high-energy x-ray* studies of real materials under real conditions and in real time fermilab...
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High-Energy X-ray* Studies of Real Materials under Real Conditions and
in Real Time
Fermilab Colloquium SeriesMay 11, 2011
Jonathan AlmerAdvanced Photon Source
Argonne National Laboratory
* From perspective of a materials scientist NOT a high-energy physicist!
Advanced Photon Source
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Acknowledgements
APS– Ulrich Lienert – HEDM program– Sarvjit Shastri – High-energy optics– Francesco Decarlo – High-energy tomography
Nuclear Materials: Meimei Li (ANL) and Mark Daymond (Queens U) Nano-synthesis: Bo Iversen (Aarhus U) and Y. Sun (ANL-CNM) Biomechanics: Stuart Stock and David Dunand (Northwestern U)
Department of Energy, Office of Basic Energy Science
Outline
• X-ray techniques: from beginning to the synchrotron• Size and penetration of selected probes• APS Upgrade and high-energy x-ray probes
• HE Sources• HE Optics• End Stations
• Scientific scope overview and examples• Lightweight materials• Nuclear energy• Batteries / nanoscale materials• Geoscience (carbon sequestration)• Biological materials
• Conclusions and outlook
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Advanced Photon Source Upgrade (APS-U) project
X-ray Vision: The BeginningThe first nobel prize in physics (1901) was awarded to Roentgen for the ‘discovery of the remarkable rays subsequently named after him”
First radiograph(Mrs. Roentgen)
In subsequent decades the three main uses of x-rays were established:• Imaging (electron density and phase contrast)• Spectroscopy (inelastic scattering - chemical and electronic speciation)• Scattering (elastic scattering - atomic structure)These modes remain the three ‘pillars’ of x-ray science.
X-ray diffraction (elastic scattering)
* Constructive interference between x-rays and atomic spacing (electrons)* Works b/c x-ray wavelength is same order as atomic spacing d
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1-ID (XOR)High energy x-rays
70 possible x-ray ports– 35 ID, 35 BM
~43 currently operating Beam time available through
peer reviewed general user proposals– No charge
Operates 5000 hrs/year Users from around the world
– Over 3000 per year Multidisciplinary
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Tunable X-ray energy Large variety of specialized instruments Much higher intensities than lab sources
– 9 orders of magnitude higher brilliance!– Faster experiments– More sensitivity– Small beams– Increased coherence– More penetration
Why not use a synchrotron?– Not portable– Can be tough to get beam time– Small beams– Beam damage
Why Use a Synchrotron?
Resolution & penetration depth of selected techniques
Surface
1-100nm
1 mm
10 mm
100 mm
1 mm
10 mm
10 cm
1nm 10nm 100nm 1mm 1mm10mm100mm 10mm
TEM SEM/Auger Optical
Pen
etr
ati
on
dep
th
Spatial resolution (1-d or 2-d)
Synchrotron (E =10 keV)
NeutronDiffraction
Gra
zing
Incid
ence
, R
eflectiv
ity
Focusing optics
0.1nm
HE Synchrotron (E = 80 keV)focusing
optics
‘Wide- angle’ scattering
‘Small-angle’ scattering
USAXS
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APS upgrade and high-energy X-rays
CDR Title Panel Priority
4.2.2 SPX Hard X-ray - Diffraction & Imaging 1 A1
4.2.2 SPX Hard X-ray - Spectroscopy 1 A1
4.3.2 Wide-Field Imaging Beamline 4 A1
4.3.4 High-Energy Tomography 4 A1
4.3.7,4.3.8 In Situ Nanoprobe/Cryonanoprobe (NGN) 4 A1
4.4.4 Resonant Inelastic X-ray Scattering (MERIX) 3 A1
4.5.4 High-Energy Diffraction 2 A1
4.5.5 Magnetic Spectroscopy 3 A1
4.6.2 XIS - Tunable ID Beamlines 2 A1
4.6.4 Micro and 3D Diffraction 2 A1
4.7.3 Cryo Sample Preparation Facility 5 A1
4.7.4 Enhanced SAXS/WAXS 5 A1
4.7.5 Microfocus MX Beamline 5 A1
4.7.6 Enhanced Pump/Probe for Physical Sciences 1 A1
4.7.6 Enhanced Time-Resolved MX Beamline 5 A1
APS built ~20 years agoRequesting 350M upgrade to DOE with themes:
Real materials under real conditions in real timeUnderstanding hierarchical structures through imaging
-50 proposals were ranked by scientific advisory board (top priority shown)
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High Energy X-ray Undulator Sources
Advanced Photon Source Upgrade (APS-U) project
Request canted undulators & long straight section:(i) superconducting (fixed period w/3rd
harmonic ~70 keV) (ii) revolver PM (2.3 & 2.5 cm) for
continuous coverage
Heat loads more tolerable with short-period devices• 1.6cm SCU 300kW/mrad2 at min gap 9.5mm
Specialized undulators will increase brilliance by 5-10x at high energies, providing the highest brilliance at 100keV worldwide
Advanced Photon Source Upgrade (APS-U) Project
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High Energy X-ray Optics
Mono2: Bent double-Laue geometry•Continuously tunable from 40-140 keV• Bending on-rowland conditions results in 10x increase in flux w/o divergence increase• Source-preservation demonstrated
Combining HR mono and focusing optics(sawtooth lens as virtual parabolic lens)
Laue optics preserve brilliance enabling mm-level focusing at 100 keV and flexibility to combine optical elements for highest q-resolution.
