HARD X-RAY SPECTROSCOPY AND IMAGING AT THE BAMLINE AND SPOT BEAMLINES

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www.bam.de

@BESSY II (BERLIN, GERMANY) Dr. Ana Guilherme Buzanich

Structural Analysis division / Dept. Analytical Chemistry

01.02.2019

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Division Structural Analysis – Department of Analytical Chemistry

2 Hard X-ray Spectroscopy and Imaging at the BAMline and µSpot beamlines

30.01.2019

Fields of expertise

• Quantitative analysis of X-ray powder diffraction

• Investigation of materials at different length scales

• Identification and refinement of crystalline structures

• Liquid and solid state NMR

• Synchrotron-based spectroscopies (XRF, XAS) & diffraction (XRD, SAXS, WAXS)

• Combination of several analytical methods: In Situ

• Surface and pore analysis of porous solids and nanomaterials

• Characterization of polymers (size, weight, chemical heterogeneity)

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BAM  BESSY-II close connection

30.01.2019 Hard X-ray Spectroscopy and Imaging at the BAMline and µSpot beamlines 3

400 meters

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Outline

Hard X-ray Spectroscopy and Imaging at the BAMline and µSpot beamlines 4 30.01.2019

Cu

100 µm Cu

Co

175 µm

Applications

&

Collaboration Partners Analytical

Methods

Future

Perspectives

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Applications

&

Collaboration Partners

BAMline

& µSpot

Analytical

Methods Future

Perspectives

Hard X-ray Spectroscopy and Imaging at the BAMline and µSpot beamlines 30.01.2019

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Analytical methods – BAMline

Analytical Methods Information DCM

7-30 keV (10

⁹

ph/s)

XAS - XANES

- EXAFS

Chemical speciation:

-Oxidation state - Local coordination

geometry

DMM 4-50 keV (10

¹¹

ph/s)

-(µ-)EDXRF XRF

- WDXRF Elemental composition

0.00E+00 2.00E+08 4.00E+08 6.00E+08 8.00E+08 1.00E+09 1.20E+09 1.40E+09 1.60E+09 1.80E+09

0 10 20 30 40 50

Si (111) including 0.8 mm Be filter

Energy (keV) Photon Fl ux densi ty ( ph /s

-1

/m m

2

)

DCM Si (111) DMM

W/Si 300 layer

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Analytical methods – µSpot beamline

Analytical Methods Information

DCM 5-20 keV (10

¹¹

p/s)

XAS Chemical speciation - Oxidation state

XRD Crystal structure SAXS/WAXS Size, shape,

polydispersity DMM

5-20 keV (10

¹³

p/s)

XRF Elemental composition Raman

spectroscopy Molecular structure

0 2E+10 4E+10 6E+10 8E+10 1E+11 1.2E+11

0 10 20 30 40

Si (111)

Energy (keV) Photon Fl ux densi ty ( ph /s

-1

/m m

2

)

DCM

Si (111) / Si (311) ML (Mo/BC)

Toroidal

focusing mirror

Max. Spotsize:

300 µm x 2 mm

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XAS modus operandi – standard

8

I 0 I(x)

Sample Slits

Monochromator Absorption /

Transmission

Fluorescence

I(x) = I 0 e -µ(E)x

µ(E)  I F /I 0

I

_F

I 0

Sample

30.01.2019 Hard X-ray Spectroscopy and Imaging at the BAMline and µSpot beamlines WLS

B = 7 T 1.7 GeV

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XAS modus operandi – micro-XAS

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I

_F

CRL Sample

μ(E)

∝ I

_F

/I

₀

WLS B = 7 T 1.7 GeV

G. Buzanich et al. J. Anal. At. Spectrom. (2012) 27, 1803.

30.01.2019 Hard X-ray Spectroscopy and Imaging at the BAMline and µSpot beamlines

Compound refractive lens (CRL)

 narrow bandwidth (~100 eV)

workable focal lengths (350 mm)

 focusing regions from 100 nm

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 Simple

 Scanningless

 Time & spatial resolution

 no scattering contribution

 Time-resolution  1 s

 Spatial-resolution:  20 µm

 Beam size up to 20 x 8 mm

²

XAS modus operandi – dispersive XAS (S 2 XAFS)

10

DMM

in total Reflection

Sample



Filter 2

Band-pass

Convexly bent Si (111)

WLS B = 7 T

A. Guilherme Buzanich, M. Radtke, U. Reinholz, H. Riesemeier, F. Emmerling.

J. Synchrotron Rad. (2016), 23, 769-776.

1.7 GeV

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XAS modus operandi – dispersive XAS (S 2 XAFS)

11 30.01.2019 Hard X-ray Spectroscopy and Imaging at the BAMline and µSpot beamlines

V Cr Mn Fe Co Ni Cu Zn K-lines

L

₃

-lines

Ce Pr Nd Pm Sm Eu Gd Tb

Ba La

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XAS modus operandi – total reflection XAS (TXRF-XAS)

