sample environments and technique combinations for sas ... synew/bras.pdfsample environments and...
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![Page 1: Sample environments and technique combinations for SAS ... SYNEW/Bras.pdfSample environments and technique combinations for SAS beamlines Wim Bras DUBBLE @ ESRF Netherlands Wim Bras](https://reader035.vdocuments.us/reader035/viewer/2022081621/611fb3c0d48508620375269b/html5/thumbnails/1.jpg)
Sample environments and technique combinations for SAS
beamlines
Wim Bras DUBBLE @ ESRF
Netherlands Organisation for Scientific Research (NWO) Wim Bras
DUBBLE @ ESRF
Netherlands Organisation for Scientific Research (NWO)
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Outline
• Very brief synchrotron radiation
• Technique combinations
• Sample environments
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ESRF: the Dutch-Belgian National SR facility
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DUBBLE - EXAFS beamline - SAXS beamline - free access - beam time application every 6 months
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To start with SAXS/SANS
TEM
TEM
TEM
TEM
TEM
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Technique combinations
First dedicated SAXS/WAXS set-up 1993
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Somewhat more modern SAXS/WAXS
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When does one combine techniques?
• Time-resolved experiment
• There must be synergy between the data sets, e.g. what comes first?
• Precious samples
• Inhomogeneous samples
• Etc.
Data should be obtained from the same sample spot
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Example: SAXS and FTIR
+10 +20
Note: - This is old stuff - Good illustrations don’t always have to be done with latest equipment - Experimental ingenuity has existed through the ages
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Old FTIR; hacksawed holes to get X-ray beam in.
High tension safety cover
Safety officers
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Example: SAXS and FTIR
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The question:
Is hydrogen bond formation the driving force or the consequence of the phase separation?
No SAXS No FTIR signal
SAXS FTIR signal
What comes first? The SAXS signal or the FTIR?
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• Optimum thickness for transmission only for one technique
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SAXS invariant and Hydrogen bond absorption band
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Result:
• Long range order first
• FTIR signal increase later
• The phase separation induces hydrogen bond formation and not the other way around
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Differential Scanning Calorimetry
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Timing markers from synchrotron data acquisition system
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DSC/SAXS/WAXS on lauric fat
pk41002 (exp.11; B05*.427)
-20000
-15000
-10000
-5000
0
5000
10000
15000
0 10 20 30 40 50 60
time (min)
dsc s
ign
al
-40
-30
-20
-10
0
10
20
30
40
50
60
70
tem
p (
°C
)
dsc
temp
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Where is the limitation?
• SAXS/WAXS data will still be good
• DSC maybe less good
• DSC best with full thermal isolation of sample
• This would block X-rays
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Differential Scanning Calorimetry
X-ray frame 27
X-ray frame 68
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Responsive molecules change shape
• Polyelectrolytes
• Responsive to solvent quality
• ON-OFF response to pH
Macroscopic shape change
pH or ions
ON OFF
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The data:
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Combinations here:
• Light scattering
• Mechanical
– Attach a STM tip to the polymer
– Measure the force it generates
• Is this simple to do?
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The reaction of bromate, sulfite and ferrocyanide ions in a continuously stirred tank
reaction vessel exhib its sustained oscillations in pH3. A low acid input is also required.
The pH oscillations display a sustained period. Since the amplitude of the pH change is
large, the relative change in [H+] is dramatic and thus will affect the conformation of
the polymers.
The pH meter was hooked up to a laptop computer with
METTLER TOLEDO software which allows the variance
of pH with time to be recorded and subsequently plotted.
A v ideo camera was
focussed on the
hydrogel throughout
the experiment and a
small movie of the
macroscopic volume
change was recorded.
Two st ill images are
shown here, capturing
the polymer at the
extremes of the pH
range.
