Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept.

2010
Manfred Schreiner, Michael Melcher
Institute of Science and Technology in Art,
Academy of Fine Arts Vienna
http://www.ntk.akbild.ac.at
Application of transportable XRF
Application of transportable XRF
and
and

-
-
XRF in art and archaeology
XRF in art and archaeology
~
~
analysis of pigments, metals and inks
analysis of pigments, metals and inks
X-Ray Fluorescence Analysis (XRF)
X-Ray Tube
Spectrum
Detector
Primary X-ray
Beam
Secondary X-ray
Radiation
Sample, Object
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
Requirements for the analysis of artifacts
Requirements for the analysis of artifacts
non-destructive analysis: non-sampling !!
(non-invasive: no changes of the object !!)
air path system (no vacuum !!)
transportation of the artifact / instrument
fast simultaneous analysis
surface (patina) and bulk analysis
costs
X-Ray Fluorescence Analysis (XRF)
+ non-destructive technique
+ multielemental analysis energy dispersive
detector
+ air system
+ transportable
- x-ray radiation
- light elements < Si (S)
- coincidence of element specific radiations
Portable XRF: Instrumentation
a portable XRF instrument for in-situ
field measurements with lab-like precision:
components of a conventional laboratory-XRF
assembled in a compact and managable way
art objects in museums and galleries
mural paintings in churches and cathedrals
archeological findings at the excavation site
Portable XRF: X-ray tube
- Rh tube, 50 W (50 kV, 1 mA), Oxford XTF5011
Source: OXFORD Instruments
- Rh tube, 50 W (50 kV, 1 mA), Oxford XTF5011
- 1mm pin-hole collimator
Portable XRF: Collimator
Rh Anode
Filament
Alignment of the
sample / object by
using two laser
beams:
Their cross-over
coincides with the
axes tube-sample
& sample-detector
Rh x-ray tube
SDD
2 laser pointing
devices
Object
- Rh tube, 50 W (50 kV, 1 mA), Oxford XTF5011
- 1mm pin-hole collimator
- Silicon Drift Detector (SDD), Roentec XFlash:
Portable XRF: Detector
energy resolution
<220 eV at
250.000 cps
FWHM @ MnK
Peltier cooling (at -10C)
due to extremely low
capacitance, count rates
close to 10
6
possible
Source: KETEK Gmbh
Portable XRF: LabVIEW
- Rh tube, 50 W (50 kV, 1 mA), Oxford XTF5011
- 1mm pin-hole collimator
- Silicon Drift Detector (SDD)
- MAX-XFlash Signal Processing Unit
- LabVIEW (National Instruments) application
software
HV generator, X-ray tube
power supplies
detector, Peltier cooling
spectrometer electronics, DAQ
LabVIEW - front panel
The user interface to the virtual instrument
Publication:
V. Desnica, M. Schreiner: A LabVIEWcontrolled portable x-ray fluorescence
spectrometer for the analysis of art objects.
X-Ray Spectrometry 35 (2006) 280-286
- Rh tube, 50 W (50 kV, 1 mA), Oxford XTF5011
- 1mm pin-hole collimator
- Silicon Drift Detector (SDD)
- MAX-XFlash Signal Processing Unit
- LabVIEW (National Instruments) application
software
- WinAxil

Software (Canberra Eurisys/Belgium)

