Wim Bras DUBBLE @ ESRF Netherlands Organisation - Big Science

Wim Bras
DUBBLE @ ESRF
Netherlands Organisation for Scientific Research
(NWO)

Outline
• Short introduction synchrotron radiation
• European Synchrotron Radiation Facility
• DUBBLE
• Examples of research on Dubble

Synchrotron as X-ray source
Bending magnet
Electron orbit

What is the advantage of SR?
Number
of photons
10000 1000 100 10 1 0.1
10 14
10 13
10 11
10 10
10 9
Wavelength (Å)
• High flux
• Continues spectrum
• Good collimation
• Beams 1 – 300 micron
10 8
10 7
1 eV 10 eV 100 eV 1 keV 10 keV 100 keV
Energy
sunlight
conventional
X-ray generator

Scheme beam line
storage
ring
Control cabin
experiment
Optics
monochromator
focussing

• These labs are set up as user facilities
• They are relatively large scale
• Belgium and the Netherlands have
made the choice to participate in
international facilities
• However….

Once upon a time in the
Watergraafsmeer
1979
Nomen est omen???

NWO and synchrotron radiation
Daresbury also birth place of
Lewis Carrol
Alice en the
Cheshire cat
Daresbury lab in Cheshire
- About 30 years ago
ZWO/NWO started participation
in Daresbury Lab (UK)
- About 15 years ago transfer to
ESRF
-The Netherlands has a strong
SR user community

European Synchrotron Radiation Facility
Grenoble France

European Synchrotron Radiation Facility
• ∼ 50 beam lines (= experimental set ups)
• ∼ 25 different techniques
• 6 days/ week, 24 hours/day
• 270 days/year (minus strike days, after all it is
France….)
• ∼ 1500 publications/year

the ESRF
270 meter

Many different experiments
Protein crystallography
About 25% of the beam lines
About 35% of publication output
Crystal distortions due to high
(30 Tesla) magnetic fields
Spider silk
Chocolate butter crystallisation

Dutch ESRF participation
• 6% of the experimental time on public beam
lines is for the Benesync consortium (50/50
Be/Nl)
• This is not sufficient for the Dutch/Belgian
demand for some techniques
• Two ‘own’ beam lines
• DUBBLE (part of the Dutch research
infrastructure)

DUBBLE: 5/6/2000 the official opening
The ministers The financing The workers

DUBBLE research areas
surfaces
Geology/surface
pollution
instrumentation
catalysis
surfactants
biological/medical
polymers
structure
foods
colloids

Two beam lines and techniques
on DUBBLE
• Extended X-ray Absorption Fine
Structure spectroscopy
(EXAFS/XANES)
• Small and Wide Angle X-ray Scattering
(time-resolved SAXS/WAXS)
3-4 user groups/week
At present 70 – 80 publications/year

X-ray scattering
1 – 8 meter
detector
sample
Diffracted X-rays
X-rays
λ
= 2d
sinθ
θ small d large

SAXS/WAXS
1
1
2
3
4
5
1 limit q → 0
electron density contrast
density fluctuations
2 Guinier range
particle size
3 particle shape
500 nm
0.2 nm
4 Porod range
particle surface
5 Intermolecular/atomic
ordering

X-ray scattering and diffraction
• Combined SAXS-WAXS experiments
• WAXS crystalline structure
• Small angle: shape and size of clumps of
atoms
• SR not only static
also time-resolved
• 0.4 – 200 nm ‘visible’

• diffractiepatronen
Scattering/diffraction patterns collected on
DUBBLE

Multidisciplinary applications
hip replacements
polymer fibers
nano technology
Unwashed Eskimo hair tubulin, cell division Car exhaust
Etc., etc., etc….
Soot of diesel

esearcher (no safety glasses…)
SAXS
detector
sample
WAXS
detector
National Geographic Magazine

Human skin
Epidermis
(150 μm)
Dermis
(2000 μm)
Subcutaneous
fat
Joke Bouwstra
Division of Drug Delivery Technology
Leiden/Amsterdam Center for
Drug Research (LACDR)

