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Fundamentals of Small-Angle Neutron Scattering

SANS: A Tool for Relating Nanoscale


Structure to Bulk Properties

Charles Glinka
NIST Center for Neutron Research
Gaithersburg, Maryland

(http://www.ncnr.nist.gov)

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Techniques for the Measurement of Microstructure

Neutron
reflectivity

USANS

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SANS or SAXS?

SANS SAXS

Source of Differences in Differences in


scattering scattering electron density
length density

Sources Few and weak Many and strong

Size scale 1 nm – 1000 nm 1 nm – 1000 nm

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SANS or SAXS?

SANS SAXS

Special • D labeling and • msec resolution


Features H/D contrast for time-resolved
variation measurements
• Magnetic
•Superior Q-
scattering
resolution
• Conducive to
extreme •Anomalous
envivonments scattering
• nondestructive
•Small sample size

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SANS or SAXS?

SANS SAXS

Complications • Incoherent • Radiation damage


scattering to some samples
• H/D isotope
effects • Parasitic
scattering

• Fluorescence

• Beam stability

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Concepts Common to SANS and Neutron Reflectometry

For a steady state source


Scattered
Collimated beam of neutrons
monochromatic counted as a
neutrons incident on n
S
2θ function of
sample, S
vi pi ki scattering
scattering angle, 2θ
Sample
Incident neutron angle
r 2π
wave vector, ki =
λi Scattering Triangle ki - kf = Q

Q scattering vector

ki

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For elastic scattering (ki = kf = 2π/λ)
r r r
Q = ki − kf
kf r
2θ Q Q = 2k sinθ

ki  4π 
Q =   sinθ
 λ 

Recall Bragg’s Law λ = 2d sinθ


2π λ 2π
or d= = =
2 sinθ  4π  Q
  sin θ
 λ 
In general, diffraction (SANS or NR) probes length scale
2π λ
d≈ , for small scattering angles, d ≈
Q 2θ
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In general, diffraction (SANS or NR) probes length scale
2π λ
d≈ , for small scattering angles, d ≈
Q 2θ

More specifically, diffraction (SANS or NR) probes


r
structure in the direction of Q, on a scale, d ≈ 2π Q

ki r ki
2θ Q 2θ
kf kf

r cf. Appendix A.
same I(Q)
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Diffraction Probes rStructure
r rin the Direction of Q
ki − k f = Q
Specular Reflection Geometry SANS Geometry

ki kf kf Q
ki 2
2 Q

SANS probes structure in


Reflectivity probes
plane of sample (parallel to
structure perpendicular to
Q), and averages over
surface (parallel to Q), and
structure perpendicular to
averages over structure in
sample surface.
plane of sample.

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SANS Instrument Schematic

Small-Angle Neutron Scattering (SANS) probes structure on


a scale d , where
0.5 nm < λ < 2 nm (cold neutrons)

d ≈ λ (wavelength)
0.1° < θ < 10° (small angles)
2θ (scattering angle)
1 nm < d < 300 nm

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SANS Fundamentals
• For Length Scale Probed by SANS Can Use Continuum Approximation
- consider H2O, v ~ 30 Å3, r ~ 2 Å
Scattering Length
Density

neutrons X rays
b Z re

( > 100 H2O molecules)


• Therefore we can use material properties rather than atomic
properties when doing small-angle scattering
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SANS Fundamentals

•Inhomogeneities in scattering length density, ρ(r ),


give rise to small-angle scattering

• Angular dependence of scattering, I(q), is given by:

2
r 1 r rr r
I(q) = ∫ ρ (r )e iq⋅r
dr Rayleigh-Gans eqn.
V V
Entire volume of sample

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SANS Fundamentals: Coherent vs. Incoherent Scattering
N 2
Consider scattering from N r 1 rr
A
atoms of a single element, Z X I(q) =
V
∑b e i
i
iq ⋅ri

X rays Neutrons
A1
A1 A1
A2
A1

A3 A2
A2
A2
electron
atomic radius atom scattering A3
number form factor lengths, b’s, A3
depend on isotope A3
and isotope spin
scattering length
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SANS Fundamentals: Coherent vs. Incoherent Scattering
N 2
Consider scattering from N r 1 rr
A
atoms of a single element, Z X
I(q) =
V
∑b e i
i
iq⋅ri

