power Programme

1 h 1. To maximize the energy potential from domestic Uranium

d h and Thorium resources.2. Energy security and demonstrate gy y

sustainability of nuclear power.3. Minimize Green House GasNuclear Energy would

provide prosperity to 3. Minimize Green House Gasemissions while meeting the huge demand for electricity.

provide prosperity todeveloping countries.Homi  BhabhaFirst U.N.Conf. demand for electricity.

Closed fuel cycle is the integral part of this strategy

First U.N.Conf.Geneva,1955

4

Closed fuel cycle is the integral part of this strategy

Three Stage Indian Nuclear Power Programme - Strategy g gy

Thorium in the centre stage

Th

PHWR FBTR AHWR

300 GW YU fueledPHWRsNat. U

Dep U

Th

ThElectricity

300 GWe-Year42000 GWe-Year

Pu FueledFast Breeders

Dep. U

Pu U233 FueledU233

Electricity

Electricity

155000 GWe-Year

U FueledBreeders

Pu

Electricity

P ti i il b PHWR Expanding power programme Thorium utilization for

U233

Stage 1Stage 1 Stage 2Stage 2 Stage 3Stage 3

Power generation primarily by PHWRBuilding fissile inventory for stage 2

Expanding power programmeBuilding U233 inventory

Thorium utilization forSustainable power programme

5

Pushing the burn-upg p

• For better nuclear fuel utilisation• To extend re‐load intervals• Lower fuel cycle cost

Fuel Structural materials

• Fuel restructuring • Radiation damageFuel restructuring• Fission gas release• Fuel clad interactions• Reactivity Control

• Radiation damage

‐ Dimensional stability

‐ Property degradation• Safety Behavior

p y g

• Clad ‐ coolant compatibility

6

Mixed Oxide (MOX) Fuels for Pressurized H v W t r R ct rs (PHWRs)Heavy Water Reactors (PHWRs)

Development of high burnDevelopment of high burn--up fuels for use in PHWRsup fuels for use in PHWRsDevelopment of high burnDevelopment of high burn up fuels for use in PHWRsup fuels for use in PHWRs

50 MOX fuel bundles fabricated at BARC.All the MOX bundles are irradiated in KAPS-1 and peak

burn up achieved is 20,000Mwd/t.Demonstration of capability to manufacture & utilizeDemonstration of capability to manufacture & utilize

MOX fuels for PHWRs

Fuel subassembly inside glove box

End plate welding of PHWRMOX bundle at AFFF

UAl3 Dispersion Fuel for KAMINI Reactor

• Kamini is a Neutron Source Reactor fuelled by U233

b d U lU l d f ly

based UAlUAl33 dispersion fuel.• Ingot metallurgy & powder

metallurgy routes metallurgy routes developed.

• Hot rolling, swaging & KAMINI Fuel Sub-Assemblyg, g gpicture framing technique.

8Microstructure of Al-20%U alloy

Development efforts for high density Development efforts for high density uranium compounds/alloys

Development of U3Si2 compound by an i ti d t ll t finnovative powder metallurgy route for modified APSARA core.

Development of U-Mo alloys for dispersion p y pfuel application for advanced research reactors

9

Fabrication of Mixed Carbide Fuel for Fast B d T t R t (FBTR) t K l kkBreeder Test Reactor (FBTR) at Kalpakkam

(U P ) Mi d C bid (MK I) d (U P )(U0.3Pu0.7) Mixed Carbide (MK I) and (U0.45Pu0.55)Mixed Carbide fuel  (MK II) was chosen as fuel for FBTR t K l kkFBTR at Kalpakkam.

High thermal conductivity and metal density in MC lead to compact core & high breeding ratio.

Performance of this fuel has been proved to be pexcellent and is at present beyond 150,000 MWD/T.

Technology is highly complex but can be adoptedTechnology is highly complex but can be adopted for small cores.

