Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

1

EXAFS-SAXS-WAXS

G.N. Greaves

Institute of Mathematics and Physics,

Aberystwyth University,

Aberystwyth SY23 3BZ, UK

GN Greaves and S Sen,

Inorganic Glasses, Glass-Forming Liquids and Amorphising Solids,

Advances in Physics, 2007, 56, 1-166

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

2

• Combining x-ray techniques

• EXAFS – modifier channels and MRN

• SAXS – IRO and diffusion

• WAXS – amorphisation

• EXAFS-SAXS-WAXS–formation of glass ceramics

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

3

Combining x-ray techniques

SAXS/WAXS

Bras W, Derbyshire G E, Ryan AJ, Mant G R, Felton A, Lewis R A, Hall C J and Greaves G N

Nucl. Instr. and Methods. A326, 587-591 (1993)

EXAFS/WAXS

Sankar G, Wright P A, Srinivasa N, Thomas J M, Greaves G N, Dent A J, Dobson B R,

Ramsdale C A and Jones R H,

J. Phys. Chem. 97, 9550-9554 (1993)

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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Environment of nucleating species from XAFS

Fluorescence XAFS

XRD

SAXS

X-rays from

MPW-6

levitator

gas

CO 2

laser

• ••

•• •• •• ••

•• ••••

•••

••• •• ••

•••

•

•

OO

OO

O

OCrystal phases

from XRD

Crystalline/amorphous

microstructure from SAXS

Ceramic bead

at 2000 °C

Cr

combined x-ray techniques

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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Mirrors

Monochromator

LevitatorFurnace

SAXS detector

WAXS detector

Control Room

Experimental Hutch

Optics Hutch

High Speed Camera

Figure 2

Figure 2

Beamline 6.2 at Synchrotron Radiation Sourcenow moving to I22 at Diaampond Light Source

SAXS/WAXS

Combined small angle scattering and XRDSRS 6.2, ESRF DUBBLE, I22 Diamond Light Source

W. Bras, G.E. Derbyshire, A.J. Ryan, G.R. Mant, A. Felton, R.A. Lewis, C.J. Hall and G.N. Greaves,

Nucl. Instr. and Methods. 1993, A326, 587

W Bras, IP Dolbnya, D Detollenaere, R van Tol, M Malfois, GN Greaves, AJ Ryan and E Heeley

J Appl. Cryst. 36,791-794 (2003)

Neville Greaves

EXAFS-SAXS-WAXS

6NSLS Glass Workshop 6-7 April

2009

furnace

XRD of alumina in 0.1s

cooling at 105 deg min-1

aerodynamic

levitator furnace

MPW6.2

alumina

Neville Greaves

EXAFS-SAXS-WAXS

7NSLS Glass Workshop 6-7 April

2009

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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EXAFSModifier channels and MRN

The Local Structure of Silicate Glasses

Greaves G N, Fontaine A, Lagarde P, Raoux D and Gurman S J

Nature, 293, p611-616 (1981)

Cation Microsegregation and Ionic Mobility in Mixed Alkali Glasses

Vessal B, Greaves G N, Marten P T, Chadwick A V, Mole R, Houde-Walter S

Nature 356, 504-507 (1992)

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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22sin2exp2

exp),()(

)(22

2QRQ

RQf

R

N

Q

QAQ

Element specific:

Coordination Number, N Inter-atomic Distance, R Debye-Waller Factor ,

EXAFS - basics

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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A Structural Basis for Ionic Diffusion in Oxide Glasses

Greaves G N, Gurman S J, Catlow C R A, Chadwick A V, Houde-Walter S,

Dobson B R and Henderson C M B

Phil. Mag. A65, 1059-1072 (1991)

N and R

Modifiers adopt well-defined sites in oxide glass networks

modifier polyhedra

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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N and R

Environments of intermediates in silicates

modified random networkMolecular Dynamics

Neville Greaves

EXAFS-SAXS-WAXS

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2009

AFM

modified random network

Neville Greaves

EXAFS-SAXS-WAXS

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2009

network isosurface and cutaway for Na2Si2O5

modified random networkVirtual Reality

Neville Greaves

EXAFS-SAXS-WAXS

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2009

Solids,

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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SAXSIntermdiate range order and diffusion

Long Range order and LL Transitions

Inorganic Glasses, Glass-Forming Liquids and Amorphising Solids,

GN Greaves and S Sen,

Advances in Physics, 2007, 56, 1-166

G.N. Greaves, M.C. Wilding, S. Fearn, D. Langstaff, F. Kargl, S. Cox, Q. Vu Van, O. Majérus,

C.J. Benmore, R. Weber, C.M. Martin, L. Hennet Science 2008, 322, 566-570.

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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SAXS - basics2

3

cossin3)(

qR

qRqRqRCqI

monodispersed particles

fractal structures

0 .2 0 .4 0 .6 0 .8 1 .0

1 E -1 1

1 E -1 0

1 E -9

1 E -8

1 E -7

1 E -6

1 E -5

1 E -4

1 E -3

0 .0 1

0 .1

1

1 0

I sa

xs

Q Å-1

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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0 .2 0 .4 0 .6 0 .8 1 .0

1 E - 1 1

1 E - 1 0

1 E - 9

1 E - 8

1 E - 7

1 E - 6

1 E - 5

1 E - 4

1 E - 3

0 .0 1

0 .1

1

1 0

I sa

xs

Q Å-1

Lo

g I

saxs

Log Q

Lo

g I

saxs

bulk dimensionallity

2<p,3

interface

roughness/overlap

3.5<p<4.5

Guinier

Porod

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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SAXS and the Structure Factor, S(Q)

