Analyse par faisceaux d ions

Analyse par

Analyse par faisceaux faisceaux d d ’ ’ ions ions appliqu

appliqu é é s s à à l l ’ ’ Art Art et et à à l l ’ ’ Arch Arch é é ologie ologie

Thomas Calligaro

Centre de recherche et de restauration des musées de France CNRS UMR 171

Palais du Louvre - Paris - France

SéSéminaire minaire INSTN Saclay INSTN Saclay 24 octobre 2007, Saclay 24 octobre 2007, Saclay

Plan de la pr

Plan de la pré

é

sentation

•• Pourquoi des faisceaux pour l’éPourquoi des faisceaux pour l’étude du patrimoine cultureltude du patrimoine culturel

•• Faisceaux d’Faisceaux d’ions en Arts et Archions en Arts et Archééologie ologie

•• Principe de lPrincipe de l’analyse par faisceaux d’analyse par faisceaux d’’ionsions PIXE, RBS, ERDA, NRA

PIXE, RBS, ERDA, NRA

•• AGLAE et le faisceau extrait àAGLAE et le faisceau extrait à ll’’airair

•• Autres laboratoires Autres laboratoires

•• Exemples d’Exemples d’applicationapplication

•• Datation indirecte par l’Datation indirecte par l’analyse analyse ééllémentaire : émentaire :

authentification d

authentification d’’une peintureune peinture

•• Indentification de matéIndentification de matériaux riaux andand dédétermination de termination de provenance

provenance

Les yeux de la d

Les yeux de la dééesse Ishtar esse Ishtar

•• Bibliographie et perspectivesBibliographie et perspectives

Principales motivations de l

Principales motivations de l’é’étude du patrimoine

tude du patrimoine culturel par des m

culturel par des mé

é

thodes scientifiques

Diagnostics rapides, rapides, éétudestudes de servicede service

•• acquisition (authentificationacquisition (authentification))

•• prépréalablementalablement àà uneune restaurationrestauration

•• avantavant expositionexposition

Programmes de

Programmes de rechercherecherche àà long termelong terme

•• archéarchéometrieometrie : é: étude des technologies anciennes et de la provenancetude des technologies anciennes et de la provenance

•• science de la conservation : comprendre la technique des artistesscience de la conservation : comprendre la technique des artistes

•• conservation prconservation prééventiveventive : é: étudetude des mdes méécanismescanismes d’d’altaltéérationration

Démarche et contraintes

ProblmatiquesProblmatiques en Art & en Art & ArchArchééologieologie

•• identification des materiauxidentification des materiaux analyse des constituantsanalyse des constituants majeursmajeurs

•• provenance des provenance des materiauxmateriaux éléléémentsments tracestraces

•• ProcessusProcessus dd’alt’altéérationration caractécaractérisationrisation de la surfacede la surface ContraintesContraintes

•• ObjetsObjets préprécieuxcieux Pas de

Pas de prprééllèèvemementvemement mmééthodesthodes nonnon--invasivesinvasives Pas de

Pas de dommagedommage méméthodesthodes non-non-destructivesdestructives

•• composition inconnuecomposition inconnue méméthodesthodes panoramiquepanoramique

•• composition non-composition non-homoghomogèènene lateralement

lateralement sondesonde de faiblede faible diamèdiamètretre

En profondeurEn profondeur profilageprofilage d’éd’élléémentsments en profondeuren profondeur

Principe de l

Principe de l ’ ’ analyse par faisceaux d analyse par faisceaux d ’ ’ ions (IBA) ions (IBA)

• intéraction d’ions légers (p, d, α) d’une énergie de qq MeV avec les atomes de la cible

• selon la distance d’approche au noyau, interaction atomique (avec les electrons) ou interaction nucléaire

• produits d’intéraction recueillis et triés selon leur énergie (spectre)

• énergie élément (analyse qualitative)

• intensité du signal concentration (analyse quantitative)

