applications of ultra-modern x-ray (and ftir) microscopes ...malayaite-cassitérite casnsio 5:cr,...
TRANSCRIPT
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
Composition in the future?
Composition at the time of creation?
Components?Processes?
Ageing reactions?Manufacturing processes?
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
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).
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
Composition in the future?
Composition at the time of creation?
Components?Processes?
Ageing reactions?Manufacturing processes?
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
Composition in the future?
Composition at the time of creation?
Components?Processes?
Ageing reactions?Manufacturing processes?
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
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).
XANES linescan:• on glass cross-section• perpendicular to original surface• prior to treatment• step-size: 5 µm (total: 290 µm)
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
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
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).
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
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.
E1 E2
Valence state maps: calibration curve
Mn inclusions
Gel layerBulk glass
Mn SPECIATION BEFORE AND AFTER CLEANING TREATMENT
Courtesy G. Nuyts
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.
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
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.
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
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.
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
TECHNICAL CHALLENGES AND OPPORTUNITIES
Photodiode
Undulator
Crystal monochromator
Focusingoptics
Aperture
Sample raster scanned
Detector
Chemical complexity (analyzing mixtures) XRF XAS in XRF mode
Chemical heterogeneity Beam size (radiation damage!) Beam stability Field of view
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
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).
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
TECHNICAL CHALLENGES AND OPPORTUNITIES
Photodiode
Undulator
Crystal monochromator
Focusingoptics
Aperture
Sample raster scanned
Detector
Chemical complexity (analyzing mixtures) XRF XAS in XRF mode
Chemical heterogeneity Beam size (radiation damage!) Beam stability Field of view
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
TECHNICAL CHALLENGES AND OPPORTUNITIES
Photodiode
Undulator
Crystal monochromator
Focusingoptics
Aperture
Sample raster scanned
Detector
Chemical complexity (analyzing mixtures) XRF XAS in XRF mode
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
TECHNICAL CHALLENGES AND OPPORTUNITIES
Photodiode
Undulator
Crystal monochromator
Focusingoptics
Aperture
Sample raster scanned
Detector
Chemical complexity (analyzing mixtures) XRF XAS in XRF mode
Chemical heterogeneity Beam size (radiation damage!) Beam stability Field of view
Sample preparation
Sample environment
ISSUES WITH RADIATION DAMAGE: Mn SPECIATION IN HISTORICAL GLASSES
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).
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.
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.
TECHNICAL CHALLENGES AND OPPORTUNITIES
Photodiode
Undulator
Crystal monochromator
Focusingoptics
Aperture
Sample raster scanned
Detector
Chemical complexity (analyzing mixtures) XRF XAS in XRF mode
Chemical heterogeneity Beam size (radiation damage!) Beam stability Field of view
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
TECHNICAL CHALLENGES AND OPPORTUNITIES
Photodiode
Undulator
Crystal monochromator
Focusingoptics
Aperture
Sample raster scanned
Detector
Chemical complexity (analyzing mixtures) XRF XAS in XRF mode
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)
Mn SPECIATION IN A DEGRADED HISTORICAL GLASS
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
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.
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
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
ANOTHER WAY TO OBTAIN 2D-XAS MAPS: IN TRANSMISSION
polychromatic X-rays
monochromaticX-rays
synchrotron source monochromator
sample
Transmission: The absorption is measured directly
I = I0 e −μ (E)d μ(E) d = − ln (I/I0) BulkAir/Vacuum
• no substrate• concentrated
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
TECHNICAL CHALLENGES AND OPPORTUNITIES
Photodiode
Undulator
Crystal monochromator
Focusingoptics
Aperture
Sample raster scanned
Detector
Chemical complexity (analyzing mixtures) XRF XAS in XRF mode
Chemical heterogeneity Beam size (radiation damage!) Beam stability Field of view
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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