00:30 01:00 01:30 02:002
3
4
5
6
7
8
Time (hh:mm)
pH
pH 3 pH 7
The 2D SAXS detector image featured a ring with an alternating
radius, determined by the q value, which was dependent on the
pH of the system. Radial integrals of each frame were taken to
give a q value for every 60 seconds of data recorded.
One has to set up a whole chemical factory on line
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Cordierite based ceramics
Ceramic chip carriers
Pizza baking stones
Car exhaust soot filters
Refractory parts
Louis Cordier 1777- 1861
Ceramic replacement teeth
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glass ceramic
• Crystalline regions in a glass matrix
• Shock resistant even at high temperatures
• Manufacturing process empirically well understood
• But in fact industries often don’t have a clue what they’re doing
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Cordierite glass devitrivication
Temperature
Mg2Al4Si5O18
doped with 0.34 mol% Cr2O3
(crystallization enhancer)
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time
temperature
Soak or nucleation 2 hours (~ 900° C)
Crystal growth several hours (~ 1000° C)
Experiment on 75 micron thick platelet
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The sample is a platelet
Not a powder
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Structure development
0 0.05 0.10
25
225
425
Time (min)
q (Å-1)
I(q) (a.u)
SAXS
1010° C
C
10 35 60
I() (a. u.)
2() (deg)
25
225
425
Time (min)
sq(011)sp(400)
sp(440)sp(331)
D
WAXS
1010° C
SAXS WAXS
Data taken at 1 minute/frame
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15x103
10
5
0
inte
nsity
40302010
two theta (degrees)
Wavelength 0.5 Angstrom Indexed FCC, a = b = c = 4.02
111
200
220
222 400
420422
440
High resolution powder diffraction patternon Swiss-Norwegian Beamline
spinel
sq 110
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Post mortem powder diffraction: three different phases
spinel stuffed quartz
+ large amount glass matrix
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time (30 sec/frame)
0
log I(q)
0.006
0.2
325q (A )
-1
Structure factor
Form factor peaks (up to 5th order) DR/R 0.04
SAXS I(q) = S(q)*|F(q)|2
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Morphology (1)
glass crystalline sphere (monodisperse)
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Neutron scattering
0
2 10-6
4 10-6
6 10-6
8 10-6
1 10-5
1.2 10-5
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.160
2 10-8
4 10-8
6 10-8
8 10-8
1 10-7
1.2 10-7
0 0.02 0.04 0.06 0.08 0.1
A13 frame 99
I(q)q4
q-axis (A-1
)X-ray neutron
Chromium in crystalline spheres
Neutron data courtesy Stuart Clarke
no fringes !
I(q)q4
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• Particle size
• Minima in form factor (no Guinier needed in this case)
50
100
150
200
250
300
350
0 50 100 150 200 250 300 350
average sphere radius as determined from minima in the scattering curve
rad
ius
(A
ng
str
om
)
time (30 sec/frame)
A13
0
2 10-8
4 10-8
6 10-8
8 10-8
1 10-7
1.2 10-7
0 0.02 0.04 0.06 0.08 0.1
A13 frame 99
I(q)q4
q-axis (A-1
)
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For fixed number of globular particles I(q=0) = CR6
Fixed number of monodisperse particles
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time(30 sec/frame)
0
325
6552
Spinel Stuffed quartz
WAXS data
Spinel unit cell increases in time MgOAl2O3 FCC a = b = c = 8.06 Å
Stuffed quartz unit cell decreases in time
trigonal a = b = 5.13 Å c = 5.37 Å
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Question:
• Is one crystalline phase templating the other due to local composition changes? Or are they independent?
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Morphology (2)
So far all possible
“ ”
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22
0
( ) 1eQ I q q dq n
2
1 4( )
KI q K
q
2 1K S
Q V
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Can this be correct?
• Radius of particle stops growing
• Surface/Volume ratio of particle keeps increasing
• Maybe new crystallites created ?
