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, Belgium
b Department of Chemistry, Universita' di Firenze, Sesto Fiorentino (Fi), Italy
c Jobin-Yvon – Raman Division, Villeneuve d'Ascq, France
d Institut für Gerätebau, Berlin, Germany
e Department of Chemistry, Universitat Rovira I Virgili, Tarragona, Spain
f Sacred Convent of the Annunciation IMSP, Ormylia-Chalkidiki, Greece
g Department of Chemistry, University of Warsaw, Poland
h 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, Amsterdam
ISBN 0-444-50738-8
December 2004 - 17 Chapters, 800 pages
ND Microanalysis of
Cultural Heritage materials
Methods
•
•
•
•
•
•
•
Electron microscopy
Ion-beam microanalysis
LA-ICP-MS
X-ray based methods
XPS / AES
Secondary ion microscopy
IR & Raman spectroscopy
Electrons, X-rays
Protons, X-rays
Laser, MS
X-rays
X-rays, electrons
Heavy ions, MS
Laser, photons
Atomic
Mixed
Molecular
Problems
•
•
•
•
•
•
•
•
Copper alloy artifacts
Precious metal artifacts
Glass artifacts
Medieval silver coins
Byzantine frescoes and icons
Illuminated manuscripts
Corrosion of glass/enamels
Iron-gall ink corrosion
ESEM, XRD, FTIR
PIXE, PIGE, XRF
LA-ICP-MS, XRF, SEM, NAA
XRF, PIXE
Raman, FTIR, UV
Raman, XRF
SEM, SIMS, IR
SEM, XRF, XANES, ICP-MS
PRAXIS
Portable Raman – X-ray Instrument
RS
↓
Molecular information
Surface information
XRF
↓
Elemental information
‘Deep’ information
fluorescent photons  scattered photons
μ-XRF
confocal μ-RS
Portable μ-XRF
Remote probe μ-RS
PRAXIS
X-ray fluorescence analysis
Energy dispersive spectra: characteristic lines
Ka and Kb line-emission
X-ray fluorescence analysis
conventional instrumentation
irradiated area: 1-2 cm2
↑ Polarized excitation
← Direct excitation
X-ray Capillary Optics
X-ray
S
q0
q0
q0
q0
Straight capillary
X-ray
S
q0
q1
Conical capillary
S
X-ray
Ellipsoidal capillary
Polycapillary lens
X-ray
Transportable µ-XRF
Compact instrumentation for in-situ analyses
M. Schreiner et al., Academy of Fine Arts, Vienna
X-ray
Tube
+
PC lens
Zoom Microscope
Si Drift
Chamber
Detector
Academy of Fine Arts,
Vienna
Loetz
glass
Exhibition of Assyrian Gold Artefacts, January-June 2001
Kunsthistorisches Museum, Vienna
Portable µ-XRF
Compact instrumentation for in-situ analyses
Axial X-ray beam
Polycapillary lens → 60-80 μm
Drift-chamber EDX-detector
3 laser pointers (positioning)
Optical Microscope
He-flushing system (low-Z)
XYZ scanning of head
[H. Bronk et al., TU Berlin]
Microscopic RS
Various instrument mfg
visual/NIR lasers
dispersive Raman
with parallel
CCD detection
Microscopic RS
Confocal measurements
Remote probe RS
Fibre optics – confocality ?