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Techniques for microstructural mapping
Absorption or phase tomography– Full field 2D image (mm^2) of direct beam– Absorption contrast (near) to phase contrast
(far) by changing sample-detector– Take image and rotate M times (M images)– Reconstruct ->3D volume
Diffraction tomography (High Energy Diffraction Microscopy- HEDM)– Thin beam (~ 1mm x 5um)– Take image at N different distances and rotate
M times (NxM images)– Reconstruct distinct spots on detector - >2D
diffraction contrast– Move sample vertically to build up 3D sample
volume– Semi-transparent beamstop for simultaneous
AT Incident beam E= 50-80 keVScattering angles <10 deg
Polycrystal
1-3m
m
Bulk samples (mm’s)
Rotation & loading axis
In situ measurements of bulk, irradiated materials under thermo-mechanical loading
Simultaneous WAXS/SAXS and full-field imaging– WAXS: lattice strain, texture, phases– SAXS: nanoscale voids, bubbles, particles– Imaging: microsize cracks, porosity
2D detector array for long sample-detector distance– High-resolution data (small beams)– Ability to use large beam (imaging) w/sufficient
WAXS resolution for combined studies– improved signal-to-background ratio
Combining techniques for in situ studiesW beamstop(0.5-2 mm dia)
Translatingfull field imaging detector 2×2k pixels, 1 m resolution
Ionchamber
Guardslits
Beam from optimized HE undulator & monochromator E ~ 50-100 keV
Definingslits
Quad-paneled array for WAXS/SAXSfour 22k detectors,each 4040 cm (active)
MTS mechanical test frame
SAXS CCD1×1k, 22.5 mm pixels
Irradiated specimen loaded in a shielded containment
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Scientific scope
Energy: efficiency– High specific strength materials– Thermal barrier coatings for engine
efficiency Energy: production/storage
– Batteries and fuel cells– Fossil fuel extraction (high-pressure
oil/coal/gas properties)– Nuclear materials
• damage tolerant materials for new reactors
• degradation of existing materials (corrosion/void formation/etc)
Energy: environment– CO2 sequestration (fluid movement in
rock/capillary trapping) Biology
– Response of bone and teeth to applied load, environment, dose
Porous Anode Porous cathode
H2 & CO O2
e-
H2O & CO2
e-
O=
• Controlled porosity• Thermal mismatch• Chemical durability• Mechanical integrity
Dense electrolyte
SOFC (battery)
• New lightweight composites • Optimizing metal sheet forming
High-energy scattering and imaging:• Penetrating in situ probes -> real conditions• High flux -> real time• High q-resolution -> real/complex materials
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real size samples in real operational conditions
3D Analysis of Probability of Cracking as a Function of Particle Size and Aspect Ratio
Metal Matrix Composite Materials transportation technology, new material, industrial applications
Acta Mater. 58 (18), 6194-6205 (2010)
High Energy Tomography: Mechanical Properties of MMCs
Use of new advanced weight-saving alloys in vehicles is limited by the inability to determine the mechanical properties under load, to monitor creep/fatigue interaction, crack formation and sample expansion during temperature cycles and the evolution of defects during loading and corrosion of real size samples.
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Combining HE tomography with diffraction microscopy
Raw image (shock-deformed copper)Attenuated direct beam
Near-field orientation map Tomographic reconstruction
‘Near field’ diffraction - Non-destructive EBSD –type info.
