high-energy x-ray* studies of real materials under real conditions and in real time fermilab...

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

2

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

3

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

6

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


7

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

PDF

‘Wide- angle’ scattering

‘Small-angle’ scattering

USAXS


9

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


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.


12

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


14

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

15

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.


16

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


18

Scientific scope



– Batteries, fuel cells, material discovery– Fossil fuel extraction (high-pressure








H2 & CO O2

e-

H2O & CO2

e-

O=


Dense electrolyte

SOFC (battery)



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

PDF

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


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In-situ synthesis of nano-particles for Li-ion batteries

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

22

? ? ?

?

?

?

?

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


23

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.


24

Scientific scope



– Batteries, fuel cells, material discovery– Fossil fuel extraction (high-pressure








H2 & CO O2

e-

H2O & CO2

e-

O=


Dense electrolyte

SOFC (battery)



25

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)


31

Scientific scope











H2 & CO O2

e-

H2O & CO2

e-

O=


Dense electrolyte

SOFC (battery)



32

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


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


33

Scientific scope











H2 & CO O2

e-

H2O & CO2

e-

O=


Dense electrolyte

SOFC (battery)



34

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.


38

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.


39

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


40

Energy-sensitive detectors for imaging + scattering

XANES full-field imagingRau et al, Nuc. Inst. Meth B (2003), 200

Energy-discriminating detectors (chemistry+structure)

• Triple phase boundaries in SOFCs• SEI in batteries

Current R&D efforts : CdZnTe sensors

high-energy x-ray* studies of real materials under real conditions and in real time fermilab...

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