Analytical Methods for the investigation

of paintings in the Second Year

Bachelor’s Project
Contents
Build up of an easel painting ................................................................................................................... 2
Excurse: Detection of photons in semi-conductors ................................................................................ 3
Light Microscopy ..................................................................................................................................... 3
Polarized Light ..................................................................................................................................... 4
Ultraviolet illumination ....................................................................................................................... 6
Infrared illumination............................................................................................................................ 6
X-Ray Fluorescence Analysis.................................................................................................................... 7
Source .................................................................................................................................................. 8
Detector............................................................................................................................................... 9
Local information and imaging ............................................................................................................ 9
Scanning Electron Microscopy .............................................................................................................. 12

1
Build up of an easel painting

Figure 1 Schematic build-up of a painting. Reproduced from: M. Alfeld, J.A.C. Broekaert, Mobile depth profiling and sub-
surface imaging techniques for historical paintings—A review, Spectrochim. Acta Part B At. Spectrosc. 88 (2013) 211–230.
doi:10.1016/j.sab.2013.07.009.

This section is a brief summary of the build-up of an easel painting. The visual impression of a
painting is mainly defined by the paint layers. This paint consist of pigments (solid, microscopic
particles) applied in a liquid binder to color an object. The color effect is the result of the wavelength
dependent absorption and reflection of light, e.g. a red pigment absorbs all light but red light, which
it reflects. The pigment is applied in a suspension of the binder (commonly linseed oil), which
polymerizes with time and gives the painting a permanent form. Oil painting allows for the
application of new paint on not fully polymerized (dried) paint. This superposition allows for a free
creative operation of the artist, elaborate optic effects but can result in a complex stratigraphy of
paint layers.
The paint is applied on a support, commonly canvas or wood. The surface of canvas is commonly
sealed with a water based glue size, in order to protect it and prevent the absorption of the ground’s
organic medium in the support. On the prepared support the first ground layer is applied. It provides
a smooth surface to execute the painting on.
Often, but not always, the paintings motive is sketched on the ground layers, before it is executed in
paint. The sketch can provide insight in the artist’s original intention. On top of the paint layers are
sometimes glazes, which are transparent layers with a high binder to pigment ratio that add to the
visual impression. In a final step a layer of varnish is applied. This organic layer on the one hand
saturates the colours, on the other it protects the paint layers. It yellows and darkens with time, so
that it should be removed and a new varnish applied after a few decades.
Pigments slowly degrade in a painting so that the visual impression can change. Further, paintings get
damaged from handling and storage conditions. A restoration to the initial visual impression requires
one to replace the original varnish.

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Excurse: Detection of photons in semi-conductors
Most experiments in this chapter concern the detection of photons, either of the visible light,
infrared or X-ray range. The detectors used in this class are based on semi-conductors. This means
that they are under normal conditions insulators and do not conduct electricity. All their electrons
are in the so called “valence band”1, which is holding/binding the atoms in the material together. The
atoms in this band do not conduct electricity. At a slightly higher energy is the “conduction band”.
Electrons here conduct electricity and in a perfect semi-conductor this band is empty. The energy
difference between the upper part of the valence band and the lower end of the conduction band is
the so called “band gap”. No electron can occupy an energy level in this region. If a photon interacts
with the semi-conductor it can lift electrons from the valence in the conduction band proportional to
its energy (leaving nominally positive holes in the valence band). Consequently, the semi-conductor
becomes for a small amount of charge conducting and we can measure the original energy of the
photon indirectly by the charge.2

Figure 2 Principle of a semi-conductor. Adapted from de.wikipedia.org, author: Cepheiden. License: CC BY-SA 3.0.

Light Microscopy
The best lateral resolution that can be obtained by the human eye is in the range of a single hair or
approx. 50 µm (0.05 mm). The resolution can be defined, independent of the method of imaging
used, as the minimum distance at that two neighboring objects (in the simplest case lines) can be
resolved, i.e. discriminated.
To observe smaller features one can use a microscope (see Figure 3). It is based on lenses that exploit
the fact that light is refracted on a smooth interface between two media with different refractive
indexes, e.g. the glass of a lens and the surrounding air. The real image is projected in a magnified
image. This magnification allows one to observe many features, such as single cells or pigment grains,
which provide insight in the working of materials on the microscopic scale. In a classical microscope
the image is observed with the human eye. We use here digital microscopes in that a charge coupled
device (CCD) is used to record the image. It is a pixilated Si based semi-conductor device and in each

1
You may wonder what a “band” is. You know that electrons are in discrete orbitals in an atom. Atoms bond to
one another by overlapping their orbitals, forming one orbital system over the entire solid body. As in quantum
mechanics it is forbidden to have identical (or: entartete) orbitals the seemingly identical orbitals start differing
by minor amounts of energy resulting in a continuous energy band instead of discrete orbitals.
2
This is a simplified explanation, omitting many problems. Do not refer to it later in your life but get a good
text book. If you think that this is lazy of me, remember: What I do not teach you I may not ask in the exam!
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pixel the light is transformed to an electric charge that is later read out and transformed into the
image.