Outer layer: Stratum Corneum
‘designed’ as barrier for externl influences
Transdermal drug delivery
corneocyte
Penetration
route
Lipiden (fat)
matrix
Hoorn
laag
Stratum granulosum
Stratum spinosum
Stratum basale
Epidermis
Dermis
Blood vessels

Lateral order of SC lipids
~0.46 nm 0.41 nm 0.41 nm 0.37 nm
d
liquid
hexagonal
orthorhombic
More rigid penetration more difficult

SR required
- In 5 seconds a pattern
- Weak peaks not visible with
conventional rotating anode

Since we have plenty of X-rays:
• We can measure fast
• Phase diagram of lipids can
be determined
• The effect of pharmacutcals
can be studied on-line
• Relatively small amounts of
material required (important
in patient derived samples)

In fact three (related) research areas:
1. Development of biofilms based upon vernix
caseosa.
2. Studying lipid structure of diseased skin
3. Development of lipid substitutes for skin
penetration studies (saves some test animals)
‘high five rabbits’
Patent granted

In our first experiments in Daresbury, about 20 years
ago, we used about 50 neatly stacked strips of skin.
Nowadays we only have to use a single one. I can
estimate that we require 100 x less material.
Prof. Joke Bouwstra
Since 1990:
> 60 publications with SR
10 cited ≈ 100 or more

X-ray spectroscopy

X-ray spectroscopy
‘electron orbits’
deformed
‘electron orbits’
Metal atom
Metal atom
‘neighbours’

ionisation
Röntgen photon
( )
absorbed
E
I t
I
0

Difference in surroundings of metal atom;
difference in absorption spectrum

Powder diffraction
Incoming intensity
absorbed intensity
Sample cell

Again multidisciplinary
catalysis
Hydrogen storage
liquid metals
pharmaceuticals
Environmental pollution
Etc., etc., etc….
electro chemistry
cultural heritage

Catalysis: are small particles
always better?
Marcel di Vece, .., P. Lievens PRL 100, 236105, 2008

• Small catalytic particles have a high
surface/volume ratio.
• Reactions take place at the surface.
• Should we always try to make particles
as small as possible?
• Effects of hydrogen.

• Movie unable to incorporate in pdf

• Some atoms get disconnected due to the
hydrogen treatment
• They re-attach predominantly to larger
particles
• The large particles grow at the expense of the
small ones (Ostwald ripening)
• Conclusion: loss of active catalytic surface
Only with EXAFS we can see what happens with the smallest particles

Technique combinations
• Movie unable to incorporate in pdf
Groep Bert Weckhuijsen, Utrecht
How do I make a working catalyst?

Structure grows
1. Early in reaction, no crystal, X-ray
spectroscopy (XAFS)
2. A little later, X-ray diffraction WAXS
3. When it has grown sufficient, SAXS
4. In the end catalytic activity XAFS,
(UvVis, Raman spectroscopy)

All these steps one wants to study on-line
• Infrastructure
• Industrially
relevant
conditions
• High gas
pressure
• Flow
• Operando
conditions

In-situ multi-technique approach of zeolite synthesis
1.5
B
Normalised Absorption
1.0
0.5
0
20
30
40
66.7
A
50
0.0
640 660 680
7700 7800 7900
Energy (eV)
Raman Shift cm -1
Raman
XAFS
1.5
UV-Vis
584 625
542
SAXS
WAXS
Absorbance
1.0
0.0016
*
525
470
400 600 800
Wavelength (nm)
I(q).q 3.3 [a.u]
0.0008
0.0000
0.01 0.1
log(q) Å -1

Unique instrumentation
• Sample at high pressure/temperature
• Simultaneous 5 techniques possible
• All aspects of the sample and kinetics
can be studied simultaneously

We can:
• Follow particle growth
• Study the catalytic actions
• Follow the life cycle of the
catalyst
Catalyst crystals
All in a single experiment !

