applications of ultra-modern x-ray (and ftir) microscopes ...malayaite-cassitérite casnsio 5:cr,...

Applications of ultra-modern

X-ray (and FTIR) microscopes

to study ancient glasses

(and other materials)

M. Cotte1,2

1- ID21, European Synchrotron Radiation Facility, 71 av. des martyrs 38000 Grenoble, France

2- Sorbonne Université, CNRS, UMR 8220, Laboratoire d’archéologie moléculaire et structurale (LAMS), 4 place Jussieu 75005 Paris, France

Acknowledgments: all staff involved in maintenance and development of instruments, and our users

In particular Louisiane Verger, Sofia Lahlil and Gert Nuyts

Li-Hill, 2019, Grenoble

THE STUDY OF ANCIENT GLASSES, ENAMELS…

Very rare, highly decorated and coloured Etruscan

glass vessels and beads from the VII to the IV C. BC

Arletti et al, Applied Physics A, 2008

Sicilian mosaic, 1st C. A.D., ItalyLahlil et al, Applied Physics A, 2010

Vase from Achères (1900), from the collection of the

Cité de la céramique, ©RMN-Grand Palais.

Verger et al., Journal of the American Ceramic

Society, 2017

Browning of glass in Middle Age

stained glass windowsBlue decors in Chinese porcelains

(Ming dynasty, 1368-1644)Wang et al, Analytica Chimica Acta,

2016

TWO MAIN QUESTIONS: CHEMICAL REACTIONS FROM BIRTH TO DEATH

Components:natural?,

synthetic?reused?

Synthesis protocols:Fire conditions

(temperature, redox)?

Evolution of techniques in time

and space?

Conservation state?

Composition of

degradation?

Efficiency of conservation treatments?

Triggers responsible for degradation?

Composition today

Composition in the future?

Composition at the time of creation?

Components?Processes?

Ageing reactions?Manufacturing processes?

HOMOGENEOUS OR NOT?

2 µm300 nm

100 nm

Visible microscope

Scanning electron microscope

Transmission electron microscope

TWO MAIN WAYS TO OBTAIN IMAGES

Bertrand, L., M. Cotte, et al., (2012), "Development and trends in synchrotron studies of ancient and historical materials.“, Physics Reports, 519(2): 51-96.

2D detector

Full-field imaging

Mapping or raster-scanning

• Visible microscopy• Transmission electron microscopy• X-ray radiography / tomography• X-ray phase contrast tomography• Full-field XAS• µFTIR with FPA• …

• Scanning electron microscopy• micro X-ray fluorescence (µXRF)• Micro X-ray diffraction (µXRD)• Micro X-ray absorption spectroscopy

(µXAS)• Micro infrared spectroscopy (µFTIR)• µRaman• AFM• ……

(X-RAY) IMAGING: COMBINING CHEMICAL CHARACTERIZATION AND LOCATION

The synchrotron light:Intense, collimated, polychromatic beam

From X-rays to infrared

Ideal for micro- spectroscopy!

WHAT ABOUT SYNCHROTRON-BASED MICROSCOPIES?

ESRF Grenoble

France

EXAMPLE 1 : REVEALING THE MANUFACTURING OF

ANCIENT GLASSES BY MEASURING ELEMENT

SPECIATION (XAS) SELECTIVELY IN THE GLASS MATRIX

Composition today





Revealing the manufacturing of opaque glasses µXAS study of antimony oxidation state

Sophia Lahlil, Isabelle BironCenter of Research and Restoration of French museums

Sb

Ca

Si

10 µm

calcium antimonate

crystal

vitreous

matrix

How were these glasses made opaque?

S. Lahlil, I. Biron, M. Cotte, J. Susini, N. Mengui, “Synthesis of calcium antimonate nano-crystals by the 18th dynasty Egyptian glassmakers”, Applied Physics A, 98 (1), 1-8 (2010).S. Lahlil, I. Biron, M. Cotte, J. Susini, “New insight on the in situ crystallization of calcium antimonite opacified glass during the Roman period”, Applied Physics A, 100(3) 683-687 (2010).

Devitrification

crystal

Roman Empire Renaissance

16th C. 0

Mesopotamia and Ancient Egypt

5th C. 15th C. 16th C. 1st C. 19th C.12th-13th C.

Modern times

Alabasters6th-4th C. B.C.Mesopotamia

Sicilian mosaic 1st C. A.D.

Italy

Merovingian tumbler 6th C.

A.D.France

Binding plaque12th C. A.D.

FranceGlass bottle18th C. A.D.Germany


OPACIFIED GLASS ACROSS HISTORY

1 cm

1 cm1 cm

Nano-crystals of calcium antimonate

18th Dynasty, (1570-1292 B.C.).

2 µm300 nm

100 nm

S. Lahlil, I. Biron, M. Cotte, J. Susini, N. Mengui, “Synthesis of calcium antimonate nano-crystals by the 18th dynasty Egyptian glassmakers”, Applied Physics A, 98 (1), 1-8 (2010).

CALCIUM ANTIMONATES NANO-CRYSTALS AS GLASS OPACIFIERS IN ANCIENT EGYPT

IN-SITU VS EX-SITU SYNTHESIS?

In-situSb2Oy

Ca

Ca1+nSb2O6+n

(n=0, 1)

Ex-situCa1+nSb2O6+n

(n=0, 1)

Ca1+nSb2O6+n

(n=0, 1)Ca1+nSb2O6+n

(n=0, 1)

Can Sb XANES help in differentiating these two processes?