Fundamentals of ion

Fundamentals of ion beam beam methods methods

3-3-MeV protonsMeV protons e-

Si(Li)

Si(Li) detectordetector XX

-- rays rays

accelerator accelerator target

target atomsatoms

expelled

expelled electronelectron

γγ--rays rays

HPGe

HPGe detectordetector

Beryllium :

Be(p, αγ )

Li 3562 keV

Lithium :

Li(p,p’ γ )

Li 477 keV

Fluorine :

F(p,p’ γ )

F 197 keV

Fundamentals of ion

Fundamentals of ion beambeam analysisanalysis

PIXE : particle induced X-ray emission

E

= k(Z-1)

• Z range 10 < Z < 92

• incident beam 3-MeV protons

• low current ~1 nA ⇒ no damage

• high sensitivity ~ 1 µg/g

• probing depth 1-50 µm

• microprobe Ø 10-30 µm

Applications

•

• determination of trace elements

3-step atomic process :

• inner-shell ionisation

• electronic

rearrangement

• X-ray emission

PIXE spectra of a medieval glass

Fundamentals of ion

Fundamentals of ion beambeam analysisanalysis

RBS :

RBS : Rutherford Rutherford Backscattering Backscattering Spectrometry Spectrometry

K=E/E

= f(M, depth)

incident beam : 3-MeV ⁴He or protons

• suitable for profiling

• high Z elements in a low Z matrix

• probing depth 1-10 µm

Applications

•

• example : guilding of jewels

purely electrostatic elastic process

d30m a018.a3 S im ulated

Channel

500 450

400 350

300 250

200 150

100 50

0

Counts

2 200 2 000 1 800 1 600 1 400 1 200 1 000 800 600 400 200 0

400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800

Energy [keV]

RBS analysis of metallic lustre of islamic ceramics He

beam 3 MeV

Pb Si

O

Ag

Energy kev

Fundamentals of ion

Fundamentals of ion beam beam analysis analysis

ERDA :

ERDA : Elastic Elastic recoil recoil detection detection analysis analysis

K=E/E

= f(M, depth)

σ ~ Z₁²Z₂² E^-2[sin(θ/2)]^-4

incident beam : 3-MeV ⁴He

• suitable for profiling elements lighter

• than projectile

• very low Z element (mainly hydrogen)

• probing depth 1-5 µm

Applications

•

• example : weathering of glass

purely electrostatic elastic process

( ⁺ ) ^Θ

=4 ₂ cos²

r p

r p

M M

M K M

( ⁺ ) ^Θ

=4 ₂ cos²

r p

r p

M M

M K M

M₁ Z₁

M₂ Z₂

θ θ

0 100 200 300 400 500 600 700 800 900

0 20 40 60 80 100 120

Channel

Yield

Mica lab Mica Troc Rubis Colombie Habachtal MAN 24.573 MAN 87.191 MAN 87.166

ERDA analysis of H

in antique emeralds He⁺⁺ beam 3 MeV

Principle of nuclear reactions

residual nucleus

θ φ

a X b

Y a + X Y + b

X(a,b)Y

emitted particle

= ejectile target

nucleus incident

particle

=

projectile

Fundamentals of ion

Fundamentals of ion beambeam analysisanalysis

NRA :

NRA : Nuclear Nuclear Reaction Reaction Analysis Analysis

incident beam : ¹H, ²H or ³He of a few MeV

PIGE : γ -ray detection E

= f(isotope)

• bulk composition for 1<Z<11

• complementary to PIXE

• high sensitivity ~ ppm level

NRA : particle detection E

= f(isotope, depth)