N
r 1 (
r r r
)
∑ bi b j e
iq⋅ ri − r j
A1 I(q) = Since b’s are
V uncorrelated with
A2 i, j
the atom positions
neutron r 1 N iq⋅(ri − r j )
r r r r r
A3
I(q) = ∑ bi b j e = ICoh (q ) + I Incoh (q )
V i, j
where structural
N
r 1 (
r r r
)

A1 A2 2 iq⋅ ri − r j information
A1 A2 ICoh (q) = b e
A1 A2 V i, j

( )∑
N
A3 r 1 2 2 (
r r r
iq ⋅ r j − r j )
A3 I Incoh (q) = b − b e
A3 V j, j
scattering lengths: depend
on isotope and isotope spin
no structural 1
information
General Results for a Two-Phase System

‘phase’ in this context


refers to scattering
length density

• Incompressible phases of scattering length density ρ1 and ρ2

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From the Rayleigh-Gans equation:
2
r 1 rr r rr r
I(q) = ∫ ρ1 e iq⋅r
dr1 + ∫ ρ 2 e iq⋅r
dr2 break total volume
V V1 V2 into two sub-volumes

2
r 1 iq⋅r r
rr  iqr ⋅rr r iq⋅r r 
rr
I(q)= ρ1 ∫ e dr1 + ρ 2  ∫ e dr − ∫ e dr1 
V V1 V V1 
2
r 1 iq⋅r r
I(q) = ( ρ1 − ρ 2 ) ∫ e dr1
rr
2

V V1

Contrast Factor
(depends on materials Spatial arrangement
and radiation properties) of material

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General Results for a Two Phase System
2
dΣ r 1 iq⋅r r
(q) = (ρ1 − ρ2 ) ∫ e dr1
rr
2

dΩ V V1

‘Particles’(i.e. discrete
Non-particulate systems
inhomogeneities)

r − iqr⋅rr r
I(q ) = ( ρ1 − ρ 2 ) F(q) S(q) I(q) ∝ ( ρ1 − ρ2 )
N
∫ γ ( r )e
2
2 2
dr
V V
single particle
contrast
shape correlation function
2 interparticle
r
rr


iq ⋅ r correlations
e dr
Vp

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Scattering Invariant

10 % black
90 % white
in each square

• Scattered intensity for each would certainly be different

• For an incompressible, two-phase system:

• Domains can be in any arrangement


*Guinier and Fournet, pp. 75-81.

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Porod Scattering
• At large q:

S/V = specific surface area of sample

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Porod Scattering

*Glatter and Kratky, pp. 30-31.


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SANS and Thermodynamics

Thermal density fluctuations also produce


small-angle scattering

ρ2
I(0) = kT β T Isothermal compressibility
V
Composition fluctuations also produce small-
angle scattering

∆ρ 2 ∂ 2Gm Curvature of Free Energy of Mixing


I(0) = kT /
V ∂φ 2

Ref: Introduction to Polymer Physics, M. Doi, 1996

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Multi-Phase Materials

• “contrast” and “structure” terms can still be factored


as for 2 - phase systems

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Multi-Phase Materials

• for ‘p’ different phases in a matrix ‘0’

• Scattering is now a sum of several terms with


possibly many unknown Sij’s
*Higgins and Benoit, pp. 121-122.
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Solving Multi-Phase Structures
Contrast Matching
reduce the number of phases “visible”

ρ solvent = ρ core
(shell visible)

or

(core visible)
ρ solvent = ρ shell

• The two distinct two - phase systems can be easily understood

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Contrast Variation

• A set of scattering experiments can yield a set of equations


of known contrasts and unknown ‘partial structure functions’

• Sturhmann Analysis
Determine structure from Rg = f (contrast)

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NIST Center for Neutron Research (NCNR)
• 20 MW Reactor (4 x 1014 n/cm2-s • 21 beam facilities (7 thermal, 14 cold)
peak thermal flux)
• 6 irradiation facilities
• Large liquid H2 cold source (25 K)

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SANS Instrumentation at the NCNR
CHRNS 30-m SANS
8-m Pinhole SANS 0.010 nm-1 < Q < 6 nm-1
0.05 nm-1 < Q < 0.5 nm-1