4.69 4.70 4.71 4.72 4.73 4.74 4.75 4.76

No

rma

lize

d a

bs

orp

tio

n (

a.u

.)

Energy (keV)

4,69 4,70 4,71 4,72 4,73 4,74 4,75 4,76

Sb2O3

Sb2O5

Sb2O4

Sb2S3

SbIII SbV

Sb references (powder)

4.69 4.70 4.71 4.72 4.73 4.74 4.75 4.76

No

rma

lize

d a

bs

orp

tio

n (

a.u

.)

Energy (keV)

10 wt % Sb2O3

10 wt % Sb2O5

10 wt % Sb2O4

10 wt % Sb2S3

SbIII SbV

Experimental glass

In-situ crystallization

introduction of Sb oxide or sulfide in glass

4.69 4.70 4.71 4.72 4.73 4.74 4.75 4.76

No

rma

lize

d a

bs

orp

tio

n (

a.u

.)Energy (keV)

SbIII SbV

Ca2Sb2O7,

powder

10 wt%

Ca2Sb2O7, in

glass

Ex-situ crystallisation(Ca2Sb2O7 directly introduced into glass)

Powder and experimental

glass

IN-SITU VS. EX-SITU CRYSTALLIZATION, SB LI-EDGE XANES ANALYSIS, ID21

Direct identification of

the oxidation state

In-situ: with oxides, always a SbIII-SbV mixture

SbIII/SbV ratio is related to the initial Sb oxidation state

Ex-situ: no SbIII in the

glass matrix

No

rma

lize

d a

bs

orp

tio

n (

a.u

.)SbIII SbV

Blue Roman glass

Blue Roman

glass

Experimental glass

10 wt % Sb2O4

Blue Roman glass

Energy(keV)

White Egyptian

glass

White Egyptian

glass

Blue Egyptian glassEgyptians made opaque glasses using

ex-situ synthesized Ca2Sb2O7

nanocrystals

Romans made opaque glasses by in-situ

crystallization, using Sb2O4

Experimental glass

10 wt % Ca2Sb2O7

IN-SITU VS. EX-SITU CRYSTALLIZATION, SB LI-EDGE XANES ANALYSIS

S. Lahlil, I. Biron, M. Cotte, J. Susini, N. Mengui, “Synthesis of calcium antimonate nano-crystals by the 18th dynasty Egyptian glassmakers”, Applied Physics A, 98 (1), 1-8 (2010).

S. Lahlil, I. Biron, M. Cotte, J. Susini, “New insight on the in situ crystallization of calcium antimonite opacifiedglass during the Roman period”, Applied Physics A, 100(3) 683-687 (2010).

EXAMPLE 2 : UNDERSTANDING ENAMEL COLOR BY

MEASURING ELEMENT SPECIATION (XAS)

SELECTIVELY WITHIN PIGMENT PARTICLES

Composition today





The stability of the ZnAl2O4:Cr pigment in

enamels from the "Manufacture de Sèvres"

Louisiane Verger1,2

Laurent Cormier1

Olivier Dargaud2

Gwenaelle Rousse1,3

1 Institut de Minéralogie, de Physique des Matériaux et deCosmochimie (IMPMC), Sorbonne Universités, UPMC UnivParis 06, CNRS UMR 7590, Paris, France2 Cité de la Céramique - Sèvres et Limoges, Sèvres, France3 Chimie de Solide et Energie, FRE 3677 Paris, France

L. Verger, O. Dargaud, G. Rousse, E. Rozsályi, A. Juhin, D. Cabaret, M. Cotte, P. Glatzel and L. Cormier,

"Spectroscopic properties of Cr3+ in the spinel solid solution ZnAl2-xCrxO4", Phys Chem Minerals, 1-10 (2015).

L. Verger, O. Dargaud, G. Rousse, M. Cotte, & L. Cormier, “The stability of gahnite doped with chromium pigments

in glazes from the French manufacture of Sèvres”. Journal of the American Ceramic Society, accepted (2016).

Controlling pigment colors in porcelains from Manufacture of Sèvres

Combination of XRD, diffuse reflectance spectroscopy and XAS to correlate color change with chemical changes

MANUFACTURE DE SEVRES: A MUSEUM AND A FACTORY

The Manufacture of Sèvres, founded in 1740=> Production of fine porcelain with the same spirit and quality, but always renewing its knowledge

- chromium introduced in the Manufacture in 1804 by Brongniart- today, among the 130 pigments produced, 75 contain a chromium oxide

Courtesy L. Verger

CHROMIUM OXIDE: A WIDE RANGE OF COLOURS

Brown Green

« Empire »

Light

Green

Pink

Courtesy L. Verger

CREATING NEW ENAMELS

(A–B) Extract from the laboratory notebooks of the years 1893 and 1896, referring to the synthesis of a gahnite with chromium type pigment on October 8th, and its test in a porcelain decoration on December 25th, respectively. (C) Porcelain slab composed of the porcelain decoration prepared on December 25th, 1896. (D) Vase de Chagny A (1899) from the collection of the “Cité de la céramique”, MNC12652, dimensions: 120 cm (height), 55 cm (diameter). ©RMN-Grand Palais. [Verger, 2018, CRP]

