Chapter 2: Principles of Radiography, X-

Ray Absorption, and X-Ray Fluorescence

• Radiography is a method
to study invisible details,
cracks, joints, in different
archaeological artifacts
• X-ray fluorescence is a
method to understand the
There is a multitude of applications:
chemical and elemental
Analysis of coins,
constituency of the artifacts
or metal materials,
• Radiography is the first pottery techniques,
survey technique; paper & paintings.
• X-ray fluorescence is
on-site analysis technique
The Value of Art and Paintings
 Investment in Analytical Techniques

X-ray facilities as quick testing tool

Electron Beam

Tungsten or
molybdenum
Nature & Origin of X-Rays – a Reminder
2.1. Physics of X-ray Sources
Char. X-Rays: Ex = h·ν = h·c/λ = ∆Ekin = Ekin(i) - Ekin(f)

Bremsstrahlung: electrons being stopped;

minimum wavelength: λm= h·c/Ekin(i)
bremsstrahlung

K-lines
Char. X-rays
EK=RH·(Z-1)2 ·(1-1/4)

ionization λm
 X-ray beam
The X-ray energy distribution is characterized by
Bremstrahlung and characteristic lines depending
on anode material and electron energy. The use
of filters originates a quasi-monochromatic x-rays beam.

Quasi monochromatic x-rays

Low energy x-rays are absorbed in filter material

 X-ray absorption mechanism
Incoming
L-edge
X-ray photon
K-edge

M-edge

X-rays are increasingly absorbed λ~1/E

in matter with decreasing energy
K-edge
Absorption: µ ~ σ ~ E-3.
Absorption edges indicate the
additional excitation of electron
from an inner shell (M,L,K),
which requires more energy.

As higher energy as less absorption

 Absorption edges
The absorption edges correspond to the ionization energies for
electrons from the inner shells of the atom: K=edge, L-edge, M-edge ...

K-edge: EK= (Z-1)2·13.6 Absorption edges for each element

L-edge: EL= (Z-σL)2·13.6·1/4 can be found in tabulations e.g.
M-edge: EM= (Z-σM)2·13.6·1/9 http://www.csrri.iit.edu/mucal.html

Data for Zn; Z = 30 Data for Pb; Z = 82

atomic weight = 65.3800; atomic weight = 207.210;
density = 7.14000 density = 11.3400
K-edge: 9.65900 keV K-edge: 88.0060 keV
L-edges: 1.19600, 1.04400, 1.02100 keV L-edges: 15.8600, 15.1980, 13.0350 keV
M-edge: 0.139000 keV M-edge: 3.85000 keV
 2.2. Radiography with X-rays
Classical technique (photography) only with high energy
photons (X-rays). X-ray sensitive film or photomultiplier.
X-rays partly absorbed

Image from
transmitted
x-rays

Material has no (or reduced) opacity for X-rays, can be

used for depth profiling and material structure analysis.
J. Lang & A. Middleton; Radiography of Cultural Material;
Butterworth Heinemann, Oxford 1997; Library # N 8558 .R33 1997
The Virgin and the Child
Workshop of Dirck Bouts
Netherland, c. 1420-1475
Oil on wood, 30.5 x 21.6 cm

X-ray tube
painting
photo-plate

The cradle at the back of the panel

appears as grid on the X-radiograph.
To improve the image, the spaces
in the cradle were filled with a resin
with an X-ray opacity similar to
that of the wooden cradle.
 X-ray energies
X-rays need energy to pass through the material to be
analyzed and to reach the detector or photographic plate.
X-rays had insufficient energy to pass through the wood.