Perfect-Xtal USANS 30 m

5 x 10-4 nm-1 < Q < ~ .01 nm-1 NIST / ExxonMobil 30-m SANS
0.008 nm-1 < Q < 7 nm-1

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SANS Instruments at the NCNR
1992

Triple-bounce
Detector
analyzer xtal
shielding

NIST/NSF 30-m SANS

John Barker at Perfect-Crystal


USANS Instrument

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SANS APPLICATIONS
POLYMERS:
• Conformation of Polymer Molecules in Solution and in the bulk
• Structure of Microphase-Separated Block Copolymers
• Factors Affecting Miscibility of Polymer Blends

BIOLOGY:
• Organization of Biomolecular Complexes in Solution
• Conformation Changes Affecting Function of Proteins, Enzymes, DNA/Protein
complexes, Membranes, etc.
• Mechanisms and Pathways for Protein Folding and DNA Supercoiling
CHEMISTRY:
• Structure and Interactions in Colloidal Suspensions, Microemulsions,
Surfactant Micelles, etc.
• Microporosity of Chemical Absorbents
• Mechanisms of Molecular Self-Assembly in Solutions and on Surfaces
of Microporous Media

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Using Deuterium Labeling to Reveal Polymer Chain Conformation
bD
I(Q) ∝ c (b H − b D ) P (Q) 2

P (Q) < - - Single Chain


bH
" Form Factor"
N z rr
∑∑ e
1 iq ⋅ri , j
P (Q) = 2
z i j

High Concentration Labeling


- if labeled chains are randomly dispersed

I(Q) ∝ x (1 - x) (b H − b D ) 2 P(Q)
homopolymer blend
I(Q) ∝ ( x b D + (1 - x)b H ) 2 ST (Q) +
x (1 - x) (b H − b D ) 2 P (Q)
Can determine ST and P(Q) from 2 measurements, with different fractions (x) of labeled chains

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SANS APPLICATIONS
METALS AND CERAMICS:

• Kinetics and Morphology of Precipitate Growth in Alloys and Glasses

• Defect Structures (e.g. microcracks, voids) Resulting from Creep,


Fatigue or Radiation Damage

• Grain and Defect Structures in Nanocrystalline Metals and Ceramics

MAGNETISM:
• Magnetic Ordering and Phase Transitions in Ferromagnets, Spin Glasses,
Magnetic Superconductors, etc.

• Flux-Line Lattices in Superconductors

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General References: SANS and SAXS

Methods of X-Ray and Neutron Scattering in Polymer Science


By R.-J. Roe, Oxford University Press (2000).

X-Ray Diffraction in Crystals, Imperfect Crystals, and


Amorphous Bodies, A. Guinier, Dover Books (1994).

Small-Angle Scattering of X-Rays, A. Guinier and G.


Fournet, John Wiley & Sons (1955).

Polymers and Neutron Scattering, J.S. Higgins and H.C.


Benoit, Clarendon Press-Oxford (1994).
Small Angle X-Ray Scattering, O. Glatter and O.
Kratky, Academic Press (1982).
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Appendix A. Scattering from Two Nuclei
∆d
d Ψscat
∆φ = 2π
λ
r r r r
kf ∆φ = r ⋅ ki − r ⋅ k f
1
r r r
incident
neutrons
r Q ∆φ = r ⋅ (ki − ⋅k f )
r r
∆φ = r ⋅ Q
2
ki
b1 ikR b 2 i ( kR + ∆φ )
Ψscat =− e − e Scattered wave function
R R
SAS of X rays - Guinier (1955), Ch.1
for N nuclei
Polymers and Neutron Scattering,
Higgins & Benoît (1994), p.11

N 2
r r
dσ 1
=
dΩ N ∑b e
1
i
iQ⋅ ri

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Appendix A. Scattering from N Nuclei

2 Scattering cross section: #


N r r
dσ 1 neutrons scattering in
=
dΩ N ∑b e 1
i
iQ⋅ ri
direction corresponding to
Q, divided by # incident per
unit area
r r r Only components
ri = r// + r⊥ r
ri of ri parallel to Q
r r r contribute to
Q ⋅ ri = Q r// Q summation

Therefore, diffraction probes structure in the


direction of Q only!!

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