Increasing enamel thicknessColor: green pink

Courtesy L. Verger

PREPARATION OF THE SAMPLES: FROM THE PIGMENT TO THE ENAMEL

inorganic pigmentsenamel

=> composed of kaolin, feldspar, chalk and quartz

Calcination at 1280 or 1400°CMetallic oxides

(of Cr, Al, Zn…)

uncoloured frit

Firing processusually applied

on porcelain1280°C- 1400°C

Painted on the porcelain

1 2 3 4 5 6

Eskolaite

Cr2O3

Solid solution

Al2O3-Cr2O3

Spinel doped with Cr

ZnAl2O4:Cr, MgAl2O4:Cr

Spinel rich in Cr

CoCr2O4

Malayaite-Cassitérite

CaSnSiO5:Cr, SnO2: Cr

Uvarovite

Ca3Cr2(SiO4)3

Courtesy L. Verger

COLOUR CHANGE OCCURRING WITH THE PIGMENT ZNAL2O4:CR

Chromium present in aggregates Reaction layer between the grain of pigment and the uncoloured frit Dissolution of the grains of pigments

Cross section

porcelain

enamel

enamel

Porcelain (body)

Scanning Electron Microscope observations

Courtesy L. Verger

μ-XANES on the enamel (Cr K-edge, beam size: 0.2 x 0.7μm2), ID21

LOCAL ENVIRONMENT AROUND CR IN THE ENAMEL

Al

Cr Si

Two different environments of Cr in the enamel (role of 2nd neighbours)

What about colour?

Courtesy L. Verger

THE SPINEL SOLID SOLUTION ZNAL2O4 - ZNCR2O4

Lattice parameters as a function of Cr content in references (green), in pigment and enamel (red)

ZnAl2O4

ZnCr2O4

phase formedduring firing

pigment

Synthesis of references ZnAl2-xCrxO4 , x from 0 to 2 => the lattice parameter follows Vegard’s law => quantification of chromium content

ZnAl2O4:Cr

ZnCr2O4

Local environment around Cr probed by XANES

Cr-Cr pair role (peak γ)

Explain the colour change in enamelCourtesy L. Verger

USE OF XAS TO REVEAL MANUFACTURING PROCESSES

Aesthetics value

Optical effects:

Color

Transparency

Opacity

Metallic Shine

Colored iridescence…

Due to:

opacifying crystals,

ionic chromophores(transition elements)

metallic nano-particles …

Controlling the oxidation state within the vitreous matrix:

Firing conditions (time, temperature, atmosphere)

Choice of ingredients

Request for an analytical method:

Probing the chemical environment,

Applicable to amorphous materials

EXAMPLE 3 : UNDERSTANDING WINDOW GLASS

DARKENING AND ASSESSING CONSERVATION

TREATMENTS

Composition today





Manganese staining of archeological glass:

formation and removal

S. Cagno,1 G. Nuyts1, O. Schalm,1 K. Janssens,1 1 Department of Chemistry, University of Antwerp, Universiteitsplein 1, B-2610 Antwerp, BelgiumS. Bugani2, K. De Vis,3 J. Caen3, L. Helfen,4 P. Reischig4

2 Department of Industrial Chemistry and Materials, University of Bologna,Viale del Risorgimento 4, I-40136 Bologna, Italy3 Conservation Studies, Artesis University College of Antwerp, Blindestraat 9, B-2000 Antwerp, Belgium4 Karlsruhe Institute of Technology, D-76021 Karlsruhe, Germany

Cagno, S., G. Nuyts, et al., (2011), "Evaluation of manganese-bodies removal in historical stained glass windows via SR-µ-XANES/XRF and SR-µ-CT.”, Journal of Analytical Atomic Spectrometry, 26: 2442-2451.Nuyts, G., S. Cagno, et al., (2015), "Micro-XANES study on Mn browning: use of quantitative valence state maps.“, Journal of Analytical Atomic Spectrometry, 30(3): 642-650.

Assessing speed and efficiency of a conservation treatment used of stained glass

Combination of µXAS, µXRF, µCT to monitor glass composition during treatment by hydroxylamine hydrochloride

GLASS DARKENING

Formation of dark Mn bodiesMacroscopical darkening/browning of glass

Required conditions1) Formation of a gel layer

2) Manganese source (int./ext.)

→ Impurities in raw material

→ Added as pyrolusite (MnO2), decolorizing agent

(Fe2+ → Fe3+)

Courtesy G. Nuyts

GLASS DARKENING

If a manganese source is available (from glass or environment), manganese rich bodies can be formed inside the leached layer:

Lynch, M. E., D. C. Folz, et al. (2007), "Use of FTIR reflectance spectroscopy to monitor corrosion mechanisms on glass surfaces.“, Journal of Non-Crystalline Solids, 353(27): 2667-2674.Nuyts, G., S. Cagno, et al. (2013), "Study of the Early Stages of Mn Intrusion in Corroded Glass by Means of Combined SR FTIR/μXRF Imaging

Glass weathering: induced by water presence

1. Penetration of molecular water: Hydrolysis of glass => breaking and forming of silicon-oxygen bonds

• ≡Si−O−Si≡ + H2O(aq) → 2≡Si−OH

• 2≡Si−OH → ≡Si−O−Si≡ + H2O(glass)

2. Leaching of mobile cations (in acidic conditions),

density decreases

• ≡Si−O-M+(glass) + H+

(aq)→ ≡Si−OH + M+(aq)

3. Ion exchange → pH rise → network degradation

• ≡Si−O−Si≡ + OH-(aq) → ≡Si−OH + ≡Si−O-

• ≡Si−O- + H2O(aq) → ≡Si−OH + OH-(aq)

GEL

LAYER

Mn SPECIATION IN A DEGRADED HISTORICAL GLASS

Courtesy G. Nuyts

K (red), Ca (green) and Mn (blue) elemental distribution maps of a cross-section of historical sample (14th C., UK) (1.84×0.67 mm2).