• profiling low Z elements in a high Z matrix

• C,N,O composition of bronze patina

• weathering of glasses

• dating archaeological flint tools by F profiling examples of nuclear reaction

• ¹H(¹⁹F,αγ)¹⁶O fluorine profiling

• ¹⁹F(¹H,αγ)¹⁶O

hygrogen profiling

• ¹⁶O(²H,p)¹⁷O oxygen profiling

non-resonant ion-gamma reactions (PIGE) – bulk analysis

element reaction Eγ keV yield /µC/Sr applications 3.5-MeV protons

lithium ⁷Li(p,p’γ)⁷Li 478 9 10⁶ emeralds beryllium ⁹Be(p,αγ)⁶Li 3562 2.5 10⁶ emeralds fluorine ¹⁹F(p,p’γ)¹⁹F 197 3 10⁶ bone sodium ²³Na(p,p’γ)²³Na 439 9.6 10⁶ glass silicon ²⁸Si(p,p’γ)²⁸Si 1779 1.2 10⁶ glass

copper ²⁸Cu(p,p’γ)²⁸Cu 152 2.3 10⁶ bronze, gold silver ²⁸Ag(p,p’γ)²⁸Ag 309 1.1 10⁵ gold

gold ²⁸Au(p,p’γ)²⁸Au 279 6 10⁴ gold 1.8 MeV deuterons

carbon ¹²C(d,pγ)¹³C 3089 1.5 10⁷ copper alloys nitrogen ¹⁴N(d,pγ)¹⁵N 7301 1.2 10⁷ copper alloys oxygen ¹⁶O(d,pγ)¹⁷O 871 1.1 10⁷ copper alloys

sulfur ³²S(d,pγ)³³S 841 2.4 10⁵ copper & gold alloys

Egamma(keV)

coups

1 10 100 1000 10000

010002000300040005000

Na 439 keV

Al 843 keV

Be 3562 keV Si 1778 keV

Al 1014 keV F 197 keV

Li 478 keV

Na 1634 keV

resonant ion-gamma reactions – depth profiling

element Reaction E_r MeV Eγ ΜeV ∆R µm R µm applications H ¹H(¹⁵N, αγ)¹²C 6.385 4.44 0.004 2-3 obsidian dating H ¹H(¹⁹F, αγ)¹⁶O 16.2 6-7 0.08 glass weathering

F ¹⁹F(p,αγ)¹⁶O 0.872 6-7 0.1 1.4 flint dating

Na ²³Na(p,αγ)²⁰Ne 1.01 1.632 0.1 0.5 glass weathering

S ³²S(p,p’γ)³²S 3.094 2.23 bronze patina

ion-ion reactions – depth profiling

Element Reaction E ∆R µm R µm applications

C ¹²C(d,p)¹³C 2.0 0.5 4.0 bronze, gold surface

N ¹⁴N(d,p)¹⁵N 2.5 0.7 15 bronze patina

O ¹⁶O(d,p)¹⁷O 1.6 0.15 7 bronze patina

S ³²S(d,p)³³S 2.0 gold soldering

Na ²³Na(p,α)²⁰Ne 0.592 0.015 0.7 glass weathering

Specificity

Specificity of IBA techniques of IBA techniques

Advantages

• multi-elemental including light elements

• non-destructive

• no sampling

• sensitivity to trace elements (µg/g)

• highly quantitative (1-3 %)

• several techniques combined simultaneously

• concentration profiles (RBS, NRA)

• surface analysis (up to 1-30 µm) Disadvantages

• no information about the chemical state (XPS, XAS)

• no structural information (XRD, IR, Raman)

• near surface (1 – 30 µm) (problems with altered objects)

• expensive large scale facility

Usefulness

Usefulness of IBA for Archaeometry of IBA for

Materials identification

analysis of major elements by PIXE and PIGE

Materials provenance

(sources of raw materials and trade routes) analysis of trace elements by PIXE

Artistic or manufacture technology

Spatial distribution required: lateral by µPIXE, in depth by RBS

Usefulness

Usefulness of IBA for of IBA for Conservation science

Assessment of state of conservation of museum objects study of alteration mechanisms affecting the surface

Preventive conservation

monitoring the museum environment (air)

