Cheiron School 2010 @ SPring-8

Small-Angle X-ray Scattering

Basics & Applications

Yoshiyuki Amemiya and Yuya Shinohara

Graduate School of Frontier Sciences,

The University of Tokyo

 Overview

 Introduction
 What’s SAXS ?
 History
 Application field of SAXS
 Theory
 Structural Information obtained by SAXS
 Experimental Methods
 Optics
 Detectors
 Advanced SAXS
 Microbeam, GI-SAXS, USAXS, XPCS etc...
2
What’s Small-Angle X-ray Scattering ?

scattered area detector

x-ray 2θ
Imaging Plate,
transmitted
CCD etc.
sample beam stop

Bragg’s law:

small angle large structure

(1 - 100 nm)

crystalline sample --> small-angle X-ray diffraction: SAXD

solution scattering / inhomogeneous structure --> SAXS

3
 History of SAXS (< 1936)
Krishnamurty (1930)
Observation of scattering
Hendricks (1932)
from powders, fibers, and colloidal
Mark (1932) dispersions
Warren (1936)

carbon black
Molten silica - silica gel

courtesy to Dr. I.L.Torriani 4

 History (> 1936)
A. Guinier (1937, 1939, 1943)
Interpretation of inhomogeneities in Al alloys
“G-P zones”, introducing the concept of “particle
scattering” and formalism necessary to solve
the problem of a diluted system of particles.

O. Kratky (1938, 1942, 1962)

G. Porod (1942, 1960, 1961)
Description of dense systems of
colloidal particles, micelles, and
fibers.
Macromolecules in solution.

Single crystals of Al-

Cu hardened alloy Hemoglobin
courtesy to Dr. I.L.Torriani 5
 Application of SAXS

Typical SAXS image

gel Proteins in solution (Dr. Svergun, EMBL)

100 nm

Nanocomposite
6
 Application of SAXS

 Size and form of particulate system

 Colloids, Globular proteins, etc...
 Inhomogeneous structure
 Polymer chain, two-phase system etc.
 Distorted crystalline structure
 Crystal of soft matter

7
 SAXS of particulate system
larger structure smaller structure

Form of particle
I(q) ~ q-1 (rod)
  ~ q-2 (plate)
Scattering Intensity I(q)

Surface structure
Interparticle I(q) ~ q-(6 - ds)
(ds: surface fractal dimension)

Inter-atomic structure
Size of particle (WAXD)
I(q) ~ exp (-q2Rg2/3)
(Rg: radius of gyration)

Scattering angle 2θ or Scattering vector q

q = 4π sin θ /λ
8
 Basic of X-ray scattering
Scattered X-ray
(wavenumber: ks)
Incident X-ray
Scattering vector
(wavenmber: ki) ks q = k s - ki ρ(r) : electron density
r 2θ
ki
Sample
q = |q|= 4π sin θ /λ

Amplitude of scattered X-ray

Fourier transform of electron density

Scattering intensity per unit volume:

9
 Correlation Function & Scattering Intensity
Correlation function of electron density per unit volume

Patterson Function
(Debye & Bueche 1949)

asymptotic behavior of the correlation function

Scattering Intensity : Fourier Transform of correlation function

10
 Real space and Reciprocal Space

Real Space Reciprocal Space

Electron Density Fourier Trans. Scattering amplitude

ρ(r) A(q)
Autocorrelation

Squaring
Inv. Fourier Trans.

γ(r) I(q)
Autocorrelation Scattering Intensity
Function
11
 Diffraction from Lamellar Structure
ρe
γ (r)
L dc
Q

ρc - ρa dc
ideal ordering
L r

ρe
γ (r)
Q

ρc - ρa dc
Long period changes.
r

ρe
γ (r)
Q

Thickness of crystal changes. ρc - ρa dc

r

real space autocorrelation

12
 Normalized Correlation Function
Local electron density fluctuations:

average density fluctuaitons

Normalized Correlation Function

substitution

Only the average density fluctuations Not observable.

contribute to the signal.
13
 Invariant Q

Omitted.
Parseval’s equality

Parseval’s equality
Fourier Trans.

Invariant:

14
 Spherical sample

ρ (r) I (q)

Fourier Transform

& squared
r

15
Homogeneous sphere

isotropic scattering

courtesy to Dr. I.L.Torriani 16

 Homogeneous elipsiod

Fixed particle Random orientation

anisotropic scattering isotropic scattering

courtesy to Dr. I.L.Torriani 17

 Size distribution

0.1 % Based on Gaussian distribution

Larger distribution 1%
3%
5%
7%
Scattering Intensity

10 %
15 %
20 % When the form has distribution,
30 % fringes are missed.