Nuyts, G., S. Cagno, et al., (2015), "Micro-XANES study on Mn browning: use of quantitative valence state maps.“, Journal of Analytical Atomic Spectrometry, 30(3): 642-650.

Mn inclusions

Gel layerBulk glass


Courtesy G. Nuyts


XANES linescan:• on glass cross-section• perpendicular to original surface• prior to treatment• step-size: 5 µm (total: 290 µm)


Mn inclusions

Bulk glass

Gel layer

HeterogeneousMn(IV) ~ 55-90%

Mn(II): ~ 80%Mn(IV): ~ 15%

Mn(II) ≈ Mn(III)

How to obtain 2D valence state maps?

Mn inclusions

Gel layerBulk glass


Courtesy G. Nuyts


XRF maps recorded at two energies:• the white-line of Mn in bulk glass E1 = 6553.2 eV• the white-line energy of Mn in the enrichment (E2 = 6560.5 eV)IMn(E1)/IMn(E2) indicative of valence state


E1 E2

Valence state maps: calibration curve

Mn inclusions

Gel layerBulk glass

Mn SPECIATION BEFORE AND AFTER CLEANING TREATMENT

Courtesy G. Nuyts


Treatment:• cotton, drenched in 5 wt% Hydroxylamine hydrochloride, NH2OH.HCl• contact with the original glass surface• 24 h

A cross-section was examined before and after treatment

Mn before and after treatment No Mn removal

Valence state maps before and after:Mn is reduced.

→ observed in the Mn enriched zone and gel layer;bulk glass remains unaffected

Before After

Manganese staining of archeological glass:

simulation of glass corrosion

S. Cagno,1 G. Nuyts1, O. Schalm,1 K. Janssens,1 1 Department of Chemistry, University of Antwerp, Universiteitsplein 1, B-2610 Antwerp, BelgiumS. Bugani2, K. De Vis,3 J. Caen3, L. Helfen,4 P. Reischig4

2 Department of Industrial Chemistry and Materials, University of Bologna,Viale del Risorgimento 4, I-40136 Bologna, Italy3 Conservation Studies, Artesis University College of Antwerp, Blindestraat 9, B-2000 Antwerp, Belgium4 Karlsruhe Institute of Technology, D-76021 Karlsruhe, Germany

Nuyts, G., S. Cagno, et al. (2013), "Study of the Early Stages of Mn Intrusion in Corroded Glass by Means of Combined SR FTIR/μXRF Imaging and XANES Spectroscopy.“, Procedia Chemistry, 8(0): 239-247.

Simulating accelerated weathering under

controlled conditions, to create artificially

altered glass for the use of evaluation of

conservation methods

Combination of µXAS, µXRF, µFTIR to monitor glass composition during early stage of Mn intrusion in glass models

µXRF MAPS ON MODEL SAMPLES DURING EARLY CORROSION

Glass treated n hours in 1M HCl (n=2, 4, 6) + 24h in 0.5M MnCl2µXRF elemental maps:• Ca leached out

homogeneously, partially. • K leached out completely

(in leached layer)• Leaching thickness : 58µm

after 6h

Requirements for Mn browning:

1) Formation of a gel layer

→ Immersed sensor glass in HCl solution: pH (0,2,4,7), treatment time (1-8h)

2) Manganese source

→ MnCl2 0.5 Mtreatment time (24 h, 48 h, 72 h)

Healthy glass

Gel layer 100 µm

Artificially aged Fraunhofer Glass

4h 1M HCl + 24h 0,5 M MnCl2

IDENTIFICATION OF Mn SPECIES ON MODEL SAMPLES DURING EARLY CORROSION

Courtesy G. Nuyts

XRF + XANES

Map = 270 x150 µm2

Step = 2x2 µm2

75% Hausmannite (Mn2+Mn3+2O4)

25% manganese (1%) in glass

Pt 2

. 1

. 2

. 3

. 4

. 5

. 6

µXRF/XANES

Mn-K

Si-K

Gel layer

Artificially aged Fraunhofer Glass

4h 1M HCl + 24h 0,5 M MnCl2

Healty glass

MnO2 inclusions observed on historical samples: probably require a slow oxidation of Mn3O4

Conditions too alkaline? Recommend more acidic conditions for future experiments


µFTIR MAPS IN REFLECTION MODE ON POLISHED SAMPLES (ID21)

Si-O-Si-O-Si

SR µFTIR mapping

• Reflection mode

• 800 cm-1 – 4000 cm-1

• 50 spectra/pixel (15 x 15 µm2)

• HCA performed one each map

• 3 clusters → healthy, gel layer (corroded glass), resin• ≠ (Si−O-):(Si−O−Si) ↓• Si−O- stretch ↓ (glass leaching)• Si−O−Si antisym. stretch ↑ (formation of vitreous SiO2)

• Gel layer grows rapidly in acidic conditions• Maximal depth: 40-50 µm

1 M HCl 0 h 3 h 6 h

Original glass

Gel layer

Resin

Glass corrosion, FTIR cluster spectra

Possibility to monitor alterations in silica network during the leaching of earth alkali and alkali metals from the glass network


Rembrandt’s impasto deciphered via identification of unusual

plumbonacrite by multi-modal Synchrotron X-ray Diffraction

Portrait de Marten Soolmans, 1634 (210x135 cm²), Rijksmuseum

THE STUDIED PAINTINGS-1

d) Susanna, 1636 (47.4x38.6 cm²), Mauritshuis. e) Bethsabée, 1654 (142x142 cm²), Louvre.