A microscopes limit is that one still observes the same colors as with the bare eye, i.e. no physical or
chemical properties. Its best lateral resolution (d) is given by the diffraction limit of the visible light. It
is described by the Abbe limit, which is given as the wavelength employed (λ) divided by twice the
numerical aperture (NA) of the objective lens (see Figure 3).
𝜆 𝜆
𝑑= =
2𝑛 sin𝜃 2𝑁𝐴
The numerical aperture (NA) is a crucial figure of merit of a microscope and it is defined as the
product of the refractive index of the medium surrounding the lens (n) and half the opening angle of
a cone of light being accepted by the lens (θ).
In air (n=1.0) the numerical aperture cannot exceed 1. Better numerical apertures are achieved by
immersing objective lens and object in a medium with higher refractive index, such as water or oil.
This, however, would contradict the need for a non-destructive investigation of cultural heritage
objects. Also, only high end microscopes reach the Abbe limit, common ones are more constrained
by imperfections of their optics and vibrations.
The size of pixels on the image detector is typically above 10 µm, but this is not limiting the lateral
resolution, as the image is magnified to a degree that the pixel size is not defining the lateral
resolution. It might be tempting to simply enhance the number of pixels by making them smaller.
This might on the first moment seem like a good idea, but the observed contrast in an image is
dependent on the number of photons counted and smaller pixels record proportional less photons,
so that the pixel size is a design parameter of microscopes that needs to be well balanced.

Figure 3 Left: Principle of a simple digital microscope. Right: Numerical aperture.

Polarized Light
Due to the wave-particle duality we can describe a photon as a particle and as a longitudinal electro-
magnetic wave, oscillating with a given wavelength dependent on its energy. The electric and
magnetic oscillations are perpendicular to one another in this case, but we will in the following only
describe the electric field.
If all photons in a beam of light are oscillating in the same plane the light is polarized. In the light
emitted by natural sources, such as the sun or light bulbs, the light is unpolarized. Between these two
states is partial polarized light. In elliptical, resp. circular polarized light the polarization vector is
changing with time describing either a circle or an ellipse (i.e. the polarization in one direction is
stronger than the other). The human eye is not capable to perceive the polarization of light.
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Figure 4 Polarization of light. a) oscillation in electric and magnetic field. b) linear polarized light. c) unpolarized light. d)
circular polarized light. In b) to d) only the electric component is shown.

The easiest way to obtain polarized light is to use a polarization filter that lets only light of a certain
polarization pass. Another way is reflection on a weakly absorbing medium (see Figure 5). Most of
the incident ray is refracted in the medium, while a smaller part is reflected. The light reflected under
Brewster’s angle (θB) is completely polarized. In air (n(air)=1.0) it is dependent on the refractive index
of the reflecting medium (n): 𝜃𝐵 = tan𝑛. As the refractive index is wavelength dependent
polychromatic light is never completely polarized when reflected by such a surface.

Figure 5 Principle of Brewster's angle. Source: en.wikipedia.org, author: Pajs.

A polarized light microscope can support the investigation of historical paintings in two ways: It can
suppress reflection and it can support the identification of pigments.
Paintings are often covered with a thin layer of transparent varnish. The light reflected by it can
render the observation of paintings difficult. A polarization filter in front of the microscope can
remove the polarized part of the light reflected by the varnish and allow for a better observation of
paint layers below it.
Most materials only have a single refractive index, i.e. they are optically isotropic. Complex crystals
with low symmetry can have different refractive indices, depending on the direction that light travels
through them. By selecting only light polarized in a certain plane this optical anisotropy can be
highlighted and allow one to identify grains of pigments by comparing them to known references.
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Ultraviolet illumination
Ultraviolet radiation is the part of the electromagnetic spectrum behind the violet. Its wavelength is
below 400 nm and it is more energetic than visible light. While UV light itself is not visible, it can
excite different substances to emit visible light. Among those substances are bodily fluids, which
makes UV fluorescence of interest for forensics. Also varnish emits visible fluorescence and the
intensity of emitted fluorescence rises with its age. However, the intensity depends next to age also
on the exact composition of the varnish and the storage conditions. Consequently a precise dating of
varnish by UV illumination is not possible, but differences in the age of the varnish on the same
painting can be revealed. This allows one to identify areas in that the original varnish was removed
for restoration treatments.
Beyond this, some pigments, such as Cadmium Yellow (CdS) emit visible light upon UV illumination,
but pigments that do this were commonly introduced in the 19th century or later.