PRAXIS
Major integration tasks
• 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 sector
in forensic investigations
PRAXIS
Decrease the effect of the fluorescent background
Intensity, c/s
bankink_a1_50la_d00_h1015_novideo.txt
3.2E4
3.0E4
2.8E4
2.6E4
2.4E4
2.2E4
2.0E4
PITTCON’05
announcement
‘standard’
remote
probes
offer
P/B
ratio
A new non-optimal
confocal Raman
fibre
optic
conventional
laboratory Raman
800
red/purple:
anthocyanine colourant
1000 1200 1400 1600
Raman wave nr., cm-1
bankinkt_a1_e.txt
3.0E5
2.8E5
2.6E5
2.4E5
2.2E5
2.0E5
conventional
Raman remote probe
800
1000 1200 1400 1600
Raman wave nr., cm-1
Intensity, c/s
Intensity, c/s
3.2E5
8000
7500
7000
6500
6000
5500
5000
4500
bankinkA1_1200_10x1s.txt
redesigned
ULWD Raman probe
800
1000 1200 1400 1600
Raman wave nr., cm-1
l = 632.8 nm (HeNe laser)
probe brings new opportunities
→
use high-magnification
for Raman sampling
objective
F. Adar, S. Morel,lens
B. Roussel, JOBIN
→ use fibreYVON
entrance
K. Janssens,
as confocal
pinhole
UNIVERSITY OF ANTWERP
→ permit
different
λ’s
L. Chrit,
C.Hadjur,
to be
used
L’OREAL
~ 5 μm lateral resolution
~ 8 μm depth resolution
MArtA
Mobile Art Analyser
20x LWD objective lens
P. Vandenabeele, T.L. Weis, E.R. Grant, L.J. Moens, ABC 379 (2004) 137-142
µ-XRF/µ-RAMAN
Combined atomic and molecular spectrometry
R
T
P
M
C
D
ultra-long working distance 50x
objective lens
lateral focus: ~ 5 mm; depth focus: ~ 8 mm
+ working distance: 2 cm
Raman signals
XRF signals
→ enough room for
X-ray irradiation and detection
XRF part of PRAXIS
Beam size/intensity
8-10 mm WD for X-ray lens
Two lenses were produced
and 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
Mo X-ray tube
XOS 2727
~ 25 μm
~2000
µ-XRF/µ-RAMAN
3D CAD views
Bottom view
University of Antwerp, B
Institut für Gerätebau, Berlin, D
Jobin-Yvon S.A., Lille, F
P
D
D
T
C
E
R
P: Polycapillary lens
T: X-ray tube
D: Drift-chamber XRF-detector
C: Centerpiece (Al)
E: Endoscope
R: Raman head
M: ULWD microscope objective
R
D
E
M
Side view
PRAXIS
Current Outlook of combined instrument
sample stage
Raman spectra with and w/o XRF: identical
Raman spectra with and w/o endoscope: identical
XRF spectra with and w/o Laser: identical
PRAXIS
Trace elements in Glass: MDLs
NIST SRM 611
Ca
10000
Ti
Fe Zn
Sr
1000
Ni Ge
Cr
100
100
Rb
90
80
Zr
70
MDL, ug/g
Intensity, counts
nbs611_noHe.spe
Y
60
50
40
30
10
20
10
500 ppm of transition elements
1
0
5
10
15
Energy, keV
0
20
20
25
30
Atomic Number
unfiltered conditions
35
40
PRAXIS
Use of 12.5 μm Mo filter to improve MDLs
Intensity, counts
nbs611_noHe.spe
Ca
10000
Zn
Ti Fe
1000
Cr
100
Ni Ge
Sr
Rb
Zr
Y
10
1
0
500 ppm of transition elements
5
10
15
20
Energy, keV
PRAXIS (unfiltered): 40 ppm MDLs
μ-XRF (filtered): 10 ppm MDLs
µ-XRF/µ-RAMAN
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
“Byzantine style” Icon, Chalkidiki, Greece (Ormylia Art Diagnostics Centre)
µ-XRF/µ-RAMAN
White rim of
Christ’s halo
Ti Fe
Ca
Cu
Pb
Pb
Mn
10000
1000
100
80
60
rutile – TiO2
Ti-white
40
20
10
0
5
10
Energy, keV
15
Yellow-brown
ic_05.SPE
Ca
Ti
1.0E4
Fe
500
1000
1500
Raman wave nr., cm-1
2000
ic-05.txt
80
Intensity, c/s
Intensity, counts
1.0E5
ic-06.txt
100
Intensity, c/s
Intensity, counts
ic_06.SPE
1.0E3
1.0E2
60
40
?
