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PRAXIS: A Combined micro-Raman – micro-XRF
Instrument
K. Janssensa,a Department of Chemistry, University of Antwerp, Belgium
E. Castelluccib, B. Rousselc, J. Oswaltc, J. Schmalzd, J. Tilgnerd, A. Bjeoumikhovd, N. Langhoffd,
P. Ramose, I. Ruisáncheze, K. Andrikopoulosf, E. Bulskag, J. Zieba-Palush
a Department of Chemistry, University of Antwerp, Belgiumb Department of Chemistry, Universita' di Firenze, Sesto Fiorentino (Fi), Italy
c Jobin-Yvon – Raman Division, Villeneuve d'Ascq, Franced Institut für Gerätebau, Berlin, Germany
e Department of Chemistry, Universitat Rovira I Virgili, Tarragona, Spainf Sacred Convent of the Annunciation IMSP, Ormylia-Chalkidiki, Greece
g Department of Chemistry, University of Warsaw, Polandh Institute of Forensic Research, Krakow, Poland
Part I: Analytical Reference (461 pp.)• UV, IR, X-ray imaging• Electron microscopy• X-ray based methods• Ion-beam microanalysis• XPS / AES• LA-ICP-MS• IR & Raman spectroscopy• Secondary ion microscopy
Part II: Case-studies (335 pp.)• Copper alloy artifacts• Precious metal artifacts• Byzantine frescoes and icons• Medieval silver coins• Illuminated manuscripts• Glass artefacts• Corrosion of glass/enamels• Iron-gall ink corrosion
Elsevier Science Publishers, AmsterdamISBN 0-444-50738-8December 2004 - 17 Chapters, 800 pages
Methods• Electron microscopy Electrons, X-rays Atomic• Ion-beam microanalysis Protons, X-rays• LA-ICP-MS Laser, MS• X-ray based methods X-rays Mixed• XPS / AES X-rays, electrons• Secondary ion microscopy Heavy ions, MS• IR & Raman spectroscopy Laser, photons Molecular
Problems• Copper alloy artifacts ESEM, XRD, FTIR• Precious metal artifacts PIXE, PIGE, XRF• Glass artifacts LA-ICP-MS, XRF, SEM, NAA• Medieval silver coins XRF, PIXE• Byzantine frescoes and icons Raman, FTIR, UV• Illuminated manuscripts Raman, XRF• Corrosion of glass/enamels SEM, SIMS, IR• Iron-gall ink corrosion SEM, XRF, XANES, ICP-MS
ND Microanalysis of Cultural Heritage materials
PRAXISPortable Raman – X-ray Instrument
XRF↓
Elemental information‘Deep’ information
RS↓
Molecular informationSurface information
PRAXIS
μ-XRF
Portable μ-XRF
confocal μ-RS
Remote probe μ-RS
fluorescent photons scattered photons
X-ray fluorescence analysisconventional instrumentation
↑ Polarized excitation
← Direct excitation
irradiated area: 1-2 cm2
SX-ray
X-ray
X-ray
S
S
00
0 0
01
Straight capillary
Conical capillary
Ellipsoidal capillary
X-ray
Polycapillary lens
X-ray Capillary Optics
Transportable µ-XRFCompact instrumentation for in-situ analyses
X-rayTube
+PC lens
Si DriftChamberDetector
Zoom Microscope
Exhibition of Assyrian Gold Artefacts, January-June 2001Kunsthistorisches Museum, Vienna
Academy of Fine Arts,Vienna
Loetzglass
M. Schreiner et al., Academy of Fine Arts, Vienna
Portable µ-XRFCompact instrumentation for in-situ analyses
Axial X-ray beamPolycapillary lens → 60-80 μmDrift-chamber EDX-detector3 laser pointers (positioning)Optical MicroscopeHe-flushing system (low-Z)XYZ scanning of head
[H. Bronk et al., TU Berlin]
• find mutually compatible geometry of XRF and Raman components
• improve confocality characteristics of Raman part→ increase P/B ratio
• decrease XRF analyzed area
• demonstrate use in the cultural heritage sectorin forensic investigations
PRAXISMajor integration tasks
PRAXISDecrease the effect of the fluorescent background
‘standard’ remote probesoffer non-optimal P/B ratio