DES CLÉS DANS LES TEXTES?THE STUDIED PAINTINGS-2

C: cerusite PbCO3

HC: hydrocerusite Pb3(CO3)2(OH)2

PN: plumbonacrite, Pb5(CO3)3O(OH)2

Impasto

Paint layer

V. Gonzalez, M. Cotte, G. Wallez, A. van Loon, W. de Nolf, M. Eveno, K. Keune, P.Noble and J. Dik, "Rembrandt’s impasto deciphered via identification of unusualplumbonacrite by multi-modal Synchrotron X-ray Diffraction", Angewandte Chemie(2019).

Identification of plumbonacrite specifically and systematically in empastos

Impasto

Paint layer

SOME RESULTS WITH MICRO-DIFFRACTION X (ID13, ESRF)

Sir Theodore Turquet de Mayerne (1573-1655)

SOME CLUES IN THE TEXTS?

TECHNICAL CHALLENGES AND OPPORTUNITIES

Chemical complexity (analyzing mixtures) XRF XAS in XRF mode

Chemical heterogeneity Beam size (radiation damage!) Beam stability Field of view

Sample preparation

Sample environment

Photodiode

Undulator

Crystal monochromator

Focusingoptics

Aperture

Sample raster scanned

Detector


Photodiode

Undulator


Focusingoptics

Aperture


Detector



Sample preparation

Sample environment

XRF on a pigment

Cl

K

CrTi or

Ba?Pb or

S?

Si?

Ca or

Sn or

Sb?

Non-invasive

Portable

Micro-imaging (2D/3D)

All elements are excited simultaneously

XRF techniques

+ Pb (L) / As(K) (painting, glass,

ambrotype…)

+ Cu(Kb) / Zn (Ka) (Zn in copper-based

alloys)

+ Cd (L)/Ag (L) (Cd in ancient silver-gold

solders)

?

Energy (keV)

Co

un

tsX-RAY FLUORESCENCE LINE OVERLAP, A FREQUENT PROBLEM IN CULTURAL HERITAGE STUDIES

1

10

100

0 20 40 60 80 100

Atomic number (Z)

Ph

oto

n e

nerg

y (

ke

V)

Kα1

Lα1

Mα1

ID21

Pb

Elements accessible for fluorescence mapping at the :

K-edge L-edge M-edge

H He

Li Be Bold characters: Elements accessible for XANES B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Rf Db Sg Bh Hs Mt Uun Uuu Uub Uuq Uuh Uuo

LanthanidesLa Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Actinides Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lw

1 10 100KeV

X-rays @ID21

X-RAY LINE OVERLAP, A FREQUENT PROBLEM AT ID21 (ESRF)

Principles:

• fit with constraints on the fitting parameters (detector characteristics,

detection geometry, matrix composition, excitation energy, etc.)

• complete emission line series (i.e., M, L or K series)

http://pymca.sourceforge.net/

Energy (keV)

Co

un

ts S

PbCl

K

Sb

Ca

Sn

Ba

Ti Cr

Si

USING THE SOFTWARE SOLUTION : PYMCA

FITTED XRF SPECTRA ON ETRUSCAN GLASSES

! Importance to fit XRF spectra!

Pb M and

S K lines

Sb L and

Ca K lines

a suite of very rare, highly decorated

and coloured glass vessels and

beads from the VII to the IV C. BC

R. Arletti, G. Vezzalini, S. Quartieri, D. Ferrari, M. Merlini and M. Cotte, "Polychrome glass from Etruscan sites: First non-destructive characterization with synchrotron µXRF, µXANES and XRPD", Applied Physics A, 92, 127-135 (2008).

Favorable conditions

Nevers, XVIIIe,

les Arts Décoratifs

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5

countsfit

NaMgAl

Si

S

Cl

K

Ca

Sb

Energy (keV)

Co

un

ts

XRF mapping, fitted with PyMca

Beam size: 0.3×0.7µm2

Map size : 90× 50 μm2

Dwell time 0.3s

10 µm

calcium

antimonate

crystal

vitreous

matrix

Sb

Ca

Si

P1

P2

Quantification:

P1: Sb/Ca= 1.98 (CaSb2O6)

P2: Sb/Ca= 0.98 (Ca2Sb2O7)

QUANTITATIVE XRF FITTING


Energy (keV)

Co

un

ts

162eVSb

CaSn

Ba

Ti Cr

Co

un

ts

10

4 4.5 5 5.5 6

10

0

100

0

25eV

SbCa

BaTiCr

Sn

Energy (keV)

WDS (Ge(220))EDS

?

HOW TO IMPROVE THE DETECTION SPECTRAL RESOLUTION?

•parallel beam geometry

• polycapillary optics for x-ray fluorescence collection

•flat crystal arrangement

• simple design

• adaptable to the existing experimental setup

• resolution ~few tens of eV

• high efficiency

IMPROVING SPECTRAL RESOLUTION : WAVELENGTH DISPERSIVE SPECTROMETER

Szlachetko, J., M. Cotte, et al., (2010), "Wavelength-dispersive spectrometer for X-ray microfluorescence analysis at the X-ray microscopy beamline ID21 (ESRF).“, Journal of Synchrotron Radiation, 17: 400-408.Cotte, M., J. Szlachetko, et al., (2011), "Coupling a Wavelength Dispersive Spectrometer with a synchrotron-based X-ray microscope: a winning combination for micro-X-ray fluorescence and micro-XANES analyses of complex artistic materials.“, Journal of Analytical Atomic Spectrometry, 26(5): 1051-1059.