10

Development of shorter doubling time fast reactor fuel

Glove box set-up for injection Injection Casting Set-up

Demoulding & Shearing Set-up

Automated Inspection Set-upfor injection casting & swaging and testing of U gfuel slugs fully installed. FBR metallic fuel fabrication facility at BARC

Cold commissioning trials with U-5%Zr rods

Mould Pallet up‐down mechanism

rods.Optimization of parameters

Top Chamber

View Portparameters.Bottom Chamber

Injection casting set up

Fuel fabrication for Prototype-FBR

• Fabrication Technology for MOX Fuel Established

• Experimental irradiation of PFBR MOX fuel (with U-p (233) in FBTR: fuel has reached 60 GWd/t burn-up

• Fuel specifications optimised for product recovery as Fuel specifications optimised for product recovery as well as performance

• R&D on metallic fuel for achieving shorter doubling R&D on metallic fuel for achieving shorter doubling time

12

Carbide fuel for Fast Breeder Test Reactor

Comprehensive Post Irradiation E i i f FBTR f lExamination of FBTR fuelat 25, 50 and 100 GWd/t in hotcells under inert atmosphere:cells under inert atmosphere:

Destructive as well as non‐

100 GWd/t

destructive techniques employed

FBTR M k I F l h h dFBTR Mark I Fuel has now reached155 GWd/t without fuel pin failurein the corein the core 

Fuel discharged at 25, 50 and 100

13

GWd/t reprocessed in CORALfacility 

Fuel for Compact High Temperature Reactor

14

Structural Materials Research( For Thermal Reactors)1 Zi i ll f l ddi 1. Zirconium alloys for cladding, pressure

tubes for thermal reactors(for High Temp. Reactors)1 R f t t l ll1. Refractory metal alloys2. Beryllium and its alloysy y3. Carbon based materials(f F R )(for Fast Reactors)1. Ni based alloys1. Ni based alloys2. Oxide dispersed stainless steel

Comprehensive Condensed Matter Research Programme

Neutron

El

High Pressure

High Strain rateElectron

h

High magnetic field

X-ray SynchrotronLow and high Temperature

Basic & Applied Research

Structure, Dynamics, Magnetism, Electrical & Thermal Transport, Optics, etc.

Bulk Nano AmorphousBulk, Nano, Amorphous…

Capabilities of National Facility for Neutron Beam Research

Diffraction (structure)Diffraction (structure)Wide-angle scattering (crystals, strain distribution)Very-large angle scattering (glasses, liquids)S ll l i (l l l hi fil )Small-angle scattering (large molecules, thin films)Neutron polarization analysis (magnetic systems)

S (D i )Spectroscopy (Dynamics)Inelastic and quasi-elastic scatteringNeutron Imaging/Tomography/Radiographyg g g p y g p yNeutron Optics / Fundamental Physics

Another emphasis will be on R&D on Magnetic Materials for Energy Systems such as molecular magnets and high magnetocaloricmaterials.

Condensed Matter Research

Studies using NeutronsStudies using Neutrons

Structure- Wide angle diffraction (crystallography, magnetism, strain distribution)

Very large angle diffraction (glasses liquids)- Very large angle diffraction (glasses, liquids)- Polarized neutron scattering (magnetism)- Small angle scattering (large molecules, thin films)

D iDynamics- Inelastic scattering (deterministic) and - Quasi-elastic scattering (stochastic)g

Fundamental Quantum Physics - Neutron OpticsQ y pNeutron Imaging - Tomography/Radiography

Carbon Based Materials

• Pyrolytic carbony y

• Carbon Nanotubes and Nanofibres

• Carbon coated fuels

• Metal carbides like SiC

• Diamond and diamond-like carbon films

• Boron carbide for nuclear applications

• Carbon based composites• Carbon based composites

Research on Glasses

• Glasses for nuclear waste immobilization

• Glass sealants for Solid Oxide Fuel Cells

• Radiation stable glasses

• Laser Glasses

• Machinable glasses

• Glass to ceramic / metal seals• Glass to ceramic / metal seals

• Glass-ceramicsGlass ceramics

Development of Borosilicate glasses for Nuclear Waste Immobilization

Higher waste loading, Thermal and Radiation stability, Low leaching rates

Immobilization in inert solid i i l

Phase IInterim storage of vitrified 

f 2 30Final disposal in deep 

l i l it

Phase II Phase IIIg g, y, g

matrix, viz., glass waste for 25‐30 years geological repository

Metallic melter, WIP Trombay

Canister C i t

Vitrified Waste Product

Multiple barrier

Canister & 

overpack

~100

0 m

eter

s Canister

Overpack

Backfill

Geological media (granitic host rock)

Canister cap

Near field region

Ceramic melter, AVS TarapurSolid Storage & Surveillance

(g a itic ost oc )

Far field region

Underground 

C ld ibl D f ilit

Surveillance Facility Repository Lab  

Cold crucible, Demo facility

Conceptualgeological

it

Overpack placement cask

21

repository

Materials for Energy Conversion

• Electrolytes, Cathode, Anode and Interconnect materialsfor Solid Oxide Fuel Cells