-2
0 1 2 3 4 5 6x10
-1
q/Å 18
Radius of Gyration -- Guinier Plot

Guinier plot: log (I(q)) vs q2

O. Glatter & O. Kratky ed., “Small Angle

X-ray Scattering”, Academic Press (1982).
19
 Structure Factor & Form Factor
Form of particle
I(q) ~ q-1 (rod)
  ~ q-2 (plate)
Scattering Intensity I(q)

Surface structure
Interparticle I(q) ~ q-(6 - ds)
(ds: surface fractal dimension)
Structure Factor Form Factor
Inter-atomic structure
Size of particle (WAXD)
I(q) ~ exp (-q2Rg2/3) intra-particle
(Rg: radius of gyration) structure
inter-particle structure

Scattering angle 2θ or Scattering vector q

q = 4π sin θ /λ
Separation of S(q) & F(q)
Everlasting issue
(especially, for non-crystalline sample)
Proposed remedy:
•GIFT (Generalized Inverse Fourier Trans.) by O. Glatter

20
 Scattering from Inhomogeneous Structure
Electron Density Autocorrelation Function Scattering Intensity
! "
r Debye-Bueche
ρ̃(r) = exp −
ξ 1
I(q) =
(1 + ξ 2 q 2 )2

two phase system

Autocorrelation Fourier trans.
! " Ornstein-Zernike
ξ r
ρ̃(r) = exp − 1
r ξ
I(q) =
1 + ξ2 q2

polymer chain etc.

21
 Two-phase system
Phase 1: ρ1, volume fraction ϕ Phase 2: ρ2 volume fraction 1 - ϕ

Babinet’s principle
Two complementary structures produce the same scattering.
22
 Two-phase system -- cont.
Averaged square fluctuation of electron density

where

Invariant: does not depend on the structure of the two phases but
only on the volume fractions and the contrast between the two phases.

23
 Porod’s law
For a sharp interface, the scattered intensity decreases as q-4.

internal surface area

Combination of Porod’s law & Invariant

surface-volume ratio
important for the characterization of porous materials

24
Intensity for random particle system
Scattering intensity:

Pair distance distribution function :PDDF

the set of distances joining the volume elements within a particle,
including the case of non-uniform density distribution.

Particle’s SHAPE and maximum DIMENSION.

histogram o all intra-particle distances

pairs of volume
elements i-j

25
Spherical particle

courtesy to Dr. I.L.Torriani 26

Cylindrical particle

courtesy to Dr. I.L.Torriani 27

Flat particle

courtesy to Dr. I.L.Torriani 28

 Ellipsoids
Prolate

Oblate

courtesy to Dr. I.L.Torriani 29

Two ellipsoid = dimer

courtesy to Dr. I.L.Torriani 30

 Diffraction from Periodic Structure
Diffraction from Unit cell (Crystalline structure factor)
!
Incident X-ray
F(q) = f (q) exp(−iq · r j )
j
rj f (q) : Atomic Form Factor

Diffraction
!! !!2 !! !!2
Intensity:
I(q) ∼ !G(q)! !F(q)!
!! !!2 sin2 (πNq · r)
Laue function: !G(q)! =
sin2 (πq · r)
 Maximum ~ N2
 FWHM ~ 2π/N
 FWHM --> Size of crystal

31
 Laue Function
!! !!2 sin2 (πNq · r)
Laue function: !G(q)! =
sin2 (πq · r) N = 100

 Large crystal
 High diffraction intensity
 Narrow FWHM
 Soft matter (crystal size: small)
 Low diffraction intensity
 Wide FWHM N = 50

low S/N N = 10

Crystal size --> Intensity & FWHM of diffraction

32
 Imperfection of crystal (2D)

Imperfection of 1st kind Imperfection of 2nd kind

Thermal fluctuation etc. in the case of soft matter

33
 Imperfection of crystal
Imperfection of 1st kind Imperfection of 2nd kind

Autocorrelation

34
 Imperfection of lattice (1D)
Perfect lattice
(a)

(b)
Imperfection of 1st kind

(c)
Imperfection of 2nd kind

 Effect of imperfections on diffraction ?

35
Diffraction from lattice-structure
A(q)

Diffraction

rj
q

Form of lattice

z(r) with imperfection ---> calculate Z(q)

36
 Imperfection of 1st kind

: distribution function
Fourier trans.

Diffraction with imperfection:

Thermal fluctuation (p(r): Gaussian) ideal lattice

Debye-Waller factor:

- decrease diffraction intensity (no effect on FWHM)

- background at larger angle diffraction
37
 Imperfection of 2nd kind
4

|Z(q)|2/N
2

Paracrystal theory 0
0 1 2 3 4 5 6
q / (2d!)

