A Big-Angle View of

Small-Angle
Measurements:
SAXS Techniques
Welcome

„ A Tour of the Nano-Cosmos

• Introduction to SAXS
• 1D SAXS Instruments
• 1D SAXS Application
Examples
• 2D Method - NanoSTAR
• 2D Simultaneous
SAXS/WAXS
Brian Jones
Sr. Applications Scientist • NanoSTAR – Typical
Bruker AXS Inc. Applications
• Summary
Kurt Erlacher
Sr. Applications Scientist • Q&A
Bruker AXS GmbH
Introduction to SAXS

Brian Jones
 The SAXS Experiment

sinθ = λ / 2d XRD
diffraction at crystal lattice
Large θ Æ small d diffraction angles: 4 - 170°
Small θ Æ large d

SAXS
scattering at particles or
d electron density changes
incident scattering angles: 0 - 4°
X-ray beam

d Æ 10 – 100nm
Nanostructural Parameters
Obtained from SAXS

„ Mean size, size distribution

„ Shape (spheric, cylindric,

platelet, cubic ...)

„ Orientation, degree of orientation

„ Mean distance between particles

Scattering Vector q

ks
q
2θ

ki

q ≡ 4π sin θ / λ
d = 2π / q
For isotropic systems (fluids, glasses,
polycrystals):
→ no direction dependence of the scattered
radiation
 Example SAXS Scattering Curve
log – log Scale
HDPE
100

HDPE: 600 s

10

0.1

0.01

0.001
0.001 0.01 0.1 1

q [Å-1]

0.014° 0.14° 1.4°

2θ
Transmission SAXS

„ X-rays are incident normal to the surface of the

sample and transmission is sufficient to provide
suitable SAXS scattering intensity.

I0 Is
Liquid dispersions, gels, powders,
sheets, etc.
Grazing Incidence Small-Angle X-Ray
Scattering (GI-SAXS)
GI – Incident angle close to the critical angle (0.1 to 1 degree)
SAXS - length scale, beam definition by multiple slits, and
(usually) an area detector.

Nanoscale particles embedded in a

matrix subsurface, supported on a
substrate or buried in a thin layer on
a substrate.

Examples:
Semiconductor quantum
dots/islands
Porous films on substrates
Condensed powder
Nanoparticles embedded in polymers
1D SAXS Instruments

Brian Jones
 SAXS Breakdown by Instrument Type

Transmission SAXS
NanoSTAR
Point GI-SAXS
collimation
Transmission SAXS
D8 GADDS
GI-SAXS
1D
Transmission SAXS
D8 Advance
GI-SAXS
Line
collimation Transmission SAXS
D8 Discover
GI-SAXS
Bruker AXS Instruments
1D SAXS

D8 Advance D8 Discover
1D SAXS Line Collimation Goals

„ Monochromatic X-rays

„ High intensity beam

„ Well collimated beam

„ Axial divergence minimal

„ Beam width is narrow and adjustable for high-flux / high-

resolution trade-off.

„ Background to either side of direct beam is very low

„ (optional) Can scan over the direct beam to determine sample

transmission.
1D SAXS Line Collimation Goals
„ Monochromatic X-rays
Gobel Mirror
„ High intensity beam
Gobel Mirror
„ Well collimated beam
Gobel Mirror + aperture slits
„ Axial divergence minimal
Soller slits
„ Beam width is narrow and adjustable for high-flux / high-
resolution trade-off
2 incident beam slits and 2 diffracted beam slits of various
sizes
„ Background to either side of direct beam is very low
4 aperture slit system with narrow apertures and optional knife
edge
„ (optional) Can scan over the direct beam to determine sample
transmission
Rotary absorber
Gobel Mirror – Monochromatic, High
Intensity, Collimated

„ Parabolic, laterally
graded, multilayer
mirror

„ Captures a large solid

angle of divergent
radiation and converts
to collimated,
monochromatic beam
Soller Slits
Reduce Axial Divergence

„ Many closely spaced

metal foil pieces
stacked parallel to
one another.

„ Controls the angular

acceptance angle
along the axial
direction.
D8 SAXS Transmission Configuration

soller1
Gobel mirror
detector

slit1 slit2 slit3 slit4

and/or knife edge

Hardware Configuration

Slit4 Slit3 Slit2 Slit1

Rotary Gobel
Soller1 Absorber Mirror
D8 Advance/Discover
Typical Experimental Setup

„ Measurement diameter = 500mm – 600mm

„ Cu tube (40kv, 40mA)
„ 60mm 3rd generation Gobel mirror
„ 0.2 mm mirror exit slit
„ Rotary Absorber (RA)
„ 0.1 mm slit after RA
„ 0.1 deg anti-scatter slit
„ 1.5 degree Soller slit
„ 0.1 mm detector slit
„ Scintillation counter
 Audience Poll

„ Please use your mouse to answer

the question on your screen:

What types of samples do you

analyze? (Check all that apply):

‰ liquid
‰ powder
‰ gel
‰ sheet
‰ fiber
‰ thin film
‰ solid/bulk
SAXS Transmission Sample Holders

„ Holder for
sheets,
powders,
gels, etc.
SAXS Transmission Sample Holders

„ Liquids, powders,
deposited in
capillary tube
D8 Advance Goniometer Head-Mount
Stage

„ Entire stage can

be quickly
removed and
replaced
D8 Advance Goniometer Base Stage
Sample Holder Attached
D8 Advance
Primary Beamstop and Knife Edge

„ Mounts to primary
beam track.