(U. Lienert, A. Khounsary and P. Kenesei) Carnegie Mellon
MRSEC
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HEDM reveals in-situ microstructural evolution vs temperature
Carnegie Mellon
MRSEC
Misorientation
4 deg color scale 2 deg boundaries
orientation changes located at boundaries* Information is being used to drive and test computational materials science predictions
Annealing response
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Scientific scope
Energy: efficiency– High specific strength materials– Thermal barrier coatings for engine
efficiency Energy: production/storage
– Batteries, fuel cells, material discovery– Fossil fuel extraction (high-pressure
oil/coal/gas properties)– Nuclear materials
• damage tolerant materials for new reactors
• degradation of existing materials (corrosion/void formation/etc)
Energy: environment– CO2 sequestration (fluid movement in
rock/capillary trapping) Biology
– Response of bone and teeth to applied load, environment, dose
Porous Anode Porous cathode
H2 & CO O2
e-
H2O & CO2
e-
O=
• Controlled porosity• Thermal mismatch• Chemical durability• Mechanical integrity
Dense electrolyte
SOFC (battery)
• New lightweight composites • Optimizing metal sheet forming
High-energy scattering and imaging:• Penetrating in situ probes -> real conditions• High flux -> real time• High q-resolution -> real/complex materials
LDRD: Hard X-ray Sciences Initiative, 2010-074-R1
Li+ insertion ~ nm
Grain fracturing ~ μm
L i + d i f f us ion ~ mm
SAXS
Imaging
EXAFS
In situ
Reverse Monte Carlo modeling of ALL data
+Echem
CHALLENGES IN ENERGY STORAGE SPAN
MULTIPLE LENGTH SCALES
HARD X-RAY TOOLS CAN PROBE DIFFERENT
LENGTH SCALESRMC METHODS ALLOW COMBINED ANALYSIS OF
VARIETY OF DATA
→ Insight into challenges in battery technology
→ Infrastructure for research in electrical energy storage
→ New RMC computational algorithms capable of addressing large systems
→ A versatile experimental+analytical tool applicable to diverse challenges in
materials science
IMPACTS SPANNING MANY STRATEGIC
AREAS
Combined Approaches Towards a Hierarchical Understanding of Battery Materials
Prec
urso
r CoO
OH
Inte
rmed
iate
Co 3O
4
Fina
l LiC
oO2
Intermediate disappears.
Tim
e (s
)
Channels
SAXS WAXS
supp
ress
ion
of s
teel
supp
ress
ion
of s
teel
In-situ synthesis of LiCoO2 nano-particles for Li-ion batteries
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? ? ?
?
?
?
?
Xia, Sun, Yang, Murphy, Mirkin, et al.
?First Generation of nanoparticles:Size Decrease
Second Generation of nanoparticles:Shape Control
Application?Third Generation?
2000 2009+
In situ tools to control nanoparticle formation
•Joint effort between APS (characterization) and ANL-Center of Nanoscale Materials (synthesis)
• Goal: control shape and size of nanoparticles for functional application (catalysis, photonics, etc)
• Needed: real-time probe of morphology during nucleation and growth in solution
Current limitations - impurity - low reproducibility - wide distribution
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Probing nanophase evolution at semiconductor interface
•Nucleation and growth of anisotropic Ag nanoplates on GaAs distinguished (1s resolution)• Additional nanoparticles of Ag7NO11 formed; x-ray generated oxidation; x-ray nano-patterning application?• Future: real-time feedback and msec resolutions; tweak process variables (eg. temp) to produce desired properties (sizes, morphology, etc)
