nondestructive analysis of 16th century fore-edgenondestructive analysis of 16th century fore-edge...

Nondestructive analysis of

16th century fore-edge

miniatures

Igor Lukačević

Dept. of Physics, University J. J. Strossmayer

Osijek, Croatia

EUCMOS, 24-29 August 2014

Düsseldorf, Germany

About the book...

Jerónimo Osório,

De rebus Emmanuelis Regis

Lusitaniae...

King Manuel I of

Portugal (1469 –

1521)

Book timeline

Birckmann

print, Köln,

1575.

?

Count

Rudolf

Normann

Ehrenfels

Museum

of

Slavonija,

Osijek

1600.

2000.

1900.

1800.

1700.

Why is it so interesting?

Historical significance of

Normann-Prandau library in

Valpovo, Croatia


Colorful fore-edge miniatures

• when were they made?


Who was the owner of the

book?

Methods

Art history

Spectroscopy

Multidisciplinary study

Methods

Spectroscopy methods

UV-Vis FORS

PIXE

Raman

Complementary techniques Non-destructive

techinques

Methods – UV-Vis FORS

Experimental setup

USB2000 (OceanOptics)

200-1100 nm

Tungsten halogen light bulb

Diffuse reflectance mode

Methods – PIXE

Experimental setup

2 MeV proton beam

1 nA current

Si(Li) detector; 80 mm2; 20 mm distance

Z > 13

Methods – Raman (Ar+)

Experimental setup

Horiba Jobin-Yvon T64000

Ar+ 514.5 nm

20 mW / filters

3 cm-1 resolution

Acc time 1-2.5 min

Liquid nitrogen CCD detector 140K

Methods - samples

Results – UV-Vis FORS – red sample (B)

(■) vermilion

(♦) minium

(▲) red ochre

(∙) red sample (B)

Results – PIXE – red sample (B)

E/keV

cou

nts

• litharge (PbO)

• minium (Pb3O4)

• vermilion (HgS)

• red ochre (Fe2O3)

Results – Raman (Ar+) – red sample (B)

• minium (Pb3O4)

• vermilion (HgS)

Results – PIXE – pink sample (C)

E/keV

cou

nts

• litharge (PbO)

• minium (Pb3O4)

• lead white

(2PbCO3∙Pb(OH)2)

• red ochre (Fe2O3) minium vermilion

Results – Raman (Ar+) – pink sample (C)

• minium (Pb3O4)

• vermilion (HgS)

• realgar (As4S4)

• minium (Pb3O4) ?

• lead white

(2PbCO3∙Pb(OH)2)

Results – Raman (Ar+) – yellow sample (G)

Results – summary Area FORS PIXE Raman (Ar+)

A (gilded) gold

B (red) vermilion of

minium

vermilion and minium vermilion and minium

C (pink) minium and white lead minium and white lead

D (dark blue) any copper blue pigment any copper blue

pigment

E (light blue) any copper blue pigment and lead

white

any copper blue

pigment

F (green) malachite or verdigris or a mixture of

copper blue pigment and massicot

G (yellow) massicot

H (brown) minium + ?

Discussion

Scattering volume

1 paper thick

air

pigment layer

Methods – Raman (diode)

Experimental setup

DeltaNu Advantage 785 + NuScope Inspector

diode 785 nm

< 80 mW

5 cm-1 resolution

Acc time < 10 sec

Results – Raman (diode) – yellow sample (G)

Results – summary Area FORS PIXE Raman (Ar+) Raman (diode)

A (gilded) gold gold

B (red) vermilion of

minium

vermilion and minium vermilion and

minium

vermilion and minium

C (pink) minium and white lead minium and white

lead

minium and white lead

D (dark blue) any copper blue pigment any copper blue

pigment

egyptian blue

E (light blue) any copper blue pigment and

lead white

any copper blue

pigment

egyptian blue + lead

white

F (green) malachite or verdigris or a

mixture of copper blue pigment

and massicot

malachite

G (yellow) massicot massicot

H (brown) minium minium + carbon black

Research team U

niv

. J.J

. S

trossm

ayer,

Cro

ati

a

• I. Lukačević

• I. Ergotić TE

I of Lam

ia, G

reece

• T. Ganetsos

Mu

seu

m o

f S

lavon

ija, C

roati

a

• M. Vinaj

Special thanks to:

D. Kirin and L. Mikac, Ruđer Bošković Institute/Raman

M. Jakšić, T. Tadić, R. Smith and V. Grilj, Ruđer Bošković Institute/PIXE

References 1) W. Schmitz, Die Überlieferung deutscher Texte im Kölner Buchdruck des 15.

und 16. Jahrhunderts, Philos. Fak. der Universität zu Köln, 1990.