M t i l f H d ti• Materials for H2 production (Thermochemical and photochemical routes)

• Materials for H2 storage

• Materials for Solar Energy utilization (Photovoltaic cells)

Th l t i t i l• Thermoelectric materials

• High purity materialsHigh purity materials

Material issues in SOFC technology • Poor sinter-activity of Electrolyte and Inter-connect

materials: Role of Nanoscience

• Design of new Ionic conductors based on structure-propertycorrelation (for Low Temperature-SOFC)

• Design of new cathode and anode materials

An optimum degree of disorder leads to highest ionic conductivity in a system

Brownmillerite Ba In O Ba2In2(1 x)Ti2xO5+x 1 xBrownmillerite Ba2In2O5(Ordered lattice)

Ba2In2(1-x)Ti2xO5+x 1-x(Disordered perovskite)

Iodine-Sulfur process for H2 production (material-related challenges)

Materials for H2SO4Liquid phase at low temperatures: Hastelloy B850850ooCC

HEAT

850850ooCC

HEAT

850850ooCC850850ooCC

HEATHEAT

temperatures: Hastelloy B, Incoloy 815, Alloy 20 and in some cases AISI 316Liquid and Vapour phases (300HH O SOO SO ½ O½ O

HH22SOSO44 HH22O + SOO + SO22 + ½ O+ ½ O22850850ooCC

HH O SOO SO ½ O½ O

HH22SOSO44 HH22O + SOO + SO22 + ½ O+ ½ O22850850ooCC

HH22SOSO44 HH22O + SOO + SO22 + ½ O+ ½ O22850850ooCC

HH22SOSO44 HH22O + SOO + SO22 + ½ O+ ½ O22850850ooCC

H2SO4 DecompositionLiquid and Vapour phases (300 <T<400 °C): Refractory bricksVapour phase (400<T<900 °C) I l 800 (M i

HH22SOSO44HH22O + SOO + SO22 + ½ O+ ½ O22

120120ooCC

HEATHH22SOSO44HH22O + SOO + SO22 + ½ O+ ½ O22

120120ooCC

HEAT

Incoloy 800 (Maximum temperature 900 °C) and AISI 310 (Maximum temperature700 °C)2HI IIHEAT

2HI + H2HI + H22SOSO44 II22 + SO+ SO22 + 2H+ 2H22OO120120 CC

WATERWATEROO22

2HI IIHEATHEATHEAT

2HI + H2HI + H22SOSO44 II22 + SO+ SO22 + 2H+ 2H22OO120120 CC

WATERWATEROO22

Bunsen reaction700 C) Ceramics like Al2O3, ZrO2, SiC, Si3N4, and SiSiC

2HI2HI II22

2HI2HI HH22 + I+ I22

450oC

HEAT2HI2HI II22

2HI2HI HH22 + I+ I22

450oC

HEAT

2HI2HI HH22 + I+ I22

450oC2HI2HI HH22 + I+ I22

450oC

HEATHEAT

Fe-Si alloy (Si>13%) – Low Si core and high Si surface

Materials for HIx

22 22

H2

22 2222 2222 22

H2

Ch ll i l d d l t f

HI Decomposition

Zirconium, tantalum, Durichlor51, and Hastelloy B2

Challenges include development of new materials, fabrication technologies, coatings & compatibility trials with acids

BARC has developed a high current density compact electrolyser (10 Nm3 /hr of Hydrogen capacity)

A 40-cell electrolysis module (weighing 900 kg) incorporating (weighing 900 kg) incorporating porous nickel electrode operates at a high current density of 4500 ASM (amperes per square metre of electrode area) which is much higher than conventional is much higher than conventional cells in the market (operates at 1500 ASM or below)The electrolyser produces 10 Nm3 of hydrogen and 5 Nm3 of oxygen per hour at a oxygen per hour at a temperature of 55 °C and at a pressure of 0.16 MPa

Nano-materials for hydrogen storage

Helical multiwall nanotube Nanotube rope from Cobalt catalyzed Helical multiwall nanotube from Fe catalyzed CCVD

Nanotube rope from Ni catalyst

ycarbon nanotube

1 Inter metallic hydride systems (Fe Ti etc )1. Inter-metallic hydride systems (Fe-Ti etc.)2. Carbon nano-tubes

• Multi wall Carbon NanoTubes (CNT) synthesised by Catalytic Chemical Vapour Deposition (CCVD) on different catalyst structures like Nickel Vapour Deposition (CCVD) on different catalyst structures like Nickel Formate, Cobalt Formate etc. at 700 °C

• CNT content of 86% achieved• Gas used: Acetylene-Nitrogen (600 - 900°C)

Molecular electronics: New functional molecules containing M u gsigma and pi groups will be designed and synthesized and their Electrical characteristics will be studied for fabrication of rectifiers, negative differential resistance and memory devices.