Infrared illumination
Below the red region of the visible light is the Infrared with wavelengths longer than 700 nm. While
our eyes are not sensitive to this radiation, Si based sensors are. The band gap in the Si semi-
conductor allows one to record photons with a wavelength below 1000 nm, as above these photons
do not have enough energy to lift an electron from the valence into the conduction band. As IR
radiation cannot be seen they would influence pictures in unwanted ways. For this reason in most
cameras an IR filter is fixed before the sensor in an digital camera.
When investigating historical paintings IR illumination has two advantages. First of all, pigments have
different reflectance and absorption behavior in this range, so that IR images can provide additional
information on the pigments studied. This can be observed in Figure 6. While both blue pigments are
virtually identically in the visible range, ultramarine is much stronger reflecting IR light.

Figure 6 Reflectance spectra of azurite and ultramarine in linseed oil. Source: chsopensource.org

The second point is that many pigments become transparent at higher wavelengths, so that one can
see through the surface layers into the layers below. This is very well suited to see charcoal sketches
below 16th century paintings. However, the wavelength best suited for this is 1700-2000 nm, a
wavelength that cannot be detected by a Si based sensor. For this dedicated (and expensive) sensors,
such as CdHgTe arrays are needed. To distinct between imaging in the IR range below 1000 nm with
common semi-conductors and that above 1000 nm with dedicated sensors the first is called IR
photography and the second IR reflectography.

6
X-Ray Fluorescence Analysis
An atom can interact with high energetic radiation in different ways.3 The photons can of course be
scattered, either in a coherent (Rayleigh scattering, without energy loss) or incoherent (Compton
scattering, with energy loss) way. Further, the photoelectric effect can be observed: A photon of
higher energy than an electron’s binding energy can transfer its energy to it, so that it is ejected from
the atom as a photoelectron. The photoelectron has a kinetic energy of the difference of the photons
energy and the binding energy.

The atom is in an excited (i.e. energetically unfavorable state): the missing electron left an inner shell
vacancy, which can be seen as a positive charge next to the positive core of the atom. The atom can
reach a less excited state by an outer shell electron descending and filling the inner shell vacancy.
The outer shell vacancy is finally filled by an electron from the surrounding (e.g. photo electrons).
The energy by that the atom is stabilized is emitted. Either as a photon in the form of fluorescence
radiation or the energy is transferred to an outer shell electron that is emitted as an Auger electron.

The binding energy of an electron to its atom is depending on the positive charge of the atom’s core
(its number of protons, i.e. its atomic number Z) and in which shell it is.4 Thus we can conclude from
the energy of fluorescence radiation, photo- and Auger electrons on the elemental composition of a
sample.

However, electrons are strongly absorbed by the air, so that photoelectrons and Auger electrons can
only be studied in vacuum and not in ambient conditions. When we look at the Bohr atom model in
Figure 7, we see that there are not that many possible transitions, i.e. fluorescence lines. These lines
are names after the shell of the vacancy (K, L or M) and the distance to the shell from that it is filled
(one: α, two: β, three: γ).5

Most elements have fluorescence lines in the energy range between 1 and 30 keV and all elements
heavier than Mg (Z=12) can be detected by X-ray fluorescence analysis (XRF). An XRF spectrometer is
build up like most spectrometers: it has a radiation source to emit the primary radiation to interact
with the sample and a detector to record the emitted radiation. Detector and source are on the same
side of the sample so that we measure in the so called reflection geometry. However, we measure
radiation emitted by the sample, not reflected by it.

Figure 7 The photoelectric effect. a) excitation, b) relaxation, c) line nomenclature.

3
When one talks about the energy of radiation one can talk about the total energy of a beam that is
transferred to an object (e.g. when destroying rebellious planets with the Death Star) or about the energy of
the individual photon (e.g. when one is studying inner atomic electron transitions). In this text we will discuss
the latter.
4
The chemical state of the atom IS influencing the binding energy of the electrons. It is exploited in advanced
spectroscopic techniques, such as X-ray Absorption Near Edge Structure XANES. But the instruments we discuss
here lack the energy resolution to resolve these minor effects, so that we neglect this fact.
5
And spectroscopic selection rules actually result in the fact that it is not getting much worse when we look at
the atom in a quantum physical way.
7
Figure 8 XRF spectrum with indicated main lines.