→ use high-magnification objective lens→ use fibre entrance as confocal pinhole→ permit different λ’s
to be used
~ 5 μm lateral resolution~ 8 μm depth resolution
bankinkA1_1200_10x1s.txt
800 1000 1200 1400 1600Raman wave nr., cm-1
45005000
5500
6000
6500
7000
75008000
Inte
nsity
, c/s
bankink_a1_50la_d00_h1015_novideo.txt
800 1000 1200 1400 1600Raman wave nr., cm-1
2.0E4
2.2E4
2.4E4
2.6E4
2.8E4
3.0E4
3.2E4
Inte
nsity
, c/s
bankinkt_a1_e.txt
800 1000 1200 1400 1600Raman wave nr., cm-1
2.0E5
2.2E5
2.4E5
2.6E5
2.8E5
3.0E5
3.2E5
Inte
nsity
, c/s
conventionallaboratory Raman
conventionalRaman remote probe
redesignedULWD Raman probe
red/purple:anthocyanine colourant
= 632.8 nm (HeNe laser)
PITTCON’05 announcement
A new confocal Raman fibre optic probe brings new opportunities
for Raman samplingF. Adar, S. Morel, B. Roussel,
JOBIN YVON K. Janssens,
UNIVERSITY OF ANTWERPL. Chrit, C.Hadjur,
L’OREAL
MArtAMobile Art Analyser
P. Vandenabeele, T.L. Weis, E.R. Grant, L.J. Moens, ABC 379 (2004) 137-142
20x LWD objective lens
µ-XRF/µ-RAMANCombined atomic and molecular spectrometry
ultra-long working distance 50xobjective lens
lateral focus: ~ 5 m; depth focus: ~ 8 m+ working distance: 2 cm
→ enough room for X-ray irradiation and detection
T
DPC
R
M
Raman signalsXRF signals
XRF part of PRAXISBeam size/intensity
8-10 mm WD for X-ray lens
Two lenses were producedand evaluated• IfG Lens Praxis-7• XOS Lens 2727
Both lenses have identical focal distances/length,i.e., they are interchangeable
Beam size 10 keV 17 keV@ 17 keV Gain Gain
IFG Praxis-7 ~ 40 μm 2500 2500 XOS 2727 ~ 25 μm ~2000 Mo X-ray tube
µ-XRF/µ-RAMAN3D CAD views
R
E
M
DP: Polycapillary lensT: X-ray tubeD: Drift-chamber XRF-detectorC: Centerpiece (Al)E: EndoscopeR: Raman headM: ULWD microscope objective
Bottom view
Side view
T
E
D
PC
University of Antwerp, BInstitut für Gerätebau, Berlin, DJobin-Yvon S.A., Lille, F
D R
PRAXISCurrent Outlook of combined instrument
Raman spectra with and w/o XRF: identicalRaman spectra with and w/o endoscope: identicalXRF spectra with and w/o Laser: identical
sample stage
PRAXISTrace elements in Glass: MDLs
NIST SRM 611
0
10
20
30
40
50
60
70
80
90
100
20 25 30 35 40
Atomic Number
MD
L,
ug
/g
nbs611_noHe.spe
0 5 10 15 20Energy, keV
1
10
100
1000
10000
Inte
nsity
, cou
nts
500 ppm of transition elements
Ca
Ti
Cr
Fe
Ni
ZnSr
Zr
RbY
Ge
unfiltered conditions
PRAXISUse of 12.5 μm Mo filter to improve MDLs
nbs611_noHe.spe
0 5 10 15 20Energy, keV
1
10
100
1000
10000
Inte
nsity
, cou
nts
500 ppm of transition elements
Ca
Ti
Cr
Fe
Ni
ZnSr
Zr
RbY
Ge
PRAXIS (unfiltered): 40 ppm MDLs
μ-XRF (filtered): 10 ppm MDLs
µ-XRF/µ-RAMAN
“Byzantine style” Icon, Chalkidiki, Greece (Ormylia Art Diagnostics Centre)
Combined use on a ‘Test’ icon
• painted panel• egg-tempera-based paints• traditional substrate material
• mostly traditional pigments• a few ‘modern’ pigments
• known paint layer order
ic_04.SPE
0 5 10 15Energy, keV
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
ic_05.SPE
0 5 10 15Energy, keV
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
µ-XRF/µ-RAMANic-06.txt
500 1000 1500 2000Raman wave nr., cm-1
20
40
60
80
100
Inte
nsity
, c/s
rutile – TiO2
Ti-white
ic_06.SPE
0 5 10 15Energy, keV
10
100
1000
10000
Inte
nsity
, cou
nts
White rim of Christ’s halo
Ca
PbPb
Cu
Fe
Mn
Ti
Brown-red lines
CaFe
Ti
Yellow-brown
Byzantine style Icon, OADC, Chalkidiki, Greece
Ca
Fe
Ti
Mn Cu
ic-05.txt
500 1000 1500 2000Raman wave nr., cm-1
20
40
60
80
Inte
nsity
, c/s
?