Y. Sun et al, Nanoletters 10 (2010), 3747-3753.
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Scientific scope
Energy: efficiency– High specific strength materials– Thermal barrier coatings for engine
efficiency Energy: production/storage
– Batteries, fuel cells, material discovery– Fossil fuel extraction (high-pressure
oil/coal/gas properties)– Nuclear materials
• damage tolerant materials for new reactors
• degradation of existing materials (corrosion/void formation/etc)
Energy: environment– CO2 sequestration (fluid movement in
rock/capillary trapping) Biology
– Response of bone and teeth to applied load, environment, dose
Porous Anode Porous cathode
H2 & CO O2
e-
H2O & CO2
e-
O=
• Controlled porosity• Thermal mismatch• Chemical durability• Mechanical integrity
Dense electrolyte
SOFC (battery)
• New lightweight composites • Optimizing metal sheet forming
High-energy scattering and imaging:• Penetrating in situ probes -> real conditions• High flux -> real time• High q-resolution -> real/complex materials
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Irradiated materials: scientific challenges
Irradiation causes serious degradation of mechanical properties– Delayed hydride formation & cracking in Zr-alloys– Stress-corrosion cracking
Predictions of materials long-term performance and development of high-performance, radiation-resistance materials in nuclear environments requires a mechanistic understanding– ‘Radiation resistant’ materials e.g. ODS steels– CMCs for higher temperature operation/efficiency
Desire microstructural-level understanding of deformation and fracture mechanisms and phase stability under stress and temperatures
Tomography to study intergranular stress corrosion cracking (King et al 2008)
Hydride formation and growth at stress concentrations(Daymond and Motta 2008-2010)
Fiber-matrix interactions in CMCs (Faber)
Integrated approach of theory, modeling and experiment
B. Wirth et al, J. Nucl. Mater. 329-333 (2004) 103
Nuclear materials: understanding Zr-hydrides
Zircaloy Fuel Cladding – Pressurized or
unpressurizedH2O coolant
– Temperatures range from 100 to greater than 300oC
Corrosion reaction at Zr surface: Zr + 2H2O ZrO2 + 4H
Need to measure hydrogen concentrations at ~100ppm corresponding to hydride phase fractions below 1% -> high flux!
Reactors World Wide
Hydride Diffraction Pattern
Single peak fits (GSAS and Matlab) Diffraction directly measures the elastic strain in the lattice – internal strain gage
– Plastic behavior only inferred through load transfer behavior For comparison to elastic strain in Finite Element (FE) calculations, a weighted average of
single diffraction peaks was used (multiplicity, texture, etc)MR Daymond, Journal of Applied Physics 96 (2004) 4263
2D pattern
Integrate segments
HE Diffraction: Hydride Strain Mapping
200 mm
50 mm2 spot size
20 mm2 spot size
X-Axis (mm)
Y-A
xis
(mm
)
-1.2 -1 -0.8 -0.6 -0.4 -0.2 0
-0.2
0
0.2
0.4
0.6
0.8
1
1.2
Lattice Strain
(x10-3)
-2
-1
0
1
2
3
4
5eyy – ZrHx {111}
Y-Ax
is (e
yy)
X-Axis (exx)
30% Overload (relative to hydride growth)
-0.5 -0.45 -0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0-3
-2
-1
0
1
2
3
4
5
6
X-Axis (mm)La
ttice
Stra
in (x
10-3
)
-0.5 -0.45 -0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0-3
-2
-1
0
1
2
3
4
5
6
X-Axis (mm)
Latti
ce S
train
(x10
-3)
Hydride Fracture
eyy Zr (Avg)eyy ZrHx {111}
20% Overload relative to hydride growth load
30% Overload relative to hydride growth load
At a 20% overload, hydride is intact at the notch At a 30% overload, the notch tip hydride has fractured transferring load to the
surrounding matrix Data combined with FE analysis used to derive critical hydride size for fracture (~4um)
Kerr et al, J. Nuc. Mat. (2008)
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Scientific scope
Energy: efficiency– High specific strength materials– Thermal barrier coatings for engine
efficiency Energy: production/storage
– Batteries and fuel cells– Fossil fuel extraction (high-pressure
oil/coal/gas properties)– Nuclear materials
• damage tolerant materials for new reactors
• degradation of existing materials (corrosion/void formation/etc)
Energy: environment– CO2 sequestration (fluid movement in
rock/capillary trapping) Biology
– Response of bone and teeth to applied load, environment, dose
Porous Anode Porous cathode
H2 & CO O2
e-
H2O & CO2
e-
O=
• Controlled porosity• Thermal mismatch• Chemical durability• Mechanical integrity
Dense electrolyte
SOFC (battery)
• New lightweight composites • Optimizing metal sheet forming
High-energy scattering and imaging:• Penetrating in situ probes -> real conditions• High flux -> real time• High q-resolution -> real/complex materials
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in-situ studies of real size samples
The pores distribution of large samples are now only possible in static conditions and after a
lengthy and disruptive sample preparation process.
Carbon sequestration, mine and oil exploration
Nature Vol. 459 18 June 2009
Thermal expansion cracking in rocks
Advanced Photon Source Upgrade (APS-U) project
200 C 395 C100 um 100 um
2 cm
Understanding thermal cracking in fine-grained granite: increase in porosity with temperature facilitates the percolation of fluid through the rock.