20
1.0E1
0
5
10
Energy, keV
ic_04.SPE
Brown-red lines
25
Fe
Mn Cu
Ca
1.0E4
Intensity, c/s
Intensity, counts
1.0E5
15
1.0E3
1.0E2
Ti
15
0
5
10
Energy, keV
15
2000
ic-04.txt
407
615
289
1350
10
5
1.0E1
Byzantine style Icon, OADC, Chalkidiki, Greece
20
500
1000
1500
Raman wave nr., cm-1
hematite
500
1000
1500
Raman wave nr., cm-1
2000
µ-XRF/µ-RAMAN
Red gowns
SCa
Pb
1.0E5
1.0E4
Intensity, c/s
Intensity, counts
ic_14.spe
Pb
Pb
HgHg
1.0E3
1.0E2
1400
1200
1000
800
600
400
200
343
cinnabar
1.0E1
5
10
Energy, keV
ic_08.SPE
CdTi
Fe
S
Intensity, counts
1.0E5
1.0E4
1.0E3
Ca
1.0E2
15
Red blood stains
Intensity, c/s
0
Pb Pb
Se
300
5
10
Energy, keV
500
1000
1500
Raman wave nr., cm-1
2000
ic-08.txt
298
200
100
1.0E1
0
ic_14.txt
252
cadmium red
500
1000
1500
Raman wave nr., cm-1
15
2000
Intensity, c/s
ic-07.txt
Byzantine style Icon, OADC, Chalkidiki, Greece
140
120
100
80
60
40
20
Cadmium red
+ Ti-white
+ Carbon-black
500
1000
1500
Raman wave nr., cm-1
2000
µ-XRF/µ-RAMAN
Dark blue background
ic_03.SPE
Cu
Fe
1.0E4
S
1.0E3
8
Intensity, c/s
Intensity, counts
1.0E5
ic03.txt
Pb
Pb
Co
1.0E2
Mn
1.0E1
0
5
7
6
5
403
250
1098
carbon
azurite
black
4
10
Energy, keV
15
500
1000
1500
Raman wave nr., cm-1
2000
Blue sleeve of Virgin Mary
ic-12.txt
ic_12.SPE
1000
Ca Fe
Ti
SiS
100
Pb
Pb
Mn
no Co, no Cu
10
0
Byzantine style Icon, OADC, Chalkidiki, Greece
300
Intensity, c/s
Intensity, counts
10000
5
10
Energy, keV
250
200
150
100
50
15
ultramarine
500
1000
1500
Raman wave nr., cm-1
2000
µ-XRF/µ-RAMAN
Brown background
ic-09.txt
Ca Mn
Fe
1.0E5
1.0E4
1.0E3
20
Intensity, c/s
Intensity, counts
ic_10.SPE
Pb Pb
Ti
1.0E2
umber ?
1.0E1
0
5
10
Energy, keV
15
10
hematite
5
500
1000
1500
Raman wave nr., cm-1
15
2000
Dark green background
Ca Mn
Fe
1.0E5
1.0E4
1.0E3
250
Pb Pb
Cr
1.0E2
no Cu
1.0E1
0
Byzantine style Icon, OADC, Chalkidiki, Greece
ic-10.txt
Intensity, c/s
Intensity, counts
ic_10.SPE
5
10
Energy, keV
15
Cr-green
200
?
150
100
50
carbon black
500
1000
1500
Raman wave nr., cm-1
l = 632.8 nm (HeNe laser)
2000
ICONEYE1.SPE
Intensity, counts
µ-XRF/
µ-RAMAN
1.0E5
Pb
Fe Pb Pb
Zn
S Ca
1.0E3
Pb
Si
1.0E4
1.0E2 (?)
1.0E1
no Co, no Cu
1.0E0
0
Ca, Fe
5
10
15
Energy, keV
20
Intensity, c/s
iconblue_1200_20x5s.txt
796
1500
251
1086
1000
545
500
Na8..10Al6Si6O24S2..4
Hg, Pb
Cr, Co
500
1000
1500
Raman wave nr., cm-1
2000
µ-XRF/µ-RAMAN
ICONRED1.SPE
Intensity, counts
1.0E5
Pb
S
1.0E4
Fe Zn Pb
Pb
Ca
1.0E3
Pb
1.0E2
Hg
1.0E1
1.0E0
0
5
10
15
Energy, keV
20
ICON_RED_SM.txt
Intensity, c/s
100
80
60
40
20
0
-20
252
Cinnabar
343
500
1000
1500
Raman wave nr., cm-1
Hg, Pb Cr, Co
Ca, Fe
2000
µ-XRF/µ-RAMAN
paint layer cross-section
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, UK
632 nm Renishaw 1000, Ormylia, Greece
S. Daniilia et al.,
J. Raman Spectrosc. 2002; 33: 807–814
‘Our Lady, the Life-giving Spring’ (1534)
Saint Modestos’s Church
in Kalamitsi, Chalkidiki, Greece
paint layer