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• I(0) = CRg6
(only true for constant number of particles)
• We see many form factor
maxima
• Polydispersity ~ 4%
New crystallites can be ruled out:
0
2 10-8
4 10-8
6 10-8
8 10-8
1 10-7
1.2 10-7
0 0.02 0.04 0.06 0.08 0.1
A13 frame 99
I(q)q4
q-axis (A-1
)
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-Spinel increases regularly in time - Stuffed quartz increases irregular - Spinel starts at same time as particle growth observable in SAXS
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texture effects !
Crystals impinge on each other variations in intensity
Growth of stuffed quartz
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Prediction Morphology:
This is (so far) the correct morphology
quartz
glass spinel
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SEM
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Note on bulk/surface crystallisation:
• This would have been impossible to derive from time-resolved diffraction on powdered samples
• Using a platelet sample was lucky choice
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Summarising:
• Spinel grows in bulk
• Stuffed quartz grows on surface
• This explains why the particle radius can stop growing but the total S/V ratio keeps increasing (spinel fixed but increase quartz/glass interface)
• …..but can we find out more about the
system …….?
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What’s the growth mechanism of the bulk crystallites ?
Conventional tool for solid state crystallization is Avrami analysis
( )1nKt
cV e
The parameter n determines what the mechanism is (i.e. diffusion or reaction rate limited)
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Model
Phase boundary control
Diffusion control Three dim growth
Nucleation rate
1 constant
4
2.5
2 instantaneous
3
1.5
3 deceleratory
3 – 4
1.5 – 2.5
Two dim growth
Nucleation rate
1 constant
3
2.0
2 instantaneous
2
1.0
3 deceleratory
2 – 3
1.0 – 2.0
One dim growth
Nucleation rate
1 constant
2
1.5
2 instantaneous
1
0.5
3 deceleratory
1 – 2
0.5 – 1.5
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Dear Wim, Are you serious? To such
an equation I can fit anything…….
Signed: Cynic
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Dear Cynic, Maybe that is true, but I’m a careful ‘man’….. I double check……
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WAXS: peak intensity Vc
Avrami coefficient 1.49 ± 0.01
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For SAXS data
• For fixed number of particles N which are monodisperse
• N x R3 is also related to the Vc
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SAXS
Avrami coefficient 1.51 ± 0.05
For the people with poor memories: from WAXS 1.49 ± 0.01
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What does this mean according to mr. Avrami?
Means diffusion limited growth
1.5( )1 Kt
cV e
For a pre-nucleated system
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For pre-nucleated, monodisperse spheres
diffusion limited growth predicts that the particle
size in the initial stages should behave like:
~R time
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And so it does !
3 independent ways of checking (hope Cynic is happy now)
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Warning: How well can we trust data?
0
2 10-8
4 10-8
6 10-8
8 10-8
1 10-7
1.2 10-7
0 0.02 0.04 0.06 0.08 0.1
A13 frame 99
I(q)q4
q-axis (A-1
)
0 0.02 0.04 0.06 0.08 0.1
q
That’s a good fit!!
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Forget it !!!
The first curve is a polydisperse sphere The second is a monodisperse cube
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TEM BF image
200 nm
The particles are not spherical but “cubes”………
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The correct morphology (3)
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Muscle diffraction
Arnie (the second most well known Graz native) in better days
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Galvani revisited:
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Dangerous when using large animals
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Tom Irving APS Biocat
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• Very small sample volume
• Radiation damage
• Moving target
That doesn’t look easy….
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And it certainly is not easy!!!
• But the crucial point is
• It might not be easy
• But it can be done
• Only the will to do it has to be there
• Technologically we can do this and other complicated experiments
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Other toys we have played with:
on-line film blowing
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Rheology on line
Commercial equipment
Or home built Shear machine (built like a German Panzer) According to G. Eeckhaut….
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On-line deformation
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Deformation/stretching: Not only with an academic little tensile tester
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This guy is talking about his hobbies again
And he can go on and on and on……
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Thanks for your attention