PIXE analysis of aerosols collected in musems RBS analysis of monitors

Localisation de l’accélérateur AGLAE

charged particles in air : the external beam charged particles in air : the external beam

Benefits Benefits

•• direct analysis of artefactsdirect analysis of artefacts any shape and any size any shape and any size

•• no sampling no sampling

•• no charging, no preparationno charging, no preparation

•• no heating, reduced damageno heating, reduced damage

•• easy sample positioningeasy sample positioning

•• 120-120-mm air path for 3mm air path for 3--MeV pMeV p

•• thin exit foil thin exit foil

sample

L

H

He flow

⊗

⊙

«« lowlowenergyenergy»» L -L -detectordetector

«« highhigh energyenergy »» H -H - detectordetector entrance

entrance window window

0.25

0.25 µµm boronm boron nitride nitride

6 µ6 µm m BeBe absorber

absorber 1 µ1 µm carbonm carbon HeHeatmosphereatmosphere

100 µ100 µmm aluminum aluminum energy

energy range range

0,6 -0,6 - 20 keV20 keV 5 -5 - 40 keV40 keV

element element range range

major

major elementselements Na-Na-FeFe

trace

trace elementselements Ca-Ca-UU

solid

solid angleangle 1 msr1 msr 100 msr100 msr

extending the range extending the range of measured elements of measured elements the multi

the multi- - detector set detector set - - up up

J.D. MacArthur et al. 1990

J.D. MacArthur et al. 1990 atat Florence, ItalyFlorence, Italy

•• COST action G8COST action G8

non-destructive analysis and testing of museum objects

cooperationooperation betweenbetween 20 European20 European countriescountries representatives

representatives : 50/50 scientists: 50/50 scientists andand curators/curators/archaeologistsarchaeologists meetings

meetings andand short-short-termterm missionsmissions

•• Eu-Eu-ARTECH ARTECH

Access, research and technology for the conservation of the European Cultural Heritage

networking

networking of 13 conservation labsof 13 conservation labs andand institutionsinstitutions Transnational

Transnational accessaccess to :to : AGLAE

AGLAE accelerator-accelerator-basedbased facilityfacility MOLAB

MOLAB, a set of mobile instruments for , a set of mobile instruments for «« on theon the fieldfield »» measurements

measurements.. www.eu

www.eu--artech.orgartech.org European

European networks networks

for thefor the studystudy of cultural heritageof cultural heritage withwith ion beamsion beams

Laboratory Accelerator type Experimental setups

Main research fields

Belgium Liège Cyclotron external beam paintings glasses

Belgium Namur 2 MV tandem external µprobe gold metallurgy

Finland Helsinki 5 MV tandem external beam gold metallurgy paintings

France Paris C2RMF 2 MV tandem external µprobe ceramics stones gems metals glasses enamels glazes manuscripts paintings

Germany Berlin Cyclotron external beam metals

Germany Rossendorf 5 MV tandem external µprobe bones paintings drawings glasses

Greece Athens 5 MV tandem external beam metals ceramics

Hungary Budapest 2 MV Van de Graaff external beam manuscripts bronzes

Hungary Debrecen 5 MV Van de Graaff µprobe paintings gemstones glasses Italy Florence 3 MV Van de Graaff external µprobe manuscripts ceramics

Mexico UNAM 2 MV tandem external µprobe stones, pigments, jewellery Slovenia Ljubljana 2 MV tandem external µprobe coins stones