Wavelength dispersive X-ray

micro-fluorescence

1st prototype 2nd prototype

0

10

20

30

40

50

0 5000 10000R

eso

luti

on

(e

V)

Energy (eV)

TlAP (001)

ADP (101)

Si (111)

Ge (220)

LiF (220)

Down to 1eV with 2-crystals configuration

GOING TO HIGH SPECTRAL RESOLUTION

gordon_2crystals_WDS.pptx

gordon_2crystals_WDS.pptx


Photodiode

Undulator


Focusingoptics

Aperture


Detector



Sample preparation

Sample environment

polychromatic X-rays

monochromaticX-rays

synchrotron source monochromator incident flux

monitor

sampleI0

IF

Transmission: The absorption is measured directly

I = I0 e −μ (E)d μ(E) d = − ln (I/I0)

Fluorescence: The re-filling of the deep core hole is detected

μ(E) ~ IF / I0

Electron Yield: The quantity (current) of photoelectron and Auger Electrons is detected

μ(E) ~ Ie / I0

It

Ie

Bulk

Surface/bulk (µm)

Surface (10nm)

Air/Vacuum

Air/Vacuum

Ultra-high Vacuum

• no substrate• concentrated

• substrate• traces

• Top layer (< 1µm)• clean

THE CLASSICAL SET-UP FOR XAS MEASUREMENTS

CaSb2O6

Ca2Sb2O7

Ca K-

edge

Sb LIII edge

Sb LII edgeSb LI edge

Ab

so

rpti

on

(a.u

.)

Energy (keV)

XANES on reference powders, in transmission

Sb L1-EDGE µXANES ANALYSIS ON CALCIUM ANTIMONATES

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5

countsfit

NaMgAl

Si

S

Cl

K

Ca

Sb

Energy (keV)

Co

un

ts

1

10

100

1000

10000

3 3.5 4 4.5

ROI chosen

for L1-edge

XANES

Co

un

ts

Energy (keV)

XRF spectrum excited below Sb L1 edge

XRF spectrum excited above Sb L1 edge

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

4.68 4.7 4.72 4.74 4.76

No

rmal

ized

ab

sorp

tio

n (a

.u.)

Energy (keV)

ROI calculation

Fit calculation

Sb L1 peak area

Energy (keV)

No

rma

lize

d a

bs

orp

tio

n (

a.u

.)

100

1000

10000

100000

2.9 3.4 3.9 4.4

Co

up

s

Energie (keV)

counts

fit

Ca

SbL1

SbL2

SbL3

Fit by

decomposing

Sb L1,2,3 lines

- No more background contribution

from Ca and Sb L3 and L2

- integration over the entire (set of)

lines increased signal

XANES AT Sb L-EDGES IN A Ca MATRIX IN XRF MODE

CaSb2O6

1

10

100

1000

10000

3 3.5 4 4.5

Counts

Energy (keV)

below L1 edge

above L1 edge

EDS

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

4.68 4.7 4.72 4.74 4.76

No

rmal

ized

ab

sorp

tio

n (a

.u.)

Energy (keV)

XANES measured with an EDS

ROI calculation

1

10

100

1000

10000

3.5 4

Counts

Energy (keV)

below L1 edge

above L1 edge

Sb

L3-M5

Ca

K-L3

Sb

L2-M4

Sb

L1-M2Sb

L1-M3Sb

L2-N4

Sb

L3-N5

Ca

K-L2

WDS

0

0.002

0.004

0.006

0.008

0.01

0.012

4.68 4.7 4.72 4.74 4.76

No

rmal

ized

ab

sorp

tio

n (a

.u.)

Energy (keV)

XANES measured on Sb L1-M3 line

fit calculation

XANES AT Sb L-EDGES IN A Ca MATRIX

quasi-parallel beam

polycapillary optics

X-ray micro beam

crystalcrystal

XRF

nl=2dsin(q)

detector

0

20

40

60

80

100

120

140

160

180

200

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

3.55 3.6 3.65

Counts

(d

ouble

-cry

sta

l)

Counts

(sin

gle

-cry

sta

l)

Energy (keV)

single-crystal

double-crystal

Resolution ~2eV

1 crystal

2 crystals

CaSb2O6

Sb L3-edge

µXAS WITH DOUBLE-CRYSTAL WDS


Photodiode

Undulator


Focusingoptics

Aperture


Detector


Chemical heterogeneity Beam size Beam stability Field of view

Sample preparation

Sample environment

MICRO/NANO XAS BEAMLINES AT THE ESRF AND WITH EBS

ID16B10 – 100 nmHARD X-RAY

NANO-SPECTROSCOPY

ID260.1-1 mm

HIGH RESOLUTION

XAS, XESDILUTED SYSTEMS

ID243 µm

TIME RESOLVED & EXTREME CONDITIONS

EXAFS

BM235 µm - mmGENERAL

PURPOSE EXAFS

ID210.5 – 1 µm

TENDER SUB MICRO X-RAY

SPECTROSCOPY

ID121-10 µm

POLARIZATION DEPENDENT XAS

SPECTROSCOPY @ESRF

ID3210-100 µm

SOFT X-RAY SPECTROSCOPY

ID205-50 µm

RESONANT AND NON-RESONANT

INELASTIC SCATTERING

nan

o m

icro

su

bm

illi

Energy rangeHardTender

Late

ral r

eso

luti

on

ESRF 2018 As planned in EBS

Some overlap but different scientific focus, techniques, energy domain and sample environments Filling the gap between nano and micro beamlines Filling the gap between tender and hard X-ray beamlines