„ Beamstop behind the

sample.

„ Knife edge in front of

sample.

„ Compatible with many

D8 Advance
transmission sample
holders
D8 Advance
Primary Beamstop and Knife Edge

„ Knife edge
used to
reduce
parasitic
scatter
D8 Advance
Primary Beamstop and Knife Edge
D8 Discover

Vertical Horizontal
D8 Discover
Centric Eulerian Cradle

„ Mounted on
diffractometer
permanently
D8 Discover - Capillary Spinner for
Eulerian Cradle Stage

„ Beamstop and knife edge

are adjustable or can be
completely removed from
beam path.

„ Goniometer head base will

accommodate numerous
sample holders.
D8 Discover – Capillary Spinner
Mounted to Eulerian Cradle

„ Drawing of capillary
spinner mounted to
Eulerian cradle on a
horizontal system
D8 Discover – Capillary Spinner
Mounted to Eulerian Cradle

„ Only knife edge

is mounted
D8 Discover – Capillary Spinner
Mounted to Eulerian Cradle

„ Knife edge and

capillary
holder are
mounted to
the capillary
spinner for the
Eulerian cradle
 1D SAXS –
Application Examples

Brian Jones
Example 1: Glassy Carbon

„ Glassy Carbon is a porous material often used as a standard in

SAXS. The pore size and shape have been previously
determined with high accuracy.

„ Ellipsoid pore shape

„ Outer radius ~ 20-23 A
„ b/a (aspect ratio) = 0.3
 Example 1: Glassy Carbon
1D SAXS Scattering Curve

1e7 „ Glassy carbon

1e6
„ Empty beam

1e5
Log (Cps)

1e4

1000

100

10

-2 -1 0 1 2 3 4 5

2-Theta - Scale
File: MES=0.2, RA=0.1, AS=0.1 deg, double soller, DetS=0.1.raw
File: MES=0.2, RA=0.1, GC, AS=0.1 deg, double soller, DetS=0.1.raw
Example 1: Glassy Carbon
Analysis with DiffracPlus Nanofit

„ Least-squares data analysis

program for small angle
scattering data by direct
modeling

„ Supports basic geometric

models and polymer models,
polydispersity, and
concentration effects
Example 1: Glassy Carbon
Direct Modeling with Nanofit
„ The graph shows the
experimental data (blue)
and the fit (red)

„ The measured scattering

profile can be nicely
described by using a
model for ellipsoids

„ Previously determined
Pore dimensions:
• Outer radius:
r = 20-23 Å
• Aspect Ratio:
b/a = 0.3

„ Results of D8 SAXS fit:

• Outer radius:
r = 19.7Å
• Aspect Ratio:
b/a = 0.303

Good Agreement!
Example 1: Glassy Carbon

Lower limit of fit Æ q = 0.0106 A-1

d = 2π/q ~ 60 nm
 Example 1: Glassy Carbon
Using Knife Edge
1e5

1e4

1000
Log (Cps)

100

10

6
5
4
3
2

0.1 1 2

2-Theta - Scale
File: MES=0.1, RA=none, KE3, AS=0.1 deg, 1.5 soller, DetS=0.1 background.raw
File: MES=0.1, RA=none, KE3,GC, AS=0.1 deg, 1.5 soller, DetS=0.1.raw
 Example 1: Glassy Carbon
Improved Resolution with Knife Edge
2e5

1e5

„ Meaningful
SAXS data as
low as q =
1e4

0.0085 Å-1
Log (Cps)

1000

„ d ~ 75nm
100

10

6
5
4
3
2

0.1 1 2

2-Theta - Scale
File: MES=0.1, RA=none, KE3,GC, AS=0.1 deg, 1.5 soller, DetS=0.1.raw
Example 2: NIST Reference Standard
Au Nanoparticles in Liquid Suspension

Mean particle size

Particle size distribution

*https://srmors.nist.gov/view_detail.cfm?srm=8011
 Example 2: NIST SRM 8011 Au
Nanoparticles –1D SAXS Scattering Curve

„ Scaled direct beam

scattering

„ NIST SRM 8011

scattering
Log (Counts)

0.2 1 2
2θ
Example 2: NIST SRM 8011 Au
Direct Modeling with Nanofit
„ Background
corrected SAXS
(blue) and fitted
SAXS (red)

„ Fitting results:

Mean sphere radius

= 45.54 Å

Size distribution
modeled by a
Gaussian
distribution with
sigma = 3.65 Å
Example 2: NIST SRM 8011 Au
Nanoparticles – Comparison

Results from D8 Advance SAXS

modeled with Nanofit

Mean particle size = 9.108 nm

Example 3: Nano-Metallic Particles
Deposited on Carbon Black Substrate

„ For SAXS measurements, sample was deposited

between 2 pieces of adhesive tape.