Spain Madrid 5 MV tandem external µprobe ceramics

Spain Sevilla 2 MV tandem external µprobe jewellery ceramics

Sweden Lund 3 MV tandem external µprobe manuscripts glasses

Syria Damas 3 MV tandem vacuum chamber

Lebanon Beyruth 1.7 MV tandem vacuum chamber ceramics

USA Tempe 2 MV tandem external beam ceramics

China Shanghai 3 MV tandem external beam ceramics manuscripts metals

Japan Tokyo 2 MV tandem external beam ceramics

Singapore 2.5 MV Van de Graaff µprobe bones gemstones

Taiwan Taipei 3 MV tandem external beam coins

Australia Lucas Heights

3 MV Van de Graaff external beam ceramics obsidians South Africa Faure 5 MV Van de Graaff external beam ceramics

First

First application of IBA : application of IBA : authentication

authentication of of a a painting painting by PIXE by PIXE

Analysis Analysis of of

The The (presumed ( presumed) portrait of Bernard Palissy ) portrait of Bernard Palissy

French

French scientistscientist andand artistartist of theof the RenaissanceRenaissance (1510

(1510--1589)1589) Painting Painting supposedly supposedly representing representing

B. Palissy B. Palissy

kilnkiln usedused by by Palissy for Palissy for making

making ceramicsceramics Precisely

Precisely unearthed

unearthed duringduring thethe building ofbuilding of thethe

laboratory laboratory

PIXE analysis of paint layers

Dark background contains chromium green PbCrO4 available after 1850 grey collar contains Naples yellow lead antimoniate only used after 1650

This paintingThis painting isis probablyprobably a forgerya forgery

Second

Second example example of of application of IBA : application of IBA : Identification

Identification

and and provenancing provenancing of gemstones of gemstones

Ishtar

Ishtar ’ ’ s s eyes eyes

Statuette

Statuette exhibited exhibited in in the the Louvre Louvre

Dated

Dated to theto the ParthianParthian periodperiod (1(1^stst BC –BC – 22^{nd nd} AD)AD)

Likely

Likely representingrepresenting Ishtar

Ishtar, the, the famousfamous mesopotamian

mesopotamian mothermother goddess

goddess (Astart

(Astartéé or Venus)or Venus) Discovered

Discovered in 1863 inin 1863 in Hillah

Hillah, close to Babylon, close to Babylon

Materials identification :

Ishtar’s statuette was placed in the external beam

PIXE

PIXE spectraspectra recordedrecorded on oneon one eyeeye

X-ray energy (keV)

counts

1 10 100 1000 10000 1e5

0 5 10 15 20 25

high energy X-ray detector spectrum low energy X-ray detector spectrum

O_K

AlK

Ti K V

K Cr

K Fe

K

GaK

SriLank

India 1 India 2

Burma

Cambodia Thailand

Afghanistan

VietNam Babylon

Map of Middle East and Asia : sources of rubies

Sri Lanka

Iron(ppm)

Chromium (ppm) T T TTT

T T TT TT

T T TT

V

V VV

V VV

V V

VV

KK KK

KK

MM

MM

MM MM

MM

MM MM

MM

M M MM BB

B BB

B B

B

B B B B

B B B

B B

B

B B

B B B

B BB B

B B

B B

B B

B BB B

B B

BB B B

B B B

BB BB B BB B

B BB B

BB BBB

B B

B B BB

B B B

B BB B B B

BB B

B B B B

B B B B

B B

BB B B B B BB

BBB B B

B

B BB BB B

B B

B

B B

BBB B BBB B

B B

BBB

B B B B

B B

B B B B BB

BB B B

B B

BBB B BB

B B B B BB B

B B BB

B B

B B BB BB BB

B BB

BB B B B

B BB

B

B

B B

B B

A A A A A

A A

A

AA A

A A

B A

B B

T T TC C V C

VV

S S S

MM M

I I I I

II I I I II I

B B

B B B

B B

B

B B

B B

B B

B B

B

X X

X

X B

X

X X X

S SSS S S

S S

SS

SS

S

S S S

S S

S S SS SS S

S S S SS

S S

S S

S

S

S

S S

SS S S

S S S

S

S

S

S

S

SS

S SS S

S

S

S S

SS B

T

10 100 1000 10000

10 100 1000 10000

Statuette of Ishtar group I

Burma Vietnam A

group II Afghanistan SriLanka Vietnam B

group III Thailand Cambodia Kenya

Madagascar India

Trace

Trace elementelement fingerprintfingerprint of rubiesof rubies fromfrom Ishtar andIshtar and variousvarious depositsdeposits

SriLank

India 1 India 2

Burma

Cambodia Thailand

Afghanistan

VietNam Babylon

Map of Middle East and Asia : sources of rubies

Sri Lanka

Proof of

Proof of authenticity authenticity of of the the statuette statuette

Original report of Mr P.