2) I. Lukačević, I. Ergotić, and M. Vinaj, Croatica Chemica Acta 86 (2013) 207-214.

3) P.G. Bietenholz and T. B. Deutscher, Contemporaries of Erasmus: A Biographical Register of the Renaissance and Reformation, Volumes 1-3, University of Toronto Press, Toronto, 2003.

4) C. De Hamel, Illuminated Manuscripts in Croatia, in: Croatia – Aspects of art, architecture and cultural heritage, Frances Lincoln Limited, London, 2009.

5) M. Vinaj, Ž. Vujić, Muzeologija, No.48/49, November, 2012.

6) http://www.webexhibits.org/pigments/

7) H.G.M. Edwards and J.M. Chalmers, Raman spectroscopy in archaeology and art history, Royal Society of Chemistry, Cambridge, 2005.

8) E. Ciliberto and G. Spoto, Modern analitical methods in art and archaeology, John Wiley & Sons, New York, 2000, pp. 341-356.

9) http://codexsinaiticus.org/en/project/conservation_msi.aspx

10) I. M. Bell, R. J. H. Clark, and P. J. Gibbs, Spectrochim. Acta A.-M. 53 (1997) 2159−2179.

http://www.webexhibits.org/pigments/

http://www.webexhibits.org/pigments/

http://codexsinaiticus.org/en/project/conservation_msi.aspx

http://codexsinaiticus.org/en/project/conservation_msi.aspx

Results – summary Area FORS PIXE Raman (Ar+) Raman (diode) Pigment

usage (c.)

A (gilded) gold gold

B (red) vermilion

of minium

vermilion and minium vermilion and

minium

vermilion and minium < 19.

< 19.

C (pink) minium and white lead minium and white

lead

minium and white

lead

present

D (dark

blue)

any copper blue pigment any copper blue

pigment

egyptian blue < 10.

> 1814.

E (light blue) any copper blue pigment and

lead white

any copper blue

pigment

egyptian blue + lead

white

F (green) malachite or verdigris or a

mixture of copper blue

pigment and massicot

malachite < 17.

G (yellow) massicot massicot < 19.

H (brown) minium minium + carbon

black

present

Additional materials

Raman in art

Pros

Minimal sample preparation

Weak water/glass scattering

I ~ c

Coupling to microscopes & fibers

Portable

Non-destructable

Cons

Fluorescence

Sample degradation

Examples of sample degradation

cinnabar „blackening”: α-HgS → β-HgS

minium (Pb3O4) → massicot (PbO) when λ = 514.5 nm

color changes in: massicot, litharge, plattnerite, minium

Results – PIXE – dark blue sample (D)

?

?

Results – Raman (Ar+) – dark blue sample

(D)

• egyptian blue

• azurite

• posnjakite

• egyptian blue

• azurite

• posnjakite

• azurite

• egyptian blue

Results – Raman (diode) – dark blue sample

(D)

0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

D

Ra

ma

n In

ten

sity

Wavenumber (cm-1)

Dark blue pigment

Raman peaks:372,430,480,731,811,1082,1198,1617

Egyptian Blue

d e m o d e m o d e m o d e m o








Results – PIXE – green sample (F)

• green pigments

• blue pigments

• massicot

• yellow ochre

Results – Raman (Ar+) – green sample (F)

• malachite

• verdigris no.2

• ?

• terre-verte

• verdigris raw

• verdigris no.1

• malachite

• ?

Results – Raman (diode) – green sample (F)

0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200

0

5000

10000

15000

20000

25000

30000

35000

F

Ra

ma

n In

ten

sity

Wavenumber (cm-1)

Green pigment

peaks: 348, 436, 532, 755,1054, 1086, 1232, 1498

Malachite









Results – Raman (diode) – light blue sample

(E)

0 200 400 600 800 1000 1200 1400 1600 1800 2000 22000

2000

4000

6000

8000

10000

12000

14000

16000

B

Ra

ma

n In

ten

sity

Wavenumber (cm-1)

Light Blue pigment

Raman peaks:372,428,483,563,715,1058,1078,1258,1633

Egyptian Blue - Lead white









Results – Raman (diode) – brown sample (H)

0 200 400 600 800 1000 1200 1400 1600 1800 2000 22000

20000

40000

60000

80000

100000

120000

H

Ra

ma

n In

ten

sity

Wavelength (cm-1)

Brown pigment

Raman peaks:292,360,487,571,751,1350,1600

minium and carbon









Results – Raman (Ar+) – paper (cellulose)

• O-H stretching

region

• C-H stretching

region

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