„ For comparison, this sample was run on the 2D

Bruker AXS dedicated SAXS instrument, the NanoSTAR
 Example 3: Metallic Nanoparticles
1D SAXS Scattering Curve from NanoSTAR

1e+5
„ Azimuthally
averaged intensity
1e+4 vs. scattering
1e+3
vector q and the
scattering intensity
1e+2 of the holder that is
Log (Intensity)

1e+1
used for correction

1e+0 4π
q= sin θ
λ
1e-1

1e-2 „ where 2θ is the

scattering angle
1e-3
and λ is the used
0.01 0.1
wavelength
q (A-1)
q vs Sample 1
q vs tape only
 Example 3: Metallic Nanoparticles
1D SAXS Scattering Curve from D8 Advance
Powder in tape „ Detector scan:
1e7
Tape only (background) 2θ = -2 to 3°

1e6

„ Step size = 0.02°

1e5

„ Count time = 2.3

Log (Cps)

1e4
seconds/step

1000

100

-2 -1 0 1 2

2-Theta - Scale
File: sample 1 in tape.raw - Type: Detector Scan
File: just tape.raw - Type: Detector Scan
 Example 3: Metallic Nanoparticles
1D SAXS Scattering Comparison

1e+5
„ Comparison of
background-
1e+4 corrected SAXS
1e+3
scattering shown on
a double-log scale
1e+2
Log (Intensity)

1e+1 „ Intensity is given in

1e+0
arbitrary units and
the profiles are
1e-1 Nanostar U separated by a
1e-2
D8 Advance scaling factor

1e-3
„ Note the similarity
0.01 0.1
of the scattering
q (A-1) profiles
 Example 3: Metallic Nanoparticles
Analysis - Comparison

1e+5 1000

1e+4
100

Log (Intensity)
Log (Intensity)

1e+3
10

1e+2

1
1e+1

D8 Advance 0.1
NanoSTAR
1e+0
0.01 0.1
0.01 0.1
-1
q (A )
q (A-1)

„ Scattering profiles after Carbon black is removed

Example 3: Metallic Nanoparticles
Direct Modeling with Nanofit - NanoSTAR

„ This profile is fitted

assuming a model
for spherical
structures.

„ The best fit is

obtained using size
polydispersity
(Schultz).

„ Fit results:
• Radius: 32.4 Å
• σ of Schultz size
distribution: 11.9Å.
Example 3: Metallic Nanoparticles
Direct Modeling with Nanofit – D8 Advance
„ This profile is fitted
assuming a model
for spherical
structures

„ The best fit is

obtained using size
polydispersity
(Schultz)

„ Fit results:
• Radius: 32.2 Å
• σ of Schultz size
distribution: 9.7Å.
Example 3: Metallic Nanoparticles
Nanofit Comparison

„ Fit results (NanoSTAR):

• Radius: 32.4 Å
• σ of Schultz size distribution: 11.9Å

„ Fit results (D8 Discover):

• Radius: 32.2 Å
• σ of Schultz size distribution: 9.7Å
GI-SAXS Examples
GI-SAXS Geometry Configuration

„ Grazing incidence angle near the

critical angle is set to make the
configuration surface sensitive.

„ Detector on secondary diffracted

beam track is scanned along qy

„ Scattering geometry combining

SAXS condition with conditions
diffuse x-ray reflectivity
GI-SAXS Geometry
Modify Ultra GID Configuration

Ultra GID geometry

Replace Beam Compressor with

Soller slit for GI-SAXS configuration
0,12 0,12 GM
GI-SAXS Example 1 - Au Nanoparticles
Embedded a Polymer Matrix

Fit result: 80 Å diameter

spherical nanoparticles
 GI-SAXS Example 2 – Quantum Dot Film

„ Parallel beam
„ 0.2 mm slit after
1e6

mirror
1e5
„ 0.12 degree thin film
attachment (incident)
1e4
„ 0.12 degree thin film
(diffracted beam)
Log (Counts)

1000 „ Secondary Detector

Scan
100
• Incident angle = 0.5
deg.
• 2θ = -5 to 5 degrees
10
• 0.024 degree
stepsize
1
• 0.4 s / step
• Total scan time < 3
-5 -4 -3 -2 -1 0 1 2 3 4 5

2-Theta - Scale
File: GISAXS3 .raw - Type: Detector Scan minutes
Operations: Import
GI-SAXS Example 2 – Quantum Dot Film

„ Peaks are fit

with TOPAS and
positions are
given in d-
spacing

89.41(49) Å „ 1st and 2nd

order peaks are
visible
45.2(10) Å
Summary
1D SAXS with D8 Advance/Discover

„ 1D SAXS capability integrated into multipurpose instruments,

D8 Advance and D8 Discover

„ Sample stages for investigating liquids, powders, gels, sheets,

fibers, thin-films, etc.

„ Configuration can be easily modified to obtain maximum

resolution or maximum intensity to accommodate the sample

„ Powerful GI-SAXS capability using a modification of the Ultra GID

configuration

„ Dedicated software, Nanofit, for direct modelling of SAXS

scattering resulting in a detailed analysis of particle shapes, sizes,
size distributions, and concentration effects
2D Method - NanoSTAR

Kurt Erlacher
 Audience Poll

„ Please use your mouse to answer

the question on your screen:

What method do you need to

analyze preferred-orientation
samples?