I ( d ) = I 0 ⋅ e − µ ⋅d µ = n0 ⋅ ∑ σ i More absorption with d

i more absorption with ρ
10000 1.2
X-ray absorption coefficient X-ray transmission
1
30% reduced
Transmission I(d)/I0

1000 carbon
cadmium
transmission
µ coefficient

0.8
100
lead
through wood
0.6 >50% reduced
10
0.4 Cadmium (0.1cm) transmission
wood (2cm)
1 0.2 canvas (0.2cm)
in heavy metal
Lead (0.1cm) paint content.
0.1 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
energy [keV]
energy [keV]
Details of the Face
Some pigments, including lead white and
lead-tin yellow, contain elements of high
atomic weight. These colors will absorb
X-rays, will locally block the blackening of
the film, and will appear as light areas in
the X-radiograph. Here, lead white was
locally applied in the under-modeling of
the Virgin's face, on the ridge of the nose,
on the upper lip, and in the eye sockets.
Other pigments and cracks absorbed the
X-rays to a lesser extent, and thus appear
dark on the X-radiograph.
 Choice of Energy
Z=48 Cadmium
Z=51 Antimony

Z=79 Gold
Z=29 Copper

Co-Au,Cd,Sb

Optimum energy for X-ray beam depends on interaction cross

section and on nature (density) of material. The differences in
attenuation coefficients should be maximized by choice of energy.
 Portrait of a Man, 1541
Master of the 1540s
Netherland, 1540-1551
Oil on wood, 40.3 x 35 cm

Analysis of past
damage & repair

The X-radiograph of Portrait of a Man reveals that the white

paint for the collar extends under the area that is now black.
The join between two boards shows up as a light area in the
X-radiograph because the boards had come apart and were
glued together using an adhesive mixed with lead white.
 Lead in the Portrait of a Man
Suppose you have an X-ray source with an intensity
of I0. Calculate the difference in absorption for the
dPb= 0.1 cm layer of white lead based paint with an
attenuation coefficient of µPb=22.6 cm-1 versus the
absorption in the doil/canvas= 0.3 cm thick layers of canvas
and oil paint with an attenuation coefficient µC=0.21cm-1.

I (d Pb ) = I 0 ⋅ e − µ Pb ⋅d Pb = I 0 ⋅ e −2.26 = 0104
. ⋅ I0
only 10% of the x − rays pass through the lead - paint layer!
I (d C ) = I 0 ⋅ e − µ C ⋅dC = I 0 ⋅ e −0.063 = 0.94 ⋅ I 0
94% of the x − rays pass through the canvas - oil paint layer!
Vermeer’s Woman with a String of Pearls
1660-1665

Covered wall-hanging
tile structure of the floor
details of the chair
Another Vermeer

Vermeer van Delft; The woman with the balance

 LOOKING INSIDE A WORK
OF ART
The Thinker by
Auguste Rodin,
France 1880

The sculpture is extremely frontal, with most of its weight projecting forward. Such an
imbalance is anchored by a lead counterweight placed in the interior of the base. In the
x-radiograph, the lead anchor is visible as a white mass at the back of the base. Also
visible in the x-radiograph are iron armatures inside the sculpture. Seen as curling gray
forms, the armatures were used to hold internal core material in place during casting.
Get the right energy!

To get difference in intensity:

I Cu (d ) ( µ Pb − µ Cu )⋅d
=e
I Pb (d )
high energy x-rays are required to
penetrate massive metal material

For calculation of attenuation coefficients µ see:

http://www.csrri.iit.edu/mucal.html
 Reconstruction of Art
X-ray radiograph

before after

Ornate iron cross of unknown origin from around the mid-17th century.
Traces of gold on the surface indicate that the cross was once gilt. X-ray
radiography reveals original design and guided the restoration process.
Back to the value of paintings
Summary X-ray radiography
Radiography is a powerful tool with a wide range
of applications. Its usefulness is mainly based on
the differences in material densities which affects
the x-ray attenuation coefficients. This determines
the x-ray opacity for heavy metal or high density
material compared to low density material like paper.
The method gives only qualitative differences on
photo-screen, it is a tool for first investigation, a
detailed analysis requires more sophisticated studies.