for spectra analysis
Portable XRF: Summary
Measurements in the Gallery of the
Academy of Fine Arts, Vienna
Portable XRF
V. Desnica, M. Schreiner: A LabVIEWcontrolled portable x-ray fluorescence spectrometer
for the analysis of art objects. X-Ray Spectrometry 35 (2006) 280-286
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
The New Sinaitic
Glagolitic
Sacramentary
Fragments
Analysis of
pigments and inks
Radiation Physics in Cultural Heritage , Vienna Summer School, 20. 24. Sept. 2010
September 27
th
October 4
th
2007
Seven different Glagolitic manuscripts (fragments)
Expedition
Expedition
X
X
-
-
ray
ray
Fluorescence
Fluorescence
Analysis
Analysis
X-ray tube
Detector
Laser
X
X
-
-
Ray Fluorescence Analysis
Ray Fluorescence Analysis
Glagolitic Manuscripts, Cod.Sin.Slav. 1/N and 38/O, 11
th
cent. AD
Objects
Objects
Glagolitic Manuscripts, Cod.Sin.Slav.38/O, 11
th
cent. AD
Objects
Objects
XRF
XRF
Results
Results
of Pigment Analysis
of Pigment Analysis
Pigments identified by XRF in the Glagolitic
manuscripts, 11
th
cent. AD:
Green Cu Malachite or Verdigris
Red Pb Minium
Blue Si, S, K, Ca, Fe Lapislazuli
Yellow --- organic material (dye)
XRF
XRF
Results
Results
of
of
Yellow
Yellow
S
As
S
XRF spectrum of parchment (white) and an area with yellow dye (red)
K
Ca
Fe
Ar
XRF
XRF
Results
Results
of
of
Yellow
Yellow
S
As
XRF spectrum of parchment (white) and yellow area (red): As-sulfide
Ca
Fe
XRF
XRF
Results
Results
of Pigment Analysis
of Pigment Analysis
Pigments identified by XRF in the Glagolitic
Manuscripts, 11
th
cent. AD:
Green Cu Malachite or Verdigris
Red Pb Minium
Blue Si, S, K, Ca, Fe Lapislazuli
Yellow --- organic material (dye)
As, S Realgar, Orpiment
XRF
XRF
Results
Results
of
of
Ink
Ink
Analysis
Analysis
Elements determined in the inks
components:
ink: Fe, (Cu, Zn, Pb .)
parchment: (Si, S, P) Cl, K, Ca, Fe
XRF
XRF
Results
Results
of
of
Ink
Ink
Analysis
Analysis
K
Ca
Fe
XRF spectrum of parchment (white) and ink (red)
Cu
XRF
XRF
Results
Results
of
of
Ink
Ink
Analysis
Analysis
Elements determined in the inks
components:
ink: Fe, (Cu, Zn, Pb .)
parchment: (Si, S, P) Cl, K, Ca, Fe
differences of Zn, Cu, Pb can be used
statistical analysis
(Principal Component Analysis: PCA)
clusters
Conclusion
Conclusion
XRF
- non-invasive and transportable technique
- can be applied for material analysis of
pigments and inks in manuscripts
PCA of the data yields
- to a clustering of the parchments
- and in some aspect also of the inks
used in the Cod. Sin. Slav.
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
Investigations on ancient
Investigations on ancient
Artemision
Artemision
gold objects using
gold objects using
portable
portable

-
-
XRF
XRF
The
The
Temples
Temples
of
of
the
the
Artemis in Ephesos
Artemis in Ephesos
First temple 460 BC
building time more than 100 years
dimensions 60 x 106 m
columns hight 19 m, 106 columns
destroyed by fire in 356 BC
Second temple around 350 BC
building time approx. 100 years
dimensions 72 x 125 m
columns hight 18 m, 117 columns
destroyed by gothic soldiers in 263 AD
Beautiful Artemis
(Efes Mzesi, Seluk,
Inv.No.718)
Excavations:
Excavations:
1869: John Turtle Wood
(Architect)
1904-05: D.G. Hogarth
London British Museum
Archaeological Museum
Istanbul
1965-94: A. Bammer
Efes Mzesi, Seluk
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
The area of the Temple of Artemis in Efes/Turkey in July 2007
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
Gold objects excavated in the Artemision (6
th
cent. BC)
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
Gold objects excavated in the Artemision (7-5
th
cent. BC)
Archaeological Museum Seluk
Gold objects of the Artemision/Ephesos, 7 5
th
cent. BC
Archaeological Museum Seluk
Gold coins of the Artemision/Ephesos, 6 5
th
cent. BC
First gold coins of mankind ?
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
Questions of the archaeologists:
Questions of the archaeologists:
Chemical composition of the gold objects
native gold river Pactolus
refined gold
Au-Ag-Cu alloys
Technology production of the artefacts
(granulated gold)
Dating provenance / age of the objects
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
Analysis of gold artefacts?
1) Archaeological Museum in Istanbul
2) Museum in Seluk
non-destructive analysis (non-sampling)
objects can not be moved from the collections
transport XRF to Istanbul and Seluk
A)Appliqu
A)Appliqu