 1D SAXS
 2D SAXS
 Not sure
NanoSTAR

Collimation systems for high flux, Automatic XY

high resolution or Nanography sample stage Motorized
reference sample
holder

Multiple
X-ray
sources
available

Sample can be
simple
investigated
alignment
under vacuum
concept
or atmospheric
condition

D8 based electronics Integrated radiation safety

IμS - Incoatec Microfocus Source
The Brightest Sealed Tube X-ray Source
„ no moving parts,
„ very long lifetime without
maintenance
„ extremely stable
„ no water-cooling required
„ easy to replace
„ low cost of ownership -
comparable to common
sealed tubes
„ significantly more intense
than previous microfocus
source designs
„ operation power 30 W
„ 2D parallel beam Montel
mirror in an evacuated
housing
Turbo X-Ray Source TXS

„ Implementation of advanced
technologies
„ Direct drive anode
„ Ceramic feed through for
cathode powder supply
„ Alignment-free filament
mounting
„ New shutter and safety
concept, similar to sealed
tube D8
Optics
Montel Multilayer Mirror

„ Arrangement
• two identical mirrors in a
side-by-side configuration

„ Benefits:
• more compact
• easy alignment
• symmetrical divergence spectrum

Montel mirror: two identical

mirrors in a side-by-side
configuration (W/C coating,
deposit by magnetron sputtering)
Variable Source to Sample Distance
„ Pin hole alignment better than 10µm, even
under vacuum conditions
„ Integration of primary beam path into the
radiation safety system
„ Easy exchange of pin holes for configuring high
resolution set up (larger structures)

„ Easy reconfiguration to scanning SAXS

2 pin hole collimation by removing the beam
path tubes and pin hole pedestal and sliding
the X-ray source along the track
Pinhole Collimation

„ Distances between pinholes:

1st pinhole - 2nd pinhole - 3rd pinhole – sample - detector:
925 mm – 482 mm – 35 mm - variable
„ Diameter of first / second / third pinhole:
SAXS configuration: 0.75 / 0.4 / 1.0 [mm]
HRSAXS configuration: 0.5 / 0.15 / 0.5 [mm]
„ Available beamstop diameters: 2.0 - 4.2 mm
„ SAXS configuration provides approximately 10 times higher flux
„ Typical experimental q-range with e.g. 105 cm sample to
detector distance:
SAXS configuration: 0.009 Å-1 to 0.21 Å-1 (700 Å to 30 Å)
HRSAXS configuration: <0.005 Å-1 to 0.22 Å-1 (>1250 Å to 30 Å)
Nanography
Scanning-SAXS

X-ray Nanography is
the non-destructive
investigation of
nm structures of
mm sized samples
with µm resolution

SAXS pattern at the

beginning of the
crack

SAXS pattern
outside the crack
HI-STAR
2D Multi-Wire Detector
„ Multi wire gas filled proportional counter
„ Real time data collection and display
„ High sensitivity and low background
„ Dynamic range > 106
„ Energy resolution <20%
„ >80% single photon sensitivity for Cu-
radiation

„ The beamstop is made of low fluorescence

material to ensure minimum background
„ Mounted with Kapton strings for full 360
access to scattered photons
„ Alignment accuracy better than 10µm
VÅNTEC-2000
2D Mikro-GapTM X-Ray Detector

„ High Spatial Resolution

unrivalled data accuracy in
precision and accuracy
„ High Local and Global Count
Rate
„ High Dynamic Range
„ Radiation Hard
„ Inert Counting Gas
no maintenance required
„ Large active area
conveniently increases qmax
 Data Evaluation with
DIFFRACplus NanoFit
„ NanoFit is an interactive
graphic-based, non-
linear, least-squares
data analysis program
for small angle X-ray
scattering (SAXS) data
by direct modeling.

„ The displayed data (blue dots) are the calculated scattering

data for a model of Polydisperse Spherical Block Copolymer
Micelles with a smooth interface and a Hard Sphere
Structure Factor with statistical noise added.
„ The red line is the fitted scattering profile using the same
model.
DIFFRACplus NanoFit

„ Set of several built-in nano particle models

„ Basic geometrical models (spherical, ellipsoidal, cylindrical).
„ Selected polymer models (flexible and semi-flexible chains, Gaussian star,
spherical block copolymer micelle)
„ Polydispersity (Gaussian or Schultz size distribution)
„ Concentration effects (Hard-Sphere or RPA structure factor)
„ Automatic Fitting
„ Different refinement methods for automatic evaluation:
„ Levenberg-Marquardt
„ Simplex
„ Online display of intermediate results and changes of the chi² cost function.
„ Selectable fit region.
„ Graphical evaluation of one-dimensional data sets
„ Display and comparison of measured and simulated data.
„ Simple, interactive evaluation of SAXS measurements:
„ Easy interactive adjustment of all available model parameters.
„ Wide selection of commonly used axis scaling.
2D Simultaneous SAXS/WAXS

Kurt Erlacher
Simultaneous SAXS/WAXS
Experimental Setup
„ Turbo X-ray Source, focal spot = 0.1 mm x 1 mm
„ Cu-Kα 50 kV / 24mA, from point focus (0.1 mm x 0.1 mm)
„ Montel-P multilayer optics
„ Diameter of first / second / third pinhole = 750 mm / 400 mm /
1000 mm
„ Diameter of beamstop: 4.3 mm
„ SAXS:
sample – detector distance: 1063.5 mm
Bruker AXS HI-STAR position sensitive area detector
„ WAXS:
sample – detector distance: 51.8 mm
FUJIFILM FLA-7000 Imaging Plate reader system
„ Software: SAXS for WindowsTM NT
SigmaPlotTM
Simultaneous SAXS/WAXS

„ FUJI FLA-7000 IP WAXS

DETECTOR
„ Image Plate detector system for
recoding WAXS (wide angle x-ray
scattering)
„ About 20 x 25 cm large IP is
mounted into the NanoSTAR
sample chamber
„ Read-out of the signal is executed
off-line using a FLA-7000 scanner
(Fuji)
„ Obtained SAXS/WAXS data are
read by Bruker AXS 2D software
for further data evaluation
Simultaneous SAXS/WAXS
Samples

„ Reference Materials: Silver Behenate

Corundum (NBS SRM 674)

„ Ordered Mesoporous silica: Meso-SiO2 1)

„ Samples were measured at room temperature

„ SAXS and WAXS signals were collected simultaneously!