Source

Figure 9 Schematics of an X-ray tube with (A) anode, (C) cathode, (W) water cooling, which was not used during the
experiments and (U) the acceleration and heating voltages. Source: en.wikipedia.org

In the experiments in this practicum X-ray tubes were used (Figure 9). In a vacuum a cathode and an
anode are mounted. By applying a high acceleration voltage (typically 30-50 kV) between these two
electrons are accelerated towards the anode. They have at the moment of impact an energy
proportional to the acceleration voltage (30-50 keV), which is the maximum energy of a photon
emitted. In the anode they are decelerated and their kinetic energy is emitted in the form of X-rays.
This is a continuous radiation up to the maximum energy called Bremsstrahlung (German for
“Decleration Radiation”). This radiation is scattered by the sample and the main source for the
background under the fluorescence lines. Next to this the high energetic electrons also knock inner
shell electrons out of the atoms, resulting in fluorescence radiation as described above. This
characteristic radiation is based on the anode material and is part of the excitation spectrum. To
enhance the number of electrons (and thus photons) the cathode can be heated by a heating current
and to prolong the lifetime of the anode it can be water cooled. The X-rays leave the tube via a
Beryllium window. While the maximum energy of emitted radiation is only dependent on the
acceleration voltage, the amount of emitted photons and the energy distribution of photons depend
on the anode material, the acceleration current and the design of the X-ray tube.

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X-ray tubes are lightweight, comparably cheap and reliable. The two most important alternatives are
radioactive sources and synchrotron sources. Radioactive sources are very reliable, independent of
an external energy source but demand high safety standards.
Accelerated electrons can interact with magnetic fields (synchrotron sources) or lasers (Inverse
Compton Sources), which provides monochromatic radiation of high intensity. This allows for
advanced X-ray techniques, but requires large installations (synchrotrons can have a circumference
of more than a kilometer) and are only accessible for short experiments. In an emergency you can
make your X-rays by unrolling scotch tape really fast.6

Detector
The wave-particle duality allows for two principal strategies when detecting X-ray photons. One can
exploit the wave character and use a diffracting crystal to separate lines and measure their
intensities. This is possible, but allows only for the observation of a limited number of lines and the
resulting detector is heavy, bulky and expensive.
But we can regard the photons as particles with a kinetic energy and exploit a Si based semi-
conductor detector, as discussed above for the microscope. In the microscope we use filters to group
the photons in red, green and blue photons and count them based on a calibration made by the
manufacturer. For XRF we want to have for each photon the precise energy, which means that we
chose the measurement conditions in a way that only one photon at a time interacts with the
detector and is processed. The electronics needed for amplifying and detecting the small charge
created by a single X-ray photon are capable of processing several tens of thousands of photons per
second.
Si based semi-conductor detectors are light weight and easily usable. Two artifacts can occur: pile-up
peaks and escape peaks. A pile-up peak happens if two photons enter the detector in a very small
time window and are detected as one photon of the summed energy. The probability for observing a
pile-up peak is of course highest for the strongest signals in the spectrum.
An escape peak happens when the semi-conductor itself is excited to emit fluorescence radiation and
this radiation “escapes” the detector undetected. This is typical close to the detector’s surface. In the
spectrum this is observed as a peak of an energy 1.74 (the Si-Kα energy) below the main peak.
As the probabilities for both artifacts are known and constant they are predictable as we deal with
huge numbers of photons.

Local information and imaging

X-ray tubes emit radiation in all directions from the anode. As we want to avoid direct irradiation of
the detector (blinding it) or us (and other people) it is shielded, so that X-rays are emitted only in one
direction onto the sample. If our sample is homogeneous (e.g. a sample ground and pressed into a
pallet) the size of the primary beam is not so much an issue, we just need to know it. If we, however,
want to analyze details on the surface of a sample (e.g. the red color of the lips of a painting) we
need a smaller beam. The easiest way is to use a collimating optic, as it is done for handheld XRF
instruments. Here the beam has a diameter of a few millimeters and only a small area is excited. It is
possible to mount a small X-ray tube with a small detector in a handheld XRF instrument.