Fig.: 5-(4 undecenyloxyphenyl)-10 15 20 t i h l h i (TPP

negative differential resistance and memory devices.

10,15,20-triphenylporphyrin (TPP-C11) designed and synthesizedearlier at BARC shows hysteresis andmemory effectmemory effect.

Thermoelectric devicesD i b d PbT ith 6%•Devices based on PbTe with 6%

efficiency prepared with upto 16 elements.

2 4 16•Larger devices will be prepared in 2009 to get voltages of above 1.5 V, with improved packaging.

Czochralski Crystal Pullers at BARC

• Growth of single crystals of LiTaO3, an important ‘Smart M i l’ ill b k f d i d l Material’, will be taken up for device development.

ABO PerovskitesABO4structure

PerovskitesABO3

FluoritesMO2

PyrochloresA2B2O7

Solid State Chemistry

A2B2O7

Sol d State hem stry

SpinelsSpinelsAB2O4

Aurvillius Phase[Bi2O2]2+ [Am 1BmO3m+1]2-

Inorganic Framework

[Bi2O2] [Am-1BmO3m+1]

gfluorides

Framework solids

Aurivillius phases

(ferroelectric materials)

Intergrowth (layered) d f th compounds of the

perovskite and fluorite lattices

[M2O2] 2+ [Am-1BmO3m+1]2-

M = Bi3+

[Am-1BmO3m+1]2- perovskite slab

m = thickness of perovskite slab

Bi4Ti3O12 Bi7Ti3Fe3O12

m = thickness of perovskite slab

m = 2 m = 6

Multiferroic MaterialsCoexistence of two or more than two ferroic ordering

(magnetic Ms, electric Ps and strain εs)

• Most of the existing multiferroic materials are Antiferromagnetic (AFM)and Ferroelectric (FE)

• Need of the hour: Materials with Ferromagtism (FM) and Ferroelectricity (FE)

(A t i ti bi ti )

Aim ?

(Antagonistic combination)

How to achieve this combinationAim ?Better understandingHigher value of polarization

How to achieve this combination (FE/ FM coexistence) ?

Coupling effects Pb free compounds

• Crystallographic approach• Chemical approach• Composite approachComposite approach• Core-shell configuration

Ba and Mn co-doped BiFeO3 system with coexistence of FE and FM

BiF O BiF M O

Preparation: Xerogel method

BiFeO3 BiFe0.8Mn0.2O3

(I) (II)

Magnetization with Field

Bi0 9Ba0 1FeO3

(III)(IV)

Bi0.9Ba0.1FeO3

TEM d SAED tt fBi0.9Ba0.1Fe0.8Mn0.2O3 Bi0.9Ba0.1FeO3 RT

TEM and SAED patterns ofBi1-xBaxFe1-yMnyO3

Electric polarization with Field

Spintronics materials

Prerequisites

• Wide band gap semiconductor hostlattice (2 to 4 eV)

Charge Spin

• Charge carrier density (about 1020 / cc)photon

• Appreciable solubility of transitionmetal ions

C h i l C dCommon host materialsZnO (3.37 eV)In2O3 (3.79 ev)

Common dopantsMn, Co, Fe, Cr

2 3 ( )TiO2 (3.2 eV) Co-dopant : Li

Pristine ZnO Zn0.97Co0.03O Zn0.95Co0.05O

1D morphology1D morphology Stabilization afterLi substitution in ZnO (template free)

Zn acetate, Co acetate,

Zn0 90Co0 05Li0 10O

Zn acetate, Co acetate, Li acetate heatedin try-octylamine at 320 oCZn0.90Li0.10O

0.90 0.05 0.10at 320 oC.