1) samples were kindly provided by M.-O. Coppens, Delft University

of Technology, and Rensselaer Polytechnic Institute, Troy NY
System Calibration
Silver Behenate (AgBh)
„AgBh is ideal because it 1e+6

can be used as a 1e+5

calibrant for both, the

Measured intensity I(q)

1e+4

SAXS (top) as well as the

1e+3

WAXS (bottom) signal

1e+2

„http://srs.dl.ac.uk/NCD/st 1e+1

ation82/silver_behenate. 1e+0

html 0.00 0.05 0.10

q [Å-1]
0.15 0.20 0.25

1e+0

„Debye-Scherrer rings are

0.0 0.5 1.0 1.5 2.0 2.5 3.0
2 Theta [deg]

used for determination

of: 1e+7

„ exact sample-

Measured intensity I(q)

1e+6

detector distance
„ center position of 1e+5

primary beam
„Measurement time was 1e+4
0 1 2 3 4 5
120s. 1e+4
q [Å-1]

0 20 40 60
2 Theta [deg]
NBS SRM 674
α-Al2O3
„ α-Al2O3 is a good standard for
the WAXS region only (and
was used as a cross
reference)
„ Notice the sharp peak profile
„ Measurement time was 300s
„ Incident beam was
attenuated by a factor of 10

6e+6
Measured intensity I(q)

4e+6

2e+6

0 10 20 30 40 50 60 70

2 Theta [deg.]
MESO-SiO2
2D SAXS / WAXS Pattern

„ Individual SAXS (left) and WAXS (right) pattern

that were measured simultaneously
„ Measurement time was 318 s
 MESO-SiO2

1e+5 1e+7

1e+4

Measured intensity I(q)

Measured intensity I(q)

1e+6
1e+3

1e+2
1e+5

1e+1

1e+0 1e+4
0.00 0.05 0.10 0.15 0.20 0 1 2 3 4
q [Å-1] q [Å-1]
1e+0 1e+4
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0 20 40 60
2 Theta [deg] 2 Theta [deg]

„ Individual SAXS (left) and WAXS (right) profiles

that were measured simultaneously
„ Measurement time was 318 s
 MESO-SiO2
Combined SAXS/WAXS Profile
1e+5 1e+5

1e+4 1e+4

Measured intensity I(q)

Measured intensity I(q)

1e+3 1e+3

1e+2 1e+2

1e+1
1e+1

1e+0
1e+0

1e-1
1e-1

1e-2
1e-2
0 20 40 60 80
0 1 2 3 4
q [Å-1] 2 Theta [deg]

„ SAXS/WAXS profiles that were measured simultaneously

„ Intensities are plotted vs. reciprocal lattice vector q (left) and vs.
scattering angle 2 Theta (right)
„ Measurement time was 318 s
Summary SAXS/WAXS

„ Simultaneous SAXS/WAXS experiments were performed on the

standards Silver Behenate, α-Al2O3 as well as on the mesoporous
silica samples MESO-SiO2
„ All samples show distinct scattering characteristic in the wide angle
regime
„ In order get a fully continuous profile from the SAXS towards the
WAXS region it is possible to asymmetrically align the Image Plate for
WAXS experiments
„ In addition the sample to Image Plate position can be varied such that
the max. 2 Theta angle is either around 50°, 70° (current data) or
82°
 NanoSTAR U
Typical Applications

Kurt Erlacher
Typical Applications
„ Gold Nanoparticles
„ Size dependence on preparation temperature
„ Biological Macromolecues
„ Dimension of viruses and its monodispersity
„ Conformation state
„ Block Copolymer Micelles
„ Shape and dimension of micelles
„ Radial excess electron density profile
„ Liquid Crystals
„ Microdomain structure like lamellar, cylinder or hexagonal array
„ HDPE
„ Lamellar thickness
„ Nanography
„ Distribution of mineral particles in trabecular bone
„ Superalloys
„ Size of precipitates as a function of temperature treatment
Application Gold Nano-Particles
„Preparation according
HAuCl4.3H 2 O Oct4 N +Br-toluene
aq
Schiffrin Procedure1) for
series 1 and 8
„Modified procedure to
Oct4N + AuCl4-toluene HBr aq avoid water in the
synthesis for an
n-C 12H 25 SH
extended temperature
Applying the desired NaBH 4 aq
range
temperature
„All samples were
Water with excess NaBH 4
prepared with the same
relative amount of of
Work-up
gold/thiol (4:1) and
gold/NaBH4 (1:10)

MPC's 1) Brust, M.; Walker, M.; Bethell, D.; Schiffrin,

D.J.;Whyman, R. J. Chem. Commun. (1994) 801- 802
 SAXS Profiles and Results

⎛ 3 sin (qR ) - qR cos(qR ) ⎞

2
SAXS
P(q, R) = ⎜⎜ ⎟
⎟
⎝ (qR ) 3
⎠
4π
1.1a
1
q= sin(θ )
1.1c
1.2b
1.3a λ
1.3c
0.1 1.4b
I(q) ∝ ∫ D( R) V ( R) 2 P(q,R) dR
dσ/dΩ [cm ]