6
Not really, it only works in vacuum, but you can check it here: C.G. Camara, J.V. Escobar, J.R. Hird, S.J.
Putterman, "Correlation between nanosecond X-ray flashes and stick–slip friction in peeling tape" Nature,
2208, 455, 1089–1092.
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Figure 10 A handheld XRF instrument

It would of course be nice if we could acquire images by XRF, where we have for every pixel of an
image a full XRF spectrum. This is possible, but not trivial. The first problem is X-ray optics. As for X-
rays the refractive index of all materials is close to one, one cannot simply use refractive optics, as in
a microscope.7 The most versatile way of focusing X-rays is to exploit the fact that under very shallow
angles X-rays are totally reflected by smooth surfaces. So, arrays of very smooth glass capillaries can
be used to guide and focus X-rays, the so called polycapillary lenses.

Figure 11 a) X-ray guided in a single capillary. Below: focusing of a parallel X-ray beam by a polycapillary lens.

With polycapillaries beam diameters down to 25-30 µm are realistic. With such a narrow beam the
surface of a painting can be scanned pixel by pixel, line by line.8 This results in a hyperspectral data
set (i.e. an image with more than 12 colour/energy channels), as it is shown in Figure 13. You can
clearly see the dominant X-ray lines in the spectral dimension. One can evaluate such a data set by
integrating spectral ranges of interest, albeit also advanced statistical methods and multivariate
analysis can be used.

7
Refractive X-ray optics exists, but do not work well with laboratory X-ray sources. X-ray optics are an active
field of research that allows in high end applications to focus beams down to a few tens of nanometers.
However, this is beyond this class.
8
One might wonder why not instead use an X-ray camera and acquire the image quickly in a single exposure.
They exists, but they have problems. Remember, what I do not explain I may not ask in the exam.
10
Figure 12 The Bruker M6 Jetstream XRF scanner, with which the painting was scanned. Image adapted from: M. Alfeld, J.
Vaz Pedroso, M. van Eikema Hommes, G. van der Snickt, G. Tauber, J. Blaas, M. Haschke, K. Erler, J. Dik, K. Janssens, A
mobile instrument for in situ scanning macro-XRF investigation of historical paintings, J. Anal. At. Spectrom. 28 (2013)
760–767. doi:10.1039/C3JA30341A.

Figure 13 Example of a hyperspectral data set with one spectral and two lateral dimensions.

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Scanning Electron Microscopy

Figure 14 Schematics of a scanning electron microscope. Note to scale. Source: en.wikipedia.org, author: Steff.

In a “Scanning Electron Microscope” (SEM) the sample is scanned with an electron beam (see Figure
14). The electrons are emitted from an electron gun (commonly a cathode, as used in the X-ray tube)
by the application of a strong voltage (a few kV) and accelerated towards the sample. On this path
the electron beam is focused by the magnetic condenser lenses and apertures. The deflection coils
are magnets whose strength is varied to scan the surface of the sample.
The electrons create two main forms of contrast: the backscattered electrons and secondary
electrons. In addition the sample can be excited by the electron beam to emit characteristic X-rays,
which is labeled energy dispersive X-ray spectroscopy (SEM-EDX).
Secondary electrons are similar to the photoelectrons discussed above (but were not created by
photon excitation, thus a different name). They have a low energy and only those from the surface
escape the sample and reach the secondary electron detector. This image gives high resolution
images of the surface that can resolve objects of a few nanometers in size (10-9 m). The contrast
observed is based on the fact that heavier atoms scatter electrons more strongly, so that these areas
appear brighter in the image. Also the surface structure of the sample creates for each spot a
different excitation geometry, so that the image also contains information on this.
Electrons scattered back from the sample have a higher energy and describe also deeper layers of
the sample, thus complement the secondary electron detector.
For the excitation of characteristic X-rays higher currents than for secondary electron imaging are
needed. Also here the electrons penetrate deep into the sample, so that the resulting lateral
resolution is in the range of a micrometer. However, this method allows one to acquire elemental
distribution images with a microscopic resolution. Further, as the measurement is under vacuum and
no air absorption occurs also lighter elements, such as C, can be detected.

SEM and SEM-EDX investigations provide deep insights, but they have strong limitations. They
provide information on samples, so only of small parts of an object that need to be removed.
Further, as electrons are absorbed in the atmosphere, the experiments are done under vacuum, so
that the samples need to be stable under such conditions. As the sample is bombarded with
electrons, the sample needs to be conducting to prevent a buildup of charge. This is normally
prevented by coating the sample with a thin conducting layer of graphite or gold.

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