s
s

examplesI:
examplesI:
ObjectNo.112/61/84
Au:72.5%
Ag:25.1%
Cu:2.5%
ObjectNo.29/51/91
Au:61.2%
Ag:36.1%
Cu:2.8%
B)Brooches
B)Brooches
(objectno.3157similarinthestylewithearringno.3033:
ObjectNo.3157
Au:98.9%
Ag:
Cu:1.1%
ObjectNo.3033
Au:98.3%
Ag:
Cu:1.7%
B)
B)
Brooches
Brooches
TypicallyhighAucontent
verysimilarcomposition
meanconcentration(range)
Au:91.5%(91.0 92.4)
Ag:4.4%(3.8 4.8)
Cu:4.2%(3.9 4.4)
Exceptions
ObjectNo.3157(98.9%Au,1.1%Cu)
C)
C)
Anthropomorphic
Anthropomorphic
/
/
zoomorphic
zoomorphic
statues
statues
ObjectNo.1/42/93(cast)
Au:67.5%
Ag:31.9%
Cu:0.6%
ObjectNo.2/59/80(metalfoil)
Au:55.1%
Ag:43.8%
Cu:1.7%
C)Anthropomorphic/zoomorphicstatues
C)Anthropomorphic/zoomorphicstatues
ObjectNo.1336187
Au:91.6%
Ag:6.7%
Cu:1.7%
ObjectNo.3093
Au:60.8%
Ag:36.3%
Cu:2.9%
higher quality
higher gold content
D)GoldCoins
D)GoldCoins
Au:57.1 64.5% ~60%
Ag:41.1 34.7%~38%goldfromtheriverPactolus (?)
Cu:1.8 0.8%<2%(lit.zgenztrk,1996)
Exceptions:43.4/51.1/5.6;83.2/15.6/1.2
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
Conclusion
Conclusion
I
I
Appliqus
Au-Ag-Cu alloys with high Ag contents
the higher the artistic quality the higher the
gold content
Fibula (brooches)
high content of Au (up to 99 %) refined gold
Statuettes
high variation in the Au content: 40 60 (90) %
serial production either cast or metal sheets
Gold coins first coins of the mankind
weight: 1,2 15 g
chemical composition ~ 60 Au/38 Ag /2 Cu
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
Conclusion II
Conclusion II
(A. Ramage P. Craddock: King Croesus Gold
Excavations at Sardis and the History of Gold Refining)
Pactolus alluvial gold grains: 74 86 % Au
17 24 % Ag
N.D. Meeks (chapt.5, p. 148):
typical unrefined native gold - ca. 70 % Au, 30 % Ag,
0.6%Cu
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
The Denarius under
Traian:
1860 Theodor Mommsen
ca. 70 coins free market
Project:
- Numismatic Commission,
Austrian Academy of
Sciences
- Kunsthistorisches Museum
- Academy of Fine Arts
Traian: AD 98 - 117
ultrasound,
EtOH/
Komplexone III
State of preservation after excavation
Ag-rich layer
homogeneous layer
Tiroler Kreuzer
100m
primary X-ray beam
Ag-L Ag-K
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
Trajan Coin No. 20,
4th Traianic consulate
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
Trajan Coins: Coin No. 20,
4th Trajanic Consulate
Corrosion layer
Core
BE image
Ag
*EU-Projekt Nr. SMT4 - CT98 2237
Coordinator: Prof. Dr. Koen Janssens
Mikro X-ray fluorescence
(-XRF)
transportable transportable instrument instrument
COPRA*
Mo tube (Oxford Instr.)
Si-drift detector (Rntec)
polycapillary polycapillary
beam diameter
ca. 0.15 mm (150 m)
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
From bulk to micro-analysis
X-Ray source
Sample
Lateral resolution measured in cm
Lateral resolution measured in m
primary radiation primary radiation
focused focused
primary radiation primary radiation
Principle of Polycapillary
COPRA - instrument
Scheme of the COPRA instrument
COPRA - instrument
Polycapillary
Rntec SDD
Stage
Sample
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
Trajan Coins: Results of ED-XRF
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60
70
80
90
100
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coin number
w
t
%

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Identification of Inks by -XRF
Letter of Bonaparte to General Michael von Melas 1800,
STA (Austrian State Archives)
Signiture Bonaparte Text
Letter of Bonaparte to General Michael von Melas 1800,
STA
Area of analysis in the signature Bonaparte
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010
Spectrum of the ink in the letter: Blue - signature Bonaparte, yellow - line under the signature,
red text of the letter, green - paper
Radiation Physics in Cultural Heritage, Vienna Summer School, 20. 24. Sept. 2010