Fit
-1 -1

Size Distribution
1.0
0.01 1.1a
1.1c
1.2b
0.8 1.3a
1.3c
1.4b

0.6
0.001

D(R)
0.4

0.2
0.0001
0.01 0.1 0.0
0 10 20 30 40 50
-1
q [Å ] R [Å]
Results

3.0

2.8

2.6

2.4
Rg / nm

2.2

2.0

1.8

1.6

1.4
-40 -20 0 20 40 60 80 100
o
T/ C

„ The Radius of Gyration Rg

can be calculated from the 3 M8
Rg 2 = with M n = ∫ D( R ) R n dR
particle size distribution 5 M6
D(R) by
Comparison with TEM

T = 81.4°C

T = 31.5°C

T = -17.0°C
Conclusion

„ A clear relation between the average size of the colloids and their
preparation temperature is observed
„ The size of the colloids is not only controlled by the gold to thiol ratio
but also by the temperature
„ By means of a non aqueous approach it is possible to expand the
temperature interval in which the gold colloids are prepared
„ A trend towards a similar temperature dependence was found

Jørgen M. Jørgensen, Kurt Erlacher, Jan S. Pedersen,

and Kurt V. Gothelf. Langmuir 2005, 21, 10320-10323
 Application TBSV
Tomato Bushy Stunt Virus
Physical and biochemical properties

Particle morphology
Virions isometric; 30 nm in diameter.

Physical properties
One sedimenting component in purified
preparations; sedimentation coefficient 135
S. Density 1.36 g cm-3 in CsCl (unfixed).

Biochemical properties
Genome consists of RNA; single-stranded.
Total genome size 4.7 kb. Genome
unipartite; largest (or only) genome part 4.7
kb.

Features of proteins
Virion protein(s) one; Mr 37000; coat Brunt, A.A., Crabtree, K., Dallwitz, M.J., Gibbs, A.J.,
protein. Watson, L. and Zurcher, E.J. (eds.) (1996 onwards).
`Plant Viruses Online: Descriptions and Lists from the
Cytopathology VIDE Database. Version: 20th August 1996.' URL
Virions found in cytoplasm, in nuclei, and in http://biology.anu.edu.au/Groups/MES/vide/
mitochondria
SAXS Data
2D Pattern of TBSV 20 mg/mL

„ The sample
shows an
isotropic
scattering
behavior

„ Measurement
time is 5400 s
Experimental Data and Fit

TBSV20mg/mL
TBSV 18.9 mg/mL „ Background
corrected data of the
100
Experiment
azimuthally averaged
10 Fit scattering intensities
of the TBSV sample.
1
„ The red line gives
dσ/dΩ [cm ]
-1

0.1 the fit of the Fourier

Transform of the pair
0.01
distance distribution
0.001
function p(r) to the
experimental data.
0.0001
0.0 0.1 0.2 0.3
q [Å-1]
TBSV Compact
Pair Distance Distribution Function p(r)

TBSV 20mg/mL
TBSV 18,9 mg/mL „ The shape of the p(r)
0.06 functions indicates
spherical particles
0.05
„ Rg = 123.1 ± 0.1 Å
0.04 „ I(0) = 121.2 ± 0.4 cm-1
„ Dmax = 320 Å
p(r)

0.03

0.02
„ Note that the error bars of
0.01 the p(r)-function are smaller
than the thickness of the
0.00 drawn red line
0 50 100 150 200 250 300

r [Å] „ The data were fitted using a

program written by Jan Skov
Pedersen
TBSV Compact
Experiment and Fit

TBSV
TBSV1mg/mL
TBSV 0.91
0.91 mg/mL
mg/mL „ Background corrected
data of the azimuthally
10
10 averaged scattering
Experiment intensities of the TBSV
Experiment
11
Fit
Fit sample.
„ Measurement time was
5400s.
[cm-1]]
-1

0.1
0.1
dσ/dΩ [cm

„ The red line gives the fit

dσ/dΩ

0.01
of the Fourier Transform
0.01
of the pair distance
distribution function p(r)
0.001
0.001
to the experimental
data.
0.0001
0.0001
0.0
0.0 0.1
0.1 0.2
0.2 0.3
0.3
-1
[Å-1]]
qq [Å
TBSV Compact
Pair Distance Distribution Function p(r)
TBSV 1mg/mL
0,91 mg/mL
The shape of the p(r)
0.0025
functions indicates spherical
particles
0.0020
„ Rg = 120.7 ± 0.3 Å
„ I(0) = 4.77 ± 0.03 cm-1
0.0015
„ Dmax = 320 Å
p(r)

0.0010

0.0005

0.0000
0 50 100 150 200 250 300
„ The data were fitted using
r [Å] a program written by Jan
Skov Pedersen
TBSV Compact
Experiment and Fit
TBSV
TBSV
TBSV20mg/mL
18.9
18.9 mg/mL
mg/mL
1.0
1.0

0.8 Experiment
Experiment
0.8
„ Linear plots of the
Fit
Fit
[cm-1]]
-1
dσ/dΩ [cm

0.6
0.6
low-q-range of the
dσ/dΩ

0.4
0.4
TBSV samples
0.2
0.2
„ Intensity ratio
0.00
0.00 0.02
0.02 0.04
0.04 0.06
0.06 0.08
0.08 0.10
0.10 between first peak
-1
[Å-1]]
qq [Å
and the previous
TBSV
TBSV
TBSV 0.91
0.91 mg/mL
1mg/mLmg/mL minimum is around
0.05
0.05