Original report of Mr P. Delaporte

Delaporte

, French consul

Bagdad

who

who

discovered

the

statuette

Document

Document writtenwritten atat HillahHillah, , close to

close to BabylonBabylon January

January 21, 186321, 1863

Results

The eyes and the navel of Ishtar are not made of red glass, nor red garnets, as previously reported, but rather proved to be fine rubies.

According to the age of the statuette, this is the most ancient rubies found in Middle-East.

Evidence of a gem route between South-East Asia and

Mesopotamia during the 1

century BC.

Conclusion et perspectives

• Les techniques IBA procurent une moisson d’information sur les matériaux des oeuvres d’art et d’archéologie

• faisceau extrait spécialement adapté à l’étude des oeuvres du patrimoine précieuses et fragiles

• combination PIXE-PIGE la plus courante

• intérêt croissant pour des techniques basés sur les particules chargées RBS, ERDA and NRA depth information

• versatilité du faisceau extrait permet des expériences particulières: par ex. Mesure en temps réel et en atmosphère contrôlée

Dans le futur

• PIXE concurrencé par techniques XRF Portable, ICP/MS, Raman…

• Combinaison PIXE-RBS (NRA) n’a pas encore d’équivalent

Bibliographie Bibliographie PIXEPIXE

•• PIXE a PIXE a novelnovel technique for elementaltechnique for elemental analysisanalysis, , Wiley, 1988Wiley, 1988

•• ParticleParticle InducedInduced X-X-Ray Ray EmissionEmission SpectrometrySpectrometry (PIXE)(PIXE), , WileyWiley, 1995, 1995

RBS, NRA, PIGE RBS, NRA, PIGE

•• Ion Ion BeamsBeams for for MaterialMaterial AnalysisAnalysis, , AcademicAcademic Press, 1989Press, 1989

•• HandbookHandbook of Modern Ion Beamof Modern Ion Beam AnalysisAnalysis. . MaterialMaterial ResearchResearch Society, 1995Society, 1995

•• Fundamentals of Surface andFundamentals of Surface and ThinThin Film AnalysisFilm Analysis, , Elsevier, 1986Elsevier, 1986

Application

Application àà ll’arch’archééometrieometrie

•• Ion beamIon beam techniques in archaeologytechniques in archaeology andand thethe artsarts

Nuclear

Nuclear Science Applications, 1 1983Science Applications, 1 1983

•• Intern. Workshop on ion BeamIntern. Workshop on ion Beam AnalysisAnalysis in in thethe Arts andArts and ArchaeologyArchaeology

Nuclear

Nuclear Instruments & MethodsInstruments & Methods. 1986. 1986

•• Ion beamIon beam studystudy of art andof art and archaeologicalarchaeological objectsobjects

COST G1, Official Publications of

COST G1, Official Publications of thethe EuropeanEuropean Communities. 2000Communities. 2000

•• ParticleParticle inducedinduced X-X-ray ray EmissionEmission

Modern

Modern AnalyticalAnalytical MethodsMethods in Art andin Art and AchaeologyAchaeology, Chemical, Chemical Analysis, Analysis, WileyWiley, 2000, 2000

•• Ion beamIon beam microanalysismicroanalysis

Non

Non--Destructive Destructive MicroanalysisMicroanalysis of Cultural Heritageof Cultural Heritage Materials, Elsevier, 2004Materials, Elsevier, 2004

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