ic-04.txt
500 1000 1500 2000Raman wave nr., cm-1
5
10
15
20
25
Inte
nsity
, c/s
hematite
289
407615
1350
ic_14.spe
0 5 10 15Energy, keV
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
ic_14.txt
500 1000 1500 2000Raman wave nr., cm-1
200
400
600
800
1000
12001400
Inte
nsity
, c/s
ic_08.SPE
0 5 10 15Energy, keV
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
ic-08.txt
500 1000 1500 2000Raman wave nr., cm-1
100
200
300
Inte
nsity
, c/s
µ-XRF/µ-RAMAN
Red blood stains
SPb
Hg
Ca
Red gowns
CdFe
Ti
Secadmium red
cinnabar
298PbPb
Ca
S
Hg
PbPb
343
252
ic-07.txt
500 1000 1500 2000Raman wave nr., cm-1
20
40
60
80
100
120
140
Inte
nsity
, c/s
Cadmium red+ Ti-white
+ Carbon-black
Byzantine style Icon, OADC, Chalkidiki, Greece
µ-XRF/µ-RAMANDark blue background
Blue sleeve of Virgin Maryic-12.txt
500 1000 1500 2000Raman wave nr., cm-1
50
100
150
200
250
300
Inte
nsity
, c/s
ultramarine
ic_12.SPE
0 5 10 15Energy, keV
10
100
1000
10000In
tens
ity, c
ount
s
Ca
PbPb
Fe
Mn
Ti
no Co, no Cu
SiS
ic03.txt
500 1000 1500 2000Raman wave nr., cm-1
4
5
6
7
8
Inte
nsity
, c/s
carbonblack
azurite
ic_03.SPE
0 5 10 15Energy, keV
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
PbPb
Fe
Mn
Cu
SCo
4031098
250
Byzantine style Icon, OADC, Chalkidiki, Greece
ic_10.SPE
0 5 10 15Energy, keV
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
ic-09.txt
500 1000 1500 2000Raman wave nr., cm-1
5
10
15
20
Inte
nsity
, c/s
ic-10.txt
500 1000 1500 2000Raman wave nr., cm-1
50
100
150
200
250
Inte
nsity
, c/s
ic_10.SPE
0 5 10 15Energy, keV
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
µ-XRF/µ-RAMAN
hematite
Brown background
Ca
PbPbFe
Mn
Ti
Dark green background
?Ca
PbPbFe
Mn
Cr
no Cu
umber ?
Cr-green
carbon black
= 632.8 nm (HeNe laser)Byzantine style Icon, OADC, Chalkidiki, Greece
µ-XRF/µ-RAMAN
iconblue_1200_20x5s.txt
500 1000 1500 2000Raman wave nr., cm-1
500
1000
1500
Inte
nsity
, c/s
545
1086 251
796
Na8..10Al6Si6O24S2..4
ICONEYE1.SPE
0 5 10 15 20Energy, keV
1.0E0
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
Si(?)