0.04
0.04 Experiment
Experiment
10 for the high
concentration sample
[cm-1]]

Fit
-1

Fit
dσ/dΩ [cm

0.03
0.03
dσ/dΩ

0.02
0.02

0.01
0.01

0.00
0.00 0.02
0.02 0.04
0.04 0.06
0.06 0.08
0.08 0.10
0.10
-1
[Å-1]]
qq [Å
 Application Lysozyme
Vizualization of hen egg
0.1 white lysozyme as
6.6 mg/mL provided by the Protein
2.63 mg/mL Data Bank (PDB 2LYZ).
Fit 6.6 mg/mL
Fit 2.6 mg/mL Pair Distance Distribution Function
0.01 0.00025
dσ/dΩ [cm-1]

6.6 mg/mL
0.00020 2.6 mg/mL

0.00015

p(r)
0.001 0.00010

0.00005

0.00000
0 10 20 30 40 50
0.0001
0.0 0.1 0.2 0.3 0.4 r [Å]

q [Å-1] „ Resultant pair distance distribution function

p(r) normalized by the concentration.
„ Lysozyme in aqueous solution „ 6.6 mg/mL:
„ The red lines give the fit of the Fourier „ Rg = 14.8 ± 0.1 Å
Transform of the pair distance distribution „ I(0) = 0.060 ± 0.004 cm-1
function p(r) to the experimental data „ Dmax = 45 Å
„ The sample was measured in an quartz „ 2.6 mg/mL:
capillary at T=4°C „ Rg = 14.3 ± 0.2 Å
„ Measurement time was 5400s for both, the „ I(0) = 0.024 ± 0.003 cm-1
sample and the solvent „ Dmax = 42 Å
 Application Urate Oxidase
Vizualization of
UNCOMPLEXED
10 URATE OXIDASE
FROM ASPERGILLUS
Experiment
FLAVUS provided by
Fit
the Protein Data
1
Bank (PDB 1R56).
dσ/dΩ [cm ]
-1

Pair Distance Distribution Function

0.1
0.0025
17.0 mg/mL
0.0020
0.01
0.0015

p(r)
0.0010
0.001
0.0 0.1 0.2 0.3 0.0005

q [Å-1] 0.0000
„ The concentration is about 1.7wt%. 0 20 40 60 80

r [Å]
„ The red lines give the fit of the Fourier
Transform of the pair distance distribution „ Resultant pair distance
function p(r) to the experimental data. distribution function p(r)
normalized by the concentration.
„ The sample was measured in an quartz „ Rg = 31.28 ± 0.03 Å
capillary at T=4°C „ R= 40.4 Å
„ Measurement time was 5400s for both, the „ I(0) = 1.230 ± 0.003 cm-1
sample and the solvent. „ Dmax = 82 Å
Urate Oxidase:
DIFFRACplus NanoFit

„The experimental data

can be described very
well with a model for
spherical particles with a
smooth interface and a
Hard Sphere structure
factor
„The obtained particle size
is 40.0 Å with a moderate
Gaussian size distribution
(σ of 2.5Å)
Application Brij 700 in Water

„ Concentration is 1wt%.
„ Measurement time was „ Excess electron density
7200s.
distribution
„ Fit using advanced model
with compact core and highly
solvated corona of PEO
Application Liquid Crystal

„ Liquid crystal sample is a mixture of

Pluronic P84 (41wt%), water (33 wt%) and p-xylene (26 wt%)
„ The 2D pattern show a weak anisotropy. The anistotropy was maybe caused by
slightly squeezing the gel-like sample within the Paste Sample holder.
„ Measurement time from left to right was

1min. 5min. 10min.

„ Images show 2D pattern of the scattering intensity

Background Corrected Data

1000 „ Background corrected

scattering intensity of
Sample A the sample.
„ 4 Peaks are identified:
100 d [Å] q[Å-1]
127.9 0.0491
Internsity I(q) [a.u.]

63.9 0.0982
42.6 0.1475
10
31.7 0.198

„ Peak positions
0.1 (1:2:3:4) indicate
0.05 0.10 0.15 0.20 0.25
lamellar
q [Å-1] microstructure!
Application Liquid Crystal II

„ Polymer (34EO)
content 60%
„ Measurement
time was 20 min
SAXS Profile

1000
q=0.0683Å-1
„ Azimuthaly
averaged
scattering
Measured intensity I(q) [a.u.]

100
q=0.1181Å-1
intensity
„ Transmission of
q=0.1351Å-1 the sample was
10
0.2894
„ Peak positions
(1:√3:2) indicate
1
hexagonal
microstructure
0.1
0.01 0.1

q [Å-1]
Application HDPE
Using the High Resolution Setup
„ diameter of first / second / third pinhole = 500 mm / 150 mm / 500 mm
„ diameter of beamstop: 2.0 mm
High Resolution SAXS Data
High Density Polyethylene
q<0.004Å-1 HDPE
„ Azimuthally
100
d=2π/q>1500Å averaged
HDPE: 600 s
scattering
10
intensity of
the HDPE
1
I(q) [cm-1]

sample
(background
0.1
corrected)

0.01
„ Intensities are
given in
absolute units
0.001
0.001 0.01 0.1 1
„ Measurement
-1
q [Å ]
time was 600s