Technique combinations and
sample control
• Already for 20 (10) years a speciality of
the NWO (DUBBLE) beam lines
• Studies of physical-chemistry processes
on-line

Another SAXS example

From picture to ‘icon’
Yousuf Karsh

Picture Icon
Required:
• Good picture
• Good quality reproduction
• Large scale/volume reproduction
H. Terryn, T Rayment and coworkers

Offset rotation printing
Ink roller
Dampening roller
“Offset” Blanket
Paper
Impression cylinder
Ink film
Plate cylinder
with printing
plate Oleophilic image area
Hydrophilic non-image area
This lithographic method is being used for high quality printing
750 x 10 6 m 2 /jaar

The Aluminium surface
• Is being prepared with electrochemistry
• Controlled roughness required (uniform pitting)
surface
Aluminium hydroxide layer
AC current
High Voltage
High Amperage
Small pit blocked

During electrolysis:
• Roughness changes
• Layer of ‘smut’ forms
• Composition unclear
• So far only studied with off-line
techniques
• SEM, XPS etc. (vacuum
required)

With on-line SAXS experiments:
• Electrolysis creates gas
bubbles
• This influences the
transport properties of
‘smut’
∞
2 2
Q q I q dq ρ ϕ ϕ
= = Δ ∫
0
( ) ( )
smut gas
• SAXS gives unique
possibilities to study this
process on-line

• Fundamental knowledge of electrochemical
problems
• But applications very close

The perfect garbage bag
Groepen:
P. Lemstra
H.E.H. Meijer

polyethylene
Molten it looks like spaghetti
SAXS
In solid state semi-crystalline
- amorphous parts
- crystalline parts
The ratio amorphous/crystalline and the
spatial orientation determine the
macroscopic properties
WAXS

Polymer processing
With a little pre treatment crystallisation is easier
Orient the polymer chains first
Chains can be oriented by pulling,
Pushing, shearing etc
After that crystallisation is much easier

Why polyethylene?
• Invented already in 1933
• 80 million metric tons/year
• It used to be low quality materials

Better materials
• Through better catalysis, better materials
• Controlled polymer chain lengths
• Mixtures of bimodal chain lengths have
unique properties
• Recycling no problem
• Fundamental knowledge of the crystallisationprocess
of blends has to be improved

Film blowing
•Movie unable to incorporate in pdf
• Way to make films
• Molten polymer
• Annular die
•Extrusion

SAXS
WAXS
X-ray beam
Scattering pattern
elongation multiaxial

Each year:
• We use enough of
this to cover the
earth 3x
• A reduction in
thickness whilst
retaining strength….
• Less oil required
• Less polution
• Etc.
But even a garbage bag becomes a piece of ‘high tech’

The future of EXAFS
• A conventional beam line 40 – 80 meter
• In Japan there is a line of 1 kilometre
• We want one of several light years

X-ray stars and interstellar dust

• In super novas iron rich dust is created
• In super novas dust is also being
destroyed
• There is a surplus of dust in the universe
• Where does this come from and is it all
the same composition?

• The spectra of different classes of X-ray
stars are well known
• Measure on earth the spectrum
• The differences between the well known
source and the measured data make it
possible to reconstruct the EXAFS
pattern, i.e. the mineral structure

Use the Milky Way as radiation source
- X-ray spectrum of stars known
- On earth we can see what is absorbed

The role of DUBBLE:
• The dust is iron rich
• Pure, amorphous or crystalline iron
silicates
• Calculate the EXAFS spectrum as
function of position in Milky Way
• Different position, different dust???
• Very accurate EXAFS calibration spectra
required DUBBLE

We hope no weird
results will be found

500
400
totaal aantal
publicaties
300
June 2010
200
100
0
1996 1998 2000 2002 2004 2006 2008 2010
jaar
500 e
Group Lekkerkerker
University Utrecht
Ex VUB

• Largest Dutch-Flemish collaboration
• > 80 publications/year in many different fields
• 500-600 visiting
researchers
technicians
students
per year
• 7 DUBBLE staff and several ESRF colleagues
enable this

DUBBLE (and ESRF) research:
• Ranging from very fundamental to
very applied
• Ranging from life sciences to hard
core physics
• A real toolbox for Dutch
researchers

Thanks for your attention