ID26

ID24/BM23

ID16B

ID21

THE ESRF UPGRADE PROGRAMME- PHASE 1: MORE AND LONGER BEAMLINES

Source – optics ~140-200m

20-500 μm 10-1000 nm

Optics –sample ~100-30mm

Long beamlines =

smaller beams

+ more space for sample environments

Demagnification = optics-sample/source-optics ~103

Source Probe

MICRO/NANO XAS BEAMLINES AT THE ESRF (EBS-POST REFURBISHMENT)

BM30B4.8-20keV10×10µm²

BM235-75keV (5-95)3×3µm² (up to 45keV)

ID16B (nano-hard)4-30keV50×50nm² to 0.1×1.0 µm²

ID24-ED (new branch ID24-DCM)5-27keV (5-45)3×3µm² (1µm)Flux up to 1013-1014, HP (300GPa)/ HT (5000K)

ID21 (micro-tender)2.1-9.1keV (2-11)0.3×0.7µm² (0.1×0.1)

ID20 (inelastic scattering)4.0-20.0keV 18×9µm²

ID12 (tender, HP<100GPa)2.05-15keV5×50µm² (5×5µm²)

ID26 (XAS, XES, HERFD-XANES, RIXS)2.4-27keV0.1×0.5 mm² (0.1×0.2 mm²)

X-RAY FOCUSING OPTICS

Kirkpatrick Baez mirror system (reflection) Achromatic High efficiency Expensive Mechanical complexity

Fresnel zone plates (diffraction) Reach ultimate resolution (low energies) Very compact Cheap Chromatic Low efficiency

Compound refractive lens (refraction) High efficiency at high energy High absorption at low energy Chromatic

X-ray beam

Sample stage

Videomicroscope

DetectorSampleFocusing optics

Design by E. Gagliardini, ESRF ISDD

THE ID21 X-RAY MICROSCOPE


Photodiode

Undulator


Focusingoptics

Aperture


Detector



Sample preparation

Sample environment

ISSUES WITH RADIATION DAMAGE: Mn SPECIATION IN HISTORICAL GLASSES

Courtesy G. Nuyts


0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

6535 6585

µ (

a.u

.)

Energy (eV)

Repetitive XANES scan

1

2

3

4

5

6

7

Photo-reduction

• To test possible beam damage (caused by photo-reduction) 10 repetitive spectra (27 s.spectra-1) arerecorded on the same spot in the Mn enrichedzone, using a focussed beam (1.13 x 0.80 µm2).

• Spectra are analysed by linear combination fittingwith pure-valence references

→ contribution of each valence state

Photo-reduction: during first 3 XANES scans.• Mn(IV): ~ 30% → ~ 15%• Mn(II): ~ 40% → ~ 55%• Mn(III): ~constant ~ 30%

- 1 step: Mn(IV) → Mn(II)- 2 steps: Mn(IV) → Mn(III) → Mn(II) with equal speed rates.

For further measurements photo-reduction isprevented/reduced using slightly unfocused beam.



Photodiode

Undulator


Focusingoptics

Aperture


Detector



Sample preparation

Sample environment

OPTICS CHROMATICITY IMPACTS BEAM STABILITY

Compensation of reproducible micro-beam movements during energy scans

Calibration table built from video images of beam displacement

Beam tracking by moving sample / ZPWith compensation

Δy= 0.25 µm

Δz= 0.19 µm

Without compensationΔy= 1.6 µm

Δz= 5.1 µm

-2

-1

0

1

2

3

4

-0.5 0 0.5 1 1.5

Beam trajectory

Video table

Compensated beam

trajectory

µm

µm

Zone plates

Improved stability compared to ZP setup

Reproducibility of the drift compensation strategy “Spot tracking”

Without compensationΔy= 0.185 µm

Δz= 0.93 µm

KB

10µmThe Isenheim Altarpiece, Grünewald1512-1516; Colmar

Elemental analysis (portable instrument):

Sb, Pb, S

Portable XRF

apparatus

IMPORTANCE OF BEAM STABILITY: PIGMENT IDENTIFICATION

IMPORTANCE OF BEAM STABILITY: PIGMENT IDENTIFICATION

2.46 2.48 2.5

Energy (keV)

No

rmalized

ab

so

rpti

on

(a.u

.)

10µm

With

correction

Pb M-edge

The Isenheim Altarpiece, Grünewald1512-1516; Colmar

Elemental analysis (portable instrument):

Sb, Pb, S

Portable XRF

apparatus


Photodiode

Undulator


Focusingoptics

Aperture


Detector


Chemical heterogeneity Beam size (radiation damage!) Beam stability Field of view = towards 2D-XAS

Sample preparation

Sample environment

TOWARDS 2D-XANES

Standard XANES dwell time in XRF mode : >1 minute (>0.1s/energy)

Decrease dwell time: - Improvement of double crystal

monochromators- Improvement of XRF detector

1 XANES spectrum over e energy steps, repeated over p pixels

1 XRF map over p pixels,repeated over e energy steps

- Dispersive set-up (e.g. ID24)


Courtesy G. Nuyts

XRF maps recorded at two energies:• the white-line of Mn in bulk glassE1 = 6553.2 eV• the white-line energy of Mn in the enrichment (E2 = 6560.5 eV)IMn(E1)/IMn(E2) indicative of valence state


E1 E2

Valence state maps: calibration curve

How to go from multi-spectral (few energies) to hyper-spectral (hundreds energies)?