First principle theoretical modeling (DFT) Magnetization data at RT

(a) Zn0.97Co0.03O (b) Zn0.91Co0.03Li0.06O ZnO (Diamagnetic)Zn0.90Li0.10O (Diamagnetic)Z C O (FM)Demonstrating strong relaxation

effects due to presence of Li substitutional Dopants, which restores the 1 D

Zn0.97Co0.03O (FM)Zn0.95Co0.05O (FM)Zn0.85Co0.05Li0.10O (Enhanced FM)

Dopants, which restores the 1 D morphology

InkInk--jet printed oriented jet printed oriented ZnO:2%Co ZnO:2%Co FilmFilm

1 pass 1time dried at 180 heated at 500 15 min.

1 pass 2 times dried at 180 heated at 500 15 min. after each pass

1 pass 3 times dried at 180 heated at 500 15 min. after each pass

1 3 ti d i d t 180 h t d t 500 15 i l fi ll

ink jet printed highly (002) axis oriented ZnO film on Si

1 pass 3 times dried at 180 heated at 500 15 min. only once finally

tens

ity (a

.u)

30 35 40 45 50 55 60

Int

30 35 40 45 50 55 60

2θ

0.00004

Best orientedFilm of Co2%:ZnO

RTPolyimide

-0.00002

0.00000

0.00002

M(e

mu)

Silicon

-10000 -5000 0 5000 10000

-0.00004

H(Oe)

Different patterns printed Different patterns printed M H t RT hM H t RT h

p pon different substrates

p pon different substratesM vs. H at RT shows

ferromagnetismM vs. H at RT shows ferromagnetism

Tb, Dy doped Gd2O3: A white light emitting material

CIE co C l t dPoint II almost coincides with D65

pointPoints

Excitation Wavelength

(nm)

CIE co-ordinates

Correlated Color

Temperature (CCT)

I K l ix y In Kelvinsy

I 2300.418 0.489

3884

II 2470.315 0.316

6508

III 2770 291 0 355

7415III 2770.291 0.355

7415

Based on the CIE coordinates and CCT values, double doped Gd O (Tb ; 0 05 Dy; 1 95%) when excited at 247 nm emitsBased on the CIE coordinates and CCT values, double doped Gd O (Tb ; 0 05 Dy; 1 95%) when excited at 247 nm emitsGd2O3 (Tb ; 0.05, Dy; 1.95%), when excited at 247 nm, emits white light, which is closest to the standard noon daylight.Gd2O3 (Tb ; 0.05, Dy; 1.95%), when excited at 247 nm, emits white light, which is closest to the standard noon daylight.

Studies of Nanostructures for Gas sensing

• Role of intra-grain and grain boundary characteristics of oxide nano-structures will becharacteristics of oxide nano-structures will be investigated to develop more sensitive and selective gas-sensors. g

• Studies will use nanowires, nano-heterostructures of different materials as SnO2, CuO, In2O3, ZnO etc thatdifferent materials as SnO2, CuO, In2O3, ZnO etc that have already been prepared. (Figures below show a few nanostructures and single wire senor)

Gold ElectrodeGold Electrodesb (a)

10 μm400 nm20μm

Te nanotubes Nano-heterostructures:WO3 on SnO2

ZnO tetrapodsSingle nanowire sensor

Single Crystal Quasicrystal

Condensed Matter Research – Bulk, Nano, Amorphous…

Bright-field electron

i hmicrographExhibits five fold symmetry

Single crystal embedded in amorphous matrix of Zr based glass.

Electron diffraction pattern of as-grown Al6CuMg4

Nanocrystal Nanowire Thin Films Amorphous ribbons

Electron Diffraction

TEM image of γ-Fe2O3 Nanoparticles SEM micrograph of ZnOAmorphous Zr-35 at % Ni ribbon g γ 2 3 p SEM micrograph of ZnO

Contact Details

Dr. S. Banerjee,Director,Bhabha Atomic Research Centre,

Dr. T. Mukherjee,Director, Chemistry GroupBhabha Atomic Research Centre,Bhabha Atomic Research Centre,

Mumbai - 400 085, INDIATelephone: +91-22- 25593653F 91 22 25592107 / 25505151

Bhabha Atomic Research Centre,Mumbai - 400 085, INDIATelephone: +91-22-25595234 F 91 22 25505331 / 25505151Fax: +91-22-25592107 / 25505151

http://www.barc.gov.in/E-mail : sbanerji@barc gov in

Fax: +91-22-25505331 / 25505151http://www.barc.gov.in/E-mail : mukherji@barc gov inE mail : sbanerji@barc.gov.in E mail : mukherji@barc.gov.in

Thank You

41