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 2-fold increased intensity

 Trace element speciation in ng to pg range I

_F

Sample μ(E) ∝ I

_F

/I

₀

Reflector

WLS B = 7 T

Monochromator

1.7 GeV

XRF Detector

U. E. A. Fittschen, A. Guilherme et al. J. Synchrotron Rad. (2016), 23, 820-824.

SDDetector

Amount of Ni

(pg) LOD

Sy-TXRF (pg) LOD conventional

-TXRF (pg)

10 0.06 < DL

100 0.07 8

NIST water 1640

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Applications

&

BAMline

& µSpot

Analytical

Methods Future

Perspectives

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micro-XAS – Morbus Wilson´s Disease:

Cu speciation in liver

14 200 µm

Cu K-edge XANES on two areas

Cu distribution on a liver specimen

O. Hachmöller, A. Guilherme Buzanich, et al. Metallomics (2016) 8, 648.

Institute for Inorganic and Analytical Chemistry

Partners

8980 9000 9020

0.0 0.4 0.8

Normalized µ(E) a.u.

Energy (eV)

8980 8990 9000 9010

0.0 0.1 0.2

Normalized µ(E) a.u.

Energy (eV)

8990 Cu-I

8994 Cu-II

1 µm spot size

Cellular resolution

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micro-XAS – identification of corrosion phases in steel

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Ferritic steel with 2% Cr content Fe2Cr (250h @ 650°C)

2 µm Gas

Metal 200 µm

^0,0₇₀₆₀ ₇₀₈₀ ₇₁₀₀ ₇₁₂₀ ₇₁₄₀ ₇₁₆₀ ₇₁₈₀ ₇₂₀₀ ₇₂₂₀

0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8

A b s o rb iert e I n te n s it ä t

Energie [eV]

26 µm 104 µm 182 µm 260 µm 338 µm 416 µm 494 µm

Energy (keV)

Normal iz ed µ(E) (arb . Units)

Gas Metal

ex situ XANES @ Fe K-edge 2 µm spotsize

K. Nützmann, A. Guilherme Buzanich, et al. Materials and Corrosion (2019) accepted.

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micro-XAS: Understanding the corrosion of Fe2Cr alloys in situ

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7080 7100 7120 7140 7160 7180 7200 7220 7240

0,0 0,2 0,4 0,6 0,8 1,0 1,2

Normalized µ(E) (arb. units)

Energy (eV)

Fe2Cr

Fe2Cr @650°C, 2 min. 0.5% SO

₂

Fe 3 O 4 is formed under extreme conditions – inverse spinel

Fe K-edge XANES

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Dispersive XAS (S 2 XAFS) – In Situ Crystallization of ZIF-8

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XANES Zn K-edge 1 second time resolution

A. Kulow et al. J. Anal. At. Spectrom. (2019) 34, 239-246.

Ionic

Covalent

Sample holder for liquids

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TXRF-XANES – speciation of traces in ng range

18 I_F

Sample μ(E) ∝ I_F/I₀

Reflector

WLS B = 7 T

Monochromator

1.7 GeV

XRF Detector

10450 10500 10550 10600 10650 10700

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

N o rma lize d µ (E) a .u .

Energy (eV)

Re-Unknown NaReO4 ReI3

Re L 3 -edge XANES on 4 ng!

2p  5d

2p  continuum

Energy

2p 5d 6d 7d 8d Continuum

U. E. A. Fittschen, A. Guilherme, et al. J. Synchrotron Rad. (2016), 23, 820-824.

Material Analysis and Functional Solid Matter

Partners 3+

7+

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XAS + Scattering (SAXS) – in situ formation of Fe nanoparticles

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CCD

Levitated doplet

Sy-Beam X-ray detector SAXS

XANES

A. Kabelitz, et al. CrystEngComm. (2015) 17, 8463-8470

Understanding of Metal Oxide/Water Systems

at the Molecular Scale:

Structural Evolution, Interfaces, and Dissolution

Humboldt University Partners

Fe K-edge XANES

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XRF – Co distribution in bone by implants

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XRF Detector

Sample/

Cell

LLA Instruments GmbH & Co. KG

Ca Co

1000 5000 100 400

Counts (a.u.)

‘on-the-fly’ XRF scan: 350 x 290 µm 2

2 µm stepsie; 4 s per point Partners

UKE (Eppendorf)

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Applications

&

BAMline

& µSpot

Analytical

Methods Future

Perspectives

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The future of our hard X-ray beamlines for material characterization

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Automation

•Control of adjusment parameters

•Faster sample adjustment

•High-throughput experiments

Reproducibility

•Ensure equal measuring conditions

•Reliable data

Flexibility

•Different technical specifications

•Cover more fields of applications

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Thank you

for your attention !

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