Decrease of diffraction intensity and

Increase of FWHM
R. Hosemann, S. N. Bagchi, Direct Analysis of Diffraction by Matter,
North-Holland, Amsterdam (1962). 38
 X-ray Source for SAXS
Brilliance -- Product of size and divergence of beam

beam divergence

[photons/(s⋅mrad2⋅mm2⋅0.1% rel.bandwidth)]

Brilliance is preserved (Liouville’s theorem).

beam size

SAXS with a low divergence and small beam

High brilliance beam is required !

39
 SAXS Optics

Ge Bent Monochromator
Sample
Focal Point
PF BL-15A Storage-Ring
2.5 GeV
250-400 mA Bent Mirror
X-ray CCD Detector

PF BL-10C

40
SAXS slits

41
 Detectors for SAXS
Good Point Drawback

•time-resolved •counting-rate
PSPC •photon-counting limitation
•low noise

Imaging •wide dynamic range

•large active area •slow read-out
Plate

CCD
with Image
•time-resolved •image distortion
Intensifier
•high sensitivity •low dynamic range

Fiber-
tapered •fast read-out •not good for time-
•automated measurement resolved
CCD

42
X-ray CCD detector with Image Intensifier

Image Lens Cooled

Intensifier system Cooling
water CCD
Vacuum In Out
Analog I/F Control Unit
Readout
e- Unit &
Driver 14 bit A/D

e-

Be RS-232C
Phosphor screen
RbCsSb CCD Thermoelectro
(Zn, Cd)S:Ag cooler
CsI:Na Digital I/F

Gate High-voltage Pentium Pro

power-supply 200MHz Data
256MB Memory acquisition
IC-PCI included system
Monitor
43
 Advanced SAXS
Microbeam X-ray Time-resolved
- Inhomogeneity of nano-structure - time evolution of structure
- local time evolution of structure

GI-SAXS XPCS
- surface, interface,
thin films
SAXS - structural fluctuation
- dynamics

Combined measurement with DSC, viscoelasticity

wide-q (USAXS-SAXS-WAXS) 2D measurement
- hierarchical structure - anisotropic structure

44
 Application of paracrystal theory
Collab. with Kao ltd.

Single Fiber
(30 - 100 µm)

African Caucasian Asian

X-ray Microbeam
( 5 µm x 5 µm)
Relationship between macroscopic form
and microscopic structure?

Local observation with an X-ray microbeam 45

 Internal structure of wool

α-helix
SEM 像
Coiled-coil dimer

Intermediate Filament - 10 nm
Matrix
Cuticle
（ globular protein ）
Cortex
R. D. B. Fraser et al., Proc. Int. Wool Text. Res.
Conf., Tokyo, II, 37, (1985) partially changed.

H. Ito et al., Textile Res. J. 54, 397-402 (1986).

Relationship between IF distribution

and hair curlness?
46
 Structure of Intermediate Filament
Scattering pattern 1D intensity profile Real space structure
Diameter
Fiber axis

IF
<d>
IF-IF Distance
Fibre Axis

0˚
IF Tilt Angle

FWHM
180˚ IF
0˚ 90˚ 180˚

47
 Diffraction intensity profiles
Diffraction peak originating from IF

scattering intensity [a.u.]

ABCD
inner outer

Inner
A
B
C
D
Outer
scattering vector s = 2 sinθ/λ (Å-1)
Difference in diffraction intensity
--> Structural difference in cortex.
48
 Deformation process of spherulite
drawing direction

130 110

040
0˚

direct beam

POM
(a) SAXS
(b) WAXD
(c)
BL40XU @ SPring-8
Local deformation manner of polypropylene during uniaxial elongation process
Combined measurement of polarized microscope
and microbeam SAXS/WAXD.

50
(a) (b)

(c) (d)

(e)
 Deformation model of PP
(a) (b) (c)

a*

(d)

(a) (b) (c)

Y. Nozue, Y. Shinohara, Y. Ogawa et al., Macromolecules, 40, 2036 (2007).

52
 Grazing Incidence SAXS
Advantage
Surface/interface sensitive (beam footprint).
In-plane structure and out-of-plane structure can be separated.
Thin film sample on substrate can be measured.

Ex: from Web page of Dr. Smiligies @ CHESS

AFM image GI-SAXS image

53
USAXS using medium-length beamline

detector
- 160 m
sample

54
USAXS patterns from elongated rubber
Rubber filled with spherical silica

Stress [MPa]
3

TEM image 2

0 50 100 150 200

strain [%]
elongation

Scattering pattern also shows hysteresis.

