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 analysisEnergy dispersive spectra: characteristic lines

K and K line-emission

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]

Microscopic RSVarious instrument mfg

visual/NIR lasers

dispersive Raman with parallelCCD detection

Microscopic RSConfocal measurements

Remote probe RSFibre optics – confocality ?

• 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

PRAXIS I & IIcurrent/future activities

• PRAXIS I : laboratory instrument

Raman : 5 μmXRF: 25 μm

depth-positioning: to within 3-5 μm

• PRAXIS IIa : SR-based instrument

add remote Raman probeto SR beam linebest quality data

• PRAXIS IIb : Mobile instrument

minimal sizeand weightlimited quality