cross-section
Intensity, c/s
40
30
20
10
1350
289
615
407
252
caput mortuum + cinnabar
500
1000
1500
Raman wave nr., cm-1
Intensity, counts
kal19c.txt
µ-RAMAN/µ-XRF
kal19c.SPE
Fe
1.0E5
1.0E4
1.0E3
Hg
1.0E2
1.0E1
0
2000
5
kal19b.txt
Intensity, counts
Intensity, c/s
0.6
1350
407
615
289
0.4
0.2
500
1000
1500
Raman wave nr., cm-1
2000
1.0E5
S
1.0E4
Ca
Pb
1.0E2
0
caput mortuum
5
10
Energy, keV
15
kal19a.SPE
1052
CO3-2
40
gesso (chalk)
20
2000
Intensity, counts
Intensity, c/s
Pb
1.0E1
80
500
1000
1500
Raman wave nr., cm-1
Fe
1.0E3
kal19a.txt
60
15
kal19b.SPE
1.0
0.8
10
Energy, keV
Ca Fe
1.0E5
S
1.0E4
Pb
Pb
1.0E3
1.0E2
1.0E1
0
5
10
Energy, keV
15
paint layer
cross-section
no Raman
Intensity, counts
µ-RAMAN/µ-XRF
kal19g.SPE
10000
1000
100
10
0
5
10
Energy, keV
15
kal19f.SPE
Intensity, counts
Intensity, c/s
kal19f.txt
15
10
550
5
500
1000
1500
Raman wave nr., cm-1
2000
S
Pb
10000
100
0
341
100
cinnabar
50
500
1000
1500
Raman wave nr., cm-1
2000
Intensity, counts
Intensity, c/s
150
Pb
10
caput mortuum + minium + C-black
252
Pb
1000
5
10
Energy, keV
15
kal19e.SPE
Fe
Pb
S Ca
Pb
kal19d.txt
200
Fe
10000
1000
100
10
0
5
10
Energy, keV
15
Bank security inks
20 inks supplied by security firms
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
purple
purple
purple
dark pink/purple
dark pink/purple
dark pink/purple
dark pink/purple
purple
purple
pink-red
purple
grey-black
black
pink-red
dark blue
grey-black
pink-red
dark purple
black
red
purple
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
small bottle
Bank security inks
XRF part of PRAXIS
FINK1_11HO.SPE
S
Cl
1.0E4
Cu
1.0E3
Ho
K
1.0E2
Br
Br
1.0E1
1.0E0
Cu
S
Cl
1.0E4
1.0E3
Br
Br
Pr
1.0E2
K
1.0E1
1.0E0
0
5
10
15
Energy, keV
20
0
FINK17_1LA.SPE
1.0E5
Fe
1.0E4
S
1.0E3
1.0E2
5
La
1.0E1
1.0E0
10
15
Energy, keV
20
FINK10.SPE
1.0E5
Intensity, counts
Intensity, counts
FINK1_1PR.SPE
1.0E5
Intensity, counts
Intensity, counts
1.0E5
Undoped ink
S
Cl Mn Cu
1.0E4
1.0E3
1.0E2
K
1.0E1
1.0E0
0
5
10
15
Energy, keV
20
0
5
10
15
Energy, keV
20
Bank security inks
ink-drops on glass slides
FINKT11A_10X10S.txt
purple
Intensity, c/s
Intensity, c/s
160
250
140
120
100
80
200
100
methyl-violet
600 800 100012001400160018002000
Raman wave nr., cm-1
FINKT10A_10X10S.txt
FINKT17B_10X50S.txt
260
240
red
600 800 100012001400160018002000
Raman wave nr., cm-1
same colour
- same line pattern
- different P/B or
other extra lines
Intensity, c/s
280
Intensity, c/s
purple
150
600 800 100012001400160018002000
Raman wave nr., cm-1
220
FINKT1_10X3S.txt
55
50
45
40
35
30
25
purple
600 800 100012001400160018002000
Raman wave nr., cm-1
PRAXIS I & II
current/future activities
• PRAXIS IIa : SR-based instrument
• PRAXIS I : laboratory instrument
add remote Raman probe
to SR beam line
best quality data
• PRAXIS IIb : Mobile instrument
Raman : 5 μm
XRF: 25 μm
depth-positioning: to within 3-5 μm
minimal size
and weight
limited quality