„ 2D SAXS pattern
Application X-ray Nanography
Investigation of a Bone Section
macrostructure microstructure nanostructure
1.5 nm
corticalis
spongiosa
67 nm

collagen-
mineral
fibre
composite

thickness of
calcium-
phosphate
platelets:
~ cm 2-4 nm
~ mm
Application Nanography
Investigation of a Bone Section

P. Fratzl, H.F. et. Al.

J. Appl. Cryst. 30, 765-769 (1997) orientation distribution map
Detector
of mineral crystals
m
y bea in human bone
X -ra
GC
y
x
specimen SAXS
Nanography

1 mm
0,1 nm-1

x
 Nanography
Two Scales in One
X-ray Nanography is
the non-destructive
investigation of
nm structures of
mm sized samples
with µm resolution

X-ray scattering
(nm-range)
Diameter of Specimen Detector
X-ray beam
(μm-range)
Application Superalloys
Precipitates in Inconel 718

Ni Cr Fe Nb Mo Al Ti Mn Si C
wt % 52,67 18,37 18,06 6,00 2,91 1,00 0,45 0,21 0,29 0,04
at % 51,79 20,39 18,66 3,73 1,75 2,14 0,54 0,22 0,60 0,19

„ Temperature treatment „ Precipitates:

2h homogenized at 960°C (Serie A)
Ni3M-Type:
Ni3(Nb, Al, Ti)
at 1060°C (Serie B)
γ‘, fcc
annealed at 720°C for
(γ‘‘, bcc)
(30, 60, 120, 240, 480 and 960) min

sample preparation for SAXS

Inconel
Data Treatment
1000
„ Background correction 0h
0.5 h

I raw − τ I bg 100
1h

Intensity [a.u.]
Ic =
2h

− ln τ
4h
8h
10 16 h

1
q-4
„Subtraction of „large“ particles 0.1
0.01 0.1

I = I c − aq −4
-1
q [Å ]

100
0h
3e-6 0.5 h
1h

Intensity [a.u.]
2e-6 2h
10 4h
2e-6
8h
a [Å ]
-4

2e-6 16 h

1e-6
1
5e-7

0
0 200 400 600 800 1000 1200
0.1
annealing time [min.]
0.01 0.1 -1
q [Å ]
Inconel
Scaling Behavior
10
0h

I (q, t ) = β m (t )G (q / α m (t )) 0.5 h
1h
1 2h

I / βm(t)
4h
8h
0.1 16 h

0.01

0.001
0.01 0.1 1
„ 2 main parameters -1
q/αm(t) [Å ]
Mean particle distance
350 Radius of Gyration
300 Serie B 80
70 Serie B
250 Serie A
2π/αqmax [Å]

60
Serie A
200 50

Rg [Å]
150 40
2
30 1⎛ q ⎞ 2
100 − ⎜⎜ ⎟ Rg
I S (q) 3⎝ α m ⎟
D=2π/(q αm(t))max 20
=λ e ⎠
50 10 βm
0 0
0 200 400 600 800 1000 0 500 1000
Annealing time [min.] Annealing time [min.]
 Comparison
SAXS / SANS

SAXS SANS
Co-NanoSTAR D11 facility at the Institute Laue-
Langevin (ILL), Grenoble, France
„ Co- Kα (λ = 1.79 Å) 35 kV / 34 mA
„λ=8Å
„ cross coupled Göbel mirrors
„ Δλ/λ = 9%
„ two pinhole system (100 μm, 300 μm)
„ Sample to detector distance: 1.1 m
„ sample to detector distance: 64 cm
and 4.0 m
100 m 40 m 40 m
sample
neutron guides Imax = 107 n/(cm2s)
cold source
evacuated detector tube

ω
64 cm
monochromator 2D-multidetector
(mechanical

64 cm
2
(resolution 1cm )
Uranium velocity selector)
fuel element
Inconel
SANS Data
SANS
0h
„ at q<0.02Å q-4 10 0.5 h

Intensity [cm-1]
1h
2h
„large“ particles 4h
8h
16 h
1

„ 2 main parameters 0,1

0,01 0,1
q / Å-1
mean particle distance radius of gyration
300 60
250 50
2 π/q max [Å]

200 Rg [Å] 40
150 30
100 20 SANS
SANS
50 SAXS
SAXS 10
0 0
0 5 10 15 20 0 5 10 15 20
anne aling time [h] anne aling time [h]
Inconel
TEM Dark Field Micrographs
500 Å
[100]

[001] [100]
radius of gyration
60
50
40
„ disc like shape
Rg [Å]

30 SANS
20 SAXS
d 2 h2
R g = 8 + 12
2 10 TEM
0
0 5 10 15 20
anne aling time [h]
Summary
2D SAXS with NanoSTAR

„ Nearly synchrotron like performance on weakly scattering

systems
„ Fast and automated measurements on virtually any application
(analysis of polymers, biological materials, fibres, metals,
nanopowders, complex fluids, proteins, etc)
„ Analysis of sizes, size distributions, shapes and orientation
distributions
„ Efficient solution for scientists as well as researchers requiring
fully automated measurements
„ All in one instrument
„ nanostructure analysis by means of Small Angle X-ray
Scattering (SAXS)
„ nanostructure mapping with scanning SAXS / X-ray
Nanography
„ molecular structure determination by Wide Angle X-ray
Scattering (WAXS)
SAXS – The Big-Angle View

Brian Jones
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