Y. Shinohara et al., J. Appl. Cryst., 40, s397 (2007).
55
Structural information from USAXS
10 5
Size of agglomerate
4
10
Scattering Intensity

3
Mass fractal
10 dimension of agglomerate dm
2 larger I(q) ~ q-dm
10
structure
Surface fractal dimension
10 1 of aggregate/particle ds
I(q) ~ q-(6-ds)
10 0 Size of aggregate

-1
10
-2
10
2 4 6 8 2 4 6 8 2 4 6 8
0.001 0.01 0.1
-1
q /Å 56
 X-ray Photon Correlation Spectroscopy: XPCS

 Measurement of fluctuation of X-ray scattering intensity

--> Structural fluctuation in sample
!"#$%&'()&*+,(-'$,,./&#*((0(!)-(1
0(2+3,3#('3//.4$,&3#(56.',/35'36"(7((8#,.#5&,"(94:',:$,&3#(56.',/35'36" 1
4)&*"5(
4)&*"5( ∗
1/)''$%$% speckle
*+66%)/'+"&(
71.$/80$9(
!"#"$
!(2)
!I(q, 0)I (q, τ)#
!""""""""""""""

!"#$%$&'((
pattern
.)''$%& g (q, τ) =
%)*+)'+"&
!
3/)''$%+&-(:$/'"% ! !I(q)#2
$,-,(0)1$%( %" !
#% "#$
0+-#' $,-,(.)%'+/0$( $ !
121.$&1+"& 3/%$$& Time-resolved SAXS with coherent X-ray
1%&!&$')%&!&$,&'2
Fluctuation of intensity;&'$&1+'<( 1%(!2
>1(1/)''$%+&-(5$*+25($:"0:$1?( %
!
) + '#0& (*! relaxation time in system
1.$/80$(.)''$%&(602/'2)'$1 )2'"/"%%$0)'+"&(
62&/'+"& 1%(2!
'()* 1.030
5
%&!&$' )* ()*+,-
Scattering Intensity

Autocorrelation

Autocorrelation
./)*+% "
;&'$&1+'<()'( 1.020
15)00(4 @$0)<('+5$(((((&
*$'$/'"%
'()* 3'%2/'2%$("6(!"#$%&$'!(#$)*+(##$%!",)-."+#!/"?( 1.010
3 +&#&&'0 -+:$1(+&6"%5)'+"&("&(1/)''$%$% *<&)5+/1
=+5$((((((((((((((((((((($
1.000
0 50 100 150 200 2 4 6 8 2 4 6 8 2
1 10 100
Time /s Time /sec
57
 Dynamics of nanoparticles observed with XPCS

Scattering Intensity
coherent x-ray 4

100nm 0 50 100 150 200

Time /s
nano-particles in rubber speckle pattern fluctuation of
scattering intensity

Dependence of dynamics on...

- Volume fraction of nano-particles 1.030

- Vulcanization (cross-linking)

Autocorrelation
1.020

- Type of nano-particles 1.010

- Temperature etc. 1.000
2 4 6 8 2 4 6 8 2
1 10 100
Time /sec

Dynamics of Filler in Rubber

58
 WAXS SAXS USAXS
1 0 -1 -2 -3 -4 -5
t/s 10 10 10 10 10 10 10 q/nm-1
103
E /eV
X-ray Photon Correlation -15
10
0 10
Spectroscopy

-12

Light Scattering
10
-3 10
Photon Correlation

10 -6 10-9
"cold"
Neutron Scattering
NSE
10
-9 10-6
BS

-3
-12 Brillouin 10
10 TOF Raman

Inelastic X-ray Scattering 0

10 -15 10

10-1 100 101 102 103 104 105 r/nm

 Bibliography

 A. Guinier and A. Fournet (1955) “Small angle scattering of X-rays” Wiley &
Sons, New York. out-of-print
 O. Glatter and O. Kratky ed. (1982) “Small Angle X-ray Scattering” Academic
Press, London. out-of-print
 L. A. Feigin and D. A. Svergun (1987) “Structure Analysis by Small Angle X-ray
and Neutron Scattering” Plenum Press. out-of-print ?
 P. Lindner and Th. Zemb ed. (2002) “Neutron, X-ray and Light Scattering: Soft
Condensed Matter”, Elsevier.
 Proceedings of SAS meeting (2003 & 2006). Published in J. Appl. Cryst.
 R-J. Roe (2000) “Methods of X-ray and Neutron Scattering in Polymer Science”,
Oxford University Press.

60