4.5
4.0
3.5
3.0
2.5
1.5
1.0
0.5
µm
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Scientific scope
Energy: efficiency– High specific strength materials– Thermal barrier coatings for engine
efficiency Energy: production/storage
– Batteries and fuel cells– Fossil fuel extraction (high-pressure
oil/coal/gas properties)– Nuclear materials
• damage tolerant materials for new reactors
• degradation of existing materials (corrosion/void formation/etc)
Energy: environment– CO2 sequestration (fluid movement in
rock/capillary trapping) Biology
– Response of bone and teeth to applied load, environment, dose
Porous Anode Porous cathode
H2 & CO O2
e-
H2O & CO2
e-
O=
• Controlled porosity• Thermal mismatch• Chemical durability• Mechanical integrity
Dense electrolyte
SOFC (battery)
• New lightweight composites • Optimizing metal sheet forming
High-energy scattering and imaging:• Penetrating in situ probes -> real conditions• High flux -> real time• High q-resolution -> real/complex materials
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Mineralized Tissue and Implants Bone and dentin have a complex hierarchical structure –
composite of mineral (calcium hydroxyapatite), organic protein and water
Macroscopic mechanical properties well studied; properties at the basic level not well understood Fundamental properties needed for better restoration materials, formulate more accurate models
High-energy X-ray scattering gives distinct information from the mineral, collagen fibril and implant phases.
HAP lattice planes diffract
WAXS pattern
SAXS pattern
~67 nm
Phase response vs loadModel Setup
L
R
spring
HAPcollagen
67 nm
Interstitial space
-5 -4 -3 -2 -1 0-80
-70
-60
-50
-40
-30
-20
-10
0
WAXS(222)WAXS(004)SAXS
longitudinal strain (e22x103)ap
plie
d st
ress
(M
Pa)
EWAXS=39.6GPa
ESAXS=19.8GPa
•Elastic Properties of Pure Phases: HAP: E=114 GPa, ν=0.28 Collagen: E=1 GPa, ν=0.25•Volume Fraction of HAP: 35%
Dashed lines are simulation results
Nanoscale model and experimental validation
Perfect bonding between HAP and collagen
Creep behavior
Delamination at HAP-collagen interface
Low dose
Experiment Simulation
0 20 40 60 80 100 120
-6000
-5000
-4000
-3000
-2000
-1000
0
Time (min)
Pha
se S
trai
n (μ
ε)
Fibril -1.9 με/min
HAP -0.8 με/min
0 20 40 60 80 100 120 140 160 180 200
-25000
-20000
-15000
-10000
-5000
0
-5900
-5700
-5500
Time (min)
Lon
gitu
dina
l Str
ain
(με)
HAP
Fibril
0 20 40 60 80 100 1200
-2000
-4000
-6000
-8000
-10000
-12000
Time (min)
Phase
Str
ain
() Fibril
HAP
High dose
-8000
-6000
-4000
-2000
00 20 40 60 80 100 120
Time (min)
Phase
Strain
()
HAP
Fibril
Systematic studies have shown dose threshold of ~10kGray (Cancer therapy 5-60 Gray, sterilization 20-100kG)
Bone Implant – highest level of hierarchy
Structure
bone
screw head
implant
Bone: bovine femurScrew head: solid cp-3 TiImplant: porous cp-1 Ti
HAP Strain Distribution
implant boundary
-3 -2 -1 0 1 2 3 4
-6
-5
-4
-3
-2
-1
0
1
2
3
Horizontal position
Applied stress = 60 MPa
Ver
tical
pos
ition
-2000
0
2000
4000
6000
8000
mapping boundary
These studies will focus on interface between implant and bone, to better understand load transfer / implant effectiveness.
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Summary
High-energy x-ray techniques provide new insights into complex systems, with particular impact on energy research– Irradiated materials– Batteries/fuel cells– Energy efficiency– Biomechanics
Trend is to combine techniques: High-energy SAXS/WAXS/Imaging– Access a range of length scales (sub-nm to mm) using the same probe, msec
resolution– Non-destructive– Microstructural evolution in extreme environments
APS upgrade will provide the brightest source of high-energy x-rays worldwide, allowing us to push spatio-temporal resolution limits.
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Some common technical challenges / opportunities Detectors
– Efficient at E>50keV w/good resolution (e.g. structured scintillators)– Readout >=1kHz & >=Mpix– Energy discrimination
In-situ environment ‘centers’– Capacity to follow processes is often limited by ability to simulate service/
processing conditions– Combined with penetrating x-rays: allow complex development / real conditions– Intermittent use for long-time processes (e.g. creep)– Unite with advanced characterization tools
Analysis & visualization of multi-dimensional datasets Efficient data reduction Real time feedback Interface with materials modeling community