Fe
Pb
PbS
no Co, no Cu
PbCa Zn Pb
Hg, Pb Cr, Co
Ca, Fe
Hg, Pb Cr, Co Ca, Fe
ICONRED1.SPE
0 5 10 15 20Energy, keV
1.0E0
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
Fe
Pb
PbS
Pb
Ca
Zn Pb
Hg
ICON_RED_SM.txt
500 1000 1500 2000Raman wave nr., cm-1
-20
0
20
40
60
80
100
Inte
nsity
, c/s
Cinnabar
343
252
µ-XRF/µ-RAMAN
‘Our Lady, the Life-giving Spring’ (1534)Saint Modestos’s Church
in Kalamitsi, Chalkidiki, Greece
S. Daniilia et al., J. Raman Spectrosc. 2002; 33: 807–814
varnish (10-40 μm) [FTIR]Red lake (20 μm) [FTIR]lead white (10-15 μm)minium + caput mortuum + cinnabar (10-20 μm)caput mortuum + carbon black (10 μm)yellow bole base (0-5 μm)preparation layer (gesso)
1064 nm, Bruker 100 FT-Raman, UCL, UK632 nm Renishaw 1000, Ormylia, Greece
µ-XRF/µ-RAMANpaint layer cross-section
kal19b.txt
500 1000 1500 2000Raman wave nr., cm-1
0.2
0.4
0.6
0.8
1.0
Inte
nsity
, c/s
kal19a.txt
500 1000 1500 2000Raman wave nr., cm-1
20
40
60
80
Inte
nsity
, c/s
kal19c.txt
500 1000 1500 2000Raman wave nr., cm-1
10
20
30
40
Inte
nsity
, c/s
1052CO3
-2
289
407615
1350
289
407615
1350
252 caput mortuum + cinnabar
caput mortuum
gesso (chalk)
µ-RAMAN/µ-XRFpaint layer
cross-section
kal19c.SPE
0 5 10 15Energy, keV
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
kal19b.SPE
0 5 10 15Energy, keV
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
kal19a.SPE
0 5 10 15Energy, keV
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
Hg
FePb
Pb Ca
S
Fe
Pb Pb
Ca S
Fe
caput mortuum + minium + C-black
cinnabar
µ-RAMAN/µ-XRFpaint layer
cross-section
kal19d.txt
500 1000 1500 2000Raman wave nr., cm-1
50
100
150
200
Inte
nsity
, c/s
kal19f.txt
500 1000 1500 2000Raman wave nr., cm-1
5
10
15
Inte
nsity
, c/s
252
341
550
kal19g.SPE
0 5 10 15Energy, keV
10
100
1000
10000
Inte
nsity
, cou
nts
kal19f.SPE
0 5 10 15Energy, keV
10
100
1000
10000
Inte
nsity
, cou
nts
kal19e.SPE
0 5 10 15Energy, keV
10
100
1000
10000
Inte
nsity
, cou
nts
Fe Pb Pb
SPb
Fe Pb Pb Ca S
no Raman
Bank security inks20 inks supplied by security firms
1 purple small bottle2 purple small bottle3 purple small bottle
4 dark pink/purple small bottle 5 dark pink/purple small bottle 6 dark pink/purple small bottle 7 dark pink/purple small bottle
8 purple small bottle9 purple small bottle10 pink-red small bottle11 purple small bottle12 grey-black small bottle13 black small bottle14 pink-red small bottle15 dark blue small bottle16 grey-black small bottle17 pink-red small bottle18 dark purple small bottle19 black small bottle20 red small bottle21 purple small bottle
Bank security inksXRF part of PRAXIS
FINK1_1PR.SPE
0 5 10 15 20Energy, keV
1.0E0
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
FINK1_11HO.SPE
0 5 10 15 20Energy, keV
1.0E0
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
FINK17_1LA.SPE
0 5 10 15 20Energy, keV
1.0E0
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
FINK10.SPE
0 5 10 15 20Energy, keV
1.0E0
1.0E1
1.0E2
1.0E3
1.0E4
1.0E5
Inte
nsity
, cou
nts
BrBr
BrBr
Cu Cu
Ho Pr
Undoped ink
SCl
K
SCl
K
MnCuS
La
Fe
SCl
K
Bank security inksink-drops on glass slides
FINKT17B_10X50S.txt
600 800 1000 1200 1400 1600 1800 2000Raman wave nr., cm-1
220
240
260
280
Inte
nsity
, c/s
FINKT1_10X3S.txt
600 800 1000 1200 1400 1600 1800 2000Raman wave nr., cm-1
100
150
200
250
Inte
nsity
, c/s
FINKT10A_10X10S.txt
600 800 1000 1200 1400 1600 1800 2000Raman wave nr., cm-1
25
30
35
40
45
50
55
Inte
nsity
, c/s
FINKT11A_10X10S.txt
600 800 1000 1200 1400 1600 1800 2000Raman wave nr., cm-1
80
100
120
140
160
Inte
nsity
, c/s
red
purple purple
purple
same colour- same line pattern- different P/B or other extra lines
methyl-violet