With higher flux and improved detection technology (detectors + electronics), dwell time can be reduced to few ms


monochromaticX-rays

synchrotron source monochromator incident flux

monitor

sampleI0

IF


I = I0 e −μ (E)d μ(E) d = − ln (I/I0)

Fluorescence: The re-filling of the deep core hole is detected

μ(E) ~ IF / I0

Electron Yield: The quantity (current) of photoelectron and Auger Electrons is detected

μ(E) ~ Ie / I0

It

Ie

Bulk

Surface/bulk (µm)

Surface (10nm)

Air/Vacuum

Air/Vacuum

Ultra-high Vacuum


• substrate• traces

• Top layer (< 1µm)• clean

ANOTHER WAY TO OBTAIN 2D-XAS MAPS: IN TRANSMISSION


monochromaticX-rays

synchrotron source monochromator

sample


I = I0 e −μ (E)d μ(E) d = − ln (I/I0) BulkAir/Vacuum


ANOTHER WAY TO OBTAIN 2D-XAS MAPS: IN TRANSMISSION

Sample radiography (data)Dark image

Beam image with decoheror (reference)

Sample radiography (data)

Eo

E1

Image realignment)

darkI

ref(I

)darkI

data(I

)0

I(E

Beam image with decoheror (reference)

THE ID21 XANES FULL-FIELD END-STATION

De Andrade et al., Anal Chem, 2011Fayard et al., J, of Physics, 2013

Study of Chinese Qinghua porcelains: structure

and chromogenic mechanisms of blue decors

Tian Wang 1

Philippe Sciau1

T.Q. Zhu 2

1 CEMES, CNRS, Toulouse University, Toulouse, France 2 School of Sociology and Anthropology of Sun Yat-sen

University, Guangzhou, China

Controlling blue decors in Chinese porcelains

Combination of portable XRF, µXRF, µXANES (in focused mode and full-field mode) and µXRD, to explain the different blue decors in Qinghua porcelains

T. Wang, T. Q. Zhu, Z. Y. Feng, B. Fayard, E. Pouyet, M. Cotte, W. De Nolf, M. Salomé and P. Sciau, "Synchrotron

radiation-based multi-analytical approach for studying underglaze color: The microstructure of Chinese

Qinghua blue decors (Ming dynasty)", Analytica Chimica Acta, (2016), 928, 20-31.

FULL-FIELD XANES ANALYSES OF CHINESE PORCELAINS

Transmission map Edge jump map

Image segmentation map and average XANES

Maps obtained by linear combination of spectra of reference CoAl2O4 and Co in glaze

T. Wang, T. Q. Zhu, Z. Y. Feng, B. Fayard, E. Pouyet, M. Cotte, W. De Nolf, M. Salomé and P. Sciau, "Synchrotron radiation-based multi-analytical approach for studying underglaze color: The microstructure of Chinese Qinghua blue decors (Ming dynasty)", Analytica Chimica Acta, 928, 20-31 (2016).

Full spectral information over large 2D field of view

However, constraints in terms of sample composition

and sample preparation


Photodiode

Undulator


Focusingoptics

Aperture


Detector



Sample preparation

Sample environment

EXPLOITING THE COHERENCE OF X-RAY SOURCES

Incoherent light

Coherent light

Possibility to exploit coherence and obtain new contrasts:

phase-contrast tomography

Propagation phase contrastAbsorption

Opaque amber, 100 M years old

ABSORPTION VS PHASE CONTRAST

Complex refractive index

n=1-d+ib

b: absorption

d: phase shift

Courtesy P. Tafforeau

FAST IN SITU NANOTOMOGRAPHY AT HIGH TEMPERATURE – ID16B

● Fast acquisition speed with continuous acquisition (multi-turns):

Fastest time scan : 7s

● Multiscale measurements : pixel size from 27nm to 600nm

● Temperature range : 200 °C to 900°C

● Two energies available : 17.5 and 29.6 keV

Villanova et al. Materials Today (20) 2017

Time

1 scan = 7s

Time

Movie of 3D microstructure

evolution with time

HIGH TEMPERATURE PROCESS

82

Sintering of glass particles:

Temperature: 670°C

Energy range: 17.5 keV

Pixel size: 100 nm

Time scan : 33 s

Comparison with Frenkel model and the tangent-circle approximation

Perspectives : Develop finer model Better understanding of the influence of local packing on sintering defects

Villanova et al. Materials Today (20) 2017

Real time: 1h45min ; FOV: 120 x 80 µm2

Collaboration with C. L. Martin, D.

Jauffrès, P. Lhuissier and L. Salvo

from SIMaP/UGA

CONCLUSION

Chemical contrast (XRF, XAS, XRD, FTIR, absorption, phase …)

Resolution / Field of view

Sample composition, preparation, environment

Combination of micro-imaging techniques!

Annu. Rev. Anal. Chem. 2013. 6:399–425

XAS and XES; theory

and applications

Book just edited

Editors: C. Lamberti &

J. A. van Bokhoven

Publisher: John Wiley

& Sons

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