TB

N

TKkWISV )/()0(/)0(/2

...00

2

0

2

First Sharp

Diffraction Peak

FSDP

Thermal Limit

Long Range Order

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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R. Bruning, C. Levelut, A. Faivre, R. LeParc,

J.-P. Simon, F. Bley, and J.-L. Hazemann:

Europhys. Lett. Vol. 70, (2005), p.211.

density fluctuations & compressibility SAXS from liquid and glassy SiO2

(a) (b)

Figure 3

I(0)

)exp()0()(2

bQIQI

liquid 1812K

glass Tg~1500K

Q independent

KT, compressibility

TB

N

TKkWISV )/()0(/)0(/2

...00

2

0

2

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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nanostructure &

long range fluctuations in OTPOrnstein-Zernike approximation

nanostructure

H.E. Stanley, Introduction to phase transitions and critical phenomena,

Oxford University press Oxford, 1971

22

0

1)(

Q

IQI

correlation length

Long-range density fluctuations in orthoterphenyl as studied by meansof ultrasmall-angle x-ray scattering,

A. Patkowski, Th. Thurn-Albrecht, E. Banachowicz, W. Steffen, P. Bo secke, T. Narayanan, and E. W. Fischer

(2000) Phys Rev E, 61, 6909-6912

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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Figure 5

Yttria-alumina liquids & L-L Transitions

Liquid-liquid transitions, crystallisation and long range fluctuations in supercooled yttrium oxide-aluminium oxide.

G.N. Greaves, M.C. Wilding, L. Hennet, W. Bras, O. Majérus, S. Fearn, F. Kargl

Journal of Non-Crystalline Solids (2009), doi:10.1016/j.jnoncrysol.2009.01.030

22

0

1)(

Q

IQI correlation length

T T

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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ionic diffusion/electrical conductivity

0 .0 5 0 .1 0 0 .1 5 0 .2 0 0 .2 5 0 .3 0 0 .3 5

0 .6

0 .7

0 .8

0 .9

1 .0

1 .1

1 .2

(N a2O )

x(S iO

2)

1 -x

W e

V

x

Single alkalis

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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SAXS and dimensionality and ionic diffusion

Solids,

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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WAXSpartial structure factors

Inorganic Glasses, Glass-Forming Liquids and Amorphising Solids,

GN Greaves and S Sen,

Advances in Physics, 2007, 56, 1-166

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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Element specific:

Structure Factor, S(Q) Partial Structure Factors, S (Q) Radial Distribution Factor, J(r)

WAXS - basics

)()( QSWWQS

NN

Qr

QrQS

sin)(

2

00

4]sin1)([2

)( rdQQrQSQr

rJ

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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In situ X-ray Scattering and Diffractionmelting alumina ID16 ESRF

In situ structural studies of alumina during melting and freezing, G. N. Greaves, M. C. Wilding, S. Fearn, D. Langstaff,

F. Kargl, Q. Vu Van, L.Hennet, I. Pozdnyakova, O. Majérus, Advances in Synchrotron Radiation (in press 2009)

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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Partial structure factors

in silica glass -

RMC from XRD and ND

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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Polyhedra in silicate glasses EXAFS, ND and Molecular Dynamics

A Structural Basis for Ionic Diffusion in Oxide Glasses

Greaves G N, Gurman S J, Catlow C R A, Chadwick A V, Houde-Walter S, Dobson B Rand Henderson CMB

Phil. Mag. A65, 1059-1072 (1991)

Cation Microsegregation and Ionic Mobility in Mixed Alkali Glasses

Vessal B, Greaves G N, Marten P T, Chadwick A V, Mole R, Houde-Walter S

Nature 356, 504-507 (1992)

Computer Simulation of Sodium Disilicate Glass

Smith W, Greaves GN and Gillan MJ

J. Chem. Phys. 103, 3091-3097 (1995)

Solids,

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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EXAFS-SAXS-WAXSprocessing of glass ceramics

Bras, W, Clark, SM, Greaves, GN, Kunz, M, van Beek, W, Radmilovic, V,

Nanocrystal growth in cordierite glass ceramics studied with x-ray scattering

Crystal Growth and Design, doi: 10.1021/cg07056v (in press 2009)

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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Cr EXAFS cordierite (Mg2Al4Si5O18) glass

doped with 0.34 mol% Cr2O3

chromo-aluminate spinels

(MgCr2xAl2(1-x)O4)

MgCr0.18Al1.82O4

30Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

In situ SAXS/WAXScordierite (Mg2Al4Si5O18)

glass heat treated

at different temperatures

875C/920C

875C/1040C

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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SAXS and form factor

ln Isaxs v Q

MgCr0.18Al1.82O4

cordierite/Cr glass

875C/925C

Isaxs Q4 v Q

i.e with thermal fluctuations removed

20nm crystallites highly monodispersed

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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distinguishing nanocrystalline phasesspinel (MgCr0.18Al1.82O4) in bulk & stuffed quartz (µ- cordierite) at surface

111 200 220

spinel

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

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in situ spinel particle growth and internal strain

3

5g

R R

Guinier radius

Particle radius

Monday, 23 June 2008 Centre for Advanced Functional

Materials and Devices

2

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

34

• Combining x-ray techniques

• EXAFS – modifier channels and MRN

• SAXS – IRO and diffusion

• WAXS – amorphisation

• EXAFS-SAXS-WAXS–formation of glass ceramics

Neville Greaves

EXAFS-SAXS-WAXS

NSLS Glass Workshop 6-7 April

2009

35